JP2007039507A - Resorcinol-based wire-like polymer particle and its compound method and use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide resorcinol-based polymer particles prepared by a new synthetic process and having new physical properties and forms. <P>SOLUTION: This method for producing the wire-like, resorcinol-based polymer particles comprises adding a monomer for reacting to form a specific polymer to a solution comprising one or more surfactants selected from the group consisting of alkyl ammonium salts and alkylamines and water in a specific molar ratio in the presence of a basic condensing agent, and copolymerizing the monomer in the presence of the surfactant as a template. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is based on a resorcinol / formaldehyde copolymer used as a high-performance separating agent, adsorbent, substance storage agent, additive to fibers, rubber, film, plastic products, ink, paint, etc., heat insulating material, etc. The present invention relates to a layered structure as a component or a wire-like polymer particle having a wire-like structure having a layered structure as a structural unit, a method for producing the same, and use thereof.

  In this specification, the wire shape is the outer shape of the polymer particles, refers to a state in which the polymer particles are in a wire shape, the ratio of the short axis to the long axis is a rod shape, whisker shape with a large aspect ratio, It may include a form having an outer diameter such as a string, and these are generically distinguished from so-called spherical polymer particles.

  Resorcinol resin, which is an oily or solid amorphous polymer obtained by condensing resorcinol with a hydroxyl group substituted at the meta position of phenol and aldehydes such as formaldehyde with acid or alkali, is heat-cured like phenolic resin. Utilizing the properties, it has been used for adhesives, insulating laminates, decorative boards, etc. by treating with a resin alone or varnish dissolved in alcohol, or with wood powder, dye, etc. All of these are applied liquidity, adhesion, thermosetting and moldability exclusively as liquid or solid polymers.

On the other hand, in recent years, development of technology for making resorcinol resin porous or fine particles has been progressing. Pekala et al pointed out the similarity between the resorcinol (R) -formaldehyde (F) hydrolysis / condensation reaction mechanism and the sol-gel reaction of inorganic oxides, and a specific surface area of about 700 m by supercritical drying of the RF condensate. It was found that ² / g airgel was obtained (Non-patent Document 1). And it has been reported that porous carbon can be obtained by carbonizing this porous RF gel (Non-patent Document 2).

  Furthermore, as a related technology, after preparing a composite of silica fine particles (Non-patent Document 3), polystyrene latex (Non-patent Document 4) or block copolymer (Non-patent Document 5) and resorcinol-formaldehyde resin, carbonizing this. An example of synthesizing a carbon material having a controlled pore structure by means of a method has been reported.

  In this way, the resorcinol-formaldehyde resin is used as a carbon source, and the structure and form of the resin itself, or the skeletal structure formed by introducing the resin into the pore structure of various porous bodies, is copied as a carbon structure. And carbon materials having a pore structure and technologies for creating the same have been developed.

  Generally, polymer fine particles are generally prepared by emulsion polymerization or dispersion polymerization in an aqueous dispersion medium when an oily monomer such as styrene, acrylic acid ester, methacrylic acid ester, or vinyl chloride is used as a starting material.

  In the case of a thermosetting polymer produced by polycondensation of phenols and aldehydes, the method for synthesizing fine particles varies greatly depending on starting materials. That is, in the phenol / formaldehyde resin system, fine particles are prepared by a method of physically pulverizing a solid polymer or a method of subjecting a prepolymerized prepolymer to an emulsion polymerization treatment.

  In contrast, in the resorcinol / formaldehyde resin system, spherical particles having a diameter of several μm are directly generated by polymerizing a water-soluble monomer in a hydrophobic medium. When this is fired in an inert gas, the diameter is several μm. It has been reported that spherical carbon particles have been obtained (Non-Patent Document 6).

  A technique for synthesizing a fibrous polymer by a devised method and creating a carbon nanofiber (CNF) using this as a precursor has also been developed. That is, spinning of various polymers under application of a high piezoelectric field (Non-Patent Documents 7 and 8), emulsion polymerization of polyacrylonitrile (PAN) using a liquid phase as a reaction field (Non-Patent Document 9), and fineness of the alumina film surface Pitch filling into pores (Non-patent Document 10), fibers by polymerization reaction of PAN and polybenzimidazole in porous solids such as anodized alumina (Non-patent Document 11) and sepiolite (Non-patent Document 12) It has been reported that fibrous carbon of the same size was obtained by synthesizing a polymer and calcining it in an inert gas.

  In 1992, Mobil Corporation created mesoborous silica having honeycomb-shaped mesopores having a diameter of 2 to 8 nm using surfactant micelles as a template (Non-patent Document 13). Subsequently, in the same manner, in addition to mesoporous silica having various pore structures such as cubic lattices, a number of mesoporous materials having metal oxides and sulfides as skeleton components were synthesized one after another (non- Patent Document 14).

  The present inventors also prepared a hexagonal structure-type rare earth oxide mesoporous material by preparing a composite produced by a uniform precipitation method using urea using dodecyl sulfate ions as a template, and then exchanging the template ions with acetate ions. (Non-Patent Documents 15 and 16). Furthermore, platinum nanotubes were successfully synthesized by reducing chloroplatinic acid in a liquid crystal composed of two types of nonionic surfactants, which was published in a paper (Non-patent Document 17).

  The pore diameters of the mesoporous material and nanotubes obtained as described above are substantially determined by the length of the template molecule used, and the controllable pore diameter is limited to the range of 2 nm to 6 nm. On the other hand, a method has been developed in which a surfactant micelle is swollen by adding a hydrophobic molecule such as trimethylbenzene in addition to the surfactant to expand the control range of the pore diameter (non-patent document). 18, 19).

  On the other hand, preparation methods using surfactants have been developed for polymer fine particles. The most widely used is a method (emulsion polymerization method) in which an oily vinyl monomer is polymerized in an emulsion formed in an aqueous solvent using a surfactant as an emulsifier (dispersant).

Illustrative examples include synthetic rubbers such as styrene-butadiene rubber (SBR), butadiene rubber (BR), and chloroprene rubber (CR), and synthetic latexes such as styrene-based, acrylic-based, and vinyl acetate-based resin emulsions.
The main components of this method are water as a reaction medium, a surfactant, a monomer that is hardly soluble in water, and a water-soluble initiator. To do.

  A method of polymerizing or complexing a surfactant and a monomer or polymer while coulombically bonding has also been developed. A typical example is a complexed polyacrylic acid / dodecyltrimethylammonium ion complex (Non-patent Document 20) produced by adding a surfactant to a polymer electrolyte. A phenol / formaldehyde polymer composite having a honeycomb structure has also been obtained by a similar reaction method (Non-patent Document 21).

  The present inventors also synthesized a tubular nanostructure by copolymerizing phenol and furfural in the presence of the surfactant alkyltrimethylammonium bromide (Non-patent Document 22).

  Recently, when a mixed solution composed of resorcinol, formaldehyde, sodium carbonate, ethanol, and water is subjected to a heat reaction in the presence of cetyltrimethylammonium bromide, an amorphous cluster aggregate of 100 nm or less is formed, and decyltrimethylammonium bromide or A similar reaction in the presence of tetrapropylammonium bromide produces spherical resorcinol-formaldehyde polymer particles having a diameter of 1 to 3 μm, and it is reported that spherical carbon particles of the same size can be obtained by firing this in an inert gas. (Non-Patent Document 23).

  On the other hand, the patent information includes (I) water-insoluble or slightly soluble alkoxysilanes, (II) emulsifiers, (III) water, and (IV) alkoxysilane functional groups that are stable for at least about 3 to 12 months. A water-dispersible or emulsified polymer containing a stable aqueous curable silane / polymer composition (Patent Document 1) or a dispersion of droplets and then if polymer particles are desired, It is described that desired particles are prepared by polymerizing monomers in these droplets (Patent Document 2). Furthermore, a low containing a limited amount of a defined aromatic phosphate ester compound with UL-94 V-2 rating, thermal stability, toughness, processability, hydrolysis and resistance to chemicals. A volatile aromatic phosphate ester compound-containing carbonate polymer resin has been proposed (Patent Document 3).

  And further in an oil-in-water nanoemulsion comprising an oil phase dispersed in an aqueous phase, the oil globules having a number average size of less than 150 nm, at least one oil, at least one amphiphilic lipid, and Obtaining a nanoemulsion comprising at least one nonionic polymer comprising at least one hydrophobic block and at least one hydrophilic block, wherein the ratio of the amount of oil to the amphiphilic lipid is from 1 to 10 (Patent Document 4) has been proposed.

Pekala, J. et al. Mater. Sci. , 24, 3221 1-3227 (1989) R. W. Pekala, J. et al. Non-Cryst. Solids, 145, 90 (1992) S. Han and two others, Chem. Mater. 12, 3337-3341 (2000) T. T. et al. F. Baumann et al. Non-Cryst. Solids, 350, 120-125 (2004) C. Liang and 4 others, Angew. Chem. Int. Ed. , 43, 5785-5789 (2004)] T. T. et al. Yamamoto and 4 others, Carbon, 40, 1345-1351 (2002) C. Kim et al. Raman. Spectrosc. , 35, 928-933 (2004) E. Zussman and 6 others, Carbon, (2005) J. et al. Jang and one other, Angew. Chem. 116, 3891-3894 (2004) K. Jian and four others, Adv. Mater. , 15, no. 2, 164-167 (2003) Y. Zhao and four others. Chem. And Phys. 82, 370-374 (2003) R. Fernandez-Saavedra and two others, Adv. Funct. Mater. , 14, no. 1, 77-82 (2004) C. T. T. et al. Kresga and 4 others, Nature, 359, 710-712 (1992) Takeshi Kijima et al. Soc. Inorg. Mater. , 8, 3-16 (2001) M.M. Yada and three others, Inorg. Chem. 37, 6470-6475 (1998), M.M. Yada and three others, Angew. Chem. Int. Ed. , 38, 3506-3509 (1999) T. T. et al. Kikima et al., 5 people, Angew. Chem. Intern. Ed. 43, 228-232 (2004). B. Lindlar and three others, Microporous and Mesoporous Mater. 44-45, 89-94, 2001 Y. Liang et al., Microporous and Mesoporous Mater. 44-45, 72, (2004) M.M. Antonietti and one other, Angew. Chem. Int. Ed. Eng. 33, 1869 (1994) I. Moriguchi and 5 others, Chem. Lett. 1171-1172 (1999) M.M. Uota and 7 others, MRS. Symp. Proc, 775, 29-34 (2003) Nishiyama et al. Carbon, 43, 269-274, (2005). Japanese Patent No. 3468776 Japanese Patent No. 3530527 Japanese Patent No. 3645910 JP 2001-226221 A

  The present invention has a novel composition, a new physical property, and a form different from those described above, keeping in mind various research reports and prior arts on the organic polymer particles and their preparation methods introduced and enumerated about the prior art. It aims to provide microparticles and a novel synthesis process.

  The skeleton is composed of a polymer structure whose main component is resorcinol, and the shape is a nanowire shape with a diameter of 2 to 100 μm, a length of 20 to 300 μm, or a diameter of 10 to 300 nm, and a length of 1 to 100 μm. It is intended to provide polymer particles that have substance storage ability and molecular separation ability, and that specifically express chemical, thermal, electrical, and physical functions derived from the skeleton shape and composition. is there. This also aims to provide new materials that contribute to technological innovation in the fields of chemistry, electronics, information, environment and biotechnology.

  Since the similarity between the resorcinol (R) -formaldehyde (F) hydrolysis and condensation reaction mechanism and the inorganic oxide sol-gel reaction has been demonstrated by Pekala et al., RF polymer gels have been characterized by their porosity and Utilizing a high specific surface area, it has been used as an electrode auxiliary agent or a carbon precursor for a fuel cell.

Therefore, if the shape of the RF polymer gel can be finely and precisely controlled, the material can be controlled with additives that add new functions to existing fibers, plastics, inks, paints, adhesives, etc. It can be used more widely as a separating agent / adsorbent having precise molecular sieving ability and substance storage ability unique to the structure.
However, there is no report that the RF copolymer was precisely controlled on the nano order.

  Therefore, the present inventors show that the reaction between resorcinol and formaldehyde in an aqueous solution shows a sol-gel reaction similar to silicon alkoxide, which is a silica source of the porous silica MCM-41 synthesized by the organic template method. Based on the idea that the same templating effect can be achieved with polymers, we are more keen on the types of raw materials, catalysts and surfactants used in the reaction, and reaction conditions in order to create polymer particles that will be carbon precursors. Research progressed.

  As a result, we succeeded in synthesizing highly curable polymer particles with highly controlled morphology under the condition of using cationic surfactant as template micelle and alkali as catalyst. Furthermore, a thermosetting polymer particle having a wire-like form was successfully synthesized by adding a basic condensing agent and an additive such as alkylbenzene to a reaction mixture containing a cationic surfactant for polymerization.

That is, as a result of intensive studies, the present inventors have succeeded in solving and achieving the above-described problem by the invention in which the technical configuration described below is taken.
That is, the first invention is
(1) selected from one or more monomers selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinol, and aldehydes such as formaldehyde and furfural A wire characterized by having a wire-like structure having a diameter of 2 to 100 μm and a length of 20 to 300 μm, having a layered structure with a spacing of 1 to 10 nm as a skeleton component and having a copolymer with one or more monomers as a skeleton component Polymer particles.
The second invention is
(2) One or more types of monomers selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinol, and aldehydes such as formaldehyde and furfural. Comprising a copolymer of one or more monomers and one or more surfactants selected from the group consisting of alkylammonium salts such as hexadecyltrimethylammonium bromide and alkylamines such as hexadecylamine, A compound characterized by having a wire-like structure having a diameter of 2 to 100 μm and a length of 20 to 300 μm having a layered structure with an interval of 1 to 10 nm as a structural unit.
The third invention is
(3) One or more types of monomers selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinol, and aldehydes such as formaldehyde and furfural. A wire-like polymer particle characterized by having a wire-like structure having a diameter of 10 to 300 nm and a length of 1 to 100 μm, comprising a copolymer with one or more monomers as a skeleton component.
The fourth invention is:
(4) One or more monomers selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinol, and aldehydes such as formaldehyde and furfural. Copolymer with one or more monomers, comprising a bond with one or more surfactants selected from the group consisting of alkylammonium salts such as hexadecyltrimethylammonium bromide and alkylamines such as hexadecylamine, and having a diameter of 10 Wire-like polymer particles characterized by having a wire-like structure of ˜500 nm and a length of 1 to 100 μm.

Hereinafter, the fifth, sixth, seventh and eighth inventions provide methods for producing the polymers of the first, second, third and fourth inventions.
That is, the fifth invention is
(5) In the presence of a basic condensing agent, at least one surfactant selected from the group consisting of alkylammonium salts such as hexadecyltrimethylammonium bromide and alkylamines such as hexadecylamine and water are used in a ratio of 1: 120 to 1200. A solution mixed at a molar ratio of at least one monomer selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinol and aldehydes such as formaldehyde and furfural. A product obtained by adding and reacting one or more monomers selected from among them is selected from the group consisting of one or more solvents selected from the group consisting of alcohols such as ethanol and an acid such as hydrochloric acid. Treated with a mixed solution of at least one kind of acid prepared, the method for producing a polymer according to the above item (1), A.
The sixth invention is:
(6) In the presence of a basic condensing agent, at least one surfactant selected from the group consisting of alkylammonium salts such as hexadecyltrimethylammonium bromide and alkylamines such as hexadecylamine and water are used in a ratio of 1: 120 to 1200. A solution mixed at a molar ratio of at least one monomer selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinol and aldehydes such as formaldehyde and furfural. A method for producing a polymer as described in (2) above, wherein one or more monomers selected from the above are added and reacted.
The seventh invention
(7) One or more surfactants selected from the group consisting of basic condensing agents and alkylammonium salts such as hexadecyltrimethylammonium bromide and alkylamines such as hexadecylamine and selected from the group consisting of alkylbenzenes such as mesitylene. In the presence of one or more additives, one or more monomers selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinols and aldehydes such as formaldehyde and furfural The product obtained by reacting one or more monomers selected from among the classes is selected from the group consisting of one or more solvents selected from the group consisting of alcohols such as ethanol and an acid such as hydrochloric acid. The mixture according to item (3), wherein the mixture is treated with a mixed solution of at least one kind of acid. A method of manufacturing a mer is a,.
The eighth invention
(8) One or more surfactants selected from the group consisting of basic condensing agents and alkylammonium salts such as hexadecyltrimethylammonium bromide, and alkylamines such as hexadecylamine, and selected from the group consisting of alkylbenzenes such as mesitylene. In the presence of one or more additives, one or more monomers selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinols and aldehydes such as formaldehyde and furfural A method for producing a polymer as described in (4) above, wherein at least one monomer selected from the group is reacted.

In the following, the ninth to thirteenth inventions present inventions of use of the polymers of the first, second, third and fourth inventions.
That is, the ninth invention
(9) A wire-like resorcinol-based polymer described in any one of (1) to (4) above, comprising various substances separating agent, adsorbent or storage agent, or fiber, rubber, film Or general-purpose functionality characterized by being used for many purposes such as additives and fillers for plastic products, or additives for liquid products such as paints, inks, adhesives or paper coating agents. material.
The tenth invention is
(10) The functional material as described in the item (9), characterized in that its use is provided and used as a separating agent, adsorbent or storage agent for various substances.
The eleventh invention is
(11) The functional material according to item (9), characterized in that its use is used as an additive for fibers, rubber, films or plastic products.
The twelfth invention is
(12) The functional material as described in the item (9), which is used as an additive to liquid products such as paints, inks, adhesives or paper coating agents.
The thirteenth invention
(13) The functional material described in the item (9), wherein the use is used as a heat insulating material.

  The polymer particles obtained by the present invention are similar to the spherical polymer particles described in the previous document (Non-patent Document 23) introduced earlier in the synthesis method. However, resorcinol-formaldehyde polymer particles according to the same report have a cluster aggregate having a particle size of 100 nm or less obtained by a cetyltrimethylammonium bromide-based reaction, and a diameter of 1 to 1 obtained by a decyltrimethylammonium bromide or tetrapropylammonium bromide-based reaction. Limited to 3 μm spherical particles.

  On the other hand, as is apparent from the electron microscopic images of Examples 1 and 2 described below, the resorcinol-formaldehyde polymer obtained by the present invention has a diameter 2 having a layered structure with a spacing of 1 to 10 nm as a structural unit. It is proved to be a wire-like polymer particle characterized by having a wire-like structure having a diameter of 10 to 300 μm, a length of 20 to 300 μm, a diameter of 10 to 300 nm, and a length of 1 to 100 μm. There are significant structural and morphological differences from the examples.

  Furthermore, the production method of these polymer particles is also different between the present invention and the prior literature. That is, in the prior literature, the copolymerization reaction of resorcinol and formaldehyde is proceeding in a dilute aqueous solution in which a surfactant and water are mixed at a molar ratio of 1: 3000 in the presence of sodium carbonate as a catalyst. Then, while using the same surfactant as the prior art, the reaction proceeds in a considerably concentrated solution having a molar ratio of surfactant to water of 1: 360 in the presence of sodium hydroxide as a catalyst. In the case of the products of Item 3 and Claim 4, there is a decisive difference that a hydrophobic molecule such as trimethylbenzene is added to the reaction mixture.

  That is, even in the synthesis process using a common surfactant called cetyltrimethylammonium bromide, the product obtained is a cluster aggregate in the prior art, whereas in the present invention, the layered structure is a structural unit. It is clear that wire-like structures have been obtained and the polymer particles obtained in both are completely different in morphology.

  Furthermore, in the prior literature, ethanol having an action of breaking or destabilizing the micelle form of the surfactant is added to the reaction system. For this reason, in the case of the prior art document, micelles having a dilute concentration range and a form destabilized with ethanol and a resorcinol / formaldehyde copolymer are complexed to reflect the destabilized micelle form. In the present invention, a layered or spherical structure having a structure reflecting the shape of micelles formed in a dense concentration range (for spherical polymers, another application filed on the same day as this application). It is considered that a resorcinol / formaldehyde copolymer (patent pending) is obtained.

  Thus, it is clear that the mixing ratio of the surfactant and water used makes a decisive difference in the shape and particle size of the product in the prior art and in the present invention.

With the above configuration, the present invention has a wide variety of excellent effects as listed below, and is expected to be used in various fields.
(1) When this is used as a material separation material, it can be expected to be applied to a chromatographic carrier, ion-exchange resin, and the like that are chemically stable in the acid / alkali region and whose particle form / size is controlled.
(2) When this is used as a substance storage material, it is expected to work effectively for storing small molecules such as hydrogen and ions due to its unique shape.
(3) When this is used as an additive for fibers, rubbers, films or plastic products, it is chemically and thermally stable and can contribute greatly to the modification and reinforcement of products due to its unique shape.
(4) When used as an additive to liquid products such as paints, inks, adhesives or paper coatings, it is chemically and thermally stable and can contribute greatly to product modification due to its unique shape. .
(5) When this is used as a battery material, higher performance as an electrode material can be expected from the unique shape and composition of the particles.
(6) When this is used as an electric double layer capacitor material, higher performance can be expected from the unique shape and composition of the particles.

  The invention of this application has the above-described features, and will be specifically described below with reference to the accompanying drawings. However, these examples merely disclose one aspect of the present invention, and are not intended to limit the present invention. That is, the aim of the present invention is a layered structure with a spacing of 1 to 10 nm organized as a main component of a copolymer of phenols and aldehydes having a structure in which two or more hydroxyl groups are substituted. As described above, the present invention provides a wire-like polymer particle having a wire-like structure having a diameter of 2 to 100 μm, a length of 20 to 300 μm, and a diameter of 10 to 300 nm and a length of 1 to 100 μm. It is.

  The contained components and structures are polymer particles having specific dimensions and shapes having a skeleton component of a copolymer of one or more types of phenols and one or more types of aldehydes. The constituent components are phenols and aldehydes. In addition, in addition to permitting various combinations in terms of composition, other substituents are easily introduced into the skeletal structure by an operation such as a substitution reaction, and thus various combinations are included.

  In addition, the main point of the manufacturing method is that one or more phenols and aldehydes are mixed in a surfactant solution and reacted under a basic condensing agent or by adding a hydrophobic molecule such as trimethylbenzene. In order to induce polymer particles of specific dimensions and form, the optimum reaction temperature and reaction mixture composition at each stage for constructing the structure vary depending on the target monomer species and the characteristics of the surfactant used. Change.

  On the other hand, an Example shows only the example of the aspect with respect to this invention, and the monomer seed | species and manufacturing method which comprise this invention should not be limited by this Example.

  FIG. 1A and FIG. 2A are scanning electron microscope (SEM) images of polymer particles synthesized according to the present invention. According to this, it was confirmed that all took the wire form. It was found that even when these were treated with hydrochloric acid / ethanol, the same morphology was maintained.

Example 1;
A solution with a molar ratio of resorcinol, sodium hydroxide, cetyltrimethylammonium bromide and water 1: 1: 1: 360 was prepared. While stirring this solution, a solution of resorcinol: formaldehyde 1: 4 (molar ratio) was added and reacted at 50 ° C. for 2 hours, then at 90 ° C. for 72 hours, and then further with paraformaldehyde (molar ratio 4). Hydrothermal treatment was performed at 150 ° C. for 24 hours. The obtained solid phase was centrifuged, washed, and dried under reduced pressure to obtain a solid product.
From a scanning electron microscope (SEM) image, it was found that this solid product was composed of wire particles formed by collecting fine fibrous structures having a diameter of 3 to 5 μm in a bundle (FIG. 1 (a)). . Furthermore, when this sample was pulverized and subjected to ultrasonic treatment, the laminated structure of the sheet was observed by SEM / transmission electron microscope observation (FIGS. 1B and 1C).

Example 2;
A solution with a molar ratio of resorcinol, sodium hydroxide, cetyltrimethylammonium bromide and water 1: 1: 1: 360 was prepared. While stirring this solution, a solution of resorcinol: formaldehyde 1: 4 (molar ratio) was added and reacted at 50 ° C. for 2 hours, then at 90 ° C. for 72 hours, and then further with paraformaldehyde (molar ratio 4). Hydrothermal treatment was performed at 150 ° C. for 24 hours. The obtained solid phase was centrifuged, washed, and dried under reduced pressure to obtain a solid product. Further, 1 g of the dried sample was added to a mixed solution of 5 ml of 2M hydrochloric acid and 45 ml of ethanol, and the dispersion was treated at room temperature for 24 hours to obtain a final solid product.
From the scanning electron microscope (SEM) image, it was found that this solid product was composed of wire particles formed by collecting fine fibrous structures having a diameter of 3 to 5 μm in a bundle (FIG. 1 (d)). .

Example 3;
A solution with a molar ratio of resorcinol, sodium hydroxide, cetyltrimethylammonium bromide, mesitylene and water 1: 0.25: 1: 1: 360 was prepared. While stirring this solution, a solution of resorcinol: formaldehyde 1: 4 (molar ratio) was added and reacted at 50 ° C. for 2 hours, then at 90 ° C. for 72 hours, and then further with paraformaldehyde (molar ratio 4). Hydrothermal treatment was performed at 150 ° C. for 24 hours. The obtained solid phase was centrifuged, washed, and dried under reduced pressure to obtain a solid product.
From the scanning electron microscope (SEM) image of the obtained sample, this solid product was confirmed to be in the form of aggregates of wire-like particles having a diameter of 80 to 300 nm (FIG. 2 (a)).

Example 4;
A solution with a molar ratio of resorcinol, sodium hydroxide, cetyltrimethylammonium bromide, mesitylene and water 1: 0.25: 1: 1: 360 was prepared. While stirring this solution, a solution of resorcinol: formaldehyde 1: 4 (molar ratio) was added and reacted at 50 ° C. for 2 hours, then at 90 ° C. for 72 hours, and then further with paraformaldehyde (molar ratio 4). Hydrothermal treatment was performed at 150 ° C. for 24 hours. The obtained solid phase was centrifuged, washed, and dried under reduced pressure to obtain a solid product. Further, 1 g of the dried sample was added to a mixed solution of 5 ml of 2M hydrochloric acid and 45 ml of ethanol, and the dispersion was treated at room temperature for 24 hours to obtain a final solid product.
From the scanning electron microscope (SEM) image of the obtained sample, it was confirmed that this solid product was an aggregated form of wire-like particles having a diameter of 40 to 250 nm (FIG. 2 (b)).

  As a result of accumulating various experimental examples in addition to the above examples and arranging the obtained data, the present invention provides the polymer particles described in the items (1), (2), (3) and (4). It has been confirmed that there is.

  As a result, the present invention provides a wire-like polymer particle characterized by having a wire-like structure having a lamellar structure with a spacing of 1 to 10 nm as a structural unit, organized with a resorcinol-based resin as a main component. I am convinced that it has been successful and its significance is extremely large. Disclosure of detailed physical properties, specific data on various characteristics and effects in various technical fields, and research and development of new technical possibilities and developments related to this will be conducted in the future. However, due to its composition and characteristic structure, there is a great possibility that it can provide excellent effects in various fields.

  That is, various useful functions such as the unique shape and fineness of pores, molecular sieving, substance separation, storage of small molecules, electrical conductivity or electrical insulation, and selective adsorption characteristics for specific molecules With the development of these useful functions, the high-performance separation agent, adsorbent, substance storage agent, additives for fibers, films, plastic products, inks, paints, adhesives, paper coating agents, etc. In particular, the present inventors have succeeded in obtaining polymer particles that can be used for various extremely important applications.

  Here, a polymer having a wire-like form having a diameter of 2 to 100 μm and a length of 20 to 300 μm having a layered structure as a structural unit (claim 1) and a polymer / surfactant complex (claim 1) 2), and a polymer (Claim 3) and a polymer / surfactant complex (Claim 4) which also have a wire-like form with a diameter of 10 to 300 nm and a length of 1 to 100 μm. The production method has been specifically disclosed in the above-mentioned Examples, and the reaction conditions in the production method when the production method is carried out from the preparation of the reaction mixture are summarized as follows.

  First, a polymer having a wire-like form having a diameter of 2 to 100 μm and a length of 20 to 300 μm having a layered structure as a structural unit (claim 1) and a polymer / surfactant complex (claim 2) Item).

The reaction conditions are summarized as follows by way of example.
That is, description will be made based on the polymer particles described in claims 1 and 2 using resorcinol and formaldehyde as monomers.
0.1 mol to 2 mol, preferably 1 mol of cetyltrimethylammonium bromide, 0.01 to 3 mol, preferably 1 mol of sodium hydroxide, and 120 to 1200 mol, preferably 360 mol of water are added to 1 mol of resorcinol. 1-6 mol, preferably 4 mol of formaldehyde and 0-2 mol, preferably 1 mol, of resorcinol are added to the solution, followed by stirring at 40-100 ° C., preferably 50 ° C. for 0-3 hours, preferably 2 hours, After reacting at 40-100 ° C, preferably 90 ° C for 0-100 hours, preferably 72 hours, paraformaldehyde is added with 2-6 mol, preferably 4 mol, 90-180 ° C, preferably 150 ° C, preferably 0-48 hours. Reacted for 24 hours. Thereafter, two operations were performed to synthesize polymer particles (Claim 1) or a polymer / surfactant complex (Claim 2).
In the second aspect of the claims, the obtained product was washed and dried to obtain a sample.
In the first claim, the obtained product was washed and recovered. After immersing 10 to 100 ml, preferably 50 ml, of ethanol per 0.5 g of the sample at 20 to 60 ° C., preferably 25 ° C. for 0 to 24 hours, preferably 24 hours, 1 to 12 mol / l, preferably 5 mol / l hydrochloric acid 0.5-5 ml, preferably 1 ml was added and stirred at 20-60 ° C., preferably 25 ° C., for 0-24 hours, preferably 6 hours. The obtained product was washed and dried to obtain a sample.

Next, a polymer (Claim 3) and a polymer / surfactant complex (Claim 3) having a wire-like form having a diameter of 10 to 300 nm and a length of 1 to 100 μm having a layered structure as a structural unit. (Method 4) will be described.
0.1 to 2 moles, preferably 1 mole of cetyltrimethylammonium bromide, 0.01 to 3 moles of sodium hydroxide, preferably 0.25 moles, 0.1 to 10 moles of mesitylene, preferably 1 and 1 mole of resorcinol 1 to 6 moles, preferably 4 moles of formaldehyde and 0 to 2 moles, preferably 1 mole of formaldehyde are added to a solution obtained by adding 120 to 1200 moles, preferably 360 moles of water, and 40 to 100 ° C., preferably 50, with stirring. C. for 1 to 3 hours, preferably 2 hours, followed by reaction at 40 to 100.degree. C., preferably 90.degree. C. for 0 to 100 hours, preferably 72 hours. The reaction was carried out at 180 ° C., preferably 150 ° C., for 0 to 48 hours, preferably 24 hours. Thereafter, two operations were carried out to synthesize a polymer / surfactant complex (first claim) or polymer particles (second claim).
In claim 4, the obtained product was washed and dried to obtain a sample.
In claim 3, the obtained product was washed and recovered. After immersing 10 to 100 ml, preferably 50 ml, of ethanol per 0.5 g of the sample at 20 to 60 ° C., preferably 25 ° C. for 0 to 24 hours, preferably 24 hours, 1 to 12 mol / l, preferably 5 mol / l hydrochloric acid 0.5-5 ml, preferably 1 ml was added and stirred at 20-60 ° C., preferably 25 ° C., for 0-24 hours, preferably 6 hours. The obtained product was washed and dried to obtain a sample.

  The reaction operation and reaction conditions for obtaining resorcinol-formaldehyde polymer particles have been described above, but the same procedure or the same as the reaction operation and reaction conditions described above for other resorcinol-aldehyde polymer particles was used. Implemented according to operating conditions.

  That is, the process from the preparation of the reaction mixture of polymer particles to the final product is configured as follows. First, at the time of selection of raw materials, monomers such as resorcinol and formaldehyde which are easily soluble in water among phenols which give phenoxide which binds to alkyltrimethylammonium ions are polymerized three-dimensionally, It is desirable to select a material that is easily bonded and soluble in water (aqueous solvent), and promotes structuring from a homogeneous composition solution. In the mesitylene-free system, by changing the amount of sodium hydroxide charged, wire-like particles or spherical particles having a layer or its form as a structural unit can be selectively produced. Since sodium hydroxide is considered to play a role in ionizing the hydroxyl group of resorcinol at the same time as catalyzing the reaction between resorcinol and formaldehyde, depending on the degree of interaction between anionized resorcinol and cetyltrimethylammonium bromide, It is expected that the micelle morphology will change and will also affect the final product morphology. In the mesitylene-added system, a micelle structure that leads to a fine wire-like form is obtained by adding an additive such as mesitylene that has the effect of changing the size and form of the template micelle structure while taking into account the amount of sodium hydroxide. It is considered that polymer nanowires are formed as a result of the polymerization reaction of resorcinol and formaldehyde that is formed and used as a template. In other words, it is considered that the nano-order form control of the resorcinol polymer can be performed by adjusting the amounts of sodium hydroxide and mesitylene.

  Based on the above, first, a solution having a uniform composition comprising resorcinol, a surfactant, sodium hydroxide, and water is first prepared. It is desirable to start the reaction by adding a formaldehyde solution to this solution and to stir so that the entire solution is uniformly mixed. At this time, since the viscosity of the prepared solution may increase, it is important to use an apparatus capable of obtaining sufficient stirring. The reaction temperature is set in consideration of the form and yield of the final product, but at the beginning of the reaction at a low temperature of 50 to 60 ° C. in order to make the composition uniform, and thereafter to increase the crosslinking density of the polymer. It is desirable to heat at 80 to 90 ° C. for at least 1 hour. The addition of paraformaldehyde, hydrothermal treatment in the range of 90 to 180 ° C., and ethanol / hydrochloric acid treatment are desirably performed as necessary.

In the present invention, since the copolymer has a wire shape, the following effects can be expected, and it is expected to be used in various fields and will be greatly used in various fields in the future to contribute to industrial development. Is done.
(1) When this is used as a material separation material, it can be expected to be applied to a chromatographic carrier, ion-exchange resin, and the like that are chemically stable in the acid / alkali region and whose particle form / size is controlled.
(2) When this is used as a substance storage material, it is expected to work effectively for storing small molecules such as hydrogen and ions due to its unique shape.
(3) When this is used as an additive for fibers, rubbers, films or plastic products, it is chemically and thermally stable and can contribute greatly to the modification and reinforcement of products due to its unique shape.
(4) When used as an additive to liquid products such as paints, inks, adhesives or paper coatings, it is chemically and thermally stable and can contribute greatly to product modification due to its unique shape. .
(5) When this is used as a heat insulating material, application to a heat-resistant plate or the like can be expected from the unique shape and composition of particles.

The observation photograph by the scanning electron microscope (SEM) and transmission electron microscope (TEM) of the string polymer which uses the layered structure of this invention as a structural unit. a is an SEM image of the string-like particles obtained in Example 1. b is an SEM image of a sample obtained by pulverizing and ultrasonicating the compound obtained in Example 1. c is a transmission electron microscope image of a sample obtained by pulverizing and ultrasonicating the compound obtained in Example 1. d is an SEM image of the compound obtained in Example 2. The observation photograph of the spherical polymer compound of the present invention by a scanning electron microscope (SEM) and a transmission electron microscope (TEM). (A) is the SEM image of the spherical particle obtained in Example 3. FIG. (B) is a TEM image of the spherical particles obtained in Example 3. (C) is a TEM image of the spherical particles obtained in Example 4.

Claims (13)

  One or more monomers selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinol, and one or more selected from aldehydes such as formaldehyde and furfural Wire-like polymer particles characterized by having a wire-like structure with a diameter of 2 to 100 μm and a length of 20 to 300 μm having a layered structure with a spacing of 1 to 10 nm as a skeleton component and a copolymer with a monomer of .   One or more monomers selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinol, and one or more selected from aldehydes such as formaldehyde and furfural It comprises a bond between a copolymer of the above monomer and one or more surfactants selected from the group consisting of alkylammonium salts such as hexadecyltrimethylammonium bromide and alkylamines such as hexadecylamine, and an interval of 1 to A wire-like polymer particle having a wire-like structure having a diameter of 2 to 100 μm and a length of 20 to 300 μm having a layered structure of 10 nm as a structural unit.   One or more monomers selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinol, and one or more selected from aldehydes such as formaldehyde and furfural Wire-like polymer particles characterized by having a wire-like structure having a diameter of 10 to 300 nm and a length of 1 to 100 μm having a copolymer with a monomer as a skeleton component.   One or more monomers selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinol, and one or more selected from aldehydes such as formaldehyde and furfural A copolymer with a monomer of the above, comprising an alkylammonium salt such as hexadecyltrimethylammonium bromide, and one or more surfactants selected from the group consisting of alkylamines such as hexadecylamine, having a diameter of 10 to 500 nm, Wire-like polymer particles characterized by having a wire-like structure having a length of 1 to 100 μm.   In the presence of a basic condensing agent, a molar ratio of one or more surfactants selected from the group consisting of alkylammonium salts such as hexadecyltrimethylammonium bromide and alkylamines such as hexadecylamine and water in a 1: 120 to 1200 molar ratio. Select from one or more monomers selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinols and aldehydes such as formaldehyde and furfural. A product obtained by adding and reacting one or more monomers selected from the group consisting of one or more solvents selected from the group consisting of alcohols such as ethanol and an acid such as hydrochloric acid 1 The method for producing wire-like polymer particles according to claim 1, wherein the treatment is performed with a mixed solution of at least one kind of acid.   In the presence of a basic condensing agent, one or more surfactants selected from the group consisting of alkylammonium salts such as hexadecyltrimethylammonium bromide and alkylamines such as hexadecylamine and water in a molar ratio of 1: 120 to 1200 Select from one or more monomers selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinols and aldehydes such as formaldehyde and furfural. The method for producing wire-like polymer particles according to claim 2, wherein one or more kinds of monomers are added and reacted.   One or more surfactants selected from the group consisting of basic condensing agents and alkylammonium salts such as hexadecyltrimethylammonium bromide, alkylamines such as hexadecylamine, and one type selected from the group consisting of alkylbenzenes such as mesitylene In the presence of the above-mentioned additives, one or more monomers selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinol and aldehydes such as formaldehyde and furfural A product obtained by reacting one or more monomers selected from 1 is selected from the group consisting of one or more solvents selected from the group consisting of alcohols such as ethanol and an acid such as hydrochloric acid. The wire-like polymer particles according to claim 3, which are treated with a mixed solution of at least one kind of acid. Manufacturing method.   One or more surfactants selected from the group consisting of basic condensing agents and alkylammonium salts such as hexadecyltrimethylammonium bromide, alkylamines such as hexadecylamine, and one type selected from the group consisting of alkylbenzenes such as mesitylene In the presence of the above additives, one or more monomers selected from phenols having a structure in which two or more hydroxyl groups are substituted on the aromatic ring of resorcinol and aldehydes such as formaldehyde and furfural The method for producing wire-like polymer particles according to claim 4, wherein one or more monomers selected from the above are reacted. A wire-like resorcinol-based polymer particle according to any one of claims 1 to 4, comprising a separating agent, adsorbent or storage agent for various substances, or a fiber, rubber, film or plastic product. Additives / fillers or additives for liquid products such as paints, inks, adhesives or paper coatings, battery materials, electric double layer capacitor materials, etc. General purpose functional material.   The functional material according to claim 9, wherein the functional material is used and used exclusively as a separating agent, adsorbent or storage agent for various substances.   10. The functional material according to claim 9, wherein the functional material is used as an additive for fiber, rubber, film or plastic product. The functional material according to claim 9, wherein the functional material is used as an additive to a liquid product such as a paint, ink, adhesive or paper coating agent. The functional material according to claim 9, wherein the functional material is used as a heat insulating material.