JPS5930801A - Preparation of spherical polymer and apparatus for preparing the same - Google Patents

Abstract

PURPOSE:To obtain a spherical polymer, having a large particle diameter and uniform particle size, and useful for catalyst carrier, etc., by specifying the viscosity of a vinyl monomeric mixture solution within a specific range, adjusting the specific gravity thereof to the same value as that of a dispersion, and dropping the vinyl monomeric mixture solution intermittently from capillaries into the dispersion. CONSTITUTION:The viscosity of a vinyl monomeric mixture solution is adjusted to 60-600cP, and the specific gravity thereof is adjusted to substantially the same as that of a dispersion. The resultant vinyl monomeric mixture solution is then transferred from a stock solution tank 14 to a monomeric mixture solution tank 6, and air, etc. is supplied from a pipe 9 to pressurize the monomeric mixture solution tank 6. A flow rate cock 11 is adjusted to drop the dispersion monomeric mixture solution intermittently from capillaries 8 and 8' for dropping the monomeric mixture solution into a dispersion 4 in a dispersion tank 3, and the dispersion 4 is heated by a heating means 5 to polymerize the resultant monomeric mixture droplets in the dispersion 4 and give the aimed spherical polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a spherical polymer having uniform particle size and an apparatus for producing the same. In the present invention, spherical polymers refer to linear polymers obtained by suspension polymerization, such as styrene, acrylic, etc., which are non-porous and have a uniform particle size, and bead-like porous polymers that are crosslinked and have a three-dimensional network structure. It's about polymers. Since the method and apparatus of the present invention are equally applicable to both linear polymers and bead-shaped porous polymers, the bead-shaped porous polymer will be exemplified and explained herein.

The porous bead-like polymer according to the present invention has a large particle size, is uniform in particle size, and has a large specific surface area, making it suitable as a carrier for a catalyst or a carrier for an adsorbent.

The porous polymer can be used as an ion exchange resin matrix, as a gel for gas chromatography (diameter 125-250 microns), a gel for liquid chromatography (diameter 5-20 micron), and as a carrier for catalysts (diameter 4 or more). It has been put into practical use as a catalyst for removing tritium discharged from nuclear reactors and the like, and for water-hydrogen exchange reactions, and is also being put into practical use as supports for various hydrophobic catalysts and adsorbents.

In any case, when put into practical use, it is used as particles, that is, as bead-like porous polymers.

When these are actually used as catalyst carriers or adsorption agents, bead-shaped porous polymers (hereinafter referred to as polymer beads) are usually filled in a reaction tower or an agitation absorption tower, and the filled polymer bead layer is A fluid passes through it. Therefore, polymer beads are required to have a large and uniform particle size. If the particle size is small, the resistance of the bead layer to the fluid increases, and a large pressure is required to allow the fluid to pass smoothly.9 Also, since fine D polymer beads flow easily, special means are required for fixation. It becomes necessary. Also, if the particle size distribution is wide, the flow of the fluid will become uneven and the reaction efficiency and adsorption efficiency of the fluid will decrease, so if the polymer beads are fine particles or the particle size is uneven, it may be difficult to put them into practical use. In order to compensate for the above-mentioned phenomenon, the plant must be enlarged, resulting in an extremely uneconomical plant.

Various methods have been proposed for producing polymer beads. For example, in JP-A No. 56-5140, 11
Polymer beads are obtained by injecting 7-mer into a monomer dispersion, dispersing it in a monomer dispersion, and heating it, but in this case it is difficult to control the particle size of the beads, and the particle size has a Gaussian distribution. Therefore, in order to obtain polymer beads with a certain particle size distribution, no sieving is necessary. Therefore, the yield of beads having the desired particle size is extremely low.

Also, JP-A-57-73002, JP-A-57-10290
Method No. 5 relates to a method in which a polymer is obtained by spraying into a monomer dispersion.

In all of these known methods, since there is a difference in specific gravity between the dispersion liquid and the monomer droplets in the dispersion liquid, the monomer droplets tend to collect at the top or bottom of the dispersion liquid and adhere to each other. be. For this reason, the dispersion liquid is stirred using a stirrer or the like to move the entire liquid and prevent adhesion, but in this case, the monomer droplets are cut into smaller pieces.

That is, conventionally it has been completely impossible to produce polymer beads that are uniform and have a large particle size.

Therefore, there is a strong demand for the development of a method and apparatus for producing polymer beads having large and uniform particle sizes.

The present inventors completed the present invention as a result of research to achieve the above object.

That is, the first invention (f) of the present invention is a method of producing a spherical polymer by adding vinyl monomer (#) to a liquid dispersion liquid to form a vinyl monomer mixture droplet, and then heating it to produce a spherical polymer. Liquid?, viscosity is 60-600C
P and the specific gravity is substantially the same as the specific gravity of the dispersion liquid, and then this vinyl monomer mixture is selected so that when it is dispersed in the dispersion liquid, it forms droplets of the required diameter. The second invention is an apparatus for carrying out the method, and the second invention is an apparatus for carrying out the method, in which the dispersion is intermittently dropped into a dispersion through a thin tube of a diameter, and the dispersion is heated to form a spherical polymer. It consists of a dispersion liquid tank, which is placed above the nuclide, and a vinyl monomer mixture liquid tank, which is placed above the nuclide, and a thin tube is provided at the bottom of the vinyl monomer mixture liquid tank to drip the vinyl monomer mixture into the dispersion tank. This is a unique feature.

Next, the present invention will be described in detail.

In the present invention, the vinyl monomer mixture is a monovinyl monomer and a divinyl monomer selected from styrene-based aromatic compounds or acrylic acid-based aliphatics, which are raw materials for polymers, t & initiator, diluent, and other main components. It is said that

Monovinyl monomers include styrene, 7styrene, ethylvinylbenzene, methyl acrylate, methyl methacrylate, etc.; divinyl monomers include divinylpe/zene, trihinyl he/ce/, trimethylolpropane, trimethacrylate, ethylvinylbenzene, etc. V/glycol dimethacrylic acid ester and their halides, etc. are used.

As the polymerization initiator, those commonly used in the polymerization reaction of vinyl compounds can be used, and specific examples include benzoyl peroxide, butyl peroxide, azobisisobutyl nitrile, and the like.

Depending on their physical properties, diluents can be classified as precipitants, swelling agents, or an intermediate between the two. In general, a precipitant is insoluble in water, and a monomer is a copolymer (it exists raw, but it has less affinity with the polymer produced by polymerization of the monomer, and the bore distribution of the copolymer, It has a large relationship with the pore volume.Swelling agents have a high affinity with both monomers and polymers co-collected with monomers, causing the copolymer to swell, and are greatly related to the surface area of the copolymer. It is something.

Precipitating agents include natural oils and fats, higher alcohols, higher paraffins, and their halides, while swelling agents include high-boiling point organic solvents such as low-molecular halogenated paraffins, low-molecular halogenated olefins, or Aromatic solvents or their halides are included. Specifically, toluene, carbon tetrachloride, trichloroethane, trichloroethane, chlorobenzene, dichlorope/
Examples include ze/, trichlorobenzene, etc.

The viscosity of the vinyl monomer mixture is 60 to 600 C.
It is necessary to set it to P. For this purpose, a highly viscous material such as high viscosity paraffin or grease is added to the monomer diluent, or a vinyl monomer mixture is prepolymerized. If the viscosity of the seven-mer mixture is low, when the vinyl monomer mixture is dropped into the nine-dispersion liquid from a thin tube as described below, the droplets will collide with the dispersion liquid, but at this time they will be further divided into smaller particles, resulting in a uniform liquid. The resulting polymer beads do not form particles and have a wide particle size distribution. Furthermore, if the viscosity is too high, it cannot be dripped smoothly. That is, by setting the viscosity to 60 to 600 CP, uniform l
Since the particles are polymerized at night, it is possible to form polymer beads with the desired particle size D.

As a dispersion liquid, gelatin, sodium polyacrylate, polyvinyl alcohol, which acts as a protective colloid, is added to hot water.
Alternatively, 2 to 10 of them may be dissolved in methyl cellulose alone or in a mixture to form a uniform phase. In this case, the ratio is approximately 0.99 to 1.03.

The vinyl monomer mixture solution to be dropped, the ratio of the upper monovinyl monomer to the polyvinyl monomer is in the range of 500 to 600 parts of the divinyl monomer to the monovinyl monomer toolK, and the ratio of the monomer to the diluent is the same as that of the monomer. The range of 20 to 300 parts of diluent per 100 parts is determined as appropriate to suit the physical properties of the polymer beads, such as hardness, surface area, bore distribution, pore volume, etc., depending on the purpose of use. It is necessary to strictly adjust the specific gravity so that it is substantially the same as the specific gravity of the dispersion.

In the method of the present invention, the vinyl monomer mixture Q
It is necessary to drop it into the above-mentioned dispersion liquid or drop it through a dropping tube such as a vinyl monomer mixture. At this time, there is a relationship between the diameter of the dropping tube and the diameter of the droplets dropped into the dispersion liquid.

For example, as mentioned above, the droplets to be dropped have a viscosity of 60 to 60
00P, so when a droplet tube with a diameter equal to the required droplet is used for the liquid, when the droplet falls from the droplet tube,
Complex deformation depending on the shape of the drip tube? Therefore, the required diameter will not be obtained.

The present inventors conducted various studies on the relationship between the shape of the dropping tube and the diameter of the droplets, and found that the relationship between the specific gravity of the liquid mixture, the shape of the dropping tube, etc., and the particle size of the monomer mixed droplets is shown below. The present invention was completed by elucidating the relationship between the following.

FIGS. 1 to 7 are representative examples of the dropping tube.

For example, when the vinyl monomer mixture is dropped through the thin-walled dropping tube shown in Figure 1, the inner diameter of the dropping tube is 0.
．． It has been experimentally shown that if the diameters are 5fi, lfi, 2mm, and 4mm, the diameters of the droplets will be about 1mm, about 2m, about 3.5mm, and about 5mm, respectively. If the diameter of the droplets is 3-mm, as shown in Figure 2,
It is necessary to assume that the neck has been created in L. Note that even if the diameter of the droplet is 3Mlφ or less, the neck portion may be formed. The ratio of the internal diameter of the neck (f) to the dropping tube (f') is 11.1 to 0.8, assuming that the diameter of the dropping tube (f') is 1.

In this way, due to the dispersion, liquid droplets can be formed at the desired locations.
Vinyl monomer + J that can be removed! , &M polymerize in the dispersion to form polymer beads, and the dispersion is heated. At this time, when the dispersion ty is locally heated, thermal convection occurs in the dispersion, and the reformed grains circulate while remaining spherical, ff:N!
Shiaikotoii. In addition, heated surname 1 square is usually 50-80
It is ℃. The dispersion may be heated in advance, or the liquid particles may be dispersed and heated over time.In any case, gentle stirring by heat convection and stirring are essential. be.

Next, the second invention will be explained based on the eighth illustration. Reference numeral 3 denotes a dispersion liquid tank equipped with a heating means S, in which a fractional liquid is accommodated. 6. Vinyl monomer i &l'
A vinyl monomer mixture 7 is stored inside the tank. The mixed liquid is dripped onto the bottom of the mixed liquid tank 6.
r has been made.

As mentioned above, the shape of the dropping tube is determined in consideration of various conditions such as the viscosity of the vinyl mixture, so that droplets of a desired diameter can be obtained.

The pipe 9 is an inflow R of 72 gas or nitrogen, and the pressure gauge 1
01 Nafuha Kotoku/l is attached. /41 is a raw solution tank for the vinyl monomer mixture, and the vinyl monomer mixture is fed to the mixed liquid tank 6 through a pipe/unit by a pump /3.

When actually manufacturing polymer beads using the apparatus of the present invention, the diameter of the polymer beads is 3. If the vinyl monomer mixture does not reach l/-1, it will take a long time to drop the vinyl monomer mixture by gravity, so it is necessary to harden it by using the Hokuki flow stopcock/
It is preferable to drop the liquid under pressure. If the polymer beads have a diameter of 3 or more and are dropped naturally or under pressure, is the drop tube reduced to the neck? It is necessary to have it. Without this, the mixed liquid will fall continuously and will not form a uniform liquid layer. However, dropping under reduced pressure, 7
) In the case of the flow suction cock//, it is possible to make a uniform droplet even without the reduction part by adjusting the droplet, but in reality, it is not possible to control the droplet//! -Very difficult.

Figures 3 to 7 show other rows of dropping tubes, and in Figures 3 to 6, the dropping tubes/are made up of thick-walled tubes, and in this case, the diameter of the cW grain is It is greatly affected by the outer diameter of the pipe.

FIG. 7 shows an example in which the drip tube is spread out in the shape of a funnel.

In the case of a thin tube having a neck portion, if the neck portion 2 is fixed and the thin tube portion is replaceable, polymer beads of any diameter can be easily attached.

The vinyl monomer mixture that can be dropped becomes droplets due to surface tension. Since the ratio of these droplets is actually the same as that of the dispersion liquid, they are uniformly dispersed in the dispersion liquid.If the dispersion liquid is heated by the heating means S in the extreme region, it will be dispersed. Heat convection occurs in the liquid, and the liquid droplets do not stick together.
It circulates while maintaining its spherical shape, and is heated to form a claw shape to form polymer beads. Does the droplet have a constant diameter based on the diameter and shape of the drip tube? What you do is that you can get the desired diameter of the polymer peas with a fast and high yield. Incidentally, as mentioned above, even in the production of linear polymers, the same method can be used.

As is clear from the above 7) explanation, the present invention is different from the conventional dispersion method, the Shigekura method, and is suitable for industrial cleaning and is particularly suitable for heavy methods such as suspension polymerization. can.

Next, based on Examples and Comparative Examples, is the present invention? I'm busy explaining.

Example 5 Add 2,850 parts of methylcellulose 150@SOC hot water to a liter reaction vessel, stir, and dissolve until a sufficiently homogeneous phase is obtained.Methylcellulose is a s% solution with a specific gravity of 1.01 (70°C). A dispersion was obtained.

Stire 72301+a, 270 parts of divinylpe/zene, 400 parts of chloroparaffin (precipitating agent), 120 parts of trichloroethane (swelling agent), and 5 parts of benzoyl peroxide (polymerization initiator) were mixed well in a beaker, and then bathed in water at 90°C. Heating for 20 minutes in
p, specific gravity 1.01 (70℃), f) Vinyl monomer mixture? Obtained.

Next, using the apparatus shown in FIG. 8, a thin dripping tube (with an inner diameter of 2.0 mm and a neck inner diameter of 1 tan -7) attached to the bottom of the vinyl monomer mixed liquid tank 6 was used, and the above-mentioned pipes were attached to the tanks 3 and 6, respectively. The dispersion liquid and the vinyl monomer mixture liquid were stored and added dropwise to a fraction e of the vinyl monomer mixture liquid. Then, the dispersion was locally heated to a temperature of 80° C. using the heating stage S, and the monomer in the form of liquid particles was heated for 8 hours while being circulated by thermal convection of the liquid particles in the dispersion. The modified polymer beads were obtained. Separation and particle size distribution of polymer beads rather than dispersion? It was measured.

The results are shown below.

Less than 1.0 parts Mφ 1% 1 to less than 3IIIφ 7% less than 3 to 4 parts φ 86 parts 4111+11φ or more 6 parts Comparative Example 1゜ Conventional polymerization method using vinyl monomer mixture and dispersion having the same composition as Example 1 According to the instructions, pour the mixture into the dispersion liquid and stir the upper part of the dispersion liquid twice for 3 seconds to obtain the vinyl 7-mer mixture. Suspend in a dispersion liquid and
The copolymerized wood grains were obtained by polymerizing at ℃ for 8 hours. The particle size of this copolymer wood grain is shown below.

1.0-φ not a 12 section 1-3 darkness φ less than 35% 3-4ffII less than 11φ 20% 4-throat φ or more 37 Regret In Example 1, 3-4 darkness φ is more than 4 times that of Comparative Example 1,
By attaching a dropping tube with a double inner diameter and dropping the vinyl monomer mixture, polymer beads with a uniform particle size could be obtained.

Example 2 Add 240 parts of polyvinyl alcohol to a 5 liter reaction vessel, add 2760 parts of hot water at 80°C, stir, and dissolve until it becomes a sufficiently homogeneous phase, making it an 8% polyvinyl alcohol solution with a specific gravity of 1. , 01 (70°C) D dispersion was obtained.

230 parts of styrene, 270 parts of cyvinylbenzene, 400 parts of chloroparaffin (precipitant), trichloroethane (
Swelling agent) 150 parts, be/diyl peroxide (polymerization initiator) 5
Mix well in a small beaker, then heat in a 90℃ water bath for 20 minutes, and partially heat until the viscosity is 100-200.
CP, a vinyl monomer mixture with a specific gravity of 1.02 (70°C) obtained.

Using the device shown in Figure 8, the inner diameter of the dripping tube was cut by 4, and the neck part was 1.5 mm.
The above-mentioned dispersion and vinyl monomer mixture were applied in the same manner as the layer on the practical side except for making it glossy. Polymer beads were obtained using

The particle size distribution of this polymer bead D is shown below.

Less than 2.0 lightning φ 2chi 20 to 4.0-φ not I4 4chi 4.0 to 5.3 mgφ not #84, 5.31φ
xoqb Comparative Example 2 Copolymerized wood grains were obtained in the same manner as in Comparative Example 1 using the same dispersion as MIHJ1 and the vinyl monof-mixture.

The particle size distribution of the copolymerized wood grains is shown below.

Less than 2.0 pharyngeal diameter 6% 2.0-4. Less than OvRφ 29% 4.0-5.3
Less than throat φ 22% 5.3 mm φ or more 43 In case of implementation row 2, 4.0 to 5.3 gate φ reached four times that of comparative example 2, and in the case of the present invention, compared to the conventional polymerization method. The scale of monomer beads with uniform particle size is clear b).

[Brief explanation of the drawing]

Figures 1 to 7 show examples of dripping tubes used in the present invention, and Figure 8 shows an embodiment of the apparatus of the present invention. show. In the figure/... thin tube for dripping, Yu... thin tube neck, 3
...Dispersion liquid tank, q...Dispersion liquid, evening...Heating means,
6... Monomer mixed liquid tank, 7... Monomer a combined liquid,
g. g'... Capillary tube for dropping monomer mixture, IO... Pressure gauge, l/... Gas flow cock, 13... Bonder. Patent applicant Shoko Trading Co., Ltd.

Claims (2)

[Claims] (1) In the method of producing spherical heavy bodies by adding 1 fflk of vinyl monomer mixture into a liquid solution and then heating it, the vinyl monomer mixture has a viscosity of 60 to 6000P, and The specific gravity is made to be substantially the same as that of the dispersion, and then this vinyl monomer mixture t7. is intermittently dropped into the dispersion liquid through a thin tube with a diameter selected so that when dispersed in the dispersion liquid, it becomes droplets of the required diameter, and the dispersion liquid is heated. A method for producing a characteristic spherical polymer. (2) Consists of a 5+ liquid absorbing tank equipped with a heating means and a vinyl monomer mixed liquid tank provided in the L part of the dispersion liquid tank, and the vinyl monomer mixed liquid tank is placed at the bottom of the vinyl monomer mixed liquid tank. A device for producing spherical polymers in which dripping capillaries are formed.