KR100752739B1 - Method for continuous preparation of cross-linked polymeric beads - Google Patents

Abstract

Provided is a method for preparing a crosslinked polymer bead having uniform shape and size of 1 mm or more continuously and more economically. A method comprises the steps of supplying a reactant comprising a monovinyl monomer, a crosslinking monomer and a catalyst and a carrier fluid phase separated from the reactant into the entrance of a reactor tube so as to allow them to be repeatedly branched and flow in the flow direction of the reactor pipe; converting the reactant into a polymer bead by polymerization during the retention period passing the reactor tube, and discharging the polymer bead and the carrier fluid at the exit of the reactor tube in turn.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a cross-linked polymeric beads,

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing an apparatus for a continuous production process of crosslinked polymer beads according to the present invention,

FIG. 2 is a cross-sectional view illustrating a reaction tube in a device for continuous production of cross-linked polymer beads according to the present invention and a state in which a reactant is passed through the reaction tube by a carrier fluid,

FIG. 3 is a schematic view for explaining a shape of a polymeric bead, that is, a reaction product produced by a continuous production method of cross-linked polymeric beads according to the present invention,

Fig. 4 is a schematic view showing an example in which the reactant supply pipe and the carrier fluid supply pipe are connected to the crossing means as segment supply means at the reaction pipe inlet in an apparatus for continuous production of cross-linked polymer beads according to the present invention,

FIG. 5 is a cross-sectional view of a device for continuous production of cross-linked polymeric beads according to the present invention, in which a reactant supply pipe and a carrier fluid supply pipe are connected in a T-shape to a reaction pipe inlet and a cross-over means is provided in a reactant supply pipe and / A schematic diagram showing an example,

FIG. 6 is a cross-sectional view of a device for continuous production of cross-linked polymeric beads according to the present invention, in which a reactant supply pipe and a carrier fluid supply pipe are connected in a Y-shape to a reaction pipe inlet and crossing means is provided in a reactant supply pipe and / A schematic diagram showing an example,

FIG. 7 is a cross-sectional view of a cross-linked polymeric bead according to an embodiment of the present invention; FIG. 7 is a cross-sectional view of a cross- Fig.

Description of the Related Art

1: tubular reactor 2: reaction tube

3: Reactant 3a: Monovinyl monomer

3b: Monomer for crosslinking 3c: Catalyst

3d: solvent 4: carrier fluid

5: Intermediate product, polymer bead 6, 6 ': polymer bead product

7: Polymer Bead Products 8: Applied Products

10: inlet of reaction tube 11: heat treatment means

12: drying means 13: post-treatment means

14: Carrier fluid supply part 15: Reactant supply part

20: outlet of reaction tube 24: carrier fluid residue

25: unreacted reactant and solvent residue

The present invention relates to a continuous process for producing crosslinked polymeric beads, and more particularly, to a continuous process for producing crosslinked polymeric beads by continuously making crosslinked polymeric beads having a uniform shape and size of at least 1 mm by using a tubular reactor ≪ / RTI >

Generally, cross-linked polymeric beads are polymer particles having a certain degree of cross-linking. They are porous particles having nonporous beads and pores having no pores depending on the presence of pores, Beads.

The porous beads are classified into macroporous or macroreticular beads having a pore size of several hundred angstroms or more and microporous or microreticular beads having a pore size of several tens of angstroms or less.

Also, among the microporous beads having low porosity, the one having a low degree of crosslinking is also called a gel bead, and the pore size usually has a value between the macropores and the micropores.

Meanwhile, the nonporous beads may be classified by including them in the gel beads. Herein, the polymer bead includes various states in which the polymerization reaction involving cross-linking in the reaction material or reaction mixture of the organic phase may exist in the form of independent particles in a liquid or solid state in which the polymerization reaction proceeds above a certain level.

The polymeric beads can be used as an adsorbent, a filler, a support or a carrier, an ion exchange resin, and the like necessary for separation and purification of liquid or gaseous mixture, impurity or waste after itself or after further modification, , A catalyst for chemical reaction, a carrier, a cosmetic, a decolorizing agent, a deodorant, a property adjusting agent, a heat insulating material, a biofunctioning material, a light emitting functional material and a hybrid functional material.

Generally, a large polymer bead having a size of 1 mm or more without cross-linking can be easily produced by extrusion molding by melting a polymer in the form of particles or pellets. However, a polymer having a high degree of crosslinking has a melt state And it is difficult to form it into a necessary form because it has the property of an elastic body having a viscosity close to infinity.

Therefore, in order to produce cross-linked polymeric beads having a specific shape and size, the liquid reaction material is artificially dispersed so as to have a uniform shape and size, and then the polymerization reaction including crosslinking is independently performed Ideally,

It is not easy to apply the concept of promoting the polymerization reaction to commercial mass production while maintaining the desired bead shape and size independently of the dispersed individual reaction units.

It is generally known that crosslinked polymer beads that are close to spherical shape can be prepared by suspension polymerization, emulsion polymerization, or dispersion polymerization, in general, of a reaction product containing a monovinyl monomer and a crosslinking monomer have.

Among these methods, emulsion polymerization is in principle effective for the production of fine particles having a size of several microns or less, but it can not be used for producing particles having an excess size. In order to overcome this disadvantage, the seed emulsion polymerization method proposed also includes a method of adding a monomer to a small seed polymer previously prepared by emulsion polymerization and then repeating the process of continuing the polymerization to increase the particle size .

However, this method is limited to the production of polymer particles having a size of up to several tens of microns, and is limited to the case where the seed polymer is a non-cross-linkable linear polymer.

The dispersion polymerization method is disadvantageous in that it is not suitable for the production of polymer beads having cross-linking. This method has the fundamental limitation that particle size distribution of bead product is wide due to the problem of intergranular aggregation inevitably occurring in the process of producing polymer beads having a size of 10 microns or more.

The suspension polymerization method is the most widely used method for producing crosslinked polymer beads. In principle, the polymer beads produced by this method are very small in micron level and have a wide particle size distribution. Due to such quality problems, it is difficult to use the suspension polymerization method for the industrial production of homogeneous large polymer beads.

Although many technical alternatives have been proposed in order to solve the basic problems of the suspension polymerization method, a stable method capable of continuously mass-producing large-sized polymer beads cross-linked at a size of 1 mm or more in a uniform shape and size is still difficult There is a problem.

For example, U.S. Pat. Nos. 4,444,961 (1984) and 6,365,683 (2002) disclose the provision of a multi-hole distribution plate for reactant supply with vibrational energy to form uniformly sized monomer droplets in the suspension polymerization medium, A method of proceeding polymerization while reducing dispersion or coagulation of droplets in a reactor is disclosed.

However, it is well known that the average particle diameter of the beads produced in these patents is still in the range of 0.06 mm to 0.6 mm and the particle size distribution inevitably occurs. The fundamental limitations of this suspension polymerization method are still evident in the examples of U.S. Patent 4,487,898 (1984).

A method has been proposed in which the seed polymerisation method is enlarged to obtain a relatively large polymer bead through an additional polymerization reaction to a large seed polymer. U.S. Patent No. 5,231,115 (1993) discloses that a crosslinked seed polymer having a volume average diameter of 75 to 1,000 microns is first prepared by suspension polymerization, then the monomer reactant is absorbed in the seed, It is described that crosslinked polymer beads having a volume average diameter of 95 to 1,700 micron can be prepared.

This method is also disadvantageous in terms of economy in terms of the complexity of the polymerization system over the two steps, and is inevitably present in the process of producing the seed polymer, as disclosed in the embodiment of US Patent No. 5,276,113 (1994) The particle size distribution of the polymer beads produced by the addition polymerization is inevitably widened. Therefore, this method also has a problem in that it can not be utilized in the manufacture of polymer beads having a uniform shape and size of several millimeters have.

US Patent No. 5,447,983 (1995), which suggests that a large polymeric bead having an average particle diameter of 1 mm or more can be prepared by suitably controlling the density difference between the suspending medium and the reactant in the suspension polymerization, is premised on the use of a stirring type polymerization reactor. Due to the nature of the reactor, the particle size distribution in the polymeric beads produced by this method is inevitably present.

In view of the principles applied to micromixers that can be used to produce fine inorganic particles of micron or nanometer size, the recently evolving microdevice technology is uniform There is a possibility to be used for the production of polymer beads of one size.

For example, U.S. Patent No. 6,492,471 (2002) shows that it is possible to produce uniformly sized polymer beads using a micromixer, but such microdevices are difficult to apply to commercial mass production, and micron ) Sized polymer beads, it is still unknown whether it is applicable to the production of large polymer beads having a wide range of industrial applications and a size of 1 mm to 50 mm.

Accordingly, the present inventors have found that, in a conventional stirrer-type reactor, by using a tubular reactor made of a reaction tube, a gel-like or porous crosslinked polymer bead is continuously produced in uniform shape and size As a result, the present inventors have found that a carrier fluid in which a phase separation occurs between a reactant containing a polymerization reaction raw material and the reactant can repeatedly flow and flow in a flow direction in a large diameter reaction tube having an inner diameter of 1 mm or more .

Accordingly, it is an object of the present invention to provide a method for continuously producing cross-linked polymeric beads having a uniform shape and size.

It is another object of the present invention to provide a process for separating a carrier fluid and unreacted residues, a post treatment system for polymer bead drying, and / or the manufacture of crosslinked polymeric beads that can be used with additional processing systems for the production of applications, Method.

It is a further object of the present invention to provide a process for recovering a carrier fluid component or unreacted remnant component separated by a post treatment system and reusing it as a carrier fluid and a reactant respectively to provide a crosslinked polymeric bead And a method for producing the same.

A further object of the present invention is to provide a process for the preparation of (i) an adsorbent, filler and ion exchange resin for the separation and purification of liquid or gaseous mixtures, impurities or wastes, by itself or through further processing, (ii) (vi) a heat insulating material or a soundproofing material, (vii) a bio-functional material, (viii) a light-emitting functional material or a hybrid material, Functional materials, and raw materials for these materials. The present invention also provides a process for producing crosslinked polymer beads.

Physical and / or chemical processes such as additional coating, impregnation, molding, surface treatment, chemical modification or physical processing of the intermediate product or product of the polymer bead are often required to meet the specifications of such various applications. It is also possible that such a process may be included in the post-treatment system of the polymeric bead intermediate product in the present invention, or may be directly connected and implemented.

In addition, the present invention allows the shape of the polymer bead to be large enough so that the average value of the diameter is included in the range of 1 mm to 50 mm, so that the polymer bead to be produced can be variously formed in its own form And to provide an apparatus and a system that can be effectively used as an application product.

Meanwhile, the present invention makes it possible to produce cross-linked polymeric beads of a desired shape such as spherical, elliptical, or rod-like shapes in a uniform size, and dust generation due to friction between beads during storage, transportation, The present invention further includes the object of making a polymer bead having excellent quality and high utilization which can not be expected in a powder type product of the present invention.

Another important object of the present invention is to provide a method for continuously producing all kinds of crosslinked polymer beads regardless of the structural form such as porous or less gel-like or porosity-enhanced porous, And to provide a method that can easily satisfy the physical specifications such as the degree of crosslinking of the beads, porosity, density, specific surface area, etc. through the reactant composition.

In addition, the present invention has an object to provide a means for economically mass-producing polymer beads by allowing the production amount to be increased in proportion to increasing the number of reaction tubes based on the advantages of the tubular reactor.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

In order to accomplish the above object, the present invention provides a method of manufacturing a reaction tube, which comprises reacting a reactant containing a monovinyl monomer, a crosslinking monomer, and a catalyst at an inlet of a reaction tube constituting the tubular reactor, The polymer beads and the carrier fluid are supplied to the outlet of the reaction tube through the reaction tube so that the polymer beads are converted into the polymer beads by the polymerization reaction during the residence time of the reaction product through the reaction tube, And then discharging the polymeric beads sequentially through the through-holes.

Here, the polymer bead has a spherical shape, an elliptical shape, or a rod shape, and the average value of the major axis diameter and the minor axis diameter of the polymer bead is within a range of 1 mm to 50 mm.

Further, the monovinyl monomer is characterized by being a mixture of one kind or two or more kinds selected from an aliphatic or aromatic vinyl compound and a (meth) acrylic compound.

Further, the crosslinking monomer is characterized by being a polyfunctional vinyl compound having two or more unsaturated groups.

The catalyst is characterized in that the catalyst is at least one selected from a peroxide compound, an azo compound, a thiol compound, an alkylated silver compound, and a Friedel-Craft type compound.

Further, the reaction product is added with a solvent in an amount corresponding to 20 to 400 wt% of the total weight of the monomers constituting the monovinyl monomer and the crosslinking monomer.

Particularly, the solvent is characterized by being a mixture of one kind or two or more kinds selected from aliphatic or aromatic hydrocarbons, alcohols, halogenated hydrocarbons, ethers, esters and ketones.

The carrier fluid may be water or an aqueous solution.

Particularly, the aqueous solution is characterized in that at least one selected from the group consisting of oxides, hydroxides and salts of alkali metals or alkaline earth metals, and alcohol, cellulose compound and silica is dissolved in water at a saturation concentration or less.

In addition, the average distance between the center points of the reaction product segment units formed in the reaction tube is included within the range of 1.1 to 5.0 times the flow direction length of the reaction product segment unit.

Further, the reactant is heated so that the polymerization reaction can proceed under the condition that the temperature at the outlet of the reaction tube is maintained within the range of 50 ° C to 150 ° C.

Further, at least one of the reactant and the carrier fluid is degassed before being supplied to the inlet of the reaction tube.

In addition, the reactant and the carrier fluid are supplied in phase separation at the inlet of the reaction tube.

Here, the reactant supply pipe and the carrier fluid supply pipe are separately connected to each other in a form selected from Y-type, T-type and double pipe-type at the inlet of the reaction tube, and the reactant and the carrier fluid are separately supplied through the corresponding supply pipe, And is supplied in a phase-separated manner at a pipe inlet.

Further, crossing means may be additionally provided to at least one of the reactant supply pipe and the carrier fluid supply pipe, and the reactant and the carrier fluid are supplied in phase at the inlet of the reaction tube.

In another embodiment, the cross-linking means is connected to the inlet of the reaction tube, and the reactant supply pipe and the carrier fluid supply pipe are connected to the crossing means, respectively, so that the reactant and the carrier fluid are phase- .

Further, the additive selected from the functional fine powder and the inorganic filler having a size of a dye, a stabilizer, a micrometer or a nanometer is added to the reactant.

In addition, the polymerization reaction in the reaction tube is performed until the polymer beads discharged from the reaction tube outlet are not agglomerated with each other.

As a preferred embodiment, a process of separating the carrier fluid from a mixture of the polymer beads discharged from the reaction tube outlet and the carrier fluid is further performed.

Here, the carrier fluid separated from the polymer beads is recycled to the tubular reactor for reuse.

In the post-treatment system, the polymer beads from which the carrier fluid has been separated may be subjected to a heat treatment within a range of 50 ° C to 200 ° C and a drying process within a range of -40 ° C to 350 ° C, Is further performed.

Further, the present invention is characterized in that the carrier fluid, monovinyl monomer, crosslinking monomer and / or residual solvent components separated from the polymer beads in the post-treatment system are recycled to the tubular reactor for reuse.

Also, in the dried state, the polymer beads may be a porous polymer bead having an apparent density within a range of 0.1 to 0.5 g / cc.

Also, in the dried state, the polymer beads are formed into a gel-like polymer bead having an apparent density within a range of 0.5 to 1.0 g / cc.

In addition, the post-treatment system is further characterized in that the polymer bead is further coated, impregnated, molded, surface-treated, chemically modified or physically processed after the drying process.

In another preferred embodiment of the present invention, there is provided a method of manufacturing a polymer electrolyte fuel cell, comprising the steps of: heat treating a mixture of a polymer bead and a carrier fluid discharged from the reaction tube outlet in a post treatment system within a range of 50 ° C to 200 ° C; And at least one further process is further performed during the drying process within the range.

Here, the carrier fluid, the monovinyl monomer, the crosslinking monomer and / or the residual solvent components separated from the polymer beads in the post-treatment system are recycled to the tubular reactor for reuse.

Also, in the dried state, the polymer beads may be a porous polymer bead having an apparent density within a range of 0.1 to 0.5 g / cc.

Also, in the dried state, the polymer beads are formed into a gel-like polymer bead having an apparent density within a range of 0.5 to 1.0 g / cc.

In addition, the post-treatment system is further characterized in that the polymer bead is further coated, impregnated, molded, surface-treated, chemically modified or physically processed after the drying process.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

The continuous process for producing crosslinked polymer beads according to the present invention is characterized in that crosslinked polymer beads are continuously produced in a uniform shape and size by using a tubular reactor which is a reaction tube by removing from a conventional stirred tank reactor will be.

FIG. 1 is a schematic view showing an apparatus for continuous production of cross-linked polymer beads according to the present invention. FIG. 2 is a cross- FIG. 3 is a schematic view explaining the shape of the reactant, that is, the polymer bead produced by the continuous production method of crosslinked polymer beads according to the present invention. FIG. 3 is a cross- to be.

An apparatus for continuous production of polymer beads according to the present invention comprises: (i) a tubular reactor comprising a reaction tube containing a polymerization reaction raw material and a reaction tube in which a phase separation of the reaction fluid is repeatedly divided in a flow direction, Wow; (ii) a carrier fluid supply part and a reactant supply part respectively connected to the reaction tube inlet of the tubular reactor; (iii) a fractional feed provided at the inlet of the reaction tube so that the carrier fluid, which is phase-separated from the reactant including the monovinyl monomer, the crosslinking monomer and the catalyst, and the reactant, Wherein the polymer bead and the carrier fluid are sequentially discharged at an outlet of the reaction tube.

When such a polymer bead production apparatus is used, a carrier fluid in which phase separation occurs between a reactant containing a polymerization reaction raw material and the reactant is repeatedly divided and flowed in a flow direction in a large diameter reaction tube having an inner diameter of 1 mm or more, As the polymerization proceeds, crosslinked polymer beads having a uniform shape and size can be continuously produced.

First, referring to Fig. 1, a step of introducing a monovinyl monomer (3a), a crosslinking monomer (3b) and a catalyst (3c) into an inlet (10) of a reaction tube constituting the tubular reactor (1) The reactant 3 and the reactant 3 are fed so that the carrier fluid 4 which undergoes phase separation repeatedly flows and flows in the flow direction in the reaction tube 2.

The reaction product 3 is converted into a polymer bead by the polymerization reaction proceeding during the time passing through the reaction tube 2, that is, the residence time, and the polymer bead 5 and the carrier fluid 4, which flow repeatedly, And then discharged through the pipe outlet 20 sequentially.

In the present invention, one polymer bead 5 refers to a polymeric bead 5 in which the reactant 3 is introduced into the reaction tube 2 by the carrier fluid 4 as illustrated in Figures 2 (a) to 2 (d) Refers to a polymer unit produced by a polymerization reaction proceeding while moving in the form of a cylindrical (pellet or tablet), spherical, elliptical or rod-shaped.

Each of the reactant segment units (S-3 in FIG. 2), which is phase-separated from the carrier fluid 4 and repeatedly formed in the flow direction in the reaction tube 2, The carrier fluid 4 supplied to the reaction tube 2 is also phase-separated from the reactant 3 to form a carrier fluid segment unit S-4 between the reactant segment units S-3 repeatedly And moves along the flow direction.

Therefore, in the present invention, "repeatedly segmented" means that the phenomenon that the cross section of the reaction tube 2 at an arbitrary flow direction position is mostly filled with the reactant 3 or the carrier fluid 4 over time is repeated , And the macroscopic flow state inside the reaction tube 2 in which the two segment units move at the same speed in the flow direction is as shown in FIG.

As described above, the flow state inside the reaction tube 2 is a state in which the reactant 3 and the carrier fluid 4 are repeatedly segmented as indicated by S-3 and S-4 in Fig. 2 a segmented plug flow or a two-phase plug flow.

According to the present invention, the polymerization reaction proceeds according to the reaction tube retention time within each reactant segment unit (S-3), that is, the reaction product (3) And is converted into the polymer bead 5 while maintaining its shape substantially.

According to the present invention, a polymer bead 5 having a cylindrical shape (pellet or tablet shape), a spherical shape, an elliptical shape or a rod shape formed in the reaction tube 2 having an inner diameter d1 is formed in the flow direction or in the circumferential direction So that the cross-sectional types thereof are the same as those shown in Figs. 3 (a) to 3 (c).

The size of the polymer beads 5 is determined by the ratio of the major axis diameter to the minor axis diameter which can represent the shape of the reactant segment unit (S-3) as shown in FIG. 2 in addition to the inner diameter (= d ₁ ) (d ₂ / d ₁ or d ₁ / d ₂ ), and thus can be produced by means of a tubular reactor 1 which forms the segmented plug flow as in the present invention 5).

In this case, if the average size of the polymer beads 5 is represented by the average value of the major axis diameter and minor axis diameter [= (d ₁ + d ₂ ) / 2], then the polymeric beads 5, The average size of the beads 5 may range from a few microns to tens of centimeters.

However, when the average size of the polymer beads 5 is smaller than 1 mm, the pressure loss added to the thin reaction tube 2 is too large, so that the reactant S-3 or the carrier fluid S-4 is repeatedly It is difficult to form a segmented plug flow stably while the diameter d ₁ of the reaction tube is very large even when the average size of the polymer beads 5 exceeds about 50 mm or the reactant segment unit S- ) of hard to length (d ₂₎ is too long, the segment is retained by the unit shape is repeated stably.

Therefore, according to the present invention, it is preferable to prepare the polymer beads 5 such that the size based on the average value of the major axis diameter and the minor axis diameter of the polymer beads 5 is within the range of 1 mm to 50 mm.

On the other hand, not otherwise constrained in the ratio of the major axis diameter and minor diameter has a minimum value of 1.0 (d ₂ / d ₁ or d ₁ / d ₂₎ is the ratio becomes larger as about 10 or more, i.e., d _2> 10 d ₁ Or d ₁ > 10 d ₂ , it is difficult for the plug flow segmented inside the reaction tube 2 to be stably maintained.

Therefore, the ratio of the major axis diameter to the minor axis diameter of the polymer bead 5 produced by the present invention is preferably in the range of 1.0 or more and less than 10.

As the reaction tube 2 constituting the tubular reactor 1, there can be used various types of tubes such as a linear type, a coil type or a U-type so that a segmented plug flow can be formed.

The tubular reactor 1 may be of various forms such as a single tube heat exchanger, a cell-tube heat exchanger, a thermostat, a furnace, a heating tube, etc. The tubular reactor 1 comprises a plurality of reactors Units may be connected in series or in parallel, and each of the reactor units may be assembled by connecting a plurality of reaction tubes in series or in parallel in a bundle shape.

The material of the reaction tube 2 may be selected from among (i) a metal such as carbon steel, stainless steel, alloy steel, etc., (ii) glass such as quartz, Pyrex, soda glass, (iii) fluoropolymer, have.

The inner surface of the reaction tube is preferably smooth so that the segmented plug flow can be stably formed. Otherwise, the inner wall of the tube may be mechanically polished, chemically pretreated or coated.

On the other hand, a crosslinked polymer having a crosslinking property is a polymer having a monovinyl monomer, that is, a monomer having one vinyl group [CH ₂ = C <] and a crosslinking monomer, that is, a monomer capable of participating in a crosslinking reaction (3) comprising a plurality of vinyl groups or a plurality of double bond-containing monomers.

The monovinyl monomer (3a) that can be used in the production of the crosslinked polymer bead (5) is an unsaturated hydrocarbon generally used in the art, and may be an aliphatic or aromatic vinyl compound and a (meth) acrylic compound It may be a mixture of two or more.

More specifically, for example, styrene, o-, m- and p-methyl styrenes, o-, m- and p-ethyl styrenes, butyl styrene, but are not limited to, dimethyl styrene, diethyl styrene, vinyl naphthalene, vinyltoluene, vinylanisole, vinylxylene, monochlorostyrene, dichlorostyrene, Chloromethylstyrene, isopropenyltoluene, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Butyl acrylate, tert-butyl acrylate, ethylhexyl acrylate, cyclohexyl acrylate, isobornyl acrylate, Acrylate, isobornyl acrylate, benzyl acrylate, phenyl acrylate, alkylphenyl acrylate, ethoxymethyl acrylate, ethoxyethyl acrylate, Ethoxypropyl acrylate, propoxymethyl acrylate, propoxyethyl acrylate, propoxypropyl acrylate, ethoxyphenyl acrylate, and the like. Ethoxybenzyl acrylate, ethoxycyclohexyl acrylate, a methacrylic compound substituted by methacrylic acid instead of each of the above acrylic acid, acrylonitrile, methacrylonitrile (methacrylonitrile), vinyl chloride, vinylidene chlo vinyl benzyl chloride, ethylene dichloride, vinylacetate, vinylpyridine, vinylpropionate, N-2- (N-ethyl-perfluoro (N-ethyl-perfluorooctanesulfonamide) ethyl methacrylate) and the like can be used.

In the present invention, one of the above-mentioned monovinyl monomer (3a) components may be selected and used, or two or more components may be mixed as needed.

On the other hand, the crosslinking monomer (3b) which can be used for the production of the crosslinked polymer beads (5) is not particularly limited and is generally used in the art, and basically, a plurality of vinyl groups or a plurality of double , And the crosslinking monomer (3b) constituting the reactant (3) according to the present invention may be selected from polyfunctional vinyl compounds having two or more unsaturated groups.

More specifically, there may be mentioned, for example, divinylbenzene, trivinylbenzene, divinylethylbenzene, divinyltoluenes, divinylxylene, dichloroxylene, Divinylnaphthalenes, trivinylnaphthalene, polyvinylanthracenes, divinyloxyethane, trivinyloxypropane, trivinylcyclohexane, divinylpyridine (also referred to as divinylbenzene), divinylbenzene, divinylbenzene, divinylnaphthalene, divinylnaphthalene, trivinylnaphthalene, polyvinylanthracenes, divinyloxyethane, trivinyloxypropane, trivinylcyclohexane, divinylpyridine, divinylsebacate, divinyl sulfone, divinyl ketone, divinylsulfide, ethylene glycol diacrylate, ethylene glycol dimethacrylate, Ethylene glycol dimethacrylate, glycidyl methacrylate, trimethylolpropane trimethacrylate (trim trimethylolpropane trimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol dimethacrylate, , Bis-phenol A dimethacrylate, pentaerythritol di-, tri-, tetra-methacrylates, dipentaerythritol di- tri-, tetra-methacrylates, pentaerythritol di-, tri- or tetra-acrylates, dipentaerythritol di-, tri- or tetra-methacrylates, Pentaerythritol di-, tri-, tetra-acrylates, allyl acrylate, diallyl phthalate, diallyl mal (diallyl mal diallyl fumarate, diallyl succinate, diallyl carbonate, diallyl malonate, diallyl oxalate, diallyl fumarate, diallyl fumarate, diallyl fumarate, diallyl fumarate, But are not limited to, diallyl adipate, diallyl sebacate, diallyl tartrate, diallyl silicate, triallyl tricarballylate, triallyl isocyanurate ( triallyl isocyanurate, triallyl aconitate, triallyl citrate, triallyl phosphate, N, N'-methylene diacrylamide, N , N'-methylene dimethacrylamide, N, N'-ethylenediacrylamide, glycol, glycerol, and the like. polyallyl), polyvinyl ether monothio-, dithio- derivatives of polyvinyl ethers, pentaerythritol, resorcinol, glycerol, and the like can be used.

In the present invention, only one of the components for crosslinking monomer (3b) may be selected, or two or more components may be used in combination as required.

In the present invention, the content of the crosslinking monomer (3b) constituting the reactant (3) together with the monovinyl monomer (3a) is within a range of 2 to 95 wt% of the entire monomer mixture, When the crosslinking monomer (3b) is used in an amount less than 2 wt% of the monomer mixture, the degree of crosslinking of the produced polymer beads (5) becomes too low and the effect of using the crosslinking monomer (3b) becomes insignificant. On the other hand, 3b) is used in an amount greater than 95 wt% of the entire monomer mixture, the molecular chain of the polymer chain between the crosslinks is too small to cause swelling, and the physical properties may be uneven even in the individual polymer beads 5 .

In the case of divinylbenzene, which is lower in value among the crosslinking monomers, about 95 wt% can be used, but the remaining crosslinking monomer (3b) components are more expensive than the monovinyl monomer (3a) There is no need.

The polymerization reaction to be included in the present invention is preferably carried out using a catalyst 3c having a free radical initiator function. Examples of the catalyst 3c include peroxide compound (ROO-R '), (RN = N-R '), a thiol compound, an alkylated silver compound and a Friedel-Craft type compound can be used. The monomer components constituting the reactant (3) are mixed together It is preferable to supply it to the tubular reactor 1.

Specific examples of the catalyst that can be included in the reactant 3 to produce the polymer bead 5 according to the present invention include benzoyl peroxide, t-butyl hydroperoxide, di- but are not limited to, di-tert-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, tetralin peroxide, acetyl peroxide, Caproyl peroxide, t-butyl perbenzoate, t-butyl diperphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, Dicumyl peroxide, t-butyl peroxyester, t-amyl peroxyester, t-octyl peroxyester, t-cumyl peroxy Ester (t-cumyl peroxyester), azodiisobut Azodiisobutylamide, azobis (? -,? '- dimethylvaleronitrile), azobis (? -Methyl-butylol Azobis (? -Methyl-butyronitrile), 2,2'-azobis (2,4-dimethylpentane nitrile), dimethyl, diethyl Azobis (methyl-valerate), 1-pentanethiol, ethylenated silver, hydrogen peroxide, potassium persulfate, aluminum chloride, Stannic chloride, aluminum bromide, boron fluoride, zinc chloride, ferric chloride, and the like can be used.

At this time, the amount of the peroxide compound catalyst to be used may vary depending on the monomer component constituting the reactant (3), but it is preferably within the range of about 0.01 to 5 wt% of the total monomer used.

The azo-based catalyst may be used in an amount of about 0.01 to 2 wt% of the total amount of the monomers used, although it may vary depending on the monomer component of the reactant (3).

In addition to the organic compound-based catalyst (3c), a sulfur-containing compound, an alkylated silver compound, an inorganic oxidizing agent, or a reducing agent Friedel-Crafts type catalyst may be used in an amount of about 0.001 to 5 wt% of the entire monomer.

In addition to the above, the kind of the well-known free radical initiator which can be used as the catalyst (3c) in the present invention and the conditions of use are described in the cited references, for example, J. Brandrup and E.H. Immergut, Polymer Handbook, 3rd Ed., Pp. II / 1 to II / 65, John Wiley & Sons, Inc., 1989).

Whether the selection of the catalyst (3c) to be used in the present invention or the suitability of the composition and the amount of the catalyst to be used can be easily confirmed by a simple preliminary experiment.

In order to produce the crosslinked polymer bead 5 according to the present invention, a diluent or a substance showing a function of a solvent (hereinafter referred to as a 'solvent') may be further added to the reactant 3.

In the present invention, the solvent (3d) refers to a solvent capable of dissolving (i) some components of the monomer and the intermediate product without participating in the polymerization reaction of the reactant (3), (ii) capable of swelling the crosslinked polymeric polymer (Iii) allowing the pores to develop in the polymeric beads 5 to be produced, (iv) allowing the reaction product unit (S-3) (V) an organic substance which can be added to the reaction product (3) for various purposes such as effectively removing the reaction heat generated by the polymerization reaction, or the like, by controlling the concentration of the component.

The solvent (3d) added to the monomer components (3a, 3b) in the present invention and contained in the reactant (3) is generally known in the art and can be selected from among water-soluble or water- Which is capable of dissolving the components used to carry out the process.

In the present invention, one or a mixture of two or more selected from aliphatic or aromatic hydrocarbons, alcohols, halogenated hydrocarbons, ethers, esters and ketones is used. More specifically, hexane, cyclohexane Hexane, heptane, octane, nonane, dodecane, isooctane, 2,2,4-trimethylpentane, xylene ), Toluene, carbon tetrachloride, methyl isobutyl ketone, methyl isobutyl carbinol (4-methyl-2-pentanol) pentanol, 2-ethylhexanol, 1-octanol, n-amyl alcohol, isoamyl alcohol, chlorobenzene, Ethylene dichloride, tetrachlorethylene, propylene dichloride, ylene dichloride, dichlorobenzene, petroleum ether, diphenyl ether, chloromethyl methyl ether, nitromethane, nitroethane, nitropropane, nitropropane, nitrobenzene, carbon disulfide, 2-ethyoxy ethanol, C ₂ H ₅ OCH ₂ CH ₂ OH, 2-butoxyethanol, C ₄ H ₉ OCH ₂ CH ₂ OH), ethylene glycol dimethyl ether (CH ₃ OCH ₂ CH ₂ OCH ₃ ), diacetone alcohol (4-hydroxy-4-methyl-2-pentanone _{CH 3) 2 C (OH)} CH 2 COCH 3), 4- methoxy-4-methyl-pentanone (4-methoxy-4-methylpentanone , (CH 3) 2 C (OCH 3) CH 2 COCH 3), 2 2-butanone, methyl ethyl ketone (C ₂ H ₅ COCH ₃ ), and the like can be used.

According to the present invention, when the solvent (3d) is to be contained in the reactant (3), the amount of the solvent (3d) to be used depends on the kind of the monovinyl monomer (3a) or the crosslinking monomer (3b) The physical properties of the polymer beads, the characteristics of the polymerization reaction to be controlled, etc., and it is preferable to confirm the selection, composition, and amount of the solvent 3d by a simple preliminary experiment.

According to the experimental results of the present inventors, when the solvent 3d is added so as to be less than 20 wt% of the total weight of the monomer components including the monovinyl monomer (3a) and the crosslinking monomer (3b) (3) is excessively diluted so that when the solvent (3d) is added in an amount exceeding 400 wt% of the total weight of the monomer components, It was found that the reaction rate was greatly decreased.

Therefore, when the solvent 3d according to the present invention is to be used, it is preferable that the amount of the solvent 3d used is within the range of 20 to 400 wt% of the total weight of the monomer components.

In the present invention, in addition to the components necessary for the polymerization reaction such as the monomers 3a and 3b, the catalyst 3c, and the solvent 3d, additives may be added in consideration of the end use of the polymer beads 5, The additives that can be used include functional organic compounds such as coloring matters and stabilizers, functional fine powders of micrometer or nanometer size, polymer fine particles capable of a seeding function of polymerization reaction, organic or inorganic The additives may be added to the reactant 3 within a range which does not cause any trouble in forming the plug flow repeatedly segmented inside the reaction tube 2. [

According to the present invention, it is also necessary to supply the carrier fluid (4) together with the reactant (3) in order to form the plug flow repeatedly segmented inside the reaction tube (2) to produce the crosslinked polymer bead (5).

As the carrier fluid 4, any liquid or gas which can theoretically be phase-separated from the reactant 3 in the organic phase may be used.

However, according to the experiments of the present inventors, it has been found that the use of a liquid having a density of the carrier fluid 4 that is higher than the density of the reactant 3 is used to form a plug flow which is repeatedly segmented inside the reaction tube 2 I could see the advantage.

In the present invention, the density of components constituting the monomer components (3a, 3b) and / or the solvent (3c) is usually less than 1.0 g / cc, 4), water may be used as it is, or a liquid in the form of an aqueous solution in which a solute of an inorganic component is dissolved and / or a limited amount of an organic component is mixed so that the density becomes about 1.0 g / cc or more may be used .

It is preferred that the organic components contained in the aqueous solution used as the carrier fluid 4 are not intermixed with the reactant 3 components but if the reactant 3 is recycled by repeated recycle and reuse of the carrier fluid 4, The constituent organic components may inevitably be mixed as impurities.

In this case, the concentration of the impurity is preferably limited to a maximum of 10 wt%, more preferably 5 wt% or less of the aqueous solution.

In order to form the segmented flow of the reactant 3 and the carrier fluid 4, only water may be selected as the carrier fluid 4, but an aqueous solution in which additional components are dissolved in water may be used as the carrier fluid 4, It may be more advantageous to control the physical, electrical, and chemical properties at the interface at which the fluid 4 contacts.

Here, the aqueous solution may be one or two or more selected from the group consisting of oxides, hydroxides, and salts of alkali metals or alkaline earth metals, and alcohol, cellulose compound, and silica.

That is, an oxide, hydroxide and salt of an alkali metal or an alkaline earth metal such as Na, Mg, K or Ca as an inorganic component solute and a low molecular weight alcohol such as ethanol, isopropyl alcohol and butanol and a polyvinyl alcohol ) And a cellulose compound such as hydroxylethylcellulose, hydroxylpropylcellulose, methylhydroxylethylcellulose and methylhydroxylpropylcellulose, and a cellulose compound such as methyl cellulose, An aqueous solution containing one or more selected water in the water may be used as the carrier fluid, and it is necessary to make the concentration of the solute in the aqueous solution state be not more than the saturated concentration.

According to the present invention, there is no restriction on the choice of the reactant 3 and the carrier fluid 4 as long as the conditions that the reactant 3 and the carrier fluid 4 are not reacted with each other and are phase-separated at the same time are satisfied, This basic condition can be easily tested and confirmed with a beaker or glass tube, so that the composition and composition of the reactant 3 and the carrier fluid 4 can be determined without any difficulty.

According to the present invention, since the plug flow is repeatedly formed in the reaction tube 2 to form crosslinked polymer beads 5, the average interval between the reactant segment units (S-3) To maintain the flow is an important operating parameter in producing the polymer bead 5 according to the present invention.

Since the shape of the reactant segment unit (S-3) varies as illustrated in FIGS. 2 and 3, the characteristics of the segmented plug flow can be expressed as the average between two adjacent reactant segment units (S-3) interval (= d _3), i.e. two adjacent carrier fluid segment unit (S-4) the mean spacing and the reaction segment units (S-3) flow direction mean length (= d ₂₎ the ratio of the between the center point (= d ₃ / d ₂ ).

According to the characteristics of the segmented plug flow according to the present invention, the average spacing (= d ₃ ) between the center points of the reactant segment units (S-3) in the reaction tube (2) to ensure an average length of 1.1 ~ 5.0 times included within the scope of (d = _2), i.e. good _{1.1≤ d 3 / d 2 ≤ 5.0} .

If the distance d ₃ / d ₂ <1.1, the interval between the carrier fluid segment units S-4, that is, the flow direction length (= d ₃ -d ₂ ) of the carrier fluid S- Even if a slight disturbance occurs on the flow, the adjacent reactant segment units (S-3) are stuck to each other, making it difficult to produce the polymer beads 5 having a uniform shape and size, while the d ₃ / d ₂ > 5.0, the length in the flow direction of the carrier fluid segment unit (S-4) becomes too long as compared with the flow direction length of the reactant segment unit (S-3), so that the carrier fluid segment unit (S- 2) The internal space is unnecessarily occupied, so that the production efficiency of the tubular reactor 1 is lowered.

The characteristics of the segmented plug flow as described above can be easily confirmed directly when a glass tube or a plastic tube transparent to the reaction tube 2 is used.

On the other hand, when an opaque metal pipe, a ceramic pipe or a plastic pipe is used, the plug flow characteristics can be easily estimated by measuring the shape, dimensions and production rate of the polymer bead product 5 discharged from the reaction pipe 2.

However, in the present invention, the size of the segment unit and the interval between the segment units are parameters of an average meaning, so that the size and shape of the polymer beads 5 generated and discharged from the reaction tube 2 do not deviate from the average meaning , A minute deviation in the interval between the segment units or the size of the segment unit that can actually occur in the reaction tube (2) is not an important issue.

The reaction temperature can be easily set through preliminary experiments in connection with operating parameters such as composition, composition and reaction time of the reactant. However, due to the characteristics of the tubular reactor (1), the reaction temperature is changed according to the flow direction of the reaction tube There are many cases.

In order to allow the polymerization reaction to proceed during the residence time of the reaction tube 2 within the segment unit (S-3) of each of the reactants according to the present invention, when the reaction temperature is in the range of 50 ° C to 150 ° C (S-3) or the carrier fluid (S-4) is advantageous in that the reaction speed is higher when the reaction temperature is higher than 150 ° C, However, when the reaction temperature is lower than 50 ° C, the reaction rate becomes too slow and the residence time of the reaction tube 2 must be increased. Therefore, the tubular reactor 1 is very long It is undesirable.

In order to maintain the reaction temperature higher than about 90 ° C, the reactant (S-3) or the carrier fluid (S-4) may be constituted by controlling the reaction pressure to alleviate the problems occurring at a high reaction temperature. The internal pressure of the reaction tube 2 may be maintained at 1 bar or more so as to suppress the vaporization of some components.

On the other hand, in order to maintain the reaction temperature within a desired range, it is necessary to supply a heating medium such as water, heat medium oil, steam, or gas to the space between the reaction tube 2 and the shell as in a heat exchanger for heating.

When it is desired to form a specific reaction temperature gradient in the flow direction of the reaction tube 2, the entire or part of the shell space of the tubular reactor 1 is divided into a plurality of spaces, and the heating medium is supplied separately It is good.

Alternatively, when the tubular reactor 1 is configured such that the reaction tube 2 is installed inside the thermostat, the temperature of the heating medium of the thermostatic chamber may be controlled to maintain the reaction temperature within the required range.

The reactant may be heated by making all or part of the shell space of the tubular reactor 1 to have the shape of a thermostat and heating the heating medium constituting the thermostatic chamber to a stagnant state or circulated state.

If it is not a problem in terms of economy in place of the use of the heating medium, it is possible to use an electric resistance heating method of the heating element provided on the wall surface of the reaction tube 2 itself or on the outer wall of the reaction tube 2, 2) Heating methods such as internal heating may also be utilized.

For example, it is possible to construct a tubular reactor which can supply microwaves to all or part of the shell space of the tubular reactor 1 to heat the reactants and / or the carrier fluid.

If the microwave is supplied to a part of the shell space of the tubular reactor 1, the heating medium may be supplied to the remaining shell space so that a desired reaction temperature distribution may be achieved according to the flow direction in the reaction tube 3 have.

On the other hand, it is possible to increase the heating efficiency by providing a heat insulating material or a thermal insulating material (not shown) in all or part of the shell space of the tubular reactor to which the microwave is supplied. As the thermal insulating material or the thermal insulating material used herein, The material having such properties is preferably an inorganic component such as silica, alumina or silicon nitride, or a general-purpose polymer component such as polystyrene, polyethylene, polypropylene or the like, or polytetrafluoroethylene A fluorine-based polymer component such as polytetrafluoroethylene is used.

The reactants 3 and / or the carrier fluid 4 are preheated in advance to replace the heating of the reactants 3 in the tubular reactor 1 or to reduce the burden of heating the reactants 3 in the tubular reactor 1 It may be supplied to the reaction tube inlet 10.

In this case, the preheating temperature may be selected within the range of 50 to 150 ° C. When the preheating of the reaction product (3) is excessive and the polymerization reaction partially proceeds, the reaction product can be stably supplied And the maintenance of the segmented plug flow inside the reaction tube 2 becomes difficult.

It is therefore advantageous to preheat the reactant 3 and / or the carrier fluid 4 in view of the fact that it is safe to preheat to a temperature lower than the carrier fluid 4 during the preheating of the reactant 3 and the polymerization reaction is generally an exothermic reaction. The polymerization reaction of the reactants 3 can be more effectively proceeded from the reaction tube inlet 10 by the preheating of the tubular reactor 1 and the heating load of the tubular reactor 1 can be significantly reduced.

According to the present invention, a reactant pre-heater and / or a carrier fluid preheater capable of heating the reactant 3 and / or the carrier fluid 4 within the range of 50 ° C to 150 ° C, respectively, Respectively.

The reaction temperature is higher than the boiling point of the reactant 3 or the constituent components of the carrier fluid 4 in the production of the polymer bead 5 by forming the plug flow repeatedly segmented in the reaction tube 2 according to the present invention (S-3, S-4) of the reactant and the carrier fluid, respectively, when the pressure inside the reaction tube 2 is low or when the reactant 3 or the carrier fluid 4 contains a large amount of gas, The bubbles may be generated occasionally, and once the bubbles are formed, the stability of the segmented plug flow is lowered and the shape of the polymer beads is deteriorated.

In order to reduce the possibility of generating such bubbles, the pressure inside the reaction tube 2 is increased to 1 bar or more, the reaction temperature is set low, or the reactant 3 and / or the carrier fluid 4 is introduced into the reaction tube inlet 10 Degassing treatment may be performed before supplying the gas to the reaction chamber.

If the pressure inside the reaction tube is lower than 1 bar, the bubble formation may be increased. If the pressure is too high to exceed 10 bar, the reaction product (3) and Which is a burden on the supply of the carrier fluid 4.

Therefore, it is preferable that the pressure of the inside of the reaction tube 2 is selected within a range of 1 to 10 bar based on the reaction tube inlet 10 to suppress bubble formation.

In general, the above-described degassing treatment is not necessarily required in the case where the selection of the components and the composition of the reactant 3 and the carrier fluid 4 is poor.

If the deaeration treatment is required for the reactant 3 and / or the carrier fluid 4, the dissolved gases 21 and 22 are removed from the reactant supply part 15 and / or the carrier fluid supply part 14, can do.

On the other hand, instead of performing the deaeration treatment of the reactant 3 and the carrier fluid 4 at the supply portions 14 and 15, the deaeration treatment may be performed at the deaerating means provided at the reaction tube inlet 10, Degassing treatment may be carried out separately for the specific components of the reactants 3.

A chemical degassing method using a physical degassing method such as a heating method, a vacuum method, a separation membrane method, and a centrifugal separation method or an organic or inorganic degassing agent can be applied as is well known to remove the gas dissolved in the liquid. In the present invention, any of these methods may be selected and used.

It is an important problem to supply the reactant 3 and the carrier fluid 4 to the reaction tube inlet 10 so that the plug flow repeatedly segmented inside the reaction tube 2 according to the present invention can be formed. It is most common to supply the reactant 3 and the carrier fluid 4 in phase-separation at the reaction tube inlet 10 for the formation of the plug flow.

4 (a) to 4 (c), the intersection SM is connected to the reaction tube inlet 10, (F-3) and the carrier fluid supply pipe (F-4) are connected to the intersection means SM to constitute a segment supply means.

In this way, the reaction product 3 (3) is injected into the reaction tube inlet 10 by means of the segment supply means, which are variously configured as the reaction product supply pipe F-3, the carrier fluid supply pipe F- 3 and the carrier fluid S-4 from the reaction tube inlet port 10 in the flow direction in the reaction tube 2 can be supplied in a phase-separated manner, .

According to this method, the reactant supply pipe F-3 and the carrier fluid supply pipe F-4 are connected to the crossing means SM connected to the reaction tube inlet 10, respectively, A spatial connection (connection-a) between the reactant supply pipe F-3 and the reaction pipe inlet 10 and a spatial connection (connection-a) between the carrier fluid supply pipe F-4 and the reaction pipe inlet 10 according to a pre- -b) repeatedly cross each other.

The intersection SM for this flow segment may be a switching valve, a solenoid valve, a diaphragm unit, a pulse type pressure generator, a peristatic pump, a pulsating pump, Or in combination with each other so that they can be phase-separated in a predetermined period.

During the time (? A) of the connection-a state, only the reactant (3) is supplied to the reaction tube (2) to generate the reactant fragment unit (S-3) Only the carrier fluid 4 is supplied to the carrier fluid segment unit 2 to generate the carrier fluid segment unit S-4.

Since the two segment unit volumes are determined according to the setting of the intersecting period (? A and? B) of the connection time, the length and interval of the segment unit, that is, the size of the polymer bead product (5) The number can be fixed.

Another method for stably generating the segmented plug flow in the reaction tube 2 according to the present invention is to separate the reactant supply pipe F-3 and the carrier fluid supply pipe F-4 separately from the reaction pipe inlet 10 And the reactant (3) and the carrier fluid (4) are supplied in a phase-separated manner.

According to this method, as illustrated in FIGS. 5, 6 and 7 with the reactant supply pipe F-3 and the carrier fluid supply pipe F-4 attached thereto, a Y-, T- -Type or the like to the reaction tube inlet 10 separately.

As shown in Figs. 5A, 6A and 7A, the two supply pipes F-3 and F-4 connected to the reaction tube inlet 10 are provided with different The reactant 3 and the carrier fluid 4 can be phase-separated into the reaction tube inlet 10 without using any crossing means so that the plug flow repeatedly segmented inside the reaction tube 2 can be stably formed.

On the other hand, by using the intersecting means SC and SR in the reactant supply pipe F-3 and / or the carrier fluid supply pipe F-4 connected to the reaction pipe inlet 10, And the carrier fluid 4 are supplied in phase-separated form, whereby the plug flow repeatedly divided into the reaction tube 2 can be stably formed.

According to this method, as illustrated in FIGS. 5B to 5D, 6B to 6D and 7B to 7D, the reaction tube inlet 10, (SR, SC) to at least one of the reactant supply pipe (F-3) and the carrier fluid supply pipe (F-4) connected to each other.

In the accompanying drawings, reference symbol SR denotes reactant crossing means SR installed in the reactant supply pipe, and reference symbol SC denotes a carrier fluid crossing means SC installed in the carrier fluid supply pipe.

The crossing means SC and SR may be arbitrarily selected from flow control means such as a flow rate control type, an ON-OFF type or a mixing method thereof, and both of these methods may be used at the same time.

As the flow control type crossing means, various control valves such as a ball type, a globe type, a needle type and a gate type which are widely used in chemical processes can be used. However, the flow rate control type crossing means can be used in a control system construction It has disadvantages that are followed by difficulties.

On the other hand, the ON-OFF type, that is, the OPEN-CLOSE type crossing means which can be more easily utilized includes a solenoid type valve, a pulse type metering pump, a diaphragm unit, A generator and the like may be used.

Here, the crossing means for supplying the carrier fluid S-4 is turned off during the time (connection-a;? A) during which the crossing means for supplying the reactant (S-3) And the crossing means for supplying the reactant S-3 at the time when the crossing means for supplying the carrier fluid S-4 is turned ON is turned off or closed. (Connection-a) / off (connection-b) and off (connection-a) / on (pre-determined intersection periods? A and? B) by interconnecting the two segmenting means to effect this method effectively Connection-b) may occur at the same time.

For example, as illustrated in FIG. 5C, FIG. 6C or FIG. 7B, a reactant supply pipe F-3 is connected to the reaction tube inlet 10 to form a reactant OFF type carrier fluid cross means SC provided on the carrier fluid supply pipe F-4 connected to the reaction pipe inlet 10 separately from the reactant supply pipe F-3 while supplying the carrier fluid F- The reaction fluid 3 and the carrier fluid 4 are phase-separated and supplied to the reaction tube inlet 10 so that the inside of the reaction tube 2 is supplied with the carrier fluid 4 in a pulse- It is possible to stably form the plug flow which is repeatedly divided into two portions.

Conversely, as illustrated in FIG. 5B, FIG. 6B or FIG. 7C, a carrier fluid supply pipe F-4 is connected to the reaction tube inlet 10, OFF-type reactant crossing means SR provided in a reactant supply pipe F-3 connected to the reaction pipe inlet 10 separately from the carrier fluid supply pipe F-4 while supplying the reactant supply pipe F- The reactant 3 and the carrier fluid 4 are supplied to the reaction tube inlet 10 so that the reaction fluid 3 is phase-separated and supplied into the reaction tube 2 through the reaction tube 3, It is possible to stably form the segmented plug flow repeatedly.

On the other hand, as illustrated in FIG. 5 (d), FIG. 6 (d) or FIG. 7 (d), the reactant supply pipe F- The reactant 3 and the carrier fluid 4 can be supplied in pulse form at predetermined time intervals through on-off intersection means provided in each of the reaction tube inlet 10 The reactant 3 and the carrier fluid 4 can be supplied phase-separated to the reaction tube 2 so as to stably form a repeatedly segmented plug flow in the reaction tube 2. In this case, ON-OFF) may be mutually opposite to each other to constitute a control system.

In addition, as illustrated in Figs. 5 (a), 6 (a), and 7 (a), the reactant supply pipe F-3 and the carrier fluid supply pipe F-4 may be separately connected in the form of a Y-type, a T-type or a double tube-type, and the reactant 3 and the carrier fluid 4 may be supplied separately without using any crossing means, The reactant 3 and the carrier fluid 4 can be phase-separated into the reactant 3 and the carrier fluid 4 to stably form a plug flow which is repeatedly segmented in the reaction tube 2, It is advantageous not to use the crossing means since it is based on utilizing the difference in the physical properties of the fluid 4 so that the plug flow segmented from the reactor inlet 10 occurs naturally.

However, the structure of the reactor inlet 10 in which the reactant 3 and the carrier fluid 4 are first brought into contact in consideration of the physical properties of the reactant 3 and the carrier fluid 4 must be precisely configured, (3) and the carrier fluid (4).

At the beginning of operation of the tubular reactor (1) according to the present invention, the carrier fluid (4) is sufficiently supplied in order to form a stably segmented plug flow in the reaction tube (2) And the configuration and operating conditions of such segmenting means can be easily optimized through preliminary experiments.

Meanwhile, the segment supplying means utilized in the present invention may include a preheater that can be installed in the reactant supply pipe F-3 and / or the carrier fluid supply pipe F-4 as described above.

As described above, the separated feed (3) of the reactant (3) and the carrier fluid (4) is supplied from the reaction tube inlet (10) according to the present invention so that the reactant (3) and the carrier fluid It is preferable that at least the carrier fluid 4 keeps a laminar flow state so that no vortex is generated in the plug flow inside the reaction tube 2.

The mixture of the polymer beads 5 and the carrier fluid 4 discharged from the reaction tube outlet 20 according to the present invention may contain residues of the unreacted monomers 3a and 3b or a solvent .

Accordingly, there is a need for a post-treatment system for separating and removing the carrier fluid (4) and the residue components in order to produce crosslinked polymer beads as a product.

Meanwhile, the polymer bead 5 discharged from the reaction tube outlet 20 according to the present invention can be strictly expressed as a polymer bead intermediate product requiring a post-treatment system.

In the preparation of the polymer bead intermediate product 5 using the tubular reactor 1, the polymerization reaction of the reactant 3 must be carried out in the reactant segment unit (S-3) during the residence time in the reaction tube 2 It need not be terminated.

Considering that a polymerization reaction including a crosslinking reaction proceeds slightly within the reaction product segment unit (S-3) in the reaction tube (2), all of the reaction product segment unit (S-3) ).

However, if polymerization can not proceed to such an extent that the polymer bead intermediate products 5 discharged from the reaction tube outlet 20 coalesce with each other, further processing in the post-treatment system can not be performed. Therefore, It is more preferable that the polymeric bead intermediate products 5 to be discharged are subjected to minimal polymerization in the tubular reactor 1 to the extent that they do not aggregate with each other.

According to the present invention, the polymer bead intermediate product 5 discharged from the reaction tube outlet 20 can be heat-treated and / or dried in a post-treatment system including a heat treatment means and / or a drying means.

The post-treatment system may be configured in various ways depending on the degree of polymerization of the polymer bead intermediate product 5 discharged from the reaction tube outlet 20 and the use of the polymer beads.

If the polymerization reaction of the reactant 3 according to the present invention is sufficiently carried out during the residence time in the reaction tube 2, the polymer bead intermediate product 5 discharged from the tubular reactor 1 may be mixed with the polymer bead product 6 The polymeric bead product 6 'can be used as the residue 24 of the carrier fluid 4 and the unreacted reactant 3 without being subjected to the heat treatment by the heat treatment means 11 necessary for the additional polymerization reaction. And the drying means 12 for separation and removal of components such as the residue 25 of the solvent 3d and the reaction by-products and the like can be the polymer bead product 7.

As described above, when the polymer bead intermediate product 5 is discharged from the tubular reactor 1 in the state of the polymer bead product 6 'which substantially satisfies the reaction conversion and the degree of crosslinking required in the polymer bead product 7, The polymeric bead product 7 can be manufactured through the drying means 12 without a heat treatment process.

The drying means 12 is configured to remove residual material 24 of the carrier fluid 4, unreacted reactants 3a and 3b and solvent B from the polymeric bead product 6 'through drying means, The residue (25) of the polymer (3d), the reaction by-products and the like are separated and removed to produce the polymer bead product (7).

If a large amount of the carrier fluid 4 is contained in the mixture of the polymer bead product 6 'discharged from the reaction tube outlet 20 and the carrier fluid 4, the amount of heat necessary for the drying means 12 Q3 are required in excess, a part or a substantial amount of the carrier fluid 4 may be removed and removed beforehand in advance of the drying means 12.

If the amount of the carrier fluid 4 is less than the amount of the polymer bead product 6 ', the carrier fluid 4 may be dried immediately by a single or a plurality of drying means without separating it in advance of the drying means 12 You can also lose.

On the contrary, when the reaction rate of the reaction product 3 is slow and a sufficient residence time is required, there arises a problem that the length of the reaction tube 2 must be excessively long. In this case, the reaction tube inlet 10 and the outlet The pressure loss between the tubular reactor 1 and the tubular reactor 1 is increased, which results in difficulty in the construction and operation of the tubular reactor 1.

According to the present invention, polymerization of the reactant (3) may not be sufficient or the formation of the physical structure may not be completed within the polymer bead intermediate product (5) discharged from the reaction tube outlet (20) In this case, it is preferable to perform additional heat treatment of the polymer bead intermediate product (5) in the heat treatment means (11) before drying by the drying means (12).

Here, the heat treatment means 11 means that the polymer bead intermediate product (5) is substantially satisfied with the physical properties such as the reaction conversion rate and the degree of crosslinking required in the polymer bead product (7) and the required physical structure through the additional polymerization reaction and heat treatment (6). &Lt; / RTI &gt;

As described above, in the case where the polymer beads are discharged from the reaction tube outlet 20 in the state of the intermediate product 5, the polymerization reaction is promoted in the reaction tube 2 to such an extent that the beads do not cohere with each other even if they are in contact with each other need.

As described above, the method of further performing the polymerization reaction inside the polymer beads while further subjecting the polymer bead intermediate product 5 discharged from the reaction tube 2 to further heat treatment has a drawback in that the heat treatment means 11 must be added And the residence time of the reaction tube 2, that is, the length of the reaction tube 2, does not have to be relatively long.

Therefore, the polymer beads in the present invention are (i) a state in which the polymerization reaction proceeds in the reactant segment unit (S-3) inside the reaction tube 2; (ii) the state of the polymer bead intermediate product (5) in which the polymerization has not been sufficiently carried out but the polymerization has proceeded to a level at least not coagulated with each other in the handling process after the tubular reactor (1) or in the heat treatment means; (iii) a polymer bead product (6, 6 ') state substantially satisfying physical properties such as the degree of reaction conversion and degree of crosslinking required with the polymer bead product (7) and the required physical structure; (iv) a state of polymer bead product (7) in which components such as carrier fluid residue (24), unreacted reactants (3a, 3b), solvent (3d) remnants (25), reaction byproducts and the like are separated and removed through drying means; (v) a polymer bead product (8) that is manufactured to meet the end use purpose through additional coating, impregnation, molding, surface treatment, chemical modification or physical processing of the polymer bead product (7) And can be expressed separately by each state.

The heat treatment unit 11 may be continuously connected to the tubular reactor 1, or may be semi-continuous or batch-wise. In the present invention, the mixture of the polymer bead intermediate product (5) and the carrier fluid (4) can be directly transferred to the heat treatment means (11) and heat-treated.

If the amount of the carrier fluid 4 in the mixture of the polymer bead intermediate product 5 discharged from the reaction tube outlet 20 and the carrier fluid 4 is large, the amount of heat Q 2 supplied to the heat treatment means 11 is increased, A part or a substantial amount of the carrier fluid 4 may be separated from the mixture in advance of the heat treatment means 11 in order to alleviate the heat burden.

In order to separate the polymer bead intermediate product 5 and the carrier fluid 4 from each other, it is preferable to use a means such as a layer separator and a centrifugal separator using density difference, a sieve, a mesh, Known solid-liquid separation means can be utilized.

The mixture of the polymeric bead intermediate product 5 having a small amount of the carrier fluid 4 may be directly conveyed to the heat treatment means 11 composed of a single or a plurality of apparatuses without the separation of the carrier fluid 4, It can be done.

The heat treatment means 11 may be subjected to a heat treatment with respect to the polymer bead intermediate product 5 in which polymerization is not sufficient, in a temperature range similar to the reaction temperature standarded at the reaction tube outlet 20.

Generally, the higher the heat treatment temperature, the more burdens of heating, but it is advantageous in terms of completing the additional polymerization reaction and the formation of the physical structure. However, if the heat treatment temperature is too high, Or sudden vaporization of organic residue components inside the bead, that is, flashing, can destroy the structure of the polymer beads. These problems can be solved by increasing the pressure.

However, if the heat treatment is carried out at a temperature higher than about 200 ° C, the pressure necessary for preventing the flashing phenomenon becomes too large, and the risk of pyrolysis or oxidation reaction of the polymer bead also increases.

On the other hand, if the heat treatment temperature is too low to lower than 50 캜, the reaction rate becomes too slow, which may cause a problem in terms of productivity. Therefore, the heat treatment in the heat treatment means 11 is carried out at 50 캜 to 200 캜 desirable.

There is no particular limitation on the type and shape of the heat treatment apparatus constituting the heat treatment means 11, as long as the polymer beads can be heated to a required temperature and uniformly heated to a required level of polymerization reaction and structure formation. Perry, D.W. Green and J.O. Maloney, Perry ' s Chemical Engineers' Handbook, 7th Ed., Pp. As described in references such as 12-39 ~ 12-41, McGraw-Hill, 1997 (ISBN 0-07-049841-5), the concept or form of a commercially available drying or heat- It can be modified and used in accordance with the purpose.

Further, as a simpler apparatus, a pressure vessel in the form of a packed bed, a fluidized bed, a mobile phase or a stirrer may be used.

The time required for the heat treatment means according to the present invention can be greatly changed depending on conditions such as the polymerization state of the polymer bead intermediate product 5 and the heat treatment temperature, and it is also often the case that a heat treatment means of several tens of hours or more is required.

In this regard, analysis of characteristics such as polymerization degree, crosslinking degree, or physical structure of polymer beads varying with time under the heat treatment condition can optimize the operating conditions such as time required for heat treatment, temperature and pressure.

In order to perform the heat treatment more efficiently or economically, the heat treatment means may be constituted by a plurality of apparatuses having different operating conditions, or the operating conditions may be differentiated or gradually changed over time.

The heat treatment of the polymer bead intermediate product (5) according to the present invention can be carried out in various ways such as continuous, semicontinuous and batchwise. For example, the polymer bead intermediate product (5) continuously discharged from the tubular reactor (1) The polymeric bead product 6 can be passed through the drying means 12 while the heat treatment apparatus can be operated in the tubular reactor 1, It is also possible to conduct continuous heat treatment by directly connecting with

Further, in the case of a heat treatment apparatus in which continuous operation is not possible, a plurality of apparatuses may be combined in parallel to be continuously connected to the tubular reactor 1 for operation.

The heating means for supplying the required amount of heat Q2 in the heat treatment means 11 included as part of the post treatment system of the polymer bead intermediate product 5 may be determined depending on the structure and characteristics of the heat treatment apparatus, Known heating devices such as direct or indirect heaters using media, electric resistance heating, microwave heating, infrared heating or high frequency heating can be utilized.

From the polymer bead products 6, 6 'produced directly from the tubular reactor 1 or through the further heat treatment means 11, the residues 24 of the carrier fluid 4, unreacted reactants 3a, 3b and Drying means 12 may be included as part of the post-treatment system to produce the polymeric bead product 7 through separation and removal of components such as residues 25 of the solvent 3d, reaction byproducts, and the like.

In the drying means 12, it is known that the higher the temperature, the lower the pressure is, the more advantageous in terms of the drying speed, i.e., the time required. In addition, the compositions, properties, and contents of the remnants to be removed admit.

At this time, if the drying temperature by the drying means (12) is too high to exceed about 350 ° C, it is advantageous in terms of time, but the structure of the polymer bead is destroyed or the risk of oxidation reaction or decomposition reaction is followed.

On the other hand, freeze-drying at low temperatures below 0 ° C may also have advantages in terms of quality of polymer bead products.

However, if the drying temperature is lower than -40 ° C., the energy consumption for freeze-drying becomes too high and the drying time becomes too long. Therefore, in the present invention, the drying temperature is in the range of -40 ° C. to 350 ° C. It is preferable to select it within the range.

The drying temperature may be set to be constant or varied with the drying time, and it is preferable to optimize the drying temperature according to the characteristics of the polymer beads to be produced.

In this case, it is necessary to select the pressure condition in consideration of the mechanical characteristics of the apparatus and the physical properties of the residue components, and it is convenient to carry out the drying in an air atmosphere. If the drying temperature is high, the polymer bead itself, It is necessary to carry out the reaction in an inert gas atmosphere such as nitrogen, argon, helium or the like.

This drying condition can be easily selected or optimized by referring to the thermal analysis results of the polymer bead products (6, 6 ') using a thermogravitational analyzer (TGA) or a differential scanning calorimeter (DSC) .

The drying means 12 of the polymeric bead products 6, 6 'may also be used as is, for example, as described in the aforementioned cited Perry et al. So that it can be utilized.

The operating method of the drying means 12 can also be configured to operate continuously, semicontinuously or batchwise in consideration of the production amount, the investment cost, and the economical efficiency, and there is no technical limitation in this selection.

The heating means for supplying the required amount of heat Q3 in the drying means 12 may be determined depending on the structure and characteristics of the drying apparatus and may be a direct or indirect heating device using a vapor or liquid heating medium, Well known heating means such as heaters, infrared or high frequency heating may be utilized.

In the heat treatment means 11 of the polymer bead intermediate product 5 according to the present invention, the residue 24 of the carrier fluid 4, the unreacted reactants 3a and 3b and the residue 25 of the solvent 3d, Some of the components such as byproducts can be separated and removed naturally.

Therefore, it is also possible to directly produce the dried polymer bead product 7 through the separation and removal of the residue components in the heat treatment means 11.

On the other hand, in the drying means 12 according to the present invention, the additional polymerization reaction to be carried out in the heat treatment means 11 can be advanced. As a result, although not shown in FIG. 1, sufficient polymerization reaction is performed in the tubular reactor 1 Processing system composed of one device capable of exhibiting the functions of the heat treatment means 11 and the drying means 12 in combination can be configured for the polymer bead intermediate product 5 which has not been produced.

The composite post-treatment system is used to heat the polymer bead intermediate product 5 and simultaneously remove the residues 24 of the carrier fluid 4, the unreacted reactants 3a and 3b and the residues 25 of the solvent 3d, Byproducts and the like can be separated and removed to produce a dried polymeric bead product (7).

As described above, the polymer beads 5 in the intermediate product state discharged from the reaction tube outlet 20 of the tubular reactor 1 according to the present invention are heated by the heat treatment means 11 and / / RTI &gt; and / or a drying means (12) within the range of -40 DEG C to 350 DEG C, to become the polymer beads (7) in the product state.

The polymer beads 7 in this product state can be utilized as such, but in order to be utilized for the required purpose, the post-treatment system may be provided with coating, impregnation, molding, surface treatment, chemical modification or physical processing Processing means (13) capable of performing a post-processing.

In the post-treatment system, when the post-processing means 13 adds a process, the polymer bead 7 as well as the polymer bead product 8 can be manufactured according to the present invention.

1 shows a case where the post-treatment means 13 is carried out via the drying means 12, the process to be added in accordance with the characteristics of the polymer bead application product 8 is (i) the heat treatment means 11 ), Or (ii) between the heat treatment means 11 and the drying means 12, or (iii) in combination with the heat treatment means 11 and / or the drying means 12.

Thus, the polymeric bead product (7) produced according to the present invention, either by itself or after further post-treatment, is (i) an adsorbent for separating and purifying liquid or gaseous mixtures, impurities or wastes, (Vi) drug or drug delivery system, (iii) carrier and catalyst for chemical reaction, (iv) decolorant, deodorant or cosmetic base material, (v) additive for controlling physical properties, (vi) insulation material or soundproofing material, viii) Applicable products such as light-emitting functional materials and hybrid functional materials, and raw materials of these.

The separating means for separating the carrier fluid 4 from the mixture of the polymer bead intermediate product 5 and the carrier fluid 4 discharged from the reaction tube outlet 20 according to the present invention is directly connected to the reaction tube outlet 20 Can be connected and installed.

Separating means for separating the carrier fluid 4 from the mixture of the polymer bead intermediate product 5 and the carrier fluid 4 discharged from the reaction tube outlet 20 may be replaced with a heat treatment means 11, the drying means 12, or the additional post-processing means 13.

The carrier fluid 4 as well as the monovinyl monomer (3a), the crosslinking monomer (4) as well as the crosslinking monomer (4) in the heat treatment means (11), the drying means (12) The residual components 24 and 25 of the solvent 3b or the solvent 3d are also separated.

According to the present invention, the carrier fluid 4 and the remnant components 24, 25, which can be recovered separately from the reaction tube outlet 20 or in the aftertreatment system, can be recycled to the tubular reactor 1.

Therefore, the remnant component recycling means which allows the monovinyl monomer, the crosslinking monomers and / or the remnant components of the solvent to be separated from the polymer beads and recycled to the tubular reactor in the aftertreatment system, Means may be included.

A carrier fluid recirculation means may be included in the aftertreatment system that allows the carrier fluid 4 discharged from the reaction tube outlet 20 to be separated from the polymer bead intermediate product 5 and recycled to the tubular reactor.

For example, as shown in FIG. 1, the drying means 12 is connected to the outlet side of the reactant supply portion 15 and the carrier fluid supply portion 14, respectively, using the recycle line and the carrier fluid recirculation means do.

At this time, it is preferable that the residue components are recycled separately from the residue 25 of the organic phase and the carrier fluid residue 24.

Although not illustrated in FIG. 1, the residue 25 of the organic phase is separated into monovinyl monomer (3a), crosslinking monomer (3b) or solvent (3d) components instead of being recycled to the mixture state, It can also be used continuously by recirculation to the feeding means.

The reactant 3 of the organic phase is supplied to the tubular reactor 1 in a mixed state according to the composition of the predetermined monovinyl monomer 3a, the crosslinking monomer 3b or the solvent 3d, The residue 25 of the organic phase separated and recycled in the post-treatment system is added to the reactant raw material components 3a, 3b, 3c, and 3d newly supplied without performing a separate separation process, Can be recycled to the tubular reactor (1).

According to the present invention there is provided a process for the production of polymeric beads of intermediate product 5, product 6, product 7 or application 7, The recirculation means of each of the fluid residues 24 can be easily configured as an apparatus for separation and circulation which is commonly utilized in chemical processes.

As described above, the polymer bead product 7 obtained through the drying means of the polymer bead product 6, 6 'or the complex functional post-treatment system of the polymer intermediate product 5 has the polymer bead intermediate product 5 and the shape There may be some differences in size, but they are basically the same.

Particularly, in the case of gel-type polymer beads in which the pores are not significantly developed, the size of the porous polymer bead product (7) having a highly porous structure is larger than that of the polymer bead intermediate product (5) The size thereof is inevitably reduced, and this property greatly depends on the composition of the reactant 3, particularly the content of the solvent 3d.

Nevertheless, the polymeric bead product (7) or the polymeric bead product (8) produced according to the present invention is excellent in the uniformity of the quality so that no apparent difference in the shape and size of the bead can be found.

In terms of the application of the polymer bead product (7), the porous polymer bead has a larger surface area and lower apparent specific gravity than the gel-type polymer bead having a very low porosity.

When the content of the solvent (3d) added to the reactant (3) increases in the production of the polymer beads, the porosity of the polymer bead product (7) generally increases and the apparent density becomes lower.

The physical properties of the crosslinked polymeric bead product 7 which can be produced according to the present invention are not limited because the physical properties of the crosslinked polymeric bead product 7 depend on the composition of the reactant 3 and inorganic additives or fillers having a high density are additionally added to the reactant 3 The apparent density based on the dried state of the crosslinked polymer bead product (7) obtained in the case where the crosslinked polymer bead product (7) is not added is usually 1.0 g / cc or less.

The apparent density of the gel or microcapsular crosslinked polymeric bead product (7) which can be prepared according to the present invention by not adding a solvent to the reactant (3) or adding a small amount to the monomer mixture is in the range of 0.5 to 1.0 g / cc .

The gel beads or microporous polymer beads which can be prepared according to the present invention usually have a porosity in the range of 0.0 to 0.2 cc / cc and a surface area in the range of about 0.1 to 60 m &lt; 2 &gt; / g.

In the case of the crosslinked porous polymer bead product 7 which can be produced according to the present invention, the apparent density can be included in the range of 0.1 to 0.5 g / cc based on the dried state. Particularly, when the porous polymer bead is used as the adsorbent Polymeric beads having porosity and surface area in the range of 0.3 to 0.6 cc / cc and 80 to 1,400 m &lt; 2 &gt; / g, respectively, are used according to the present invention Can be manufactured.

According to the present invention, it is possible to prepare the polymer bead product (7) having an apparent density of less than 0.1 g / cc. However, the pores are too large and the porosity is too high,

On the other hand, according to the present invention, there is no problem in producing a polymer bead product (7) having an apparent density exceeding 0.5 g / cc, and its physical strength is excellent, but its use as a porous polymer bead is somewhat limited.

The uniformity of the polymer beads produced according to the present invention is determined by measuring the diameter in the diametrical direction of the reaction tube and the length in the reaction tube flow direction for each of the samples arbitrarily extracted from among the polymer bead products (7) , And can be displayed more quantitatively by measuring weight values.

Thus, based on the measured values, the uniformity of the polymeric bead product can be expressed as a ratio (range / average) of the range of the measured value (mean value) to the mean value of the measured value And the ratio of the average, that is, the coefficient of variation.

Based on these parameters, the uniformity of the polymer bead product (5), the polymer bead product (6) or the polymer bead product (7), which can be produced by the process according to the present invention, The quantitative conditions can be established based on the state of the polymer bead product (7).

(I) the diameter of the reaction tube in the radial direction, (ii) the length of the reaction tube flow direction, ( iii) The ratio of (A) (maximum value - minimum value) to the average value and (B) standard deviation and average value based on the weight are included in the ranges shown in the following Table 1.

As shown in Table 1 above, the polymer beads included in the range of the parameters exhibit uniform characteristics such that the difference in appearance and size is not easily revealed, and the crosslinked polymer beads The crosslinked polymeric bead product 7, which can be prepared by the process according to the invention, is superior in terms of quality uniformity, as opposed to products exhibiting an extensive size distribution and irregular shape.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

Example  One

A tubular reactor was constructed by installing a coil-shaped stainless steel tube [4.23 mm (ID) × 30 M (L)] coil reaction tube whose inner wall surface was polished in a thermostatic bath at 90 ° C.

A monomer for crosslinking, a styrene monomer as a solvent, divinylbenzene (the remaining component is ethyl styrene), an isoamyl alcohol (isopropyl acrylate), and the like are added to a reactant supply tank in a stirring tank form, alcohol and benzoyl peroxide were added in amounts of 40 wt%, 25 wt% and 35 wt%, respectively, and 0.7 wt% of benzoyl peroxide was added as a catalyst (3c) Were used.

The reactant and the carrier fluid were fed phase-separated using a peristatic pump connected to the feed lines of the reactant and the carrier fluid so that the reactant and the carrier fluid were separated at a crossing period of 50 times / minute to the inlet of the reaction tube.

At this time, the feed rates of the reactant and the carrier fluid were maintained at about 60 and 80 cc / hr respectively, and the polymer beads having a diameter of about 1.4 mm were discharged together with the carrier fluid at the exit of the reaction tube.

Polymer beads and mixtures discharged from the tubular reactor outlet were collected in a beaker and then further heat treated in a constant temperature chamber controlled at 90 DEG C for about 16 hours.

Next, the heat-treated reaction product was subjected to centrifugal separation to remove the liquid residue, and the polymer beads were sufficiently dried in a hot-air dryer at about 100 ° C.

Thus, the finally obtained dried polymer beads were white spherical particles having a porosity of about 1.3 mm in diameter and exhibited apparently uniform shapes.

Also, the average surface area and pore size measured using a Microeritics Model ASAP-2400 from Micromeritics Instrument Corp. were measured to be 87.6 m 2 / g and 214 Å (Angstrom), respectively.

In order to more quantitatively indicate the degree of uniformity of polymer beads produced according to the present invention, the diameter of the reaction tube in the diameter direction, the length of the reaction tube flow direction, The weights were measured and the uniformity of the polymer bead product was expressed as the ratio of the range (maximum value - minimum value) and the mean value of the measured value (range / average) based on the measured values Or the ratio of the standard deviation to the average, that is, the coefficient of variation. The uniformity of the polymer bead according to the first embodiment is quantitatively shown in Table 2 below.

As shown in Table 2 above, according to Example 1 of the present invention, it can be seen that excellent polymer beads can be produced with excellent uniformity.

Example  2

A glass tube with a diameter of 4 mm (ID) × 6.35 mm (OD) × 4 m (L) was fixed inside a stainless steel tube with a dimension of 17 mm (ID) × 19 mm (OD) × 3.85 m (L) Were assembled first, and a tubular reactor was constructed by connecting four assembled tubular reactor units in series with a U-shaped 4 mm (ID) glass tube.

In this case, the inner glass tube of the double tube becomes the reaction tube and the total length of the reaction tube becomes 19 m. In the concentric space of the double tube, the heating medium flows countercurrently with the reactant flow in the reaction tube.

On the other hand, a capillary of 1.8 mm (ID) was installed along the center line of the reaction tube at the inlet of the reaction tube, and a carrier fluid was supplied to the inlet of the reaction tube, and reactant was supplied through the capillary tube, And a flow in which the reactants are repeatedly segmented.

At this time, monovinyl monomer, crosslinking monomer, styrene as solvent, 55% active divinylbenzene (the remaining component is ethyl styrene), 2-ethyl 30 wt% and 55 wt% of a 3: 1 mixture of 2-ethylhexanol and toluene were added to the mixture, and benzoyl peroxide was added to 1.3 wt% of the monomer mixture as the catalyst (3c) And 1.5% NaOH aqueous solution was used as the carrier fluid.

Also, the reactants and the carrier fluid were supplied at a constant flow rate so as to be separated at a crossing cycle of 60 times / minute at the inlet of the reaction tube, and the feed rates of the reactants and the carrier fluid were maintained at about 118 and 235 cc / hr, respectively.

Then, the reaction tube was heated so that 90 占 폚 water as a heating medium was caused to flow from the outlet of the tubular reactor to the inlet.

Therefore, a spherical polymer bead having a diameter of about 4 mm was discharged together with the carrier fluid at the outlet of the reaction tube.

Then, the polymer beads discharged from the outlet of the tubular reactor were separated from the carrier fluid, and further heat-treated in a constant-temperature chamber controlled at 95 ° C for about 14 hours. Thereafter, the heat-treated polymer beads were dried in a hot- As a result of thorough drying, porous polymer beads having an apparently uniform shape and size, a surface area of 542 m &lt; 2 &gt; / g and an apparent specific gravity of about 0.19 g / cc were obtained.

The uniformity of the polymer beads obtained for the 120 samples randomly selected from among the polymer beads after the drying process is quantitatively shown in Table 2 below.

As shown in Table 3, it can be seen that the polymer beads having excellent uniformity can be produced by the second embodiment of the present invention.

Example  3

In the same manner as in Example 2, the reactant and the carrier fluid were supplied at a constant flow rate so as to be divided at a crossing cycle of 26 times / minute at the inlet of the reaction tube. As a result, the reaction tube outlet had a diameter of about 4 mm and a length of about 12 mm pellet type polymer beads were discharged together with the carrier fluid.

The uniformity of the polymer beads obtained for 120 samples arbitrarily extracted from the polymer beads after the heat treatment and drying process as in Example 2 is quantitatively shown in Table 4 below.

As shown in Table 4, it can be seen that pellet-type polymer beads having excellent uniformity can be produced even by Embodiment 3 according to the present invention.

Example  4

The effect according to the present invention can be obtained even when the composition of the reactant and the carrier fluid is different in the same manner as in Example 2.

That is, in the reactant supply tank, a 1: 1 mixture of monovinyl monomer and crosslinking monomer, styrene and methyl methacrylate, and 55% active divinylbenzene (the remaining components are ethyl styrene ethyl styrene) were added to 76 and 24 wt%, respectively. In addition, a polyvinyl pyrrolidone fine powder in an amount corresponding to 0.8 wt% of the monomer mixture was added to the monomer mixture, and the catalyst 3c ) Was added azodiiosbutyronitrile to 1.0 wt% of the monomer mixture.

The carrier fluid was prepared by mixing 0.4% ammonium nitrate aqueous solution and isopropylalcohol at a volume ratio of 5: 1 and adding 0.8 wt% of polyvinyl alcohol.

In addition, the reactant and the carrier fluid were supplied at a constant flow rate so as to be segmented at a crossing cycle of 60 times / minute at the inlet of the reaction tube. As a result, it was found that a porous polymer bead having an apparently uniform shape and size was obtained.

Similarly, the uniformity of the polymer beads obtained for 120 samples randomly extracted from the dried polymer beads is quantitatively shown in Table 5 below.

As shown in Table 5, it can be seen that the polymer beads having excellent uniformity can be produced even by the fourth embodiment of the present invention.

Example  5

A glass tube having a size of 44 mm (ID) x 49 mm (OD) x 4 m (L) was fixed inside a stainless steel tube having a size of 86 mm (ID) x 90 mm (OD) x 3.85 m The tubular reactor unit as described in Example 2 was first assembled, and the remainder, tubular reactor, was constructed in the same manner as in Example 2 to prepare polymer beads.

At this time, the feed rates of the reactants and the carrier fluid were maintained at about 14 and 28 liter / hr, respectively.

Subsequently, a large-sized porous polymer bead having a diameter of about 38 mm, a surface area of 397 m &lt; 2 &gt; / g, and an apparent density of about 0.2 g / cc was prepared through the same heat treatment and drying process as in Example 2.

The uniformity of the polymer beads obtained for 120 samples randomly selected among the dried polymer beads is quantitatively shown in Table 6 below.

As shown in the above Table 6, it can be seen that large-sized polymer beads having excellent uniformity can be produced even by Embodiment 5 according to the present invention.

Example  6

The effect according to the present invention can be obtained even when the composition of the reactant and the carrier fluid is different in the same manner as in Example 2.

That is, 85% and 15% by weight of a monovinyl monomer as a reactant, styrene as a crosslinking monomer, and 55% active divinylbenzene (the other component is ethyl styrene) And azodiiosbutyronitrile as a catalyst (3c) was added in an amount of 1.0 wt% of the monomer mixture, followed by mixing.

The carrier fluid was prepared by mixing 1.0% NH ₄ OH aqueous solution and isopropylalcohol in a volume ratio of 5: 1 and adding 1 wt% of hydroxylpropylcellulose.

The reactant and the carrier fluid were supplied at a constant flow rate so as to be separated at a crossing cycle of 60 times / minute at the inlet of the reaction tube. As a result, it was found that gel polymer beads having apparently uniform shape and size were obtained.

Likewise, the uniformity of the obtained polymer beads was quantitatively expressed in 120 samples randomly selected from the dried polymer beads, as shown in Table 7 below.

As shown in Table 7, it can be seen that the gel-type polymer beads having excellent uniformity can be produced even by Example 6 according to the present invention.

Example  7

In the same manner as in Example 6, the reactant and the carrier fluid were supplied at a constant flow rate so as to be divided at a crossing cycle of 26 times / minute at the inlet of the reaction tube. As a result, the reaction tube outlet had a diameter of about 4 mm and a length of about 12 mm &lt; / RTI &gt; was discharged together with the carrier fluid.

The uniformity of the polymer beads obtained for 120 samples arbitrarily extracted from the polymer beads after the heat treatment and drying process as in Example 2 is quantitatively shown in Table 8 below.

As shown in Table 8, according to Example 7 of the present invention, it can be seen that gel-type polymer beads having a very good uniformity can be produced in a rod shape.

Example  8

The effect according to the present invention can be obtained even when the composition of the reactant and the carrier fluid is different in the same manner as in Example 2.

That is, 55% active divinylbenzene in which 55% of divinylbenzene and 45% of ethyl styrene were mixed was used as a mixture of a monovinyl monomer and a crosslinking monomer as a reactant, As a solvent, a 5: 2: 1 mixture of 2-ethylhexanol, nitrobenzene and diethylene chloride was used in an amount of 320 wt% of the monomer mixture, and the catalyst 3c ) Was prepared by adding benzoyl peroxide to 1.8 wt% of the monomer mixture.

A 1.5% NaOH aqueous solution was used as the carrier fluid,

As a result, it was found that a porous polymer bead having an apparently uniform shape and size was obtained.

The surface area of the polymer beads after drying was measured to be 864 m 2 / g. Similarly, the uniformity of the polymer beads obtained for 120 samples randomly extracted from the dried polymer beads was quantitatively shown in Table 9 below. Same as.

As shown in Table 9, according to Example 8 of the present invention, it can be seen that a large-sized polymer bead having an excellent uniformity can be manufactured.

Example  9

The effect according to the present invention can be obtained even when the composition of the reactant and the carrier fluid is different in the same manner as in Example 2.

That is, as a reactant, a mixture of a monovinyl monomer mixture mixed at a weight ratio of 1: 1 of styrene and acrylonitrile and a monomer mixture of divinyl sulfone and trivinyl cyclohexane 2: 1 mixture was mixed with 89 wt% and 11 wt%, respectively. The catalyst (3c) was prepared by adding SnCl ₄ to 80 wt% of the monomer mixture.

0.1 wt% aqueous solution of carboxymethyl methylcellulose was used as the carrier fluid.

The uniformity of the polymer beads obtained for 120 samples arbitrarily extracted from the polymer beads after the heat treatment and drying process as in Example 2 is quantitatively shown in Table 10 below.

As shown in Table 10, according to Example 9 of the present invention, it can be seen that gel-type polymer beads having a very good uniformity can be produced in a rod shape.

Example  10

40 linear glass tubes of 4 mm (ID) x 6.35 mm (OD) x 15 m (L) were placed in a stainless steel shell-and-tube type heat exchanger with five tube baffles exchanger) was constructed as a tubular reactor.

Here, the glass tube becomes the reaction tube, and the heating medium flows countercurrently with the reactant flow inside the reaction tube in the shell side space outside the reaction tube.

On the other hand, one 1.8 mm (ID) capillary tube was installed along the reaction tube center line at the entrance of each reaction tube.

In addition, the outlet of the reactor was connected to the inlet of the heat treatment chamber maintained at a substantially constant temperature, and the outlet of the heat treatment chamber was connected to the inlet of the hot-air dryer in the form of a mobile phase to enable the production of continuous polymer beads.

A carrier fluid at a constant flow rate is supplied to the inlet of each reaction tube and at the same time a constant flow rate of reactant is supplied to each of the capillaries to form a flow in which the carrier fluid and the reactant are repeatedly segmented in the flow direction in the reaction tube.

The composition of the reactant and the carrier fluid and the fluid supply conditions for each reaction tube were set as in Example 2 so that the reactant and the carrier fluid were separated at a crossing cycle of 60 times / minute at the inlet of the reaction tube.

Then, as a heating medium, the reaction tube was heated by making 90 ° C water flow from the outlet-side shell to the inlet-side shell in the countercurrent direction with the reactant flow.

Further, the polymer bead preliminary product discharged from the outlet of the reaction tube was directly supplied to a heat treatment chamber controlled at about 95 캜 and heat-treated for a residence time of about 16 hours on average.

The heat-treated polymer beads were roughly separated from the carrier fluid, and then dried continuously in a dryer in which hot air of about 180 ° C was supplied. As a result, a porous polymer bead having a uniform shape and size was obtained I could.

Similarly, the uniformity of the polymer beads obtained for 240 samples randomly selected among the dried polymer beads is quantitatively shown in Table 11 below.

As shown in Table 11, according to the tenth embodiment of the present invention, polymer beads having excellent uniformity can be continuously produced.

INDUSTRIAL APPLICABILITY As described above, the continuous production method of crosslinked polymer beads according to the present invention provides the following effects.

1) The present invention provides a method for continuously producing crosslinked polymer beads using a tubular reactor, wherein the tubular reactor comprises a post-treatment system such as an additional heat treatment process, a separation process of carrier fluid and unreacted residue, Semi-continuous or continuous, so that it can be effectively utilized in the production of polymer bead products.

2) The carrier fluid component and the unreacted remnant component separated through the post-treatment system of the present invention can be recovered and reused as the carrier fluid and the reactant, respectively. Therefore, when the polymer bead is produced according to the present invention, Emissions can be minimized.

3) The gel or porous cross-linked polymeric bead intermediate or product produced by the process of the present invention, either by itself or after further processing, can be used to (i) separate and purify a liquid or gaseous mixture, impurity or waste, (Iv) a base material for decolorizing, deodorizing or cosmetics; (v) an additive for controlling physical properties; (vi) a heat insulating material (Vii) Bio-functional materials, (viii) Applied products such as light-emitting functional materials and hybrid functional materials, and raw materials thereof.

4) Physical and / or chemical processes such as additional coating, impregnation, molding, surface treatment, chemical modification or physical processing of the intermediate product or product of the polymer bead are often required to satisfy the specifications of the above-mentioned application product This process may be included in the post-treatment system of the polymeric bead intermediate product of the present invention or may be directly connected to the post-treatment system of the present invention. Therefore, the process of producing the polymeric bead according to the present invention may be used directly or in combination .

5) According to the production method of the present invention, since the shape of the polymer bead having a large average diameter in the range of 1 mm to 50 mm is sufficiently prepared in the polymerization process inside the reaction tube, the polymer produced by the present invention The bead can be effectively used in various applications as a form of its own, and therefore, the present invention is not limited to the problems of bead size limitation, bead shape non-uniformity, wide particle size distribution, etc., To solve the problem.

6) Conventional powdered polymer bead products are basically difficult to be used in a large-scale production process, whereas large polymer beads having a size of 1 mm to 50 mm, which can be produced according to the present invention, The scope of industrial application can be greatly expanded.

7) According to the manufacturing method of the present invention, since the crosslinked polymer bead having excellent properties in terms of physical properties is based on a segmented flow due to phase separation of a reactant and a carrier fluid, the crosslinked polymer bead can be formed into a desired shape such as spherical, elliptical, In addition, unlike conventional powdered products, the present invention makes it possible to produce polymer beads that are easy to store, transport, and handle and which are highly industrially utilized.

8) According to the production method of the present invention, it is possible to provide a method and means for continuously producing crosslinked polymer beads irrespective of a structural form such as gel or porosity. Further, The physical properties such as the degree of crosslinking, porosity, density, and specific surface area of the polymer beads can be easily satisfied through the reactant composition.

9) In addition, since the production amount can be increased in proportion to increasing the number of reaction tubes based on the advantages of the tubular reactor, the production method of the present invention can be provided to economically mass-produce the polymer beads.

Claims (30)

A reaction fluid including a monovinyl monomer, a crosslinking monomer, and a catalyst is injected into an inlet of a reaction tube constituting the tubular reactor, and a carrier fluid, which is phase-separated from the reactant, is repeatedly flowed in a flow direction in the reaction tube, Wherein the polymer beads and the carrier fluid are sequentially discharged through the outlet of the reaction tube after the reaction product is converted into the polymer beads by the polymerization reaction during the residence time through the reaction tube, Method for continuous production of crosslinked polymeric beads. The polymeric bead according to claim 1, wherein the polymer bead has a spherical shape, an elliptical shape, or a rod shape, and the average value of the major axis diameter and the minor axis diameter of the polymer bead is in the range of 1 mm to 50 mm. Method for continuous production of beads. [2] The method according to claim 1, wherein the monovinyl monomer is at least one selected from the group consisting of an aliphatic or aromatic vinyl compound and a (meth) acrylic compound. The continuous process for producing crosslinked polymer beads according to claim 1, wherein the crosslinking monomer is a polyfunctional vinyl compound having two or more unsaturated groups. The continuous process for producing a crosslinked polymer bead according to claim 1, wherein the catalyst is at least one selected from a peroxide compound, an azo compound, a thiol compound, an alkylated silver compound and a Friedel-Craft type compound . [3] The continuous crosslinked polymer bead according to claim 1, wherein a solvent is added to the reactant in an amount in the range of 20 to 400 wt% of the total weight of the monomers constituting the monovinyl monomer and the crosslinking monomer Way. The continuous process for producing crosslinked polymer beads according to claim 6, wherein the solvent is at least one selected from the group consisting of aliphatic or aromatic hydrocarbons, alcohols, halogenated hydrocarbons, ethers, esters and ketones . The continuous process for producing crosslinked polymer beads according to claim 1, wherein the carrier fluid is water or an aqueous solution. [Claim 9] The method according to claim 8, wherein the aqueous solution is one in which one or more selected from oxides, hydroxides and salts of alkali metals or alkaline earth metals, and alcohol, cellulose compound and silica are dissolved in water at a saturation concentration or lower Method for continuous production of polymeric beads. [Claim 2] The crosslinked polymer bead according to claim 1, wherein the average interval between the reaction unit segment center points formed within the reaction tube is within a range of 1.1 to 5.0 times the flow direction length of the reaction unit segment Continuous manufacturing method. The continuous process for producing crosslinked polymer beads according to claim 1, wherein the reactant is heated so that the polymerization reaction proceeds under the condition that the temperature at the outlet of the reaction tube is maintained within a range of 50 ° C to 150 ° C. The continuous process for producing crosslinked polymer beads according to claim 1, wherein at least one of the reactant and the carrier fluid is degassed before being fed to the inlet of the reaction tube. The method according to claim 1, wherein the reactant and the carrier fluid are supplied phase-separated at the inlet of the reaction tube. [14] The method of claim 13, further comprising the steps of separately connecting a reactant supply pipe and a carrier fluid supply pipe in the form of a Y-type, a T-shaped or a double pipe-type at the inlet of the reaction tube and separately supplying the reactant and the carrier fluid And then supplied in a phase-separated manner at the inlet of the reaction tube. The crosslinked polymeric bead according to claim 14, characterized in that crossing means is additionally provided in at least one of the reactant supply pipe and the carrier fluid supply pipe, and the reactant and the carrier fluid are supplied in phase separation at the inlet of the reaction tube Continuous manufacturing method. [14] The method of claim 13, wherein crossing means is connected to the inlet of the reaction tube, and a reactant supply pipe and a carrier fluid supply pipe are connected to the crossing means, respectively, so that the reactant and the carrier fluid are phase- &Lt; / RTI &gt; wherein the polymeric beads are in the form of tablets. The method according to claim 1, wherein an additive selected from functional fine powder and inorganic filler having a size of a colorant, a stabilizer, a micrometer or a nanometer is added to the reactant. [2] The method according to claim 1, wherein the polymerization reaction in the reaction tube is performed until the polymer beads discharged from the reaction tube outlet are not agglomerated. [4] The method of claim 1, further comprising separating the carrier fluid from the mixture of the polymer beads and the carrier fluid discharged from the outlet of the reaction tube. The continuous process for producing crosslinked polymer beads according to claim 19, wherein the carrier fluid separated from the polymer beads is recycled to the tubular reactor for reuse. The method of claim 19, further comprising: heat treating the polymer beads from which the carrier fluid has been separated in a post-treatment system at a temperature in the range of 50 ° C to 200 ° C; Wherein the crosslinked polymeric bead is further subjected to a further process. The continuous process of cross-linked polymeric beads according to claim 21, characterized in that the carrier fluid, monovinyl monomer, crosslinking monomer and / or residual solvent components separated from the polymer beads in the post-treatment system are recycled to the tubular reactor for re- Gt; [21] The method according to claim 21, wherein in the dried state, the polymeric bead is a porous polymeric bead having an apparent density within a range of 0.1 to 0.5 g / cc. [21] The method according to claim 21, wherein the polymer beads are gel-type polymer beads having an apparent density of 0.5 to 1.0 g / cc in the dried state. The continuous process of crosslinked polymer beads according to claim 21, wherein the polymeric beads are further coated, impregnated, molded, surface treated, chemically modified or physically processed after the drying process in the post-treatment system Way. The method of claim 1, further comprising: heat treating a mixture of the polymer beads and the carrier fluid discharged from the reaction tube outlet in a post-treatment system within a range of 50 ° C to 200 ° C; Characterized in that at least one further step is carried out during the drying step in the step of drying the polymeric beads. The continuous process of crosslinked polymeric beads according to claim 26, characterized in that the carrier fluid, monovinyl monomer, crosslinking monomer and / or residual solvent components separated from the polymer beads in the aftertreatment system are recycled to the tubular reactor for reuse Gt; [26] The method of claim 26, wherein in the dried state, the polymeric bead is a porous polymeric bead having an apparent density within a range of 0.1 to 0.5 g / cc. [Claim 26] The method according to claim 26, wherein in the dried state, the polymer beads are gel-type polymer beads having an apparent density within a range of 0.5 to 1.0 g / cc. The method of claim 26, wherein the post-treatment system further comprises the step of coating, impregnating, molding, surface-treating, chemical modification, or physical processing of the polymeric beads after the drying process Gt;

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