WO2012086328A1

WO2012086328A1 - Emulsification device, polymer particle production apparatus provided with emulsification device, and polymer particle production method using production apparatus

Info

Publication number: WO2012086328A1
Application number: PCT/JP2011/075751
Authority: WO
Inventors: 貞三福田
Original assignee: Jsr株式会社
Priority date: 2010-12-24
Filing date: 2011-11-08
Publication date: 2012-06-28
Also published as: JP5311166B2; JPWO2012086328A1

Abstract

Provided are an emulsification device, a polymer particle production apparatus provided with the emulsification device, and a polymer particle production method using the production apparatus. An emulsification device (3) comprises emulsion generating means for generating an emulsion by mixing at least two liquids capable of forming an emulsion, and particle homogenizing means for homogenizing the emulsion, wherein the liquids pass through the emulsion generating means and the emulsion passes through the particle homogenizing means, and the liquids and emulsion are dynamically mixed. A polymer particle production apparatus (100) comprises this emulsification device (3). A polymer particle production method comprises an emulsion generation step for using this emulsification device (3) to make a mixture of a polymer solution and hot water into an emulsion, and a step for spraying the emulsion onto a gas phase part of a desolvation tank.

Description

Emulsifying device, polymer particle manufacturing apparatus equipped with the emulsifying device, and polymer particle manufacturing method using the manufacturing apparatus

The present invention relates to an emulsifying apparatus, a polymer particle manufacturing apparatus including the emulsifying apparatus, and a polymer particle manufacturing method using the manufacturing apparatus. More specifically, the present invention comprises an emulsifying device that has a simple structure and can easily generate a homogeneous emulsion, and includes the emulsifying device. A mixed solution of a polymer solution and hot water is used as an emulsion. Polymer particle production apparatus for producing sufficiently homogeneous polymer particles such as crumbs or powders using an emulsion, and the emulsion produced by the emulsification apparatus using this apparatus and the gas phase part of the solvent removal tank The present invention relates to a method for producing polymer particles, which is ejected to produce sufficiently homogeneous polymer particles such as crumbs or powders.

Conventionally, various devices such as a homomixer and a line blender have been used for producing emulsions. These are widely used as devices having sufficient dispersing and emulsifying functions.For example, in a homomixer, mixing and dispersion are not possible because a part of the liquid is not sufficiently mixed by a stirring blade. Uniformity may occur, and it takes a long time to uniformly mix and disperse the whole, and the equipment tends to be large. In addition, dispersed rubber particles, resin particles, and the like may become agglomerated and cannot be made into a sufficiently homogeneous emulsion. Furthermore, since the dispersed rubber particles, resin particles, and the like collide with the stirring blade many times and a shearing force is applied, the rubber and the resin may be deteriorated. On the other hand, in the line blender, the pressure loss is large due to the long residence time, and when a high viscosity polymer solution is handled, the flow path may be blocked in the pipe where the rotor blades are arranged. And when a flow path is obstruct | occluded, there exists a problem that many effort is required in order to open and clean this flow path.

In addition, various devices such as homomixers and line blenders are often used by being incorporated in a part of a process for performing a specific process or the like by connecting other devices before and after these devices. When troubles such as blockage of the blender flow path occur, it may lead to a big trouble that the entire process must be stopped. Furthermore, since neither the homomixer nor the line blender has a liquid feeding function, a liquid feeding means such as a pump may be separately required.

Specific examples in which the homomixer, the line blender, etc. are disposed in the process include, for example, a desolvation process in which the solvent is separated and removed from the polymer solution by steam stripping (see, for example, Patent Documents 1 and 2). .) In this desolvation step, the polymer solution is poured into hot water in the desolvation tank and dispersed to form an emulsion, and the solvent is separated and removed by steam stripping with water vapor blown from the bottom of the desolvation tank. The

However, in this desolvation method, the viscous polymer that is being desolvated by steam stripping may adhere to the inner wall surface of the desolvation tank, and the polymer particles become agglomerated and float on the liquid surface. Sometimes. In addition, since the particle size of the crumb produced is large and it is not easy to sufficiently remove the solvent inside the crumb particles, there is a problem that the concentration of the solvent remaining in the recovered polymer becomes high. Furthermore, in order to reduce the residual solvent, there is a problem in terms of cost that more water vapor must be put into the desolvation tank.

Many dispersants have been developed and provided to solve these drawbacks, but a sufficient dispersion effect can be obtained when used for desolvation of polymers, particularly rubbery polymers with extremely high viscosity. There are few dispersants and further research and development is needed. Also, if the amount of the dispersant is increased, the dispersion effect may be improved, but there are many problems such as adverse effects due to the increase, for example, the physical properties of the dispersant remaining in the polymer, the impact on the product price, etc. There is. Therefore, an apparatus for efficiently and sufficiently producing polymer particles such as crumb or powder from a polymer solution without requiring an increase in the amount of the dispersant or the like, or without using a dispersant, and There is a need for method development.

JP 58-147406 A Republished Patent Gazette (International Publication Number: WO01 / 030859)

The present invention has been made in view of the above-mentioned problems of the prior art, and has a simple structure, an emulsifier that can easily generate a homogeneous emulsion, and a polymer solution comprising the emulsifier. A mixed liquid with hot water is used as an emulsion, and this emulsion is used to produce sufficiently homogeneous polymer particles such as crumbs or powders. An object of the present invention is to provide a method for producing polymer particles, in which the emulsion thus produced is jetted into the gas phase part of a solvent removal tank to produce sufficiently homogeneous polymer particles such as crumbs or powders.

The present invention is as follows.
1. An emulsion generating means for mixing two or more liquids capable of forming an emulsion to generate an emulsion;
Particle homogenizing means for homogenizing the emulsion,
The emulsifying apparatus, wherein the liquid passes through the emulsion generating means, the emulsion passes through the particle homogenizing means, and the liquid and the emulsion are dynamically mixed.
2. The emulsion generating means includes a rotating body, and a first fixed body disposed on the liquid suction side of the rotating body in the vicinity of the rotating body,
The particle homogenizing means is composed of a second fixed body that is disposed on the liquid discharge side of the rotating body in the vicinity of the rotating body and has a plurality of through holes in the emulsion passing direction. The emulsifying device described in 1.
3. The rotating body has a rotating body blade portion, the first fixed body has a fixed body blade portion, the rotating body blade portion and the fixed body blade portion are close to each other, and the rotating body blade portion and the first 2. The fixed body is close to the above 2. The emulsifying device described in 1.
4). The rotating body has a liquid feeding function. Or 3. The emulsifying device described in 1.
5. 1 above. To 4. An apparatus for producing polymer particles comprising the emulsifying device according to any one of
A polymer solution bath;
A polymer solution transfer pipe having one end connected to the polymer solution tank;
A hot water supply pipe having one end connected to the polymer solution transfer pipe;
The emulsifying device connected to the other end of the polymer solution transfer pipe;
One end part is connected to the emulsifying device directly or via another member, and the other end part is opened, and an emulsion ejection pipe for ejecting the emulsion to the solvent removal tank is provided. apparatus.
6). 4. A nozzle is formed at the tip of the emulsion ejection pipe. The apparatus for producing polymer particles according to 1.
7. 5. above. Or 6. A method for producing polymer particles using the polymer particle production apparatus described in 1.
A liquid mixture preparing step of supplying hot water from the hot water supply pipe to the polymer solution transferred through the polymer solution transfer pipe,
A liquid mixture supplying step for supplying the liquid mixture to the emulsifying device;
An emulsion generating step in which the mixed solution is made into an emulsion by the emulsifying device;
And a jetting step of jetting the emulsion from the other end portion of the emulsion jetting tube to a gas phase portion of a desolvation tank.
8). 6. The hot water is hot water in which water and water vapor are mixed in advance. The manufacturing method of the polymer particle as described in any one of.
9. 6. The mass ratio of the hot water to the polymer solution is 0.1 to 10. Or 8. The manufacturing method of the polymer particle as described in any one of.
10. An emulsion transfer pipe having one end connected to the emulsification device;
A pressure regulating valve connected to the other end of the emulsion transfer pipe, and
The one end of the emulsion ejection pipe is connected to the pressure regulating valve;
The polymer according to any one of claims 7 to 9, wherein the pressure (P ₁ ) on the inlet side of the pressure adjusting valve of the emulsion is adjusted to a pressure equal to or higher than the vapor pressure (P ₂ ) of the emulsion. Particle production method.

According to the emulsification apparatus of the present invention, the formation of a fine emulsion and the homogenization of the emulsion can be carried out continuously and in a short time in the same apparatus, and a fine and homogeneous emulsion can be easily obtained. And the structure of the apparatus is simple.
Further, the emulsion generating means is constituted by a rotating body and a first fixed body arranged in the vicinity of the rotating body on the liquid suction side of the rotating body, and the particle homogenizing means is arranged on the liquid discharge side of the rotating body. In addition, in the case where the second fixed body is disposed in the vicinity of the rotating body and has a plurality of through-holes in the emulsion passing direction, the fine emulsion is continuously generated and homogenized for a short time. Thus, the emulsification apparatus can be implemented more efficiently.
Furthermore, the rotating body has a rotating body blade portion, the first fixed body has a fixed body blade portion, the rotating body blade portion and the fixed body blade portion are close to each other, the rotating body blade portion and the second fixed body, Are close to each other, droplets can be made sufficiently fine, and the emulsion can be made more uniform, and an emulsification apparatus capable of producing a particularly homogeneous emulsion can be obtained.
Moreover, when a rotary body has a liquid feeding function, it can be set as the emulsification apparatus which can transfer the produced | generated emulsion to the desolvation tank side more easily and efficiently.
According to the polymer particle production apparatus of the present invention, by providing the emulsification apparatus of the present invention, a mixture of a solution in which a polymer such as a rubbery polymer is dissolved and hot water is converted into a fine and homogeneous emulsion. In addition, it is possible to provide an apparatus that can easily produce polymer particles such as crumb or powder using the produced emulsion.
In addition, when the nozzle is formed at the tip of the emulsion ejection pipe, the homogeneous state of the emulsion ejected as a high-speed flow is sufficiently maintained, and more homogeneous polymer particles such as crumb or powder It can be set as the apparatus which can be manufactured easily.
According to the method for producing polymer particles of the present invention, since the production apparatus including the emulsification apparatus of the present invention is used, a fine and homogeneous emulsion is ejected to the gas phase portion of the desolvation tank, and a uniform crumb shape is obtained. Alternatively, polymer particles such as powder can be easily and efficiently produced.
Further, when the hot water is hot water in which water and water vapor are mixed in advance, it can be easily heated to a predetermined temperature, particularly high-temperature hot water of 100 ° C. or more, and more efficiently in a homogeneous crumb shape Alternatively, polymer particles such as powder can be produced.
Further, when the mass ratio of hot water to the polymer solution is 0.1 to 10, a homogeneous emulsion can be obtained regardless of the concentration of the polymer in the polymer solution, and a more efficient homogeneous crumb-like shape can be obtained. Alternatively, it is possible to easily produce polymer particles such as powder.
In addition, an emulsion transfer pipe having one end connected to the emulsification apparatus and a pressure adjustment valve connected to the other end of the emulsion transfer pipe are provided, and one end of the emulsion ejection pipe is connected to the pressure adjustment valve. When adjusting the pressure (P ₁ ) on the inlet side of the emulsion pressure regulating valve to a pressure equal to or higher than the vapor pressure (P ₂ ) of the emulsion, the solvent contained in the emulsion before passing through the pressure regulating valve Vaporization prevents the polymer concentration from increasing and maintains a good dispersion state, so that uniform polymer particles such as crumbs or powders can be easily produced.

It is a schematic diagram for demonstrating an example of the process which is equipped with the manufacturing apparatus of the polymer particle of this invention, and separates and collects a polymer from a polymer solution. It is typical explanatory drawing from the inflow port of an emulsion in an emulsification apparatus of this invention to an outflow port. It is a schematic diagram of the principal part of the emulsification apparatus of this invention. It is a front view of the grid which is a 2nd fixed body. It is a schematic diagram for demonstrating an example of the conventional process which isolate | separates and collects a polymer from a polymer solution.

[1] Emulsifying device Hereinafter, an embodiment of the emulsifying device of the present invention will be described in detail with reference to the drawings.
The emulsification apparatus of this embodiment includes an emulsion generation unit and a particle homogenization unit.
In the emulsion generating means, two or more kinds of liquids (including solutions) capable of forming an emulsion are mixed, and the droplets are refined to generate an emulsion. Two or more kinds of liquids capable of forming an emulsion are not particularly limited, and examples thereof include a combination of water and an organic solvent solution in which a polymer is dissolved. More specifically, a combination of an organic solvent solution such as toluene, cyclohexane, hexane or the like in which the polymer is dissolved and water used for solvent removal is used for the production of various rubber polymers. Further, in the particle homogenizing means, the emulsion produced by the emulsion producing means is made more uniform, and a more homogeneous emulsion is obtained.

Furthermore, in this emulsification apparatus, the liquid passes through the emulsion generating means, and the emulsion passes through the particle homogenizing means. This passage means that it only circulates once in one direction and does not circulate again in the opposite direction. That is, the liquid only flows once through the emulsion generating means from the upstream side to the particle homogenizing means side, and the emulsion only flows once from the emulsion generating means side through the particle homogenizing means to the downstream side. Thus, since the liquid and the emulsion do not come into contact with or collide with the constituent members of the apparatus many times, excessive shearing force or the like is not applied, and the polymer solution is contained in the emulsion. Deterioration of coalescence is suppressed.

Also, both liquid mixing and emulsion mixing are performed dynamically. This dynamic means that mixing is performed by means driven by power, and is distinguished from means not driven by power such as a static mixer.

More specifically, as an example of the emulsifying device of the present invention, an emulsifying device 3 shown in FIG. In the emulsification apparatus 3, the emulsion generating means includes a rotating body 32, and a first fixed body 31 disposed on the liquid inflow side of the rotating body 32 in the vicinity of the rotating body 32. Is arranged on the liquid outflow side of the rotator 32 in the vicinity of the rotator 32 and is constituted by a second fixed body 33 having a plurality of through holes 331 in the emulsion passing direction (see FIG. 3 showing the main part). And FIG. 4 describing the grid). In this emulsifying device 3, the rotating body 32 is fixed to and driven by a rotating shaft 36 connected to a motor (not shown), the liquid is dynamically mixed, and the emulsion is dynamically It is made uniform.

Further, in the emulsifying device 3, two or more kinds of liquids capable of forming an emulsion flow in from the liquid inlet 34, and a first fixed body 31 and a rotating body 32 disposed in the vicinity of the first fixed body 31. The liquid droplets are pulverized and mixed by a shearing force or the like applied through the gap K1. Thereafter, the liquid in which the droplets are refined and mixed flows through the gap K2 between the rotating body 32 and the second fixed body 33 disposed in the vicinity of the rotating body 32, and drops of the polymer solution. Is contained, the droplets are made more uniform, a homogeneous emulsion is produced, fed by means such as the impeller 37, and discharged from the emulsion outlet 35.

The first fixed body 31 is not particularly limited. For example, as shown in FIGS. 2 and 3, the first fixed body 31 may be a rod-like body provided so as to protrude from the diagonally upper side of the apparatus. Such a first fixed body 31 may be provided so as to protrude from below or from one side. Further, even with only one provided protruding from the upper, lower, or side, the droplets can be sufficiently miniaturized, but if necessary, it protrudes from at least one of the upper, lower, and both sides. A plurality of (usually two to three, particularly two) first fixed bodies 1 may be provided. Further, the rotating body 32 is not particularly limited, but may be any rotating body that can rotate between the first fixed body 31 and the second fixed body 33 in the vicinity thereof. Examples thereof include a rotating body provided with a stirring blade.

In addition, the dimensions of the gap K1 between the first fixed body 31 and the rotating body 32 arranged close to each other and the gap K2 between the rotating body 32 and the second fixed body 33 arranged close to each other are particularly limited. However, it can be 20 to 3,000 μm, preferably 30 to 2,500 μm, particularly preferably 50 to 2,000 μm. If the size of these gaps is 20 to 3,000 μm, a more uniform and uniform emulsion can be easily produced.
The gaps K1 and K2 are the dimensions between the opposing surfaces of the first fixed body 31 and the rotating body 32 and the dimensions between the opposing surfaces of the rotating body 32 and the second fixed body 33.

Furthermore, in the emulsifying device 3, the rotating body 32 has a rotating body blade portion on the surface facing the first fixed body 31, and the first fixed body 31 has a fixed body blade portion on the surface facing the rotating body 32. It is preferable that the rotating body blade portion and the fixed body blade portion are close to each other, and the rotating body blade portion and the second fixed body 33 are close to each other. That is, the cutting edge surface of the rotating body blade portion and the cutting edge surface of the fixed body blade portion are close to each other, and face the cutting edge surface of the rotating body blade portion and the cutting edge surface of the rotating body blade portion of the second fixed body 33. The surface is preferably close. As described above, when the rotating body 32 and the first fixed body 31 each have a blade portion, the rotating body blade portion, the fixed body blade portion, and the rotating body blade portion and the second fixed body 33 are particularly close to each other. A more homogeneous emulsion can be easily produced. Further, the dimension between the cutting edge surfaces of the rotating blade part and the fixed blade part, and between the cutting edge surface of the rotating blade part and the surface facing the cutting edge surface of the rotating blade part of the second fixed body 33. The dimensions can be 20 to 3,000 μm, respectively, preferably 30 to 2,500 μm, particularly preferably 50 to 2,000 μm. If the dimension between the blade edge surfaces of the blade portion is 20 to 3,000 μm, a more homogeneous emulsion can be easily generated.

The rotating body 32 may have only a cutter function for refining a liquid or the like, but preferably has a liquid feeding function. Thus, as the rotary body 32 which has both a cutter function and a liquid feeding function, a cutter impeller etc. are mentioned, for example. In this case, it is possible to deliver a larger amount of liquid at a higher speed as compared with liquid feeding using only the impeller 37, and to discharge a predetermined amount of the emulsion from the emulsifying device 3 more easily and more efficiently. Can do.

Although the 2nd fixing body 33 which has the some through-hole 331 in the passage direction of an emulsion is not specifically limited, For example, a grid like FIG. 4 is mentioned. In such a grid, droplets and the like are made more uniform and mixed more sufficiently by the gap between the grid-side surface of the rotator 32 and the grid-side surface of the rotator 32. Further, the uniformization of the droplets is further promoted by the gap between the grid-side surface of the rotator 32 and the peripheral edge of the opening of the grid through-hole on the rotator 32 side. The planar shape of the through-holes of the grid is not particularly limited, and may be any of a circle, an ellipse, a polygon such as a triangle, a quadrangle, and a hexagon, and may be a slit shape, but a circle (Refer to FIG. 4), it is often elliptical. Further, the size of the through hole is not particularly limited, but in the case of an emulsion containing a polymer solution, the through hole preferably has a small diameter, and the maximum length of one through hole when the grid is viewed in a plane. The (representative diameter) is preferably 3 to 90 mm, particularly 3 to 60 mm, and more preferably 3 to 30 mm. Furthermore, it is more preferable that the through holes are evenly arranged at substantially equal intervals in the plane direction of the grid. In FIGS. 2 and 3, the grid has an L-shaped cross section viewed from the side and has a flange portion, but may be a flat grid having no flange portion. Further, if the structure of the flange portion is a combination of a ring and a plate-like grid, the clearance can be adjusted, and the effect of further miniaturization and uniformization can be further improved.

[2] Polymer Particle Manufacturing Apparatus and Manufacturing Method Hereinafter, an embodiment of the polymer particle manufacturing apparatus and manufacturing method of the present invention will be described in detail with reference to the drawings.
In the polymer particle manufacturing apparatus 100 of FIG. 1, the polymer solution delivered from the polymer solution tank 1 is passed through a polymer solution transfer pipe 21 having one end connected to the polymer solution tank 1 by a pump P1. Be transported. Then, hot water is supplied from the hot water supply pipe 22 connected to the middle part of the polymer solution transfer pipe 21 and opened to become a mixed solution of the polymer solution and hot water. Next, the mixed solution is transferred through the polymer solution transfer pipe 21 and is sent to the emulsifying device 3 of the present invention connected to the other end of the polymer solution transfer pipe 21 (for transferring the polymer solution). On the downstream side of the position where the hot water supply pipe 22 of the pipe 21 is connected, the mixed solution of the polymer solution and hot water is transferred, but the whole from the polymer solution tank 1 to the emulsifier 3 is transferred. Is a polymer solution transfer pipe 21).

The liquid mixture fed into the emulsifying device 3 circulates through the gap K1 between the first fixed body 31 and the rotating body 32 disposed in the vicinity of the first fixed body 31, and the droplets are refined. The mixed liquid is then refined and mixed, and the mixed liquid flows through the gap K2 between the rotating body 32 and the second fixed body 33 disposed in the vicinity of the rotating body 32. The droplets of the solution are made more uniform, and a homogeneous emulsion is formed. The solution is sent by means such as an impeller 37 and discharged from the emulsion outlet 35. Next, the discharged emulsion is transferred through an emulsion jet pipe 24 whose one end is connected to the emulsifying device 3 directly or via another member, and is opened to the gas phase part of the desolvation tank 5. The polymer particles are ejected from the other end of 24 to produce polymer particles such as crumb or powder. In addition, it is preferable to arrange | position the emulsion transfer piping 23 and the pressure control valve 4 between the emulsification apparatus 3 and the emulsion ejection pipe | tube 24. FIG. That is, the emulsion discharged from the emulsion outlet 35 is transferred through an emulsion transfer pipe 23 having one end connected to the emulsifying device 3, and the pressure regulating valve 4 connected to the other end of the emulsion transfer pipe 23. It is preferable that the pressure is adjusted by the pressure adjusting valve 4. In this case, the emulsion whose pressure has been adjusted is transferred through the emulsion ejection pipe 24 and ejected to the gas phase portion of the solvent removal tank 5.

The hot water supplied from the hot water supply pipe 22 to the polymer solution transferred through the polymer solution transfer pipe 21 is not particularly limited. However, as shown in FIG. It is preferable to circulate and reuse the filtrate obtained by filtering the aqueous dispersion containing the polymer particles with the filter 6. In this case, the filtrate is circulated to the ejector 8 connected to the other end of the hot water supply pipe 22 by the pump P3, and the steam V is supplied to the ejector 8 together with this circulating water to be supplied as hot water at a higher temperature. It is preferable. The excess filtrate is drained from the drain pipe D.

The temperature of the hot water supplied to the polymer solution is not particularly limited as long as the emulsion generation in the emulsifying device 3 is facilitated, but the temperature of the hot water is the temperature of the mixed solution of the polymer solution and the hot water, The temperature is preferably 50 to 180 ° C., particularly 80 to 150 ° C. Moreover, when the temperature of the liquid mixture is on the higher temperature side, as described above, it is preferably hot water in which water and water vapor are mixed in advance, and when the temperature of the liquid mixture is on the lower temperature side Alternatively, hot water obtained by heating water may be used. Further, the mass ratio between the polymer solution and hot water is not particularly limited, but the mass ratio (M _p / M _w ) between the polymer solution (M _p ) and hot water (M _w ) is 0.1 to 10%. In particular, it is preferably 0.2 to 5.

The mixed solution in which hot water is supplied to the polymer solution as described above is made into an emulsion by the emulsifying device 3, and the produced emulsion is transferred through the emulsion ejection pipe 24, and the gas phase part of the desolvation tank 5 is obtained. Is erupted. Further, as described above, the produced emulsion is transferred through the emulsion transfer pipe 23 whose one end is connected to the emulsifying device 3, and is supplied to the pressure regulating valve 4 connected to the other end of the emulsion transfer pipe 23. Preferably it is supplied. The pressure of the emulsion ejected into the gas phase part of the desolvation tank 5 can be adjusted by the pressure regulating valve 4, and the pressure of the ejected emulsion is the pressure (P ₁ ) on the inlet side of the pressure regulating valve, it is preferably adjusted so that the vapor pressure of the emulsion _{(P 2)} or more pressure _{_(P 1} ≧ _P _2). Further, the pressure of the ejected emulsion needs to be equal to or higher than the pressure in the gas phase portion of the solvent removal tank 5. Even if a pressure regulating valve is not used, operation is possible if flushing due to pipe pressure loss is prevented.

Furthermore, the temperature of the emulsion when ejected into the desolvation tank 5 is preferably set according to the pressure during operation of the desolvation tank 5, the type of solvent to be removed, and the like. The pressure of the emulsion is usually 0 to 0.29 MPaG, particularly 0.05 to 0.20 MPaG, and the temperature of the emulsion when ejected is usually 50 to 200 ° C., particularly preferably 80 to 150 ° C. . The higher the emulsion temperature, the higher the vapor pressure, the better the dispersion of the emulsion in the desolvation tank 5, the more sensible heat due to preheating, and the greater the amount of solvent evaporation during ejection in the desolvation tank 5. Therefore, it is preferable. However, considering the alteration of the polymer due to heat and the pressure resistance of the apparatus, the temperature of the emulsion is limited.

Also, preferably, the emulsion whose pressure is adjusted by the pressure adjusting valve 4 is jetted from the opening at the other end of the emulsion jet pipe 24 to the gas phase part of the desolvation tank 5. The ejection of the emulsion may be made from the opening at the other end of the emulsion ejection pipe 24, but may be made from a nozzle formed at the tip of the emulsion ejection pipe 24 (the tip at the other end). preferable. Although the nozzle diameter depends on the viscosity, pressure, throughput, etc. of the emulsion, the smaller the nozzle diameter, the easier the ejection and fine dispersion of the emulsion, so it is usually 25 to 250 mm, and 50 to 200 mm. Preferably there is. Moreover, when there is much processing amount of an emulsion, it is preferable to increase the number of nozzles rather than enlarging a nozzle aperture. Further, the distance between the tip surface of the nozzle located in the gas phase portion of the desolvation tank 5 and the heated water surface of the desolvation tank 5 is preferably set according to the operating conditions, but is usually 0.2 to 4.0 m. In particular, it is 0.5 to 3.0 m.

The desolvation tank 5 is preliminarily filled with hot water up to about half of its internal volume, and this hot water is usually 50 to 150 ° C., particularly 70 to 140 ° C., by the steam supplied from the steam supply pipe 51. The temperature is maintained and stirring is performed by a stirring blade 521 attached to the stirring motor 52. Further, the higher the temperature of hot water, the shorter the desolubilization time. However, it is preferable to set in consideration of the softening temperature of the polymer, the thermal stability, and the efficiency of water vapor used for heating. Further, by stirring the hot water, it is possible to suppress the polymer particles, particularly the crumb-like polymer particles, from floating on the water surface and becoming a nodule during the solvent removal operation.

Further, after the emulsion is ejected into the gas phase on the hot water surface, the solvent contained in the emulsion dispersed in the hot water azeotropes with water vapor, and is sent to the solvent separator 92 via the condenser 91. , Separated from water W and recovered as solvent S. On the other hand, polymer particles deposited and separated in the form of crumb or powder in the hot water of the solvent removal tank 5 are transferred by the pump P2, the water is separated by the filter 6, and then the finishing step. 7 and is subjected to treatment such as drying by a conventional method, and the polymer is recovered. On the other hand, the water separated by the filter 6 is circulated and reused as described above.
In the solvent removal in the method for producing polymer particles of the present invention, the solvent removal can be performed sufficiently efficiently even if there is only one solvent removal tank, but the solvent removal tank into which the polymer solution is charged. Further, another solvent removal tank can be connected in series to remove the solvent in multiple stages.

[3] Polymer solution and surfactant The preferred polymer solution to be used for the emulsification by the emulsification apparatus of the present invention and the polymer particle production apparatus and production method of the present invention is not particularly limited, but is produced by a solution polymerization method. A solution in which the rubbery or resinous polymer to be dissolved is dissolved, and a solution in which the rubbery polymer is dissolved is particularly preferable. Examples of the rubbery polymer dissolved in the polymer solution include 1,4-polybutadiene, 1,2-polybutadiene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, polyisoprene, and styrene-butadiene. Examples thereof include a copolymer, a butadiene-isoprene copolymer, an isoprene-styrene copolymer, and an isobutylene-isoprene copolymer.

Further, the emulsifying device of the present invention used in the polymer particle manufacturing apparatus and manufacturing method of the present invention can make a mixed solution of a polymer solution and hot water into a sufficiently homogeneous emulsion. And / or a dispersant may be used, but may not be used. On the other hand, a surfactant and / or a dispersing agent may be added to the polymer solution for the purpose of suppressing aggregation of the polymer particles in the solvent removal tank. The surfactant and the dispersant are not particularly limited. Examples of the surfactant include an anionic surfactant (trade name “Demol”, manufactured by Kao Corporation), and amphoteric surfactant (trade name, manufactured by NOF Corporation). “Nissan Tracks K-40”), nonionic surfactants (trade name “Sorgen”, etc., manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like, and amphoteric surfactants are preferred. Further, examples of the dispersant include an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name “Plisurf”, etc.), a mixture of a nonionic surfactant and a phosphate ester, a phosphate ester and a metal thereof. Examples thereof include a salt, and a mixture of a nonionic surfactant and a phosphate ester is preferable.

When using a surfactant and / or a dispersant, the amount of these is slightly different depending on the operating conditions during the production of the polymer particles, but when the polymer contained in the polymer solution is 100 parts by mass, The surfactant is usually from 0.01 to 2.0 parts by weight, particularly preferably from 0.05 to 0.5 parts by weight. Further, the dispersant is usually 0.01 to 2.0 parts by mass, and particularly preferably 0.02 to 0.2 parts by mass. Further, when the surfactant and the dispersant are used in combination, the total amount is usually 0.02 to 3.0 parts by mass when the polymer contained in the polymer solution is 100 parts by mass. In particular, it is preferably 0.05 to 0.6 parts by mass.

When a hydrophilic surfactant and / or dispersant is used, each aqueous solution is prepared, and this aqueous solution and the polymer solution are used in the process or separately in a tank or the like (the surfactant tank in FIG. 1). A1 and dispersant tank A2) are mixed with an aqueous solution and a part of the polymer solution, and this mixture is blended with the other part of the polymer solution to produce polymer particles in the same manner as described above. it can. Further, in the case of using a lipophilic surfactant and / or dispersant, a solution in which the surfactant and / or dispersant is dissolved in a solvent capable of dissolving the surfactant and / or dispersant is used, and this solution and the polymer solution are combined. In the process, or separately in a tank or the like in the presence of water, the solution and a part of the polymer solution are mixed, and this mixture is blended with the other part of the polymer solution. Can be manufactured.
A valve V1 and a pump P4 are disposed in the flow path from the surfactant tank A1, and a valve V2 and a pump P5 are disposed in the flow path from the dispersant tank A2. The surfactant and / or dispersant should be adjusted so that none of them is used, either one is used, or both are used together by opening and closing valves V1 and V2 disposed in the respective flow paths. Can do. Further, for the surfactant and / or the dispersant, valves V1 and V2 are disposed in the flow paths from the surfactant tank A1 and the dispersant tank A2, respectively, and then the flow paths from the respective valves are routed. The liquid may be integrated and fed by only the pump P4 (or only P5). Also in this case, it is possible to adjust such that either one is not used, either one is used, or both are used together by opening and closing the valves V1 and V2.

Hereinafter, the present invention will be specifically described by way of examples.
Example 1
The apparatus shown in FIG. 1 was used (however, the valves V1 and V2 were closed and the surfactant and the dispersant were not used), and the polymer solution tank 1 [number average molecular weight 550 produced by a conventional method] A toluene solution (temperature: 80 ° C.) of 1,000 cis-1,4 polybutadiene (indicated as “BR (High Cis)” in Table 1) is contained. The supply amount of the polymer solution from 1] was 12.5 tons / hour, and hot water was supplied from the open hot water supply pipe 22 connected to the middle part of the polymer solution transfer pipe 21. This hot water has a temperature of 115 ° C. of a mixture of heated water prepared by feeding 90 ° C. circulating water from the filter 6 and water vapor having a pressure of 0.98 MPaG into the ejector 8 and the polymer solution. It supplied so that it might become ° C. The polymer solution (M _p ) and hot water (M _w ) were supplied so that the mass ratio (M _p / M _w ) was 0.5.

Thereafter, the mixed solution of the polymer solution and hot water was fed into an emulsifying device 3 (manufactured by Mitsui Kinzoku Engineering Co., Ltd., trade name “Sun Cutter”, see FIGS. 2 to 4), mixed and emulsified [first The fixed body 31 and the rotating body 32 are formed with blade portions as described above. Further, the gap between the blade edge surfaces of each blade portion is 1,000 μm, and the gap between the blade edge surface of the blade portion of the rotating body 32 and the second fixed body 33 is 500 μm. Furthermore, the rotation speed of the rotating body was 990 rpm. The second fixed body 33 (grid) is provided with 40 through holes having a diameter of 20 mm. ]. Next, the produced emulsion was fed into the pressure control valve 4 (back pressure was adjusted to 0.29 MPaG), and the solvent was removed from the nozzle 241 (one, diameter 100 mm) formed at the tip of the emulsion ejection pipe 24. Blow out to the gas phase part (position 1 m above the hot water surface) of the tank 5 (temperature of the jetted emulsion; 115 ° C., pressure in the gas phase part of the desolvation tank 5; 0.10 MPaG, heat in the desolvation tank 5 Clam-like particles of cis-1,4 polybutadiene were produced at a water temperature of 105 ° C. and a stirring blade speed of 100 rpm. Thereafter, solid-liquid separation was performed, followed by mechanical dehydration and drying to separate and recover cis-1,4 polybutadiene (details of the polymer solution are described in Table 1).

Examples 2-4
As the polymer solution, instead of the cis-1,4 polybutadiene toluene solution of Example 1, a solution-polymerized styrene-butadiene rubber having a number average molecular weight of 300,000 produced by a conventional method (“S-SBR” in Table 1) is used. ) In a cyclohexane solution (Example 2), an ethylene-propylene-diene rubber having a number average molecular weight of 110,000 (denoted as “EPDM” in Table 1), a hexane solution (Example 3), and a number average The crumb-like particles of each polymer were prepared in the same manner as in Example 1 except that a hexane solution (Example 4) of isoprene rubber having a molecular weight of 650,000 (indicated as “IR” in Table 1) was used. Each polymer was separated and recovered in the same manner as in Example 1 (details of the polymer solution are described in Table 1).

Comparative Examples 1 to 4
As the polymer solution, the toluene solution of cis-1,4 polybutadiene of Example 1 was used, and the emulsifier 3 was not used (Comparative Example 1), and the solution-polymerized styrene-butadiene rubber cyclohexane solution of Example 2 was used. The emulsifier 3 was not used (Comparative Example 2), the ethylene-propylene-diene rubber hexane solution of Example 3 was used, the emulsifier 3 was not used (Comparative Example 3), and the isoprene of Example 4 was used. A hexane solution of rubber was used, and the emulsifier 3 was not used (Comparative Example 4), except that crumb-like particles of each polymer were produced in the same manner as in Example 1, and in the same manner as in Example 1. Each polymer was separated and recovered (details of the polymer solution are described in Table 1).
The evaluation results of Examples 1 to 4 and Comparative Examples 1 to 4 are described together in Table 1.
The number average molecular weight of the rubber was measured by gel permeation chromatography. The Mooney viscosity is a value measured at 100 ° C. Furthermore, the dispersion state was observed visually. The particle size was measured by sampling crumb-like particles from a solvent removal tank and measuring with a ruler.
Further, the residual solvent was calculated as follows.
About 200 g of crumb-like particles containing the solvent and water sampled from the solvent removal tank are put together with about 0.5 liters of water into a round bottom separable flask equipped with a cooling tube and a recovery burette. The reflux operation was performed for a time. Thereafter, more than half of the water layer in the burette was removed, the cooling tube was washed with water and collected in the burette, and the amount of solvent collected in the burette was read (V milliliters). Next, the rubber part is taken out from the separable flask, and is dried by inserting it between a pair of heating rolls having a surface temperature of 110 ° C. (gap: 0.4 mm) until it reaches a constant weight, and then the dried rubber part is weighed. (Wg) and the residual solvent was calculated by the following formula.
Residual solvent (% by mass) = [V * ρ * 100 / [W + (V * ρ)] (ρ; density of solvent)

According to Table 1, in Examples 1 to 4 in which a mixed liquid of a polymer solution and hot water was emulsified using a specific emulsifying device to produce an emulsion, the recovered crumb-like particles had a particle size of 4 It was ˜15 mm and was sufficiently small, and there was no adhesion between the crumb-like particles, and the dispersion state was good. Further, the amount of the solvent remaining in the recovered polymer is as small as 0.6 to 0.8% by mass, which indicates that the quality of the recovered polymer is high. On the other hand, in Comparative Examples 1 to 4 in which crumb-like particles were produced in the same manner except that a specific emulsifying device was not used, the recovered crumb-like particles had a large particle size of 15 to 30 mm. Adhesion was also observed, and the dispersion state was poor. Furthermore, the amount of solvent remaining in the recovered polymer is as large as 1.2 to 2.0% by mass, indicating that the quality of the recovered polymer is low.

Comparative Examples 5-8
Using each polymer solution of Examples 1 to 4 (referred to as Comparative Examples 5 to 8 corresponding to each polymer solution), using the conventional polymer separation and recovery device shown in FIG. Each polymer was recovered.
In the apparatus shown in FIG. 5, the polymer solution heated in the polymer solution tank 41 was transferred by its own pressure or pump 42 and further heated to a predetermined temperature by the heat exchanger 43. Thereafter, a small amount of solid matter was removed by the filter 44 and then ejected from the nozzle 45 into the hot water of the solvent removal tank 47. The desolvation tank 47 was filled with hot water up to approximately half of its internal volume. This hot water was maintained at a temperature of 80 to 100 ° C. by steam blown from the pipe 48 and stirred by the electric stirrer 46. Further, the solvent contained in the polymer solution ejected into the hot water of the solvent removal tank 47 is azeotroped with water vapor, sent to the solvent separator 60 through the condenser 49, separated from water, and the solvent. 61 and water 62 were collected. On the other hand, the polymer precipitated in granular form in the hot water of the desolvation tank 47 was transferred to the filter 64 by the pump 63, and water was separated and recovered from the pipe 66. The water separated by the filter 64 was circulated through the water return pipe 65 and returned to the solvent removal tank 47.

The internal volume of the polymer solution tank 41 is 15 liters, and the internal volume of the solvent removal tank 47 is 100 liters (open to the atmosphere). Further, the amount of the polymer solution in the polymer solution tank 41 is 8 kg, the temperature is 160 ° C., the pressure is 1.96 MPaG, the rotational speed of the electric stirrer 46 is 1100 rpm, the nozzle 45 has a diameter of 2.0 mm, and the inside of the solvent removal tank The amount of hot water was 50 liters, and the temperature was 80 to 85 ° C.
The evaluation results of Comparative Examples 5 to 8 are also shown in Table 2.

According to Table 2, when the polymer was recovered using the conventional polymer separation and recovery apparatus shown in FIG. 5, the particle size of the recovered crumb-like particles was 15 to 50 mm, which is compared with Comparative Examples 1 to 4. The crumb-like particles were sticky to each other, and the dispersion state was poor. Further, the amount of solvent remaining in the recovered polymer is as large as 2.2 to 4.0% by mass, indicating that the quality of the recovered polymer is low.

Effects of Examples According to the above-described examples, by using a specific emulsifying device, a sufficiently finely dispersed and homogenized homogeneous emulsion is obtained, and the viscosity is lowered. Operability such as feeding to the regulating valve is improved. Further, according to the above embodiment, the polymer solution is atomized in hot water, stably dispersed and emulsified, so that when the emulsion is ejected into the gas phase of the desolvation tank, the solvent is heated. Vaporized instantly with water vapor, making crumb-like particles porous, increasing the surface area. As a result, the solvent removal rate is increased, the amount of residual solvent contained in the polymer to be recovered is greatly reduced, and the amount of steam introduced into the solvent removal tank can be significantly reduced. It is advantageous.

Furthermore, according to the above-described embodiment, even when fine dispersion by stirring is not easy by ejecting the emulsion from the small-diameter nozzle to the gas phase portion of the desolvation tank, that is, ejecting the emulsion toward the hot water surface. The good flash effect makes it easy to disperse the polymer particles, and it becomes easy to maintain the dispersion of the subsequent particles. Moreover, according to the said Example, while being able to collect | recover a polymer with little residual solvent amount, it can be set as the crumb-like particle | grain etc. of the particle size range which is easy to spin-dry | dehydrate in a finishing process.

DESCRIPTION OF SYMBOLS 100; Polymer particle manufacturing apparatus, 1; Polymer solution tank, 21; Polymer solution transfer pipe, 22; Hot water supply pipe, 23; Emulsion transfer pipe, 24; Emulsion jet pipe, 241; 3; emulsifying device, 31; first fixed body, 32; rotating body (cutter impeller), 33; second fixed body, 331; through hole, 34; liquid inlet, 35, liquid outlet, 36; 37; Impeller, 4; Pressure regulating valve, 5; Desolvation tank, 51; Steam supply pipe, 52; Motor for stirring, 521; Stirring blade, 6; Filter, 7; Finishing process, 8; , 92; solvent separator, K1; gap between the first fixed body and the rotating body, K2; gap between the rotating body and the second fixed body, P1, P2, P3, P4, P5; pump; D: Drain pipe, S: Solvent, W: Water, A1: Surfactant Tank, A2; dispersing agent tank, V1, V2; valve.

Claims

An emulsion generating means for mixing two or more liquids capable of forming an emulsion to generate an emulsion;
Particle homogenizing means for homogenizing the emulsion,
The emulsifying apparatus, wherein the liquid passes through the emulsion generating means, the emulsion passes through the particle homogenizing means, and the liquid and the emulsion are dynamically mixed.
The emulsion generating means includes a rotating body, and a first fixed body disposed on the liquid suction side of the rotating body in the vicinity of the rotating body,
The particle homogenizer is disposed on the liquid discharge side of the rotating body in the vicinity of the rotating body, and is constituted by a second fixed body having a plurality of through holes in the emulsion passing direction. The emulsifying device described.
The rotating body has a rotating body blade portion, the first fixed body has a fixed body blade portion, the rotating body blade portion and the fixed body blade portion are close to each other, and the rotating body blade portion and the first The emulsification apparatus according to claim 2, wherein the two fixed bodies are close to each other.
The emulsifying apparatus according to claim 2 or 3, wherein the rotating body has a liquid feeding function.
An apparatus for producing polymer particles comprising the emulsifying device according to any one of claims 1 to 4,
A polymer solution bath;
A polymer solution transfer pipe having one end connected to the polymer solution tank;
A hot water supply pipe having one end connected to the polymer solution transfer pipe;
The emulsifying device connected to the other end of the polymer solution transfer pipe;
One end part is connected to the emulsifying device directly or via another member, and the other end part is opened, and an emulsion ejection pipe for ejecting the emulsion to the solvent removal tank is provided. apparatus.
The apparatus for producing polymer particles according to claim 5, wherein a nozzle is formed at a tip of the emulsion ejection pipe.
A method for producing polymer particles using the apparatus for producing polymer particles according to claim 5 or 6,
A liquid mixture preparing step of supplying hot water from the hot water supply pipe to the polymer solution transferred through the polymer solution transfer pipe,
A liquid mixture supplying step for supplying the liquid mixture to the emulsifying device;
An emulsion generating step in which the mixed solution is made into an emulsion by the emulsifying device;
And a jetting step of jetting the emulsion from the other end portion of the emulsion jetting tube to a gas phase portion of a desolvation tank.
The method for producing polymer particles according to claim 7, wherein the hot water is hot water in which water and water vapor are mixed in advance.
The method for producing polymer particles according to claim 7 or 8, wherein a mass ratio of the hot water to the polymer solution is 0.1 to 10.
An emulsion transfer pipe having one end connected to the emulsification device;
A pressure regulating valve connected to the other end of the emulsion transfer pipe, and
The one end of the emulsion ejection pipe is connected to the pressure regulating valve;
The polymer according to any one of claims 7 to 9, wherein the pressure (P 1 ) on the inlet side of the pressure adjusting valve of the emulsion is adjusted to a pressure equal to or higher than the vapor pressure (P 2 ) of the emulsion. Particle manufacturing method.