JP2008212765A - Transition metal-immobilized reactor and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transition metal-immobilized reactor which has a sufficient amount of immobilized catalyst and is excellent in the repeated use stability, and to provide a manufacturing method of the transition metal-immobilized reactor capable of performing the preparation with a convenient operation without a long-time reaction or a high-temperature reaction. <P>SOLUTION: The transition metal-immobilized reactor has a tubular flow path and has at least a part of wall surface forming the flow path which is formed with an organic porous polymer layer having transition metal compound immobilized on the surface, wherein the organic porous polymer layer contains a polymer of a compound represented by formula 1: (CH<SB>2</SB>=CHC<SB>6</SB>H<SB>4</SB>PR<SB>1</SB>R<SB>2</SB>)<SB>2</SB>ML<SB>1</SB>L<SB>2</SB>(1) or formula 2: [CH<SB>2</SB>=CHC<SB>6</SB>H<SB>4</SB>PR<SB>3</SB>-(CH<SB>2</SB>)-<SB>n</SB>PR<SB>3</SB>C<SB>6</SB>H<SB>4</SB>CH=CH<SB>2</SB>]ML<SB>3</SB>L<SB>4</SB>(2). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a reactor having a fine channel for performing a predetermined chemical reaction with a small amount of sample, and a method for producing the same.

  Chemical reactions with catalysts containing palladium, platinum or rhodium are recognized as the most important catalytic reactions in today's organic synthesis, as represented by carbon-carbon coupling reactions. In the reaction system using these transition metal catalysts, the transition metal catalyst is usually used as a homogeneous catalyst in which the reaction solution is dissolved. However, since these transition metal catalysts are generally expensive, repeated use is required. In a homogeneous catalyst, the catalyst is dissolved in the reaction solution, so that it is not easy to separate and recover the catalyst after the reaction from the solution. Therefore, use of a heterogeneous catalyst in which a transition metal catalyst is immobilized in an insoluble solid has been studied.

  One form of transition metal catalyst immobilized on an insoluble solid is a reactor having a fine tubular channel. Such a reactor has a microtubular channel having a length of about several centimeters and a width and depth of several tens of nanometers to several hundreds of micrometers on a substrate plate having a size of several centimeters. When a reaction solution is introduced into the microchannel of such a reactor, the diffusion of the molecules due to the effect of the large specific surface area of the microchannel and the short intermolecular distance makes it efficient without special stirring operations. It is possible to perform a good chemical reaction. Moreover, since the diffusion time is proportional to the square of the width of the fine channel, it is known that the smaller the width of the fine channel, the more efficiently the mixing by diffusion proceeds and the reaction easily occurs. A reactor having such a fine tubular channel has the advantage that the reaction speed is faster because the width of the channel can be made smaller than a flow reactor using a microtube.

  Non-Patent Document 1 reports an example in which a polymerized palladium catalyst is immobilized on the wall surface of a fine channel in a glass plate and applied to a hydrogenation reaction. However, in this method, the operation for immobilizing the catalyst is complicated and the amount of the catalyst immobilized is not necessarily large because the catalyst is immobilized on the smooth glass surface having a small specific surface area.

  In Non-Patent Document 2, a polymer complex film containing a palladium catalyst is formed by an interfacial reaction at an organic layer / aqueous laminar flow interface in a fine channel in a glass plate and applied to a carbon-carbon coupling reaction. An example has been reported. However, the polymer complex film formed by this method is formed in the vicinity of the center of the fine channel in the form of being fixed to the wall on its two sides, and there is a concern about its use stability. Absent.

  On the other hand, the present inventors have disclosed a method of introducing a porous polymer layer having a large non-surface area into the bottom surface of a fine channel made of an organic polymer in Patent Document 1 and Patent Document 2. Patent Documents 3 and 4 disclose a method for introducing a functional group into the surface of a fine channel made of an organic polymer.

Japanese Unexamined Patent Publication No. 2000-2705 JP 2004-271430 A JP 2003-136640 A JP 2005-91135 A J. Kobayashi et al., Science, 2004, 304, 1305-1308. Y. Uozumi et al. J. Am. Chem. Soc., 2006, 128, 15994-15995.

  The problem to be solved by the present invention is a transition metal-immobilized reactor having a large amount of catalyst fixed and excellent in repeated use stability, and prepared by a simple operation without performing a long-time reaction or a high-temperature reaction. An object of the present invention is to provide a method for producing a transition metal-immobilized reactor.

  As a result of intensive studies, the present inventors have formed an organic porous polymer layer having a tubular fine channel and at least a part of the wall surface forming the channel having a transition metal compound fixed on the surface. It was found that a transition metal immobilization reactor having a large amount of catalyst immobilization and excellent in repeated use stability can be easily produced by using the existing reactor.

That is, the present invention is a reactor having a tubular channel, and at least a part of a wall surface forming the channel is formed of an organic porous polymer layer having a transition metal compound fixed on the surface. ,
The organic porous polymer layer has the formula 1

（式中、Ｍはパラジウム、白金またはロジウム原子、Ｒ_１及びＲ_２は置換基を有していてもよいアリール基または炭素数１〜１８のアルキル基、Ｌ_１及びＬ_２は配位子基を表す。）
または式２

(In the formula, M is a palladium, platinum or rhodium atom, R ₁ and R ₂ are aryl groups which may have a substituent or an alkyl group having 1 to 18 carbon atoms, and L ₁ and L ₂ are ligand groups. Represents.)
Or Equation 2

（式中、Ｍはパラジウム、白金またはロジウム原子、ｎは１〜１２の整数、Ｒ_３は置換基を有していてもよいアリール基または炭素数１〜１８のアルキル基、Ｌ_３及びＬ_４は配位子基を表す。）で表される化合物の重合体を含む多孔質ポリマー層であることを特徴とする遷移金属固定化リアクターを提供するものである。

(In the formula, M is a palladium, platinum or rhodium atom, n is an integer of 1 to 12, R ₃ is an aryl group which may have a substituent or an alkyl group having 1 to 18 carbon atoms, L ₃ and L _4. Is a porous polymer layer containing a polymer of a compound represented by the formula (1): a transition metal-immobilized reactor.

The present invention also provides a method for producing the above transition metal-immobilized reactor,
(1) The active energy ray-polymerizable composition (a) containing the compound represented by Formula 1 or Formula 2 and the active energy ray-polymerizable composition (a) are compatible with each other on the surface of the support. However, an organic porous polymer layer forming composition (X) mixed with a solvent (M) that does not dissolve or swell the polymer of the active energy ray polymerizable composition (a) is applied to form a coating film. ,
Step 1 of forming the organic porous polymer layer by polymerizing the active energy ray-polymerizable composition (a) by irradiating the coating film with active energy rays and then removing the solvent (M). ,
(2) The active energy ray-curable composition (Y) is coated on the organic porous polymer layer to form an uncured coating film of the composition (Y), and other than the portion that should become the flow path Irradiating active energy rays to the uncured coating film to form a cured or semi-cured coating film of the composition (Y), removing the uncured composition (Y) in the non-irradiated part, Step 2 in which the organic porous polymer layer forms a recess exposed on the bottom surface, and
(3) Step 3 of fixing the other member serving as a lid to the concave portion of the member having the concave portion to make the concave portion a hollow flow path.
The present invention provides a method for producing a transition metal-immobilized reactor characterized by comprising:

In the present invention, the transition metal compound is immobilized by utilizing the surface of the organic porous polymer layer having a large specific surface area, which constitutes a part of the tubular microchannel, so that the amount of the transition metal compound immobilized can be increased. Therefore, it is possible to provide a transition metal-immobilized reactor excellent in use stability. Further, since the transition metal compound is immobilized simultaneously with the formation of the organic porous polymer layer using the polymerizable transition metal compound, the transition metal immobilization reactor can be produced by a simple operation.

Hereafter, the principal part for implementing this invention is demonstrated.
[Shape and structure of transition metal immobilization reactor]
The transition metal-immobilized reactor of the present invention has a fine tubular channel inside thereof, and performs reaction, chemical engineering treatment, detection, and the like in the channel. The outer shape need not be particularly limited. For example, it may be a sheet shape (including film shape, ribbon shape, etc., the same applies below), plate shape, coating film shape, rod shape, tube shape, and other complicated shapes, but is easy to manufacture and easy to use. In view of this, it is preferably in the form of a sheet or plate.
The cross-sectional shape of the flow path provided inside the transition metal-immobilized reactor is arbitrary, for example, rectangular, trapezoidal, circular, semicircular, slit-like (rectangular and other cornered shapes have rounded corners) Including the shape, and so on).

  The size of the channel is arbitrary, but the depth (the inner dimension of the channel in the direction perpendicular to the surface closest to the channel of the reactor is the depth) is, for example, 1 to 300 μm, preferably 2 It is -150 micrometers, More preferably, it is 5-100 micrometers. In this range, the merit as a fine flow path and the effect of the present invention can be sufficiently exhibited. The width of the flow path is arbitrary, and may be, for example, 1 μm to the width of the entire reactor.

  The transition metal-immobilized reactor of the present invention forms a bottom member of a flow channel, a wall member that forms a side wall of the flow channel, a lid of the flow channel, and forms a ceiling of the flow channel And at least a part of the channel wall surface formed from these members is formed of an organic porous polymer layer having a transition metal compound fixed on the surface thereof. The organic porous polymer layer has the formula 1 or formula 2

（式中、Ｍはパラジウム、白金またはロジウム原子、Ｒ_１及びＲ_２は置換基を有していてもよいアリール基または炭素数１〜１８のアルキル基、Ｌ_１及びＬ_２は配位子基を表す。）

(In the formula, M is a palladium, platinum or rhodium atom, R ₁ and R ₂ are aryl groups which may have a substituent or an alkyl group having 1 to 18 carbon atoms, and L ₁ and L ₂ are ligand groups. Represents.)

（式中、Ｍはパラジウム、白金またはロジウム原子、ｎは１〜１２の整数、Ｒ_３は置換基を有していてもよいアリール基または炭素数１〜１８のアルキル基、Ｌ_３及びＬ_４は配位子基を表す。）で表される化合物を含有する活性エネルギー線重合性組成物の硬化層である。

(In the formula, M is a palladium, platinum or rhodium atom, n is an integer of 1 to 12, R ₃ is an aryl group which may have a substituent or an alkyl group having 1 to 18 carbon atoms, L ₃ and L _4. Is a cured layer of an active energy ray-polymerizable composition containing a compound represented by:

  The porous shape of the organic porous polymer layer is preferably an aggregated particle shape or a network shape, and the average pore size is in the range of 0.1 to 10 μm. The thickness of the organic porous polymer layer is preferably in the range of 1 to 100 μm, particularly preferably in the range of 3 to 50 μm. When the thickness of the organic porous polymer layer is less than 1 μm, it is not preferable because the performance as a reactor tends to be lowered. In addition, the thickness of the organic porous polymer layer can be measured by microscopic observation of the cross section using a scanning electron microscope.

R ₁ , R ₂ , and R ₃ of the transition metal compound represented by Formula 1 or Formula 2 may be a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group as an aryl group that may have a substituent. A group is available. These substituents include linear alkyl groups having 1 to 12 carbon atoms; branched alkyl groups such as sec-propyl group, tert-butyl group and 2-ethylhexyl group; unsaturated groups such as ethenyl group and propenyl group Alkyl groups; alkoxy groups such as methoxy groups and tert-butoxy groups; alkylthio groups such as methylthio groups and ethylthio groups; halogen atoms such as fluorine atoms and chlorine atoms. The position and number of substituents on the aryl group are not particularly limited. Examples of R ₁ , R ₂ , and R ₃ include alkyl groups having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a sec-propyl group, a tert-butyl group, a hexyl group, a dodecyl group, and an octadecyl group. be able to.

L ₁ , L ₂ , L ₃ and L _{4 in} Formula 1 and Formula 2 are arbitrary ligand groups. Examples of the ligand group include halogen atoms such as chlorine atom and bromine atom; aryloxy groups such as phenoxy group, naphthoxy group and anthryloxy group; amines such as diethylamine and ethylenediamine; triphenylphosphine, tolylphosphine and diethyl Examples include phosphines such as phenylphosphine and tributylphosphine, acetylacetone derivatives, phosphoric acids, carbonates, and carbonyl ligands. In addition, 1,2-biphenoxy group, 1,1′-bi-2,2′-naphthoxy group, 1,1′-binaphthyl-2,2′-diamine, 2,2′-bis (diphenylphosphino)- Chelate ligands such as 1,1′-binaphthyl, cyclooctadiene, norbornadiene can also be used. In the catalytic reaction using the transition metal-immobilized reactor of the present invention, these ligands can provide reaction sites by being replaced with reaction substrates.

[Production method of transition metal immobilization reactor]
The method for producing a transition metal-immobilized reactor of the present invention comprises (1) an active energy ray-polymerizable composition (a) containing a compound represented by the above formula 1 or formula 2 on the surface of a support, and the activity For forming an organic porous polymer layer mixed with a solvent (M) that is compatible with the energy beam polymerizable composition (a) but does not dissolve or swell the polymer of the active energy beam polymerizable composition (a) The composition (X) is applied to form a coating film, and the coating film is irradiated with active energy rays to polymerize the active energy ray polymerizable composition (a), and then the solvent (M) Step 1 for forming an organic porous polymer layer by removing (2) an active energy ray-curable composition (Y) is coated on the organic porous polymer layer, and the composition (Y) After forming the uncured coating film of the Irradiating active energy rays to the uncured coating film to form a cured or semi-cured coating film of the composition (Y), removing the uncured composition (Y) in the non-irradiated part, Step 2 of forming the concave portion where the organic porous polymer layer is exposed on the bottom surface, and (3) fixing another member serving as a lid to the concave portion of the member having the concave portion to form the concave portion as a hollow flow path. A method having step 3.

  In step 1, the polymer produced by the polymerization of the active energy ray-polymerizable composition (a) becomes incompatible with the solvent (M), and the polymer and the solvent (M) undergo phase separation, and the polymer interior Or the solvent (M) is taken in between the polymers. By removing this solvent (M), the region occupied by the solvent (M) becomes pores, and an organic porous polymer layer can be formed.

  The active energy ray polymerizable composition (a) contains a polymerizable compound represented by the above formula 1 or 2 and another polymerizable compound capable of forming a copolymer with the polymerizable compound. As the polymerizable compound represented by Formula 1 or Formula 2, the above exemplified polymerizable compounds and the like can be used.

  The other polymerizable compound that can form a copolymer with the polymerizable compound represented by the above formula 1 or 2 is one that is polymerized by active energy rays in the presence or absence of a polymerization initiator, Addition-polymerizable compounds and those having a polymerizable carbon-carbon double bond as the active energy ray-polymerizable functional group are preferred. Among them, highly reactive (meth) acrylic compounds, vinyl ethers, and photopolymerization are preferred. Maleimide compounds that cure even in the absence of an initiator are preferred. Furthermore, since it is possible to increase the shape retention in a semi-cured state and to increase the strength after curing, it is preferably a compound that forms a crosslinked polymer by polymerization. Therefore, a compound having two or more polymerizable carbon-carbon double bonds in one molecule (hereinafter referred to as “having two or more addition polymerizable functional groups in one molecule” is “polyfunctional”. More preferably).

  Examples of such a polymerizable compound include a (meth) acrylic monomer, a maleimide monomer, or a polymerizable oligomer (also referred to as a prepolymer) having a (meth) acryloyl group or a maleimide group in the molecular chain. Can be used. Examples of the (meth) acrylic monomer include diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 2,2′-bis (4- (meth) ) Acryloyloxypolyethyleneoxyphenyl) propane, 2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane, hydroxydipivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl diacrylate, bis Bifunctional monomers such as (acryloxyethyl) hydroxyethyl isocyanurate and N-methylenebisacrylamide; trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tris Acryloxy) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate and other trifunctional monomers; pentaerythritol tetra (meth) acrylate and other tetrafunctional monomers; dipentaerythritol hexa (meth) acrylate and other functional monomers Can be mentioned.

  Examples of maleimide monomers include 4,4′-methylenebis (N-phenylmaleimide), 2,3-bis (2,4,5-trimethyl-3-thienyl) maleimide, 1,2-bismaleimide ethane, 1 , 6-bismaleimide hexane, triethylene glycol bismaleimide, N, N'-m-phenylene dimaleimide, m-tolylene dimaleimide, N, N'-1,4-phenylene dimaleimide, N, N'-diphenylmethane di Maleimide, N, N′-diphenyl ether dimaleimide, N, N′-diphenylsulfone dimaleimide, 1,4-bis (maleimidoethyl) -1,4-diazoniabicyclo- [2,2,2] octane dichloride, 4 , 4'-isopropylidenediphenyl dicyanate N, N '-(methylenedi-p-phenyle ) Bifunctional maleimides such as dimaleimide; N-(9-acridinyl) maleimide having a polymerizable functional group other than the maleimide group and a maleimide group such as maleimide. These maleimide monomers can be copolymerized with a compound having a polymerizable carbon / carbon double bond, such as vinyl monomers, vinyl ethers, and acrylic monomers.

  Examples of the polymerizable oligomer having a (meth) acryloyl group or a maleimide group in the molecular chain include those having a mass average molecular weight of 500 to 50,000. For example, (meth) acrylic acid ester of an epoxy resin, polyether resin (Meth) acrylic acid ester, polybutadiene resin (meth) acrylic acid ester, polyurethane resin having a (meth) acryloyl group at the molecular end, and the like.

  These polymerizable compounds can be used alone or in admixture of two or more. Also, mixed with monofunctional monomers such as monofunctional (meth) acrylic monomers and monofunctional maleimide monomers for the purpose of adjusting viscosity, or adjusting adhesiveness and adhesiveness in a semi-cured state. May be.

  Monofunctional (meth) acrylic monomers include, for example, methyl (meth) acrylate, alkyl (meth) acrylate, isobornyl (meth) acrylate, alkoxy polyethylene glycol (meth) acrylate, phenoxydialkyl (meth) acrylate, phenoxy polyethylene glycol ( (Meth) acrylate, alkylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol acrylate methacrylate, butanediol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate 2-acryloyloxyethyl-2-hydroxypropyl acrylate, ethylene oxide Id-modified phthalic acid acrylate, w-carboxycaprolactone monoacrylate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxyethyl succinic acid, acrylic acid dimer, 2-acryloyloxypropyl hexahydrohydrogen phthalate, fluorine-substituted alkyl (meta ) Acrylate, chlorine-substituted alkyl (meth) acrylate, soda ethoxy (meth) acrylate sulfonate, sulfonic acid-2-methylpropane-2-acrylamide, phosphate group-containing (meth) acrylate, glycidyl (meth) acrylate, 2-isocyanate Natoethyl (meth) acrylate, (meth) acryloyl chloride, (meth) acrylaldehyde, sulfonic acid ester group-containing (meth) acrylate, silano group Existence (meth) acrylate, ((di) alkyl) amino group-containing (meth) acrylate, quaternary ((di) alkyl) ammonium group-containing (meth) acrylate, (N-alkyl) acrylamide, (N, N-dialkyl) Examples include acrylamide and acryloylmorpholine.

  Examples of monofunctional maleimide monomers include N-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide and N-dodecylmaleimide; N-alicyclic maleimides such as N-cyclohexylmaleimide; N -Benzylmaleimide; N-phenylmaleimide, N- (alkylphenyl) maleimide, N-dialkoxyphenylmaleimide, N- (2-chlorophenyl) maleimide, 2,3-dichloro-N- (2,6-diethylphenyl) maleimide N- (substituted or unsubstituted phenyl) maleimide such as 2,3-dichloro-N- (2-ethyl-6-methylphenyl) maleimide; N-benzyl-2,3-dichloromaleimide, N- (4′- Halogens such as fluorophenyl) -2,3-dichloromaleimide Maleimide having a hydroxyl group such as hydroxyphenylmaleimide; maleimide having a carboxy group such as N- (4-carboxy-3-hydroxyphenyl) maleimide; maleimide having an alkoxy group such as N-methoxyphenylmaleimide; N- [ Maleimides having amino groups such as 3- (diethylamino) propyl] maleimide; polycyclic aromatic maleimides such as N- (1-pyrenyl) maleimide; N- (dimethylamino-4-methyl-3-coumarinyl) maleimide, N- And maleimide having a heterocyclic ring such as (4-anilino-1-naphthyl) maleimide.

  As the solvent (M), a solvent that is compatible with the active energy ray polymerizable composition (a) but does not dissolve or swell the polymer of the active energy ray polymerizable composition (a) is used. The degree of compatibility between the solvent (M) and the active energy ray-polymerizable composition (a) may be such that a uniform composition (X) for forming an organic porous polymer layer is obtained. The solvent (M) may be a single solvent or a mixed solvent. In the case of a mixed solvent, the component alone is not compatible with the active energy ray polymerizable composition (a), The polymer of the active energy ray polymerizable composition (a) may be dissolved. Examples of such a solvent (M) include alkyl esters of fatty acids such as methyl decanoate, methyl laurate and diisobutyl adipate; ketones such as diisobutyl ketone; N, N-dimethylformamide, N, N-dimethyl Aprotic polar solvents such as acetamide, dimethyl sulfoxide and N-methylpyrrolidone; alcohols such as decanol; solvents having a high vapor pressure at room temperature such as a mixture of alcohol and water such as a mixture of 2-propanol and water Can be mentioned.

  In step 1, the pore diameter and strength of the obtained organic porous polymer layer vary depending on the content of the active energy ray polymerizable composition (a) contained in the organic porous polymer layer forming composition (X). As the content of the active energy ray polymerizable composition (a) is increased, the strength of the organic porous polymer layer is improved, but the pore diameter tends to be reduced. The preferable content of the active energy ray polymerizable composition (a) is in the range of 15 to 50% by mass, more preferably in the range of 25 to 40% by mass. When the content of the active energy ray polymerizable composition (a) is 15% by mass or less, the strength of the organic porous polymer layer is lowered, and the content of the active energy ray polymerizable composition (a) is 50% by mass or more. Then, it becomes difficult to adjust the pore diameter of the porous portion.

  The organic porous polymer layer forming composition (Z) includes a polymerization initiator, a polymerization inhibitor, a polymerization retarder, a solvent, or a soluble polymer for adjusting the polymerization rate, polymerization degree, pore size distribution, and the like. Various additives such as may be added.

  The photopolymerization initiator is not particularly limited as long as it is active with respect to active energy rays and can polymerize the active energy ray polymerizable composition (a). Polymerization initiators, cationic polymerization initiators and the like can be used, such as p-tert-butyltrichloroacetophenone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc. Acetophenones; ketones such as benzophenone, 4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone; benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin Isobutyl Benzoin ethers such as ether; and the azide such as N- azide sulfonyl phenyl maleimide; benzyl dimethyl ketal, benzil ketals, such as hydroxycyclohexyl phenyl ketone. A polymerizable photopolymerization initiator such as a maleimide compound can also be used.

  Polymerization retarders and polymerization inhibitors include α-methylstyrene, 2,4-diphenyl-4-methyl-1-pentene and other active energy ray polymerizable compounds such as vinyl monomers having a low polymerization rate; tert-butylphenol, etc. Hindantophenols and the like.

The solvent to be added is not particularly limited, and examples thereof include alcohols such as methanol and ethanol, ketones such as acetone, and chlorinated solvents such as methylene chloride.
The soluble polymer can be used without limitation as long as it gives a uniform composition as the organic porous polymer layer forming composition (Z) and is soluble in the solvent (M) alone. By being soluble in the solvent (M), it can be easily removed from the cured coating film by a washing operation after the composition (Z) is cured.

  In addition, for the purpose of imparting functions such as coatability, smoothness, and hydrophilicity, known and commonly used surfactants, hydrophobic compounds, thickeners, modifiers, colorants, fluorescent dyes, ultraviolet absorbers, enzymes, Proteins, cells, catalysts, etc. can also be added.

  The support that can be used in this method is not substantially affected by the organic porous polymer layer forming composition (X) or the active energy ray used, and does not cause dissolution, decomposition, polymerization, or the like. Any material that does not substantially invade the porous polymer layer forming composition (X) may be used. Examples of such a support include polymers, crystals such as glass and quartz, ceramics, semiconductors such as silicon, metals, and the like. Among these, they are highly transparent and inexpensive. More preferred are polymers or glass. The polymer used for the support may be a homopolymer or a copolymer, and may be a thermoplastic polymer or a thermosetting polymer. The support may be composed of a polymer blend or a polymer alloy, or may be a laminate or other complex. Further, the support may contain additives such as a modifier, a colorant, a filler, and a reinforcing material.

  The shape of the support is not particularly limited, and an arbitrary shape can be used according to the purpose of use. For example, sheet-like (including film-like, ribbon-like, and belt-like), plate-like, roll-like, and spherical shapes can be mentioned, and an organic porous polymer layer forming composition (X) is applied thereon. From the viewpoint of easy and active energy ray irradiation, it is preferable that the coated surface has a planar shape or a quadric surface shape.

  The support may be surface-treated both in the case of a polymer and other materials. The surface treatment is for the purpose of preventing dissolution of the support by the organic porous polymer layer forming composition (X), improving the wettability of the organic porous polymer layer forming composition (X), and the organic porous polymer layer. And the like for the purpose of improving the adhesion.

  The surface treatment method of the support is arbitrary. For example, the active energy ray polymerizable composition (a) is applied to the surface of the support and is cured by irradiation with active energy rays, corona treatment, plasma treatment, Flame treatment, acid or alkali treatment, sulfonation treatment, fluorination treatment, primer treatment with silane coupling agent, surface graft polymerization, application of surfactant or release agent, physical treatment such as rubbing or sandblasting, etc. Can be mentioned. Moreover, the method of reacting with the reactive functional group which the raw material of an organic porous polymer layer has and the reactive functional group introduce | transduced by said surface treatment method reacts with the compound fixed on the surface is mentioned. Among these, when glass or quartz is used as the support, for example, a method of treating with a silane coupling agent such as trimethoxysilylpropyl (meth) acrylate or triethoxysilylpropyl (meth) acrylate is used as these. Since the polymerizable group of the silane coupling agent can be copolymerized with the organic porous polymer layer forming composition (X), it is useful for improving the adhesion of the organic porous polymer layer on the support.

  The method for applying the organic porous polymer layer forming composition (X) used in Step 1 to the support may be any known method, for example, a coating method using a coater or spray. .

  According to the method of Step 1, the polymer particles having a diameter of about 0.1 μm to 1 μm aggregate together, and a porous polymer layer having an aggregated particle structure in which gaps between the particles become pores, or the polymer is a network A porous polymer layer having a three-dimensional network structure can be formed.

  In step 2, the active energy ray-curable composition (Y) is applied on the organic porous polymer layer formed in step 1, so that the organic porous polymer layer is impregnated with the composition (Y). In this form, an uncured coating film of the composition (Y) is formed in the porous polymer layer and on the porous polymer layer. After that, the active energy ray is irradiated to the uncured coating film other than the portion to be formed with the flow path, and the uncured composition (Y) in the non-irradiated portion is removed, so that the bottom surface is the porous polymer layer and the wall surface is the composition. A concave portion made of a cured or semi-cured coating of the product (Y) is obtained. On the other hand, the pores of the porous polymer layer other than the portion that becomes the flow path are blocked by the cured or semi-cured product of the impregnated composition (Y).

  The polymerizable compound contained in the active energy ray-curable composition (Y) is a compound that can be polymerized by active energy rays in the presence or absence of a polymerization initiator. Those having a polymerizable carbon-carbon double bond as the energy ray polymerizable functional group are preferred. Of these, highly reactive (meth) acrylic compounds and vinyl ethers, and maleimide compounds that cure even in the absence of a photopolymerization initiator are preferred. Further, when the polymerizable compound is a polyfunctional compound, it is polymerized to form a crosslinked structure, so that the strength after curing is also increased.

  As such a polymerizable compound, for example, a compound similar to the polymerizable compound that can be used in Step 1 described above can be used. These polymerizable compounds can be used alone or in admixture of two or more, and can be mixed with a monofunctional monomer in order to control viscosity, or to provide functions such as adhesion and tackiness. May be used. As the monofunctional monomer that can be mixed, for example, the same compound as the monofunctional monomer that can be used in Step 1 described above can be used.

  In the composition (Y), a photopolymerization initiator, a polymerization retarder, a polymerization inhibitor, a solvent, a thickener, a modifier, a colorant, and the like can be mixed and used as necessary. Examples of the photopolymerization initiator, polymerization retarder, and polymerization inhibitor that can be added to the composition (Y) include the photopolymerization initiator and polymerization of the organic porous polymer layer forming composition (X) in Step 1 described above. The same compounds as the retarder and the polymerization inhibitor can be preferably used.

  Although it does not specifically limit as a solvent, Although it is necessary to adjust suitably the kind and addition amount of a solvent by the polymerizable compound to be used, the additive added to the composition (Y), or the required viscosity, for example, , Alcohols such as methanol and ethanol, ketones such as acetone, and chlorinated solvents such as methylene chloride.

  The viscosity of the composition (Y) can vary depending on the pore size of the porous polymer layer, but when coated on the porous polymer layer, the composition (Y) is fast and within the porous polymer layer. From the viewpoint that the composition (Y) is completely removed from the porous polymer layer when the uncured composition (Y) in the non-irradiated part is removed after the penetration into the active energy ray The viscosity of the product (Y) is preferably in the range of 30 to 3,000 mPa · s at 25 ° C., and more preferably in the range of 100 to 1,000 mPa · s. When the viscosity is less than 30 mPa · s, it becomes difficult to control the depth of the concave portion. On the other hand, when the viscosity is greater than 3,000 mPa · s, it is difficult to penetrate the composition (Y) into the porous polymer layer. Further, it becomes difficult to remove the uncured composition (Y) in the non-irradiated part.

  In step 2, any coating method can be used as a method for coating the composition (Y) on the porous polymer layer. For example, a spin coating method, a roller coating method, a casting method, a dipping method, Examples thereof include a spray method, a bar coater method, an XY applicator method, a screen printing method, a letterpress printing method, a gravure printing method, extrusion from a nozzle, and casting. When the composition (Y) has a high viscosity or is applied particularly thinly, the composition (Y) is coated by adding a solvent and then volatilizing the solvent. You can also.

  The thickness of coating the composition (Y) is not particularly limited as long as a cured or semi-cured coating is obtained on the upper part of the porous polymer layer after irradiation with active energy rays, but the thickness of the porous polymer layer after irradiation with active energy rays is not limited. The range in which the thickness of the cured or semi-cured coating film formed on the upper portion, that is, the wall height of the concave portion is 3 to 150 μm is preferable, and the range in which the thickness is 5 μm to 50 μm is more preferable. If the thickness is less than 3 μm, another member that serves as a lid may be fixed to the recess to make the recess a hollow channel, and the channel may be blocked.

  Active energy rays to be irradiated include rays such as ultraviolet rays, visible rays, infrared rays, laser rays and radiant rays; ionizing radiations such as X-rays, gamma rays and radiant rays; particle rays such as electron rays, ion beams, beta rays and heavy particle rays Is mentioned. Among these, ultraviolet rays and visible light are preferable from the viewpoint of handleability and curing speed, and ultraviolet rays are particularly preferable. For the purpose of accelerating the curing and complete the curing, it is preferable to irradiate active energy rays in a low oxygen concentration atmosphere. As the low oxygen concentration atmosphere, a nitrogen stream, a carbon dioxide stream, an argon stream, a vacuum or a reduced pressure atmosphere is preferable.

  In order to form a concave portion formed on the entire bottom surface or a part of the bottom surface of the organic porous polymer layer, the active energy beam is irradiated by patterning when the active energy beam is irradiated. The patterning irradiation method is arbitrary, and for example, a photolithography technique such as masking and irradiating a portion that is not irradiated with active energy rays or scanning with a beam of active energy rays such as a laser can be used.

  When the curing of the uncured coating film of the composition (Y) is semi-cured, it is possible to fix it to another member that becomes a lid without using an adhesive, and when an adhesive is used. In addition, the adhesive strength is improved. When the cured state of the composition (Y) is semi-cured, it is preferable to carry out post-curing in any step before forming the final transition metal immobilization reactor, and to completely cure it. If the function of the transition metal-immobilized reactor is not impaired, it is not always necessary to completely cure the reactor. In the case of curing with active energy rays, the post-curing may be the same as or different from the active energy rays used for semi-curing. The post-curing may be cured by heat curing in addition to curing by active energy rays.

  Step 3 is a step of fixing another member serving as a lid to the concave portion of the member having the concave portion formed in Step 2 to form the concave portion as a hollow flow path. As a member to be a lid, a member that can be appropriately selected according to the purpose of use, and a member that is not affected by the fluid flowing through the flow path may be used, and the member is an adhesive tape, sheet or plate. It may be.

  In order to cover the concave portion with the member to be the lid, the lid member and the member having the concave portion may be bonded together. As described above, if the member having the recess is a semi-cured coating film and has good adhesion to the lid member, it may be applied as it is. Moreover, what is necessary is just to bond both members using an adhesive agent etc., when the adhesiveness of the member which has a recessed part is low or it is a cured coating film.

  In addition, a composition containing an active energy ray-polymerizable compound is applied to a support such as a polymer film or sheet, irradiated with active energy rays, the coating film of the composition is semi-cured, and the concave portion There is also a method in which the material is bonded to the concave portion of the member having, and irradiated with active energy rays to be completely cured. The active energy ray-polymerizable compound and the composition thereof used here can be the same as the polymerizable compound and composition used in Step 1 or Step 2 described above. Moreover, the coating method of a polymeric compound can use the method similar to the process 1 or the process 2.

  For example, an epoxy resin adhesive, a styrene butadiene resin adhesive, a (meth) acrylic adhesive, or the like can be used as the adhesive when the lid member and the member having the recess are bonded to each other. The hollow channel thus obtained may or may not communicate with the outside. In the latter case, the channel and the outside can be communicated with each other by drilling a hole with a drill or the like.

  As mentioned above, although manufacture about the transition metal fixed reactor was demonstrated, the manufacturing method of the transition metal fixed reactor which can be used by this invention is not limited to said illustration.

  The obtained transition metal immobilization reactor can be used as it is when the members are firmly adhered to each other. If the adhesive force is weak, it can be fixed by screwing, clamping or other methods. It is also possible to use it.

  By the method of the present invention, it is possible to provide a transition metal-immobilized reactor having a large amount of transition metal compound immobilized and excellent in repeated use stability. The reactor having a large amount of transition metal immobilized herein means that the weight of the transition metal immobilized per 1 g of the organic porous polymer layer is 20 mg or more, and preferably 50 mg or more. Moreover, the transition metal fixed reactor excellent in use stability said here points out that it can be used repeatedly 5 times or more without a change in catalyst capability in the catalytic reaction circulation test at 50 degreeC for 5 hours, Preferably, it means that it can be used repeatedly 10 times or more under the same conditions.

EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, this invention is not limited to the range of a following example.
(Synthesis Example 1)
[Synthesis of [1,2-bis (4-styryldiphenylphosphino) ethane] palladium (II) [2,3-dihydroxynaphthalene]]
A glass flask equipped with an oil bath, a stirrer, and a dropping funnel is charged with 2.73 g (112 mmol) of shaved magnesium, from which a dehydrated tetrahydrofuran solution of 3.4 mL (28.3 mmol) of 4-chlorostyrene in 16 mL is added. Was added dropwise at room temperature over 10 minutes. Next, 25 μL of methyl iodide was added to this mixture at room temperature. After adding 20 mL of dehydrated tetrahydrofuran to this mixture, 36 mL of a dehydrated tetrahydrofuran solution of 3.4 mL (28.3 mmol) of 4-chlorostyrene was added dropwise from a dropping funnel at room temperature over 10 minutes. Thereafter, the oil bath temperature was raised to 55 ° C., and the mixture was stirred for 3 hours until all contents were dissolved. After cooling this solution to room temperature, it was cannula transferred into 30 mL of a dehydrated tetrahydrofuran solution of 1.3 mL (8.61 mmol) of 1,2-bis (dichlorophosphino) ethane charged in a glass flask equipped with an oil bath and a stirrer. . The solution was then stirred at room temperature for 30 minutes. To this solution, 100 mL of an aqueous solution of 16.5 g of ammonium chloride containing 10 mg of tert-butylcatechol was added, and then 300 mL of tetrahydrofuran was added, followed by washing with 100 mL of saturated brine three times. Magnesium sulfate was added to the obtained oil phase and dried. After filtering magnesium sulfate from this solution, the solvent was distilled off and recrystallized from tetrahydrofuran / hexane to obtain 2.51 g of needle-like crystals of 1,2-bis (4-styryldiphenylphosphino) ethane. Yield was 58 mol%; ¹ H-NMR spectrum (300 MHz, deuterated methylene chloride solution) chemical shift (ppm): 7.39 (br, s, 3H), 7.37 (br, s, 5H), 7.32 (m, 8H), 6.77 (dd, 4H), 5.79 (dd, 4H), 5.29 (dd, 4H), 2.07 (t, 4H).

A glass flask equipped with a stirrer was charged with 1.52 g (3.03 mmol) of 1,2-bis (4-styryldiphenylphosphino) ethane and 80 mL of methylene chloride, and the resulting solution was stirred at room temperature for 15 minutes. This solution was cannula transferred into a solution of 0.78 g (3.03 mmol) of bis (acetonitrile) dichloropalladium (II) in methylene chloride. The solution was then stirred at room temperature for 5 hours. After evaporation of the solvent, recrystallization from methylene chloride / hexane gave 1.40 g of [1,2-bis (4-styryldiphenylphosphino) ethane] palladium (II) dichloride needles. Yield was 68 mol%; ¹ H-NMR spectrum (300 MHz, deuterated methylene chloride solution) chemical shift (ppm): 7.80 (dd, 8H), 7.53 (dd, 8H), 6 .77 (dd, 4H), 5.90 (d, 4H), 5.42 (d, 4H), 2.44 (m, 4H).

A glass flask equipped with a stirrer was charged with [1,2-bis (4-styryldiphenylphosphino) ethane] palladium (II) dichloride (0.21 g, 0.31 mmol) and methylene chloride (25 mL), and the resulting solution was cooled to room temperature. For 15 minutes. To this solution, 10 mL of an aqueous solution in which 0.14 g (2.51 mmol) of potassium hydroxide and 0.20 g (1.26 mmol) of 2,3-dihydroxynaphthalene were dissolved was added, and the resulting two-phase solution was added at room temperature. Stir for 7 hours. To this solution was added 25 mL of methylene chloride, and 10 mL of methylene chloride was added to the aqueous phase for extraction. After washing the mixed methylene chloride solution with 15 mL of water, magnesium sulfate was added and dried. After filtering magnesium sulfate from this solution, the solvent was distilled off and recrystallized from methylene chloride / hexane to give [1,2-bis (4-styryldiphenylphosphino) ethane] palladium (II) [2,3-dihydroxy. 0.15 g of needle-shaped crystals of naphthalene] were obtained. Yield was 64 mol%; ¹ H-NMR spectrum (300 MHz, deuterated methylene chloride solution) chemical shift (ppm): 7.95 (dd, 8H), 7.54 (dd, 8H), 7 .42 (q, 2H), 6.96 (q, 2H), 6.85 (s, 2H), 6.73 (dd, 4H), 5.86 (d, 4H), 5.35 (d, 4H), 2.51 (m, 4H); ¹³ C-NMR spectrum (100 MHz, deuterated chloroform solution) chemical shift (ppm): 166.4, 141.8, 136.0, 133.8, 133. 7, 133.6, 129.1, 128.3, 127.5, 127.4, 127.3, 125.1, 120.5, 117.3, 108.4, 27.2; Elemental analysis: C _{As 44} H ₃₈ O ₂ P ₂ Pd, the calculated value C, 68.91, H, 4.96, found C, 68.52, H, 4.87.

(Example 1)
[Pretreatment of support]
Matsunami Glass Industrial Co., Ltd. glass flat plate “S-1111” (26 mm × 76 mm, thickness 1 mm) was replaced with 5 mmol / L of methacrylic acid 3- (trimethoxysilyl) propyl ester “M0725” manufactured by Tokyo Chemical Industry Co., Ltd. After immersing in a methanol solution at 50 ° C. for 3 hours, the substrate was ultrasonically washed in methanol and heated under reduced pressure (0.01 Pa or less) for 1 hour in a constant temperature bath at 100 ° C. to prepare a support [A-1]. .

[Preparation of organic porous polymer layer]
Kyoeisha Chemical Co., Ltd. trimethylolpropane trimethacrylate “Light Ester TMP” 19 mmol, Kyoeisha Chemical Co., Ltd. methyl methacrylate “Light Ester M” 5.3 mmol, and Ciba Geigy 1-hydroxycyclohexyl phenyl ketone as photopolymerization initiator Irgacure 184 ”1.3 mmol was uniformly mixed to prepare a composition (X1). Further, [1,2-bis (4-styryldiphenylphosphino) ethane] palladium (II) [2,3-dihydroxynaphthalene] 1.1% by mass described in Synthesis Example 1, poly (vinyl acetate) manufactured by Aldrich "387924" (weight average molecular weight-140,000) 9.1 mass% and diethylene glycol dimethyl ether 89.8 mass% were mixed uniformly, and the composition (X2) was prepared. The composition X1 and the solution (X2) were uniformly mixed at a volume ratio of 3: 4 to prepare a composition (X3).

UE031 manufactured by Eye Graphics Co., Ltd., which uses the spin coater to coat the composition (X3) on the surface-treated support [A-1] and uses a 3000 W metal halide lamp as the light source for the coating film. Using a -353CHC type UV irradiation apparatus (hereinafter referred to as “Lamp 1”), ultraviolet rays having an ultraviolet intensity at 365 nm of 40 mW / cm ² were irradiated for 40 seconds in a nitrogen stream at room temperature to give the composition (X3). It was cured and then washed with toluene to obtain an organic porous polymer layer [A-2] having a thickness of 10 μm formed on the support.

[Formation of recesses on the organic porous polymer layer]
Tosu Gosei Co., Ltd. tris (acryloxyethyl) isocyanurate "Aronix M-315" 16 mass%, Toagosei Co., Ltd. bis (acryloxyethyl) hydroxyethyl isocyanurate "Aronix M-215" 63 mass%, first 18% by mass of 1,6-hexanediol diacrylate “New Frontier HDDA” manufactured by Kogyo Seiyaku Co., Ltd., 1.5% by mass of “Irgacure 184” as a photopolymerization initiator, and 2, manufactured by Kanto Chemical Co., Ltd. as a polymerization retarder 4-Diphenyl-4-methyl-1-pentene (1.5% by mass) was uniformly mixed to prepare a composition (X4).

The composition (X4) is applied to the organic porous polymer layer [A-2] formed on the support using a spin coater, and then the portion to be a flow path is photomasked, and a 250 W high pressure mercury lamp is installed. Using a light source unit for multi-light 250W series exposure apparatus (hereinafter referred to as “Lamp 2”) manufactured by Ushio Electric Co., Ltd. as a light source, after irradiating ultraviolet rays having an ultraviolet intensity at 365 nm of 50 mW / cm ² for 185 seconds, The unpolymerized composition (X4) is removed by washing with ethanol, and has a groove that is formed on the surface of the organic porous polymer layer and forms a flow path having a width of 1 mm, a depth of 20 μm, and a length of 340 mm. A semi-cured coating film [A-3] was produced.

[Preparation of transition metal immobilization reactor by channel formation on organic porous polymer layer]
“Aronix M-315” 18% by mass, “Aronix M-215” 72% by mass, “New Frontier HDDA” 9.8% by mass, and “Irgacure 184” 0.2% by mass as a photopolymerization initiator % Was uniformly mixed to prepare a composition (X5).
Using a biaxially stretched polypropylene sheet (hereinafter referred to as an OPP sheet) manufactured by Nimura Chemical Co., Ltd. having a thickness of 30 μm and having a corona-treated surface as a transfer support, The composition (X5) was applied using a bar coater, the lamp 1 was applied to the coating film, and ultraviolet rays having an ultraviolet intensity of 40 mW / cm ² at 365 nm were irradiated for 5 seconds at room temperature in a nitrogen stream. (X5) was semi-cured. This was laminated on the semi-cured coating film [A-3] of the composition (X4) having a groove to become the flow path, and using the lamp 1, ultraviolet light having an ultraviolet intensity at 365 nm of 40 mW / cm ² was applied at room temperature. A transition metal-immobilized reactor [R-1] having a tubular fine channel having an opening to the outside was bonded by irradiation for 10 seconds under a nitrogen stream.

[Measurement of amount of transition metal immobilized in transition metal immobilization reactor]
A Teflon (registered trademark) tube with an inner diameter of 1 mm was connected to the produced transition metal-immobilized reactor [R-1], and 20 mass% nitric acid was added at a rate of 5 μl / min using a syringe pump KDS-200 manufactured by Kd Scientific. The mixture was allowed to flow at room temperature for 36 hours at a flow rate. As a result of performing ICP emission analysis on the obtained solution, the amount of palladium immobilized in the flow path of [R-1] was 51 mg per 1 g of the organic porous polymer layer.

[Catalytic reaction test using transition metal immobilization reactor]
A reaction solution (Y1) was prepared by uniformly mixing 3.0 mmol of allylmethyl carbonate, 3.0 mmol of ethyl 3-oxobutanoate, 0.6 mmol of triphenylphosphine, and 10 mL of toluene. A Teflon (registered trademark) tube having an inner diameter of 1 mm was connected to the transition metal-immobilized reactor [R-1], and the reaction solution (Y1) was flown at a flow rate of 1 μl / min using the syringe pump KDS-200. It was circulated at 55 ° C. for 8 minutes. As a result of analysis by gas chromatography, it was confirmed that ethyl 2-allyl-3-oxobutanate was produced at a reaction rate of 98% or more. Even when the reaction solution (Y1) was continuously passed through the transition metal-immobilized reactor [R-1] for 5 hours, it was confirmed that the reaction proceeded without lowering the reaction rate. Furthermore, when the same catalytic reaction test was repeated 10 times, it was confirmed that the product could be obtained without reducing the reaction rate.

Claims (3)

A reactor having a tubular channel and at least a part of a wall surface forming the channel is formed of an organic porous polymer layer having a transition metal compound fixed on the surface thereof;
The organic porous polymer layer has the formula 1

(In the formula, M is a palladium, platinum or rhodium atom, R ₁ and R ₂ are aryl groups which may have a substituent or an alkyl group having 1 to 18 carbon atoms, and L ₁ and L ₂ are ligand groups. Represents.)
Or Equation 2

(In the formula, M is a palladium, platinum or rhodium atom, n is an integer of 1 to 12, R ₃ is an aryl group which may have a substituent or an alkyl group having 1 to 18 carbon atoms, L ₃ and L _4. Is a porous polymer layer containing a polymer of a compound represented by the formula: The transition metal immobilization reactor according to claim 1, wherein the organic porous polymer layer has a thickness in the range of 3 to 50 μm. A method for producing a transition metal-immobilized reactor according to claim 1 or 2,
(1) The active energy ray-polymerizable composition (a) containing the compound represented by Formula 1 or Formula 2 and the active energy ray-polymerizable composition (a) are compatible with each other on the surface of the support. However, an organic porous polymer layer forming composition (X) mixed with a solvent (M) that does not dissolve or swell the polymer of the active energy ray polymerizable composition (a) is applied to form a coating film. ,
Step 1 of forming the organic porous polymer layer by polymerizing the active energy ray-polymerizable composition (a) by irradiating the coating film with active energy rays and then removing the solvent (M). ,
(2) The active energy ray-curable composition (Y) is coated on the organic porous polymer layer to form an uncured coating film of the composition (Y), and other than the portion that should become the flow path Irradiating active energy rays to the uncured coating film to form a cured or semi-cured coating film of the composition (Y), removing the uncured composition (Y) in the non-irradiated part, Step 2 in which the organic porous polymer layer forms a recess exposed on the bottom surface, and
(3) Step 3 of fixing the other member serving as a lid to the concave portion of the member having the concave portion to make the concave portion a hollow flow path.
A process for producing a transition metal-immobilized reactor, comprising: