JP2003113203A - Method for polymerization and nozzle used for the same method for polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently mass-produce a high-quality polymer by a method for droplet polymerization even when a polymerizable monomer having a high rate of reaction is used. SOLUTION: This method for polymerization comprises mixing a first liquid with a second liquid in a vapor phase and carrying out polymerization in the droplet form. In the method for the polymerization, the polymerizable monomer and a polymerization initiator are respectively contained in at least one of the first liquid and the second liquid. At least one of the first liquid or the second liquid is jetted in the form of a liquid film so as to spatially spread.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymerization method and a nozzle for use in the polymerization method. More specifically, it relates to a method of polymerizing by mixing two liquids in a gas phase and an improvement of a nozzle used therefor.

[0002]

2. Description of the Related Art A droplet polymerization method is known in which a liquid containing a polymerizable monomer and a liquid containing a polymerization initiator are jetted into a gas phase and mixed to proceed a polymerization reaction. The droplet polymerization method is a particularly effective method when the polymerizable monomer is instantly polymerized by contact with a polymerization initiator. For example, a water-absorbent polymer is produced by radically polymerizing an aliphatic unsaturated carboxylic acid by contacting it with a polymerization initiator. At this time, the radical polymerization reaction becomes extremely fast depending on the selection of the polymerization initiator. Therefore, conventionally, it was general to produce a water-absorbing polymer by using a solution polymerization method or a reverse phase suspension polymerization method, but there is a limit to increase the polymerization rate because it is difficult to remove the heat of polymerization. . Therefore, in recent years, it has been proposed to produce a water-absorbent polymer using a droplet polymerization method in which the heat of polymerization is efficiently removed.

According to the droplet polymerization method, the pulverization step required in the solution polymerization method, the separation step between the water-absorbing polymer and the organic solvent required in the reverse phase suspension polymerization method, and the distillation recovery of the organic solvent. No process is required. Also, depending on the conditions, part of the heat of polymerization can be used for evaporation of the water contained in the water-absorbent polymer, so that the energy load in the subsequent drying step can be reduced and it is very advantageous in terms of energy. The advantage is that Further, the droplet polymerization method has an advantage that a water-absorbent composite can be produced in a short time without handling powder by directly dropping droplets mixed in a gas phase onto a fibrous base material. is there. At this time, the water-absorbing composite having a desired water-absorbing ability can be easily manufactured by adjusting the timing of dropping and adjusting the carry-in speed of the fibrous base material. Therefore, by utilizing the droplet polymerization method, the water absorption and the water absorption rate are high,
It is possible to provide a water-absorbent composite in which superabsorbent polymer particles are immobilized on a fibrous substrate with good stability (JP-A-9-67403, JP-A-10-113556).

[0004]

However, since the droplet polymerization method is a method of colliding and mixing the first liquid and the second liquid in the gas phase, it is different from the solution polymerization method and the reverse phase suspension method. In principle, it is considered difficult to efficiently produce a large amount of polymer. FIG. 1 shows a conventionally used droplet polymerization nozzle for producing a water-absorbing polymer. Here, the first liquid (3) is supplied to the five nozzles (1) via the introduction pipe, and the second liquid (4) is supplied to the five nozzles (2) via the introduction pipe. After the first liquid and the second liquid are ejected from the tip of the nozzle, they merge and fall to allow polymerization to proceed.

The inner diameter of the nozzle is usually set to 0.1 to 0.2 mm, but if the inner diameter is made thicker, the mixing will be uneven and the quality of the water-absorbent polymer produced will vary. Therefore, the inner diameter cannot be excessively increased for mass production. Therefore, in order to mass-produce the water-absorbent polymer, it is unavoidable to increase the number of nozzles to cope with it, but this is not realistic because the cost of the manufacturing equipment increases. Further, in order for the first liquid and the second liquid ejected from the tip of the nozzle to collide with each other without displacement, the tip of the nozzle needs to be fixed accurately, but there is a slight deviation due to long-term use. There is also a problem that manufacturing efficiency is reduced due to partial clogging of the nozzle and the nozzle.

In order to deal with such a problem, a method using a slit type nozzle as shown in FIG. 2 has been proposed (Japanese Patent Laid-Open No. 11-49805). Here, the first liquid (13) is ejected in the form of a liquid film through a slit (15) provided at the bottom of the first liquid nozzle (11), and the second liquid (14) is discharged into the second liquid nozzle (12). ) Is ejected in the form of a liquid film through a slit (16) opened at the bottom of (2), and the two liquid films join together in the gas phase and fall while advancing the polymerization. According to this method, the production efficiency of the water-absorbent polymer is certainly expected to be higher than that in the case of using the opposed nozzle shown in FIG.

However, when the slit type nozzle is actually used, the width of the liquid film ejected from the tip of the slit (15, 16) becomes smaller due to the surface tension as it falls, the present inventors have studied. Confirmed by. Further, as the width of the liquid film becomes narrower, the thickness of the liquid film also becomes uneven, and the liquid film becomes uneven. Therefore, as a result of the first liquid and the second liquid that are not uniform at the collision point, the polymerization reaction also becomes uneven. Further, the liquid mixture after the collision also has a narrower liquid film width due to the surface tension as it falls. For this reason, expected droplets are less likely to be generated, and even if droplets are generated, the particle size of the droplets varies.

As described above, in the conventional droplet polymerization method, it was not possible to efficiently produce a large amount of high quality polymer by using a polymerizable monomer having a fast reaction rate. Therefore, the present invention has an object to solve such a problem of the conventional technique. That is, an object of the present invention is to provide a method for efficiently producing a large amount of a high quality polymer by a droplet polymerization method using a polymerizable monomer having a fast reaction rate. In particular, the subject was to prevent the narrowing of the width of the liquid film due to the surface tension, which is a problem of the slit type nozzle, and to manufacture a more homogeneous polymer. Another object of the present invention is to provide a nozzle suitable for use in these polymerization methods.

[0009]

Means for Solving the Problems As a result of intensive investigations by the present inventors, at least one of the first liquid and the second liquid was
It has been found that the problems of the prior art can be solved by ejecting the liquid film so as to spread spatially, and the present invention has been provided. That is, the present invention is a polymerization method in which a first liquid and a second liquid are mixed in a gas phase and polymerized in a droplet form, wherein the polymerizable monomer and the polymerization initiator are the first liquid or the second liquid, respectively. Contained in at least one of the liquids, and
There is provided a polymerization method characterized in that at least one of the first liquid and the second liquid is jetted in a liquid film shape so as to spread spatially.

In the polymerization method of the present invention, it is preferable that at least one of the first liquid and the second liquid is jetted with a velocity component on the same plane as the jet surface. In addition, at least one of the first liquid and the second liquid is jetted in a liquid film shape so as to spread spatially, and the jetted liquid film is jetted so as to include a curved portion, or formed into a hollow circle. It can be spouted to become. It is preferable that both the first liquid and the second liquid are jetted so that the liquid film cross section at the time of jetting becomes a hollow circle. At this time, the first liquid and the second liquid are formed so that a hollow circle, which is a liquid film cross section when the first liquid is jetted, is formed inside a hollow circle, which is a liquid film cross section when the second liquid is jetted. It is preferable to eject the liquid. Further, it is preferable that the center of the hollow circle of the first liquid and the center of the hollow circle of the second liquid are on the same axis. Furthermore, it is preferable that the ejection liquid pressure is adjusted so that at least one of the first liquid and the second liquid follows a tulip-shaped or onion-shaped locus after ejection. In addition, it is preferable that the ejection liquid pressures of the first liquid and the second liquid are adjusted so that the first liquid and the second liquid follow a tulip-shaped or onion-shaped locus after mixing. The polymerization initiator used in the polymerization method of the present invention is composed of an oxidizing agent and a reducing agent that are redox-based polymerization initiators, and is a polymerizable monomer, an oxidizing agent,
It is preferable that the reducing agent is contained in at least one of the first liquid and the second liquid.

The present invention further comprises a first circular opening for ejecting the first liquid and a second circular opening for ejecting the second liquid.
A nozzle for use in the above-mentioned polymerization method, wherein a first guide portion having a circular cross section is connected to the first circular opening, and the first liquid has a spiral shape on the inner wall of the first guide portion. A first liquid supply means for supplying the first liquid so as to descend to the first circular opening while following the locus of the above; and the second guiding portion having a circular cross section in the second circular opening. Second liquid supply means is provided which is connected and further supplies the second liquid such that the second liquid descends to the second circular opening while following the spiral trajectory on the inner wall of the second guide portion. A nozzle characterized in that the first circular opening, the second circular opening, the first guiding portion, and the second guiding portion are arranged concentrically.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerization method of the present invention and the nozzle used for the polymerization method will be described in detail below. In addition, in this specification, "-" means the range which includes the numerical value described before and behind that as a minimum value and a maximum value, respectively.

In the polymerization method of the present invention, the first liquid and the second liquid
When the liquids are mixed in the gas phase and polymerized in the form of droplets, at least one of the first liquid and the second liquid is ejected in the form of a liquid film so as to spread spatially. Here, “spouting in the form of a liquid film so as to spread spatially” means that the liquid film is sprayed so as to spread over a larger area than the area of the nozzle opening where the liquid is sprayed. In the conventional droplet polymerization method using the above-mentioned slit type nozzle, the cross-sectional area of the ejected liquid film is the same as the area of the nozzle opening immediately after ejection, but gradually decreases due to surface tension as it falls. It gets smaller. In the present invention, in order to avoid the narrowing of the liquid film due to such surface tension, the liquid ejected from the nozzle opening portion is spatially spread in advance.

The mode of ejecting in a liquid film shape so as to spread spatially is not particularly limited. For example, as shown in FIG. 3, the liquid can be jetted so as to have a velocity component in the longitudinal direction of the slit formed in the slit type nozzle so that the liquid spreads in the longitudinal direction of the slit. In this way, the method of the present invention can be easily carried out if the liquid is jetted so as to spread with a velocity component on the same plane as the jetting surface (the plane including the discharge port). In addition, the ejection angle and ejection velocity in these cases are as follows:
It can be appropriately determined according to the size of the slit, the permissible range of the function of the desired water-absorbent polymer, and the like.

The method of the present invention can also be applied to the case of jetting with a nozzle other than the slit type nozzle. For example, the present invention can be applied even when the opening formed in the nozzle includes a curved portion. In particular,
The case where the opening has a semicircular shape and the case where it has a C shape, a J shape, and a U shape can be mentioned. The radius of curvature of the curved portion may or may not be constant, but the case of being constant is preferred for the present invention. For example, as shown in FIG. 4, when an opening formed of a curved portion with a constant radius of curvature is formed on the bottom surface of the nozzle, the liquid is ejected with a velocity component directed radially outward of the curved portion. be able to. Further, it is also possible to give a jet with a velocity component in the tangential direction of the curved portion.

The method of the present invention can be most preferably applied to the case where the liquid is jetted in the shape of a hollow circle from the opening on the bottom surface of the nozzle. At this time, the curvature of the hollow circle may be substantially constant, the curvature may be slightly changed within a range that does not impair the effects of the present invention, and the polygonal structure is substantially a circle. May be. A perfect circle having a constant curvature is preferable. When the present invention is applied to the case where the liquid film cross section at the time of jetting is a hollow circle as described above, the jetting is isotropic and therefore the liquid is not locally biased. Specifically, for example, as shown in FIG. 5, it is possible to eject the hollow circle with a velocity component toward the outside in the radial direction. Moreover, it is also possible to eject by giving a velocity component in the tangential direction of the circle. Furthermore, it is also possible to eject a velocity component on the same plane as the ejection surface with a velocity component appropriately combining a velocity component in the radial direction and a velocity component in the tangential direction.

The locus shape when the liquid falls is not particularly limited, but it is preferable that the liquid falls while following a so-called tulip type or onion type locus. Sixth
The figure shows a state where the liquid is ejected from a perfect circular loop-shaped opening formed on the bottom surface of the nozzle. At the time of ejection from the nozzle opening, the liquid pressure becomes high and a tangential velocity component is generated. In FIG. 6, the ejected liquid pressure increases from the left side to the right side. When the ejected liquid pressure is low, the ejected liquid drops become large droplets from the beginning (Fig. 6 (a)). And falls (Fig. 6 (b)). When the jet pressure is further increased, a hollow liquid film is formed. In the state of FIG. 6 (c), the cross-sectional diameter of the hollow liquid film reaches its maximum on the way and then shrinks due to the influence of the surface tension, and finally splits into droplets and falls. This state is called onion type. When the jet pressure increases further,
The hollow liquid film splits into droplets and drops before contracting (FIG. 6 (d)). This state is called tulip type. When the ejected liquid pressure becomes higher than this, the ejected liquid becomes a fine droplet (mist) immediately after the ejection and spreads and falls (FIG. 6 (e)). Regarding the drop behavior after these jets, AHLefebvere, "Atomization and sprays", Tay
See lor & Francis for details.

Such a trajectory of the liquid can be controlled by adjusting the velocity component on the same plane as the ejection surface and ejecting the liquid. If the velocity component on the same plane as the ejection surface is increased, it is possible to overcome the contraction, so that it is possible to control the onion type trajectory to a tulip type trajectory, for example. The velocity component on the same plane as the ejection surface may be the radial velocity component, the tangential velocity component, or a combination thereof.

In the polymerization method of the present invention, the first liquid and the second liquid
At least one of the liquids is jetted so as to spread spatially. Therefore, the jetting method of the other is not particularly limited, as long as the jetting is performed so as to spread one spatially. Further, both the first liquid and the second liquid may be jetted so as to spread spatially.

In a preferred embodiment of the present invention, it is preferable that both the first liquid and the second liquid are jetted so that the cross section of the liquid film at the time of jetting becomes a hollow circle. At this time, it is preferable that the hollow circle, which is the liquid film cross section when the first liquid is jetted, is jetted so as to be located inside the hollow circle that is the liquid film cross section when the second liquid is jetted. The centers of the two hollow circles are preferably on the same axis. At this time, it is preferable that the first liquid is jetted according to the present invention so that the diameter of the hollow circle is expanded after jetting.
On the other hand, the second liquid may be jetted so as to join the jetted first liquid. Therefore, the second liquid may be ejected so that the diameter of the hollow circle is expanded, ejected so as to be narrowed, or ejected so as not to change. Further, it may be sprayed in the form of mist.

Further, the first liquid and the second liquid are mixed with each other so as to follow a tulip type or onion type trajectory after mixing.
It is preferable to select the ejection speed (ejection liquid pressure) of the liquid and the second liquid and the ejection direction in combination. For example, an example can be given in which the first liquid is ejected by itself so as to follow a tulip-shaped or onion-shaped locus, and the second liquid is caused to collide at a speed that does not significantly change the locus of the first liquid.
Alternatively, the liquid mixture may be set to follow a tulip-type or onion-type trajectory by applying air pressure from the inside after the collision of the first liquid and the second liquid.

The size of the droplets formed after mixing the first liquid and the second liquid is 5 to 3000 μm, especially 50 to 1000 μm.
m is preferred. Polymerization is started immediately after the two liquids are mixed, and the liquid drops in the polymerization chamber while the polymerization proceeds even in the droplets.
The atmosphere in the polymerization chamber can be arbitrarily set as long as it does not hinder the polymerization reaction. Normally, nitrogen is used as the atmosphere gas,
Helium, carbon dioxide, or the like is used, but air or water vapor can also be used. When water vapor is fed into the atmosphere, based on the concentration of the polymerizable monomer-containing liquid to be subjected to the reaction, the water content required for the polymer particles to be produced, etc., how much water is evaporated from the polymerizable monomer-containing liquid It may be set from the viewpoint of whether to do it. The temperature of the atmosphere is usually room temperature to 150 ° C, preferably room temperature to 100 ° C.

The nozzle for carrying out the polymerization method of the present invention will be described below. Here, as long as the nozzle can carry out the polymerization method of the present invention, conventionally known nozzle mechanisms can be appropriately selected or combined and used. For example, by using a nozzle characterized by the shape of an ejection guide portion that guides the liquid to the opening at the bottom of the nozzle, the liquid is spatially spread from the opening at the bottom of the nozzle by applying pressure to the nozzle to introduce the liquid. Can be made to squirt. In particular,
It is possible to use a nozzle in which the ejection guide portion has a slit shape, and the slit thickness decreases from the upper part of the slit toward the lower part (opening), and the slit length increases accordingly. By using the same principle as this, even when the liquid film cross section at the time of jetting includes a curved portion or is a hollow circle, it is possible to form a nozzle capable of jetting so as to spread spatially.

Further, it is possible to use a nozzle having a nozzle opening portion or a flow path adjusting portion immediately before the opening portion. For example, by changing the flow path by colliding the liquid that has been sent through the cylindrical guide path to just above the nozzle opening with the conical deflecting section, it is possible to spread radially outward from the circular opening. A nozzle capable of ejecting liquid can be used. By selecting the shape of the deflection section appropriately,
The ejection speed and direction from the opening can be adjusted arbitrarily. Further, the thickness of the liquid film can also be controlled by changing the nozzle shape or size or adjusting the flow velocity at the time of jetting.

Further, in the present invention, it is possible to utilize a nozzle for adjusting the jetting direction and speed of the liquid by air pressure. For example, by applying air pressure to the opening in a desired direction, the liquid supplied to the opening can be ejected in that direction. Further, the air pressure may be applied to the liquid inside the opening, or may be applied to change the locus after the collision of the first liquid and the second liquid.

When the liquid film cross section at the time of jetting includes a curved portion or is a hollow circle, in order to jet the liquid with a velocity component in the tangential direction of the curve or circle, the liquid is rotated in the nozzle. It is preferable to use a nozzle provided with a mechanism for ejecting the liquid from the opening while moving. For example, it is possible to have a velocity component in the tangential direction at the opening by sending the liquid while applying pressure to the jetting guide having a spiral guide groove. Alternatively, instead of using the spiral guide groove, centrifugal force may be utilized to cause the cylindrical inner wall to spirally descend while rotating.

A particularly preferred nozzle in the present invention is a double concentric spiral jet nozzle in which two combinations of the guide portion and the circular opening for making such a rotational movement are formed concentrically. In the present specification, the double concentric swirl jet nozzle has a first circular opening for jetting a first liquid and a second circular opening for jetting a second liquid, and is used for the above polymerization method. A first guide part having a circular cross section is connected to the first circular opening, and further, the first liquid follows the spiral trajectory of the first liquid on the inner wall of the first guide part. 1st liquid supply means for supplying the 1st liquid so as to descend to the 1 circular opening is installed; a 2nd guiding part having a circular cross section is connected to said 2nd circular opening,
Further, a second liquid supply means is provided for supplying the second liquid so that the second liquid descends to the second circular opening while following the spiral trajectory of the inner wall of the second guiding portion; 1
It means a nozzle in which a circular opening, the second circular opening, the first guiding portion, and the second guiding portion are concentrically arranged.

If the double concentric spiral jet nozzle is used, the first liquid is ejected in a conical shape from the inner first liquid opening and the second liquid is ejected in a conical shape from the outer second liquid opening. Can be made. The ejection angle and ejection speed of the first liquid and the second liquid are adjusted so that they collide with each other after ejection. For example, the first
The ejection speed of the liquid may be adjusted to be higher than the ejection speed of the second liquid so that the two liquids collide with each other, or air pressure is applied to either the first liquid or the second liquid to make the ejection trajectory. The two liquids may be made to collide efficiently by adjusting. The jetting speed and the flow rate of the first liquid and the second liquid in the present invention may be the same or different.

A concrete example of the double concentric spiral jet nozzle is shown in FIG. FIG. 7 (a) is a horizontal sectional view of the upper part of the guide portion of the double concentric spiral jet nozzle, and FIG. 7 (b) is a vertical sectional view of the double concentric spiral jet nozzle. As shown in FIG. 7 (a), the first guide part (21) is provided with two introduction pipes (23a, 23b) for introducing the first liquid.
The first liquid is sent in the direction of the arrow through the introduction pipes (23a, 23b) and is vigorously introduced into the first guide portion (21). The first liquid is generated by centrifugal force and gravity by the first guiding part (2
The first circular opening (24) is reached while following the spiral trajectory on the inner wall of 1) (FIG. 7 (b)). Similarly, the second
Two guide pipes (23c, 23d) are also installed in the guide part (22), and the second liquid is vigorously introduced into the second guide part (22) through the guide pipes (23c, 23d) to form a spiral. The second circular opening (25) is reached while following a locus. The first and second liquids that have reached the circular opening are
As shown in FIG. 6C, the jet is ejected with a velocity component in the tangential direction at the opening and joins in the gas phase. The shape of the double concentric swirl jet nozzle in FIG. 7 can be appropriately changed depending on the types of the first liquid and the second liquid, the purpose of polymerization, and the like. For example, the number of introducing pipes can be increased or decreased, and the diameter or length of the guiding portion or the inner wall angle can be adjusted.

Further, it is necessary that the first liquid and the second liquid are ejected from the circular opening and join together for the first time in the vapor phase. Therefore,
It is preferable to take measures to prevent the two liquid flows from being short-circuited and mixed in the nozzle or at the nozzle inlet. For example, as shown in FIG. 8 (a), it is possible to employ a method in which an O-shaped ring (26) or the like is provided in the nozzle assembly portion and sealing is performed so that the first liquid and the second liquid do not mix. However, since the first liquid and the second liquid are introduced into the nozzle under high pressure, the sealing part of the O-shaped ring is not short-circuited by the liquid pressure during a long-term use so that the first liquid and the second liquid are not mixed. Need to be careful.

In order to reliably prevent such short circuit, the first
It is particularly preferable to adopt a structure in which the liquid introduction part and the second liquid introduction part are separated from each other and a short circuit due to liquid leakage cannot physically occur. For example, as shown in FIG. 8 (b), a short circuit can be reliably prevented by completely separating the flow path of the first liquid and the flow path of the second liquid. With this structure,
As shown in FIG. 8A, the relatively difficult assembling work of inserting the O-shaped ring at a predetermined position with high dimensional accuracy and sealing can be omitted, and the nozzle portion for the first liquid and the second liquid can be omitted. Since it is possible to assemble the liquid nozzle part by fixing it in stages, there are great practical advantages.

When a double concentric spiral jet nozzle is used, the Weber number (We1) and the first number in the first circular opening are
It is preferable that the Reynolds number (Re1) in the guiding portion satisfies the following relational expression.

[Formula 5] 10000 ≤ (We1) x (Re1) ^0.5 (We1) ^1.17 x (Re1) ^0.33 ≤ 100000 When using a double concentric spiral jet nozzle, the Weber number (We2) at the second circular opening and the above It is preferable that the Reynolds number (Re2) in the 2-lead portion satisfies the following relational expression.

[Equation 6] (We2) × (Re2) ^0.5 ≦ 40000 In the present invention, it is particularly preferable that all of the above three relational expressions are satisfied.

The Reynolds number (Re) can be obtained from the viscosity μ and density ρ of the liquid used, the diameter Ds of the spiral chamber, and the inflow velocity Vi of the liquid into the spiral chamber according to the following calculation formula.

[Equation 7] The Webber number (We) is the surface tension σ of the liquid used.
And the density ρ, the thickness of the liquid film at the ejection port (thickness in the direction perpendicular to the nozzle axis) t, and the fluid velocity Vo at the ejection port can be calculated according to the following formula.

[Equation 8]

The preferred ranges of Re1, We1, Re2 and We2 are as follows.

[Equation 9] 1000 <Re1 <5000 200 <We1 <2000 Re2 <2000 We2 <300

In the present invention, control can be performed so as to satisfy the above three relational expressions by appropriately adjusting the parameters constituting the calculation formulas of Reynolds number (Re) and Webber number (We). Specifically, the first to use
The swirl chamber of the double concentric swirl jet nozzle is designed to satisfy the above relational expression depending on the liquid and the second liquid, and the above relational expression is satisfied depending on the double concentric swirl jet nozzle used. As described above, it is possible to adjust the flow rate conditions of the first liquid and the second liquid, and further to control the physical properties by adding a thickener or a surfactant to the first liquid and the second liquid, respectively. . These designs and adjustments may be performed in combination.

The viscosity (μ) of the first and second liquids suitable for the polymerization method of the present invention is usually 0.3 to 20 mPa · s,
It is preferably 0.5 to 10 mPa · s. Surface tension (σ) is usually 10 to 100 mN / m (dyn / cm)
And preferably 20 to 50 mN / m (dyn / c
m). The density (ρ) is usually 500 to 200.
0 kg / m is ^{3 (0.5~2g} / cm ^3), preferably 700~1500kg / m ³ (0.7~1.5g / c
m ³ ).

By designing and adjusting so as to satisfy the above relational expression, it becomes possible to carry out polymerization more efficiently. That is, the first liquid and the second liquid can be efficiently mixed and reacted to smoothly produce a polymer having good properties.

In the polymerization method of the present invention, the polymerizable monomer and the polymerization initiator are contained in at least one of the first liquid and the second liquid, respectively. It is necessary to prevent the polymerization of the liquid containing the polymerizable monomer from proceeding before mixing the two liquids. For example, when a redox type polymerization initiator composed of an oxidizing agent and a reducing agent is used as the polymerization initiator, the first liquid may contain the oxidizing agent and the second liquid may contain the reducing agent. At this time, the polymerizable monomer can be contained in either one or both of the first liquid and the second liquid. Alternatively, the first liquid may contain a polymerizable monomer, and the second liquid may be prepared by mixing an oxidizing agent and a reducing agent immediately before use.

The type of polymerizable monomer used in the polymerization method of the present invention is not particularly limited. For example, vinyl compounds,
A vinylidene compound, a vinylene compound, a cyclic olefin compound or the like can be appropriately selected and used according to the application. These polymerized monomers are roughly classified into water-soluble polymerized monomers and oil-soluble polymerized monomers depending on the type of substituent.
Examples of the water-soluble polymerizable monomer include olefinic unsaturated carboxylic acid or a salt thereof, olefinic unsaturated sulfonic acid or a salt thereof, olefinic unsaturated amine, olefinic unsaturated amide, and the like. Examples of the oil-soluble polymerizable monomer include styrene, isobutene, vinyl chloride, vinyl acetate, acrylic acid esters, methacrylic acid esters and the like. For specific examples and reaction examples of the polymerizable monomer that can be used in the present invention, see Takayuki Otsu, “Chemistry of Polymer Synthesis” (Chemical Dojin) 34.
Pp. 43, etc. can be referred to. These monomers may be used alone or in combination of two or more.

By applying the polymerization method of the present invention to various monomers, various polymers conventionally obtained by the solution polymerization method, emulsion polymerization method and suspension polymerization method can be efficiently produced. Further, by applying the polymerizable monomer that has been conventionally subjected to emulsion polymerization or suspension polymerization to the polymerization method of the present invention, soap-free polymerization becomes possible. Thereby, for example, an adhesive, an adhesive, a paint, an ink, etc. can be provided. In the polymerization method of the present invention, the polymer structure is controlled (for example, core shell structure construction, microcapsule production, block polymer production) by selecting monomer species and controlling the mixed state of the two liquids. ) Is also possible. Thereby, for example, a pressure sensitive adhesive, a pressure sensitive adhesive, a sealant, a dye, a pigment, a chemical, a hard coat, a release agent, etc. can be provided.

The method for producing the water-absorbing polymer, which has been obtained by the suspension polymerization method or the solution polymerization method in the past, by the polymerization method of the present invention will be specifically described below. In the case of producing a water-absorbing polymer, an aliphatic unsaturated carboxylic acid or its salt is preferably selected as the polymerizable monomer. Specifically, unsaturated monocarboxylic acids or salts thereof such as vinyl compound acrylic acid or a salt thereof, vinylidene compound methacrylic acid or a salt thereof, maleic acid or a salt thereof, fumaric acid or a salt thereof, itaconic acid. Alternatively, unsaturated dicarboxylic acids such as salts thereof or salts thereof can be exemplified. You may use these individually or in mixture of 2 or more types. Among these, acrylic acid or a salt thereof and methacrylic acid or a salt thereof are preferable, and acrylic acid or a salt thereof is particularly preferable.
When a water-soluble or water-absorbing polymer is produced, these aliphatic unsaturated carboxylic acids or salts thereof are preferably used in an amount of 50 mol% or more, and more preferably 80 mol% or more, based on the total amount of polymerizable monomers. More preferable.

As the salt of the aliphatic unsaturated carboxylic acid, a water-soluble salt such as an alkali metal salt, an alkaline earth metal salt or an ammonium salt is usually used. The degree of neutralization is appropriately determined depending on the purpose, but in the case of acrylic acid, 20 to 90 mol% of the carboxyl groups are preferably neutralized with an alkali metal salt or ammonium salt. When the degree of partial neutralization of the acrylic acid monomer is less than 20 mol%, the water absorbing ability of the water absorbent polymer produced tends to be significantly reduced.

To neutralize the acrylic acid monomer, an alkali metal hydroxide, bicarbonate or the like or ammonium hydroxide or the like can be used, but the alkali metal hydroxide is preferred, and specific examples thereof are given. Include sodium hydroxide and potassium hydroxide.

When the water-absorbent polymer is produced by the polymerization method of the present invention, in addition to the above-mentioned aliphatic unsaturated carboxylic acid, a polymerizable monomer copolymerizable therewith, such as (meth) acrylamide, (poly ) Ethylene glycol (meth) acrylate and 2-hydroxyethyl (meth) acrylate can be copolymerized. Also,
Although it is a low water-soluble monomer, it can be copolymerized in an amount within a range that does not deteriorate the performance of the water-absorbing polymer that also produces alkyl acrylates such as methyl acrylate and ethyl acrylate. In addition, in this specification, the term “(meth) acrylic” means both “acrylic” and “methacrylic”.

The concentration of the polymerizable monomer contained in the polymerizable monomer-containing liquid used in the present invention can be appropriately determined depending on the purpose. For example, in the case of a polymerizable monomer-containing liquid containing an aliphatic unsaturated carboxylic acid or its salt as a main component, the concentration of the polymerizable monomer is preferably 20% by weight or more, more preferably 25% by weight or more. preferable. If the concentration is less than 20% by weight, the polymerization rate tends to be too slow, and the water-absorbing polymer after polymerization tends to have insufficient water absorbing ability. From the viewpoint of handling the polymerization reaction liquid, the upper limit is preferably about 80% by weight.

The polymerizable monomer-containing liquid used in the present invention may contain a crosslinking agent. For example, an aliphatic unsaturated carboxylic acid or a salt thereof, especially acrylic acid or a salt thereof may form a self-crosslinking polymer by itself, but when a crosslinking agent is used together, a crosslinked structure can be positively formed. it can. In addition, when a crosslinking agent is used in combination, the water absorption performance of the water absorbent polymer that is generally formed is improved. As the cross-linking agent, a divinyl compound copolymerizable with the above-mentioned polymerizable monomer, for example, N, N'-methylenebis (meth) acrylamide, (poly) ethylene glycol (meth) acrylate, etc., and a carboxylic acid capable of reacting 2 Water-soluble compounds having at least one functional group, for example, polyglycidyl ethers such as ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether are preferably used. Of these, particularly preferred is
It is N, N'-methylenebis (meth) acrylamide. The amount of the cross-linking agent used is 0.001 to 1% by weight, preferably 0.01 to 0.5, with respect to the charged amount of the monomer.
% By weight. In addition, these cross-linking agents may be contained in the initiator mixed liquid.

In addition to this, in the polymerization method of the present invention, Japanese Patent Laid-Open No.
The materials described in JP-A-255704 [0012] to [0015] can also be used.

The type of the polymerization initiator used in the polymerization method of the present invention is not particularly limited as long as it can initiate the polymerization of the polymerizable monomer. For example,
A thermal decomposition type polymerization initiator such as a peroxide such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, or an azo compound such as azobisisobutyronitrile can be used. In addition, the redox polymerization initiator as described above can be preferably used. As the redox-based polymerization initiator, it is generally preferable to use a combination of a radical generator exhibiting an oxidizing property and a reducing agent.

Examples of the oxidizing agent for the aqueous redox type polymerization initiator include persulfate and hydrogen peroxide.
Further, as a reducing agent for the water-based redox-based polymerization initiator,
Examples thereof include inorganic reducing agents such as ferrous salts and sodium sulfite, and organic reducing agents such as alcohols, amines and ascorbic acid. Examples of the oxidizing agent for the non-aqueous redox polymerization initiator include hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide, dialkyl peroxides, diacyl peroxides and the like. Further, as a reducing agent for the non-aqueous redox polymerization initiator, tertiary amines, naphthenates,
Examples thereof include mercaptans. The oxidizing agent of the redox type polymerization initiator is 0.0 with respect to the polymerizable monomer.
It is preferable to use 1 to 10% by weight, particularly 0.1 to 2% by weight. Further, the reducing agent of the redox polymerization initiator is preferably used in an amount of 0.01 to 10% by weight, particularly 0.1 to 2% by weight, based on the polymerizable monomer.

Regarding the polymerization initiator, in addition to the above, Takayuki Otsu, “Revised Polymer Synthesis Chemistry” (Kagaku Dojin) 59
It is also possible to use the materials and techniques described on pages 69 to 69.

When a water-absorbent composite in which a water-absorbent polymer is fixed to a fibrous base material is produced using the polymerization method of the present invention, a sheet-shaped fibrous base material is fed into a polymerization chamber. It is preferable that the polymer particles falling in the course of polymerization are attached while moving this in parallel with the floor of the polymerization chamber. As the fibrous base material, any material may be used as long as it is formed in a certain shape and polymer particles in the process of polymerization are easily attached, and cloth, paper, pulp, non-woven fabric and the like can be used. Above all, it is preferable to use a fluff pulp or a non-woven fabric, in which the fibrous base material is roughly accumulated, the polymer particles can easily enter the inside, and the polymer particles can strongly adhere to the fibrous base material. Particularly preferred is a non-woven fabric made of (semi) synthetic fibers such as polyester, polyolefin, polyamide, acetate, etc., which has high strength even in a wet state. The fiber thickness of the fibrous base material forming the nonwoven fabric is preferably 10 to 50 μm, and the basis weight of the nonwoven fabric is preferably 10 to 100 g / m ² , and particularly preferably 20 to 50 g / m ² .

The polymerization rate at the time when droplets during polymerization are in contact with each other in the gas phase or on the fibrous base material to form agglomerated particles is
Various conditions are set so as to be 3 to 97%, preferably 20 to 97%, and more preferably 50 to 95%. If the polymerization rate is too low, even if the liquid droplets collide with each other, they do not become aggregated particles and are integrated into large particles, or when the liquid droplets drop onto the fibrous base material, the liquid becomes a base material. It spreads over or is absorbed or impregnated to make it difficult to adhere to the fibrous base material in the form of agglomerated particles. If it is too high, the adhesive force with the substrate will not be developed, and the fixability between the fibrous substrate and the water-absorbent polymer will be poor.

The polymer particles are preferably attached to the fibrous base material so that the content in the finally obtained water-absorbent composite is 50 to 400 g / m ² . Although it depends on the use, it is generally more preferable that the adhesion is 80 to 300 g / m ² . When the content of polymer particles in the water-absorbent composite is low, the water-absorbing ability is naturally low.
Further, if the content is too large, it is generally uneconomical, and the ratio of the portion bonded to the fibrous base material is reduced, so that the binding force to the fibrous base material is weakened.

At least some of the polymer particles constituting the water-absorbent composite produced by the production method of the present invention are bound to each other by polymer particles in the process of polymerization (primary particles) to form agglomerated particles. It is preferable that a part of the polymer particles (primary particles) constituting the aggregated granules are not directly bonded to the fibrous base material. Since such agglomerated particles have a large specific surface area, they have a high water absorption rate,
Moreover, since only a part of the primary particles constituting the agglomerated granules are bonded to the fibrous base material, the constraint imposed by the fibrous base material when absorbing water and swelling is small, and the water absorbing ability is excellent. Further, since the bonding surfaces of the primary particles constituting the agglomerated particles are integrated, the agglomerated particles may collapse into primary particles and fall off from the fibrous base material not only before water absorption but also after water absorption. Few. It is preferable that 30% by weight or more of the polymer particles are agglomerated particles, and 50% by weight or more, particularly 80% by weight or more are agglomerated particles.
Generally, the larger the ratio of the agglomerated particles, the better the performance as a water absorbing material. The particle size of the agglomerated particles is substantially 100
It is preferably in the range of ˜3000 μm. Particle size is 10
If it is smaller than 0 μm, the water absorption performance tends not to be sufficiently exhibited. When the particle size is more than 3000 μm, the adhesive force to the sheet-shaped fibrous base material tends to be weak. The ratio and particle size of the agglomerated particles can be controlled mainly by appropriately adjusting the density, distribution state, flow state and the like of particles in the gas phase during polymerization. For example, in order to increase the ratio of agglomerated particles, the amount of falling polymer per unit cross-sectional area of the polymerization chamber should be increased or the polymerization chamber should be increased so that the chances of particles in the polymerization contacting each other during the fall increase. An ascending flow may be generated to slow down the falling speed of the polymer particles. Another method is to generate a drift in the polymerization chamber so that the distribution of the falling polymer particles is biased.

After applying the water-absorbent polymer to the fibrous base material, a water-absorbent composite can be obtained by appropriately performing a water content adjusting step, a surface cross-linking step, a residual monomer treatment step and the like.
The water-absorbent composite thus produced can be used in various applications where water-absorbent polymers have been used so far. "Water-absorbing polymers" 81-111 (Fusayoshi Masuda, Kyoritsu Shuppan, 1987), "Development trends of superabsorbent polymers and their applications" (Eizo Omori, Techno Forum, 19
87), Kenji Tanaka, "Industrial Materials" Vol. 42, No. 4, 18-25
Pp. 1994, Nobuyuki Harada, Tadao Shimomura, pp. 26-30, various uses of the water-absorbent polymer are introduced and can be used appropriately. Examples include paper diapers, sanitary products, freshness-retaining materials, moisturizers, cold-preserving agents, anti-condensation agents, and soil conditioners.

Further, JP-A-63-267370, JP-A-63-10667, and JP-A-63-29.
5251, JP-A-270801, JP-A-6
3-294716, JP-A-64-64602, JP-A-1-231940, JP-A-1-243.
No. 927, Japanese Patent Laid-Open No. 2-30522, Japanese Patent Laid-Open No. 2-2522
No. 153,731, Japanese Patent Laid-Open No. 3-21385,
JP-A-4-133728, JP-A-11-1561
It can also be used for the application of the sheet-shaped water-absorbent composite proposed in Japanese Patent No. 18, etc.

[0057]

EXAMPLES The features of the present invention will be described more specifically below with reference to examples and comparative examples. Materials shown in the following examples,
The usage amount, ratio, processing content, processing procedure, etc. can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following specific examples.

(Preparation of raw materials) 125 parts by weight of 80% by weight acrylic acid aqueous solution, 57.3 parts by weight of 48.5% by weight aqueous sodium hydroxide solution, 6.4 parts by weight of water, and N, N- as a crosslinking agent. Solution A was prepared by adding 0.15 part by weight of methylenebisacrylamide and 5.0 parts by weight of a 30% by weight aqueous hydrogen peroxide solution as an oxidizing agent. Solution A has a monomer concentration of 60% by weight, a degree of neutralization of 50 mol% and a viscosity of 7
mPa · s, density is 1200 kg / m ³ (1.2 g / c
m ² ), and the surface tension was 40 mN / m (dyn / cm).

Separately, 125 parts by weight of 80% by weight acrylic acid aqueous solution, 57.3 parts by weight of 48.5% by weight aqueous sodium hydroxide solution, 9.9 parts by weight of water, and N, N-methylene as a crosslinking agent. Solution B was prepared by adding 0.15 parts by weight of bisacrylamide and 1.5 parts by weight of L-ascorbic acid as a reducing agent. The monomer concentration and the degree of neutralization of solution B were the same as those of solution A. The viscosity of solution B is 7 mPa
s, the density was 1200 kg / m ³ (1.2 g / cm ² ), and the surface tension was 40 mN / m (dyn / cm).

(Examples 1 to 4) A double concentric spiral jet nozzle (Fig. 7) having the discharge port diameter shown in Table 1 was used, and the inner discharge port and the outer discharge port were of the types shown in Table 1, respectively. The solution was fed. The liquid temperature of each solution was 40 ° C., and jetting was performed using a pump at the flow rates and discharge pressures shown in Table 1.

The solutions A and B collided and atomized near the outlet of the nozzle to form droplets, which dropped in the gas phase (in air, temperature 50 ° C.) while advancing polymerization. Part of the droplets collide in the gas phase to form agglomerated particles, and drop onto a polyester non-woven fabric base material (weight per unit area: 30 g / m ² ) installed 3 m below the tip of the discharge port of the nozzle, Polymerization was completed on the substrate. At the same time, a part of the droplets dropped onto the base material, and after forming agglomerated particles on the base material, the polymerization was completed on the base material. Through such a complexing step, the water-absorbing polymer was supported on the base material. The water content of the water-absorbent polymer carried on the substrate was 20 to 30% by weight. Further, 0.5% by weight ethylene glycol diglycidyl ether (EGDGE) in ethanol was added to the complex as EG
It was sprayed onto the DGE-supported polymer (dry polymer base) at 3000 ppm by weight. EG
The complex treated with the ethanol solution of DGE is 11
The water content of the polymer supported by the 0 ° C warm air dryer is 5
%, The amount of supported polymer is 200 g / m ²
An absorbent complex of was obtained.

Comparative Example 1 Instead of the double concentric spiral jet nozzles of Examples 1 to 4, the opposed nozzle shown in FIG. 1 was used. Five pairs of nozzles through which the solution A flows out are arranged at 1 cm intervals, and five pairs of nozzles through which the solution B flows out are also arranged at 1 cm intervals. The nozzles from which the solution A flows out and the nozzles from which the solution B flow out face each other to form a total of five facing nozzle pairs. The inner diameter of each nozzle is 0.13
mm, the crossing angle of the solution A and the solution B flowing out from the facing nozzle was adjusted to 30 degrees, and the distance between the facing nozzle tips was adjusted to 4 mm. Solution A and solution B having a liquid temperature of 40 ° C. were supplied by a pump so that the flow rate was 20 cm ³ / min using the facing nozzle.

The solution A and the solution B join at the point where they are ejected in the form of liquid columns from the nozzles of the respective nozzle pairs, form liquid columns of about 10 mm each, and then become droplets in the vapor phase while proceeding with polymerization. (In air, temperature 50 ° C.), some of the droplets collide in the gas phase to form agglomerated particles,
It dropped onto a polyester non-woven fabric base material (Basis weight: 30 g / m ² ) installed 3 m below the tip of the nozzle outlet, and the polymerization was completed on the base material. At the same time, some of the droplets drop onto the base material to form agglomerated particles on the base material,
Polymerization was completed on the substrate. Through such a complexing step, the water-absorbing polymer was supported on the base material. The water content of the water-absorbent polymer carried on the substrate was 20% by weight. Then, the same treatments as in Examples 1 to 4 were carried out to obtain an absorbent composite having a water content of the polymer of 5% and a supported amount of the polymer of 200 g / m ² .

(Comparative Example 2) A slit type nozzle shown in FIG. 1 of JP-A-11-49805 was used in place of the double concentric spiral jet nozzles of Examples 1 to 4. The slits from which solution A and solution B flow out are each 0.0
The length was 5 mm and the length was 10 mm. The crossing angle between the solution A and the solution B flowing out from each of the opposing slits was 30 degrees, and the distance between the opposing slit tips was 10 mm. Using this opposing nozzle, the solution A and the solution B having a liquid temperature of 40 ° C. were flowed at a flow rate of 150.
It was supplied by a pump so as to have a cm ³ / min.

Solution A and solution B were discharged from each slit in the form of a liquid film, but the liquid film width became shorter as the distance from the discharge port increased. Both liquid films collide with each other at a position 2 cm from the discharge port, atomize into droplets, and fall into the gas phase (in air, temperature 50 ° C) while polymerization progresses, and some of the droplets are in the gas phase. Collide with each other to form agglomerated granules, and drop onto a polyester non-woven fabric substrate (basis weight: 30 g / m ² ) installed 3 m below the tip of the nozzle outlet to complete the polymerization on the substrate. It was At the same time, some of the droplets drop onto the substrate,
After forming agglomerated granules on the substrate, the polymerization was completed on the substrate. Through such a complexing step, the water-absorbing polymer was supported on the base material. The water content of the water-absorbent polymer carried on the substrate was 30% by weight. Then, Examples 1 to 1
The same treatment as in Example 4 was performed to obtain an absorbent composite having a water content of the polymer of 5% and a supported amount of the polymer of 200 g / m ² .

(Comparative Example 3) Using the same double concentric spiral jet nozzle as in Example 4, the flow rate of solution A and solution B was 400 cm.
It was carried out using a pump so that the flow rate was ³ / min. Both the solution A and the solution B were ejected in the form of mist when ejected from the nozzle and dropped in the gas phase (in air, temperature 50 ° C.) while being mixed near the outlet. After a while, the monomer particles remaining in the vicinity of the nozzle adhere to the nozzle outlet,
Polymer lumps were generated near the nozzle outlet, clogging the nozzle and rendering it inoperable. As a result, Examples 1 to 1
It was not possible to obtain a water-absorbing complex like No. 4.

(Evaluation) The water-absorbing composites obtained in Examples 1 to 4 and Comparative Examples 1 to 2 were subjected to the following measurements. 1) Measurement of average particle minor axis of agglomerated particles After taking optical micrographs of a plurality of locations of a water-absorbing composite, 100 particles are arbitrarily selected from the photographed agglomerated particles to determine the minor axis of each particle. Measured. Obtain the average value of the measured values,
The average particle minor axis of the agglomerated particles was used. In addition, the particle minor axis here means the largest of the diameters orthogonal to the major axis taken so that the particle diameter becomes the longest.

2) Measurement of water retention capacity of physiological saline The water-absorbent composite was cut so that the weight W1 of the water-absorbent polymer supported on the water-absorbent composite was 1 g, and a 250 mesh nylon bag (20 cm × 10 cm) was cut. to put, at room temperature saline (concentration 0.9 wt%) 500 cm 3 in ³
Soak for 0 minutes. Then pull out the nylon bag, suspend it for 15 minutes to drain water, then use a centrifuge to remove 90G.
It was dehydrated for 90 seconds. After dehydration, the weight W2 of the nylon bag was measured. Further, the non-woven fabric not supporting the water-absorbent polymer was cut into the same size as the water-absorbent composite, and the same operation was performed to measure the weight W3 after dehydration. The water retention capacity of physiological saline was calculated according to the following formula. Here, the units of W1 to W3 are all g.

[Equation 10]

3) Calculation of manufacturing speed The supply speed Ra of the solution A supplied to the discharge port and the supply speed Rb of the solution B supplied to the discharge port are measured, and the sum is the monomer concentration of 0.6 (60%). And the number of discharge port pairs n
The production rate was calculated by dividing by. The calculation formula is as follows. In Examples 1 to 4 using the double concentric spiral jet nozzle, the calculated production speed is the production speed per nozzle having one inner discharge port and one outer discharge port, and the counter nozzle is In Comparative Example 1 used and Comparative Example 2 using the slit type nozzle, the manufacturing speeds are for a pair of nozzles facing each other.

[Equation 11]

[0070]

[Table 1]

As is clear from Table 1, in the examples in which the solution was jetted using the double concentric swirl jet nozzle so as to satisfy the conditions of the present invention, the water absorbency having a desired particle size and high water retention ability was obtained. The complex could be efficiently produced. On the other hand, in Comparative Example 1 using the counter nozzle, the manufacturing efficiency was low, and when the slit type nozzle was used, the particle size and the water retention capacity were poor.

[0072]

According to the present invention, a high-quality polymer can be efficiently produced in a large amount by the droplet polymerization method even when a polymerizable monomer having a fast reaction rate is used. According to the present invention, it is possible to prevent the narrowing of the width of the liquid film due to the surface tension, which is a problem of the slit type nozzle, and to manufacture a more homogeneous polymer. Further, by using the nozzle of the present invention, a high quality polymer can be efficiently produced by a simple operation.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a counter nozzle that has been conventionally used.

FIG. 2 is a diagram showing an example of a slit-type nozzle that has been conventionally used.

FIG. 3 is a diagram showing an example of a liquid ejection mode of the present invention.

FIG. 4 is a diagram showing another example of a liquid ejection mode of the present invention.

FIG. 5 is a diagram showing still another example of a liquid ejection mode of the present invention.

FIG. 6 is a diagram showing a state where liquid is ejected from a perfect circular loop-shaped opening at different speeds.

FIG. 7 is a cross-sectional view and a perspective view showing a specific example of a double concentric spiral jet nozzle.

FIG. 8 is a cross-sectional view showing a specific example of a double concentric spiral jet nozzle.

[Explanation of symbols]

1,11 Nozzle for first liquid 2,12 Nozzle for second liquid 3,13 1st liquid 4,14 second liquid 15 and 16 slits 21 First induction part 22 Second guiding part 23a, 23b 1st introduction pipe 23c, 23d 2nd introduction pipe 24 First circular opening 25 Second circular opening 26 O type ring

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shunichi Hinomori             1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Corporation             Inside the company (72) Inventor Kiichi Ito             1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Corporation             Inside the company F-term (reference) 4J011 AA01 AA04 AA08 BA08 BB01                       BB03 BB13 BB17 DB18

Claims (16)

[Claims] 1. A first liquid and a second liquid are mixed in a gas phase,
A polymerization method of polymerizing in a droplet form, wherein a polymerizable monomer and a polymerization initiator are contained in at least one of the first liquid and the second liquid, respectively, and the first liquid and the second liquid. A polymerization method characterized in that at least one of the liquids is jetted in the form of a liquid film so as to spread spatially. 2. The polymerization method according to claim 1, wherein at least one of the first liquid and the second liquid is jetted with a velocity component on the same plane as the jet surface. 3. The at least one of the first liquid and the second liquid is jetted in a liquid film shape so as to spread spatially, and the liquid film cross section at the time of jetting includes a curved portion. The polymerization method according to 1 or 2. 4. A liquid film jetting at least one of the first liquid and the second liquid so as to spatially spread, and a liquid film cross section at the time of jetting is a hollow circle. The polymerization method according to any one of 1 to 3. 5. The first liquid and the second liquid are both jetted in a liquid film shape so as to spread spatially, and the liquid film cross-sections at the time of jetting are both hollow circles. 4. The polymerization method according to item 4. 6. The first liquid and the first liquid so that a hollow circle that is a liquid film cross section when the first liquid is jetted is formed inside a hollow circle that is a liquid film cross section when the second liquid is jetted. The polymerization method according to claim 5, wherein the second liquid is jetted. 7. The center of a hollow circle, which is a liquid film cross section when the first liquid is jetted, and the center of a hollow circle, which is a liquid film cross section when the second liquid is jetted, are on the same axis. The polymerization method according to claim 6. 8. The ejected liquid pressure is adjusted so that at least one of the first liquid and the second liquid follows a tulip-shaped or onion-shaped locus after being ejected. The polymerization method described in. 9. The jet liquid pressure is adjusted so that both the first liquid and the second liquid follow a tulip-shaped or onion-shaped locus after being jetted.
The polymerization method according to any one of 1. 10. A first circular opening for ejecting a first liquid and a second circular opening.
A nozzle having a second circular opening for ejecting a liquid, wherein a first guiding part having a circular cross section is connected to the first circular opening, and further, the first guiding part inner wall is A first liquid supply means for supplying the first liquid is installed so that the first liquid descends into the first circular opening while following a spiral trajectory, and the second circular opening has a circular cross section. A second liquid is connected to the second guiding part, and further supplies the second liquid so that the second liquid descends to the second circular opening while following the spiral trajectory on the inner wall of the second guiding part. A supply means is installed, and the first circular opening portion, the second circular opening portion, the first guiding portion, and the second guiding portion are concentrically arranged in a nozzle. It uses, The polymerization method in any one of Claims 3-9 characterized by the above-mentioned. 11. The polymerization method according to claim 10, wherein the Webber number (We1) in the first circular opening and the Reynolds number (Re1) in the first guiding portion satisfy the following relational expression. [Equation 1] 10000 ≤ (We1) x (Re1) ^0.5 (We1) ^1.17 x (Re1) ^0.33 ≤ 100000 12. The polymerization method according to claim 10, wherein the Webber number (We2) in the second circular opening and the Reynolds number (Re2) in the second guiding portion satisfy the following relational expression. [Formula 2] (We2) × (Re2) ^0.5 ≦ 40000 13. The Webber number (We1) in the first circular opening and the Reynolds number (Re1) in the first guiding portion satisfy the following relational expression, and the following expression is satisfied: 10000 ≦ (We1) × ( Re1) ^0.5 (We1) ^1.17 x (Re1) ^0.33 ≤ 100000 The Weber number (We2) in the second circular opening and the Reynolds number (Re2) in the second guiding portion satisfy the following relational expressions. The polymerization method according to claim 10. [Equation 4] (We2) × (Re2) ^0.5 ≦ 40000 14. The polymerizable monomer and the polymerization initiator,
It is contained in at least one of the said 1st liquid and the said 2nd liquid, The polymerization method in any one of Claims 1-13 characterized by the above-mentioned. 15. The polymerization initiator comprises an oxidizing agent and a reducing agent, which are redox polymerization initiators, and a polymerizable monomer,
The oxidizing agent and the reducing agent are respectively the first liquid or the second liquid.
15. The polymerization method according to claim 1, wherein the polymerization method is contained in at least one of the liquids. 16. A first circular opening for jetting a first liquid and a second
A second circular opening for ejecting a liquid is provided, wherein the first circular opening is provided.
5. The nozzle for use in the polymerization method according to any one of 5, wherein a first guide part having a circular cross section is connected to the first circular opening, and the first guide part inner wall is a first guide part. A first liquid supply means for supplying the first liquid is installed so that the liquid descends to the first circular opening while following a spiral trajectory, and the second circular opening has a circular cross section. A second liquid supply that connects the two guide parts and further supplies the second liquid so that the second liquid descends to the second circular opening while following the spiral trajectory of the inner wall of the second guide part. A means is installed, and the first circular opening, the second circular opening, the first guiding portion, and the second guiding portion are arranged concentrically.