JP2020183464A - Method for producing chiral polymer, and chiral polymer - Google Patents

Abstract

To provide a method for producing a metal compound and a luminous compound having chiral properties.SOLUTION: A method for producing a chiral polymer includes: a silica layer formation step of obtaining a composite body in which a silica layer is formed on the surface of a chiral supramolecular crystal by a hydrolysis condensation reaction of making a hydrolyzable silicon compound act on a chiral supermolecular crystal of an acid-base type complex including a polymer having a straight chain-type polyethyleneimine skeleton and a chiral dicarboxylic acid compound that has two carboxyl groups and 4 or more carbon atoms; an acid treatment step of acid-treating the composite body to obtain an acid-treated composite body; a polymerization step of radical-polymerizing a compound having an ethylenically-unsaturated bond as a monomer in the presence of treated particles derived from the acid-treated composite body, and forming the polymer including the monomer as a repeating unit on the surface of the treated particles to obtain a resin composite body; and a removal step of removing silica forming the silica layer from the resin composite body.SELECTED DRAWING: Figure 7

Description

The present invention relates to a method for producing a chiral polymer and a chiral polymer.

In recent years, nanostructures having a specific spatial shape and a regular structure on the order of nanometers, which are obtained by self-assembling organic compounds in an equilibrium or non-equilibrium state by intermolecular interaction, have been actively proposed. .. These nanostructures can be used not only as a base for constructing organic / inorganic composite nanomaterials having various compositions, but also as a template for forming nanostructures made of various materials. Because of this, it is attracting attention from interdisciplinary fields and industrial fields.

As an example of such a nanostructure, for example, in Patent Document 1, a surfactant having a specific chemical structure is self-assembled in a solution, and a compound that becomes a silica source is sol-gel-reacted around the surfactant to make mesoporous. It has been proposed to form silica particles. Further, in Patent Document 2, a microphase-separated structure is formed from two kinds of polymers that are incompatible with each other and are water-insoluble and water-soluble, and based on this, pores having a cylinder structure having an average pore diameter of 1 to 200 nm are formed. It has been proposed to form a porous membrane with. It is also well known that DNA and proteins, which are biopolymers, become nanostructures having a unique three-dimensional structure by self-assembly.

Further, it has been proposed to transfer the chirality of the template to the metal oxide by using a nanostructure having chirality as a template and growing a layer of a metal oxide such as silica around it. As such an example, in Patent Document 3, a polymer having an optically active chiral orientation structure such as a spiral structure is used as a template, and a metal source is allowed to act on the template to obtain a chiral organic / inorganic composite. Has been proposed. In such an organic / inorganic composite, the kirarity is transferred to the metal oxide. Therefore, for example, if a metal oxide having catalytic activity is selected as the inorganic component of the organic / inorganic composite, a chiral reaction can be obtained. It is considered that a metal oxide catalyst having a field may be obtained. The present inventors have proposed a structure in which chiral metal oxide nanostructures are combined as having the possibility of becoming such a metal oxide catalyst (see Patent Document 4). ..

On the other hand, it has also been proposed to bond a compound exhibiting light emission to a compound having chirality by means such as complex formation to obtain an optical functional material exhibiting circularly polarized light emission. As an example of such a material, Non-Patent Document 1 reports that the fluorescence emitted from a rare earth complex changes from non-circularly polarized light emission to circularly polarized light emission by binding a chiral compound to the rare earth complex. There is. Further, Non-Patent Document 2 reports that circularly polarized light emission was observed in a supramolecular solid complex of thiophene, which is a compound exhibiting fluorescence emission, and chiral (R) -1- (2-naphthyl) ethylamine. Has been done. Further, Patent Document 5 reports that a 7-coordinated rare earth complex having a chiral ligand exhibits circularly polarized light emission.

JP-A-2010-208907 JP-A-2009-256592 Japanese Unexamined Patent Publication No. 2005-239863 Japanese Patent No. 6004272 Japanese Unexamined Patent Publication No. 2013-121921

Hao Chen et al. , RSC Adv. , 2015, 5, 39946-39951 Xin-Ling Liu et al. , J. Mater. Chem. B, 4,626-634 (2016)

Metal compounds and luminescent compounds having the above-mentioned chiral properties are promising as catalysts and circularly polarized light emitting materials that provide a chiral reaction field. Against this background, it is an object of the present invention to provide a new material having chirality.

The present inventor has diligently proceeded with the following studies in order to solve the above problems. First, a chiral supermolecular crystal of an acid-base complex obtained by reacting a polymer having a linear polyethyleneimine skeleton and a chiral dicarboxylic acid compound was used, and a hydrolyzable silicon compound was allowed to act on the supermolecular crystal. A silica layer was formed to obtain a composite. The chirality of supramolecular crystals is transferred to this silica layer, and the obtained complex has a chiral structure composed of a silica layer. Then, the dicarboxylic acid compound is removed from the complex by acid treatment and converted into an acid-treated complex, and then a compound having an ethylenically unsaturated bond is radically polymerized as a monomer on the surface of the acid-treated complex to carry out a polymer. When the compound is formed, the circular dichromaticity induced in the chiral silica layer is observed in the absorption wavelength range of the polymer. And, surprisingly, since this circular dichroism was observed even after the silica layer was removed, it was not simply induced and expressed in the chiral silica layer, but was expressed by the structure of the polymer itself. The present inventor has found that it is a thing. As described above, when the monomer is polymerized on the surface of the acid-treated structure, (1) the imino group (nitrogen atom) contained in the linear polyethyleneimine skeleton and the desorbing group for the nucleophilic reagent By interacting with a compound having a structure in which an alkyl group having a substituent is bonded to a benzene ring, the nitrogen atom of polyethyleneimine can be modified, or (2) an acid-treated structure can be calcined to form chiral silica. The present inventor also found that better results can be obtained by modifying the surface of chiral silica with a silane coupling agent. The present invention has been made based on such findings, and provides the following.

(1) The present invention comprises an acid-base type complex comprising a polymer having a linear polyethyleneimine skeleton and a chiral dicarboxylic acid compound having two carboxyl groups and four or more carbon atoms. A silica layer forming step of obtaining a composite in which a silica layer is formed on the surface of the chiral supermolecular crystal by a hydrolysis condensation reaction in which a hydrolyzable silicon compound is allowed to act on the chiral supermolecular crystal, and an acid treatment of the composite. In the acid treatment step of obtaining an acid-treated complex and the presence of particles to be treated derived from the acid-treated complex, a compound having an ethylenically unsaturated bond is radically polymerized as a monomer, and the monomer is repeatedly used as a unit. A method for producing a chiral polymer, comprising a polymerization step of forming a polymer contained in the above on the surface of the particles to be treated to obtain a resin composite, and a removal step of removing the silica forming the silica layer from the resin composite. Is.

(2) Further, in the present invention, after the monomer is brought into contact with the particles to be treated in the polymerization step, if the monomer is water-insoluble, it is in a water-soluble solvent, and if the monomer is water-soluble, it is not. The method for producing a chiral polymer according to item (1), which comprises performing the above radical polymerization in a water-soluble solvent.

(3) Further, in the present invention, the acid-treated complex is allowed to act on the nucleophile with a compound having a structure in which an alkyl group having a substituent as a leaving group is bonded to a benzene ring. It further includes a tertiaryization step of obtaining a tertiaryized composite in which the nitrogen atom of polyethyleneimine is tertiaryized, and the tertiaryd composite obtained in this step is subjected to a polymerization step as the particles to be treated. , (1) or (2), the method for producing a chiral polymer.

（上記一般式（１）中、Ｅは、求核試薬に対して脱離基となる置換基であり、Ｒは、一価の有機基である。） (4) Further, in the present invention, the above-mentioned compound having a structure in which an alkyl group having a substituent as a leaving group is bonded to a benzene ring with respect to a nucleophile is a compound represented by the following general formula (1). , The method for producing a chiral polymer according to item (3).

(In the above general formula (1), E is a substituent serving as a leaving group for the nucleophile, and R is a monovalent organic group.)

（上記一般式（２）中、Ｅは、求核試薬に対して脱離基となる置換基である。） (5) Further, in the present invention, the above-mentioned compound having a structure in which an alkyl group having a substituent as a leaving group is bonded to a benzene ring with respect to a nucleophile is a compound represented by the following general formula (2). , The method for producing a chiral polymer according to any one of paragraphs (3) and (4).

(In the above general formula (2), E is a substituent serving as a leaving group for the nucleophile.)

(6) The production of the chiral polymer according to any one of (1) to (5), wherein the present invention uses a compound having two or more ethylenically unsaturated bonds as the monomer. The method.

(7) Further, the present invention further includes a surface treatment step of obtaining chiral silica particles by firing the acid-treated composite and then reacting the silica particles with a silane coupling agent to obtain surface-treated silica. The method for producing a chiral polymer according to item (1) or (2), wherein the surface-treated silica obtained in this step is subjected to a polymerization step as the particles to be treated.

(8) The present invention is the method for producing a chiral polymer according to item (7), wherein a compound having two or more ethylenically unsaturated bonds is used as the monomer.

(9) The present invention is the method for producing a chiral polymer according to item (7) or (8), wherein the silane coupling agent has a radically polymerizable residue.

(10) The present invention is also a chiral polymer containing a repeating unit using a compound having an ethylenically unsaturated bond as a monomer, and a positive or negative Cotton effect is observed in circular dichroism spectrum measurement. ..

(11) Further, the present invention is the chiral polymer according to item (10), wherein the monomer is divinylbenzene, ethylene bismethacrylate or N, N'-methylenebisacrylamide.

According to the present invention, a new material having chirality is provided.

FIG. 1 is an FT-IR spectrum for the complex (PEI / Tart @ SiO ₂ ). FIG. 2 is a circular dichroism spectrum for the D- / L-complex (D- and L-PEI / Tart @ SiO ₂ ). FIG. 3 is an FT-IR spectrum showing a comparison between the acid-treated complex (PEI @ SiO ₂ ) and the complex (PEI / Tart @ SiO ₂ ). FIG. 4 is a circular dichroism spectrum of the D- / L-acid-treated complex (D- and L-PEI @ SiO ₂ ). FIG. 5 is a circular dichroism spectrum of the D- / L-tertiary complex (D- and L-bp @ SiO ₂ ) obtained in the process of preparing the chiral polymer of Example 1. FIG. 6 is a circular dichroism spectrum of the D- / L-resin composite (D- and L-bp @ SiO ₂ @ PDVB) obtained in the process of preparing the chiral polymer of Example 1. FIG. 7 is a circular dichroism spectrum of the D- / L-chiral polymer (D / L-PDVB) of Example 1. FIG. 8 is a circular dichroism spectrum of the D- / L-tertiary complex (D- and L-CMS @ SiO ₂ ) obtained in the process of preparing the chiral polymer of Example 2. FIG. 9 is a circular dichroism spectrum of the D- / L-resin composite (D- and L-CMS @ SiO ₂ @ PMBA) obtained in the process of preparing the chiral polymer of Example 2. FIG. 10 is a circular dichroism spectrum of the D- / L-chiral polymer (D / L-PMBA) of Example 2. FIG. 11 is a circular dichroism spectrum of D- / L-surface-treated silica (D- and L-SiO ₂ @ TPM) obtained in the process of preparing the chiral polymer of Example 3. FIG. 12 is a circular dichroism spectrum of the D- / L-resin composite (D- and L-SiO ₂ @ TPM @ PDVB) obtained in the process of preparing the chiral polymer of Example 3. FIG. 13 is a circular dichroism spectrum of the D- / L-chiral polymer (D / L-PDVB) of Example 3.

Hereinafter, the first and second embodiments of the method for producing a chiral polymer of the present invention, and one embodiment of the chiral polymer will be described. The present invention is not limited to the following embodiments and embodiments, and can be carried out with appropriate modifications within the scope of the present invention.

<First Embodiment of Method for Producing Chiral Polymer>
The method for producing a chiral polymer according to the present invention is an acid comprising a polymer having a linear polyethyleneimine skeleton and a chiral dicarboxylic acid compound having two carboxyl groups and four or more carbon atoms. A silica layer forming step of obtaining a composite in which a silica layer is formed on the surface of the chiral supermolecular crystal by a hydrolysis condensation reaction in which a hydrolyzable silicon compound is allowed to act on the chiral supermolecular crystal of the basic complex, and the above-mentioned composite. In the acid treatment step of acid-treating the body to obtain an acid-treated complex, and in the presence of the particles to be treated derived from the acid-treated complex, a compound having an ethylenically unsaturated bond is radically polymerized as a monomer to obtain the said compound. It includes a polymerization step of forming a polymer containing a monomer as a repeating unit on the surface of the particles to be treated to obtain a resin composite, and a removal step of removing silica forming the silica layer from the resin composite. When the method for producing a chiral polymer according to the present invention includes the above-mentioned steps, first, a supramolecular crystal reflecting the chirality of the chiral dicarboxylic acid compound becomes a template, and the supramolecular crystal is based on the template. The chirality is transferred to the silica layer formed on the surface of the crystal. Then, after removing the dicarboxylic acid compound from the particles of the supermolecular crystal by acid treatment, the monomer was radically polymerized on the surface of the particles, and finally the silica layer was removed to transfer the chirality of the silica layer. A chiral polymer is produced. Since this chiral polymer has the chirality of the silica layer transferred and exhibits circular dichroism, it can be used, for example, for security applications utilizing circular dichroism.

In addition, as the embodiment of the present invention, it is possible to classify into the first embodiment and the second embodiment according to the treatment from the acid treatment complex to the radical polymerization. First, each step will be described below with respect to the first embodiment.

[Silica layer forming step]
In the silica layer forming step, a chiral of an acid-base type complex comprising a polymer having a linear polyethyleneimine skeleton and a chiral dicarboxylic acid compound having two carboxyl groups and four or more carbon atoms. A hydrolyzable silicon compound is allowed to act on the supermolecular crystal. By this step, a composite in which a silica layer is formed on the surface of the chiral supramolecular crystal is obtained.

The polymer having a linear polyethyleneimine skeleton used in the present invention has a structure represented by the following chemical formula in the molecule. The structure represented by the following chemical formula contains a secondary amino group, and the nitrogen atom of this amino group interacts with the carboxyl group contained in the chiral dicarboxylic acid compound described later to form an acid-base type complex. .. Since the chiral dicarboxylic acid compound is a dibasic acid having two carboxyl groups and can form a complex with each of the amino groups contained in the two molecules of the polymer, the polymer is a chiral dicarboxylic acid. Crosslinked by the compound. As a result, an acid-base complex type supramolecular crystal having a structure in which a plurality of polymers and a plurality of chiral dicarboxylic acid compounds are self-assembled is formed. This supramolecular crystal has structural chirality induced by the chiral dicarboxylic acid compound.

（上記化学式中、ｎは１以上の整数である。）

(In the above chemical formula, n is an integer of 1 or more.)

A polymer having a linear polyethyleneimine skeleton need only have the linear polyethyleneimine skeleton represented by the above chemical formula in the molecule, and the structure of other parts is not particularly limited. Therefore, not only the linear structure but also the star It may have a shape or comb-like structure, a homopolymer having the above chemical formula, or a copolymer having other repeating units. When the polymer having a linear polyethyleneimine skeleton is a copolymer, it is preferable from the viewpoint that stable crystals can be formed if the molar ratio of the linear polyethyleneimine skeleton portion in the polymer is 20% or more. , It is more preferable that the block copolymer has a linear polyethyleneimine skeleton having 10 or more repeating units. The polymer having a linear polyethyleneimine skeleton is most preferably a homopolymer having the above chemical formula.

Further, as the polymer having a linear polyethyleneimine skeleton, it is preferable that the polymer has a higher ability to form a crystalline aggregate with a chiral dicarboxylic acid compound described later. Therefore, the polymer having the linear polyethyleneimine skeleton, whether it is a homopolymer or a copolymer, has a molecular weight of 500 to 1 in a portion corresponding to the linear polyethyleneimine skeleton portion represented by the above chemical formula. It is preferably in the range of about 1,000,000. As the polymer having the linear polyethyleneimine skeleton, a commercially available product may be used, or it can be obtained by a synthetic method disclosed by the present inventors in JP-A-2009-30017.

The chiral dicarboxylic acid compound used in the present invention comprises 4 or more carbon atoms. As already described, the two carboxyl groups contained in this dicarboxylic acid compound crosslink the above polymer to form a supramolecular crystal, and the structural kirarity derived from this dicarboxylic acid is formed. Induced in molecular crystals. The dicarboxylic acid compound may be in the D-form or the L-form. The optical purity of the dicarboxylic acid compound does not necessarily have to be 100% ee, but is preferably 90% ee or more, more preferably 95% ee or more, and further preferably 98% ee or more. preferable.

The dicarboxylic acid compound may have four or more carbon atoms, two carboxyl groups and an asymmetric carbon, and may be linear or branched. Examples of such a dicarboxylic acid compound include tartaric acid, altralic acid, glucaric acid, mannal acid, glulonic acid, idalic acid, galactalic acid, taluronic acid and the like, and tartaric acid is preferably exemplified.

The hydrolyzable silicon compound used in the present invention may be any compound as long as it is hydrolyzed by reacting with water to cause a condensation reaction. Examples of such compounds include tetramethoxysilane, trimethoxysilane, dimethoxysilane, tetraethoxysilane, triethoxysilane, diethoxysilane, tetrapropoxysilane, tripropoxysilane, dipropoxysilane, tetraisopropoxysilane, and triisopropoxy. Examples thereof include alkoxysilanes such as silane and diisopropoxysilane, halogenated silanes such as dichlorosilane and tetrachlorosilane, and tetraethyl orthosilicate. Among these, alkoxysilane is preferably mentioned, and tetramethoxysilane, tetraethoxysilane and the like are particularly preferable. One of these silicon compounds may be used alone, or a plurality of types may be used in combination.

In this step, first, a polymer having a linear polyethyleneimine skeleton and a chiral dicarboxylic acid are allowed to act in water to form supramolecular crystals composed of these and water molecules. Next, one aspect for forming such a supramolecular crystal will be described. In this embodiment, the polymer aqueous solution preparation small step, the dicarboxylic acid aqueous solution preparation small step, the mixing small step, and the precipitation small step are sequentially performed. Hereinafter, these steps will be described.

In the polymer aqueous solution preparation substep, an aqueous polymer solution having a linear polyethyleneimine skeleton is prepared. At this time, the water used to prepare the aqueous solution is preferably hot water having a temperature of 80 ° C. or higher by being heated. Further, the polymer having a linear polyethyleneimine skeleton used at this time is as described above.

As an example of the procedure for preparing an aqueous solution of a polymer, the polymer can be dissolved by adding the polymer powder to distilled water and heating it to 80 ° C. or higher. At this time, the concentration of the polymer in the aqueous solution is preferably in the range of 0.5 to 8% by mass.

The prepared aqueous solution of the polymer is subjected to a small mixing step described later in a warmed state.

The dicarboxylic acid aqueous solution preparation sub-step is not particularly limited, but is preferably performed in parallel with the polymer aqueous solution preparation sub-step. In this small step, an aqueous solution of the above-mentioned dicarboxylic acid compound is prepared. The dicarboxylic acid compound used here is a chiral (optically active substance). The water used to prepare the aqueous solution is preferably hot water having a temperature of 80 ° C. or higher by being heated.

As an example of the procedure for preparing an aqueous solution of a dicarboxylic acid compound, the powder of the dicarboxylic acid compound is added to distilled water and heated to 80 ° C. or higher to dissolve the dicarboxylic acid compound. At this time, the concentration of the dicarboxylic acid compound in the aqueous solution is preferably in the range of 0.5 to 15% by mass.

The prepared aqueous solution of the dicarboxylic acid compound is subjected to a small mixing step described later in a heated state.

In the small mixing step, the aqueous solution of the polymer and the aqueous solution of the dicarboxylic acid compound are mixed to obtain a mixed aqueous solution. At this time, it is preferable that the two aqueous solutions to be mixed are both heated to a temperature of about 80 ° C. or higher.

When the aqueous solution of the polymer and the aqueous solution of the dicarboxylic acid compound are mixed, the carboxyl group contained in the dicarboxylic acid compound is 0.5 to 1 equivalent with respect to 1 equivalent of the secondary amino group contained in the linear polyethyleneimine skeleton of the polymer. It is preferably 1.5 equivalents, more preferably 0.9 to 1.1 equivalents, and even more preferably 1 equivalent.

The mixed aqueous solution prepared in this small step is subjected to the precipitation small step.

In the small precipitation step, an acid-base complex of the polymer and the dicarboxylic acid compound is precipitated in the mixed aqueous solution obtained in the small mixing step. As already mentioned, this acid-base complex is a chiral supramolecular crystal (chiral supramolecular crystal). In the following description, the chiral supramolecular crystal is also simply referred to as a supramolecular crystal.

In performing this small step, the mixed aqueous solution in a heated state is cooled. The cooling method at this time is not particularly limited, but as an example, a method of naturally cooling in an air atmosphere to lower the water temperature to room temperature can be mentioned. In this process, a white solid precipitates in the aqueous solution, and this powder is a porous complex formed by agglomeration of nano-sized acid-base complex crystals (supramolecular crystals). When the natural cooling is performed as described above, the mixed aqueous solution may be left to stand, or the aqueous solution may be stirred or vibrated to promote the precipitation of solids. The obtained white precipitate is isolated by means such as filtration. The precipitate after isolation may be appropriately washed with distilled water or an organic solvent such as ethanol or acetone and dried.

The supramolecular crystal obtained as described above is subjected to the reaction with the hydrolyzable silicon compound described above. This reaction is carried out by adding a hydrolyzable silicon compound or a mixture of a hydrolyzable silicon compound and water to a chiral supramolecular crystal dispersed in water and stirring the mixture. In this process, the hydrolyzable silicon compound causes a hydrolysis condensation reaction to form a silica layer on the surface of the chiral supramolecular crystal. This layer contains a polymer [(-Si-O-) _n ] composed of a silicon atom (Si) and an oxygen atom (O), a hydroxide of silicon, and the like, but these are also used as silica in the present invention. deal with.

The mixing ratio of the chiral supramolecular crystal and the hydrolyzable silicon compound is not particularly limited, and may be appropriately adjusted so that a silica layer is formed on almost the entire chiral supramolecular crystal. As an example of such a mixing ratio, when tetramethoxysilane is used as the hydrolyzable silicon compound, 80 mL of water and 12 mL of tetramethoxysilane are added to about 1.2 g of chiral supramolecular crystals. Addition can be mentioned, but is not particularly limited. Further, in carrying out this reaction, stirring at room temperature for about 2 hours can be mentioned as a reaction condition, but the reaction is not particularly limited.

The composite in which the silica layer is formed on the surface of the chiral supramolecular crystal through the silica layer forming step is subjected to the acid treatment step.

[Acid treatment process]
In the acid treatment step, the complex obtained in the silica layer forming step is acid-treated. As a result, the dicarboxylic acid compound is removed from the supramolecular crystals contained in the complex, and the complex becomes an acid-treated complex. As a result, the polymer having the linear polyethyleneimine skeleton constituting the supramolecular crystal and the silica layer are left in the composite. The dicarboxylic acid compound that is the source of the chiral is removed from the complex, but the chirality of the dicarboxylic acid compound has been transferred to the silica layer, and the complex that has undergone this step still has structural chirality. .. Further, by removing the dicarboxylic acid compound from the supermolecular crystal of the polymer having the linear polyethyleneimine skeleton and the dicarboxylic acid compound, the dicarboxylic acid compound is contained in the polyethyleneimine skeleton in the later polymerization step requiring a base catalyst. The secondary amino group will function as a base catalyst.

Examples of the acid used for the acid treatment include acids such as hydrochloric acid, sulfuric acid and nitric acid. When hydrochloric acid is used as the acid, for example, the complex may be added to a hydrochloric acid aqueous solution of about 2.5 mol / L and stirred at room temperature for about 1 hour. The amount of the aqueous hydrochloric acid solution can be exemplified by about 50 mL per 1 g of the complex, but is not particularly limited, and may be appropriately increased or decreased while observing the degree of dispersion of the complex.

After the above acid treatment, the complex is separated from the dispersed acid aqueous solution of the complex by means such as centrifugation, and washed with dilute ammonia water and then distilled water. The acid-treated complex is obtained by separating the complex after washing and drying it.

The acid-treated complex prepared in the acid-treating step is subjected to a tertiaryization step.

[3rd grade process]
The tertiary step is a step of preparing the particles to be treated used in the polymerization step described later. In this step, the acid-treated complex that has undergone the acid-treating step is allowed to act on the nucleophile with a compound having a structure in which an alkyl group having a substituent as a leaving group is bonded to a benzene ring. A tertiary complex in which the nitrogen atom of polyethyleneimine is tertiary is obtained. The acid-treated complex contains polyethyleneimine derived from the above-mentioned chiral supermolecular crystal, and in this step, the nucleophilic nitrogen atom of the imino group (secondary amino group) of the polyethyleneimine is used. The nucleophile is reacted with a compound having a structure in which an alkyl group having a substituent as a leaving group is bonded to a benzene ring. As a result, the nitrogen atom of polyethyleneimine in the acid-treated complex is triturated and the alkylbenzene skeleton is introduced into the acid-treated complex. The acid-treated complex that has undergone this treatment is called a tertiary complex.

Forming such a tertiary complex in preparation for the polymerization step described later has the following two advantages. The first is that surface modification is performed to facilitate the introduction of monomers onto the surface of the tertiary composite. In order to obtain a polymer to which the chirality of the silica layer is transferred in the polymerization step described later, it is necessary to polymerize the monomer on the surface of the tertiary composite, and such surface modification is performed. As a result, more monomers are assembled on the surface of the tertiary composite by physsisorption. The second is to further enhance the chirality of the obtained polymer. Polyethyleneimine contained in the tertiary complex has structural chirality by being fixed to a chiral silica layer, and a bulky benzene ring is introduced along the main chain of this polyethyleneimine. By doing so, the benzene rings are arranged in a state of having chirality such as a spiral structure. As a result, the monomers assembled on the surface of the tertiary complex are arranged according to the arrangement of the benzene rings described above, and by polymerizing these, the chirality of the silica layer is more strongly transferred to the polymer. It is expected to become. That is, this step is a preparation for more strongly transferring the chirality of the silica layer contained in the acid-treated composite to the polymer.

As a compound having a structure in which an alkyl group having a substituent as a leaving group is bonded to a benzene ring with respect to the nucleophile, a compound represented by the following general formula (1) can be preferably mentioned.

In the above general formula (1), E is a substituent serving as a leaving group for the nucleophile. Examples of such a substituent include a chlorine atom, a bromine atom, an iodine atom, a tosyl group, a mesyl group and the like. Among these, a chlorine atom is preferably exemplified.

In the above general formula (1), R is a monovalent organic group. Examples of such an organic group include an aryl group which may have a substituent, an alkyl group having 1 to 8 carbon atoms, a vinyl group and the like. Among these, an aryl group which may have a substituent and a vinyl group are preferably exemplified, and an aryl group which may have a substituent is more preferably exemplified, and further desorbed from the nucleophilic reagent. An aryl group having an alkyl group having a substituent as a leaving group is particularly preferably exemplified. Since R is an aryl group which may have a substituent or an alkyl group having an alkyl group which is a substituent for the nucleophilic reagent, the side along the main chain of polyethyleneimine Substituents introduced as chains become more bulky and the glitter of the silica layer is more strongly transferred to the polymer. Among these, those represented by the following general formula (2) are preferably mentioned as the above-mentioned compounds.

In the above general formula (2), E is a substituent serving as a leaving group for the nucleophile. Examples of such a substituent include a chlorine atom, a bromine atom, an iodine atom, a tosyl group, a mesyl group and the like. Among these, a chlorine atom is preferably exemplified.

Since the above compound is represented by the general formula (2), two nitrogen atoms of the plurality of imino groups contained in polyethyleneimine are crosslinked with each other by the compound having a biphenyl structure, so that the silica layer It is expected that the glitter of the substance will be transferred to the polymer more strongly.

As a method for treating the acid-treated complex with the above compound, the acid-treated complex is dispersed in an appropriate solvent, the above compound and an alkaline salt are mixed, and the mixture is stirred at about 50 to 100 ° C. for about one day. Be done. As the solvent, alcohols, particularly methanol and ethanol can be preferably mentioned. Further, as a mixing ratio of the acid-treated complex and the above-mentioned compound, one equivalent or more of the above-mentioned compound with respect to the imino group in the acid-treated complex can be mentioned. As an example of such a case, the amount of the above compound is about 0.3 g per 1 g of the acid-treated complex, but the amount is not particularly limited. After the reaction, the acid-treated complex is filtered off and washed with an appropriate solvent to obtain a tertiary complex.

The tertiary compound that has undergone the tertiaryization step is subjected to the polymerization step.

[Polymerization process]
In the polymerization step, in the presence of particles to be treated derived from an acid-treated complex, a compound having an ethylenically unsaturated bond is radically polymerized as a monomer, and a polymer containing the monomer as a repeating unit is contained on the surface of the particles to be treated. This is a step of obtaining a resin composite by forming a resin composite. In this embodiment, the particles to be treated derived from the acid-treated complex mean the above-mentioned tertiary complex.

In the polymerization step, in order to transfer the chirality of the tertiary complex to the polymer formed by the polymerization, it is desirable to devise a way to allow the monomer to be present near the surface of the tertiary complex. As an example of such a device, after contacting the monomer with the tertiary complex (that is, the particles to be treated), if the monomer is water-insoluble, it is in a water-soluble solvent, and if the monomer is water-soluble, it is water-insoluble. It can be mentioned that radical polymerization is carried out in a sex solvent. In this way, for example, when the monomer is water-insoluble such as divinylbenzene, the tertiary complex was immersed in the liquid divinylbenzene to adsorb divinylbenzene on the surface of the tertiary complex. After that, the solid of the tertiary complex is filtered off, and this is put into water. Then, the water-insoluble divinylbenzene stays on the surface of the tertiary complex without diffusing into water. Therefore, if radical polymerization is carried out in this water using a radical polymerization initiator, the surface of the tertiary complex is formed. A polymerization reaction can be carried out. The chirality of the silica layer contained in the tertiary complex will be transferred to the polymer thus obtained. Contrary to the above, when a water-soluble monomer such as N, N'-methylenebisacrylamide is used, radical polymerization may be carried out in a water-insoluble solvent.

Examples of the aqueous solvent include a polar solvent that can be mixed with water, and examples of such a polar solvent include water, methanol, ethanol, and the like, and among these, water is preferably mentioned. Further, examples of the water-insoluble solvent include hydrocarbons such as toluene and xylene, and among these, toluene is preferably mentioned.

As the monomer, a compound having an ethylenically unsaturated bond can be mentioned without particular limitation, but if it becomes a liquid at room temperature or by heating, the monomer is placed on the surface of the tertiary complex as described above. It is preferable because it can be adsorbed. Examples of such monomers include styrene, divinylbenzene, methyl (meth) acrylate, t-butyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, triphenylmethyl (meth) acrylate, N, N'. -(Meta) acrylates such as dimethylamino (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, ethylenebis (meth) acrylate, 3- (trimethoxysilyl) propyl (meth) acrylate, acrylic acid , Methacrylate, N, N'-methylenebisacrylamide and the like. Among these monomers, those having two or more ethylenically unsaturated bonds are preferable, and from such a viewpoint, divinylbenzene, ethylene bis (meth) acrylate, N, N'-methylenebisacrylamide and the like are preferably mentioned. These monomers can be used alone or in combination of two or more. In addition, "(meth) acrylate" means methacrylate and / or acrylate.

Examples of the radical polymerization initiator include known ones such as organic peroxides and azo compounds. Examples of such a radical polymerization initiator include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylpropion amidine) dihydrochloride, benzoyl peroxide and the like.

The radical polymerization may be carried out at a temperature of, for example, room temperature to 100 ° C. for about 1 to 24 hours. After the completion of radical polymerization, the solid was recovered by means such as centrifugation and filtration, washed with an appropriate solvent, and then dried to form a polymer on the surface of the tertiary complex (that is, particles to be treated). A resin composite is obtained.

The obtained resin composite is subjected to a removal step.

[Removal process]
The removing step is a step of removing the silica forming the silica layer from the resin composite.

To remove the silica layer from the resin composite, the resin composite may be immersed in an alkaline solution or a hydrofluoric acid solution capable of dissolving silica. A chiral polymer can be obtained by stirring for several hours after immersion, recovering the solid by means such as centrifugation or filtration, washing with water or an appropriate solvent, and then drying. As the alkaline solution, a sodium hydroxide aqueous solution of about 5% by mass is preferably exemplified.

<Second Embodiment of Method for Producing Chiral Polymer>
Next, a second embodiment of the method for producing a chiral polymer according to the present invention will be described. In the second embodiment, a firing step of calcining the acid-treated composite obtained through the silica layer forming step and the acid treatment step described in the first embodiment, and a silane cup on the chiral silica particles obtained in the firing step. A surface treatment step of reacting a ring agent to obtain surface-treated silica is provided, and the surface-treated silica is subjected to a polymerization step and a removal step as particles to be treated. The silica layer forming step, the acid treatment step, the polymerization step, and the removing step are the same as those in the first embodiment already described, and thus the description thereof will be omitted here.

[Baking process]
The firing step is a step of obtaining chiral silica particles by firing the acid-treated composite obtained in the acid treatment step. The acid-treated complex contains a silica layer to which chirality is transferred from chiral supramolecular crystals and polyethyleneimine derived from chiral supramolecular crystals, of which polyethyleneimine, which is an organic substance, is removed by firing and acid-treated. In this step, the chiral silica layer contained in the composite is obtained as silica particles.

The firing conditions include heating at about 300 to 800 ° C. in an air atmosphere, but the firing conditions are not particularly limited. The Cotton effect of the calcined silica particles was observed by circular dichroism spectrum measurement, and it can be confirmed that the chirality transferred from the chiral supramolecular crystals is maintained.

The chiral silica particles that have undergone the firing step are subjected to the surface treatment step.

[Surface treatment process]
The surface treatment step is a step of reacting the silica particles obtained in the firing step with a silane coupling agent to obtain surface-treated silica. The surface-treated silica obtained in this step is subjected to the polymerization step as particles to be treated.

By treating the silica particles with a silane coupling agent before the polymerization step, the same effect as the above-mentioned tertiary step can be expected. That is, by facilitating the introduction of the monomer on the surface of the surface-treated silica (particles to be treated) and introducing a bulky substituent on the surface of the silica particles having chirality, the chirality of the silica particles is further transferred to the polymer. There are two effects of strong transcription.

From the above viewpoint, it is preferable to perform the surface treatment using a silane coupling agent having a bulky substituent. Preferred examples of such a silane coupling agent include trimethoxyphenylsilane, (p-chloromethyl) phenyltrimethoxysilane, and 3- (trimethoxysilyl) propylmethacrylate. The silane coupling agent preferably has a radically polymerizable residue (that is, an ethylenically unsaturated bond), and from such a viewpoint, 3- (trimethoxysilyl) propyl methacrylate and the like are more preferable.

When surface-treating silica particles, it is possible to dissolve a silane coupling agent in a hydrocarbon solvent, add the silica particles into this solution, and stir at about 30 to 50 ° C. for about 24 hours. it can. Toluene is preferably used as the hydrocarbon solvent. The mixing ratio of the silane coupling agent and the hydrocarbon solvent is not particularly limited, and an example is such that the volume ratio of the silane coupling agent: the hydrocarbon solvent is about 1: 4. Examples of mixing the mixed solution of the silane coupling agent and the hydrocarbon solvent and the silica particles include, but are not particularly limited, about 10 mL of the mixed solution with respect to 0.3 g of the silica particles. After the surface treatment is completed, the solid is taken out by means such as centrifugation or filtration, and the solid is washed with an appropriate solvent and dried to obtain surface-treated silica.

The obtained surface-treated silica is subjected to a polymerization step and a removal step as particles to be treated. A chiral polymer can be obtained through these steps. As already described, divinylbenzene is preferably used as the monomer in the polymerization step.

<Chiral polymer>
The chiral polymer obtained by the above method for producing a chiral polymer is also one of the present inventions. This chiral polymer contains a repeating unit using a compound having an ethylenically unsaturated bond as a monomer, and is characterized in that a positive or negative Cotton effect is observed in a circular dichroism spectrum measurement. This chiral polymer is in the form of particles and maintains the chirality derived from chiral silica. Therefore, the Cotton effect is exhibited in the circular dichroism spectrum measurement. As described above, divinylbenzene or N, N'-methylenebisacrylamide is preferably used as the above-mentioned monomer.

Hereinafter, the present invention will be described in more detail by showing examples, but the present invention is not limited to the following examples.

[Synthesis of linear polyethyleneimine (LPEI)]
30 g of commercially available polyethyloxazoline (mass average molecular weight 50,000, average degree of polymerization about 500, manufactured by Aldrich) was dissolved in a 5 mol / L hydrochloric acid aqueous solution (150 mL). The solution was heated to 90 ° C. in an oil bath and stirred at that temperature for 10 hours. Acetone (500 mL) was added to the reaction solution to completely precipitate the polymer, which was filtered off and washed 3 times with methanol to give a white polyethyleneimine powder. When the obtained powder was analyzed by ¹ H-NMR (heavy water), a peak of 1.2 ppm (CH ₃ ) and a peak of 2.3 ppm (CH ₂ ) derived from the ethyl group of the side chain of polyethyloxazoline were observed. Was confirmed to have completely disappeared. Therefore, it was shown that in the obtained polymer, polyethyloxazoline was completely hydrolyzed and converted to polyethyleneimine.

[Preparation of D- and L-complexes (D- and L-PEI / Tart @ SiO ₂ )]
0.60 g (4.0 mmol) of D-tartaric acid and 200 mL of distilled water were added to a 200 mL beaker and dissolved by heating at 100 ° C. to prepare a tartaric acid solution. 0.63 g of LPEI (8.0 mmol in terms of repeating unit) and 200 mL of distilled water were added to a 500 mL beaker and dissolved by heating at 100 ° C., and the entire amount of the above tartaric acid solution was added and stirred at 100 ° C. for 3 minutes. The reaction solution was rapidly cooled to room temperature in a water bath, and then ammonia water was added to adjust the pH to 4.0. The obtained solution was allowed to stand in a refrigerator for 20 hours, and then the white solid was collected by centrifugation from the obtained suspension and washed twice with distilled water to obtain chiral supermolecular crystals. The chiral supramolecular crystals obtained in the above procedure were added to a mixed solution of 12 mL of tetramethoxysilane (TMS) and 80 mL of distilled water, and the mixture was stirred at room temperature for 2 hours. The solid is recovered by centrifugation, washed once with distilled water and twice with acetone, and then dried under reduced pressure at room temperature to obtain a D-complex (also referred to as D-PEI / Start @ SiO ₂ ) of a white solid. It was. The D-complex is obtained by forming a silica layer on the surface of a chiral supramolecular crystal containing D-tartaric acid by a hydrolysis condensation reaction. Further, an L-complex (also referred to as L-PEI / Tart @ SiO ₂ ) was obtained by the same procedure except that L-tartaric acid was used instead of D-tartaric acid.

For the obtained complex (PEI / Tart @ SiO ₂ ), FT-IR was measured by the KBr method in a solid state. The result is shown in FIG. FIG. 1 is an FT-IR spectrum of the obtained complex (PEI / Tart @ SiO ₂ ). As shown in FIG. 1, N-H bonds in 3322Cm ^-1, vibration of C = O groups to 1597cm ^-1 were observed respectively, the presence of supramolecular complexes of LPEI and tartaric acid was confirmed. Further, since the expansion and contraction vibration of the O—Si—O bond was observed at 1071 cm- ¹ , the presence of the complex in which the silica layer was precipitated (that is, PEI / Tart @ SiO ₂ ) was confirmed.

Circular dichroism (CD) measurements were performed on each of the obtained D- / L-complexes. The result is shown in FIG. FIG. 2 is a circular dichroism spectrum for the obtained D- / L-complex (D- and L-PEI / Tart @ SiO ₂ ). As shown in FIG. 2, L-PEI / Tart @ SiO ₂ showed a positive Cotton effect at 210 nm, and D-PEI / Tart @ SiO ₂ showed a negative Cotton effect, on the contrary. Since these have a cotton effect having a sign opposite to that of tartaric acid itself, it is considered that the chirality of tartaric acid is transferred to the complex.

[Preparation of D and L-acid-treated complex (D and L-PEI @ SiO ₂ )]
1.0 g of D-complex (D-PEI / Tart @ SiO ₂ ) was placed in a screw tube, 50 mL of a 2.5 M hydrochloric acid aqueous solution was added, and the mixture was stirred at room temperature for 1 hour, and a white solid was recovered by centrifugation. After repeating this operation 5 times, wash once with distilled water and once with acetone, add 0.5 mg of white powder dried at room temperature and 0.1 mL of 0.1 wt% aqueous ammonia to the screw tube, and at room temperature. The mixture was stirred for 30 minutes. The solid was recovered by centrifugation, washed once with distilled water and twice with acetone, and then dried under reduced pressure to obtain a D-acid-treated composite (also referred to as D-PEI @ SiO ₂ ). Further, it is also referred to as an L-acid-treated complex (L-PEI @ SiO ₂ ) in the same procedure except that the L-complex (L-PEI / Tart @ SiO ₂ ) is used instead of the D-complex. ) Was obtained.

For the obtained acid-treated composite (PEI @ SiO ₂ ), FT-IR was measured by the KBr method in a solid state. The result is shown in FIG. FIG. 3 is an FT-IR spectrum showing a comparison between the obtained acid-treated complex (PEI @ SiO ₂ ) and the complex (PEI / Tart @ SiO ₂ ). As shown in FIG. 3, expansion and contraction vibration of the O—Si—O bond of silica was observed at 1071 cm ^-1, and the presence of silica was confirmed. On the other hand, since the expansion and contraction vibration of the C = O group derived from tartaric acid is reduced, it can be seen that tartaric acid was removed by the aqueous hydrochloric acid solution.

Circular dichroism measurements were performed on each of the obtained D- / L-acid-treated complexes. The result is shown in FIG. FIG. 4 is a circular dichroism spectrum of the obtained D- / L-acid-treated complex (D- and L-PEI @ SiO ₂ ). As shown in FIG. 4, it can be seen that the Cotton effect of tartaric acid at 210 nm is reduced in the circular dichroism spectrum and the absorption near 200 nm is also reduced in the absorption spectrum as compared with FIG. From these facts, it can be seen that tartaric acid is removed in the acid-treated complex.

[Example 1]
Based on the acid-treated composite obtained in the above procedure, a tertiaryization step by treatment with 4,4'-bis (chloromethyl) biphenyl (bp), a polymerization step using divinylbenzene (DVB) as a monomer, and water. The chiral polymer of Example 1 was obtained through a removal step using an aqueous sodium oxide solution. The procedure is as follows.

Triadization step 0.4 g of D- or L-acid-treated complex (PEI @ SiO ₂ ), 80 mL of methanol, 0.27 g of potassium carbonate and 4,4'-bis (chloromethyl) biphenyl in a 100 mL reaction vessel. 0.12 g of (bp) was added, and the mixture was stirred at 70 ° C. for 24 hours. The solid was collected by suction filtration, washed with deionized water, methanol, and acetone, and then dried under reduced pressure to obtain a white solid of a tertiary complex (bp-treated product). Circular dichroism measurements were performed on each of the obtained D- / L-terticycled complexes. The result is shown in FIG. FIG. 5 is a circular dichroism spectrum of the obtained D- / L-tertiary complex (D- and L-bp @ SiO ₂ ). As shown in FIG. 5, positive and negative Cotton effects were observed at 220 to 310 nm, respectively. In addition, mass spectrometry by TGA confirmed that the amount of organic matter increased more than that of the acid-treated complex, suggesting that bp was introduced by the tertiary formation.

-Polymerization step To a 5 mL screw tube, 0.3 g of D- or L-tertiary compound (bp-treated product) and 3 mL of divinylbenzene (DVB) were added, and the mixture was stirred at room temperature for 2 hours. The solid was collected by suction filtration to obtain a white solid. Next, 0.3 g of this white solid, 5 mL of deionized water and 0.03 g of 2,2'-azobis (2-methylpropion amidine) dihydrochloride (AAPH, radical polymerization initiator) were added to a 10 mL reaction vessel. After replacing the inside of the container with nitrogen, the mixture was stirred at 80 ° C. for 20 hours. The solid was recovered by centrifugation, washed with tetrahydrofuran (THF), methanol, and acetone, and then dried under reduced pressure to obtain a resin composite. Circular dichroism was measured for each of the obtained D- / L-resin composites. The result is shown in FIG. FIG. 6 is a circular dichroism spectrum of the obtained D- / L-resin composite (D- and L-bp @ SiO ₂ @ PDVB). As shown in FIG. 6, positive and negative Cotton effects were observed at 300 to 340 nm, respectively. Further, in the obtained resin composite, CH expansion and contraction vibration of 2927 cm ^-1 was observed in the IR spectrum, and it was confirmed by mass spectrometry by TGA that the amount of organic matter was increased as compared with the tertiary composite. Therefore, the formation of a polymer was confirmed by radical polymerization of DVB.

-Removal step 0.1 g of the resin composite and a 5 wt% NaOH aqueous solution (15 mL) were added to a 5 mL screw tube, and the mixture was stirred at room temperature for 4 hours. The solid was recovered by centrifugation, washed with deionized water and acetone, and then dried under reduced pressure to obtain the chiral polymer of Example 1. Circular dichroism measurements were performed on each of the obtained D- / L-chiral polymers. The result is shown in FIG. FIG. 7 is a circular dichroism spectrum of the D- / L-chiral polymer (D / L-PDVB) of Example 1. As shown in FIG. 7, positive and negative Cotton effects were confirmed at 270 to 320 nm, respectively. In the obtained chiral polymer, a decrease in O-Si-O absorption at 1085 cm- ¹ was observed in the IR spectrum, and it was confirmed by mass spectrometry by TGA that the silica content was 2.60%. It was. From these results, it can be seen that the chirality of the silica layer in the D- / L-complex is transferred to the chiral polymer of Example 1, and the chirality is maintained even after the removal of the silica.

[Example 2]
Based on the acid-treated complex obtained in the above procedure, a tertiary step by treatment with chloromethylstyrene (CMS), a polymerization step using N, N'-methylenebisacrylamide as a monomer, and an aqueous sodium hydroxide solution are used. The chiral polymer of Example 2 was obtained through the removal step. The procedure is as follows.

-Triadization step 0.3 g of chloromethylstyrene obtained by adding 1 g of D- or L-acid-treated complex (PEI @ SiO ₂ ) and 0.3 g of potassium carbonate to a 50 mL reaction vessel and further dispersing in 40 mL of dehydrated methanol. Was added, and the mixture was stirred at 70 ° C. for 24 hours. The solid was recovered by centrifugation, washed with THF, deionized water, and acetone, and then dried under reduced pressure to obtain a white solid of a tertiary complex (CMS-treated product). Circular dichroism measurements were performed on each of the obtained D- / L-terticycled complexes. The result is shown in FIG. FIG. 8 is a circular dichroism spectrum of the obtained D- / L-tertiary complex (D- and L-CMS @ SiO ₂ ). As shown in FIG. 8, positive and negative Cotton effects were observed at 250 to 300 nm, respectively. This CD activity is considered to be an organic CD of vinyl residues induced by chiral silica. Moreover, when mass spectrometry by TGA was performed, it was confirmed that the amount of organic matter was increased as compared with the acid-treated complex, suggesting that CMS was introduced by the tertiary formation.

-Polymerization step To a 5 mL screw tube, add 0.3 g of D- or L-tertiary complex (CMS-treated product), 0.5 g of N, N'-methylenebisacrylamide (MBA) and 2 mL of methanol at room temperature. The mixture was stirred for 2 hours. The solid was collected by suction filtration to obtain a white solid. Next, 0.3 g of this white solid, 5 mL of toluene and 0.03 g of 2,2'-azobis (isobutyronitrile) (AIBN, radical polymerization initiator) were added to a 10 mL reaction vessel, and the inside of the vessel was replaced with nitrogen. Then, the mixture was stirred at 80 ° C. for 20 hours. The solid was recovered by centrifugation, washed with deionized water, methanol, and acetone, and then dried under reduced pressure to obtain a resin composite. Circular dichroism was measured for each of the obtained D- / L-resin composites. The result is shown in FIG. FIG. 9 is a circular dichroism spectrum of the obtained D- / L-resin composite (D- and L-CMS @ SiO ₂ @ PMBA). As shown in FIG. 9, positive and negative Cotton effects were observed at 240 to 300 nm, respectively. Further, in the obtained resin composite, an increase in absorption due to C = C was observed at 1700 cm ^-1 in the IR spectrum, and an increase in organic substances was observed in the mass spectrometry by TGA as compared with the tertiary composite. Since it was confirmed that, the formation of a polymer was confirmed by radical polymerization of MBA.

-Removal step 0.1 g of the resin composite and a 5 wt% NaOH aqueous solution (15 mL) were added to a 5 mL screw tube, and the mixture was stirred at room temperature for 4 hours. The solid was recovered by centrifugation, washed with deionized water and acetone, and then dried under reduced pressure to obtain the chiral polymer of Example 2. Circular dichroism measurements were performed on each of the obtained D- / L-chiral polymers. The result is shown in FIG. FIG. 10 is a circular dichroism spectrum of the D- / L-chiral polymer (D / L-PMBA) of Example 2. As shown in FIG. 10, positive and negative Cotton effects were confirmed at 260 to 310 nm, respectively. In addition, in the obtained chiral polymer, a decrease in the absorption of O-Si-O at 1085 cm- ¹ was observed in the IR spectrum, and it was confirmed by mass spectrometry by TGA that the silica content was 2.80%. It was. From these results, it can be seen that the chirality of the silica layer in the D- / L-complex is transferred to the chiral polymer of Example 2, and the chirality is maintained even after the removal of the silica.

[Example 3]
Based on the acid-treated composite obtained in the above procedure, a firing step of decomposing an organic substance into silica particles by firing, a surface treatment step of treating 3- (trimethoxysilyl) propyl methacrylate (TPM), and divinylbenzene (divinylbenzene). The chiral polymer of Example 3 was obtained through a polymerization step using DVB) as a monomer and a removal step using an aqueous sodium hydroxide solution. The procedure is as follows.

-Baking step and surface treatment step The D- or L-acid-treated composite was fired at 600 ° C. for 3 hours to obtain silica particles. After 0.3 g of the silica particles were placed in a 10 mL reaction vessel, 8 mL of dehydrated toluene and 2 mL of 3- (trimethoxysilyl) propyl methacrylate (TPM) were added under nitrogen, and the mixture was stirred at 40 ° C. for 24 hours. The solid was collected by suction filtration, washed with methanol, and dried under reduced pressure to obtain a white solid of surface-treated silica (TPM-treated product). Circular dichroism measurements were performed on each of the obtained D- / L-surface-treated silicas. The result is shown in FIG. FIG. 11 is a circular dichroism spectrum of the obtained D- / L-surface-treated silica (D- and L-SiO ₂ @ TPM). As shown in FIG. 11, positive and negative Cotton effects were observed at 210-300 nm, respectively. Further, in the obtained surface-treated silica, absorption due to C = C was observed at 1700 cm ^-1 in the IR spectrum, and the presence of organic substances was confirmed by mass spectrometry by TGA.

-Polymerization step To a 5 mL screw tube, 0.3 g of D- or L-surface-treated silica (TPM-treated product) and 3 mL of divinylbenzene (DVB) were added, and the mixture was stirred at room temperature for 2 hours. The solid was collected by suction filtration to obtain a white solid. Next, 0.3 g of this white solid, 5 mL of deionized water and 0.03 g of 2,2'-azobis (2-methylpropion amidine) dihydrochloride (AAPH, radical polymerization initiator) were added to a 10 mL reaction vessel. After replacing the inside of the container with nitrogen, the mixture was stirred at 80 ° C. for 20 hours. The solid was recovered by centrifugation, washed with THF, methanol, and acetone, and then dried under reduced pressure to obtain a resin composite. Circular dichroism was measured for each of the obtained D- / L-resin composites. The result is shown in FIG. FIG. 12 is a circular dichroism spectrum of the obtained D- / L-resin composite (D- and L-SiO ₂ @ TPM @ PDVB). As shown in FIG. 12, positive and negative Cotton effects were observed at 250 to 320 nm, respectively. Further, since it was confirmed by mass spectrometry of the obtained resin composite by TGA that the amount of organic substances increased as compared with the surface-treated silica, the formation of a polymer was confirmed by radical polymerization of DVB.

-Removal step 0.1 g of the resin composite and a 5 wt% NaOH aqueous solution (15 mL) were added to a 5 mL screw tube, and the mixture was stirred at room temperature for 4 hours. The solid was recovered by centrifugation, washed with deionized water and acetone, and then dried under reduced pressure to obtain the chiral polymer of Example 3. Circular dichroism measurements were performed on each of the obtained D- / L-chiral polymers. The result is shown in FIG. FIG. 13 is a circular dichroism spectrum of the D- / L-chiral polymer (D / L-PDVB) of Example 3. As shown in FIG. 13, positive and negative Cotton effects were confirmed at 250 to 320 nm, respectively. In the obtained chiral polymer, a decrease in O-Si-O absorption at 1085 cm- ¹ was observed in the IR spectrum, and it was confirmed by mass spectrometry by TGA that the silica content was 4.90%. It was. From these results, it can be seen that the chirality of the silica layer in the D- / L-complex is transferred to the chiral polymer of Example 3, and the chirality is maintained even after the removal of the silica.

Claims (11)

Hydrolyzed into chiral supermolecular crystals of acid-base complex comprising a polymer having a linear polyethyleneimine skeleton and a chiral dicarboxylic acid compound having two carboxyl groups and four or more carbon atoms. A silica layer forming step of obtaining a complex in which a silica layer is formed on the surface of the chiral supermolecular crystal by a hydrolysis condensation reaction in which a carboxylic silicon compound acts.
An acid treatment step of acid-treating the complex to obtain an acid-treated complex, and
In the presence of particles to be treated derived from the acid-treated complex, a compound having an ethylenically unsaturated bond is radically polymerized as a monomer to form a polymer containing the monomer as a repeating unit on the surface of the particles to be treated. Polymerization process to obtain a resin composite
A method for producing a chiral polymer, comprising a removing step of removing silica forming the silica layer from the resin composite. In the polymerization step, after the monomer is brought into contact with the particles to be treated, the radical is in a water-soluble solvent if the monomer is water-insoluble, or in a water-insoluble solvent if the monomer is water-soluble. The method for producing a chiral polymer according to claim 1, wherein polymerization is carried out. By allowing a compound having a structure in which an alkyl group having a substituent as a desorbing group is bonded to a benzene ring, the acid-treated complex is allowed to act on the nucleophilic reagent, the nitrogen atom of the polyethyleneimine is tertiary. The third aspect of claim 1 or 2, further comprising a tertiaryization step of obtaining a modified tertiary compound, and subjecting the tertiary compound obtained in this step to a polymerization step as the particles to be treated. A method for producing a chiral polymer. The chiral polymer according to claim 3, wherein the compound having a structure in which an alkyl group having a substituent as a leaving group for a nucleophile is bonded to a benzene ring is a compound represented by the following general formula (1). Manufacturing method.

(In the above general formula (1), E is a substituent serving as a leaving group for the nucleophile, and R is a monovalent organic group.) Any of claims 3 or 4, wherein the compound having a structure in which an alkyl group having a substituent as a leaving group is bonded to a benzene ring with respect to the nucleophile is a compound represented by the following general formula (2). The method for producing a chiral polymer according to item 1.

(In the above general formula (2), E is a substituent serving as a leaving group for the nucleophile.) The method for producing a chiral polymer according to any one of claims 1 to 5, wherein a compound having two or more ethylenically unsaturated bonds is used as the monomer. After obtaining chiral silica particles by firing the acid-treated composite, a surface treatment step of reacting the silica particles with a silane coupling agent to obtain surface-treated silica is further included, and the surface treatment obtained in this step is further included. The method for producing a chiral polymer according to claim 1 or 2, wherein silica is subjected to a polymerization step as the particles to be treated. The method for producing a chiral polymer according to claim 7, wherein a compound having two or more ethylenically unsaturated bonds is used as the monomer. The method for producing a chiral polymer according to claim 7 or 8, wherein the silane coupling agent has a radically polymerizable residue. A chiral polymer containing a repeating unit containing a compound having an ethylenically unsaturated bond as a monomer, wherein a positive or negative Cotton effect is observed in circular dichroism spectrum measurement. The chiral polymer according to claim 10, wherein the monomer is divinylbenzene, ethylene bismethacrylate or N, N'-methylenebisacrylamide.

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