JP5503133B2 - Organic porous body and method for producing the same - Google Patents

Description

  The present invention is a porous body having a three-dimensional network structure skeleton and voids made of an organic polymer prepared by reversible transfer catalytic polymerization, and a method for producing the same, and in particular, a chromatographic separation medium, a blood separation porous body Body, sample concentration medium for environmental analysis, porous body for moisture absorption, porous body for low molecular weight adsorption such as deodorizing, porous membrane used for membrane emulsification method for producing fine particles of uniform diameter, or porous body for enzyme carrier and catalyst carrier In particular, the present invention relates to a porous body suitable for the above and a manufacturing method thereof.

  A porous body having a continuous skeleton having three-dimensional network structure and voids is generally called a monolithic column, and is mainly used as a separation medium called a column in the chromatography field. Such separation media are roughly classified into silica gel and the like formed from inorganic materials, and organic polymers formed from organic materials.

  Silica gel separation media are mainly used as high-performance separation media because they are characterized by little swelling of the material by the solvent and little influence of diffusion due to mass transfer, but on the other hand, pH of acids, alkalis, etc. Due to poor durability and non-specific adsorption of biological samples, organic polymer separation media superior to these have been used favorably for the separation of environment and biological samples. Various researches and developments on organic polymers have been made, and it has also been proposed to use them as separation media for chromatography.

  Conventionally, radical polymerization has been well known as a method for obtaining vinyl polymers by polymerizing monomers having vinyl-based functional groups. However, radical polymerization is generally difficult to control the molecular weight of the resulting polymer. There was a drawback of being. In addition, the obtained polymer becomes a mixture of compounds having various molecular weights, and it is difficult to obtain a polymer having a narrow molecular weight distribution. Specifically, even if the reaction was controlled, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) could only be reduced to about 2-3. .

  For example, a monolithic organic polymer prepared by a general radical polymerization method described in Patent Document 1 is disclosed, but basically a skeleton is formed based on the probabilistic aggregation and joining of fine particles. It tends to be a fine particle aggregation type structure formed by the nucleation-growth process. Therefore, there is a problem in mechanical properties such as strength as a porous body. In free radical polymerization, the porosity and average pore diameter of the porous body obtained by changing the amount of the diluent in the polymerization system, as well as the skeleton diameter of the resulting porous body can be changed. Since a skeleton is formed based on the probabilistic aggregation and bonding of fine particles, it is difficult to control each of them independently. For this reason, it is difficult to design and manufacture a porous body corresponding to various uses required as a separation medium or uses other than the separation medium.

  Patent Documents 2 and 3 disclose a porous body having voids communicating with a three-dimensional network skeleton of an epoxy resin, and an application example as a chromatographic separation medium is also disclosed. Is an epoxy resin and has relatively high hydrophilicity, so it has low retention on hydrophobic samples, and it can be used to prepare porous materials with low molecular weight compounds containing vinyl functional groups that occupy a large range of raw materials for polymer materials. Is not supported.

  Patent Document 4 discloses a porogen solution in which a monomer having a weight average molecular weight of at least 100,000 and a molecular weight distribution Mw / Mn of 1.5 or less is dissolved in a good solvent for the monomer in the presence of a polymerization initiator. A method for preparing a porous body having a three-dimensional network structure to be polymerized is disclosed. However, in the conventional preparation process by free radical polymerization, in addition to controlling the molecular weight, it is difficult to control the polymerization rate, so that it is difficult to independently control the skeleton diameter and the pore diameter.

  Further, in Patent Document 5, the living radical polymerization method is used for the preparation of a monolithic polymer, whereby the molecular weight can be controlled, and at the same time, by adding an organic polymer that is a phase separation organic component, The preparation of a porous body having a continuous skeleton and voids of an original network structure is disclosed. However, in these methods, it is necessary to introduce a special protecting group used as a stable radical into the polymer growth chain, and this protecting group has a drawback that it is very expensive. Moreover, there exists a fault that high temperature (for example, 110 degreeC or more) is required for a polymerization reaction. Furthermore, there is a drawback that the polymer produced tends to have undesirable performance. That is, there is a drawback that the polymer to be produced tends to be colored in a color different from the original color of the polymer, and the polymer to be produced tends to have an odor.

  As other catalysts currently used in the living radical polymerization method, transition metal complex catalysts are known. For example, a ligand is added to a compound having a central metal such as Cu, Ni, Re, Rh, and Ru. Coordinated complexes are used. However, when such a transition metal complex catalyst is used, a large amount of the transition metal complex catalyst is required as a use amount, and it is not easy to completely remove a large amount of the catalyst used after the reaction from the product. was there. In addition, there is a drawback that environmental problems may occur when the catalyst that is no longer needed is discarded. In addition, many transition metals are highly toxic, and the toxicity of the catalyst remaining in the product may be an environmental problem, making it difficult to use transition metals in food packaging materials, biological / medical materials, etc. there were. In some cases, the toxicity of the catalyst removed from the product after the reaction becomes an environmental problem. Furthermore, when the conductive transition metal remains in the polymer, the polymer is imparted with conductivity, which makes it difficult to use it for electronic materials such as resist and organic EL. Moreover, since it does not melt | dissolve in a reaction liquid unless it forms a complex, it must use the compound used as a ligand. For this reason, cost becomes high and the total weight of the catalyst used increases further. There was a problem that. Furthermore, the ligand is usually expensive or has a problem of requiring complicated synthesis.

Further, Patent Document 6 discloses a central element selected from germanium, tin, or antimony as a catalyst for a living radical polymerization method that solves these problems, and at least one halogen atom bonded to the central element. By using a catalyst containing a catalyst, it has advantages such as low toxicity, low usability, high solubility, mild reaction conditions, no coloration, and odorlessness of the catalyst. However, there is no example of application as a monolithic porous material using these catalysts or optimization as a separation / analysis medium for chromatography.
JP 07-501140 A (Patent No. 3168006) International Publication WO2006 / 073173A1 International Publication WO2007 / 083348A1 International Publication WO2006 / 126387A1 International Publication WO2007 / 043485A1 Japanese Patent Laid-Open No. 2007-92014

  In the prior art porous material, the catalyst and protecting group used in living radical polymerization are very expensive, the high temperature is required for the polymerization reaction, and the catalyst used after the reaction can be easily removed In connection with this, the presence of a catalyst, etc. at the end of the polymer to be produced causes performance different from the original properties and causes problems due to toxicity. As a separation medium, there is a problem that it is difficult to use.

  In addition, a porous separation medium (for example, a chromatography column) prepared by conventional living radical polymerization requires a high temperature (for example, polymerization at 95 ° C. for 90 minutes and then at 125 ° C. for 48 hours). Therefore, it is considered that there is a large temperature difference between the inside and the outside of the template for polymerizing the porous body, and it is difficult to produce a separation medium with high column performance. Even when this was prepared in a capillary tube, fine distortion of the porous structure due to temperature rise became a problem.

  The monolith type porous body of the present invention has been made in view of the above points, and makes it easier to prepare a porous body having a continuous skeleton and voids of a three-dimensional network structure than before, and a polymer produced To provide a porous body that can exhibit the original performance of a monolithic porous body by easily removing a terminal catalyst, and that can be suitably used in the fields of environment, food, living body, and medical system, and a method for producing the same. It is intended.

Method for producing a porous body according to claim 1 of the present invention, the porous characterized by having a backbone with a gap of three-dimensional network structure at least one is made from the polymerization of organic low molecular compound is a polyfunctional compound In the method for producing a body, the reversible transfer catalyst having a living radical polymerization property, a polymerization initiator, and a polymerization solvent are used, and the reversible transfer catalyst having a living radical polymerization property contains phosphorus, nitrogen, oxygen And at least one central element selected from carbon atoms and at least one halogen atom bonded to the central element.

The method for producing a porous body according to claim 2 of the present invention has a three-dimensional network structure skeleton formed by polymerization of an organic low-molecular compound, at least one of which is a polyfunctional compound, and voids. In the method for producing a body, the reversible transfer catalyst having a living radical polymerization property, a polymerization initiator and a polymerization solvent are used in a system, and the reversible transfer catalyst having the living radical polymerization property is generated from the radical initiator. It is characterized by comprising a catalyst precursor compound having carbon or oxygen as a central element capable of reacting with a radical to generate an activated radical.

The method for producing a porous body according to claim 3 of the present invention is characterized in that, in claim 1 or 2 , an organic polymer is included as a phase separation inducer.

In the method for producing a porous body according to claim 4 of the present invention, in any one of claims 1 to 3 , the halogen bonded to the central element of the reversible transfer catalyst for living radical polymerization is iodine. It is a feature.

The method for producing a porous body according to claim 5 of the present invention has a carbon-halogen bond as a protective group used simultaneously with the reversible transfer catalyst having living radical polymerizability in any one of claims 1 to 4. An organic halide is used.

The method for producing a porous body according to claim 6 of the present invention is characterized in that, in claim 5 , the halogen of the organic halide used as the protective group is iodine.

Method for producing a porous body according to claim 7 of the present invention, in any one of claims 1 to 6, by mixing an azo-type radical initiator and a halogen molecule in a reaction solution, azo in the reaction solution The method includes a step of decomposing a system radical initiator to produce an organic halide.

The method for producing a porous body according to claim 8 of the present invention is characterized in that, in any one of claims 1 to 7 , a polymerization temperature for performing living radical polymerization is 20 to 100 ° C. .

The method for producing a porous body according to claim 9 of the present invention is the method for producing a porous body according to any one of claims 1 to 8 , wherein the porous body is prepared and then the reversible transfer catalyst or organic halide having living radical polymerizability is used. The iodine used as the halogen is removed from the porous body by sublimation, decomposition or extraction.

  According to the present invention, there is provided a porous body having a three-dimensional network structure skeleton and voids prepared by a reversible transfer catalytic polymerization system using a catalyst for living radical polymerization.

  First, in the conventional method for producing a porous body by living radical polymerization, an organic polymer is contained in the polymerization solution as a phase separation inducing agent. However, by selecting a polymerization solvent, a monolithic material can be obtained without containing the organic polymer. The present invention provides a porous body in which a mold porous body can be prepared and an organic polymer does not come out during a cleaning operation or use.

  In addition, reversible transfer catalysts used for living radical polymerization have various advantages such as high activity, low toxicity, and high solubility after the reaction. Therefore, it is necessary to add a ligand to form a complex. Nor. Therefore, since this catalyst has high activity, it does not require a high temperature for the polymerization reaction as in the prior art, and the amount of catalyst used can be reduced. Further, unlike the prior art, an expensive special protecting group is not required to protect the polymer growing chain during the reaction. Furthermore, the present invention provides a porous body having an advantage that it can be removed from being colored or smelled at the time of molding.

  In addition, a porous body prepared by including an organic polymer in the system as a phase separation inducer can adjust a skeleton size, a void size, or a ratio of a skeleton size / a void size in a wide range. A porous body having a void size is provided.

  Furthermore, by having pores (mesopores) with a small pore diameter in the skeleton forming the three-dimensional network structure, the surface area can be expanded, and a separation medium with high separation performance and adsorption performance can be formed. It can be done. As a high-performance separation medium, it is necessary to have a mesopore for retaining a solute separated by interaction, and therefore, a superior separation medium is provided.

  According to the production method of the present invention, an easy production method of a porous body having a three-dimensional network structure skeleton and voids prepared by a reversible transfer catalytic polymerization system using a catalyst for living radical polymerization is provided.

  First of all, it is mentioned that polymerization at low temperature due to the advantages of the above catalyst, inexpensive catalyst, high safety, high versatility of monomer, and sublimation and decomposition of terminal halogen by using iodine as halogen. Alternatively, the present invention provides a method for producing a porous body that makes it easy to extract a new function by removing by extraction or converting to another functional group. In this regard, an organic halide as a protective group used simultaneously with the catalyst provides the same advantage.

  Further, in the prior art, polymerization at a high temperature was required, but by the production method of the present invention, polymerization at 100 ° C. or less is possible, there is little distortion of the structure, and halogen used for the catalyst or the like is removed. Thus, a high performance column as a separation analysis medium (for example, a chromatography column) is provided.

  Hereinafter, terms particularly used in the present specification will be described.

  In this specification, the “monolithic porous body” refers to a porous body having a three-dimensional network structure skeleton composed of a skeleton phase and a solvent phase and voids. The monolith means an integral type, and the monolith type porous body means a monolithic porous body having a skeleton and voids having a three-dimensional network structure. In the chromatography field, monolith uses the above meaning as a common name. In the present invention, a monolithic porous body made of an organic polymer compound is described.

  In the present specification, the “macropore” means a void portion of the monolith type porous body, and constitutes a three-dimensional network structure. Macropores refer to the flow path portion of a column in the chromatography field. In the present invention, the application to the column is described in the specification as the use of the porous body, and is used in the description portion of the column.

  In the present specification, “mesopore” means small pores formed in the skeleton of the monolith type porous body. Since the mesopore is not a constituent part of the three-dimensional network structure of the monolith porous body, the mesopore has a pore diameter smaller than the void size. In the chromatography field, mesopores generally indicate micropores in particles that are used by being packed in a column, and the mesopores in the skeleton of the present invention are also called mesopores because they function similarly.

  In this specification, “reversible chain transfer catalyzed polymerization (RTCP)” means that a growth radical generated from an initiator extracts a halogen (for example, iodine) of a catalyst (chain transfer agent), and a central element. After the radical is generated in situ (with the dormant species), the central element radical acts as an active agent for the dormant species, and a catalyst in which the growth radical and iodine are combined is produced. This process is a reversible chain transfer to the catalyst, and dormant species are catalytically activated by this reversible chain transfer. Polymerization by this activation mechanism is called reversible transfer catalytic polymerization.

  In this specification, “halogen” refers to a monovalent group of an element such as fluorine (F), chlorine (Cl), bromine (Br), iodine (I) belonging to Group 7B of the periodic table. Preferred is bromine or iodine, and more preferred is iodine.

  In this specification, “living radical polymerization” means a polymerization reaction in which chain transfer reaction and termination reaction do not substantially occur in radical polymerization reaction, and the chain growth terminal retains activity even after the monomer has reacted. Say. In this polymerization reaction, the polymerization activity is maintained at the end of the produced polymer even after the completion of the polymerization reaction, and when the monomer is added, the polymerization reaction can be started again. Living radical polymerization is characterized by the ability to synthesize polymers having an arbitrary average molecular weight by adjusting the concentration ratio of monomer and polymerization initiator, and the molecular weight distribution of the resulting polymer is extremely narrow. It can be applied to polymers. The living radical polymerization may be abbreviated as “LRP”.

  In the present specification, the “central element” means an atom which is mainly responsible for catalysis by being bonded to a halogen atom among atoms constituting the catalyst compound. Although it has the same meaning as the term “center metal” used in the prior art, germanium used in the present invention is generally a semiconductor and is often not classified as a metal, and nitrogen, phosphorus, oxygen and carbon are generally Since it is not classified as a metal, in order to avoid misunderstanding, the term “central element” is used instead of the term “central metal” in the prior art.

  In this specification, “capillary” indicates a quartz tube having an inner diameter of 1 mmφ or less. Capillaries are widely used in organic synthesis, biological fields, analytical fields, mass spectrometer spray parts, etc., but the monolithic porous body of the present invention is prepared in a capillary tube and used as an analytical column. It is called. By using a capillary for a chromatography column, the solvent (mobile phase) used for the analysis can be reduced to about 1/1000 amount, and thus it is attracting attention as a next-generation separation and analysis column.

  Hereinafter, the present invention will be described in detail.

(Monolith porous body)
A monolithic porous body having a three-dimensional network skeleton composed of a skeletal phase and a solvent phase and voids (hereinafter simply referred to as a “monolithic porous body”) is formed by an organic polymer that is a phase separation-inducing component used in some cases. Phase separation into a concentrated phase rich in the polymer of the low-molecular compound and relatively rich in the polymer, and a dilute phase rich in the polymerization solvent and a relatively low concentration (typically spinodal Decomposition-type phase separation) is induced and formed. The skeletal phase and the solvent phase each have a continuous three-dimensional network structure and are intertwined with each other.

  At this time, it is important that the polymer of the low molecular weight compound (monomer) is formed by living radical polymerization. For example, in free radical polymerization which is a conventional method for producing an organic porous material, a nucleation-growth process After the formation of a plurality of polymer particles in the polymerization system, the porous body structure is formed while these particles are probably aggregated and precipitated, so that a gel having a co-continuous structure cannot be formed.

  The voids composed of a skeleton and a solvent phase (hereinafter referred to as “macropores”) obtained by polymerization of the monomer of the monolith type porous material according to the present invention correspond to the structures of the skeleton phase and the solvent phase of the gel. Each has a continuous three-dimensional network structure and is intertwined with each other.

  The monolithic porous body of the present invention has a more uniform skeleton structure than a conventional porous body formed by stochastic aggregation and joining of a plurality of polymer particles prepared by a conventional free radical polymerization technique. It is excellent in mechanical properties such as strength, and a new living radical polymerization that does not use a conventional transition metal complex catalyst, nitroxyl catalyst or dithioester catalyst as the catalyst added to the preparation solution before polymerization. Since it is a catalyst, the polymerization temperature is limited in the preparation process described above, and the properties of the obtained polymer are high, and it can be prepared without appearance, odor, restriction of the washing process, catalyst toxicity and environmental problems. Monolithic porous bodies have excellent material properties.

  In living radical polymerization using the catalyst described in this specification, the molecular weight and molecular weight distribution of the resulting polymer can be controlled by controlling the polymerization system, for example, forming a polymer having a narrow molecular weight distribution. it can. Thereby, the temporal control of the polymerization system becomes possible, and the timing of phase separation with respect to the degree of polymerization of the polymer can be controlled.

  “Controlling the polymerization system” means, for example, changing the polymerization temperature or polymerization time, using low molecular weight compounds, organic polymers used as needed, polymerization initiators, catalysts and polymerization solvents, and their ratios It means changing things.

  For this reason, since the monolith type porous body of the present invention can independently control the skeleton size and the void size, and the ratio of the skeleton size / void size, for example, a porous body having a desired skeleton size or void size can be formed. Or a porous body having a narrow size distribution of skeleton size and void size can be formed. That is, according to the method for producing a monolith type porous body of the present invention, it is possible to form a porous body in which the structure of the skeleton and voids is controlled more precisely than the conventional porous body by free radical polymerization.

(Living radical polymerization)
Living radical polymerization may be performed based on a method generally used as a polymerization method. For example, a solution is prepared by dissolving an organic polymer that is a phase separation inducing component to be used as necessary in a polymerization solvent, and the prepared solution, a low molecular weight compound, a polymerization initiator, a catalyst specified in the present specification, and Mix with protecting groups. What is necessary is just to superpose | polymerize the said low molecular weight compound on polymerization conditions for this prepared solution. In actual polymerization, select the type and amount of polymerization initiator, polymerization solvent, phase separation inducing component, catalyst and low molecular weight compound (monomer) as needed, and control the polymerization temperature, polymerization time, etc. This makes it possible to create a monolithic porous body having an arbitrary skeleton size and void size.

(monomer)
As the low molecular weight compound (monomer), a radical polymerizable monomer is used. The radical polymerizable monomer refers to a monomer having an unsaturated bond that can cause radical polymerization in the presence of an organic radical. Such an unsaturated bond may be a double bond or a triple bond. That is, in the polymerization method of the present invention, any conventionally known monomer capable of performing living radical polymerization can be used.

  For example, as methacrylate monomers, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, n-octyl Methacrylate, 2-methoxyethyl methacrylate, butoxyethyl methacrylate, methoxytetraethylene glycol methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxy-3-phenoxy Propyl methacrylate And diethylene glycol methacrylate, polyethylene glycol methacrylate, 2- (dimethylamino) ethyl methacrylate and the like. Methacrylic acid can also be used.

For example, acrylate monomers include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, benzyl acrylate, cyclohexyl acrylate, lauryl acrylate, n-octyl. Acrylate, 2-methoxyethyl acrylate, butoxyethyl acrylate, methoxytetraethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-chloro 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxy 3-phenoxy Propyl acrylate, diethylene glycol acrylate, poly Ethylene glycol acrylate, 2- (dimethylamino) ethyl acrylate, N, N- dimethyl acrylamide, N- methylolacrylamide, etc. N- methylol methacrylamide. Acrylic acid can also be used.

  Examples of styrene derivatives include o-, m-, p-methoxystyrene, o-, m-, pt-butoxystyrene, o-, m-, p-chloromethylstyrene, and vinyl monomers include alkylene. Is mentioned.

  In the present invention, a monomer having two or more vinyl groups can also be used. For example, diene compounds (such as butadiene and isoprene), compounds having two allyl compounds (such as diallyl phthalate), dimethacrylates of diol compounds such as alkylene dimethacrylate and hydroxyalkylene dimethacrylate, diacrylates of diol compounds Etc.

  Furthermore, vinyl monomers other than those described above can also be used in the present invention. For example, vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate), vinyl ketones (for example, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone), N-vinyl compounds (for example, N -Vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole), (meth) acrylic acid derivatives (for example, acrylonitrile, methacrylonitrile, acrylamide, isopropylacrylamide, methacrylamide), vinyl halides (for example, Vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropylene, vinyl fluoride), acrylic acid, methacrylic acid, and the like.

  The combination of the type of monomer described above and the type of catalyst of the present invention is not particularly limited, and a reversible transfer catalyst arbitrarily selected with respect to an arbitrarily selected monomer can be used. However, regarding the methacrylate monomer, it is preferable to use a catalyst having a substituent having an aromatic ring, more specifically, a catalyst having aryl or substituted aryl, from the viewpoint of reactivity.

  Among these, a low molecular compound having two or more unsaturated bonds in the molecule is preferable. The low molecular weight compound may be a monomer or a state in which the monomer is polymerized to some extent (an oligomer or the like and a molecular weight of about 1000 or less is preferable). Furthermore, it is possible to provide functionality by introducing a functional functional group other than the functional group used for polymerization into the low molecular compound molecule, for example, a site having hydrophobicity, hydrophilicity, or ionicity. .

  In the production method of the present invention, two or more kinds of low molecular compounds may be polymerized in the polymerization system. In this case, at least one of the two or more kinds of low molecular compounds is a multiple bond between carbons (double bond). Use of a polyfunctional compound (so-called crosslinker) having 2 or more) plays a major role in forming a three-dimensional network structure at the time of polymerization, and makes it easy to form a monolithic porous body. In the production method of the present invention, the proportion of the crosslinker in the low molecular weight compound can be increased as compared with the conventional production method of a porous body using free radical polymerization.

  As described above, since the monolith type porous body of the present invention is a skeleton substrate made of a polymer containing a large amount of crosslinkers, it can form a porous body having superior mechanical properties such as strength compared to conventional porous bodies. .

(Organic polymer that is a component that induces phase separation)
The organic polymer, which is a phase separation inducing component used as necessary, is not particularly limited as long as it is an organic polymer that can be added to the polymerization system in a uniform state, such as being dissolved in a polymerization solvent. For example, polystyrene , Vinyl polymers such as polyethylene glycol, polyethylene oxide, polydimethylsiloxane, and polymethylmethacrylate, and copolymers thereof. In addition, these may be used independently and may be used together. When the organic polymer is dissolved in the polymerization solution, it is necessary to prepare a uniform solution.

  As the organic polymer which is a phase separation inducing component, for example, solid polyethylene oxide having a weight average molecular weight of 2000 or more may be used. For example, waxy (semi-solid) polyethylene oxide having a weight average molecular weight of 600 to 2000 is used. For example, liquid polyethylene glycol having a weight average molecular weight of 600 or less may be used.

  Although the reason why phase separation that forms a co-continuous structure is induced by adding such an organic polymer to the polymerization system is not clear, the compatibility with the organic polymer increases as the polymerization of low molecular weight compounds proceeds. It is conceivable that the phase separation by spinodal decomposition is induced when the conditions such that the molecular weight distribution of the polymer of the low molecular weight compound falls within a certain range (the molecular weight distribution is narrow) are met.

  The amount of the organic polymer added to the polymerization system varies depending on the polymerization system, such as the type of the low molecular compound, but is, for example, in the range of 1 part by weight to 100 parts by weight with respect to 100 parts by weight of the low molecular compound. The range of parts to 20 parts by weight is preferred.

(Monolith type porous material without phase separation inducing component)
It is also possible to prepare a monolithic porous body without using the phase separation inducing component as described above. In the case of a monolithic porous body made by living radical polymerization using a conventional nitroxyl catalyst and polymerization in which phase separation inducing components coexist, it is necessary to remove the phase separation inducing components from the porous body by washing after the porous body is prepared If this is neglected, it may be extracted by a solvent (mobile phase), an analyte (sample) or a fraction used in the analyzer when used as a chromatography column, for example.

  The preparation method without adding a phase separation inducing component is also introduced in the following examples. However, it is necessary to appropriately select the type of solvent with respect to the monomer, and these selections are applied to the monomer attempting to prepare the monolithic porous material. It is necessary to experimentally adjust the types and amounts of the solvent, initiator and catalyst, polymerization temperature and polymerization time, and search for the optimum solvent. As the solvent, it is preferable to select a solvent that has an interaction with the functional group of the monomer and has a high viscosity. Preferably, the solvent has a viscosity of 1.5 cP or more. Examples thereof include amides such as formamide and n-methylformamide, and glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. It is necessary to add these solvents as a second solvent to the polymerization solvent described below.

  In this way, the monolithic porous body prepared in a system that does not use a liquid organic polymer or phase molecule inducing component is free from the precipitation of the organic polymer due to the solvent in the cleaning step after the preparation or in actual use. The cleaning process is remarkably easy and preparation with simple equipment is possible, leading to reduction in preparation cost.

(Polymerization solvent)
The polymerization solvent is not particularly limited as long as it is a solvent in which a low molecular compound and an organic polymer are dissolved, and a solvent generally used for living radical polymerization may be used. Examples include alkylbenzenes such as toluene, halogen-substituted benzenes such as chlorobenzene and dichlorobenzene, xylene, trimethylbenzene (mesitylene), dimethylformamide, formamide, alcohols such as methanol and ethanol, ketones such as acetone and tetrahydrofuran, benzene, and water. It is done.

  Since the amount of the solvent used is the void amount of the monolith type porous body as it is, when all the charged monomers are the skeleton of the monolith type porous body, the volume of the solvent is directly the porosity. The porosity is preferably controlled to 20 to 95%, more preferably 50 to 95%. Furthermore, when using a monolith type porous body as a column for chromatography, it is preferably 75 to 95%. If it is less than 50%, when used as a separation medium, there is an increase in pressure due to a low porosity. The higher the porosity, the higher the performance of the chromatography column can be prepared at a low pressure, but the problem arises in the gel strength. This can be solved by using a polyfunctional monomer as the monomer.

(Polymerization initiator)
The polymerization initiator is not particularly limited as long as the low molecular weight compound can be subjected to living radical polymerization, and a polymerization initiator generally used for living radical polymerization may be used. For example, an azo-based radical initiator and a peroxide-based radical initiator can be used. Specific examples of the azo radical reactive initiator include azobis (isobutyronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile). Specific examples of the peroxide-based radical initiator include, for example, benzoyl peroxide, dicumyl peroxide, t-butylperoxybenzoate, di (4-t-butylcyclohexyl) peroxydicarbonate, potassium peroxide disulfate Is mentioned. In addition, these may be used independently and may be used together.

(catalyst)
As the reversible transfer catalyst (hereinafter referred to as “catalyst”), a compound whose central element is germanium, tin, antimony, nitrogen, phosphorus, oxygen or carbon is used.

  The atom to which the central element is bonded preferably has a double bond or a triple bond between adjacent atoms (for example, carbon). That is, the atom to which the central element is bonded is a carbon having an unsaturated bond of an alkenyl group (for example, a vinyl group), an alkynyl group, or an aryl group (for example, a phenyl group) or a heteroaryl group. Is preferred. In the case of an alkenyl group or alkynyl group, a double bond or a triple bond is preferably present at the terminal, and a central element is particularly preferably bonded to the terminal carbon. In addition, it is the same also with the catalyst precursor compound mentioned later that such a structure is preferable.

  When the radical of the catalyst or catalyst precursor compound in which the central element is bonded to the double bond or triple bond carbon as described above (for example, oxygen radical or carbon radical), the resonance (for example, radical (for example, (Oxygen radicals and carbon radicals) are stabilized, and it is considered that the performance as a living radical polymerization catalyst is improved.

  The catalyst used for the production of the monolith type porous body of the present invention can be used in combination with an organic halide having a carbon-halogen bond, which is a kind of dormant species. The catalyst pulls out halogen from the organic halide during living radical polymerization to generate radicals. Therefore, in the present invention, the catalyst removes the group that suppresses the growth reaction of the compound used as the dormant species and converts it into an active species to control the growth reaction. The dormant species is not limited to organic halogen.

  The catalyst compound has at least one central element. In one preferred embodiment, it has one central element, but may have more than one central element.

(Halogen atom in the catalyst)
In the catalyst compound, at least one halogen atom is bonded to the central element. When the catalyst compound has two or more central elements, at least one halogen atom is bonded to each central element. This halogen atom is preferably chlorine, bromine or iodine. More preferably, it is iodine. Two or more halogen atoms may be present in one molecule. For example, there may be 2 atoms, 3 atoms, 4 atoms, or more. Preferably, it is 2-4. When two or more halogen atoms are present in one molecule, the plurality of halogen atoms may be the same or different.

(Group other than halogen in the catalyst)
The catalyst compound may have a group other than halogen as necessary. For example, an arbitrary organic group or inorganic group can be bonded to the central element.

  Such a group may be an organic group or an inorganic group. Examples of the organic group include aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkenyl group (eg, vinyl group), alkynyl group, alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), ester group ( An aliphatic carboxylic acid ester), an alkylcarbonyl group (such as a methylcarbonyl group), and a haloalkyl group (such as a trifluoromethyl group). In one preferred embodiment, it is an aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkenyl group (eg, vinyl group), or alkynyl group. Examples of the inorganic group include a hydroxyl group, an amino group, and a cyano group.

  A catalyst compound having aryl, heteroaryl, substituted aryl, or substituted heteroaryl as the organic group is preferable because the radical activity tends to be higher.

Examples of the substituent bonded to aryl or heteroaryl in substituted aryl or substituted heteroaryl include alkyl or alkyloxy, cyano group, amino group and the like. As alkyl, lower alkyl is preferable, and C1-C5 is more preferable.
It is alkyl, more preferably C1-C3 alkyl, and particularly preferably methyl. The alkyl in alkyloxy is preferably lower alkyl, more preferably C1 to C5 alkyl, still more preferably C1 to C3 alkyl, and particularly preferably methyl. That is, in one embodiment, the organic group bonded to the central element is phenyl, lower alkylphenyl or lower alkyloxyphenyl.

  The number of the organic group and inorganic group is not particularly limited, but is preferably 3 or less, more preferably 1.

  The number of the substituents in the substituted aryl or substituted heteroaryl is not particularly limited, but is preferably 1 to 3, more preferably 1 to 2, and further preferably 1.

  The position of the substituent in the substituted aryl or substituted heteroaryl is arbitrarily selected. When aryl is phenyl (that is, when substituted aryl is substituted phenyl), the position of the substituent may be any of ortho, meta, and para with respect to the central element. The para position is preferred.

(Catalyst compound with carbon as the central element)
As the catalyst compound having carbon as a central element, any known compound corresponding to the above definition can be used. A compound in which hydrogen or a methyl group is not bonded to the central element carbon is preferable. Preferable specific examples of the catalyst compound having carbon as a central element are, for example, compounds used in Examples described later.

The central element is further bonded with 1 to 3, preferably 2 to 3 substituents that form an electron-withdrawing substituent or a resonance structure together with the central element. That is, preferably, two to three electron-withdrawing substituents are attached, two to three substituents that form a resonance structure with the central element are bonded, or electron withdrawing. Two to three bonds are formed in combination with the substituent that forms a resonance structure together with the ionic substituent and the central element. More preferably, two to three electron-withdrawing substituents are bonded, or two to three substituents that form a resonance structure together with the central element are bonded.
Specific preferred examples of catalyst compounds having carbon as a central element, halocarbons (e.g., C ^l _4), halogenated alkyl or halogenated aryl _{^{(e.g., R 1 3 CX, R 1}} 2 CX 2 or R ^1, CX _{3 includes} , for example, diphenylmethane iodide (Ph ₂ Cl ₂ ) or a heteroaryl halide.

  In the present specification, the electron-withdrawing substituent, the substituent that forms a resonance structure together with the central element, and the electron-donating substituent are collectively referred to as a “radical stabilizing substituent”.

  By the radical stabilizing substituent bonded to the central element, the carbon radical generated by elimination of the halogen atom from the central element is stabilized. By stabilizing the carbon radical, the activity of the catalyst becomes very high, and it becomes possible to control living radical polymerization with a small amount of catalyst.

  One or two substituents other than the halogen and the radical stabilizing substituent may be bonded to the central element carbon. Examples of the substituent other than the halogen and the radical stabilizing substituent include hydrogen. The number of substituents other than halogen and radical stabilizing substituents is preferably 1 or less, and more preferably absent.

  In one embodiment, a compound in which an electron-donating substituent is not bonded to the central element can be used.

  In another embodiment, an electron donating substituent capable of stabilizing a carbon radical generated by elimination of a halogen atom from a central element can be used in the present invention. For example, a compound in which one to three, preferably two to three, electron-donating substituents capable of stabilizing a carbon radical generated by elimination of a halogen atom from the central element is bonded to the central element. It may be used as a catalyst compound.

  For each of the electron-withdrawing substituent, the substituent that forms a resonance structure with the central element, or the compound having an electron-donating substituent, there are two radical-stabilizing substituents bonded to the central element. In some cases, the two radical stabilizing substituents may be linked to each other. That is, a structure in which a ring is formed by the two radical stabilizing substituents and the central element may be used. In addition, when there are three radical stabilizing substituents, two of the three radical stabilizing substituents may be linked to each other, and the three radical stabilizing substituents may be linked to each other. May be. That is, a structure in which two radical stabilizing substituents and a central element form a ring may be used, or a structure in which three radical stabilizing substituents form a ring.

  Note that the structure in which two radical stabilizing substituents are linked to each other can be considered as one large divalent radical stabilizing substituent, but for convenience, in this specification, 2 Two radical stabilizing substituents are present and are linked. In other words, in considering the mechanism of the present invention, it is not important to consider one large divalent radical stabilizing substituent as a whole. Rather, two atoms are bonded to the carbon atom of the central element. It is important that the electronic state of the carbon atom is influenced by the two atoms.

  For example, fluorene has a structure in which two positions of biphenyl are bonded to a methylene group. In the present specification, as a structure in which two phenyl groups are bonded to a methylene group and the phenyl groups are connected to each other. Describe. In fluorene, the electronic state of the central element is affected by two phenyl groups.

  A structure in which three radical stabilizing substituents are linked to each other can be considered as one large trivalent radical stabilizing substituent as a whole. Two radical stabilizing substituents are present and are linked.

(Electron-withdrawing substituent)
The electron-withdrawing substituent is a substituent that binds to carbon of the central element and attracts electrons from the carbon of the central element. Preferred electron withdrawing substituents are halogens, specifically fluorine, chlorine, bromine or iodine. Even if it is an electron-withdrawing substituent other than halogen, a substituent that withdraws electrons from the carbon of the central element to the same extent as halogen (for example, fluorine, chlorine, bromine, or iodine) can be preferably used. Examples of such a substituent include carbonyl oxygen (═O), cyano group, nitro group, and the like.

(Electron donating substituent)
The electron donating substituent is a substituent that bonds to carbon of the central element and donates electrons to the carbon of the central element. Examples of such a substituent include an alkoxy group.

(Substituents that form a resonance structure)
A substituent that forms a resonance structure together with the central element is a substituent having a double bond or triple bond, and has a structure in which atoms constituting the double bond or triple bond are bonded to the central element. . That is, three atoms of a central element and an atom constituting a double bond or triple bond are
“C−M ¹ = M ² ” (formula IIIa) or “C−M ³ ≡M ⁴ ” (formula IIIb)
It is combined to become a structure. That is, the central element is adjacent to the double bond or triple bond.

In the above formulas IIIa and IIIb, M ¹ is an atom constituting a double bond and binding to the central element. M ² is an atom constituting a double bond. M ³ is an atom that forms a triple bond and bonds to the central element. M ⁴ is an atom constituting a triple bond. By adopting such a structure, when the central element becomes a carbon radical, the carbon radical is stabilized by the resonance effect of the carbon radical and the electron of the double bond or triple bond. Will show activity.

Specific examples of M ¹ include, for example, carbon, silicon, phosphorus, nitrogen and the like. Carbon is preferred. When M ¹ is a tetravalent atom, M ¹ further has one monovalent group. Such groups can be hydrogen, alkyl, and the like. When M ¹ is a pentavalent atom, M ¹ further has one divalent group or two monovalent groups. Such groups can be hydrogen, alkyl, and the like.

Specific examples of M ² include carbon, silicon, phosphorus, nitrogen, oxygen and the like. Carbon is preferred. When M ² is a trivalent atom, M ² further has one monovalent group. Such groups can be hydrogen, alkyl, and the like. When M ² is a tetravalent atom, M ² further has one divalent group or two monovalent groups. Such groups can be hydrogen, alkyl, and the like. When M ² is a pentavalent atom, M ² further has one trivalent group, one divalent group and one monovalent group, or three monovalent groups. Such groups can be hydrogen, alkyl, and the like.

Specific examples of M ³ include, for example, carbon, silicon, phosphorus and the like. Carbon is preferred. When M ³ is a pentavalent atom, M ³ further has one monovalent group. Such groups can be hydrogen, alkyl, and the like.

Specific examples of M ⁴ include, for example, carbon, silicon, phosphorus, nitrogen and the like. Carbon is preferred. When M ⁴ is a tetravalent atom, M ⁴ further has one monovalent group. Such groups can be hydrogen, alkyl, and the like. When M ⁴ is a pentavalent atom, M ⁴ further has one divalent group or two monovalent groups. Such groups can be hydrogen, alkyl, and the like.

In one preferred embodiment, M ¹ and M ² are both carbon. When the central element has a substituent having a double bond between two carbon atoms, that is, when M ¹ and M ² are carbon, the double bond between the carbon atoms is an aromatic double bond. A bond may be sufficient and an ethylenic double bond may be sufficient. For example, a structure in which an alkenyl group or an alkynyl group is bonded to the central element, or a structure in which aryl, heteroaryl, substituted aryl, or substituted heteroaryl is bonded to the central element is preferable. However, since the catalyst is preferably not polymerized in the radical reaction, a structure in which aryl, heteroaryl, substituted aryl or heteroaryl is bonded to the central element is very preferable. In the case of ethylenic double bonds, those having low radical polymerization reactivity are preferred.

  Preferably, the central element has two or three substituents having the above-described double bond or triple bond. That is, it preferably has a structure in which a central element is sandwiched between two or three double bonds or triple bonds.

For example, in the case of a structure in which a central element is sandwiched between two double bonds, the following structure is obtained.
“M ⁶ = M ⁵ −C−M ⁷ = M ⁸ ” (formula IIIc)
Here, M ⁵ and M ⁷ are the same atoms as M ^1, and M ⁶ and M ⁸ are the same atoms as M ² . In a compound having such a structure, the carbon atom of the central element becomes a stable carbon radical during living radical polymerization and exhibits high activity as a catalyst.

  When there are two substituents that form a resonance structure together with the central element, the two substituents and the central element preferably constitute one resonance structure as a whole. For example, it is preferable that two substituents and the central element constitute an aromatic ring structure as a whole. As a more specific example, for example, iodobenzene has a substituent composed of a hydrocarbon at the 2nd, 3rd and 4th positions and a substituent composed of a hydrocarbon at the 5th and 6th positions on the carbon atom at the 1st position. It can be considered to have a structure in which two substituents are connected between the carbon at the 4-position and the carbon at the 5-position. And the benzene ring comprised as a whole of the two substituents and the central element constitutes one resonance structure, and the radical in the central element is stabilized by the resonance structure.

  In one preferred embodiment, the catalyst compound is represented by the following general formula Ie:

(Ie)

Here, M ¹¹ is an atom bonded to the central element, preferably carbon, silicon, phosphorus or nitrogen, and more preferably carbon. M ¹² is an atom bonded to M ¹¹ , preferably carbon, silicon, phosphorus, nitrogen or oxygen, and more preferably carbon or oxygen. The bond between M ¹¹ and M ¹² is a double bond or a triple bond. R ¹⁰ and R ¹¹ are any substituents present depending on the valence of M ¹¹ , and are, for example, hydrogen, alkyl, alkoxy and the like. R ¹² and R ¹³ are any substituents present depending on the valence of M ¹² , and are, for example, hydrogen, alkyl, alkoxy and the like.

M ²¹ is an atom bonded to the central element, preferably carbon, silicon, phosphorus or nitrogen, and more preferably carbon. M ²² is an atom bonded to M ²¹ , preferably carbon, silicon, phosphorus, nitrogen or oxygen, and more preferably carbon or oxygen. The bond between M ²¹ and M ²² is a double bond or a triple bond. R ²⁰ and R ²¹ are any substituents present depending on the valence of M ²¹ , and are, for example, hydrogen, alkyl, alkoxy and the like. R ²² and R ²³ are any substituents present depending on the valence of M ²² , and are, for example, hydrogen, alkyl, alkoxy and the like. R ¹³ may be linked to R ²³ .

  In one preferred embodiment, the catalyst compound is represented by the following general formula If:

(If)

Here, M ⁴¹ is an atom bonded to the central element, preferably carbon, silicon, phosphorus or nitrogen, and more preferably carbon. M ⁴² is an atom binding to M ^41, preferably carbon, silicon, phosphorus, nitrogen or oxygen, more preferably, carbon or oxygen. R ⁴⁰ and R ⁴¹ are any substituents present depending on the valence of M ⁴¹ , and are, for example, hydrogen, alkyl, alkoxy and the like. R ⁴² and R ⁴³ are any substituents present depending on the valence of M ⁴² , and are, for example, hydrogen, alkyl, alkoxy and the like.

M ⁵¹ is an atom bonded to the central element, preferably carbon, silicon, phosphorus or nitrogen, and more preferably carbon. M ⁵² is an atom bonded to M ⁵¹ , preferably carbon, silicon, phosphorus, nitrogen or oxygen, and more preferably carbon or oxygen. R ⁵⁰ and R ⁵¹ are any substituents present depending on the valence of M ⁵¹ , and are, for example, hydrogen, alkyl, alkoxy and the like. R ⁵² and R ⁵³ are any substituents present depending on the valence of M ⁵² , and are, for example, hydrogen, alkyl, alkoxy and the like.

R ⁴³ may be linked to R ⁵³ . Furthermore, when R ⁵³ is not present, R ⁴³ may be directly linked to M ⁵² . The structural formula in this case is shown below.

(Ig)

In this case, among the atoms constituting R ⁴³ , it is preferable that an atom bonded to M ⁴² is also bonded to M ⁵² because a stable six-membered ring can be formed. In one preferred embodiment, R ⁴³ is CH or N, the bond between M ⁴² and R ⁴³ is a single bond, R ⁵³ is absent, and R ⁴³ is directly bonded to M ⁵² The bond between R ⁴³ and M ⁵² is a double bond. In this case, an extremely stable resonance structure is formed in the 6-membered ring.

Further, when both R ⁴³ and R ⁵³ are not present, M ⁴² may be directly bonded to M ⁵² . In this case, the carbon atom of the central element and M ⁴¹ , M ⁴² , M ⁵¹ and M ⁵² form a 5-membered ring.

  The substituent that forms a resonance structure together with the central element may be an electron-withdrawing substituent or an electron-donating substituent.

(Specific examples of catalyst compounds with carbon as the central element)
Further, preferred specific examples of the catalyst compound having carbon as a central element include carbon halide (for example, CI ₄ ), halogenated alkyl or aryl halide (for example, R ¹ ₃ CX, R ¹ ₂ CX ₂ , or R ¹ CX ₃ , for example, diphenylmethane iodide (Ph ₂ CI ₂ )) or halogenated heteroaryl. PE-I and CP-I described below act only as dormant species, and do not act as catalysts. PE-I and CP-I, such as those in which one or more hydrogens and one or more methyl groups are bonded to carbon to which halogen is bonded, or those in which two or more methyl groups are bonded to carbon to which halogen is bonded Does not act as a catalyst.

  Conventionally, it has been known that an organic halide is used as a dormant species described later. The dormant species is used in combination with a living radical polymerization catalyst. Halogen is released from the dormant species by the action of the catalyst, radicals (polymerization growth species) are generated, and polymerization proceeds. Also in the present invention, alkyl halides such as PE-I and CP-I are always used as dormant species regardless of the type of catalyst. In the present invention, when a compound having carbon as a central element is used as a catalyst, an alkyl halide having a structure and reactivity different from that of the dormant species as well as an alkyl halide to be a dormant species such as PE-I and CP-I. Are used together as a catalyst. Alkyl halide as a catalyst has a strong affinity with halogen (strong ability to extract halogen from dormant species) and does not react with monomer (does not become a growth species for polymerization). Compared to CP-I, alkyl halides that are slightly unstable electronically (highly active) and slightly bulky to avoid reaction with monomers are preferred. That is, it is preferable that the catalyst has a weak carbon-halogen bond, easily releases a halogen to become a carbon radical, and the carbon radical has a strong ability to extract halogen from a dormant species.

  It has not been conventionally thought that these organic halides such as alkyl halides can act as a catalyst. For this reason, there is no prior art using an alkyl halide as a catalyst.

However, studies by the present inventors have revealed that there is an error in the conventional technical common sense that all organic halides can act only as dormant species. That is, hybrid orbital of the p-orbital or s orbital and p orbital (e.g., sp ³ hybrid orbital) since radical based on electron is found that can serve as effective as a catalyst, p in the organic halide, such as the organic halogenated alkyl It has been found that radicals based on electrons in orbitals or hybrid orbitals of s orbitals and p orbitals can also act as catalysts.

  Such an organic halide that can act as a catalyst can be easily confirmed by conducting a radical reaction experiment. Specifically, an organic halide and a representative dormant species (for example, PE-I) are combined to conduct a living radical polymerization reaction, and if a narrow molecular weight distribution is obtained, the organic halide is used as a catalyst. It is confirmed that it worked. The catalyst compound is preferably one having no radical reactive double bond.

Preferable specific examples of the catalyst compound having carbon as a central element are described below.
(1) A compound in which a halogen (preferably iodine) is directly bonded to an aromatic ring can be used. For example, a compound having the following structure can be used.

(2) A compound in which halogen (preferably iodine) is bonded to carbon adjacent to the conjugated aliphatic double bond can be used. In particular, a compound in which iodine is bonded to carbon sandwiched between two double bonds can be used. For example, a compound having the following structure can be used.

(3) A compound in which halogen (preferably iodine) is bonded to carbon adjacent to the aromatic double bond can be used. In particular, a compound in which a halogen (preferably iodine) is bonded to carbon sandwiched between two or more aromatic rings can be used. For example, a compound having the following structure can be used.

  A compound in which a halogen (preferably iodine) is bonded to carbon sandwiched between three aromatic rings can also be used. For example, halogenated triphenylmethane can be used.

(4) A compound in which a halogen (preferably iodine) is bonded to carbon adjacent to a double bond such as an ester bond can be used. In particular, a compound in which a halogen (preferably iodine) is bonded to carbon sandwiched between two double bonds can be used. For example, a compound having the following structure can be used.

  (5) A compound having a C-I (carbon-iodine) structure or a C-Br (carbon-sulfur) structure, in which the carbon is further bonded to three halogen atoms, can be used. is there. That is, tetrahalogenated methyl having at least one iodine or sulfur can be used. Preferably, it is a compound having iodine. For example, a compound having the following structure can be used.

CI ₄ CF ₃ I CF ₂ I ₂
However, when methyl tetrahalide does not have either I or Br (for example, CCl ₄ ), the activity as a catalyst is very low, which is not preferable.

(Catalyst compound with oxygen as the central element)
As a specific example of the catalyst compound having oxygen as a central element, any known compound corresponding to the above definition can be used. Preferable specific examples of the catalyst compound having oxygen as the central element include halogenated oxygen (for example, oxygen iodide), alkoxy halide or carboxyl halide (R ¹ OX, for example, iodobenzoic acid (PhCOOI)), phenolic compound Examples thereof include compounds in which H of the phenolic hydroxyl group is substituted with halogen (for example, thymol iodide). The catalyst compound is preferably one having no radical reactive double bond.

(Catalyst compound with phosphorus as the central element)
As the catalyst compound having phosphorus as a central element, any known compound corresponding to the above definition can be used.

For example, a compound in which P is phosphorus in R ¹ _n P _h X ¹ _m (= Z) _k can be used. Here, R ¹ is preferably alkyl, alkoxy, aryl or substituted aryl. X ¹ is halogen, Z is oxygen or nitrogen, and is bonded to P. The bond between Z and M may be not only a double bond but also a triple bond.

Specific preferred examples of the catalyst compound for phosphorus as the central element include halogenated phosphorus (e.g., 3 iodide phosphorus, 5 iodide phosphorus), halogenated phosphonic (R ¹ ₂ PX or R ¹ PX _2, for example, iodide Diphenylphosphine (Ph ₂ PI)), halogenated phosphorous acid derivatives (R ¹ ₂ PX (═O), R ¹ PX ₂ (═O), or PX ₃ (═O), for example, iodinated phosphorous acid Diester ((C ₂ H ₅ O) ₂ (═O), ethylphenylphosphinate (Ph (C ₂ H ₅ O) ₂ PI (═O)) diphenylphosphine oxide (Ph ₂ PI (═O)) and the like It is done.

(Catalyst compound with nitrogen as the central element)
As the catalyst compound having nitrogen as a central element, any known compound corresponding to the above definition can be used.

For example, a compound in which M is nitrogen in R ¹ _n M _h X ¹ _m (= Z) _k can be used. Here, R ¹ is alkyl, alkylcarboxyl, alkylcarbonyl, haloalkyl, hydroxyl group, amino group, cyano group, alkoxy, aryl or substituted aryl, preferably alkyl, alkoxy, aryl or substituted aryl. X ¹ is halogen, Z is oxygen, nitrogen or sulfur, and is bonded to M. The bond between Z and M may be not only a double bond but also a triple bond. A double bond is preferred when Z is oxygen or sulfur. A triple bond is preferred when Z is nitrogen.

Here, n is preferably 0 to 3, more preferably 0 to 2. h is preferably 1, and m is preferably 1 to 3. k is preferably 0. In the above, when M is nitrogen, two R ¹ may be bonded to form a ring together with M. In this case, it is preferable that two R ¹ are both alkylcarbonyl, vinylcarbonyl, or phenylcarbonyl.

Preferable specific examples of the catalyst compound having nitrogen as a central element include nitrogen halides (for example, nitrogen iodide 3), halogenated amines or halogenated imides (R ¹ ₂ NX or R ¹ NX ₂ ), for example, iodide. Diphenylamine (Ph ₂ NI), iodinated succinimide ((CH ₂ ) ₂ (C═O) ₂ NI) (NIS), iodinated maleimide ((CH) ₂ (C═O) ₂ NI), iodinated Examples thereof include phthalimide (C ₆ H ₄ (C═O) ₂ NI), and derivatives thereof (compounds having one or more substituents bonded thereto).

(Catalyst precursor compound with carbon as the central element)
The compound that is a precursor of the catalyst having carbon as a central element is a compound in which halogen bonded to a carbon atom in the catalyst compound is replaced with hydrogen, and the above-described catalyst compound except that the halogen is replaced with hydrogen. The above description basically applies to the catalyst precursor compound as it is.

  Therefore, for example, a compound in which one or one hydrogen atom and two or three radical stabilizing substituents are bonded to the central element carbon can be preferably used. Here, the substituent for radical stabilization is preferably a substituent that forms a resonance structure together with the central element. The carbon of the central element may be bonded to one substituent other than the hydrogen atom and the substituent for radical stabilization, but the substituent other than the hydrogen atom and the substituent for radical stabilization may be bonded to the carbon of the central element. Preferably they are not bonded.

  Examples of the compound in which the halogen bonded to the carbon atom in the catalyst compound is replaced with hydrogen include a compound having a structure in which a C—H group is bonded to carbon, silicon, nitrogen, or phosphorus.

  The catalyst precursor compound is preferably a compound having a structure in which two aromatic rings are bonded to methylene.

  The atom to which carbon of the central element of the precursor compound is bonded (hereinafter referred to as “position 1 atom” for convenience) is preferably carbon, nitrogen, or phosphorus, and more preferably carbon. In addition to the carbon, only an atom selected from carbon and hydrogen is preferably bonded to the 1-position atom. The atom adjacent to the 1-position atom (hereinafter referred to as “2-position atom” for convenience) is preferably carbon. It is preferable that only an atom selected from carbon, oxygen and hydrogen is bonded to the 2-position atom. Moreover, it is preferable that a double bond exists between the 1-position atom and the 2-position atom. In a preferred embodiment, a compound in which two 2-position atoms are present and a double bond is present between one 2-position atom and the 1-position atom can be used as the catalyst precursor compound. For example, a catalyst precursor compound is a compound in which the first atom is carbon, two carbon atoms exist as the second atom, and a double bond exists between one carbon and the first carbon atom. Can be used. It is preferable that two or more 2-position atoms are present, and a double bond between one 2-position atom and the 1-position atom and a short bond between another 2-position carbon and the 1-position carbon. Are preferably part of the conjugated system. For example, the first atom is carbon, two carbons are present as the second atom, a double bond between one second atom and the first atom, another second atom and the first atom, It is preferable that the short bond between the two is part of the conjugated system.

  Therefore, as the precursor compound, a hydrocarbon compound having a structure in which a hydrocarbon group is bonded to an aromatic ring is preferable. For example, a compound in which a hydrocarbon group is bonded to aryl, heteroaryl, substituted aryl, or substituted heteroaryl is preferable. . For example, a compound in which two aromatic substituents are bonded to a methylene group is preferable. Here, as aryl, phenyl or biphenyl is preferable. Here, the substituent in the substituted aryl or substituted heteroaryl is preferably an alkyl group, an alkoxyl group, a cyano group or the like. A lower alkyl group and a lower alkoxyl group are more preferred.

  The catalyst precursor compound is preferably one having no radical reactive double bond. The catalyst precursor compound may have a double bond having low reactivity with a radical, such as an aromatic double bond (for example, a double bond of a benzene ring). Even if it is an aliphatic double bond, the double bond with low reactivity with a radical has no trouble in using as a catalyst precursor.

  On the other hand, a compound having a double bond or a triple bond only at a position away from the hydrocarbon group (that is, the first carbon does not have a double bond or a triple bond, and the second carbon or a carbon further away from the hydrocarbon group has two The compound having a heavy bond or a triple bond) tends not to have a relatively high performance as a catalyst precursor compound. Therefore, it is preferable to select a compound other than a compound having a double bond or a triple bond only at a position away from the hydrocarbon group as the catalyst precursor compound.

  In one embodiment, a compound having a hydrocarbon group (that is, Si—CH, N—CH, or P—CH) bonded to silicon, nitrogen, or phosphorus can also be used as the precursor compound.

The structure of a preferable compound is illustrated as a precursor compound used for preparation of the monolith type porous body of this invention.
(1) A compound in which hydrogen is bonded to carbon adjacent to an aliphatic double bond can be used. In particular, compounds in which hydrogen is bonded to carbon sandwiched between two aliphatic double bonds can be used. For example, compounds having methylene sandwiched between two aliphatic double bonds can be used. For example, a compound (1,4-cyclohexadiene) having the following structure can be used.

  In addition, as a compound having a structure similar to 1,4-cyclohexadiene, there is 1,3-cyclohexadiene. In 1,3-cyclohexadiene, one methylene is present between the double bond and the double bond. Since the structure is not sandwiched between groups, the effect of stabilizing the carbon radical of the methylene group is low, and it is not suitable as a catalyst.

(2) A compound in which hydrogen is bonded to carbon adjacent to the aromatic ring can be used. In particular, compounds in which hydrogen is bonded to carbon sandwiched between two or more aromatic rings can be used. For example, a compound having methylene sandwiched between two aromatic rings. For example, a compound having the following structure can be used.

  In one embodiment, compounds in which hydrogen is bonded to carbon sandwiched between three aromatic rings can be used. For example, triphenylmethane can be used.

(3) A compound in which hydrogen is bonded to carbon adjacent to a double bond such as an ester bond can be used. In particular, compounds in which hydrogen is bonded to carbon sandwiched between two double bonds can be used. For example, compounds having methylene sandwiched between two double bonds can be used. For example, a compound having the following structure can be used.

(Catalyst precursor compound with oxygen as the central element)
The compound that becomes the precursor of the catalyst having oxygen as a central element is a compound in which halogen bonded to an oxygen atom in the catalyst compound is replaced with hydrogen, and the catalyst compound described above is replaced except that halogen is replaced with hydrogen. The same applies to the catalyst precursor compound as it is.

  As a compound that becomes a precursor of a catalyst having oxygen as a central element, any compound in which a halogen bonded to an oxygen atom in the catalyst compound is replaced with hydrogen can be used. That is, any compound having a structure in which a hydroxyl group is bonded to carbon, silicon, nitrogen or phosphorus can be used.

  The catalyst precursor compound is preferably a phenol compound having a structure in which OH is bonded to an aromatic ring, or an aliphatic alcohol compound having a structure in which OH is bonded to carbon of an aliphatic group.

  The atom to which the hydroxyl group of the central element of the precursor compound is bonded (hereinafter referred to as “position 1 atom” for convenience) is preferably carbon, nitrogen or phosphorus, more preferably carbon. In addition to the hydroxyl group, it is preferable that only an atom selected from carbon and hydrogen is bonded to the 1-position atom. The atom adjacent to the 1-position atom (hereinafter referred to as “2-position atom” for convenience) is preferably carbon. It is preferable that only an atom selected from carbon, oxygen and hydrogen is bonded to the 2-position atom. Moreover, it is preferable that a double bond exists between the 1-position atom and the 2-position atom. In a preferred embodiment, a compound in which two 2-position atoms are present and a double bond is present between one 2-position atom and the 1-position atom can be used as the catalyst precursor compound. For example, a catalyst precursor compound is a compound in which the first atom is carbon, two carbon atoms exist as the second atom, and a double bond exists between one carbon and the first carbon atom. Can be used. It is preferable that two or more 2-position atoms are present, and a double bond between one 2-position atom and the 1-position atom and a short bond between another 2-position carbon and the 1-position carbon. Are preferably part of the conjugated system. For example, the first atom is carbon, two carbons are present as the second atom, a double bond between one second atom and the first atom, another second atom and the first atom, It is preferable that the short bond between the two is part of the conjugated system.

  Accordingly, the precursor compound is preferably a phenol compound having a structure in which a hydroxyl group is bonded to an aromatic ring, and for example, a compound in which a hydroxyl group is bonded to aryl or substituted aryl is preferable. Here, as aryl, phenyl or biphenyl is preferable. Here, the substituent in the substituted aryl is preferably an alkyl group, an alkoxyl group, a cyano group, or the like. A lower alkyl group and a lower alkoxyl group are more preferred.

The catalyst precursor compound is preferably one having no radical reactive double bond. The catalyst precursor compound may have a double bond having low reactivity with a radical, such as an aromatic double bond (for example, a double bond of a benzene ring). Even in the case of an aliphatic double bond, a double bond having low reactivity with a radical, such as a double bond in vitamin C, has no problem for use as a catalyst precursor. Therefore, vitamin C can be used as a catalyst precursor. In general, a double bond bonded to a hydroxyl group has no reactivity with a radical. For example, vinyl alcohol (CH ₂ ═CH—OH) is not a radical polymerizable monomer. Similarly, triple bonds bonded to hydroxyl groups are not radically reactive and such compounds are not radically polymerizable monomers.

  On the other hand, a compound having a double bond or a triple bond only at a position away from the hydroxyl group (that is, the carbon at the 1st position does not have a double bond or a triple bond, and the carbon at a position 2 or higher is a double bond). Or a compound having a triple bond) tends to have a relatively low performance as a catalyst precursor compound. Therefore, it is preferable to select a compound other than a compound having a double bond or a triple bond only at a position away from the hydroxyl group as the catalyst precursor compound.

  In one embodiment of the present invention, a compound having a hydroxyl group (that is, Si—OH, N—OH, P—OH) bonded to silicon, nitrogen, or phosphorus can also be used as the precursor compound.

(Catalyst production method)
Most of the compounds used as the catalyst used in the production of the monolith type porous body of the present invention are known compounds, and those commercially available from reagent sales companies can be used as they are, or known compounds It can be synthesized by a method. Moreover, the compound which exists in a natural product can also be obtained by methods, such as extracting from the natural product.

When a catalyst in which an organic group R ¹ (for example, alkyl, alkoxy, aryl, heteroaryl, substituted aryl or substituted heteroaryl) is bonded to carbon, oxygen, nitrogen, phosphorus, germanium, tin or antimony is used as a catalyst, Commercially available compounds can be used. Alternatively, such a compound can be synthesized by a known method.

For example, the method of reacting the iodine or P ₂ I ₄ in the methods and R ¹ ₃ COH reacting N- iodosuccinimide in R ¹ ₃ CH, etc. R ¹ ₃ CI is to synthesize a halogen to carbon and the organic group R A compound to which ¹ is bonded can be synthesized.

For example, a compound in which halogen and an organic group R ¹ are bonded to oxygen can be synthesized, for example, ROI is synthesized by a method in which ICl is reacted with R ¹ OH.

For example, iodoform to _{^{R 1 2 PH (= O)}} , by a method of reacting iodine or N- iodosuccinimide, and R ¹ ₂ PI (= O) is synthesized, halogen and organic groups R ¹ to phosphorus Bound compounds can be synthesized.

For example, a compound in which halogen and an organic group R ¹ are bonded to nitrogen can be synthesized by, for example, synthesizing R ¹ ₂ NI by a method of reacting iodine with R ¹ ₂ NH using Ag ₂ O as a catalyst.

For example, R ¹ Gel ₃ can be synthesized by a method in which germanium iodide is reacted with the iodide R ¹ I of the organic group R ¹ .

For example, it is possible to synthesize (R ¹⁾ by a method of reacting the SnI ₄ to _{^{4 Sn, (R 1) n}} SnI m (n + m = 4 and n = 1, 2 or 3).

  For example, antimony can also be synthesized by the same method as in the case of germanium or tin.

(Amount of catalyst used)
The catalyst used for the production of the monolith type porous body of the present invention is extremely high in activity and can use living radical polymerization as a catalyst in a small amount. The amount of the catalyst used will be described below, but the amount when the catalyst precursor is used is the same as the amount of the catalyst.

  In the production method of the present invention, the compound used as a catalyst or a catalyst precursor may be a liquid compound that can theoretically be used as a solvent. However, when it is used as a solvent or a catalyst precursor, it is not necessary to use it in such a large amount as to exhibit an effect as a solvent. Therefore, the amount of the catalyst or catalyst precursor used can be smaller than the so-called “solvent amount” (that is, the amount necessary to achieve the effect as a solvent). In the method of the present invention, as described above, the catalyst or catalyst precursor may be used in an amount sufficient to use living radical polymerization as a catalyst, and it is not necessary to add any more.

  Specifically, for example, in a preferred embodiment, the amount of catalyst used can be 10 mmol (mM) or less per liter of reaction solution. In a more preferred embodiment, the amount of catalyst used can be 5 mmol or less per 1 liter of reaction solution, or 2 mmol or less. Furthermore, it can be 1 mmol or less, and can also be 0.5 mmol or less. In the weight standard, the amount of catalyst used can be 1% by weight or less of the reaction solution. In a preferred embodiment, it can be 0.75 wt% or less, and can be 0.70 wt% or less, and in a more preferred embodiment, 0.5 wt% or less. It is possible to make it 0.2% by weight or less, further 0.1% by weight or less, and 0.05% by weight or less. That is, the amount can be “significantly” smaller than that effective as a solvent.

  The amount of the catalyst used is preferably 0.02 mmol or more, more preferably 0.1 mmol or more, and further preferably 0.5 mmol or more with respect to 1 liter of the reaction solution. . On a weight basis, the amount of catalyst used is preferably 0.001% by weight or more of the reaction solution, more preferably 0.005% by weight or more, and still more preferably 0.02% by weight or more. . If the amount of catalyst used is too small, the molecular weight distribution tends to be wide.

  In one embodiment, in the living radical polymerization method of the present invention, for example, a living radical polymerization catalyst or catalyst precursor compound other than a catalyst or catalyst precursor compound having a carbon atom as a central element (hereinafter referred to as “multi-catalyst or multi-catalyst”). Even if the precursor compound “) is not used in combination, it is possible to sufficiently perform living radical polymerization. However, if necessary, a multi-catalyst or a multi-catalyst precursor compound can be used in combination. In that case, for example, it is preferable to use a large amount of the catalyst or catalyst precursor compound having a carbon atom as a central element and reduce the amount of the multi-catalyst or multi-catalyst precursor compound. In such a case, the amount of the multi-catalyst or multi-catalyst precursor compound used can be, for example, 100 parts by weight or less with respect to 100 parts by weight of the catalyst or catalyst precursor compound centered on carbon atoms. It can also be 50 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 2 parts by weight or less, 1 part by weight or less, 0.5 parts by weight or less, 0.2 parts by weight or less. Alternatively, it may be 0.1 parts by weight or less. That is, for example, a living radical reaction can be performed in a reaction solution that does not substantially contain a catalyst other than a catalyst having a carbon atom as a central element.

(Protecting group)
In the method for producing a monolith type porous body of the present invention, a protective group for protecting a growing chain during the reaction of living radical polymerization is used. As such a protecting group, various known protecting groups can be used as protecting groups conventionally used in living radical polymerization. Here, it is preferable to use halogen as the protecting group. As described above with respect to the prior art, when a special protecting group is used, there are disadvantages such as the fact that the protecting group is very expensive.

(Organic halide (dormant species))
In the method for producing a monolith type porous body of the present invention, preferably, an organic halide having a carbon-halogen bond is added to the reaction material, and a halogen imparted from the organic halide to the growing chain is used as a protective group. Since such organic halides are relatively inexpensive, they are advantageous over other arable land compounds used for protecting groups used in living radical polymerization. If necessary, a dormant species in which halogen is bonded to an element other than carbon can be used.

  The organic halide used as the dormant species is not particularly limited as long as it has at least one carbon-halogen bond in the molecule and acts as the dormant species. In general, however, those in which one or two halogen atoms are contained in one molecule of the organic halide are preferred.

  Here, the organic halide used as the dormant species preferably has an unstable carbon radical when the halogen is eliminated and a carbon radical is generated. Therefore, as an organic halide used as a dormant species, when a halogen is eliminated and a carbon radical is generated, two or more substituents that stabilize the carbon radical are bonded to the carbon atom that becomes the carbon radical. What is there is not suitable. However, those in which one substituent that stabilizes the carbon radical is bonded to the carbon atom that forms the carbon radical often show appropriate radical stability and can be used as a dormant species.

  That is, in the living radical polymerization method of the present invention, it is preferable to combine a catalyst compound in which the carbon radical is stable and a dormant species in which the carbon radical is not so stable but has an appropriate stability. A living radical polymerization reaction can be performed with high efficiency. For example, a catalyst in which two or more substituents that stabilize a carbon radical are bonded to a carbon atom that forms the carbon radical is used as a catalyst, and a carbon atom that uses one substituent that stabilizes the carbon radical serves as the carbon radical. By using the one bonded to the dormant as a dormant, the combination of the catalyst and the dormant shows a high reaction activity in living radical polymerization.

  The number of hydrogen atoms of the organic halide used as the dormant species to which the halogen is bonded (hereinafter referred to as “the 1st carbon of the organic halide”) is preferably 2 or less, and preferably 1 or less. More preferably, it is more preferable not to have hydrogen. Further, the number of halogens bonded to the 1-position carbon of the organic halide is preferably 3 or less, more preferably 2 or less, and even more preferably 1. In particular, when the halogen bonded to the 1st carbon of the organic halide is chlorine, the number of chlorine is very preferably 3 or less, and even more preferably 2 or less, One is particularly preferred.

One or more carbon atoms are preferably bonded to the 1-position carbon of the organic halide used as the dormant species, and it is particularly preferable that two or three carbon atoms are bonded.
The halogen atom of the organic halide used as the dormant species may be the same as or different from the halogen atom in the catalyst. This is because even if the halogen atom is different, the halogen atom can be exchanged between the organic halide and the catalyst compound. However, if the halogen atom of the organic halide used as the dormant species and the halogen atom in the catalyst are the same, the exchange of the halogen atom between the organic halide used as the dormant species and the catalyst compound Is preferred because it is easier.

Preferable specific examples of the organic halide used as the dormant species include, for example, the following CH (CH ₃ ) (Ph) I and C (CH ₃ ) ₂ (CN) I.

  Other specific examples of organic halides used as dormant species include, for example, methyl chloride, methylene chloride, chloroform, chloroethane, dichloroethane, trichloroethane, bromomethyl, dibromomethane, bromoform, bromoethane, dibromoethane, tribromoethane, tetra Bromoethane, bromotrichloromethane, dichlorodibromomethane, chlorotribromomethane, iodotrichloromethane, dichlorodiiodomethane, iodotribromomethane, dibromodiiodomethane, bromotriiodomethane, iodoform, diiodomethane, methyl iodide, isopropyl chloride , T-butyl chloride, isopropyl bromide, t-butyl bromide, triiodoethane, ethyl iodide, diiodopropane, isopropyl iodide, t-butyl iodide, Lomodichloroethane, chlorodibromoethane, bromochloroethane, iododichloroethane, chlorodiiodoethane, diiodopropane, chloroiodopropane, iododibromoethane, bromoiodopropane, 2-iodo-2-polyethylenebricosylpropane, 2-iodo-2 -Amidinopropane, 2-iodo-2-cyanobutane, 2-iodo-2-cyano-4-methylpentane, 2-iodo-2-cyano-4-methyl-4-methoxypentane, 4-iodo-4-cyano-pentane Acid, methyl-2-iodoisobutyrate, 2-iodo-2-methylpropanamide, 2-iodo-2,4-dimethylpentane, 2-iodo-2-cyanobutanol, 4-methylpentane, cyano-4- Methylpentane, 2-iodo-2-methyl-N- (2- Droxyethyl) propionamide 4-methylpentane, 2-iodo-2-methyl-N- (1,1-bis (hydroxymethyl) -2-hydroxyethyl) propionamide 4-methylpentane, 2-iodo-2- (2 -Imidazolin-2-yl) propane, 2-iodo-2- (2- (5-methyl-2-imidazolin-2-yl) propane, etc. These halides may be used alone, You may combine.

  In the method for producing a monolith type porous body of the present invention, the organic halide used as the dormant species is not used as a solvent, and therefore it is not necessary to use it in a large amount so as to exhibit the effect as a solvent. Therefore, the amount of the organic halide used as the dormant species can be less than the so-called “solvent amount” (that is, the amount necessary to achieve the effect as a solvent). In the method of the present invention, the organic halide used as the dormant species is used to provide halogen as a protective group to the growing chain as described above, so that a sufficient amount of halogen for the growing chain in the reaction system is used. Is sufficient. Specifically, for example, the amount of the organic halide used as the dormant species in the method of the present invention is preferably 0.05 mol or more per mol of the radical polymerization initiator in the polymerization reaction system. Preferably it is 0.5 mol or more, More preferably, it is 1 mol or more. Moreover, it is preferable that it is 100 mol or less per 1 mol of radical polymerization initiators in a polymerization system, More preferably, it is 30 mol or less, More preferably, it is 5 mol or less. Further, it is preferably 0.001 mol or more, more preferably 0.005 mol or more per mol of the vinyl monomer (monomer). Further, it is preferably 0.5 mol or less per mol of the vinyl monomer, more preferably 0.4 mol or less, still more preferably 0.3 mol or less, and particularly preferably 0.2 mol or less. It is less than or equal to mol, most preferably less than or equal to 0.1 mol. Furthermore, if necessary, the amount may be 0.07 mol or less, 0.05 mol or less, 0.03 mol or less, 0.02 mol or less, or 0.01 mol or less per mol of the vinyl monomer. It is.

  Many of the organic halides used as the dormant species are known compounds, and reagents commercially available from reagent sales companies can be used as they are. Or you may synthesize | combine using a conventionally well-known synthesis | combining method.

The organic halide used as the dormant species can be charged with its raw materials, and the organic halide can be produced in situ during the polymerization, that is, in the reaction solution, and used as the organic halide in this polymerization method. For example, an azo radical initiator (for example, azobis (isobutyronitrile)) and a halogen single molecule (for example, iodine) are used as raw materials, and an organic halide (for example, C which is an alkyl iodide is obtained by the reaction between the two. (CH ₃ ) ₂ (CN) I) can be generated in situ during the polymerization and used as a dormant species for this polymerization process.

  As the organic halide used as the dormant species, those immobilized on a surface such as an inorganic or organic solid surface or an inorganic or organic molecular surface can be used. For example, an organic halide immobilized on the surface of a silicon substrate, the surface of a polymer film, the surface of inorganic or organic fine particles, the surface of a pigment, or the like can be used. For immobilization, for example, chemical bonds or physical bonds can be used.

(Reaction temperature)
The reaction temperature in the method of the present invention is not particularly limited. The temperature is preferably 10 ° C or higher, more preferably 20 ° C or higher, still more preferably 30 ° C or higher, still more preferably 40 ° C or higher, and particularly preferably 50 ° C or higher. Further, it is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower, still more preferably 105 ° C. or lower, and particularly preferably 100 ° C. or lower. .

  If the temperature is too high, there is a drawback that the heating equipment is costly. When the temperature is lower than room temperature, there is a disadvantage that costs are required for equipment for cooling. In addition, when a reaction mixture is prepared so as to polymerize at room temperature or lower, the reaction mixture is unstable and reacts at room temperature, which makes it difficult to store the reaction mixture. Therefore, the above-described temperature range slightly higher than room temperature and not excessively high (for example, 50 ° C. to 100 ° C.) is very suitable in a practical sense.

(Reaction time)
The reaction time in the method of the present invention is not particularly limited. Preferably, it is 15 minutes or more, More preferably, it is 30 minutes or more, More preferably, it is 1 hour or more. Moreover, Preferably it is 3 days or less, More preferably, it is 2 days or less, More preferably, it is 1 day or less.

  If the reaction time is too short, it is difficult to obtain a sufficient molecular weight (or polymerization rate (monomer conversion rate)). If the reaction time is too long, the overall efficiency of the process is poor. By setting an appropriate reaction time, excellent performance (moderate polymerization rate and reduction of side reactions) can be achieved.

(atmosphere)
The polymerization reaction in the method of the present invention may be performed under conditions where air is present in the reaction vessel. Moreover, you may substitute air with inert gas, such as nitrogen and argon, as needed.

(precursor)
In the polymerization method of the present invention, the above-described catalyst may be used directly (that is, the catalyst is charged into the polymerization vessel) to carry out the reaction, but the catalyst precursor is not used directly. You may perform reaction using. Here, the catalyst precursor refers to a compound that does not correspond to the above-mentioned definition of the catalyst in a state where the compound is charged into the reaction vessel, but can be chemically changed in the reaction vessel to be in a state capable of acting as a catalyst. Here, “to be in a state where it can act as a catalyst” preferably means that the precursor is converted into the catalyst compound.

  A compound capable of generating an activated radical similar to the activated radical generated during the polymerization reaction from the catalyst compound corresponds to the precursor. For example, carbon hydride corresponds to the precursor. That is, radicals generated by decomposition of radical initiators and polymer radicals derived from them can generate activated radicals of carbon compounds if they pull out hydrogen of hydrides of carbon, and perform living radical polymerization. Can do.

  Therefore, in one embodiment of the polymerization method of the present invention, the reaction can be carried out directly using the catalyst described above, but in another embodiment, the precursor of the catalyst compound can be used without directly using the catalyst described above. The body can be used. In this case, a step of chemically changing the precursor is performed before the step of performing the polymerization reaction. This chemical change step of the precursor may be performed in a container for performing the polymerization reaction, or may be performed in a container different from the polymerization reaction container. Performing simultaneously with the polymerization reaction step in the vessel for carrying out the polymerization reaction is advantageous in that the entire process is simplified.

  As the usage-amount of a precursor, the same amount as the usage-amount of the catalyst mentioned above can be used. It is preferable that the amount of activated radicals obtained from the precursor is the same as the amount of activated radicals when the above-mentioned amount of catalyst is used.

  The living radical polymerization method of the present invention can be applied to homopolymerization, that is, production of a homopolymer, but it is also possible to produce a copolymer using the method of the present invention for copolymerization. The copolymerization may be random copolymerization or block copolymerization.

  The block copolymer may be a copolymer in which two or more types of blocks are bonded, or may be a copolymer in which three or more types of blocks are bonded.

  In the case of block copolymer consisting of two types of blocks, for example, a block copolymer can be obtained by a method including a step of polymerizing a first block and a step of polymerizing a second block. In this case, the method of the present invention may be used for the step of polymerizing the first block, and the method of the present invention may be used for the step of polymerizing the second block. It is preferable to use the method of the present invention for both the step of polymerizing the first block and the step of polymerizing the second block.

  More specifically, for example, after polymerizing the first block, the block copolymer can be obtained by polymerizing the second block in the presence of the obtained first polymer. The first polymer can be subjected to polymerization of the second block after being isolated and purified, or the first polymer is not isolated and purified, and the first polymer can be subjected to the first polymerization during or after the polymerization of the first polymer. The block can be polymerized by adding a second monomer to the polymerization.

  In the case of producing a block copolymer having three types of blocks, as in the case of producing a copolymer in which two or more types of blocks are bonded, a step of polymerizing each block is performed to obtain a desired copolymer weight. Coalescence can be obtained. And it is preferable to use the method of this invention in superposition | polymerization of all the blocks.

(Reaction mechanism)
Although the present invention is not particularly bound by theory, the presumed mechanism will be explained.

  The basic concept of the living radical polymerization method is a reversible activation reaction of a dormant species (polymer-X) to a growing radical (polymer.), Using a halogen as the protecting group X and a transition metal complex as an activation catalyst. The system is one of the useful living radical polymerization methods. According to the present invention, a carbon compound can be used to extract a halogen of an organic halide with high reactivity, and a radical can be generated reversibly (Scheme 1).

  Conventionally, transition metals are generally known to be excellent in the action of catalyzing various chemical reactions because their electrons can be in various transition states. For this reason, it has been considered that transition metals are excellent as a catalyst for living radical polymerization. Conversely, typical elements were thought to be disadvantageous for such catalysts.

  However, unexpectedly, according to the present invention, by using a catalyst having carbon as a central element, halogen is exchanged between the catalyst compound and the reaction intermediate as shown in the schematic diagram of FIG. However, the polymerization reaction proceeds very efficiently. This is considered to be due to the fact that the bond between the central element and the halogen is appropriate for the halogen exchange with the reaction intermediate. Therefore, basically, a compound having a bond between the central element and halogen is considered to be able to satisfactorily catalyze living radical polymerization even with a compound having a substituent other than the central element and halogen.

Scheme 1 below shows the reaction formula when the catalyst of the present invention is used.
(Scheme 1)

When a precursor (R—CH (hydrocarbon)) is used, an activated radical (R—C ·) is generated from the precursor before or simultaneously with the reaction based on the above-described mechanism. A process is performed. Specifically, radicals generated by decomposition of radical initiators (for example, peroxides) or growth radicals generated therefrom (both expressed by R ′ ·) extract active hydrogen atoms from the precursor. Can be obtained (Scheme 2 (a)).
(Scheme 2)

(Removal of halogen bonded to the terminal)
The monolith type porous body of the present invention has a halogen (for example, iodine) at the terminal. When using this porous material, if necessary, the terminal halogen can be removed by sublimation, decomposition or extraction. Moreover, it is also possible to actively utilize the terminal halogen and convert it to another functional group to bring out a new function. The reactivity of the terminal halogen is generally high and can be removed or converted by a wide variety of reactions. In the case of the monolith type porous body of the present invention, since a crosslinker is used as a monomer, the molecular structure is formed by forming a branched polymer body to remove even halogen inside the skeleton portion. It is difficult. However, due to the relatively surface portion being cleaned by the removal method, it can be used without problems for normal applications. The cleaning of the monolith type porous body of the present invention requires a process such as applying a little heat or extending the cleaning time, preferably using a solvent such as acetone or THF. More preferably, THF that can further swell the porous body is used. In addition, if possible, cleaning can be facilitated by reducing the crosslink density by reducing the amount of the crosslinker at the monomer ratio when preparing the monolith type porous body, thereby facilitating swelling.
(Scheme 3)

(Measurement of skeleton and void size)
The skeleton size in the monolith type porous body of the present invention can be evaluated by, for example, the average skeleton diameter of the skeleton (the diameter of the cross section perpendicular to the extension direction in the skeleton is the skeleton diameter), and the average skeleton diameter is, for example, The simplest method is to check with an electron micrograph. More specifically, for example, the cross section of the porous body may be observed with a microscope such as an electron microscope or a laser confocal microscope, and the obtained photograph may be obtained by image processing. Note that it is preferable to smooth the cross section of the porous body by polishing or the like during microscopic observation.

  The void size in the monolith type porous body of the present invention can be evaluated by, for example, the average pore diameter of the voids, and for example, the simplest method is to confirm with an electron micrograph. The pore size distribution can be measured by a pore distribution measurement for a porous material, for example, a mercury intrusion method or a nitrogen adsorption method, and the mercury intrusion method and the nitrogen adsorption method may follow a general method.

(Void size)
The void size (macropores) in the monolith type porous body of the present invention is not particularly limited, but since a porous body having a co-continuous structure is formed based on induction of phase separation, usually, the average pore diameter is set, It is in the range of about 100 μm or less exceeding 100 nm. When the porous body of the present invention is used as a separation medium for an LC column, the average pore diameter of the macropores is preferably in the range of about 500 nm or more and 5 μm or less from the viewpoint of achieving both separation ability as a separation medium and pressure loss. A range of about 3 μm or less is preferable.

(Skeleton size)
The skeleton size in the monolith type porous body of the present invention is not particularly limited. However, since a porous body having a co-continuous structure is formed based on induction of phase separation, the average skeleton diameter is usually about 100 nm to 50 μm. Range.

(Washing)
The method for removing the polymerization solvent formed by phase separation is not particularly limited. For example, solvent replacement with a solvent that does not dissolve the polymer that is the base material of the skeleton phase may be performed, and then the whole may be dried.

  The method for producing a monolith type porous body of the present invention may further include a step of removing the organic polymer remaining in the obtained porous body. All or part of the organic polymer added to the polymerization system as a phase separation inducing component may remain in the porous body skeleton. In particular, the organic polymer moves to the skeleton of the porous body due to phase separation. In that case, the residual amount tends to increase. For example, when the obtained porous body is used as a separation analysis medium for HPLC, the remaining organic polymer may reduce the separation ability as a separation medium. Therefore, in such a case, the organic polymer remaining in the porous body may be removed as necessary.

  The method for removing the organic polymer is not particularly limited. For example, the solvent may be removed after the inside of the porous body is filled with a solvent that dissolves the organic polymer without dissolving the skeleton. When removing the polymerization solvent from the gel formed by phase separation, the polymerization solvent and the organic polymer may be removed at the same time by performing solvent substitution with the solvent.

  In the method for producing a monolithic porous body that does not use an organic polymer that is a phase separation inducing component of the present invention, a monolithic porous body can be obtained by a simple washing method such as washing the solvent component of the obtained porous body. Is possible. In this case, the remaining organic polymer is not extracted continuously during use when used as a separation analysis medium.

(Mesopore)
The monolith type porous body of the present invention forms pores (mesopores) having a pore size smaller than the voids (macropores) on the surface of the skeleton by controlling the polymerization system. It is also possible to control the distribution of. For example, when the living radical polymerization of a low-molecular compound is performed, it is possible to control these by changing the concentration ratio of the polymerization initiator and the catalyst contained in the polymerization system. As the catalyst concentration with respect to the polymerization initiator increases, the amount of mesopores formed on the surface of the skeleton tends to increase.

  According to the method for producing a monolith type porous body of the present invention, a separation medium having a predetermined mesopore diameter and a separation medium having a narrow distribution of mesopore diameter can be obtained. In the present specification, “mesopore” means “mesopore” which is a term generally used in the chromatography field.

  The size of the mesopores in the monolith type porous body of the present invention is not particularly limited, but is usually in the range of 2 nm to 100 nm in terms of the average diameter. When the porous material of the present invention in which mesopores are formed is used as an analytical column for high-performance liquid chromatography (HPLC), the average pore size of mesopores is different when the analyte is a low-molecular substance, although it varies depending on the substance to be measured by HPLC. Is preferably about 10 nm, and when the analysis target is a polymer substance, a range of about 20 nm to 30 nm is preferable. Furthermore, when analyzing biological samples such as proteins and peptides, mesopores of about 80 to 120 nm may be required. The average pore size of the mesopores may be obtained from the pore size distribution, and the distribution can be measured by pore distribution measurement (mercury intrusion method or nitrogen adsorption method) for the monolith type porous body.

(shape)
The monolithic porous body of the present invention may be changed in its shape as necessary. For example, when it is formed by cutting, cutting or the like, or is made into a porous body for a catalyst carrier, it is pulverized and the like. Also good. When the porous body of the present invention is used as a separation medium for LC, it may be formed in a columnar shape or a disk shape.

(Use)
The monolith type porous body of the present invention can be used for separation media for separation analysis (particularly, separation media for chromatography), porous materials for blood separation, reagent concentration media used for environmental analysis, etc., porous materials for moisture absorption, and deodorization. Low molecular adsorption porous material, enzyme carrier, catalyst carrier, porous membrane used in membrane emulsification method to produce uniform fine particles, polishing slurry separation and purification such as chemical mechanical polishing method, cooling of electronic equipment parts such as semiconductor It can be applied to a wide range of applications such as a wick of a heat pipe that transports heat as the latent heat of vaporization of a working fluid used in the industry.

(Separation analysis column)
The monolith type porous body of the present invention can be used as a separation analysis medium, a separation material for a column for high performance liquid chromatography (HPLC), and in this case, the voids become macropores that are flow paths of the mobile phase. That is, according to the production method of the present invention, a separation medium having a predetermined macropore diameter and / or a separation medium having a narrow macropore diameter distribution can be obtained. The “macropore” in the present specification means “macropore” which is a term generally used in the field of LC columns.

  Chromatography is a chemical analysis method widely used for precision separation, analysis, fractionation, and purification of natural, synthetic organic compounds, pharmaceuticals, and biological materials. Chromatographic systems are composed of two phases. One phase is a solvent moving at a constant rate (mobile phase) and the other phase is a fixed medium (stationary phase). The monolithic porous material can be used as a medium (hereinafter also referred to as “column”) of this stationary phase. In the chromatographic analyzer, the solute (sample) injected into this column moves through the column at the same speed as the mobile phase when dissolved in the mobile phase solvent, and on the stationary phase when associated with the stationary phase. Stay on. The solute flows back and forth between these phases with the mobile phase, passes through the column, is detected by the detector, and is depicted as a peak on the chromatogram (chart on the personal computer screen). In the column, the separation of the mixed sample is achieved by the difference in the probability that the solute is present in the mobile phase of each solute component due to the difference in the solute partition coefficient between the stationary phase and the mobile phase.

  Therefore, if the catalyst remains in the monolithic porous material that can be used as the stationary phase of the column, the separation efficiency deteriorates, the separation pattern differs from the original performance, or the catalyst is a solvent (mobile phase). ) And solutes (samples). When the transition metal complex system, nitroxyl system or dithioester system of the prior art was used as the catalyst, the catalyst present at these terminals could not be easily removed from the porous body, but the monolith type porous body of the present invention Since it is possible to remove the terminal catalyst (for example, halogen such as iodine) by a simple method, the range of applications is widened as a column for chromatography.

  The performance of a column for chromatography is not only the elements described above, but the original performance of the column greatly depends on the diffusion of the solute when the solute (sample) passes through the column. That is, by reducing the diffusion in the column, the width of the detected peak is narrowed, and solute peaks that are similar on the chromatogram can be separated, thereby improving the separation performance. The contribution of diffusion in the column can be roughly divided into three: <1> Contribution of diffusion in the mobile phase, <2> Contribution of diffusion of solute in the column axis direction, and <3> Mobile phase As well as the contribution of resistance to mass transfer in the stationary phase. Since the contribution of these diffusions is also affected by the void size and skeleton size when the monolithic column is produced, it is necessary to adjust the balance with the column load pressure. Furthermore, in addition to the constituent size of the porous body, it is said that the influence is great due to the uniformity of the porous body structure.

  Therefore, a column with a small structural distortion has a small mobile phase flow rate and channel disturbance in the column, resulting in a small solute diffusion and a sharp and symmetrical peak on the chromatogram. It becomes possible. The chromatography column using the conventional technique requires polymerization at high temperature (Patent Document 5), and therefore, the temperature difference between the outside and inside of the mold for producing the monolithic column is generated, which is confirmed by the electron microscope. It is thought that the uniformity of the structure is lost on a micro scale that cannot be done. In the method for producing a monolith type porous body of the present invention, preparation at 100 ° C. or lower is possible, so that a highly porous body having a small temperature difference in the mold is prepared. Therefore, as shown in FIG. 11, a sharp and highly targetable peak is obtained on the chromatogram, and a monolithic porous body with high column performance can be created.

(Capillary column)
When used as a separation / analysis medium for chromatography, for example, the monolithic porous body of the present invention is covered with a pressure-resistant plastic (for example, polyetheretherketone), glass fiber, carbon fiber, fiber reinforced plastic, etc. What is necessary is just to attach a storage or a connection component etc. and to make it a column. It is also possible to prepare a monolithic porous body directly in a capillary and perform capillary column. Most of the raw material of the monolith type porous body is a liquid, and even if it contains a solid, it is used as a prepared solution, so that it can be fed to a capillary. Here, attention should be paid to the shrinkage of the porous body during the polymerization process, and selection of raw materials, composition, and polymerization conditions is required.

(Solid phase extraction column)
When the monolithic porous material of the present invention is used as a separation medium for a solid phase extraction column in the chromatography field, the pore size (macropores) is preferably in the range of about 5 μm to 30 μm, more preferably 10 μm to 20 μm. The range of the degree. In this case, since the high-performance separation is not required as much as it is used for the HPLC column, the skeleton size is not particularly limited, but the skeleton size needs to be set in consideration of the adsorption ability and the applied pressure depending on the adsorption area. A range of about 3 μm to 25 μm is preferable, and a range of about 5 μm to 15 μm is more preferable.

  Since the monolithic porous body of the present invention includes a porous body having a skeleton based on an organic polymer, the monolithic porous column of the present invention is stable even in a strong or strongly alkaline atmosphere. A wide variety of solvents and substances to be measured can be selected as mobile phases.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, it is not limited by these Examples.

[Example 1]
As a phase separation inducing component, 0.8 g of polyethylene oxide (manufactured by Aldrich, average molecular weight 100,000) and 20 g of dimethylformamide (manufactured by Nacalai Tesque) as a solvent are uniformly dissolved at 60 ° C. in a screw tube, A solution was obtained. After cooling to room temperature, 6.7 g of glycerol dimethacrylate (GDMA, manufactured by Kyoeisha Chemical Co., Ltd., GP-101P, molecular weight 227) was added as a monomer, and a uniform solution was prepared by stirring. Furthermore, 0.02 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.), iodine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0 as an initiator and a reversible transfer catalyst 0.04 g, 0.004 g of N-iodosuccinimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution, and a uniform solution was prepared by stirring. Next, after removing bubbles in the polymerization solution with an ultrasonic device, the remaining oxygen was replaced by bubbling with nitrogen gas. This solution was subjected to a polymerization reaction at 60 ° C. for 24 hours. Thereafter, the obtained polymer was cooled to room temperature, taken out from the container, washed with acetone and methanol, and dried to obtain a porous body. As a result of confirming the structure of the porous body with a scanning electron microscope, a co-continuous structure as shown in FIG. 1 was formed.

[Example 2]
As a phase separation inducing component, 0.8 g of polyethylene oxide (manufactured by Aldrich, average molecular weight 100,000) and 20 g of dimethylformamide (manufactured by Nacalai Tesque) as a solvent are uniformly dissolved at 60 ° C. in a screw tube, A solution was obtained. After cooling to room temperature, 6.7 g of glycerol dimethacrylate (GDMA, manufactured by Kyoeisha Chemical Co., Ltd., GP-101P, molecular weight 227) was added as a monomer, and a uniform solution was prepared by stirring. Furthermore, 0.02 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.), iodine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0 as an initiator and a reversible transfer catalyst 0.04 g, 0.004 g of N-iodosuccinimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution, and a uniform solution was prepared by stirring. Next, after removing bubbles in the polymerization solution with an ultrasonic device, the remaining oxygen was replaced by bubbling with nitrogen gas. This solution was subjected to a polymerization reaction at 100 ° C. for 24 hours. Thereafter, the obtained polymer was cooled to room temperature, taken out from the container, washed with acetone and methanol, and dried to obtain a porous body. As a result of confirming the structure of the porous body with a scanning electron microscope, a co-continuous structure as shown in FIG. 2 was formed.

[Example 3]
As a phase separation inducing component, 1.25 g of trimethylsiloxy-terminated polymethylsiloxane (DMS-T22, manufactured by Gelest), 12 g of mesitylene (manufactured by Nacalai Tesque) as a solvent, and divinylbenzene (Wako Pure Chemical Industries, Ltd.) as a monomer A uniform solution was prepared by stirring 10 g of a molecular weight of 130.19) manufactured by Kogyo Co., Ltd. in a screw tube bottle. Furthermore, 0.1 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.), iodine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0 as an initiator and a reversible transfer catalyst 0.05 g, 0.005 g of N-iodosuccinimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution, and a uniform solution was prepared by stirring. Next, after removing bubbles in the polymerization solution with an ultrasonic device, the remaining oxygen was replaced by bubbling with nitrogen gas. This solution was subjected to a polymerization reaction at 80 ° C. for 24 hours. Thereafter, the obtained polymer was cooled to room temperature, taken out from the container, washed with acetone and methanol, and dried to obtain a porous body. As a result of confirming the structure of this porous body with a scanning electron microscope, a co-continuous structure as shown in FIG. 3 was formed.

[Example 4]
As a phase separation inducing component, 1.25 g of trimethylsiloxy-terminated polymethylsiloxane (DMS-T22, manufactured by Gelest), 12 g of mesitylene (manufactured by Nacalai Tesque) as a solvent, and divinylbenzene (Wako Pure Chemical Industries, Ltd.) as a monomer A uniform solution was prepared by stirring 10 g of a molecular weight of 130.19) manufactured by Kogyo Co., Ltd. in a screw tube bottle. Furthermore, 0.1 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.), iodine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0 as an initiator and a reversible transfer catalyst 0.05 g, 0.005 g of N-iodosuccinimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution, and a uniform solution was prepared by stirring. Next, after removing bubbles in the polymerization solution with an ultrasonic device, the remaining oxygen was replaced by bubbling with nitrogen gas. This solution was subjected to a polymerization reaction at 100 ° C. for 24 hours. Thereafter, the obtained polymer was cooled to room temperature, taken out from the container, washed with acetone and methanol, and dried to obtain a porous body. As a result of confirming the structure of the porous body with a scanning electron microscope, a co-continuous structure as shown in FIG. 4 was formed.

[Example 5]
As a phase separation inducing component, 1.6 g of polyethylene oxide (manufactured by Aldrich, average molecular weight 100,000) and 40 g of dimethylformamide (manufactured by Nacalai Tesque) as a solvent are uniformly dissolved at 60 ° C. in a screw bottle, A solution was obtained. After cooling to room temperature, 13.5 g of glycerol dimethacrylate (GDMA, manufactured by Kyoeisha Chemical Co., Ltd., GP-101P, molecular weight 227) was added as a monomer, and a uniform solution was prepared by stirring. Furthermore, as an initiator and a reversible transfer catalyst, 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.32 g, iodine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0 0.08 g and phenol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.002 g were added to the solution, and a uniform solution was prepared by stirring. Next, after removing bubbles in the polymerization solution with an ultrasonic device, the remaining oxygen was replaced by bubbling with nitrogen gas. This solution was subjected to a polymerization reaction at 60 ° C. for 24 hours. Thereafter, the obtained polymer was cooled to room temperature, taken out from the container, washed with acetone and methanol, and dried to obtain a porous body. As a result of confirming the structure of this porous body with a scanning electron microscope, a co-continuous structure as shown in FIG. 5 was formed.

[Example 6]
As a phase separation inducing component, 0.36 g of polyethylene oxide (manufactured by Aldrich, average molecular weight 100,000) and 9 g of dimethylformamide (manufactured by Nacalai Tesque) as a solvent were uniformly dissolved at 60 ° C. in a screw tube, A solution was obtained. After cooling to room temperature, 3 g of glycerol dimethacrylate (GDMA, manufactured by Kyoeisha Chemical Co., Ltd., GP-101P, molecular weight 227) was added as a monomer, and a uniform solution was prepared by stirring. Furthermore, 0.02 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.), iodine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0 as an initiator and a reversible transfer catalyst 0.02 g and phosphorus triiodide (Aldrich) 0.004 g were added to the solution, and a uniform solution was prepared by stirring. Next, after removing bubbles in the polymerization solution with an ultrasonic device, the remaining oxygen was replaced by bubbling with nitrogen gas. This solution was subjected to a polymerization reaction at 74 ° C. for 24 hours. Thereafter, the obtained polymer was cooled to room temperature, taken out from the container, washed with acetone and methanol, and dried to obtain a porous body. As a result of confirming the structure of the porous body with a scanning electron microscope, a co-continuous structure as shown in FIG. 6 was formed.

[Example 7]
As a phase separation inducing component, 0.9 g of polyethylene oxide (manufactured by Aldrich, average molecular weight 100,000) and 23 g of dimethylformamide (manufactured by Nacalai Tesque) as a solvent were uniformly dissolved at 60 ° C. in a screw tube, A solution was obtained. After cooling to room temperature, 7.6 g of glycerol dimethacrylate (GDMA, manufactured by Kyoeisha Chemical Co., Ltd., GP-101P, molecular weight 227) was added as a monomer, and a uniform solution was prepared by stirring. Furthermore, 0.02 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.), iodine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0 as an initiator and a reversible transfer catalyst 0.04 g and 0.003 g of diphenylmethane (manufactured by Aldrich) were added to the solution, and a uniform solution was prepared by stirring. Next, after removing bubbles in the polymerization solution with an ultrasonic device, the remaining oxygen was replaced by bubbling with nitrogen gas. This solution was subjected to a polymerization reaction at 100 ° C. for 24 hours. Thereafter, the obtained polymer was cooled to room temperature, taken out from the container, washed with acetone and methanol, and dried to obtain a porous body. As a result of confirming the structure of this porous body with a scanning electron microscope, a co-continuous structure as shown in FIG. 7 was formed.

[Example 8]
As a phase separation inducing component, 0.75 g of polyethylene oxide (manufactured by Aldrich, average molecular weight 100,000) and 18.6 g of dimethylformamide (manufactured by Nacalai Tesque) as a solvent are uniformly dissolved at 60 ° C. in a screw tube bottle. To give a solution. After cooling to room temperature, glycerol dimethacrylate (GDMA, manufactured by Kyoeisha Chemical Co., Ltd., GP-101P, molecular weight 227) 5 g and methyl methacrylate (MMA, Tokyo Chemical Industry Co., Ltd., molecular weight 100.12) 1.25 g as monomers Was added to the solution, and a uniform solution was prepared by stirring. Furthermore, 0.02 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.), iodine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0 as an initiator and a reversible transfer catalyst 0.04 g, 0.004 g of N-iodosuccinimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution, and a uniform solution was prepared by stirring. Next, after removing bubbles in the polymerization solution with an ultrasonic device, the remaining oxygen was replaced by bubbling with nitrogen gas. This solution was subjected to a polymerization reaction at 80 ° C. for 24 hours. Thereafter, the obtained polymer was cooled to room temperature, taken out from the container, washed with acetone and methanol, and dried to obtain a porous body. As a result of confirming the structure of this porous body with a scanning electron microscope, a co-continuous structure as shown in FIG. 8 was formed.

[Example 9]
As a solvent, 5 g of formamide (manufactured by Nacalai Tesque) and 15 g of diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) were uniformly dissolved in a screw tube to obtain a solution. As a monomer, 6.72 g of glycerol dimethacrylate (GDMA, manufactured by Kyoeisha Chemical Co., Ltd., GP-101P, molecular weight 227) was added to the solution, and a uniform solution was prepared by stirring. Furthermore, 0.02 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.), iodine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0 as an initiator and a reversible transfer catalyst 0.04 g, 0.004 g of N-iodosuccinimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution, and a uniform solution was prepared by stirring. Next, after removing bubbles in the polymerization solution with an ultrasonic device, the remaining oxygen was replaced by bubbling with nitrogen gas. This solution was subjected to a polymerization reaction at 60 ° C. for 24 hours. Thereafter, the obtained polymer was cooled to room temperature, taken out from the container, washed with acetone and methanol, and dried to obtain a porous body. As a result of confirming the structure of this porous body with a scanning electron microscope, a co-continuous structure as shown in FIG. 9 was formed.

[Comparative Example 1]
As a phase separation inducing component, 0.3 g of polyethylene oxide (manufactured by Aldrich, average molecular weight 100,000) and 3 g of dimethylformamide (manufactured by Nacalai Tesque) as a solvent are uniformly dissolved at 60 ° C. in a screw bottle, A solution was obtained. After cooling to room temperature, 3 g of glycerol dimethacrylate (GDMA, manufactured by Kyoeisha Chemical Co., Ltd., GP-101P, molecular weight 227) was added as a monomer, and a uniform solution was prepared by stirring. Further, 0.1 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the solution as an initiator, and a uniform solution was prepared by stirring. Next, after removing bubbles in the polymerization solution with an ultrasonic device, the remaining oxygen was replaced by bubbling with nitrogen gas. This solution was subjected to a polymerization reaction at 60 ° C. for 24 hours. Thereafter, the obtained polymer was cooled to room temperature, taken out from the container, washed with acetone and methanol, and dried to obtain a porous body. As a result of confirming the structure of this porous body with a scanning electron microscope, a particle aggregation type structure as shown in FIG. 10 is formed, and a polymer lump having no pores is formed. doing.

  Table 1 shows a list of the preparation conditions of Examples 1 to 9 and Comparative Example 1 and the results of structure confirmation by an electron microscope.

* 1 GDMA is an abbreviation for glycerol dimethacrylate.
* 2. ADVN is an abbreviation for 2,2'-azobis (2,4-dimethylvaleronitrile).
* 3. DMS-T22 is an abbreviation for trimethylsiloxy-terminated polymethylsiloxane.

[Example 10]
As a phase separation inducing component, 0.63 g of trimethylsiloxy-terminated polymethylsiloxane (DMS-T22, manufactured by Gelest), 6 g of mesitylene (manufactured by Nacalai Tesque) as a solvent, and divinylbenzene (Wako Pure Chemical Industries, Ltd.) as a monomer Co., Ltd., molecular weight 130.19) 5 g was stirred in a screw tube bottle to prepare a uniform solution. Furthermore, 0.05 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.), iodine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0 as an initiator and a reversible transfer catalyst 0.003 g, 0.003 g of N-iodosuccinimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution, and a uniform solution was prepared by stirring. Next, after removing bubbles in the polymerization solution with an ultrasonic device, the remaining oxygen was replaced by bubbling with nitrogen gas. This solution was sent to the capillary using gas pressure, and a polymerization reaction was carried out at 85 ° C. for 24 hours. Thereafter, the capillary was cooled to room temperature and washed with methanol and acetonitrile to obtain a capillary column.

[Example 11]
As a phase separation inducing component, 0.7 g of polyethylene oxide (manufactured by Aldrich, average molecular weight 100,000) and 18 g of dimethylformamide (manufactured by Nacalai Tesque) as a solvent are uniformly dissolved at 60 ° C. in a screw tube, A solution was obtained. After cooling to room temperature, 3.36 g of glycerol dimethacrylate (GDMA, manufactured by Kyoeisha Chemical Co., Ltd., GP-101P, molecular weight 227) and 3.36 g of dipentaerythritol hexaacrylate (DPHA, manufactured by Shin-Nakamura Chemical Co., Ltd.) are used as a monomer. And a homogeneous solution was prepared by stirring. Furthermore, 0.02 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.), iodine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0 as an initiator and a reversible transfer catalyst 0.035 g, N-iodosuccinimide (Tokyo Chemical Industry Co., Ltd.) 0.004 g was added to the solution, and a uniform solution was prepared by stirring. Next, after removing bubbles in the polymerization solution with an ultrasonic device, the remaining oxygen was replaced by bubbling with nitrogen gas. This solution was sent to the capillary using gas pressure, and a polymerization reaction was carried out at 85 ° C. for 24 hours. Thereafter, the capillary was cooled to room temperature and washed with methanol and acetonitrile to obtain a capillary column.

[Comparative Example 2]
As a phase separation inducing component, 1.15 g of trimethylsiloxy-terminated polymethylsiloxane (DMS-T22, manufactured by Gelest), 14 g of mesitylene (manufactured by Nacalai Tesque) as a solvent, and divinylbenzene (Wako Pure Chemical Industries, Ltd.) as a monomer A uniform solution was prepared by stirring 10 g of a molecular weight of 130.19) manufactured by Kogyo Co., Ltd. in a screw tube bottle. Furthermore, 0.1 g of benzoyl peroxide (manufactured by Nacalai Tesque) as an initiator and 0.1 g of 2,2,6,6-tetramethyl-1-piperidinyloxy (manufactured by Tokyo Chemical Industry Co., Ltd.) as a stabilizing radical Then, 0.05 ml of acetic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution, and a uniform solution was prepared by stirring. Next, after removing bubbles in the polymerization solution with an ultrasonic device, the remaining oxygen was replaced by bubbling with nitrogen gas. This solution was fed to the capillary using gas pressure, heated to 95 ° C. for about 90 minutes, and then heated to 125 ° C. for 24 hours to conduct a polymerization reaction. Thereafter, the capillary was cooled to room temperature and washed with methanol and acetonitrile to obtain a capillary column.

[Example 12]
The capillary columns obtained in Examples 10 and 11 and Comparative Example 2 were evaluated for performance as chromatography columns. Reverse phase chromatography was performed under mobile phase conditions of acetonitrile / water = 60/40 (v / v) to separate samples of uracil and alkylbenzene (n = 0-6). The elution order is uracil, benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, amylbenzene, and hexylbenzene, and all capillary column lengths are 250 mm. The obtained separation chromatograms are shown in FIG. 11, FIG. 12, and FIG.

FIG. 11 shows evaluation data of the capillary column of Example 10 under conditions of a column linear velocity of 0.87 mm / s and a column load pressure of 2.9 MPa.
FIG. 12 shows evaluation data of the capillary column of Example 11 under conditions of a column linear velocity of 0.91 mm / s and a column load pressure of 10.0 MPa.
FIG. 13 shows evaluation data of the capillary column of Comparative Example 2 under conditions of a column linear velocity of 3.5 mm / s and a column load pressure of 2.0 MPa.

  The capillary column of Example 10 in FIG. 11 had a narrower peak width (higher number of theoretical plates) than that of Comparative Example 2 in FIG. 13, and a chromatogram having good peak symmetry could be obtained. Although the detailed reason has been described above, it can be said that the monolith type porous body of the present invention is a porous body with small diffusion of solute and is useful as a separation analysis medium for chromatography. Further, by selecting the monomer composition as obtained from the monolith type porous body of Example 11 shown in FIG. 12, it is possible to prepare a chromatography column having different retention even with the same solute.

[Example 13]
A monolithic porous material obtained under the same conditions as in Example 11 was subjected to normal phase chromatography under a mobile phase condition of hexane / 2-propanol = 98/2 (v / v), and samples of toluene, dinitrotoluene and dinitrobenzene Separated. The elution order is toluene, dinitrotoluene, and dinitrobenzene. The obtained separation chromatogram is shown in FIG. The monolith type porous body obtained in Example 11 is a monolith type porous body having glycerol dimethacrylate and dipentaerythritol hexaacrylate as monomers and having a relatively low surface functional group hydrophobicity (in contrast, a highly hydrophilic surface functional group). Therefore, it is possible to separate a highly polar solute under normal phase conditions.

[Example 14]
In order to compare the residual iodine ratio, the monolithic porous material prepared by the same preparation method as in Example 3 was washed with acetone and methanol, and then washed for half a day with a mixed solvent of THF and acetone at 50 ° C. Further, another washing was performed under the same conditions. Next, acetone was used as a solvent, and drying was performed at 100 ° C. for 2 days.

[Example 15]
In order to conduct a comparative examination of the residual iodine ratio, the monolithic porous material prepared by the same preparation method as in Example 3 was washed with acetone and methanol, and then half day at 50 ° C. with a 0.1N aqueous sodium hydroxide solution. Washing was carried out, and washing was performed again under the same conditions. Next, acetone was used as a solvent, and drying was performed at 100 ° C. for 2 days.

[Example 16]
The residual iodine content of the monolithic porous material obtained in Example 3 was compared with the iodine content containing the residual iodine content of the monolithic porous material obtained in Examples 14 and 15 by elemental analysis measurement. . The obtained results are shown in Table 2.

  From the obtained results, it is possible to remove the residual iodine of the monolith type porous body by using a mixed solvent of THF and acetone and an aqueous sodium hydroxide solution, and drying by applying heat rather than normal drying at the time of drying. there were.

It is the photograph which expanded the porous body obtained in Example 1 5000 times with the scanning electron microscope. It is the photograph which expanded the porous body obtained in Example 2 5000 times with the scanning electron microscope. It is the photograph which expanded the porous body obtained in Example 3 2000 times with the scanning electron microscope. It is the photograph which expanded the porous body obtained in Example 4 2000 times with the scanning electron microscope. It is the photograph which expanded the porous body obtained in Example 5 2000 times with the scanning electron microscope. It is the photograph which expanded the porous body obtained in Example 6 5000 times with the scanning electron microscope. It is the photograph which expanded the porous body obtained in Example 7 5000 times with the scanning electron microscope. It is the photograph which expanded the porous body obtained in Example 8 5000 times with the scanning electron microscope. It is the photograph which expanded the porous body obtained in Example 9 2000 times with the scanning electron microscope. It is the photograph which expanded the porous body obtained by the comparative example 1 10,000 times with the scanning electron microscope. 10 is a diagram showing a separation chromatogram obtained by evaluating the capillary column obtained in Example 10 under the conditions of Example 12. FIG. 10 is a diagram showing a separation chromatogram obtained by evaluating the capillary column obtained in Example 11 under the conditions of Example 12. FIG. 10 is a diagram showing a separation chromatogram obtained by evaluating the capillary column obtained in Comparative Example 2 under the conditions of Example 12. FIG. 14 is a diagram showing a separation chromatogram obtained by evaluating a monolith type porous body obtained under the same conditions as in Example 11 under the conditions in Example 13. FIG.

Claims (9)

  A method for producing a porous body characterized by having a three-dimensional network structure skeleton consisting of polymerization of an organic low molecular weight compound, at least one of which is a polyfunctional compound, and having a living radical polymerizability The reversible transfer catalyst, which is carried out under a system containing a transfer catalyst, a polymerization initiator and a polymerization solvent and has the living radical polymerizability, has at least one central element selected from phosphorus, nitrogen, oxygen and carbon atoms, A method for producing a porous body, comprising at least one halogen atom bonded to an element.   A method for producing a porous body characterized by having a three-dimensional network structure skeleton consisting of polymerization of an organic low molecular weight compound, at least one of which is a polyfunctional compound, and having a living radical polymerizability The reversible transfer catalyst having a living radical polymerization property is generated under a system including a transfer catalyst, a polymerization initiator and a polymerization solvent, and can react with radicals generated from the radical initiator to generate activated radicals. A method for producing a porous body comprising a catalyst precursor compound having carbon or oxygen as a central element. 3. The method for producing a porous body according to claim 1 or 2 , wherein the organic low-molecular compound is polymerized by containing an organic polymer as a phase separation inducer. The method for producing a porous body according to any one of claims 1 to 3 , wherein the halogen bonded to the central element of the reversible transfer catalyst for living radical polymerization is iodine. The porous body according to any one of claims 1 to 4 , wherein an organic halide having a carbon-halogen bond is used as a protective group used simultaneously with the reversible transfer catalyst having a living radical polymerizability. Manufacturing method. 6. The method for producing a porous body according to claim 5 , wherein the halogen of the organic halide used as the protective group is iodine. By mixing the azo radical initiator and a halogen molecule in a reaction solution, according to claim 1 to 6 by decomposing the azo-type radical initiator in the reaction solution, characterized in that it comprises a step of producing an organic halide The manufacturing method of the porous body of any one of these. The method for producing a porous body according to any one of claims 1 to 7 , wherein a polymerization temperature for performing living radical polymerization is 20 to 100 ° C. The method for producing a porous body according to any one of claims 1 to 8 , wherein the porous body is prepared and then used as a reversible transfer catalyst having a living radical polymerization property or a halogen of an organic halide. Is removed from the porous body by sublimation, decomposition or extraction.