JP2017203134A - Method for producing porous polymer particles - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide porous polymer particles having a large pore diameter and a method for producing the same.SOLUTION: The method for producing the porous polymer particles includes: a step A of dissolving water in a monomer mixture containing a polymerizable monomer, an alcohol having a solubility in water of 0.01 g/L or less, and a polymerization initiator; a step B of forming an emulsion which contains a dispersed phase containing the monomer mixture and a continuous phase containing water; and a step C of thermally polymerizing the monomer in the emulsion to produce the porous polymer particles.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing porous polymer particles.

  The resin particles used for liquid crystal panel spacers, chromatographic fillers, diagnostic reagent carriers and the like are required to have a uniform particle size (monodispersity). In recent years, uniformity of particle diameter has also been demanded for resin particles for light diffusing materials. Many techniques have been reported for producing such monodisperse resin particles.

  For example, by combining reactive monomers into an aqueous medium using an ultrafine flow path, minute droplets are generated one by one, and the droplets are polymerized by heating or using active energy rays, thereby forming minute resin particles. A method of manufacturing is known (see, for example, Patent Document 1).

  Emulsions containing monomer droplets are prepared by discharging monomers into an aqueous medium through a porous film such as an SPG film, and the particle diameters are compared by polymerizing the droplets by heating or using active energy rays. A method for producing aligned resin particles is known (see, for example, Patent Document 2).

  After obtaining the emulsion containing droplets of the reactive monomer by discharging the reactive monomer into the aqueous medium through the substrate having a large number of microchannels, the polyvinyl alcohol solution is added to the emulsion while stirring. There is also known a method for producing monodisperse resin particles by polymerizing droplets by heating (see, for example, Patent Document 3).

  There is known a seed polymerization method in which seed particles are prepared by soap-free emulsion polymerization or dispersion polymerization, and the emulsified polymerizable monomer is absorbed into the seed particles to perform polymerization (see, for example, Patent Document 4). .

JP 2004-122107 A JP 2004-352882 A Japanese Patent Laid-Open No. 2001-181309 JP 2005-272779 A

  However, it is difficult to synthesize particles having a large pore size by the method described in the above patent document.

  An object of this invention is to provide the manufacturing method of the porous polymer particle which has a big pore diameter.

The present invention provides a method for producing porous polymer particles as described in [1] to [7] below.
[1] Step A in which water is dissolved in a monomer mixture containing a polymerizable monomer, an alcohol having a solubility in water of 0.01 g / L or less, and a polymerization initiator, and a dispersed phase containing the monomer mixture Of porous polymer particles, comprising: step B of forming an emulsion containing water and a continuous phase containing water; and step C of producing porous polymer particles by heat polymerization of the monomer in the emulsion. Method.
[2] The production method according to [1], wherein the monomer mixture further contains an alcohol having a solubility in water of 0.1 to 30 g / L.
[3] The production method according to [1] or [2], wherein the polymerizable monomer contains divinylbenzene.
[4] In any one of [1] to [3], the monomer mixture contains 20 parts by mass or more of the alcohol having a solubility in water of 0.01 g / L or less with respect to 100 parts by mass of the monomer. The manufacturing method as described.
[5] The production method according to any one of [1] to [4], wherein the alcohol having a water solubility of 0.01 g / L or less contains dodecanol.
[6] The production method according to any one of [1] to [5], wherein in step B, an emulsion is formed so that the coefficient of variation of the particle diameter of the obtained porous polymer particles is 10% or less.
[7] The production method according to any one of [1] to [6], wherein the mode diameter in the pore size distribution of the porous polymer particles is 0.5 μm or more.

  According to the production method of the present invention, porous polymer particles having a large pore diameter can be obtained.

6 is a graph showing the pore size distribution of porous polymer particles of Example 5.

  Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to these embodiments. In the present specification, “(meth) acrylate” means at least one of acrylate and methacrylate corresponding thereto. The same applies to other similar expressions such as “(meth) acrylic acid”.

  The method for producing a porous polymer according to the present embodiment is a process A in which water is dissolved in a monomer mixture containing a polymerizable monomer, an alcohol having a solubility in water of 0.01 g / L or less, and a polymerization initiator. And a step B of forming an emulsion containing a dispersed phase containing the monomer mixture and a continuous phase containing water, and a step C of producing porous polymer particles by heat polymerization of the monomer in the emulsion. Including.

(Process A)
Step A is a step of dissolving water in a monomer mixture containing a polymerizable monomer, an alcohol having a solubility in water of 0.01 g / L or less, and a polymerization initiator.

  In the production method according to this embodiment, the monomer mixture contains a polymerizable monomer. The polymerizable monomer may be, for example, a monomer having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include an ethylenically unsaturated group such as a vinyl group, an allyl group, and a (meth) acryloyl group. Can be mentioned. The polymerizable monomer may be either a polyfunctional monomer or a monofunctional monomer. Examples of the polymerizable monomer include a styrene monomer and a (meth) acrylic monomer. The styrene monomer refers to a monomer having a styrene skeleton. A styrene polymer containing a styrene monomer as a monomer unit has higher acid and alkali resistance than a polymer obtained by polymerizing a monomer of a conventional (meth) acrylic acid ester derivative. Therefore, it is preferable that the polymerizable monomer contains a styrene monomer. When the monomer mixture contains a styrene monomer, acid and alkali resistance of the porous polymer particles obtained by polymerization can be improved. Therefore, when the obtained porous polymer particles are used as a column filler, excellent acid resistance and alkali resistance can be obtained.

  Examples of the styrenic polyfunctional monomer include divinyl compounds such as divinylbenzene, divinylbiphenyl, and divinylnaphthalene. Among these, divinylbenzene is preferably used from the viewpoints of durability and swellability. The content of divinylbenzene is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more, based on the total mass of the monomer. The monomer may be all divinylbenzene.

  Examples of the styrene monofunctional monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 2, 4-dimethylstyrene, pn-butylstyrene, pt-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn -Styrene and its derivatives, such as dodecyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, 3,4-dichloro styrene. Among monofunctional monomers, styrene is preferably used from the viewpoint of acid resistance and alkali resistance. One type of styrene monomer may be used alone, or two or more types may be used in combination.

  Examples of (meth) acrylic polyfunctional monomers include (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate, and the like ( Poly) alkylene glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,1, Tri- or higher functional (meth) acrylates such as 1-trishydroxymethylethane tri (meth) acrylate and 1,1,1-trishydroxymethylpropane triacrylate; ethoxylated bisphenol A di (meth) acrylate Propoxylated ethoxylated bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,1,1-trishydroxymethylethanedi (meth) acrylate, ethoxylated cyclohexanedimethanol di (meta) ) Di (meth) acrylates such as acrylate. Examples of other polymerizable polyfunctional monomers include diallyl phthalate and isomers thereof; triallyl isocyanurate and derivatives thereof. A polyfunctional monomer may be used individually by 1 type, and may be used in combination of 2 or more type. Among these monomers, NK ester (A-TMPT-6P0, A-TMPT-3E0, A-TMM-3LMN, A-GLY series, A-9300, AD-TMP, AD-TMP, manufactured by Shin-Nakamura Chemical Co., Ltd. -4CL, ATM-4E, A-DPH) and the like are commercially available.

  Examples of (meth) acrylic monofunctional monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) Examples include (meth) acrylic acid esters such as 2-chloroethyl acrylate, phenyl (meth) acrylate, and methyl α-chloro (meth) acrylate. Other polymerizable monofunctional monomers include, for example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate; N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone. N-vinyl compounds such as fluorinated monomers such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, trifluoroethyl acrylate and tetrafluoropropyl acrylate; conjugated dienes such as butadiene and isoprene It is done. A monofunctional monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the production method according to the present embodiment, an alcohol having a water solubility of 0.01 g / L or less is used as the porosifying agent. The solubility in water is expressed as a value at 25 ° C. In the conventional method for producing porous polymer particles, it is difficult to maintain the dispersion stability of the emulsion, and coalescence occurs during the recovery of the emulsion or during the polymerization, and the resulting particles tend to be polydispersed. It was. According to the manufacturing method according to the present embodiment, porous polymer particles having a large pore diameter and a smaller coefficient of variation in particle diameter can be obtained.

  As the alcohol having a solubility in water of 0.01 g / L or less, for example, an alcohol having 12 or more carbon atoms can be used. The alcohol preferably has 12 to 22 carbon atoms. The alcohol may be, for example, a saturated or unsaturated aliphatic alcohol. The hydrocarbon group possessed by the alcohol may be linear or branched. The solubility of the alcohol in water may be 0.005 g / L or less. The solubility of the alcohol in water may be 0 g / L or more, for example, or 0.1 mg / L or more. It is preferable that an alcohol having a water solubility of 0.01 g / L or less does not substantially exhibit emulsifying ability. Not showing emulsification ability means that the continuous phase is not emulsified (white turbid) when the dispersed phase containing alcohol and the continuous phase are mixed and stirred at a ratio of 8/2 and allowed to stand. As such an alcohol, generally a cosurfactant can be used.

  Specific examples of alcohols having a solubility in water of 0.01 g / L or less include dodecanol (lauryl alcohol), cetyl alcohol, cetearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hexyl decanol, octyldodecanol, Examples include stearyl alcohol. Among these, it is preferable to use dodecanol because the improvement in the viscosity of the monomer mixture can be suppressed. The said alcohol may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the alcohol in the monomer mixture is preferably 20 parts by mass or more, more preferably 30 parts by mass or more with respect to 100 parts by mass of the monomer, from the viewpoint of the stability of the emulsion droplets. More preferably, it is 50 parts by mass or more. The content of the alcohol in the monomer mixture may be, for example, 300 parts by mass or less, and preferably 200 parts by mass or less, based on the total mass of the monomer.

  A solvent that promotes phase separation at the time of polymerization and promotes the porosity of particles can be used in combination as a porosifying agent. Specific examples include aliphatic or aromatic hydrocarbons, esters, ketones, ethers, and alcohols. Specific examples include toluene, diethylbenzene, xylene, cyclohexane, octane, butyl acetate, methyl ethyl ketone, dibutyl ether, 1-hexanol, isoamyl alcohol, 2-octanol, decanol, and cyclohexanol. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, it is preferable to use an alcohol having a solubility in water of 0.1 to 30 g / L. By using an alcohol having a solubility in water of 0.1 to 30 g / L together with an alcohol having a solubility in water of 0.01 g / L or less, the amount of water that can be dissolved in the monomer mixture is increased. However, the pore diameter tends to be larger. The solubility of the alcohol used in combination in water is more preferably 0.1 to 25 g / L, further preferably 0.1 to 15 g / L, and more preferably 0.1 to 10 g / L. Further preferred. The content of the porous agent other than alcohol having a solubility in water of 0.01 g / L or less in the monomer mixture may be, for example, 10 to 300 parts by mass with respect to 100 parts by mass of the monomer. It is preferably 10 to 200 parts by mass, and more preferably 10 to 150 parts by mass.

  The porosity (pore volume) of the particles can be controlled by the blending amount of the porous agent. Further, the size and shape of the pores can be controlled by the kind of the porosifying agent.

  Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, tert-butylperoxy-2-ethylhexano Organic peroxides such as ate and di-tert-butyl peroxide; 2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexanecarbonitrile, 2,2′-azobis (2,4- And azo compounds such as dimethylvaleronitrile). The polymerization initiator may be used in the range of 0.1 to 7.0 parts by mass with respect to 100 parts by mass of the monomer.

  In step A, it is preferable that the polymerization initiator is uniformly dissolved in advance in the monomer mixture containing the monomer and the porous agent before adding water to the monomer mixture. When water is dissolved in the monomer mixture, it is preferable to add water to the monomer mixture and dissolve the water uniformly. By adding water to the monomer mixture and stirring, the water can be uniformly dissolved in the monomer mixture. Since the amount of water that can be dissolved varies depending on the type of porosifying agent used, it is desirable to add excess water. When the monomer mixture has high hydrophobicity, it takes time to dissolve water. Therefore, after adding water to the monomer mixture, it is preferable to stir for 1 hour or more.

(Process B)
In Step B, an emulsion containing a dispersed phase and a continuous phase is formed. The dispersed phase contains the monomer mixture obtained in step A, and the continuous phase contains water. An emulsifier or the like can be used for forming the emulsion.

  In the manufacturing method according to the present embodiment, an aqueous medium is used as the continuous phase. Examples of the aqueous medium include water or a mixed medium of water and an aqueous solvent (for example, a lower alcohol). The aqueous medium preferably contains at least one of a dispersion stabilizer and a surfactant.

  The dispersion stabilizer is, for example, a polymer compound. Examples of the dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, etc.), polyvinyl pyrrolidone, inorganic water-soluble polymer compounds (sodium tripolyphosphate, etc.), and the like. Of these, polyvinyl alcohol or polyvinyl pyrrolidone is preferred. A dispersion stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type. It is preferable that the addition amount of a dispersion stabilizer is 0.01-5 mass% with respect to the total mass of a continuous phase. It can suppress more that a monomer drop unites in a flow path after emulsification as the addition amount of a dispersion stabilizer is 0.01 mass% or more. When the amount of the dispersion stabilizer added is 5% by mass or less, the particles can be easily collected.

  As the surfactant, any of anionic, cationic, nonionic and zwitterionic surfactants can be used. The surfactant is preferably capable of adsorbing tricalcium phosphate (TCP).

  Examples of the anionic surfactant include fatty acid oils such as sodium oleate and castor oil potassium, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylnaphthalene sulfone. Acid salts, alkane sulfonates, dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate, alkenyl succinates (dipotassium salts), alkyl phosphate esters, naphthalene sulfonate formalin condensates, polyoxyethylene alkylphenyl ether sulfates Examples thereof include salts, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate, and polyoxyethylene alkyl sulfate salts. Among these, it is preferable to use sodium dodecylbenzenesulfonate because of its high adsorbability of TCP.

  Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.

  Nonionic surfactants include, for example, hydrocarbon nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines, or amides. Agents, polyether-modified silicon-based nonionic surfactants such as polyethylene oxide adducts of silicon and polypropylene oxide adducts, and fluorine-based nonionic surfactants such as perfluoroalkyl glycols.

  Examples of zwitterionic surfactants include hydrocarbon surfactants such as lauryl dimethylamine oxide, phosphate ester surfactants, and phosphite ester surfactants.

  Surfactant may be used individually by 1 type and may be used in combination of 2 or more type. Among the above surfactants, anionic surfactants are preferable from the viewpoint of excellent dispersion stability during monomer polymerization.

  The concentration of the surfactant is preferably 0.01 to 0.5% by mass with respect to the total mass of the continuous phase. When the concentration of the surfactant is 0.01% by mass or more, the dispersion stability can be further improved and the occurrence of particle aggregation can be suppressed. When the concentration of the surfactant is 0.5% by mass or less, concurrent occurrence of emulsion polymerization in a solvent can be suppressed.

  In order to suppress the generation of particles that are emulsion-polymerized in water alone, water-soluble polymerization inhibitors such as nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin Bs, citric acid, and polyphenols are used. It may be used.

  Since the monomer mixture may be altered by heat, emulsion production at high temperatures is not preferred. The emulsion production temperature in step B is preferably 10 to 40 ° C, more preferably 20 to 40 ° C.

  The formation of the emulsion is preferably carried out so that the resulting emulsion particles are monodispersed. The coefficient of variation of the particle size of the emulsified particles may be, for example, 10% or less. As an apparatus used for emulsification to obtain monodisperse emulsified particles, a general monodisperse emulsifier can be used. As the monodisperse emulsifier, for example, a micro process server (manufactured by Hitachi, Ltd.), a micro flow path (manufactured by YMC Co., Ltd.), a micro channel emulsifier (manufactured by EP Tech Co., Ltd.), or the like can be used. The emulsion is formed so that the porous polymer particles obtained by subsequent polymerization become monodisperse, specifically, for example, the coefficient of variation of the particle diameter of the obtained porous polymer particles is 10% or less. Preferably.

  As a method for supplying the monomer mixture (dispersed phase) and the aqueous medium (continuous phase) to the emulsifier, known methods can be used. For example, the method of supplying with a pump, the method of supplying with water pressure using gravity, etc. are mentioned. Examples of the pump include a syringe pump, a Mono pump, a plunger pump, a diaphragm pump, a rotary pump, a tube pump, and a gear pump. As a method for supplying water with gravity using gravity, for example, by adjusting the height difference between the microsphere manufacturing apparatus and the tank for supplying each of the monomer mixture and the aqueous medium, the difference in water pressure between the monomer mixture and the aqueous medium is determined. The method of adjusting each flow volume balance is mentioned.

  When a pulsating flow is generated in each flow of the dispersed phase and the continuous phase, the monodispersity of the obtained particles is affected. Therefore, it is preferable to take a method in which the pulsating flow is suppressed as much as possible.

  Tricalcium phosphate (TCP) may be added to the emulsion. TCP can be added as an aqueous solution, for example. By using TCP, the dispersion stability of the obtained porous polymer particles is improved, so that the coefficient of variation of the particle diameter can be further reduced.

(Process C)
In Step C, porous polymer particles are produced by heat polymerization of the monomer in the obtained emulsion. The polymerization temperature can be appropriately selected according to the type of monomer and polymerization initiator. The polymerization temperature is preferably 25 to 110 ° C, and more preferably 50 to 100 ° C.

  The ratio of the pore volume to the total volume (including the pore volume) of the porous polymer particles is preferably 30% or more and 70% or less. More preferably, the ratio of the pore volume is 50% or more and 70% or less. The porous polymer particles are preferably those having most pores having a pore diameter of 0.5 μm or more, that is, having macropores. The porous polymer particles preferably have a mode diameter in the pore size distribution of 0.5 μm or more, and more preferably 0.5 μm or more and less than 3 μm. If the mode diameter in the pore size distribution is 0.5 μm or more, the number of substances that can enter the pores is increased, and if it is less than 3 μm, the specific surface area of the porous polymer particles can be increased, which is preferable. . The ratio of the pore volume and the mode diameter in the pore size distribution can be adjusted by the above-described porous agent.

  The average particle diameter of the porous polymer particles obtained by the production method according to this embodiment is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 150 μm or less. The average particle diameter of the porous polymer particles is preferably 10 μm or more, more preferably 30 μm or more, and further preferably 50 μm or more. As the average particle size increases, productivity improves. The average particle diameter is a volume average particle diameter.

  By the production method according to this embodiment, porous polymer particles that are monodispersed can be obtained. In this specification, the monodispersion means that the dispersion width of the particle size distribution is narrow, for example, the variation coefficient of the particle size is 10% or less. The variation coefficient of the particle diameter of the porous polymer particles may be, for example, 1 to 10%, or 3 to 9%.

The porous polymer particles preferably have a specific surface area of 10 m ² / g or more. From the viewpoint of higher practicality, the specific surface area is more preferably 15 m ² / g or more, and further preferably 20 m ² / g or more. When the specific surface area is 20 m ² / g or more, the adsorption amount of the substance to be separated tends to increase.

  The mode diameter and specific surface area in the pore size distribution of the porous polymer particles are values measured with a mercury intrusion measuring apparatus (Autopore: Shimadzu Corporation), and are measured as follows. As a sample, 0.05 g is taken as it is in a standard 5 mL powder cell (stem volume 0.4 mL), and measured under conditions of an initial pressure of 21 kPa (about 3 psia, corresponding to a pore diameter of about 60 μm). Mercury parameters are set to a device default mercury contact angle of 130 degrees and a mercury surface tension of 485 dynes / cm. Further, each value is calculated by limiting to a pore diameter range of 0.05 to 5 μm.

The average particle diameter and the coefficient of variation (CV) of the porous polymer particles can be determined by the following measurement method.
1) Disperse the particles in water (including a dispersant such as a surfactant) using an ultrasonic dispersion device to prepare a dispersion liquid containing 1% by mass of porous polymer particles.
2) Using a particle size distribution meter (Sysmex Flow, manufactured by Sysmex Corporation), the average particle size and the coefficient of variation of the particle size are measured from an image of 10,000 particles in the dispersion.

  The porous polymer particles obtained by the production method according to the present embodiment are useful as a filler for chromatography, vaccine purification, cell culture particles and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

Example 1
(Process A)
A monomer mixture was prepared by mixing 12 g of divinylbenzene (DVB) with a purity of 96% as a monomer, 19.2 g of 1-dodecanol as a porosifying agent, and 0.64 g of benzoyl peroxide as a polymerization initiator. Thereafter, 5 g of water was added to the monomer mixture, and the mixture was stirred with a stirrer (1 hour), and water was saturated and dissolved in the monomer mixture. An emulsified mixed solution containing a monomer mixed solution containing dissolved water and water that could not be completely dissolved was obtained.

(Process B)
An aqueous solution containing 0.05% by mass of polyvinyl alcohol as a dispersion stabilizer and 0.03% by mass of sodium dodecylbenzenesulfonate (SDS) was prepared. Using a microprocess server, the aqueous solution and the emulsified mixed solution were monodispersed and emulsified to obtain an emulsion containing a continuous phase containing the aqueous solution and a dispersed phase containing the monomer mixed solution.

(Process C)
100 g of an emulsion was collected in 100 g of a 1% aqueous TCP solution (manufactured by Taihei Chemical Sangyo Co., Ltd.), and TCP was adsorbed to monomer droplets in the emulsion. After the emulsion after adsorption was transferred to a 500 mL separable flask, the temperature was raised to 80 ° C. and polymerization was carried out for 7 hours. The resulting particle dispersion was adjusted to pH 2 using hydrochloric acid. After dissolving TCP which is a dispersing agent, it filtered. Furthermore, porous polymer particles were obtained by immersing the particles in 300 mL of acetone, stirring for 30 minutes, and then filtering three times to perform washing. The particle size of the obtained particles was measured with a flow type particle size measuring device (FPIA-3000, manufactured by Sysmex Corporation), and the average particle size (volume basis) and C.D. V. Values were calculated (Table 1).

  The average particle size of the porous polymer particles obtained in Example 1 is 107 μm. V. Was 7.8%.

(Example 2)
Porous polymer particles were synthesized and evaluated in the same manner as in Example 1 except that 12 g of 1-dodecanol and 12 g of isoamyl alcohol were used as the porosifying agent.

(Example 3)
Porous polymer particles were synthesized and evaluated in the same manner as in Example 1 except that 12 g of 1-dodecanol and 12 g of 1-hexanol were used as the porosifying agent.

Example 4
Porous polymer particles were synthesized and evaluated in the same manner as in Example 1 except that 12 g of 1-dodecanol and 12 g of 1-octanol were used as the porosifying agent.

(Example 5)
Porous polymer particles were synthesized and evaluated in the same manner as in Example 1 except that 7.2 g of 1-dodecanol and 16.8 g of 1-octanol were used as the porosifying agent. The pore size distribution of the porous polymer particles obtained in Example 5 is shown in FIG.

(Example 6)
Porous polymer particles were synthesized and evaluated in the same manner as in Example 1 except that 3.6 g of 1-dodecanol and 20.4 g of 1-octanol were used as the porosifying agent.

(Comparative Example 1)
Porous polymer particles were synthesized and evaluated in the same manner as in Example 1 except that 24 g of isoamyl alcohol was used without using 1-dodecanol as the porosifying agent.

(Comparative Example 2)
Porous polymer particles were synthesized and evaluated in the same manner as in Example 1 except that 24 g of 1-hexanol was used instead of 1-dodecanol as a porosifying agent.

(Comparative Example 3)
Porous polymer particles were synthesized and evaluated in the same manner as in Example 1 except that 24 g of 1-octanol was used instead of 1-dodecanol as a porosifying agent.

(Comparative Example 4)
Porous polymer particles were synthesized and evaluated in the same manner as in Example 4 except that the step of dissolving water in the monomer mixture was not performed.

As shown in the table, porous polymer particles having a monodispersed and large pore diameter could be synthesized in the examples.

Claims (7)

A step A of dissolving water in a monomer mixture containing a polymerizable monomer, an alcohol having a solubility in water of 0.01 g / L or less, and a polymerization initiator;
Forming an emulsion containing a dispersed phase containing the monomer mixture and a continuous phase containing water; and
And C for producing porous polymer particles by heat polymerization of the monomer in the emulsion.   The manufacturing method of Claim 1 with which the said monomer liquid mixture further contains the alcohol whose solubility in water is 0.1-30 g / L.   The production method according to claim 1, wherein the polymerizable monomer contains divinylbenzene.   The said monomer liquid mixture contains the said alcohol whose solubility to water is 0.01 g / L or less 20 mass parts or more with respect to 100 mass parts of monomers, The manufacture as described in any one of Claims 1-3. Method.   The manufacturing method as described in any one of Claims 1-4 with which the said alcohol whose solubility to water is 0.01 g / L or less contains dodecanol.   The manufacturing method as described in any one of Claims 1-5 which forms an emulsion so that the variation coefficient of the particle size of the obtained porous polymer particle may be 10% or less in the process B. The manufacturing method as described in any one of Claims 1-6 whose mode diameter in the pore diameter distribution of the said porous polymer particle is 0.5 micrometer or more.

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