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WO2021095721A1 - Complexe polymère, et procédé de fabrication de celui-ci - Google Patents

Complexe polymère, et procédé de fabrication de celui-ci Download PDF

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Publication number
WO2021095721A1
WO2021095721A1 PCT/JP2020/041900 JP2020041900W WO2021095721A1 WO 2021095721 A1 WO2021095721 A1 WO 2021095721A1 JP 2020041900 W JP2020041900 W JP 2020041900W WO 2021095721 A1 WO2021095721 A1 WO 2021095721A1
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Prior art keywords
polymer
polymer complex
polymer composite
component
aqueous solution
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English (en)
Japanese (ja)
Inventor
雄一 冨永
裕司 堀田
雅一 西田
定寛 柳下
拓 西川
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Daiichi Kigenso Kagaku Kogyo Co Ltd
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Daiichi Kigenso Kagaku Kogyo Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/10—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to inorganic materials

Definitions

  • the present invention relates to a polymer composite having excellent mechanical strength in which a metal component is dispersed in a matrix made of a polymer, and a method for producing the same.
  • Polymer gel is a soft material consisting of a polymer network and a large amount of liquid medium, and is widely used in fields such as food, environment, energy, medicine, and sports.
  • One of the problems required for such an elastic material is improvement of mechanical strength.
  • Patent Document 1 discloses a topological gel in which a cross-linking point moves along a main chain.
  • Patent Document 2 discloses a nanocomposite gel using hydrophilic clay as a cross-linking point.
  • Patent Document 3 discloses a double network gel in which two types of network structures intrude into each other.
  • Patent Document 1 has a problem that the elastic modulus and breaking strength are not sufficient and the manufacturing process is complicated. Further, although the technique of Patent Document 3 can produce an unprecedented gel having both strength and flexibility, it is necessary to immerse the polymerized gel in another monomer for polymerization, and the production process is complicated. ..
  • the present invention provides a polymer composite having excellent mechanical strength such as compressive elastic modulus, tensile strength, tensile elongation at break, low volume expansion rate, and excellent shape stability, and such a polymer composite.
  • the purpose is to provide a method for efficiently manufacturing a body.
  • the present inventors have excellent mechanical strength and shape stability when water or the like is contained in a polymer composite in which fine metal-containing components such as zirconia are dispersed in a matrix made of a polymer.
  • the polymer composite in the present invention comprises a polymer containing a structural unit derived from an unsaturated monomer and a metal component dispersed in a matrix composed of the polymer, and the metal component is a zirconium component. , At least one selected from the yttrium component, the cerium component and the neodymium component.
  • the polymer complex in the present invention can further contain water and / or an organic solvent.
  • the method for producing a polymer composite in the present invention includes a mixing step of mixing a sol containing water and a metal oxide, an aqueous solution containing a metal ion, an unsaturated monomer, and a polymerization initiator, and an unsaturated step. It is characterized in that a polymerization step of polymerizing a monomer is sequentially provided.
  • the method for producing a polymer composite in the present invention can further include a contact step of bringing water and / or an organic solvent into contact with the reaction product obtained by the polymerization step.
  • the polymer complex containing water and / or an organic solvent is excellent in mechanical strength and shape stability. Therefore, the durability of the product is expected by retaining water and / or the organic solvent.
  • the method for producing a polymer composite only a sol containing water and a metal oxide, an aqueous solution containing a metal ion, an unsaturated monomer, and a polymerization initiator are used. It is possible to efficiently produce a polymer composite having the above effects. Further, for example, the mechanical strength of the polymer complex can be easily controlled by appropriately changing conditions such as temperature and time to polymerize the unsaturated monomer.
  • the polymer composite of the present invention includes a polymer containing a structural unit derived from an unsaturated monomer and a metal component (metal-containing component) dispersed in a matrix composed of the polymer.
  • This metal component is at least one selected from a zirconium component, an yttrium component, a cerium component and a neodymium component.
  • the polymer complex of the present invention is preferably a soft material having elasticity and excellent mechanical strength and shape stability by containing (retaining) water and / or an organic solvent.
  • the reaction product obtained by the mixing step and the polymerization step in the production method described later usually contains (retains) water, but after that, water may be distilled off to solidify the reaction product. Since it is possible, the polymer composite of the present invention does not necessarily contain water. Since the polymer composite obtained by subjecting the reaction product or solidified product to a contact step in which water and / or an organic solvent is brought into contact with the reaction product or the solidified product contains water and / or an organic solvent, the above-mentioned effect of the present invention can be obtained. Demonstrate surely.
  • the polymer complex of this embodiment will be described as a “highly elastic polymer complex”.
  • the organic solvent is preferably a water-soluble or hydrophilic compound, for example, alcohol (methanol, ethanol, propanol, etc.). ), alkylene glycol (ethylene glycol, etc.), cyclic ether (tetrahydrofuran, etc.), ketone (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), dialkylformamide (dimethylformamide, etc.), dialkylacetamide (dimethylacetamide, etc.), dialkyl sulfoxide (dimethyl sulfoxide, etc.) Etc.), alkylene glycol monoalkyl ether and the like.
  • alcohol methanol, ethanol, propanol, etc.
  • alkylene glycol ethylene glycol, etc.
  • cyclic ether tetrahydrofuran, etc.
  • ketone acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
  • the lower limit of the content ratio of the liquid is preferably 100 parts by mass, more preferably 200 parts by mass when the mass of the polymer is 100 parts by mass. It is a mass part.
  • the upper limit is usually 2000 parts by mass, preferably 1000 parts by mass.
  • the polymer according to the present invention contains at least one structural unit derived from an unsaturated monomer.
  • the number of polymerizable unsaturated bonds contained in this unsaturated monomer is not particularly limited.
  • the polymer usually has a linear shape, but in the case of a compound having two or more polymerizable unsaturated bonds, the polymer usually has a linear shape. It has a three-dimensional crosslinked structure.
  • the polymer according to the present invention preferably has liquid absorbency.
  • the (total) liquid absorption amount of water and / or the organic solvent is preferably 1.0 g or more, more preferably 1.5 to 20 g, and further preferably 2.0 to 10 g with respect to 1.0 g of the polymer. .. This ratio also applies to those in highly elastic polymer complexes.
  • compounds having one polymerizable unsaturated bond include acrylamide, dimethylacrylamide, N-isopropylacrylamide, methacrylamide, dimethylmethacrylicamide, N-isopropylmethacrylicamide, and methacrylicamidopropyltrimethyl.
  • amide groups having an amide group such as ammonium chloride; compounds having a hydroxy group such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; compounds having a carboxylic acid group such as acrylic acid and methacrylic acid or salts thereof; Compounds having sulfonic acid groups such as 2-acrylamide-2-methylpropanesulfonic acid and p-styrenesulfonic acid or salts thereof; compounds having phosphoric acid groups such as methacryloxyethyl trimeric acid or salts thereof; acrylic acid alkyl esters , Acrylic acid alkyl ester, acrylonitrile, 2-vinylpyridine, 4-vinylpyridine, N-vinylpyrrolidone, vinyl acetate and the like. Of these, acrylamide and acrylic acid are preferred.
  • crosslinkable monomers compounds having two or more polymerizable unsaturated bonds
  • crosslinkable monomers include N, N'-methylenebisacrylamide, N, N'. -(1,2-Dihydroxyethylene) -bisacrylamide, monoethylene glycol diacrylate, monoethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, monopropylene glycol diacrylate, monopropylene glycol dimethacrylate and the like. .. Of these, N, N'-methylenebisacrylamide is preferable.
  • the polymer When the polymer is composed of a structural unit derived from a compound having one polymerizable unsaturated bond and a structural unit derived from a crosslinkable monomer, the polymer contains a structural unit derived from the crosslinkable monomer.
  • the upper limit of the ratio is preferably 1% by mass, more preferably 1% by mass, when the total amount of the structural units constituting the polymer is 100% by mass, from the viewpoint of mechanical strength and shape stability in the highly elastic polymer composite. Is 0.1% by mass.
  • the metal component (metal-containing component) dispersed in the matrix composed of the polymer is at least one selected from a zirconium component, an yttrium component, a cerium component and a neodymium component, and these atoms of the metal component (metal-containing component).
  • a zirconium component an yttrium component, a cerium component and a neodymium component
  • these atoms of the metal component (metal-containing component) include ions, oxides, nitrides, carbides, sulfides, halides, hydroxides, nitrates, sulfates, phosphates, carbonates and organic acid metal salts.
  • the metal component contained in the polymer composite or the highly elastic polymer composite of the present invention may be either an ion or a compound, or may be both.
  • the metal components are preferably ions and oxides containing zirconium, yttrium, cerium or neodymium
  • the metal component is a compound
  • its shape and size are not particularly limited, but are averaged from the viewpoint of mechanical strength and shape stability in a highly elastic polymer composite containing a liquid of water and / or an organic solvent.
  • the particle size is preferably 100 nm or less, more preferably 1 to 50 nm.
  • the content ratio of the metal component is the total of the polymer and the metal component from the viewpoint of mechanical strength and shape stability in the highly elastic polymer composite containing a liquid of water and / or an organic solvent.
  • the content ratio of the metal component is the total of the polymer and the metal component from the viewpoint of mechanical strength and shape stability in the highly elastic polymer composite containing a liquid of water and / or an organic solvent.
  • the content ratio of the metal component is the total of the polymer and the metal component from the viewpoint of mechanical strength and shape stability in the highly elastic polymer composite containing a liquid of water and / or an organic solvent.
  • the content ratio of the metal component is the total of the polymer and the metal component from the viewpoint of mechanical strength and shape stability in the highly elastic polymer composite containing a liquid of water and / or an organic solvent.
  • ions or compounds of metals other than zirconium, yttrium, cerium and neodymium may be further dispersed in the polymer composite of the present invention.
  • the upper limit of the content ratio is usually 30 parts by mass, assuming that the content of the metal component is 100 parts by mass.
  • the polymer complex of the present invention further contains various fillers, additives for improving heat resistance, ultraviolet resistance, light resistance, oxidation resistance, flame retardancy, etc., if necessary. May be good.
  • the polymer complex of the present invention can be a highly elastic polymer complex having a structure containing water and / or an organic solvent.
  • the compressive elastic modulus is preferably 100 kPa to 30 MPa, more preferably 150 kPa to 25 MPa, and particularly preferably 200 kPa to 20 MPa.
  • the tensile strength is preferably 100 kPa to 10 MPa, more preferably 200 kPa to 10 MPa, and particularly preferably 500 kPa to 10 MPa.
  • the tensile elongation at break is preferably 50 to 500%, more preferably 80 to 500%, and particularly preferably 100 to 500%.
  • the coefficient of thermal expansion is preferably ⁇ 30 to 100%, more preferably ⁇ 20 to 80%, and particularly preferably ⁇ 10 to 60%. It can be said that these performances are superior in mechanical strength and shape stability as compared with a polymer gel containing no metal component.
  • the compressive elastic modulus, tensile strength, tensile elongation at break and volume expansion coefficient can be measured by the methods described in [Example].
  • the polymer composite production method of the present invention comprises a sol containing water and a metal oxide (at least one oxide selected from zirconium, yttrium, cerium and neodymium), or a metal ion (zirconium, yttrium, cerium and A mixing step of mixing an aqueous solution containing at least one ion selected from neodymium), an unsaturated monomer, and a polymerization initiator, and a polymerization step of polymerizing the unsaturated monomer are sequentially provided. ..
  • a sol containing water and a metal oxide zylon oxide, yttrium oxide, cerium oxide or neodymium oxide
  • an aqueous solution containing a metal ion, or a mixed solution containing water, a metal compound and a metal ion may be used. it can.
  • the metal oxide When a sol is used in the above mixing step, the metal oxide may be either crystalline or amorphous, and the average particle size thereof is preferably 100 nm or less, more preferably 1 to 50 nm, and further preferably 5 to 30 nm.
  • the concentration of the metal oxide in the sol is not particularly limited, but is preferably 1 to 50% by mass, more preferably 5 to 40, because a polymer composite is efficiently formed in the subsequent polymerization step. It is mass%.
  • an aqueous solution containing metal ions is used in the above mixing step, it is not particularly limited as long as it is an aqueous solution obtained by dissolving a water-soluble metal compound in water, an acidic aqueous solution or a basic aqueous solution.
  • concentration of the metal ion is not particularly limited, but is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, because the polymer complex is efficiently formed in the subsequent polymerization step.
  • the unsaturated monomer used in the mixing step is as illustrated above.
  • a preferred embodiment is that all unsaturated monomers are water soluble and that unsaturated monomers containing at least 50% by weight of acrylamide or acrylic acid relative to the total amount are used.
  • a particularly preferred embodiment is to use only acrylamide, and to use acrylamide in combination with a compound containing two or more polymerizable unsaturated bonds (N, N'-methylenebisacrylamide, etc.).
  • the polymerization initiator used in the above mixing step is not particularly limited, and may be either an inorganic compound or an organic compound, or a combination thereof. Further, it may be either water-soluble or oil-soluble.
  • the inorganic compound include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate (ammonium peroxodisulfate).
  • the organic compound include dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (isobutyronitrile), and 2,2'-azobis (2-methyl).
  • a polymerization initiator that combines an inorganic compound and an organic compound
  • sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate, etc. are used as reducing agents, and potassium peroxodisulfate and hydrogen peroxide are used.
  • a redox-based polymerization initiator using hydrogen, tert-butyl hydroperoxide, or the like as an oxidizing agent has been known and can be used.
  • any of a thermal polymerization initiator, a photopolymerization initiator and the like may be used as the polymerization initiator, but among these, the thermal polymerization initiator is preferable.
  • the effect of the present invention is ensured.
  • the molar ratio of the metal oxide or metal ion to the unsaturated monomer is preferably 0.1 to 10, more preferably 0.2 to 2.
  • the amount of the polymerization initiator used is not particularly limited.
  • the temperature at which these raw materials are mixed is preferably 30 ° C. or lower.
  • the polymerization step is a step of polymerizing the unsaturated monomer after the mixing step, and the formed polymer is usually a polymer composite while retaining the water of the reaction system inside. To configure.
  • the mixture obtained by the above mixing step may be used as it is, or if necessary, a mixture further added with the components described below may be used.
  • the reaction system is prepared using a sol containing water and a metal oxide or an aqueous solution containing a metal ion, and the unsaturated monomer is preferably subjected to polymerization in a state of being dissolved in water.
  • an organic solvent can be added to the reaction system as long as the dispersed state of the metal oxide or the metal ion and the polymerization reaction of the unsaturated monomer are not inhibited. Since an oil-soluble compound can also be used as the polymerization initiator, its solubility can be improved by adding an organic solvent, and even when a water-insoluble unsaturated monomer is used in combination, the organic solvent can be used. As a result, the polymerization conversion rate of all unsaturated monomers can be improved.
  • Examples of such an organic solvent include alcohol (methanol, ethanol, propanol, etc.), alkylene glycol (ethylene glycol, etc.), cyclic ether (tetratetra, etc.), ketone (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), dialkylformamide (dimethylformamide, etc.). Etc.), dialkylacetamide (dimethylacetamide, etc.), dialkyl sulfoxide (dimethyl sulfoxide, etc.) and the like.
  • reaction system may further contain various fillers, additives for improving heat resistance, ultraviolet resistance, light resistance, oxidation resistance, flame retardancy and the like.
  • the reaction conditions in the above polymerization step are not particularly limited.
  • the polymerization reaction is preferably carried out under closed conditions or under an inert gas atmosphere.
  • the polymerization temperature is preferably 30 ° C. to 100 ° C., more preferably 50 ° C. to 100 ° C.
  • the polymerization time is appropriately set depending on the composition of the reaction system, the total amount of raw materials, and the like, and is usually 10 minutes or more.
  • the upper limit of the polymerization time is usually 2 months, preferably 1 month.
  • the polymerization step by carrying out the polymerization reaction under closed conditions, it is possible to produce a polymer composite as it is contained in the reaction vessel. Therefore, by using a reaction vessel having a cavity that reflects a specific shape, a polymer complex having a predetermined shape (fibrous, rod-shaped, flat plate-shaped, columnar, spiral, spherical, etc.) can be directly produced. be able to. Needless to say, since the polymer complex of the present invention is excellent in shape stability, it is possible to obtain a predetermined shape by performing cutting or the like after producing a large-sized polymer complex.
  • a fine particle polymer complex can be produced by coexisting a conventional surfactant in the above reaction system.
  • the reaction system contains a mixture obtained by using a sol containing water and a metal oxide together with a thermal polymerization initiator, when this is subjected to polymerization, it is compared with the case where an aqueous solution of metal ions is used.
  • the reaction solution tends to become highly viscous, and the obtained polymer composite composed of the reaction product tends to form a highly elastic polymer composite having excellent mechanical strength and shape stability.
  • the present inventors have stated that the obtained polymer composite is high in that fine particles composed of metal oxides contained in the sol are formed. It is presumed that this is due to the structure that evenly fills the voids between the molecules.
  • the polymer composite formed by the polymerization step retains the water of the reaction system inside the polymer, but it is usually possible to further retain water and / or an organic solvent. Therefore, a highly elastic polymer composite having excellent mechanical strength and shape stability can be reliably obtained by the subsequent contact step.
  • the contact step it is preferable to apply a method such as immersing the polymer composite in water and / or an organic solvent, or spraying water and / or an organic solvent on the polymer composite.
  • a method such as immersing the polymer composite in water and / or an organic solvent, or spraying water and / or an organic solvent on the polymer composite.
  • the organic solvent a compound exemplified as an organic solvent that can be used in combination in the polymerization step can be used, but the organic solvent can also be replaced in this contact step.
  • the highly elastic polymer composite obtained by the production method of the present invention has the above-mentioned performance (high compressive elastic modulus, high tensile property and low volume expansion coefficient) immeasurable from the prior art, and is a medical material. It is useful as a shock absorbing material, a soundproofing material, and the like.
  • a solid polymer composite can be obtained by drying the reaction product, which usually contains water, obtained by the mixing step and the polymerization step. By subjecting this solid polymer complex to the contact step, water and / or an organic solvent can be retained, so that a highly elastic polymer complex having the above-mentioned performance can be reversibly obtained. Further, the solid polymer composite is usually porous, and can be utilized as a composite in which another polymer material is impregnated therein.
  • the polymer material is not particularly limited, but is limited to acrylic resin, epoxy resin, phenol resin, nylon resin, ABS resin, polyester (PET, PBT, etc.), polytetrafluoroethylene, polyvinyl chloride, polystyrene, polyethylene, polypropylene, etc.
  • Polyamitone, polyimide, polycarbonate, polyacetal, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, polyvinyl alcohol, melamine resin, silicone resin, epoxy resin, urethane resin and the like can be used.
  • These may be thermoplastic resins or thermosetting resins. However, in the case of a thermosetting resin, it is preferable to infiltrate the thermosetting resin into the solid polymer complex and then cure the resin.
  • MBAA ammonium peroxodisulfate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • APS ammonium peroxodisulfate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • Examples 2-5 A polymer complex and a highly elastic polymer complex were produced in the same manner as in Example 1 except that the heating temperature of the mixture was changed from 50 ° C. to 60 ° C., 70 ° C., 80 ° C. or 90 ° C., and various types were produced. Evaluation was performed. The results are shown in Table 1.
  • Examples 6-10 Change the heating time of the mixture from 3 hours to 3 days (Example 6), 7 days (Example 7), 14 days (Example 8), 21 days (Example 9) or 28 days (Example 10).
  • a polymer composite and a highly elastic polymer composite were produced in the same manner as in Example 3 except for the above, and various evaluations were performed. The results are shown in Table 1. Further, with respect to the polymer composite of Example 6, this was immersed in ethylene glycol for 7 days to produce a highly elastic polymer composite, and only the compressive elastic modulus was measured (see Table 1).
  • Examples 11-13 and 15-21 As the zirconia sol, a zirconia sol “ZSL-10T” (trade name, solid content 13.6% by mass, median diameter 15 nm) manufactured by Daiichi Rare Element Chemical Industry Co., Ltd., which has a different solid content from that used in Example 1, was used. Using. While using this zirconia sol “ZSL-10T", a 4 mol / L AAm zirconia aqueous solution (hereinafter referred to as "AAm zirconia aqueous solution (2)”) was prepared in the same manner as in Example 1, and these were used as raw materials for production. A polymer composite and a highly elastic polymer composite were produced in the same manner as in Examples 1 to 10.
  • Example 14 5 mL of 4 mol / L AAm zirconia aqueous solution (2), 0.2 mL of 0.1 mol / L APS aqueous solution, and the above zirconia sol "ZSL-10T" (trade name, solid content 13.6 mass%, median diameter 15 nm). 4.78 mL was mixed. Then, the mixture was placed in a reaction vessel, evacuated, and then heated in an oven at 70 ° C. for 3 hours to obtain a polymer complex. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) is 0.56. Then, the polymer complex was immersed in water at 25 ° C. for 7 days to obtain a highly elastic polymer complex. Various evaluations were performed on the obtained highly elastic polymer complex. The results are shown in Table 1.
  • zirconia sol “ZSL00120” (trade name, solid content 30.3% by mass, median diameter 14 nm) manufactured by Daiichi Rare Element Chemical Industry Co., Ltd. was used. While using this zirconia sol “ZSL001210", a 4 mol / L AAm zirconia aqueous solution (hereinafter referred to as "AAm zirconia aqueous solution (3)") was prepared in the same manner as in Example 1, and these were used as a production raw material in Examples. A polymer composite and a highly elastic polymer composite were produced in the same manner as in 1 to 10.
  • the molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) is 1.45. Then, various evaluations were performed on the obtained highly elastic polymer complex. The results are shown in Table 2. The polymer composite of Example 28 was immersed in ethylene glycol for 7 days to produce a highly elastic polymer composite, and only the compressive elastic modulus was measured (see Table 2).
  • Example 25 4. 5 mL of 4 mol / L AAm zirconia aqueous solution (3), 0.2 mL of 0.1 mol / L APS aqueous solution, and the above zirconia sol "ZSL001210" (trade name, solid content 30.3 mass%, median diameter 14 nm). 78 mL was mixed. Then, the mixture was placed in a reaction vessel, evacuated, and then heated in an oven at 70 ° C. for 3 hours to obtain a polymer complex. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) is 1.40. Then, the polymer complex was immersed in water at 25 ° C. for 7 days to obtain a highly elastic polymer complex. Various evaluations were performed on the obtained highly elastic polymer complex. The results are shown in Table 2.
  • Examples 33-42 As the zirconia sol, the zirconia sol "ZSL00120” manufactured by Daiichi Rare Element Chemical Industry Co., Ltd., which has a different solid content and median diameter from that used in Example 22 (trade name, solid content 34.9% by mass, median diameter 10 nm). Was used. Examples 1 to 10 except that this zirconia sol "ZSL00120" was used and a 4 mol / L AAm zirconia aqueous solution (hereinafter referred to as "AAm zirconia aqueous solution (4)") was used in the same manner as in Example 1. Similarly, a polymer composite and a highly elastic polymer composite were produced.
  • AAm zirconia aqueous solution (4) 4 mol / L AAm zirconia aqueous solution
  • Example 43 Acrylamide (AAm) was dissolved in an aqueous solution of zirconium oxynitrate manufactured by Daiichi Rare Element Chemical Industry Co., Ltd. (trade name, solid content 25.4% by mass) to prepare a 4 mol / L aqueous solution of zirconium oxynitrate. .. Next, 5 mL of a 4 mol / L AAm zirconium oxynitrate aqueous solution, 0.02 mL of a 0.2 mol / L MBAA aqueous solution, 0.2 mL of a 0.1 mol / L APS aqueous solution, and the zirconium oxynitrate solution "Zircozol ZN".
  • Example 3 The molar ratio of the metal ion (zirconim ion) to the water-soluble vinyl group-containing monomer (acrylamide) is 1.36.
  • the mass ratios of the polymer and the metal component (zirconium ion) constituting the highly elastic polymer composite are 51.4% by mass and 48.6% by mass, respectively, and the amount of liquid absorbed is 2.69 g. It was / g. Then, various evaluations were performed on the obtained highly elastic polymer complex. The results are shown in Table 3.
  • Example 44 Zirconia sol "ZSL-10T” manufactured by Daiichi Rare Element Chemical Industry Co., Ltd. (trade name, solid content 10.2% by mass, median diameter 13 nm) is diluted with water to prepare an aqueous solution of zirconia sol having a solid content of 5.4% by mass. did. Then, acrylamide (AAm) was dissolved in this zirconia sol aqueous solution to prepare a 4 mol / L AAm zirconia aqueous solution (hereinafter referred to as "AAm zirconia aqueous solution (5)").
  • the above ammonium peroxodisulfate (APS) was dissolved in water to prepare a 0.1 mol / L APS aqueous solution.
  • 5 mL of a 4 mol / L AAm zirconia aqueous solution (5), 0.2 mL of a 0.1 mol / L APS aqueous solution, and 4.8 mL of the above zirconia sol aqueous solution were mixed and bubbling with nitrogen. Then, the mixture was placed in a reaction vessel, evacuated, and then heated in an oven at 70 ° C. for 3 hours to obtain a polymer complex.
  • Example 45 As the zirconia sol, "ZSL-10T” (trade name, solid content 10.2% by mass, median diameter 13 nm) was used. Using this zirconia sol “ZSL-10T” and acrylamide (AAm), a 4 mol / L AAm zirconia aqueous solution (hereinafter referred to as "AAm zirconia aqueous solution (6)") was prepared. Next, 7.5 mL of a 4 mol / L AAm zirconia aqueous solution (6), 0.2 mL of a 0.1 mol / L APS aqueous solution, and 2.3 mL of the above zirconia sol "ZSL-10T" were mixed and bubbling with nitrogen. did.
  • AAm zirconia aqueous solution (6) 4 mol / L AAm zirconia aqueous solution
  • Example 46 2.5 mL of the 4 mol / L AAm zirconia aqueous solution (6) prepared in Example 45, 0.2 mL of the 0.1 mol / L APS aqueous solution, and 7.3 mL of the above zirconia sol "ZSL-10T" were mixed. Bubbling with nitrogen. Then, the mixture was placed in a reaction vessel, evacuated, and then heated in an oven at 70 ° C. for 3 hours to obtain a polymer complex. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) is 0.85. Then, in the same manner as in Example 1, a highly elastic polymer complex was prepared and various evaluations were performed. The results are shown in Table 3.
  • Example 47 As the zirconia sol, zirconia sol “ZSL00120” (trade name, solid content 30.3% by mass, median diameter 14 nm) manufactured by Daiichi Rare Element Chemical Industry Co., Ltd. was used. Using this zirconia sol “ZSL00120” and acrylamide (AAm), a 4 mol / L AAm zirconia aqueous solution (hereinafter referred to as "AAm zirconia aqueous solution (7)”) was prepared.
  • AAm zirconia aqueous solution (7) 4 mol / L AAm zirconia aqueous solution
  • Example 48 2.5 mL of the 4 mol / L AAm zirconia aqueous solution (7) prepared in Example 47, 0.2 mL of the 0.1 mol / L APS aqueous solution, and 7.3 mL of the above zirconia sol "ZSL00120" were mixed with nitrogen. Bubbling. Then, the mixture was placed in a reaction vessel, evacuated, and then heated in an oven at 70 ° C. for 3 hours to obtain a polymer complex. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) is 2.93. Then, in the same manner as in Example 1, a highly elastic polymer complex was prepared and various evaluations were performed. The results are shown in Table 3.
  • Example 49 The above N, N'-methylenebisacrylamide (MBAA) and 2,2'-azobis [2- (2-imidazolin-2-yl) propane] manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (hereinafter, also referred to as "AIYP"). , 0.1 mol / L MBAA aqueous solution and 0.1 mol / L AIYP solution were prepared by dissolving in water and methanol, respectively.
  • Example 45 5 mL of the 4 mol / L AAm zirconia aqueous solution (6) prepared in Example 45, 0.04 mL of the 0.1 mol / L MBAA aqueous solution, 0.2 mL of the 0.1 mol / L AIYP solution, and the above zirconia.
  • the sol "ZSL-10T” was mixed with 4.76 mL and bubbled with nitrogen. Then, the mixture was placed in a reaction vessel, evacuated, and then heated in an oven at 90 ° C. for 3 hours to obtain a polymer complex.
  • the molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) is 0.39.
  • a highly elastic polymer complex was prepared and various evaluations were performed. The results are shown in Table 3.
  • Example 50 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] (hereinafter, also referred to as "AMHP") manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. is dissolved in water and 0.1 mol / L. AMHP aqueous solution was prepared. Next, 5 mL of a 4 mol / L AAm zirconia aqueous solution (6), 0.04 mL of a 0.1 mol / L MBAA aqueous solution, 0.2 mL of a 0.1 mol / L AMHP aqueous solution, and the above zirconia sol "ZSL-10T" It was mixed with 4.76 mL and bubbled with nitrogen.
  • AMHP 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide]
  • Example 51 4,4'-azobis (4-cyanovaleric acid) (hereinafter, also referred to as "ACA") manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was dissolved in methanol to prepare a 0.1 mol / L ACA solution. Next, 5 mL of the 4 mol / L AAm zirconia aqueous solution (6) prepared in Example 45, 0.04 mL of the 0.1 mol / L MBAA aqueous solution, 0.2 mL of the 0.1 mol / L ACA solution, and the above zirconia. The sol “ZSL-10T” was mixed with 4.76 mL and bubbled with nitrogen.
  • ACA 4,4'-azobis (4-cyanovaleric acid)
  • Example 52 5 mL of the 4 mol / L AAm zirconia aqueous solution (7) prepared in Example 47, 0.04 mL of the 0.1 mol / L MBAA aqueous solution, 0.2 mL of the 0.1 mol / L AIYP solution, and the above-mentioned zirconia sol "ZSL00120". It was mixed with 4.76 mL and bubbled with nitrogen. Then, the mixture was placed in a reaction vessel, evacuated, and then heated in an oven at 90 ° C. for 3 hours to obtain a polymer complex. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) is 1.35. Then, in the same manner as in Example 1, a highly elastic polymer complex was prepared and various evaluations were performed. The results are shown in Table 3.
  • Example 53 As the zirconia sol, "ZSL-10T” (trade name, solid content 10.2% by mass, median diameter 13 nm) was used. Acrylic acid manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (hereinafter, also referred to as "AAc”) was dissolved in this zirconia sol to prepare a 4 mol / L AAc zirconia aqueous solution (hereinafter, referred to as "AAc zirconia aqueous solution").
  • AAc zirconia aqueous solution 4 mol / L AAc zirconia aqueous solution
  • Example 54 As the ceria sol, "CESL-30N” (trade name, solid content 30.2% by mass, median diameter 5 nm) was used. A 4 mol / L AAm ceria aqueous solution (hereinafter referred to as “AAm ceria aqueous solution”) was prepared using this ceria sol “CESL-30N” and acrylamide. Next, 5 mL of a 4 mol / L AAm ceria aqueous solution, 0.04 mL of a 0.1 mol / L MBAA aqueous solution, 0.2 mL of a 0.1 mol / L AIYP solution, and 4.76 mL of the above-mentioned zeria sol "CESL-30N" were added.
  • AAm ceria aqueous solution A 4 mol / L AAm ceria aqueous solution
  • Example 55 5 mL of 4 mol / L AAm ceria aqueous solution prepared in Example 54, 0.04 mL of 0.1 mol / L MBAA aqueous solution, 0.1 mL of 0.1 mol / L AIYP solution, and the above-mentioned zeria sol "CESL-30N" 4 It was mixed with .86 mL and bubbled with nitrogen. Then, the mixture was placed in a reaction vessel, evacuated, and then heated in an oven at 90 ° C. for 3 hours to obtain a polymer complex. The molar ratio of the metal oxide (ceria) to the water-soluble vinyl group-containing monomer (acrylamide) is 1.03. Then, in the same manner as in Example 1, a highly elastic polymer complex was prepared and various evaluations were performed. The results are shown in Table 3.
  • Comparative Examples 1 to 10 A polymer complex and a highly elastic polymer complex were produced in the same manner as in Examples 1 to 10 except that water was used instead of the zirconia sol. Then, various evaluations were performed on the highly elastic polymer complexes obtained in Comparative Examples 1 and 2, and the results are shown in Table 4. In Comparative Examples 3 to 10 and 13, a solid product was not obtained by polymerization by heating, or a solid product was obtained, but when it was subsequently immersed in water, it absorbed too much water and could not maintain its shape. Therefore, the evaluation could not be performed.
  • Comparative Examples 11-14 Instead of the AAm zirconia aqueous solution (1), a 4 mol / L AAm silica aqueous solution prepared using Nissan Chemical Industries' silica sol "Snowtex O" (trade name, solid content 20.6% by mass, particle size 12 nm) was used. A polymer composite and a highly elastic polymer composite were produced in the same manner as in Examples 3 to 6 except that they were used. The molar ratio of the metal oxide (silica) to the water-soluble vinyl group-containing monomer (acrylamide) is 1.68. Then, the compressive elastic modulus and the volume expansion coefficient of the highly elastic polymer composites obtained in Comparative Examples 11 and 12 were measured, and the results are shown in Table 4. In Comparative Example 14, although a solid substance was obtained, it could not be evaluated because it absorbed too much water when immersed in water and could not maintain its shape.
  • a polymer composite and a highly elastic polymer composite were produced in the same manner as in Examples 3 to 6 except that an aqueous solution was used.
  • the molar ratio of the metal oxide (alumina) to the water-soluble vinyl group-containing monomer (acrylamide) is 0.47. Then, the compressive elastic modulus and the volume expansion coefficient of the obtained highly elastic polymer complex were measured, and the results are shown in Table 4.
  • Examples 1 to 55 are examples of the highly elastic polymer composite according to the present invention, as compared with the highly elastic polymer composite containing no metal component and the highly elastic polymer composite containing silica or alumina. It was found that the compressive elastic modulus and tensile strength were high, the mechanical strength was excellent, the volume expansion coefficient was low, and the shape stability was excellent.
  • the highly elastic polymer composite of the present invention has excellent mechanical strength and shape stability, and is therefore useful as a medical material, a shock absorbing material, a soundproofing material, and the like.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
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Abstract

Le complexe polymère de l'invention est équipé d'un polymère contenant une unité structurale dérivée d'un monomère insaturé, et d'un composant métallique dispersé dans une matrice constituée de ce polymère, et est caractéristique en ce que le composant métallique consiste en au moins un élément choisi parmi un composant zirconium, un composant yttrium, un composant cérium et un composant néodymium. De préférence, le composant métallique consiste en un oxyde métallique ou en ions métalliques. Le complexe polymère de l'invention peut être fabriqué selon un procédé qui comporte dans l'ordre : une étape de mélange au cours de laquelle une solution aqueuse qui contient des ions métalliques, ou un sol contenant une eau et un oxyde métallique, un monomère insaturé, et un initiateur de polymérisation, sont mélangés ; et une étape de polymérisation au cours de laquelle le monomère insaturé, est polymérisé.
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