WO2009090959A1 - Polymer organogel, polymer composition, process for production of the polymer organogel, and process for production of polymer composition - Google Patents

Polymer organogel, polymer composition, process for production of the polymer organogel, and process for production of polymer composition Download PDF

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WO2009090959A1
WO2009090959A1 PCT/JP2009/050387 JP2009050387W WO2009090959A1 WO 2009090959 A1 WO2009090959 A1 WO 2009090959A1 JP 2009050387 W JP2009050387 W JP 2009050387W WO 2009090959 A1 WO2009090959 A1 WO 2009090959A1
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polymer
organogel
polymerization
monomer
organic medium
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PCT/JP2009/050387
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French (fr)
Japanese (ja)
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Eiichirou Shimazu
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Ntn Corporation
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    • 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

Definitions

  • the present invention relates to a polymer organogel, a polymer composition, and a production method thereof.
  • Patent Documents 1 to 5 As for polymer gels in which the skeleton component of the gel is a polymer having a three-dimensional cross-linked structure, research and development have been vigorously conducted on polymer hydrogels whose solvent component is water (Patent Documents 1 to 5). reference). In addition, extensive research has been conducted on application of such polymer hydrogels mainly for medical applications such as lubricated surface coatings for artificial joints and medical devices (Patent Documents 6 to 5). Reference 8). On the other hand, in an organogel using a liquid organic substance as a solvent, development of a general gelling agent that can form a reversible three-dimensional cross-linked structure by physical bonding as a skeleton component is progressing (see Non-Patent Document 1). .
  • the present invention has been made to cope with such problems, and is a high-molecular organogel that can retain a large amount of an organic medium such as an organic solvent or oil and is excellent in mechanical strength, particularly toughness. It is an object of the present invention to provide a polymer composition capable of producing a molecular organogel and a method for producing them.
  • the polymer organogel of the present invention is characterized by containing a liquid organic medium and a modified water-swellable layered silicate compound in a polymer having a three-dimensional crosslinked structure.
  • the modified water-swellable layered silicate compound that can be used in the polymer organogel of the present invention is a compound obtained by modifying a water-swellable layered silicate compound with a cationic organic compound by a cation exchange method.
  • the water-swellable layered silicate compound is a smectite group clay mineral.
  • the polymer that can be used in the polymer organogel of the present invention comprises a monomer having one addition polymerizable unsaturated bond (hereinafter abbreviated as “monomer A”) and at least two addition polymerizable unsaturated bonds. It is a polymer having a three-dimensional cross-linked structure obtained by polymerization with a monomer (hereinafter abbreviated as “monomer B”).
  • the polymer organogel of the present invention has a degree of swelling of 1.2 or more when the polymer organogel is immersed in the same organic medium contained in the polymer organogel at 25 ° C. for 20 days, and the compression fracture strain at the degree of swelling is 50. % Or more.
  • the method for producing the polymer organogel of the present invention comprises a dissolution step of dispersing and dissolving a modified water-swellable layered silicate compound in an organic medium, and addition polymerization of monomer A and monomer B in this solution. And a polymerization step for copolymerization.
  • the dissolution step is a dissolution step of dissolving the modified water-swellable layered silicate compound by adding a dispersant to the organic medium.
  • the dispersant is a polar liquid substance.
  • the ratio of the monomer A is larger than that of the monomer B in a molar ratio.
  • the concentration of the organic medium is 20.0% by volume or more and less than 95.0% by volume based on the polymer organogel produced.
  • the polymerization step is performed in an inert gas atmosphere.
  • the organic medium contained in the polymer having a three-dimensional crosslinked structure is replaced by immersing the polymer organogel after polymerization in another organic medium different from the organic medium at the time of polymerization. It is characterized by.
  • the polymer composition capable of producing the polymer organogel of the present invention is characterized in that a modified water-swellable layered silicate compound is uniformly dispersed in a polymer having a three-dimensional crosslinked structure.
  • the method for producing the polymer composition of the present invention comprises a dissolution step of dispersing and dissolving a modified water-swellable layered silicate compound in an organic medium, and a single amount having one addition polymerizable unsaturated bond in the solution. And a monomer having at least two addition-polymerizable unsaturated bonds by addition polymerization, and a step of removing the organic medium during the polymerization.
  • the polymer organogel of the present invention is not a viscous liquid substance using a polymer as a thickener, and the polymer chain as the skeleton has a chemical bond, particularly a three-dimensional cross-linking structure by a covalent bond, It is a solid substance swollen by absorbing an organic solvent and / or oil of about 0.2 to 100 times.
  • a non-aqueous or lipophilic modified water-swellable layered silicate compound is finely dispersed in a polymer having a non-aqueous or lipophilic three-dimensional crosslinked structure.
  • a liquid organic medium such as lubricating oil can be retained in a large amount in the polymer, and since it is a polymer having a three-dimensional cross-linked structure, it is excellent in strength, particularly toughness.
  • the method for producing the polymer organogel of the present invention comprises a dissolution step of dispersing and dissolving a modified water-swellable layered silicate compound in an organic medium, and addition polymerization of monomer A and monomer B in this solution. And a polymerization step for copolymerization, the modified water-swellable layered silicate compound can be contained at a uniform concentration in the polymer having a three-dimensional crosslinked structure. Further, a large amount of organic solvent, lubricating oil, etc. can be retained.
  • the modified water-swellable layered silicate compound is uniformly dispersed in the polymer having a three-dimensional crosslinked structure. It is possible to easily obtain a polymer organogel having excellent handling properties and improved handling properties.
  • the polymer organogel of the present invention comprises (1) an organic medium, (2) a modified water-swellable layered silicate compound, and (3) a polymer having a three-dimensional crosslinked structure.
  • Organic medium an organic medium that can uniformly disperse or dissolve the modified water-swellable layered silicate compound described later in the organic medium and serves as a solvent for addition copolymerization described later is used. it can.
  • the organic solvent during addition copolymerization is soluble in the organic medium, the organic solvent during polymerization can be exchanged by immersing in the soluble organic medium after copolymerization.
  • the organic medium include organic solvents, oils such as lubricating oils, and the like.
  • the organic medium it is preferable to use a water content adjusted to a very small amount of 5% by weight or less, particularly preferably water-free.
  • the hydrophilic water-swellable layered silicate compound before modification does not swell or hardly delaminates due to the above-mentioned organic medium and does not cause delamination due to shearing force. Precipitation occurs over time.
  • organic media examples include hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons as organic solvents, halogenated hydrocarbons in which these are halogenated, ethers, esters, Examples include ketones, alcohols, nitrogen compounds, and sulfur compounds.
  • hydrocarbons such as hexane, octane, decane, dodecane, benzene, toluene, xylene, ethylbenzene, cyclohexane, heptane, methylcyclohexane, decalin, petroleum benzine, methyl chloride, dichloromethane, Halogenated hydrocarbons such as chloroform and carbon tetrachloride, ethers such as diethyl ether, diphenyl ether, propylene oxide and dioxane, esters such as ethyl acetate and sec-butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone Ketones such as 2-heptanone and camphor, methanol, ethanol, isopropyl alcohol, octanol, benzyl alcohol, alcohols such as glycols and g
  • synthetic hydrocarbon oils such as mineral oil, vegetable oil, liquid paraffin, poly- ⁇ -olefin (PAO) oil, polyalkylene glycol, ester oils composed of monohydric alcohol and fatty acid, diester oils and neo Polyester oil such as ester oil composed of pentyl polyol and fatty acid, phenyl ether oil such as alkyl phenyl ether oil, dialkyl phenyl ether oil, alkyl polyphenyl ether oil, cyclopentane oil, silicone oil, perfluoropolyether oil, etc. Can be mentioned.
  • synthetic hydrocarbon oils such as mineral oil, vegetable oil, liquid paraffin, poly- ⁇ -olefin (PAO) oil, polyalkylene glycol, ester oils composed of monohydric alcohol and fatty acid, diester oils and neo Polyester oil such as ester oil composed of pentyl polyol and fatty acid, phenyl ether oil such as alkyl phenyl ether oil, dialkyl
  • Modified water-swellable layered silicate compound (hereinafter also referred to as modified clay)
  • the modified clay is modified so that a hydrophilic water-swellable layered silicate compound can be dispersed and dissolved in an organic medium.
  • the water-swellable layered silicate compound that is the raw material of the modified clay swells when added to water, and further, by applying shearing force to the aqueous solution by stirring or the like, the layered structure peels off between the layers.
  • Any clay mineral can be used without being limited to a specific substance as long as it can be destroyed or dispersed completely in water. Particularly preferred among these are layered clay minerals that can be exfoliated and dispersed in water to a single layer or a level close thereto.
  • hydrophilic water-swellable layered silicate compound examples include hydrophilic swellable smectite and swellable mica.
  • hydrophilic swellable smectite and swellable mica examples include hydrophilic swellable smectite and swellable mica.
  • smectite group clay minerals such as hectorite, montmorillonite, saponite, stevensite, beidellite, nontronite, bentonite, Na type tetrasilicic fluorine mica, Li type tetrasilicic fluorine mica, Na type fluorine teniolite, Li Swellable mica group clay minerals such as fluorinated teniolite and vermiculite, layered silicate minerals having a similar structure thereof, substituted or derivatives thereof, or mixtures thereof.
  • the smectite group clay mineral has a structure in which two layers of silica tetrahedron layers are sandwiched with a magnesium octahedron layer or an aluminum octahedron layer and sandwich type silicate layers are laminated several to several tens of times. Is a kind of phyllosilicate. Such a smectite silicate layer has a negative layer charge, which is neutralized by the presence of alkali metal cations or alkaline earth metal cations between the layers to balance the overall charge. ing.
  • smectite group clay minerals Compared to mica having a similar silicate structure, smectite group clay minerals have a low layer charge and easily spread between layers, so that delamination by shearing force is easy, or cation exchange ability is high, and cation exchange. It is particularly preferable because organic modification to lipophilicity or hydrophobicity is easy.
  • the modified clay is subjected to organic modification treatment so that the hydrophilic water-swellable layered silicate compound can be dispersed and dissolved in an organic medium.
  • organic modification treatment include a modification method using a coupling agent such as a silane coupling agent having a silanol group, a method using cation exchange, or a method in which these are combined as necessary, but the modification method is simple.
  • a coupling agent such as a silane coupling agent having a silanol group
  • cation exchange a method in which these are combined as necessary, but the modification method is simple.
  • To cation exchange are preferred.
  • Organic modification treatment by cation exchange is generally known as a method for producing clay organic composites (see Japanese Patent No. 2514780), and by reacting various cationic organic compounds with smectite clay minerals in water. Can be done.
  • Examples of the cationic organic compound include salts composed of quaternary ammonium ions or quaternary phosphonium ions and halogen ions such as chlorine ions or bromine ions.
  • Specific examples of quaternary ammonium salts include dimethyldialkylammonium salts such as dimethyldioctadecylammonium chloride and bromide, dimethyloctadecylbenzylammonium chloride and bromide, and dimethylstearylbenzylammonium chloride and bromide dimethylalkyl.
  • Trimethylalkylammonium salts such as benzylammonium salt, trimethylstearylammonium chloride and bromide, trioctylmethylammonium chloride and bromide, trihexadecylmethylammonium chloride and bromide, di-cured tallow alkyldimethylammonium chloride Products and bromides, di-cured tallow alkylbenzylmethylammonium chlorides and bromides, tridodecylmethylammonium chlorides and bromides, polyoxypropylene methyl List polyoxypropylene alkylammonium salt such as diethylammonium chloride and bromide, polyoxypropylene dialkylammonium salt, polyoxypropylene trialkylammonium salt, and oleylbis (2-hydroxyethyl) methylmethylammonium chloride and bromide Can do.
  • Trimethylalkylammonium salts such as benzylammonium salt, trimethylstearyl
  • quaternary phosphonium salts include tetraethylphosphonium chloride and bromide, tetrabutylphosphonium chloride and bromide or iodide, tributyloctylphosphonium chloride and bromide, tributyldodecylphosphonium chloride and bromide, and tributyl.
  • the cations constituting the quaternary ammonium salt and quaternary phosphonium salt exchange with interlayer ions such as Na + ions and Li + ions, so that the modified clay swells in an organic medium and delamination occurs due to shearing force. It will wake up and disperse and dissolve in the organic medium.
  • a quaternary ammonium salt or a quaternary phosphonium salt is selected according to the type of organic medium. These quaternary ammonium salts and quaternary phosphonium salts may be used alone or in admixture of two or more.
  • the modified clay is dispersed and dissolved in an organic medium.
  • dispersion dissolution refers to a state in which a modified clay is uniformly dispersed without being immediately separated when the modified clay is mixed in an organic medium, or a state in which the organic solution of the modified clay is visually transparent under sunlight.
  • a dispersant as an auxiliary may be used.
  • a polar additive or a polar activator functions effectively.
  • Nitroparaffin nitromethane, nitroethane, 2-nitropropane, 1-nitropropane
  • the concentration of the dispersant as the dissolution aid is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the modified clay. If it is less than 5 parts by weight, the effect as a solubilizing agent may not be obtained, and if it exceeds 100 parts by weight, the dispersibility may be deteriorated and precipitation of modified clay may occur.
  • Polymer having a three-dimensional crosslinked structure which is a main skeleton component of the polymer organogel of the present invention, comprises a monomer A and a monomer B serving as a crosslinking agent. It is a polymer.
  • Monomer A is represented by the following formula (1).
  • R 1 , R 2 , R 3 and R 4 may all have the same structure or different structures, and may be a hydrogen atom.
  • at least two of R 1 , R 2 , R 3 and R 4 are preferably hydrogen atoms because high molecular weight products are easily obtained by addition polymerization, and in the case of a structure other than hydrogen atoms, And are preferably bonded to the same carbon atom.
  • the polymer is polymerizable and soluble in the organic medium described above, and the monomer is polymerized alone in the organic medium without using a crosslinking agent.
  • the growth terminal species at the time of addition polymerization may be any of a carbocation, a carbanion, or a neutral radical as long as it is polymerized to have a high molecular weight.
  • Monomers having the structure represented by the formula (1) include acrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N-tert-butyl.
  • Acrylamides such as acrylamide, N-tert-butylmethacrylamide, N-dodecylacrylamide, N-hydroxyethylacrylamide, N, N-dimethylaminopropylacrylamide, acryloylmorpholine, vinylamides such as N-vinylacetamide, N, N- Allylamines such as diethylallylamine, aliphatic unsaturation such as 2,4-dimethyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-octene, 1-decene, 1-hexadecene and 1-octadecene Hydrocarbons, unsaturated hydrocarbons with aromatic side chains such as styrene and 1,1-diphenylethylene Vinyl esters such as vinyl n-butyrate, vinyl caproate, vinyl hexanate, vinyl octanate, vinyl laurate, vinyl stearate, vinyl pivalate, vinyl benzoate, e
  • the monomer B can be used as long as it is a compound that becomes a polymer having a three-dimensional crosslinked structure by a covalent bond by copolymerizing with the monomer having one addition polymerizable unsaturated bond.
  • the monomer is preferably soluble or miscible in the organic medium or an organic medium in which modified clay is dispersed and dissolved.
  • the three-dimensional crosslinked structure is formed by polymerizing a monomer having one addition polymerizable unsaturated bond to form a linear polymer, and then by side chain polymer reaction. It can be set as a crosslinked structure.
  • unsaturated bonds such as ethylene and acetylene, alkylene groups such as methylene, nitrile groups, mercapto groups, carboxyl groups, hydroxyl groups, epoxy groups, amino groups, methyl groups and other alkyl groups, amide groups, alkyl halides, thionyl chlorides , Sulfonic acid, carboxylic acid, chlorosulfone group, ester group, methylol group, sulfonic acid residue, sulfonate residue, azide group, isocyanate group, halogen substituent, alcohol residue, phenol residue, thiol residue, Functional groups such as a sulfone group, a silanol group, a cinnamoyl group, a cinnamylidene group, an acryloyl group, a diazo group, a dithiocarbamate group, an acid anhydride group, an active methylene group, and a coumarin group can be cited as reactive
  • Examples of the monomer B serving as a crosslinking agent include N, N′-methylenebisacrylamide, N, N′-propylenebisacrylamide, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tri Ethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, 1,10-bis ( (Acryloyloxy) decane, 1,3-bis (methacryloyloxy) -2-propanol, 1,4-bis (acryloyloxy) butane, 1,6-bis (acryloyloxy) hex Emissions, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, diviny
  • the proportion of monomer A is higher than that of monomer B in molar ratio.
  • the polymer organogel can be produced by dispersing and dissolving modified clay in an organic medium and copolymerizing the above monomers in this solution.
  • the proportion of the modified clay is preferably 0.5% by volume or more and less than 5% by volume, particularly preferably 0.5% by volume or more and less than 3% by volume, based on the polymer organogel to be produced.
  • the amount of the modified clay is less than 0.5% by volume, a sufficient reinforcing effect cannot be obtained even if the modified clay is uniformly dispersed.
  • the amount of the modified clay exceeds 5% by volume, it is difficult to disperse and dissolve the modified clay itself due to the thickening of the organic medium, and it is difficult to uniformly mix the monomers, resulting in a polymer having excellent toughness. It is difficult to obtain an organogel.
  • the ratio of the organic medium is preferably 20.0% by volume or more and less than 95.0% by volume, particularly preferably 50.0% by volume or more and less than 85.0% by volume, based on the polymer organogel to be produced.
  • the amount of the organic medium is less than 20.0% by volume, even if the swelling treatment is performed after polymerization, a sufficient degree of swelling (for example, less than 1.2 times) may not be obtained or the toughness may be inferior. A polymer organogel having a high degree of swelling cannot be obtained stably.
  • the organic medium and modified clay are finely dispersed in a polymer having a three-dimensional crosslinked structure.
  • a molecular organogel is obtained.
  • the addition copolymerization can be performed using a polymerization initiator, a catalyst, or the like that initiates polymerization by heating or ultraviolet irradiation.
  • polymerization initiators by heating include ketone peroxides, peroxyketals, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, hydro- Organic peroxides such as peroxides, persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate, 2,2'-azobis-isobutyronitrile (AIBN), 2,2'-azobis-2 , 4-Dimethylvaleronitrile (ADVN), 2,2'-azobis-2-methylbutyronitrile, azo compounds such as 4,4'-azobis-4-cyanovaleric acid, sodium ethoxide, tert-butyl Examples thereof include alkyl metals such as lithium.
  • the catalyst examples include metal salts and reducing compounds such as tertiary amine compounds such as N, N, N ′, N′-tetramethylethylenediamine.
  • the polymerization initiator and catalyst as described above can be used without being limited to specific substances as long as they are soluble in the organic medium used during the polymerization. When the polymerization initiator functions by heating, its 10-hour half-life temperature is preferably not higher than the boiling point of the organic medium.
  • the polymerization temperature is often controlled below the boiling point of the organic medium for safety reasons, etc., when the boiling point of the organic medium used exceeds the 10-hour half-life temperature, the polymerization takes a very long time, which is not preferable. . Accordingly, the preferred polymerization temperature [° C.] of the polymer organogel of the present invention is higher than the 10-hour half-life temperature [° C.] and below the boiling point [° C.] of the organic medium. If there is no problem even if the polymerization time is required for a long time, there is no particular problem even if the polymerization is performed at a temperature lower than the half-life temperature of 10 hours.
  • the polymerization atmosphere is preferably carried out in an inert gas atmosphere such as nitrogen gas, helium gas, or argon gas.
  • an inert gas atmosphere such as nitrogen gas, helium gas, or argon gas.
  • polymer organogels having various shapes can be prepared by changing the shape of the container used for polymerization.
  • it can be a polymer organogel having an arbitrary shape such as a fiber shape, a rod shape, a columnar shape, a cylindrical shape, a plate shape such as a flat plate or a disc, a spiral shape, a spherical shape, or a ring shape.
  • it can process into arbitrary shapes from these by machining.
  • the polymer organogel after polymerization can be used as a polymer organogel as it is. Further, after polymerization, the degree of swelling can be increased to an equilibrium swelling state by immersing the polymer organogel after polymerization in an organic medium used at the time of polymerization.
  • the organic medium contained in the polymer having a three-dimensional crosslinked structure is replaced by immersing the polymer organogel after polymerization in another organic medium different from the organic medium used at the time of polymerization, It can be set as the polymeric organogel which has a desired characteristic.
  • Preferred organic media that can be substituted are other organic media that are soluble with the organic media used during polymerization and have an affinity for the polymeric component.
  • the substitution may replace all of the organic medium used in the polymerization, or may partially replace it.
  • a polymer composition in which the modified clay is uniformly dispersed in the polymer having a three-dimensional crosslinked structure can be produced by removing the organic medium contained from the polymer organogel after polymerization.
  • This polymer composition can be made into a polymer organogel again by being immersed in an organic medium.
  • Examples of the method for removing the organic medium include heat drying, vacuum drying, and extraction using a solvent.
  • the polymer organogel of the present invention has a rust inhibitor, preservative, fungicide, surfactant or ion that is soluble in the organic medium, before or after polymerization, if necessary, as long as it does not impair its function.
  • a neutral liquid or the like may be added or applied.
  • a fibrous or particulate reinforcing agent made of an organic substance such as an organic polymer or an inorganic substance such as carbon, silica, or titania may be added within a range that does not impair its function.
  • it can be combined with other materials by dispersion, lamination processing or the like according to the purpose.
  • Table 1 shows a list of raw materials used in each example and each comparative example.
  • Polymerization container Flat bottom glass container with inner diameter 25 mm x height 40 mm ⁇
  • Raw material solution 10 mL (equivalent to inner diameter 25 mm x height approx. 20 mm)
  • -Polymerization initiator ADVN (10 hour half-life temperature 52 ° C), 0.3 wt% Polymerization: The gas portion in the polymerization vessel was purged with nitrogen and sealed, and then polymerized in a 55 ° C. water bath. In some comparative examples, polymerization was performed without sealing with nitrogen.
  • Polymerization time 20 hours
  • ⁇ Swelling degree evaluation> The polymer organogel obtained after polymerization is immersed in the target organic medium at 25 ° C for 10 days to swell, solid content (polymer component + modified clay) weight and polymer after swelling treatment The degree of swelling was determined from the weight of the organogel by the following formula.
  • Swelling degree Polymer organogel weight after swelling treatment [g] / Solid weight [g] Those with a degree of swelling of less than 2 are regarded as not having sufficient solvent retention as a gel material, and are evaluated as rejected. Record “ ⁇ ”, especially “5” for items of 5 or more.
  • Example 1 Solvent 1 is used as the organic medium, modified clay 1 is used as the modified clay, 0.5 g of the modified clay is added to 10 mL of the solvent, and dissolved by stirring to make Solution P. The obtained solution P was about 10.3 mL, was colorless and transparent, and no precipitate was observed.
  • the modified clay 1 used was a hydrophobic synthetic hector that was hydrophobically modified by ion-exchange of the interlayer cation of the water-swellable synthetic hectorite with a known quaternary ammonium ion such as polyoxypropylene methyldiethylammonium ion. Light. Solvent 1 was prepared by removing dissolved oxygen by bubbling using nitrogen gas for 30 minutes in advance.
  • the solvent concentration in the raw material solution remains about 80% by volume.
  • 10 mL of the raw material solution was poured into the polymerization vessel so that no bubbles were mixed and sealed.
  • the gas part in the container was sufficiently replaced with nitrogen to remove oxygen.
  • Polymerization was carried out by leaving the polymerization vessel filled with the raw material solution in a water bath prepared at 55 ° C. for 20 hours.
  • the obtained polymer organogel had high transparency and was a good solid gel that could maintain its shape as a solid even when taken out from the polymerization vessel.
  • the obtained cylindrical polymer organogel was immersed in solvent 1 for 20 days as a swelling treatment.
  • Example 2 Solution P was the same as in Example 1. Monomer A-1 and monomer B-2 were used, and a solution Q was prepared by mixing 5 mol% of monomer B-2 with respect to the whole monomer. A solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 20% by volume and stirring them sufficiently. As in Example 1, 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1. Since the obtained polymer organogel was a solid gel having high transparency similar to that in Example 1, the state of the polymer gel was determined to be “good”.
  • Example 3 Solution P was the same as in Example 1.
  • Solution Q was prepared as in Example 2.
  • a solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 50% by volume and stirring them sufficiently.
  • 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution.
  • Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1. Since the obtained polymer organogel was a solid gel having high transparency similar to that in Example 1, the state of the polymer gel was determined to be “good”. Since the degree of swelling of the obtained polymer organogel after the swelling treatment was about 17, it was judged as a pass “ ⁇ ”.
  • the compressive fracture strain was determined to be acceptable because it did not break even when 75% strain was applied. From these results, it was determined as a pass “ ⁇ ” in the overall evaluation.
  • the obtained polymer organogel was dried at 120 ° C. for 3 days.
  • a transparent polymer composition containing no solvent and uniformly dispersed in modified clay was obtained. Table 2 shows the outline and results.
  • Example 4 Solution P was the same as in Example 1.
  • Solution Q was prepared as in Example 2.
  • a solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 80% by volume and stirring them sufficiently.
  • a raw material solution was prepared by adding 0.3 wt% of a polymerization initiator to the solution R and stirring sufficiently.
  • Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1. Since the obtained polymer organogel was a solid gel having high transparency similar to that in Example 1, the state of the polymer gel was determined to be “good”. Since the degree of swelling after the swelling treatment of the obtained polymer organogel was about 18, the compression fracture strain judged as acceptable “ ⁇ ” was not acceptable even when 75% strain was applied. Was determined.
  • Example 5 Solution P was the same as in Example 1. Monomer A-1 and monomer B-2 were used, and 7.5 mol% of monomer B-2 was mixed with respect to the whole monomer as solution Q.
  • Solution R was prepared by mixing solution P and solution Q so that the solvent concentration was 90% by volume and stirring sufficiently.
  • a raw material solution was prepared by adding 0.3 wt% of a polymerization initiator to the solution R and stirring sufficiently. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1. Since the obtained polymer organogel was a solid gel with high transparency similar to Example 1, the state of the polymer gel was evaluated as a pass “ ⁇ ”.
  • Example 6 The solvent 2 was used as the organic medium, the modified clay 1 was used as the modified clay, and 0.5 g of the modified clay was added to 10 mL of the solvent.
  • the obtained solution P was about 10.3 mL, was colorless and transparent as in Example 1, and no precipitate was observed.
  • Solution Q was prepared as in Example 2.
  • a solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 75% by volume and stirring them sufficiently.
  • 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
  • the obtained polymer organogel was a solid gel having high transparency similar to that in Example 1, the state of the polymer gel was determined to be “good”. Since the degree of swelling of the obtained polymer organogel after the swelling treatment was about 18, it was determined to be a pass “ ⁇ ”. The compressive fracture strain was determined to be acceptable because it did not break even when 75% strain was applied. From these results, it was determined as a pass “ ⁇ ” in the overall evaluation. Table 2 shows the outline and results.
  • Example 7 Use solvent 3 as the organic medium, use modified clay 2 as the modified clay, add 0.3 g of modified clay to 10 mL of solvent, add 0.03 g of 95% aqueous ethanol as a dispersant, and stir well. A solution P was obtained by dissolving and finely dispersing the modified clay. The obtained solution P was about 10.1 mL, which was a slightly white translucent solution, but no precipitate was observed.
  • the modified clay 2 is modified by a cation exchange method using a known quaternary ammonium ion such as trihexadecylmethylammonium ion. Monomer A-3 and monomer B-3 were used, and 5 mol% of monomer B-3 was mixed with respect to the whole monomer as solution Q.
  • a solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 75% by volume and stirring them sufficiently.
  • 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution.
  • Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1. Since the obtained polymer organogel was a solid gel with a slightly white turbidity but a uniform appearance, the state of the polymer gel was set to pass “ ⁇ ”. Since the degree of swelling after the swelling treatment of the obtained polymer organogel was about 6, it was determined to be a pass “ ⁇ ”. When compressive fracture strain was measured, it did not break when 50% strain was applied, but partially fractured when 75% strain was applied. From this, it was determined to be a pass “ ⁇ ”. From these results, it was determined as a pass “ ⁇ ” in the overall evaluation. Table 2 shows the outline and results.
  • Example 8 Use solvent 3 as the organic medium, use modified clay 3 as the modified clay, add 0.3 g of modified clay to 10 mL of solvent, add 0.15 g of 95% ethanol aqueous solution as a dispersant, and stir well. A solution P was obtained by dissolving and finely dispersing the modified clay. The obtained solution P was about 10.3 mL and was a slightly yellow translucent solution, but no precipitate was observed.
  • the modified clay 3 is modified by a cation exchange method using natural water-swellable montmorillonite as a raw material and a known quaternary ammonium ion such as dimethyldioctadecyl ammonium ion.
  • Monomer A-3 and monomer B-2 were used, and 5 mol% of monomer B-2 was mixed with respect to the whole monomer as solution Q.
  • a solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 75% by volume and stirring them sufficiently.
  • 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution.
  • Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
  • the obtained polymer organogel was slightly yellow, but was a solid gel with a uniform appearance. Since the degree of swelling after the swelling treatment of the obtained polymer organogel was about 5, it was determined to be a pass “ ⁇ ”.
  • Example 9 The same polymer organogel as in Example 4 was polymerized. Therefore, the solvent concentration in 10 mL of the raw material solution is about 80% by volume.
  • the obtained polymer organogel was immersed in 100 mL of solvent 4 for 9 days at room temperature, and then heat treated at 120 ° C. for 4 days to remove solvent 1 to obtain a polymer organogel using solvent 4 as a solvent. It was. Since the obtained polymer organogel was a solid gel with high transparency, as in Example 4, the state of the polymer gel was determined to be “good”. Since the degree of swelling after the swelling treatment was about 5, it was judged as acceptable “ ⁇ ”. The compressive fracture strain was determined to be acceptable because it did not break even when 75% strain was applied. From these results, it was determined as a pass “ ⁇ ” in the overall evaluation. Table 2 shows the outline and results.
  • Example 10 The solvent 5 was used as the organic medium, the modified clay 2 was used as the modified clay, and the solution was added at a ratio of 0.3 g of the modified clay to 10 mL of the solvent and dissolved by stirring to obtain a solution P.
  • the obtained solution P was about 10.1 mL, was yellow and transparent, and no precipitate was observed.
  • Monomer A-1 and monomer B-2 were used, and 7.5 mol% of monomer B-2 was mixed with respect to the whole monomer as solution Q.
  • a solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 75% by volume and stirring them sufficiently.
  • 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution.
  • Example 2 Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1. Since the obtained polymer organogel was a highly transparent yellow transparent uniform solid gel, the state of the polymer gel was set to pass “ ⁇ ”. Since the degree of swelling after the swelling treatment of the obtained polymer organogel was about 5, it was determined to be a pass “ ⁇ ”. When compressive fracture strain was measured, it did not break when 50% strain was applied, but partially fractured when 75% strain was applied. From this, it was determined to be a pass “ ⁇ ”. From these results, it was determined as a pass “ ⁇ ” in the overall evaluation. Table 2 shows the outline and results.
  • Example 11 The solvent 2 was used as the organic medium, the modified clay 2 was used as the modified clay, and 0.5 g of the modified clay was added to 10 mL of the solvent.
  • the obtained solution P was about 10.3 mL, was colorless and transparent, and no precipitate was observed.
  • a solution Q was prepared by using monomer A-4 and monomer B-3 and mixing 5 mol% of monomer B-3 with respect to the whole monomer.
  • a solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 75% by volume and stirring them sufficiently.
  • 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
  • the obtained polymer organogel was a colorless and transparent solid gel.
  • the obtained polymer organogel was immersed in 100 mL of solvent 5 for 9 days and then heat treated at 150 ° C. for 1 day to remove solvent 2 to obtain a polymer organogel using solvent 5 as a solvent. Since the obtained polymer organogel was a solid gel with high transparency as in Example 2, the state of the polymer gel was set to pass “ ⁇ ”. Since the degree of swelling after the swelling treatment of the polymer organogel using the obtained solvent 5 as a solvent was about 4, it was determined to be a pass “ ⁇ ”. The compressive fracture strain was determined to be acceptable because it did not break even when 75% strain was applied. From these results, it was determined as “good” in the comprehensive evaluation. Table 2 shows the outline and results.
  • Example 12 The solvent 2 was used as the organic medium, the modified clay 1 was used as the modified clay, and 0.5 g of the modified clay was added to 10 mL of the solvent.
  • the obtained solution P was about 10.3 mL, was colorless and transparent, and no precipitate was observed.
  • Solution Q was the same as in Example 8.
  • a solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 75% by volume and stirring them sufficiently.
  • 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
  • the obtained polymer organogel was a colorless and transparent solid gel.
  • the obtained polymer organogel was immersed in 100 mL of solvent 3 for 13 days and then heat treated at 150 ° C. for 1 day to remove solvent 2 to obtain a polymer organogel using solvent 3 as a solvent. Since the obtained polymer organogel was a solid gel with high transparency as in Example 2, the state of the polymer gel was set to pass “ ⁇ ”. Since the degree of swelling after the swelling treatment of the polymer organogel using the obtained solvent 3 as a solvent was about 4, it was determined to be a pass “ ⁇ ”. The compressive fracture strain was determined to be acceptable because it did not break even when 75% strain was applied. From these results, it was determined as “good” in the comprehensive evaluation. Table 2 shows the outline and results.
  • Example 13 Solution P was prepared as in Example 11.
  • a solution Q was prepared by using monomer A-6 and monomer B-4 and mixing 5 mol% of monomer B-4 with respect to the whole monomer.
  • Solution R was prepared by mixing solution P and solution Q so that the solvent concentration was 60% by volume and stirring them sufficiently.
  • a solution obtained by adding 0.1 wt% of a polymerization initiator to Solution R and stirring sufficiently was used as a raw material solution.
  • Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
  • the obtained polymer organogel was a colorless and transparent solid gel.
  • the obtained polymer organogel was immersed in 100 mL of solvent 4 for 9 days and then heat-treated at 150 ° C.
  • Comparative Example 1 A raw material solution was prepared in the same manner as in Example 4 except that the modified clay was not used, and polymerization and swelling treatment were performed.
  • the solvent concentration in 10 mL of the raw material solution was about 80% by volume, and the obtained polymer organogel was colorless and transparent. Therefore, the state of the polymer gel was evaluated as “good”. Since the degree of swelling of the obtained polymer organogel after the swelling treatment was about 15, it was judged as a pass “ ⁇ ”. Compressive fracture strain was judged as rejected “x” because fracture occurred when 50% strain was applied. The state of fracture was very brittle. From these results, it was determined as “failed” by comprehensive evaluation. Table 2 shows the outline and results.
  • Comparative Example 2 A raw material solution was prepared in the same manner as in Example 4 except that unmodified clay was used in place of the modified clay, and polymerization and swelling treatment were performed.
  • the solvent concentration in 10 mL of the raw material solution is about 80% by volume. Further, the unmodified clay seems to swell slightly in the solvent 1, but has precipitated. Polymerization was carried out with precipitation, resulting in a polymer organogel with unmodified clay segregated at the bottom. Therefore, the state of the polymer gel was evaluated as rejected “x”. From this, it was determined as a failure “x” as a comprehensive evaluation. Table 2 shows the outline and results.
  • Comparative Example 3 A raw material solution was prepared and polymerized in the same manner as in Example 4 except that the monomer B was not used.
  • the solvent concentration in 10 mL of the raw material solution is about 80% by volume. After the polymerization, it was in a colorless and transparent state, but a solid gel was not obtained, and it was a viscous liquid. Therefore, the state of the polymer gel was evaluated as rejected “x”. From this, it was determined as a failure “x” as a comprehensive evaluation.
  • Table 2 shows the outline and results.
  • Comparative Example 4 A raw material solution was prepared in the same manner as in Example 7 except that monomer B-1 was used as monomer B. However, monomer B-1 was hardly dissolved in the raw material solution and precipitated. The solvent concentration in 10 mL of the raw material solution is about 75% by volume. Polymerization was carried out using the raw material solution in which the precipitation of monomer B-1 had occurred. As a result, only a viscous liquid similar to that in Comparative Example 3 was obtained. “ ⁇ ”. From this, it was determined as a failure “x” as a comprehensive evaluation. Table 2 shows the outline and results.
  • Comparative Example 5 A raw material solution was prepared in the same manner as in Example 4 except that the solution Q prepared using only the monomer B without using the monomer A was used, and polymerization and swelling treatment were performed.
  • the solvent concentration in the raw material solution is about 80% by volume. Since the obtained polymer organogel was a colorless and transparent solid, the state of the polymer gel was evaluated as a pass “ ⁇ ”. Since the degree of swelling after the swelling treatment was 4, it was determined to be a pass “ ⁇ ”. Compressive fracture strain was judged as rejected “x” because fracture occurred when 50% strain was applied. The state of fracture was very brittle. From these results, it was determined that the overall evaluation was x. Table 2 shows the outline and results.
  • Comparative Example 6 A raw material solution was prepared in the same manner as in Example 7 except that monomer A-5 was used as monomer A. However, monomer A-5 did not dissolve in solvent 3 and phase separation occurred. The solvent concentration in 10 mL of the raw material solution is about 75% by volume. Polymerization was performed using a raw material solution in which phase separation occurred, and no solid polymer organogel was obtained. Therefore, the state of the polymer gel was evaluated as rejected “x”. From this, it was determined as a failure “x” as a comprehensive evaluation. Table 2 shows the outline and results.
  • Comparative Example 7 The raw material solution was prepared by adding 1.8 g of modified clay 1 to 9.0 mL of the same solution Q 9.0 as in Example 4 without using any organic medium, but the modified clay 1 was added to the raw material solution. Almost did not dissolve, and precipitation occurred. Therefore, the solvent concentration in 10 mL of the raw material solution is about 0% by volume. In addition, this raw material solution is equivalent to the composition obtained by removing the solvent from Example 4. Using this raw material solution, polymerization was carried out in the same manner as in Example, but no gel was obtained because it did not contain a solvent, and the polymer composition had segregated modified clay at the bottom. From this, the state of the polymer gel was evaluated as rejected “x”.
  • the polymer composition obtained as described above is a transparent polymer composition in which the modified clay is uniformly finely dispersed, such as the polymer composition obtained by drying and removing the solvent obtained in Examples 1 and 2. I didn't. Therefore, it was determined as a failure “x” as a comprehensive evaluation. Table 2 shows the outline and results.
  • Comparative Example 8 A raw material solution was prepared and polymerized in the same manner as in Example 4 except that the solvent concentration was adjusted to 95% by volume. However, a solid polymer organogel could not be obtained because the total amount of monomer A and monomer B, which were high polymers, was less than 5% by volume. Therefore, the state of the polymer gel was evaluated as rejected “x”. From this, it was determined as a failure “x” in the comprehensive evaluation. Table 2 shows the outline and results.
  • the polymer organogel, the polymer composition and the production method thereof disclosed by the present invention are excellent in swelling property and compression property capable of holding a large amount of a liquid organic material such as an organic solvent or oil as a solvent. Therefore, it can be suitably used for machine parts that require slidability.

Abstract

Disclosed are: a polymer organogel which can carry an organic material such as an organic solvent or an oil as a solvent in a large quantity, and which has excellent strength, particularly excellent rigidity; a polymer composition; a process for producing the polymer organogel; and a process for producing the polymer composition. Specifically disclosed is a polymer organogel comprising: a polymer having a three-dimensional crosslinked structure; and a liquid organic medium and a modified water-swellable layered silicate compound both contained in the polymer, wherein the modified water-swellable layered silicate compound is produced by modifying a water-swellable layered silicate compound by the cation exchange using a cationic organic compound, and wherein the polymer is produced by the polymerization of a monomer having one addition-polymerizable unsaturated bond and a monomer having at least two addition-polymerizable unsaturated bonds and has a three-dimensional crosslinked structure.

Description

高分子オルガノゲル、高分子組成物およびこれらの製造方法Polymer organogel, polymer composition, and production method thereof
　本発明は高分子オルガノゲル、高分子組成物およびこれらの製造方法に関する。 The present invention relates to a polymer organogel, a polymer composition, and a production method thereof.
　ゲルの骨格成分を３次元架橋構造を有する高分子とする高分子ゲルは、その溶媒成分を水とする高分子ハイドロゲルについて精力的に研究開発が行なわれてきた（特許文献１～特許文献５参照）。
　またこのような高分子ハイドロゲルを人工関節や医療機器用の潤滑性表面コーティングなど、主に医療用途に適用することを目的とした応用研究も精力的に行なわれてきた（特許文献６～特許文献８参照）。
　一方、液状の有機物を溶媒とするオルガノゲルでは、物理結合による可逆的な３次元架橋構造を骨格成分として形成することができる、一般にいうゲル化剤の開発が進んでいる（非特許文献１参照）。 As for polymer gels in which the skeleton component of the gel is a polymer having a three-dimensional cross-linked structure, research and development have been vigorously conducted on polymer hydrogels whose solvent component is water (Patent Documents 1 to 5). reference).
In addition, extensive research has been conducted on application of such polymer hydrogels mainly for medical applications such as lubricated surface coatings for artificial joints and medical devices (Patent Documents 6 to 5). Reference 8).
On the other hand, in an organogel using a liquid organic substance as a solvent, development of a general gelling agent that can form a reversible three-dimensional cross-linked structure by physical bonding as a skeleton component is progressing (see Non-Patent Document 1). .
　しかしながらこのようなゲル化剤の使用により得られた物理ゲルは、通常著しく低強度の脆性材料であるため用途によっては取り扱いが困難となる場合がある。
　このようなことから機械的強度、特に靭性に優れ、かつ油や有機溶剤のような液状の有機物を溶媒として多量に保持できる高分子オルガノゲルはほとんど知られていないという問題がある。
特開平１０－１５８３７５号公報 特開２００２－５３６２９号公報 特開２００２－２１２４５２号公報 ＷＯ０１／０８３５６６号公報 特開２００６－２１３８６８号公報 特開平１０－３６５３４号公報 特表平１０－５０２８５５号公報 特表平２００１－５１４９３１号公報 高分子ゲルの最新動向　柴山充弘、梶原莞爾監修、シーエムシー出版（２００４年） However, the physical gel obtained by using such a gelling agent is usually a brittle material with extremely low strength, so that it may be difficult to handle depending on the application.
For this reason, there is a problem that a polymer organogel that is excellent in mechanical strength, particularly toughness, and that can hold a large amount of liquid organic matter such as oil or organic solvent as a solvent is hardly known.
Japanese Patent Laid-Open No. 10-158375 JP 2002-53629 A JP 2002-212453 A WO01 / 083566 JP 2006-2183868 Japanese Patent Laid-Open No. 10-36534 Japanese National Patent Publication No. 10-502855 JP-T-2001-514931 Latest Trends in Polymer Gels Mitsuhiro Shibayama, Satoshi Sugawara, CM Publishing (2004)
　本発明はこのような問題に対処するためになされたものであり、有機溶媒や油等の有機媒体を多量に保持することができ、かつ機械的強度、特に靭性に優れる高分子オルガノゲル、該高分子オルガノゲルを生成できる高分子組成物およびこれらの製造方法を提供することを目的とする。 The present invention has been made to cope with such problems, and is a high-molecular organogel that can retain a large amount of an organic medium such as an organic solvent or oil and is excellent in mechanical strength, particularly toughness. It is an object of the present invention to provide a polymer composition capable of producing a molecular organogel and a method for producing them.
　本発明の高分子オルガノゲルは、３次元架橋構造を有する高分子内に、液状の有機媒体と変性水膨潤性層状ケイ酸塩化合物とを含むことを特徴とする。
　また、本発明の高分子オルガノゲルに使用できる変性水膨潤性層状ケイ酸塩化合物は、水膨潤性層状ケイ酸塩化合物を陽イオン交換法によりカチオン性有機化合物を用いて変性した化合物であることを特徴とする。
　また、上記水膨潤性層状ケイ酸塩化合物は、スメクタイト族粘土鉱物であることを特徴とする。
　また、本発明の高分子オルガノゲルに使用できる高分子が、付加重合性不飽和結合を１つ有する単量体（以下単量体Ａと略称する）と、少なくとも２つの付加重合性不飽和結合を有する単量体（以下単量体Ｂと略称する）との重合により得られる３次元架橋構造を有する高分子であることを特徴とする。
　本発明の高分子オルガノゲルは、高分子オルガノゲルを該高分子オルガノゲルに含まれる同一の有機媒体に 25℃で 20 日間浸漬したときの膨潤度が 1.2 以上であり、該膨潤度における圧縮破壊歪みが 50％以上であることを特徴とする。 The polymer organogel of the present invention is characterized by containing a liquid organic medium and a modified water-swellable layered silicate compound in a polymer having a three-dimensional crosslinked structure.
The modified water-swellable layered silicate compound that can be used in the polymer organogel of the present invention is a compound obtained by modifying a water-swellable layered silicate compound with a cationic organic compound by a cation exchange method. Features.
The water-swellable layered silicate compound is a smectite group clay mineral.
The polymer that can be used in the polymer organogel of the present invention comprises a monomer having one addition polymerizable unsaturated bond (hereinafter abbreviated as “monomer A”) and at least two addition polymerizable unsaturated bonds. It is a polymer having a three-dimensional cross-linked structure obtained by polymerization with a monomer (hereinafter abbreviated as “monomer B”).
The polymer organogel of the present invention has a degree of swelling of 1.2 or more when the polymer organogel is immersed in the same organic medium contained in the polymer organogel at 25 ° C. for 20 days, and the compression fracture strain at the degree of swelling is 50. % Or more.
　本発明の高分子オルガノゲルの製造方法は、有機媒体に変性水膨潤性層状ケイ酸塩化合物を分散溶解させる溶解工程と、この溶液中で単量体Ａと、単量体Ｂとを付加重合により共重合させる重合工程とを含むことを特徴とする。
　上記溶解工程は、有機媒体に分散剤を加えることで変性水膨潤性層状ケイ酸塩化合物を溶解させる溶解工程であることを特徴とする。特に上記分散剤が有極性液状物質であることを特徴とする。
　また、上記重合工程において、単量体Ａの割合が単量体Ｂよりもモル比で多いことを特徴とする。特に、有機媒体の濃度が生成する高分子オルガノゲルを基準として、20.0 容量％ 以上、95.0 容量％ 未満であることを特徴とする。
　また、上記重合工程を、不活性ガスの雰囲気下で行なうことを特徴とする。
　また、上記重合工程後に重合時の有機媒体とは異なる他の有機媒体中に重合後の高分子オルガノゲルを浸漬することで、３次元架橋構造を有する高分子内に含まれる有機媒体を置換することを特徴とする。 The method for producing the polymer organogel of the present invention comprises a dissolution step of dispersing and dissolving a modified water-swellable layered silicate compound in an organic medium, and addition polymerization of monomer A and monomer B in this solution. And a polymerization step for copolymerization.
The dissolution step is a dissolution step of dissolving the modified water-swellable layered silicate compound by adding a dispersant to the organic medium. In particular, the dispersant is a polar liquid substance.
In the polymerization step, the ratio of the monomer A is larger than that of the monomer B in a molar ratio. In particular, it is characterized in that the concentration of the organic medium is 20.0% by volume or more and less than 95.0% by volume based on the polymer organogel produced.
In addition, the polymerization step is performed in an inert gas atmosphere.
Also, after the polymerization step, the organic medium contained in the polymer having a three-dimensional crosslinked structure is replaced by immersing the polymer organogel after polymerization in another organic medium different from the organic medium at the time of polymerization. It is characterized by.
　本発明の高分子オルガノゲルを生成できる高分子組成物は、３次元架橋構造を有する高分子内に変性水膨潤性層状ケイ酸塩化合物が均一に分散されてなることを特徴とする。
　また、本発明の高分子組成物の製造方法は、有機媒体に変性水膨潤性層状ケイ酸塩化合物を分散溶解させる溶解工程と、この溶液中で付加重合性不飽和結合を１つ有する単量体と、少なくとも２つの付加重合性不飽和結合を有する単量体とを付加重合により共重合させる重合工程と、重合時の上記有機媒体を除去する工程とを含むことを特徴とする。 The polymer composition capable of producing the polymer organogel of the present invention is characterized in that a modified water-swellable layered silicate compound is uniformly dispersed in a polymer having a three-dimensional crosslinked structure.
Further, the method for producing the polymer composition of the present invention comprises a dissolution step of dispersing and dissolving a modified water-swellable layered silicate compound in an organic medium, and a single amount having one addition polymerizable unsaturated bond in the solution. And a monomer having at least two addition-polymerizable unsaturated bonds by addition polymerization, and a step of removing the organic medium during the polymerization.
　本発明の高分子オルガノゲルとは、高分子を増ちょう剤とした粘ちょうな液状物ではなく、その骨格となる高分子鎖が化学結合、特に共有結合による３次元架橋構造を有し、自重の 0.2 倍～100 倍程度の有機溶媒および／または油を吸収して膨潤した固体状物質である。 The polymer organogel of the present invention is not a viscous liquid substance using a polymer as a thickener, and the polymer chain as the skeleton has a chemical bond, particularly a three-dimensional cross-linking structure by a covalent bond, It is a solid substance swollen by absorbing an organic solvent and / or oil of about 0.2 to 100 times.
　本発明の高分子オルガノゲルは、非水性または親油性の３次元架橋構造を有する高分子内に、非水性または親油性の変性水膨潤性層状ケイ酸塩化合物が微分散されてなるので、有機溶媒や潤滑油等の液状の有機媒体を高分子内に多量に保持することができ、かつ３次元架橋構造を有する高分子体であるので強度、特に靭性に優れる。 In the polymer organogel of the present invention, a non-aqueous or lipophilic modified water-swellable layered silicate compound is finely dispersed in a polymer having a non-aqueous or lipophilic three-dimensional crosslinked structure. And a liquid organic medium such as lubricating oil can be retained in a large amount in the polymer, and since it is a polymer having a three-dimensional cross-linked structure, it is excellent in strength, particularly toughness.
　本発明の高分子オルガノゲルの製造方法は、有機媒体に変性水膨潤性層状ケイ酸塩化合物を分散溶解させる溶解工程と、この溶液中で単量体Ａと、単量体Ｂとを付加重合により共重合させる重合工程とを含むので、３次元架橋構造を有する高分子内に変性水膨潤性層状ケイ酸塩化合物を均一濃度で含せることができる。また、有機溶媒や潤滑油等を多量に保持することができる。 The method for producing the polymer organogel of the present invention comprises a dissolution step of dispersing and dissolving a modified water-swellable layered silicate compound in an organic medium, and addition polymerization of monomer A and monomer B in this solution. And a polymerization step for copolymerization, the modified water-swellable layered silicate compound can be contained at a uniform concentration in the polymer having a three-dimensional crosslinked structure. Further, a large amount of organic solvent, lubricating oil, etc. can be retained.
　本発明の高分子組成物は、３次元架橋構造を有する高分子内に均一に変性水膨潤性層状ケイ酸塩化合物が微分散しているので、有機溶媒や潤滑油等に浸漬することで強度に優れ、ハンドリング性の向上した高分子オルガノゲルを容易に得ることができる。 In the polymer composition of the present invention, the modified water-swellable layered silicate compound is uniformly dispersed in the polymer having a three-dimensional crosslinked structure. It is possible to easily obtain a polymer organogel having excellent handling properties and improved handling properties.
　本発明の高分子オルガノゲルは、（１）有機媒体、（２）変性水膨潤性層状ケイ酸塩化合物、（３）３次元架橋構造を有する高分子で構成される。
（１）有機媒体
　有機媒体としては、該有機媒体中で後述する変性水膨潤性層状ケイ酸塩化合物を均一分散または溶解させることができ、かつ後述する付加共重合の溶媒となる有機媒体を使用できる。また、付加共重合時の溶媒と可溶な有機媒体であるならば、共重合後、該可溶な有機媒体中に浸漬することで重合時の有機溶媒を交換することができるので、有機媒体として使用できる。有機媒体としては、有機溶媒、潤滑油などの油等が挙げられる。また、有機媒体としては含水率 5 重量％以下の微量に調整したものを用いることが好ましく、特に水を含まないものが好ましい。
　なお、変性前の親水性の水膨潤性層状ケイ酸塩化合物は、上記有機媒体により、ほとんど／もしくは全く膨潤せず、せん断力による層間剥離が実質的に起こらないため、分散せず比較的短時間で沈澱が発生する。 The polymer organogel of the present invention comprises (1) an organic medium, (2) a modified water-swellable layered silicate compound, and (3) a polymer having a three-dimensional crosslinked structure.
(1) Organic medium As the organic medium, an organic medium that can uniformly disperse or dissolve the modified water-swellable layered silicate compound described later in the organic medium and serves as a solvent for addition copolymerization described later is used. it can. In addition, if the solvent during addition copolymerization is soluble in the organic medium, the organic solvent during polymerization can be exchanged by immersing in the soluble organic medium after copolymerization. Can be used as Examples of the organic medium include organic solvents, oils such as lubricating oils, and the like. Further, as the organic medium, it is preferable to use a water content adjusted to a very small amount of 5% by weight or less, particularly preferably water-free.
Note that the hydrophilic water-swellable layered silicate compound before modification does not swell or hardly delaminates due to the above-mentioned organic medium and does not cause delamination due to shearing force. Precipitation occurs over time.
　有機媒体を例示すれば、有機溶媒として脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素等の炭化水素類や、これらがハロゲン化されたハロゲン化炭化水素類、エーテル類、エステル類、ケトン類、アルコール類、窒素化合物、硫黄化合物が挙げられる。 Examples of organic media include hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons as organic solvents, halogenated hydrocarbons in which these are halogenated, ethers, esters, Examples include ketones, alcohols, nitrogen compounds, and sulfur compounds.
　具体例としては、通常有機溶剤として知られる、ヘキサン、オクタン、デカン、ドデカン、ベンゼン、トルエン、キシレン、エチルベンゼン、シクロヘキサン、ヘプタン、メチルシクロヘキサン、デカリン、石油ベンジン等の炭化水素類、塩化メチル、ジクロロメタン、クロロホルム、四塩化炭素等のハロゲン化炭化水素類、ジエチルエーテル、ジフェニルエーテル、プロピレンオキシド、ジオキサン等のエーテル類、酢酸エチル、酢酸 sec-ブチル等のエステル類、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、２-ヘプタノン、ショウノウ等のケトン類、メタノール、エタノール、イソプロピルアルコール、オクタノール、ベンジルアルコール、グリコール類やグリセリン等のアルコール類、ピリジン、2-ピロリドン、Ｎ-メチルピロリドン、Ｎ，Ｎ-ジメチルアセトアミド、Ｎ，Ｎ-ジメチルホルムアミド等の窒素化合物、ジメチルスルホキシド等の硫黄化合物が挙げられる。
　その他上記有機溶剤以外に油である鉱油、植物油、流動パラフィン、ポリ-α-オレフィン（ＰＡＯ）油等の合成炭化水素油やポリアルキレングリコール、１価アルコールと脂肪酸からなるエステル油、ジエステル油やネオペンチルポリオールと脂肪酸からなるエステル油等の多価エステル油、アルキルフェニルエーテル油やジアルキルフェニルエーテル油、アルキルポリフェニルエーテル油等のフェニルエーテル油、シクロペンタン油、シリコーン油、パーフルオロポリエーテル油等を挙げることができる。 Specific examples include hydrocarbons such as hexane, octane, decane, dodecane, benzene, toluene, xylene, ethylbenzene, cyclohexane, heptane, methylcyclohexane, decalin, petroleum benzine, methyl chloride, dichloromethane, Halogenated hydrocarbons such as chloroform and carbon tetrachloride, ethers such as diethyl ether, diphenyl ether, propylene oxide and dioxane, esters such as ethyl acetate and sec-butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone Ketones such as 2-heptanone and camphor, methanol, ethanol, isopropyl alcohol, octanol, benzyl alcohol, alcohols such as glycols and glycerin, pyridine, 2-pi Pyrrolidone, N- methylpyrrolidone, N, N- dimethylacetamide, N, nitrogen compounds such as N- dimethylformamide, sulfur compounds such as dimethyl sulfoxide.
Other than the above organic solvents, synthetic hydrocarbon oils such as mineral oil, vegetable oil, liquid paraffin, poly-α-olefin (PAO) oil, polyalkylene glycol, ester oils composed of monohydric alcohol and fatty acid, diester oils and neo Polyester oil such as ester oil composed of pentyl polyol and fatty acid, phenyl ether oil such as alkyl phenyl ether oil, dialkyl phenyl ether oil, alkyl polyphenyl ether oil, cyclopentane oil, silicone oil, perfluoropolyether oil, etc. Can be mentioned.
（２）変性水膨潤性層状ケイ酸塩化合物（以下、変性クレイともいう）
　変性クレイとは、親水性の水膨潤性層状ケイ酸塩化合物を有機媒体中に分散溶解できるように変性したものである。
　変性クレイの原料となる水膨潤性層状ケイ酸塩化合物は、水中に添加することで膨潤し、さらにその水溶液に撹拌等によりせん断力を加えることで、その層状構造が、層間で剥離して部分的あるいは完全に破壊し、水中に分散するようなものなら、特定の物質に限定されることなく任意の粘土鉱物を用いることができる。これらの中で特に好ましくは、水中で単一層またはそれに近いレベルに剥離し、分散可能な層状粘土鉱物である。 (2) Modified water-swellable layered silicate compound (hereinafter also referred to as modified clay)
The modified clay is modified so that a hydrophilic water-swellable layered silicate compound can be dispersed and dissolved in an organic medium.
The water-swellable layered silicate compound that is the raw material of the modified clay swells when added to water, and further, by applying shearing force to the aqueous solution by stirring or the like, the layered structure peels off between the layers. Any clay mineral can be used without being limited to a specific substance as long as it can be destroyed or dispersed completely in water. Particularly preferred among these are layered clay minerals that can be exfoliated and dispersed in water to a single layer or a level close thereto.
　親水性の水膨潤性層状ケイ酸塩化合物としては、例えば親水性の膨潤性スメクタイトや膨潤性雲母などが挙げられる。具体的には、ヘクトライト、モンモリロナイト、サポナイト、スチブンサイト、バイデライト、ノントロナイト、ベントナイト等のスメクタイト族粘土鉱物、Ｎａ型テトラシリシックフッ素雲母、Ｌｉ型テトラシリシックフッ素雲母、Ｎａ型フッ素テニオライト、Ｌｉ型フッ素テニオライトおよびバーミキュライト等の膨潤性雲母族粘土鉱物、これらの類似構造を有する層状ケイ酸塩鉱物、またはこれらの置換体や誘導体、あるいはこれらの混合物等が挙げられる。
　なお、上記の置換体には、層間イオンのＮａ+ あるいはＬｉ+イオンの一部がＫ+ イオンで置換されているもの、四面体シートのＳｉ4+ イオンの一部がＭｇ2+ イオンで置換されているものが含まれる。
　これらは天然物、合成物のどちらでも用いることができるが、不純物の混入が少なく本発明の高分子オルガノゲルとした際、意図しない着色の問題や重合阻害の問題等が発生し難いこと、および透明な高分子オルガノゲルが得られやすいことから合成物の方が好ましい。 Examples of the hydrophilic water-swellable layered silicate compound include hydrophilic swellable smectite and swellable mica. Specifically, smectite group clay minerals such as hectorite, montmorillonite, saponite, stevensite, beidellite, nontronite, bentonite, Na type tetrasilicic fluorine mica, Li type tetrasilicic fluorine mica, Na type fluorine teniolite, Li Swellable mica group clay minerals such as fluorinated teniolite and vermiculite, layered silicate minerals having a similar structure thereof, substituted or derivatives thereof, or mixtures thereof.
In addition, in the above-mentioned substituted body, a part of Na + or Li + ion of the interlayer ion is replaced with K + ion, and a part of Si 4+ ion of the tetrahedral sheet is replaced with Mg 2+ ion. Is included.
These can be used for both natural products and synthetic products. However, when the polymer organogel of the present invention contains few impurities, it is difficult to cause unintentional coloring problems and polymerization inhibition problems, and transparent. Synthetic polymer gel is preferred because it is easy to obtain a high molecular organogel.
　上記スメクタイト族粘土鉱物は、２層のシリカ四面体層がマグネシウム八面体層またはアルミニウム八面体層を間に挟んだサンドイッチ型の３層構造を有するケイ酸塩層が数～数１０倍積層した構造を持つフィロケイ酸塩の一種である。このようなスメクタイトのケイ酸塩層は負の層電荷を有しており、その電荷を層間のアルカリ金属カチオンやアルカリ土類金属カチオンの存在によって中和して、全体としての電荷のバランスを取っている。
　同様なケイ酸塩構造を持つ雲母と比べて、スメクタイト族粘土鉱物は、層電荷が小さく層間が広がり易いため、せん断力による層間剥離が容易であること、あるいは陽イオン交換能が高く、カチオン交換による親油性または疎水性への有機変性が容易であることから特に好ましい。 The smectite group clay mineral has a structure in which two layers of silica tetrahedron layers are sandwiched with a magnesium octahedron layer or an aluminum octahedron layer and sandwich type silicate layers are laminated several to several tens of times. Is a kind of phyllosilicate. Such a smectite silicate layer has a negative layer charge, which is neutralized by the presence of alkali metal cations or alkaline earth metal cations between the layers to balance the overall charge. ing.
Compared to mica having a similar silicate structure, smectite group clay minerals have a low layer charge and easily spread between layers, so that delamination by shearing force is easy, or cation exchange ability is high, and cation exchange. It is particularly preferable because organic modification to lipophilicity or hydrophobicity is easy.
　変性クレイは、上記親水性の水膨潤性層状ケイ酸塩化合物を有機媒体中に分散溶解できるように有機変性処理する。有機変性処理としては、シラノール基を有するシランカップリング剤等のカップリング剤による変性方法、陽イオン交換による方法、または必要に応じてこれらを複合した方法が挙げられるが、変性方法が簡便なことから陽イオン交換による方法が好ましい。
　陽イオン交換による有機変性処理は、一般に粘土有機複合体を製造する方法として知られており（特許第２５１４７８０号参照）、種々のカチオン性の有機化合物とスメクタイト族粘土鉱物を水中で反応させることにより行なうことができる。陽イオン交換反応では、スメクタイトのＮａ+ イオンやＬｉ+ イオン等の層間イオンとカチオンとなった有機化合物が交換することで、交換した有機化合物に由来する親油性あるいは疎水性を付与することができる。 The modified clay is subjected to organic modification treatment so that the hydrophilic water-swellable layered silicate compound can be dispersed and dissolved in an organic medium. Examples of the organic modification treatment include a modification method using a coupling agent such as a silane coupling agent having a silanol group, a method using cation exchange, or a method in which these are combined as necessary, but the modification method is simple. To cation exchange are preferred.
Organic modification treatment by cation exchange is generally known as a method for producing clay organic composites (see Japanese Patent No. 2514780), and by reacting various cationic organic compounds with smectite clay minerals in water. Can be done. The cation exchange reaction, that organic compounds became smectite Na + ions and Li + interlayer ions and cations such as ions are exchanged, it is possible to impart lipophilicity or hydrophobicity derived from organic compounds has been replaced .
　カチオン性有機化合物としては、例えば、第４級アンモニウムイオンや第４級ホスホニウムイオンと塩素イオンや臭素イオン等のハロゲンイオンからなる塩を挙げることができる。
　第４級アンモニウム塩の具体例としては、ジメチルジオクタデシルアンモニウムの塩化物や臭化物等のジメチルジアルキルアンモニウム塩、ジメチルオクタデシルベンジルアンモニウムの塩化物や臭化物やジメチルステアリルベンジルアンモニウムの塩化物や臭化物等のジメチルアルキルベンジルアンモニウム塩、トリメチルステアリルアンモニウムの塩化物や臭化物等のトリメチルアルキルアンモニウム塩、その他、トリオクチルメチルアンモニウムの塩化物や臭化物、トリヘキサデシルメチルアンモニウムの塩化物や臭化物、ジ硬化牛脂アルキルジメチルアンモニウムの塩化物や臭化物、ジ硬化牛脂アルキルベンジルメチルアンモニウムの塩化物や臭化物、トリドデシルメチルアンモニウムの塩化物や臭化物、ポリオキシプロピレンメチルジエチルアンモニウムの塩化物や臭化物等のポリオキシプロピレンアルキルアンモニウム塩やポリオキシプロピレンジアルキルアンモニウム塩、ポリオキシプロピレントリアルキルアンモニウム塩、オレイルビス（2-ヒドロキシエチル）メチルメチルアンモニウムの塩化物や臭化物等を挙げることができる。
　第４級ホスホニウム塩の具体例としては、テトラエチルホスホニウムの塩化物や臭化物、テトラブチルホスホニウムの塩化物や臭化物あるいは沃化物、トリブチルオクチルホスホニウムの塩化物や臭化物、トリブチルドデシルホスホニウムの塩化物や臭化物、トリブチルヘキサデシルホスホニウムの塩化物や臭化物、トリオクチルエチルホスホニウムの塩化物や臭化物、トリエチルベンジルホスホニウムの塩化物や臭化物、トリブチルメチルホスホニウムの沃化物、トリブチルアリルホスホニウムの塩化物や臭化物、トリブチルベンジルホスホニウムの塩化物や臭化物、トリオクチルビニルベンジルホスホニウムの塩化物や臭化物、トリブチル2-メチルアリルホスホニウムの塩化物や臭化物、トリオクチル2-メチルアリルホスホニウムの塩化物や臭化物、ジメチルジオクタデシルホスホニウムの塩化物や臭化物、ジメチルジオクタデシルホスホニウムの塩化物や臭化物、ジメチルオクタデシルベンジルホスホニウムの塩化物や臭化物、ジメチルオクタデシルベンジルホスホニウムの塩化物や臭化物、テトラフェニルホスホニウムの塩化物や臭化物、トリフェニルベンジルホスホニウムの塩化物や臭化物、トリフェニルメチルホスホニウムの塩化物や臭化物、トリフェニルブチルホスホニウムの塩化物や臭化物、ビス（ ヒドロキシプロピル） オクタデシルイソブチルホスホニウムの塩化物や臭化物、トリフェニルカルボキシエチルホスホニウムの塩化物や臭化物、トリフェニルカルボキシペンチルホスホニウムの塩化物や臭化物等を挙げることができる。 Examples of the cationic organic compound include salts composed of quaternary ammonium ions or quaternary phosphonium ions and halogen ions such as chlorine ions or bromine ions.
Specific examples of quaternary ammonium salts include dimethyldialkylammonium salts such as dimethyldioctadecylammonium chloride and bromide, dimethyloctadecylbenzylammonium chloride and bromide, and dimethylstearylbenzylammonium chloride and bromide dimethylalkyl. Trimethylalkylammonium salts such as benzylammonium salt, trimethylstearylammonium chloride and bromide, trioctylmethylammonium chloride and bromide, trihexadecylmethylammonium chloride and bromide, di-cured tallow alkyldimethylammonium chloride Products and bromides, di-cured tallow alkylbenzylmethylammonium chlorides and bromides, tridodecylmethylammonium chlorides and bromides, polyoxypropylene methyl List polyoxypropylene alkylammonium salt such as diethylammonium chloride and bromide, polyoxypropylene dialkylammonium salt, polyoxypropylene trialkylammonium salt, and oleylbis (2-hydroxyethyl) methylmethylammonium chloride and bromide Can do.
Specific examples of quaternary phosphonium salts include tetraethylphosphonium chloride and bromide, tetrabutylphosphonium chloride and bromide or iodide, tributyloctylphosphonium chloride and bromide, tributyldodecylphosphonium chloride and bromide, and tributyl. Hexadecylphosphonium chloride and bromide, Trioctylethylphosphonium chloride and bromide, Triethylbenzylphosphonium chloride and bromide, Tributylmethylphosphonium iodide, Tributylallylphosphonium chloride and bromide, Tributylbenzylphosphonium chloride And bromide, trioctylvinylbenzylphosphonium chloride and bromide, tributyl 2-methylallylphosphonium chloride and bromide, trioctyl2-methylallylphosphonium chloride And bromide, dimethyldioctadecylphosphonium chloride and bromide, dimethyldioctadecylphosphonium chloride and bromide, dimethyloctadecylbenzylphosphonium chloride and bromide, dimethyloctadecylbenzylphosphonium chloride and bromide, tetraphenylphosphonium chloride and Bromide, triphenylbenzylphosphonium chloride and bromide, triphenylmethylphosphonium chloride and bromide, triphenylbutylphosphonium chloride and bromide, bis (hydroxypropyl) octadecylisobutylphosphonium chloride and bromide, triphenylcarboxyethyl Examples thereof include phosphonium chloride and bromide, and triphenylcarboxypentylphosphonium chloride and bromide.
　第４級アンモニウム塩や第４級ホスホニウム塩を構成するカチオンがＮａ+ イオンやＬｉ+ イオン等の層間イオンと交換することで、変性クレイが有機媒体中で膨潤し、またせん断力によって層間剥離を起こすようになり、該有機媒体に分散溶解する。第４級アンモニウム塩や第４級ホスホニウム塩は有機媒体の種類に応じて選定する。
　なお、これら上述の第４級アンモニウム塩や第４級ホスホニウム塩は、単独あるいは 2 種以上を混合して用いることもできる。 The cations constituting the quaternary ammonium salt and quaternary phosphonium salt exchange with interlayer ions such as Na + ions and Li + ions, so that the modified clay swells in an organic medium and delamination occurs due to shearing force. It will wake up and disperse and dissolve in the organic medium. A quaternary ammonium salt or a quaternary phosphonium salt is selected according to the type of organic medium.
These quaternary ammonium salts and quaternary phosphonium salts may be used alone or in admixture of two or more.
　変性クレイは有機媒体に分散溶解する。本発明において、分散溶解とは、有機媒体に変性クレイを混合したとき、直ちに分離することなく均一に分散している状態、または変性クレイの有機溶液が太陽光下において目視で透明になる状態をいう。
　有機媒体への変性クレイの分散溶解は助剤としての分散剤を用いてもよい。このような分散剤としては、特に極性添加剤もしくは極性活性剤等と呼ばれるものが有効に機能する。具体例として例えば、2,5-ヘキサンジオン、イソプロピルアルコール、アセトン、エチルエーテル、トルエン、キシレンの 2 種またはそれ以上の混合物、メタノール、エタノール、アセトン、プロピレンカーボネートやこれらと微少量（ 5％程度）の水との混合物、アセトン、酢酸、ベンジルクロライド、ブチルステアリン酸、ココナッツオイル、シクロヘキサノン、エチルアセトン、エチレンジクロライド、エチルエーテル、フルフラール、イソアミルアセテート、メチルエチルケトン、ニトロベンゼン、アセトンと１から３の炭素数を有するニトロパラフィン（ニトロメタン、ニトロエタン、2-ニトロプロパン、1-ニトロプロパン）アセトンとアセトニトリルの混合物、またはアセトンとプロピルニトリルの混合物、ヘキシレングリコール、極微小量の水等が挙げられる。 The modified clay is dispersed and dissolved in an organic medium. In the present invention, dispersion dissolution refers to a state in which a modified clay is uniformly dispersed without being immediately separated when the modified clay is mixed in an organic medium, or a state in which the organic solution of the modified clay is visually transparent under sunlight. Say.
For dispersing and dissolving the modified clay in the organic medium, a dispersant as an auxiliary may be used. As such a dispersant, what is called a polar additive or a polar activator functions effectively. Specific examples include, for example, 2,5-hexanedione, isopropyl alcohol, acetone, ethyl ether, toluene, a mixture of two or more of xylene, methanol, ethanol, acetone, propylene carbonate, and a small amount (about 5%) with these. A mixture of water with acetone, acetic acid, benzyl chloride, butyl stearic acid, coconut oil, cyclohexanone, ethyl acetone, ethylene dichloride, ethyl ether, furfural, isoamyl acetate, methyl ethyl ketone, nitrobenzene, acetone and 1 to 3 carbon atoms Nitroparaffin (nitromethane, nitroethane, 2-nitropropane, 1-nitropropane) A mixture of acetone and acetonitrile, or a mixture of acetone and propylnitrile, hexylene glycol, Examples include extremely small amounts of water.
　溶解助剤としての分散剤の濃度は、変性クレイ 100 重量部に対して 5～100 重量部であることが好ましい。 5 重量部未満であると溶解助剤としての効果が得られない場合があり、100 重量部をこえると逆に分散性が悪化し、変性クレイの沈澱が発生する場合がある。 The concentration of the dispersant as the dissolution aid is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the modified clay. If it is less than 5 parts by weight, the effect as a solubilizing agent may not be obtained, and if it exceeds 100 parts by weight, the dispersibility may be deteriorated and precipitation of modified clay may occur.
（３）３次元架橋構造を有する高分子
　本発明の高分子オルガノゲルの主骨格成分となる３次元架橋構造を有する高分子は、単量体Ａと、架橋剤となる単量体Ｂとの共重合体である。
　単量体Ａは下記式（１）で示される。
Figure JPOXMLDOC01-appb-C000001
 　Ｒ1、Ｒ2、Ｒ3、Ｒ4 は全て同一の構造であっても、あるいは異なる構造であってもよく、水素原子であってもよい。付加重合により高分子量物が得られやすいことから、特にＲ1、Ｒ2、Ｒ3、Ｒ4 の内、少なくとも 2 個以上は水素原子であることが好ましく、また水素原子以外の構造の場合は、同一炭素原子と結合している方が好ましい。
　式（１）で示される単量体の中で、重合性を有してかつ上述した有機媒体に可溶であり、さらに単量体をその有機媒体中で架橋剤を用いず単独で重合した場合、重合により得られるポリマーやオリゴマー等の高分子物の沈澱が生じないものが好ましい。また、付加重合時の成長末端種は、重合して高分子量化するのであれば、カルボカチオン、カルボアニオンまたは中性のラジカルの何れであってもよい。 (3) Polymer having a three-dimensional crosslinked structure A polymer having a three-dimensional crosslinked structure, which is a main skeleton component of the polymer organogel of the present invention, comprises a monomer A and a monomer B serving as a crosslinking agent. It is a polymer.
Monomer A is represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000001
 R 1 , R 2 , R 3 and R 4 may all have the same structure or different structures, and may be a hydrogen atom. In particular, at least two of R 1 , R 2 , R 3 and R 4 are preferably hydrogen atoms because high molecular weight products are easily obtained by addition polymerization, and in the case of a structure other than hydrogen atoms, And are preferably bonded to the same carbon atom.
Among the monomers represented by the formula (1), the polymer is polymerizable and soluble in the organic medium described above, and the monomer is polymerized alone in the organic medium without using a crosslinking agent. In such a case, those which do not cause precipitation of a polymer or oligomer such as an oligomer obtained by polymerization are preferred. Further, the growth terminal species at the time of addition polymerization may be any of a carbocation, a carbanion, or a neutral radical as long as it is polymerized to have a high molecular weight.
　式（１）で示される構造を有する単量体としては、アクリルアミド、N-イソプロピルアクリルアミド、N,N-ジメチルアクリルアミド、N,N-ジメチルメタクリルアミド、N,N-ジエチルアクリルアミド、N-tert-ブチルアクリルアミド、N-tert-ブチルメタクリルアミド、N-ドデシルアクリルアミド、N-ヒドロキシエチルアクリルアミド、N,N-ジメチルアミノプロピルアクリルアミド、アクリロイルモルホリン等のアクリルアミド類、N-ビニルアセトアミド等のビニルアミド類、N,N-ジエチルアリルアミン等のアリルアミン類、2,4-ジメチル-1-ペンテン、5-メチル-1-ヘキセン、１-ヘキセン、１-オクテン、１-デセン、１-ヘキサデセン、１-オクタデセン等の脂肪族不飽和炭化水素類、スチレン、1,1-ジフェニルエチレン等の芳香族類を側鎖に有する不飽和炭化水素類、n-酪酸ビニル、カプロン酸ビニル、ビニルヘキサネート、ビニルオクタネート、ラウリン酸ビニル、ステアリン酸ビニル、ピバリン酸ビニル、安息香酸ビニル等のビニルエステル類、エチルアクリレート、エチルメタクリレート、n-ブチルアクリレート、n-ブチルメタクリレート、イソブチルアクリレート、イソブチルメタクリレート、ヘキシルアクリレート、ヘキシルメタクリレート、2-エチルヘキシルアクリレート、2-エチルヘキシルメタクリレート等の疎水性アクリル酸エステル類やメタクリル酸エステル類、2-ヒドロキシエチルメタクリレート、2-ヒドロキシプロピルメタクリレート、2-ヒドロキシ-1-メチルエチルメタクリレート、N,N-ジメチルアミノエチルアクリレート等の親水性アクリル酸エステル類やメタクリル酸エステル類等を挙げることができる。これらは単独で、あるいは 2 種類以上を混合して用いることもできる。 Monomers having the structure represented by the formula (1) include acrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N-tert-butyl. Acrylamides such as acrylamide, N-tert-butylmethacrylamide, N-dodecylacrylamide, N-hydroxyethylacrylamide, N, N-dimethylaminopropylacrylamide, acryloylmorpholine, vinylamides such as N-vinylacetamide, N, N- Allylamines such as diethylallylamine, aliphatic unsaturation such as 2,4-dimethyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-octene, 1-decene, 1-hexadecene and 1-octadecene Hydrocarbons, unsaturated hydrocarbons with aromatic side chains such as styrene and 1,1-diphenylethylene Vinyl esters such as vinyl n-butyrate, vinyl caproate, vinyl hexanate, vinyl octanate, vinyl laurate, vinyl stearate, vinyl pivalate, vinyl benzoate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n -Hydrophobic acrylic and methacrylic esters such as butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate Hydrophilic acrylic acid esters and methacrylic acid esters such as 2-hydroxy-1-methylethyl methacrylate and N, N-dimethylaminoethyl acrylate I can make it. These may be used alone or in combination of two or more.
　単量体Ｂは、上記１つの付加重合性不飽和結合を有する単量体と共重合することにより、共有結合による３次元架橋構造を有する高分子となる化合物であれば使用できる。また、該単量体は上記有機媒体、または変性クレイが分散溶解した有機媒体に可溶もしくは混和可能であることが好ましい。
　なお、３次元架橋構造は、上記共重合で形成する以外に、１つの付加重合性不飽和結合を有する単量体を重合させて線状高分子体とした後に、側鎖の高分子反応により架橋構造とすることができる。例えば、エチレンやアセチレン等の不飽和結合や、メチレン等のアルキレン基、ニトリル基、メルカプト基、カルボキシル基、水酸基、エポキシ基、アミノ基、メチル基等のアルキル基、アミド基、アルキルハライド、チオニルクロライド、スルホン酸、カルボン酸、クロロスルホン基、エステル基、メチロール基、スルホン酸残基、スルホン酸塩残基、アジド基、イソシアネート基、ハロゲン置換基、アルコール残基、フェノール残基、チオール残基、スルホン基、シラノール基、シンナモイル基、シンナミリデン基、アクリロイル基、ジアゾ基、ジチオカルバメート基、酸無水物基、活性メチレン基、クマリン基等の官能基を反応基として挙げることができる。 The monomer B can be used as long as it is a compound that becomes a polymer having a three-dimensional crosslinked structure by a covalent bond by copolymerizing with the monomer having one addition polymerizable unsaturated bond. The monomer is preferably soluble or miscible in the organic medium or an organic medium in which modified clay is dispersed and dissolved.
The three-dimensional crosslinked structure is formed by polymerizing a monomer having one addition polymerizable unsaturated bond to form a linear polymer, and then by side chain polymer reaction. It can be set as a crosslinked structure. For example, unsaturated bonds such as ethylene and acetylene, alkylene groups such as methylene, nitrile groups, mercapto groups, carboxyl groups, hydroxyl groups, epoxy groups, amino groups, methyl groups and other alkyl groups, amide groups, alkyl halides, thionyl chlorides , Sulfonic acid, carboxylic acid, chlorosulfone group, ester group, methylol group, sulfonic acid residue, sulfonate residue, azide group, isocyanate group, halogen substituent, alcohol residue, phenol residue, thiol residue, Functional groups such as a sulfone group, a silanol group, a cinnamoyl group, a cinnamylidene group, an acryloyl group, a diazo group, a dithiocarbamate group, an acid anhydride group, an active methylene group, and a coumarin group can be cited as reactive groups.
　架橋剤となる単量体Ｂの例としては、N,N’-メチレンビスアクリルアミド、N,N’-プロピレンビスアクリルアミド、エチレングリコールジアクリレート、エチレングリコールジメタクリレート、ジエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジアクリレート、テトラエチレングリコールジメタクリレート、ジプロピレングリコールジアクリラート、ネオペンチルグリコールジアクリラート、トリプロピレングリコールジアクリラート、1,10-ビス(アクリロイルオキシ)デカン、1,3-ビス(メタクリロイルオキシ)-2-プロパノール、1,4-ビス(アクリロイルオキシ)ブタン、1,6-ビス(アクリロイルオキシ)ヘキサン、1-(アクリロイルオキシ)-3-(メタクリロイルオキシ)-2-プロパノール、アジピン酸ジビニル、メタクリル酸ビニル、クロトン酸ビニル、ジビニルベンゼン等を挙げることができる。 Examples of the monomer B serving as a crosslinking agent include N, N′-methylenebisacrylamide, N, N′-propylenebisacrylamide, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tri Ethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, 1,10-bis ( (Acryloyloxy) decane, 1,3-bis (methacryloyloxy) -2-propanol, 1,4-bis (acryloyloxy) butane, 1,6-bis (acryloyloxy) hex Emissions, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, divinyl adipate, vinyl methacrylate, vinyl crotonate, divinyl benzene and the like.
　３次元架橋構造を有する高分子を製造する場合において、単量体Ａの割合が単量体Ｂよりもモル比で多いことが好ましい。この範囲とすることにより、柔軟性および靭性を付与しやすいこと、および重合時に架橋ムラが発生し難くなることから、好適な高分子オルガノゲルが得られる。 In the case of producing a polymer having a three-dimensional cross-linked structure, it is preferable that the proportion of monomer A is higher than that of monomer B in molar ratio. By setting it as this range, since a softness | flexibility and toughness are easy to provide and it becomes difficult to generate | occur | produce a crosslinking nonuniformity at the time of superposition | polymerization, suitable polymeric organogel is obtained.
　高分子オルガノゲルは、有機媒体に変性クレイを分散溶解させ、この溶液内で上記単量体を共重合することにより製造できる。
　変性クレイの割合は、生成する高分子オルガノゲルを基準として、0.5 容量％以上、5 容量％未満であることが好ましく、特に好ましくは 0.5 容量％以上、3 容量％未満である。変性クレイの量が 0.5 容量％未満では、変性クレイが均一分散していても十分な補強効果が得られない。また、変性クレイの量が 5 容量％をこえると、有機媒体の増粘のため、変性クレイ自体の分散溶解が困難であり、また単量体の均一混合も難しく、結果として靭性に優れる高分子オルガノゲルが得られ難い。 The polymer organogel can be produced by dispersing and dissolving modified clay in an organic medium and copolymerizing the above monomers in this solution.
The proportion of the modified clay is preferably 0.5% by volume or more and less than 5% by volume, particularly preferably 0.5% by volume or more and less than 3% by volume, based on the polymer organogel to be produced. When the amount of the modified clay is less than 0.5% by volume, a sufficient reinforcing effect cannot be obtained even if the modified clay is uniformly dispersed. If the amount of the modified clay exceeds 5% by volume, it is difficult to disperse and dissolve the modified clay itself due to the thickening of the organic medium, and it is difficult to uniformly mix the monomers, resulting in a polymer having excellent toughness. It is difficult to obtain an organogel.
　有機媒体の割合は、生成する高分子オルガノゲルを基準として、20.0 容量％ 以上、95.0 容量％ 未満であることが好ましく、特に好ましくは 50.0 容量％ 以上、85.0 容量％ 未満である。有機媒体量が 20.0 容量％未満では、たとえ重合後に膨潤処理を行なっても十分な膨潤度（例えば 1.2 倍未満）が得られなかったり、靭性に劣ったりする場合があり、本発明の高靭性かつ高膨潤度を有する高分子オルガノゲルを安定して得ることができない。
　一方、重合時の有機媒体量が 95.0 容量％をこえると、有機媒体中で３次元架橋構造を有する高分子の調製が難しく、またたとえ調製できたとしても非常に低強度の脆いものしか得られない。 The ratio of the organic medium is preferably 20.0% by volume or more and less than 95.0% by volume, particularly preferably 50.0% by volume or more and less than 85.0% by volume, based on the polymer organogel to be produced. When the amount of the organic medium is less than 20.0% by volume, even if the swelling treatment is performed after polymerization, a sufficient degree of swelling (for example, less than 1.2 times) may not be obtained or the toughness may be inferior. A polymer organogel having a high degree of swelling cannot be obtained stably.
On the other hand, when the amount of the organic medium during polymerization exceeds 95.0% by volume, it is difficult to prepare a polymer having a three-dimensional cross-linked structure in the organic medium, and even if it can be prepared, only a very low strength brittle material is obtained. Absent.
　変性クレイを分散溶解させた有機媒体中で単量体Ａおよび単量体Ｂを付加共重合させることにより、３次元架橋構造を有する高分子内に該有機媒体および変性クレイが微分散された高分子オルガノゲルが得られる。
　付加共重合は、加熱や紫外線照射による重合を開始させる重合開始剤や触媒等を用いて行なうことができる。
　このような重合開始剤のうち、例えば加熱による重合開始剤としては、ケトンパーオキサイド類、パーオキシケタール類、ジアルキルパーオキサイド類、ジアシルパーオキサイド類、パーオキシエステル類、パーオキシジカーボネート類、ハイドロパーオキサイド類等の有機過酸化物類、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩類、2,2’-アゾビス-イソブチロニトリル（ＡＩＢＮ）、2,2’-アゾビス-2,4-ジメチルバレロニトリル（ＡＤＶＮ）、2,2’-アゾビス-2-メチルブチロニトリル、4,4’-アゾビス-4-シアノバレリック酸等のアゾ化合物類、ナトリウムエトキシド、tert-ブチルリチウム等のアルキル金属類等を挙げることができる。
　触媒としては、例えば金属塩や、N,N,N’,N’-テトラメチルエチレンジアミン等の第３級アミン化合物のような還元性を有する化合物を挙げることができる。
　上述のような重合開始剤および触媒は、重合時に用いる有機媒体に可溶でさえあれば、特定の物質に限定されることなく用いることができる。なお重合開始剤が加熱により機能する場合、その 10 時間半減期温度が有機媒体の沸点以下であることが好ましい。 By adding and copolymerizing monomer A and monomer B in an organic medium in which modified clay is dispersed and dissolved, the organic medium and modified clay are finely dispersed in a polymer having a three-dimensional crosslinked structure. A molecular organogel is obtained.
The addition copolymerization can be performed using a polymerization initiator, a catalyst, or the like that initiates polymerization by heating or ultraviolet irradiation.
Among such polymerization initiators, for example, polymerization initiators by heating include ketone peroxides, peroxyketals, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, hydro- Organic peroxides such as peroxides, persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate, 2,2'-azobis-isobutyronitrile (AIBN), 2,2'-azobis-2 , 4-Dimethylvaleronitrile (ADVN), 2,2'-azobis-2-methylbutyronitrile, azo compounds such as 4,4'-azobis-4-cyanovaleric acid, sodium ethoxide, tert-butyl Examples thereof include alkyl metals such as lithium.
Examples of the catalyst include metal salts and reducing compounds such as tertiary amine compounds such as N, N, N ′, N′-tetramethylethylenediamine.
The polymerization initiator and catalyst as described above can be used without being limited to specific substances as long as they are soluble in the organic medium used during the polymerization. When the polymerization initiator functions by heating, its 10-hour half-life temperature is preferably not higher than the boiling point of the organic medium.
　重合温度は、安全上の問題等から有機媒体の沸点以下に制御する場合が多いことから、10 時間半減期温度が用いる有機媒体の沸点をこえる場合、重合に非常に長時間を要するため好ましくない。従って、本発明の高分子オルガノゲルの好ましい重合温度［℃］は、10 時間半減期温度［℃］をこえ、有機媒体の沸点［℃］以下である。なお、重合時間が長時間要しても問題ない場合は、 10 時間半減期温度よりも低い温度で重合しても特に問題はない。 Since the polymerization temperature is often controlled below the boiling point of the organic medium for safety reasons, etc., when the boiling point of the organic medium used exceeds the 10-hour half-life temperature, the polymerization takes a very long time, which is not preferable. . Accordingly, the preferred polymerization temperature [° C.] of the polymer organogel of the present invention is higher than the 10-hour half-life temperature [° C.] and below the boiling point [° C.] of the organic medium. If there is no problem even if the polymerization time is required for a long time, there is no particular problem even if the polymerization is performed at a temperature lower than the half-life temperature of 10 hours.
　重合雰囲気としては、窒素ガス、ヘリウムガス、アルゴンガス等の不活性ガスの雰囲気下で行なうことが好ましい。例えば酸素の存在下でラジカル重合を行なうと、酸素による重合阻害を受ける場合があり、得られるゲルの品質が不安定になるおそれがある。
　なお重合の際、例えば有機媒体の蒸発量や揮発量が大きくなる場合には、必要に応じて加圧下で重合を行なうこともできる。 The polymerization atmosphere is preferably carried out in an inert gas atmosphere such as nitrogen gas, helium gas, or argon gas. For example, if radical polymerization is performed in the presence of oxygen, polymerization may be inhibited by oxygen, and the quality of the resulting gel may be unstable.
In the polymerization, for example, when the evaporation amount or volatilization amount of the organic medium increases, the polymerization can be performed under pressure as necessary.
　高分子オルガノゲルの重合、製造においては、重合に用いる容器の形状を変化させることで、種々の形状を持った高分子オルガノゲルを調整できる。例えば、繊維状、棒状、円柱状、筒状、平板や円板等の板状、螺旋状、球状、リング状など任意の形状を有する高分子オルガノゲルとすることができる。またこれらから機械加工により任意の形状に加工することができる。 In polymerization and production of polymer organogel, polymer organogels having various shapes can be prepared by changing the shape of the container used for polymerization. For example, it can be a polymer organogel having an arbitrary shape such as a fiber shape, a rod shape, a columnar shape, a cylindrical shape, a plate shape such as a flat plate or a disc, a spiral shape, a spherical shape, or a ring shape. Moreover, it can process into arbitrary shapes from these by machining.
　重合後の高分子オルガノゲルは、そのまま高分子オルガノゲルとして使用することができる。また、重合後、重合時に用いた有機媒体中に重合後の高分子オルガノゲルを浸漬処理することで、平衡膨潤状態まで膨潤度を高めることもできる。 The polymer organogel after polymerization can be used as a polymer organogel as it is. Further, after polymerization, the degree of swelling can be increased to an equilibrium swelling state by immersing the polymer organogel after polymerization in an organic medium used at the time of polymerization.
　また、重合後、重合時に用いた有機媒体とは異なる他の有機媒体中に重合後の高分子オルガノゲルを浸漬することで、３次元架橋構造を有する高分子内に含まれる有機媒体を置換し、所望の特性を有する高分子オルガノゲルとすることができる。
　置換できる好ましい有機媒体は、重合時用いた有機媒体と可溶でかつ高分子成分と親和性を有する他の有機媒体である。なお、置換は重合時用いた有機媒体を全て置換してもよく、あるいは一部を置換してもよい。 Moreover, after the polymerization, the organic medium contained in the polymer having a three-dimensional crosslinked structure is replaced by immersing the polymer organogel after polymerization in another organic medium different from the organic medium used at the time of polymerization, It can be set as the polymeric organogel which has a desired characteristic.
Preferred organic media that can be substituted are other organic media that are soluble with the organic media used during polymerization and have an affinity for the polymeric component. In addition, the substitution may replace all of the organic medium used in the polymerization, or may partially replace it.
　重合後の高分子オルガノゲルから、内蔵されている有機媒体を除去して、３次元架橋構造を有する高分子内に変性クレイが均一に分散されている高分子組成物を製造することができる。この高分子組成物は有機媒体中に浸漬することで再度高分子オルガノゲルとすることができる。
　有機媒体の除去方法としては、加熱乾燥、真空乾燥、溶剤を用いた抽出法等が挙げられる。 A polymer composition in which the modified clay is uniformly dispersed in the polymer having a three-dimensional crosslinked structure can be produced by removing the organic medium contained from the polymer organogel after polymerization. This polymer composition can be made into a polymer organogel again by being immersed in an organic medium.
Examples of the method for removing the organic medium include heat drying, vacuum drying, and extraction using a solvent.
　本発明の高分子オルガノゲルには、その機能を害さない範囲で必要に応じ、重合の前後を問わず、その有機媒体に可溶な防錆剤、防腐剤、防カビ剤、界面活性剤やイオン性液体等を添加あるいは塗布してもよい。またその機能を害さない範囲において、有機高分子等の有機物や、炭素、シリカやチタニア等の無機物からなる繊維状や粒子状の補強剤を添加してもよい。さらに、目的に応じて分散、積層処理などにより他素材と複合化することも可能である。 The polymer organogel of the present invention has a rust inhibitor, preservative, fungicide, surfactant or ion that is soluble in the organic medium, before or after polymerization, if necessary, as long as it does not impair its function. A neutral liquid or the like may be added or applied. In addition, a fibrous or particulate reinforcing agent made of an organic substance such as an organic polymer or an inorganic substance such as carbon, silica, or titania may be added within a range that does not impair its function. Furthermore, it can be combined with other materials by dispersion, lamination processing or the like according to the purpose.
　各実施例および各比較例に用いた原料の一覧を表１に示す。
Figure JPOXMLDOC01-appb-T000002
 Table 1 shows a list of raw materials used in each example and each comparative example.
Figure JPOXMLDOC01-appb-T000002
　各実施例および各比較例における重合条件、得られたゲルの状態評価、膨潤度評価、圧縮破壊歪み評価および総合評価を以下に示す。 The polymerization conditions, the obtained gel state evaluation, the swelling degree evaluation, the compression fracture strain evaluation, and the overall evaluation in each Example and each Comparative Example are shown below.
＜重合条件＞
　　・重合容器：内径 25 mm×高さ 40 mm の平底ガラス容器
　　・原料溶液：10 mL（内径 25 mm×高さ約 20 mm 相当）
　　・重合開始剤：ＡＤＶＮ（10 時間半減期温度 52℃）、0.3 重量％
　　・重合：重合容器中の気体部を窒素置換し密封した後、55℃のウオーターバス中で重合した。なお一部の比較例は、窒素置換せず密封して重合を行なった。
　　・重合時間：20 時間 <Polymerization conditions>
・ Polymerization container: Flat bottom glass container with inner diameter 25 mm x height 40 mm ・ Raw material solution: 10 mL (equivalent to inner diameter 25 mm x height approx. 20 mm)
-Polymerization initiator: ADVN (10 hour half-life temperature 52 ° C), 0.3 wt%
Polymerization: The gas portion in the polymerization vessel was purged with nitrogen and sealed, and then polymerized in a 55 ° C. water bath. In some comparative examples, polymerization was performed without sealing with nitrogen.
・ Polymerization time: 20 hours
＜重合ゲルの状態評価＞
　重合反応後、重合容器から重合物を取り出し、状態評価を行なった。変性クレイの偏析、ポリマー分の沈澱や溶媒からの相分離がなく、均一な外観を有する高分子オルガノゲルが得られた場合を合格と評価して「○」を、それ以外の、均一な外観を有する高分子オルガノゲルが得られなかった場合、不合格と評価して「×」を、それぞれ記録する。 <Evaluation of the state of the polymer gel>
After the polymerization reaction, the polymer was taken out from the polymerization vessel, and the state was evaluated. When the polymer organogel having a uniform appearance is obtained without segregation of the modified clay, precipitation of polymer components or phase separation from the solvent, it is evaluated as “good”, and the other uniform appearance is obtained. If the polymer organogel was not obtained, it was evaluated as rejected and “x” was recorded.
＜膨潤度評価＞
　重合後得られた高分子オルガノゲルを目的とする有機媒体中に 25℃で、 10 日間浸漬することで、膨潤処理を行ない、固形分（高分子成分＋変性クレイ）重量および膨潤処理後の高分子オルガノゲル重量から次の式により膨潤度を求めた。
　　膨潤度 ＝ 膨潤処理後高分子オルガノゲル重量［ｇ］ ／ 固形分重量［ｇ］
　膨潤度が 2 未満のものはゲル材料として十分な溶媒保持性を有していないものとみなし不合格と評価して「×」を、その他を合格と評価し、膨潤度 2 以上 5 未満のものは「○」を、特に 5 以上のものは「◎」を、それぞれ記録する。 <Swelling degree evaluation>
The polymer organogel obtained after polymerization is immersed in the target organic medium at 25 ° C for 10 days to swell, solid content (polymer component + modified clay) weight and polymer after swelling treatment The degree of swelling was determined from the weight of the organogel by the following formula.
Swelling degree = Polymer organogel weight after swelling treatment [g] / Solid weight [g]
Those with a degree of swelling of less than 2 are regarded as not having sufficient solvent retention as a gel material, and are evaluated as rejected. Record “○”, especially “5” for items of 5 or more.
＜圧縮破壊歪み評価＞
　上述の膨潤処理後の高分子オルガノゲルから、高さ 10 mm の円柱状物を切り出し、試験片とした。得られた試験片の圧縮破壊歪みが、50％未満のものは十分な靭性を有していないことから不合格と評価し「×」を、その他のものを合格と評価して、50％以上 75％未満のものは「○」を、特に 75％以上のものは「◎」を、それぞれ記録する。 <Compressive fracture strain evaluation>
From the polymer organogel after the swelling treatment described above, a columnar product having a height of 10 mm was cut out and used as a test piece. If the compression fracture strain of the obtained specimen is less than 50%, it does not have sufficient toughness, so it is evaluated as “failed” and “x” is evaluated as acceptable, and 50% or more is evaluated as acceptable. Record “○” for less than 75%, and “◎” for 75% or more.
＜総合評価＞
　重合ゲルの状態、膨潤度および圧縮破壊歪みの評価が、全て合格の場合のみ合格と評価し「○」を、それ以外のものは不合格と評価し「×」を、それぞれ記録する。 <Comprehensive evaluation>
The evaluation of the state of the polymer gel, the degree of swelling, and the compression fracture strain are all evaluated as pass, and “◯” is evaluated, and the others are evaluated as fail, and “x” is recorded.
実施例１
　有機媒体として溶媒１を用い、変性クレイとして変性クレイ１を用い、溶媒 10 mL に対して変性クレイ 0.5 g を添加し、撹拌により溶解させたものを溶液Ｐとする。得られた溶液Ｐは約 10.3 mL であり、無色透明で、特に沈殿物は見られなかった。なお用いた変性クレイ１は、水膨潤性合成ヘクトライトの層間カチオンを、ポリオキシプロピレンメチルジエチルアンモニウムイオン等の公知の第４級アンモニウムイオンにイオン交換することによって疎水性に変性した疎水性合成ヘクトライトである。また溶媒１は予め 30分間窒素ガスを用いたバブリング処理により、溶存酸素を除去したものを用いた。
　次いで、単量体Ａとして蒸留により重合禁止剤を取り除いた単量体Ａ－２を用い、単量体Ｂとして単量体Ｂ－１を用い、単量体全体に対して、単量体Ｂ－１を 2.5 モル％混合した単量体溶液を準備し（溶液Ｑとする）、上述の溶液Ｐと溶液Ｑとを溶媒濃度が 80 容量％となるよう混合して十分撹拌したものを溶液Ｒとした。溶液Ｑの段階では溶解しきらない単量体Ｂ－１の沈澱物が見られたが、得られた溶液Ｒは無色透明であった。
　上記各種原料を溶解させた溶液Ｒに 0.3 重量％の重合開始剤（ＡＤＶＮ）を添加し、撹拌により分散させたものを原料溶液として用いた。添加した重合開始剤量が微量であることから、原料溶液中の溶媒濃度は約 80 容量％のままである。
　次いで、上記原料溶液 10 mL を重合容器に気泡が混入しないよう注入し、密封した。なお容器内の気体部は十分窒素置換し酸素を除去した。
　原料溶液を充填した重合容器を 55℃に調製したウオーターバス内で 20 時間静置して重合を行なった。
　得られた高分子オルガノゲルは、透明度が高く、かつ重合容器から取り出しても固体状物として形状を維持できる良好な固体状ゲルであったことから、重合ゲルの状態は合格「○」とした。
　得られた円柱状の高分子オルガノゲルを、膨潤処理として溶媒１中に 20 日間浸漬した。膨潤処理した高分子オルガノゲルの膨潤度を測定したところ、約 16 であったことから合格「◎」と判定した。
　膨潤処理した高分子オルガノゲルを、高さのみ 10 mm に加工した円柱状物を用いて圧縮破壊歪みを測定したところ、50％歪みを加えた場合は破壊しなかったが、75％歪みを加えた場合一部破壊した。このことから合格「○」と判定した。なお上述の破壊の状態は脆性的なものではなく、部分的に亀裂が見られる程度であった。これら膨潤度と圧縮破壊歪みの評価結果から、総合評価で合格「○」と判定した。
　なお、得られた高分子オルガノゲルを 120℃で 3 日間乾燥処理したところ、溶媒を含まない、変性クレイが均一に微分散した透明な高分子組成物が得られた。表２に実施概要および結果を併記する。 Example 1
Solvent 1 is used as the organic medium, modified clay 1 is used as the modified clay, 0.5 g of the modified clay is added to 10 mL of the solvent, and dissolved by stirring to make Solution P. The obtained solution P was about 10.3 mL, was colorless and transparent, and no precipitate was observed. The modified clay 1 used was a hydrophobic synthetic hector that was hydrophobically modified by ion-exchange of the interlayer cation of the water-swellable synthetic hectorite with a known quaternary ammonium ion such as polyoxypropylene methyldiethylammonium ion. Light. Solvent 1 was prepared by removing dissolved oxygen by bubbling using nitrogen gas for 30 minutes in advance.
Next, monomer A-2 from which the polymerization inhibitor was removed by distillation was used as monomer A, monomer B-1 was used as monomer B, and monomer B A monomer solution prepared by mixing 2.5 mol% of -1 (referred to as solution Q), the above solution P and solution Q were mixed so that the solvent concentration would be 80% by volume, and stirred well to obtain a solution R It was. At the stage of solution Q, a precipitate of monomer B-1 that could not be dissolved was observed, but the resulting solution R was colorless and transparent.
A solution obtained by adding 0.3% by weight of a polymerization initiator (ADVN) to the solution R in which the various raw materials were dissolved and dispersing by stirring was used as the raw material solution. Since the amount of added polymerization initiator is very small, the solvent concentration in the raw material solution remains about 80% by volume.
Next, 10 mL of the raw material solution was poured into the polymerization vessel so that no bubbles were mixed and sealed. The gas part in the container was sufficiently replaced with nitrogen to remove oxygen.
Polymerization was carried out by leaving the polymerization vessel filled with the raw material solution in a water bath prepared at 55 ° C. for 20 hours.
The obtained polymer organogel had high transparency and was a good solid gel that could maintain its shape as a solid even when taken out from the polymerization vessel.
The obtained cylindrical polymer organogel was immersed in solvent 1 for 20 days as a swelling treatment. When the degree of swelling of the polymer organogel subjected to the swelling treatment was measured, it was about 16, and it was judged as “Pass”.
When the compression fracture strain was measured using a cylindrical material that was processed to a height of 10 mm, the polymer organogel subjected to swelling treatment was not broken when 50% strain was applied, but 75% strain was added. If part destroyed. From this, it was determined to be a pass “◯”. Note that the above-described fracture state was not brittle, and only a partial crack was observed. From the evaluation results of the degree of swelling and compressive fracture strain, it was determined as a pass “◯” in the overall evaluation.
When the obtained polymer organogel was dried at 120 ° C. for 3 days, a transparent polymer composition containing no solvent and uniformly dispersed fine clay was obtained. Table 2 shows the outline and results.
実施例２
　溶液Ｐは実施例１と同様のものを調製した。単量体Ａ－１および単量体Ｂ－２を用い、単量体全体に対して、単量体Ｂ－２を 5 モル％混合したものを溶液Ｑとした。溶媒濃度が 20 容量％となるよう溶液Ｐおよび溶液Ｑを混合し十分撹拌したものを溶液Ｒとした。実施例１と同様、溶液Ｒに 0.3 重量％の重合開始剤を添加し十分撹拌したものを原料溶液とした。重合および膨潤処理、ならびに膨潤度測定、圧縮破壊歪み測定は実施例１と同様に行なった。
　得られた高分子オルガノゲルは、実施例１と同様の、透明度の高い固体状のゲルであったことから、重合ゲルの状態は合格「○」とした。得られた高分子オルガノゲルの膨潤処理後の膨潤度は約 4 であったことから合格「○」と判定した。圧縮破壊歪みを測定したところ、50％歪みを加えた場合は破壊しなかったが、75％歪みを加えた場合一部破壊した。このことから合格「○」と判定した。但し破壊の状態は、実施例１と同様であり脆性的なものではなかった。これらの結果から総合評価で合格「○」と判定した。表２に実施概要および結果を併記する。 Example 2
Solution P was the same as in Example 1. Monomer A-1 and monomer B-2 were used, and a solution Q was prepared by mixing 5 mol% of monomer B-2 with respect to the whole monomer. A solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 20% by volume and stirring them sufficiently. As in Example 1, 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
Since the obtained polymer organogel was a solid gel having high transparency similar to that in Example 1, the state of the polymer gel was determined to be “good”. Since the degree of swelling of the obtained polymer organogel after the swelling treatment was about 4, it was determined to be a pass “◯”. When compressive fracture strain was measured, it did not break when 50% strain was applied, but partially fractured when 75% strain was applied. From this, it was determined to be a pass “◯”. However, the fracture state was the same as in Example 1 and was not brittle. From these results, it was determined as a pass “◯” in the overall evaluation. Table 2 shows the outline and results.
実施例３
　溶液Ｐは実施例１と同様のものを調製した。溶液Ｑは実施例２と同様のものを調製した。溶媒濃度が 50 容量％となるよう溶液Ｐおよび溶液Ｑを混合し十分撹拌したものを溶液Ｒとした。実施例１と同様、溶液Ｒに 0.3 重量％の重合開始剤を添加し十分撹拌したものを原料溶液とした。重合および膨潤処理、ならびに膨潤度測定、圧縮破壊歪み測定は実施例１と同様に行なった。
　得られた高分子オルガノゲルは、実施例１と同様の、透明度の高い固体状のゲルであったことから、重合ゲルの状態は合格「○」とした。得られた高分子オルガノゲルの膨潤処理後の膨潤度は約 17 であったことから合格「◎」と判定した。圧縮破壊歪みは、75％歪みを加えた場合でも破壊しなかったことから合格「◎」と判定した。これらの結果から総合評価で合格「○」と判定した。
　なお、得られた高分子オルガノゲルを 120℃で 3 日間乾燥処理したところ、実施例１と同様、溶媒を含まない、変性クレイが均一に微分散した透明な高分子組成物が得られた。表２に実施概要および結果を併記する。 Example 3
Solution P was the same as in Example 1. Solution Q was prepared as in Example 2. A solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 50% by volume and stirring them sufficiently. As in Example 1, 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
Since the obtained polymer organogel was a solid gel having high transparency similar to that in Example 1, the state of the polymer gel was determined to be “good”. Since the degree of swelling of the obtained polymer organogel after the swelling treatment was about 17, it was judged as a pass “◎”. The compressive fracture strain was determined to be acceptable because it did not break even when 75% strain was applied. From these results, it was determined as a pass “◯” in the overall evaluation.
The obtained polymer organogel was dried at 120 ° C. for 3 days. As in Example 1, a transparent polymer composition containing no solvent and uniformly dispersed in modified clay was obtained. Table 2 shows the outline and results.
実施例４
　溶液Ｐは実施例１と同様のものを調製した。溶液Ｑは実施例２と同様のものを調製した。溶媒濃度が 80 容量％となるよう溶液Ｐおよび溶液Ｑを混合し十分撹拌したものを溶液Ｒとした。実施例１と同様、溶液Ｒに 0.3 重量%の重合開始剤を添加し十分撹拌したものを原料溶液とした。重合および膨潤処理、ならび膨潤度測定、圧縮破壊歪み測定は実施例１と同様に行なった。得られた高分子オルガノゲルは、実施例１と同様の、透明度の高い固体状のゲルであったことから、重合ゲルの状態は合格「○」とした。
　得られた高分子オルガノゲルの膨潤処理後の膨潤度は約 18 であったことから合格「◎」と判定した圧縮破壊歪みは、75％歪みを加えた場合でも破壊しなかったことから合格「◎」と判定した。これらの結果から総合評価で合格「○」と判定した。
　なお、得られた高分子オルガノゲルを 120℃で 3 日間乾燥処理したところ、実施例１と同様、溶媒を含まない、変性クレイが均一に微分散した透明な高分子組成物が得られた。表２に実施概要および結果を併記する。 Example 4
Solution P was the same as in Example 1. Solution Q was prepared as in Example 2. A solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 80% by volume and stirring them sufficiently. As in Example 1, a raw material solution was prepared by adding 0.3 wt% of a polymerization initiator to the solution R and stirring sufficiently. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1. Since the obtained polymer organogel was a solid gel having high transparency similar to that in Example 1, the state of the polymer gel was determined to be “good”.
Since the degree of swelling after the swelling treatment of the obtained polymer organogel was about 18, the compression fracture strain judged as acceptable “◎” was not acceptable even when 75% strain was applied. Was determined. From these results, it was determined as a pass “◯” in the overall evaluation.
The obtained polymer organogel was dried at 120 ° C. for 3 days. As in Example 1, a transparent polymer composition containing no solvent and uniformly dispersed in modified clay was obtained. Table 2 shows the outline and results.
実施例５
　溶液Ｐは実施例１と同様のものを調製した。単量体Ａ－１および単量体Ｂ－２を用い、単量体全体に対して、単量体Ｂ－２を 7.5 モル％混合したものを溶液Ｑとした。溶媒濃度が 90 容量％となるよう溶液Ｐおよび溶液Ｑを混合し十分撹拌したものを溶液Ｒとした。実施例１と同様、溶液Ｒに 0.3 重量%の重合開始剤を添加し十分撹拌したものを原料溶液とした。重合および膨潤処理、ならび膨潤度測定、圧縮破壊歪み測定は実施例１と同様に行なった。
　得られた高分子オルガノゲルは、実施例１と同様の、透明度の高い固体状のゲルであったことから、重合ゲルの状態は合格「○」と評価した。得られた高分子オルガノゲルの膨潤処理後の膨潤度は約 21 であったことから合格「◎」と判定した。圧縮破壊歪みを測定したところ、50％歪みを加えた場合は破壊しなかったが、75％歪みを加えた場合一部破壊した。このことから合格「○」と判定した。これらの結果から総合評価で合格「○」と判定した。表２に実施概要および結果を併記する。 Example 5
Solution P was the same as in Example 1. Monomer A-1 and monomer B-2 were used, and 7.5 mol% of monomer B-2 was mixed with respect to the whole monomer as solution Q. Solution R was prepared by mixing solution P and solution Q so that the solvent concentration was 90% by volume and stirring sufficiently. As in Example 1, a raw material solution was prepared by adding 0.3 wt% of a polymerization initiator to the solution R and stirring sufficiently. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
Since the obtained polymer organogel was a solid gel with high transparency similar to Example 1, the state of the polymer gel was evaluated as a pass “◯”. Since the degree of swelling after the swelling treatment of the obtained polymer organogel was about 21, it was determined to be a pass “◎”. When compressive fracture strain was measured, it did not break when 50% strain was applied, but partially fractured when 75% strain was applied. From this, it was determined to be a pass “◯”. From these results, it was determined as a pass “◯” in the overall evaluation. Table 2 shows the outline and results.
実施例６
　有機媒体として溶媒２を用い、変性クレイとして変性クレイ１を用い、溶媒 10 mLに対して変性クレイ 0.5 g の比率で添加し、撹拌により溶解させたものを溶液Ｐとした。得られた溶液Ｐは約 10.3 mL であり、実施例１と同様無色透明で、特に沈殿物は見られなかった。溶液Ｑは実施例２と同様のものを調製した。溶媒濃度が 75 容量％となるよう溶液Ｐおよび溶液Ｑを混合し十分撹拌したものを溶液Ｒとした。実施例１と同様、溶液Ｒに 0.3 重量％の重合開始剤を添加し十分撹拌したものを原料溶液とした。重合および膨潤処理、ならび膨潤度測定、圧縮破壊歪み測定は実施例１と同様に行なった。
　得られた高分子オルガノゲルは、実施例１と同様の、透明度の高い固体状のゲルであったことから、重合ゲルの状態は合格「○」とした。得られた高分子オルガノゲルの膨潤処理後の膨潤度は約 18 であったことから合格「◎」と判定した。圧縮破壊歪みは、75％歪みを加えた場合でも破壊しなかったことから合格「◎」と判定した。これらの結果から総合評価で合格「○」と判定した。表２に実施概要および結果を併記する。 Example 6
The solvent 2 was used as the organic medium, the modified clay 1 was used as the modified clay, and 0.5 g of the modified clay was added to 10 mL of the solvent. The obtained solution P was about 10.3 mL, was colorless and transparent as in Example 1, and no precipitate was observed. Solution Q was prepared as in Example 2. A solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 75% by volume and stirring them sufficiently. As in Example 1, 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
Since the obtained polymer organogel was a solid gel having high transparency similar to that in Example 1, the state of the polymer gel was determined to be “good”. Since the degree of swelling of the obtained polymer organogel after the swelling treatment was about 18, it was determined to be a pass “◎”. The compressive fracture strain was determined to be acceptable because it did not break even when 75% strain was applied. From these results, it was determined as a pass “◯” in the overall evaluation. Table 2 shows the outline and results.
実施例７
　有機媒体として溶媒３を用い、変性クレイとして変性クレイ２を用い、溶媒 10 mL に対して変性クレイ 0.3 g の比率で添加し、さらに分散剤として 95％エタノール水溶液を 0.03 g 添加したのち十分撹拌することで変性クレイを溶解、微分散させたものを溶液Ｐとした。得られた溶液Ｐは約 10.1 mL であり、やや白色の半透明状の溶液であったが、特に沈殿物は見られなかった。なお変性クレイ２は、トリヘキサデシルメチルアンモニウムイオン等の公知の４級アンモニウムイオンを用いて陽イオン交換法により変性したものである。単量体Ａ－３および単量体Ｂ－３を用い、単量体全体に対して、単量体Ｂ－３を 5 モル％混合したものを溶液Ｑとした。溶媒濃度が 75 容量％となるよう溶液Ｐおよび溶液Ｑを混合し十分撹拌したものを溶液Ｒとした。実施例１と同様、溶液Ｒに 0.3 重量％の重合開始剤を添加し十分撹拌したものを原料溶液とした。重合および膨潤処理、ならび膨潤度測定、圧縮破壊歪み測定は実施例１と同様に行なった。
　得られた高分子オルガノゲルは、やや白濁しているが均一な外観の固体状のゲルであったことから、重合ゲルの状態は合格「○」とした。得られた高分子オルガノゲルの膨潤処理後の膨潤度は約 6 であったことから合格「◎」と判定した。圧縮破壊歪みを測定したところ、50％歪みを加えた場合は破壊しなかったが、75％歪みを加えた場合一部破壊した。このことから合格「○」と判定した。これらの結果から総合評価で合格「○」と判定した。表２に実施概要および結果を併記する。 Example 7
Use solvent 3 as the organic medium, use modified clay 2 as the modified clay, add 0.3 g of modified clay to 10 mL of solvent, add 0.03 g of 95% aqueous ethanol as a dispersant, and stir well. A solution P was obtained by dissolving and finely dispersing the modified clay. The obtained solution P was about 10.1 mL, which was a slightly white translucent solution, but no precipitate was observed. The modified clay 2 is modified by a cation exchange method using a known quaternary ammonium ion such as trihexadecylmethylammonium ion. Monomer A-3 and monomer B-3 were used, and 5 mol% of monomer B-3 was mixed with respect to the whole monomer as solution Q. A solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 75% by volume and stirring them sufficiently. As in Example 1, 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
Since the obtained polymer organogel was a solid gel with a slightly white turbidity but a uniform appearance, the state of the polymer gel was set to pass “◯”. Since the degree of swelling after the swelling treatment of the obtained polymer organogel was about 6, it was determined to be a pass “」 ”. When compressive fracture strain was measured, it did not break when 50% strain was applied, but partially fractured when 75% strain was applied. From this, it was determined to be a pass “◯”. From these results, it was determined as a pass “◯” in the overall evaluation. Table 2 shows the outline and results.
実施例８
　有機媒体として溶媒３を用い、変性クレイとして変性クレイ３を用い、溶媒 10 mLに対して変性クレイ 0.3 g の比率で添加し、さらに分散剤として 95％エタノール水溶液を 0.15 g 添加したのち十分撹拌することで変性クレイを溶解、微分散させたものを溶液Ｐとした。得られた溶液Ｐは約 10.3 mL であり、やや黄色の半透明状の溶液であったが、特に沈殿物は見られなかった。なお変性クレイ３は、天然水膨潤性モンモリロナイトを原料とし、ジメチルジオクタデシルアンモニウムイオン等の公知の４級アンモニウムイオンを用いて陽イオン交換法により変性したものである。単量体Ａ－３および単量体Ｂ－２を用い、単量体全体に対して、単量体Ｂ－２を 5 モル％混合したものを溶液Ｑとした。溶媒濃度が 75 容量％となるよう溶液Ｐおよび溶液Ｑを混合し十分撹拌したものを溶液Ｒとした。実施例１と同様、溶液Ｒに 0.3 重量％の重合開始剤を添加し十分撹拌したものを原料溶液とした。重合および膨潤処理、ならび膨潤度測定、圧縮破壊歪み測定は実施例１と同様に行なった。
　得られた高分子オルガノゲルは、やや黄色に着色していたが均一外観の固体状のゲルであったことから、重合ゲルの状態は合格「○」とした。得られた高分子オルガノゲルの膨潤処理後の膨潤度は約 5 であったことから合格「◎」と判定した。圧縮破壊歪みを測定したところ、50％歪みを加えた場合は破壊しなかったが、75％歪みを加えた場合一部破壊した。このことから合格「○」と判定した。これらの結果から総合評価で合格「○」と判定した。表２に実施概要および結果を併記する。 Example 8
Use solvent 3 as the organic medium, use modified clay 3 as the modified clay, add 0.3 g of modified clay to 10 mL of solvent, add 0.15 g of 95% ethanol aqueous solution as a dispersant, and stir well. A solution P was obtained by dissolving and finely dispersing the modified clay. The obtained solution P was about 10.3 mL and was a slightly yellow translucent solution, but no precipitate was observed. The modified clay 3 is modified by a cation exchange method using natural water-swellable montmorillonite as a raw material and a known quaternary ammonium ion such as dimethyldioctadecyl ammonium ion. Monomer A-3 and monomer B-2 were used, and 5 mol% of monomer B-2 was mixed with respect to the whole monomer as solution Q. A solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 75% by volume and stirring them sufficiently. As in Example 1, 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
The obtained polymer organogel was slightly yellow, but was a solid gel with a uniform appearance. Since the degree of swelling after the swelling treatment of the obtained polymer organogel was about 5, it was determined to be a pass “◎”. When compressive fracture strain was measured, it did not break when 50% strain was applied, but partially fractured when 75% strain was applied. From this, it was determined to be a pass “◯”. From these results, it was determined as a pass “◯” in the overall evaluation. Table 2 shows the outline and results.
実施例９
　実施例４と同様の高分子オルガノゲルを重合した。従って、原料溶液 10mL中の溶媒濃度は約 80 容量％である。得られた高分子オルガノゲルを、100 mL の溶媒４中に室温で 9 日間浸漬し、その後 120℃で 4 日間熱処理することで溶媒１を除去して、溶媒４を溶媒とする高分子オルガノゲルを得た。
　得られた高分子オルガノゲルは、実施例４と同様、透明度の高い固体状ゲルであったことから、重合ゲルの状態は合格「○」とした。膨潤処理後の膨潤度は約 5 であったことから合格「◎」と判定した。圧縮破壊歪みは、75％歪みを加えた場合でも破壊しなかったことから合格「◎」と判定した。これらの結果から総合評価で合格「○」と判定した。表２に実施概要および結果を併記する。 Example 9
The same polymer organogel as in Example 4 was polymerized. Therefore, the solvent concentration in 10 mL of the raw material solution is about 80% by volume. The obtained polymer organogel was immersed in 100 mL of solvent 4 for 9 days at room temperature, and then heat treated at 120 ° C. for 4 days to remove solvent 1 to obtain a polymer organogel using solvent 4 as a solvent. It was.
Since the obtained polymer organogel was a solid gel with high transparency, as in Example 4, the state of the polymer gel was determined to be “good”. Since the degree of swelling after the swelling treatment was about 5, it was judged as acceptable “合格”. The compressive fracture strain was determined to be acceptable because it did not break even when 75% strain was applied. From these results, it was determined as a pass “◯” in the overall evaluation. Table 2 shows the outline and results.
実施例１０
　有機媒体として溶媒５を用い、変性クレイとして変性クレイ２を用い、溶媒 10 mL に対して変性クレイ 0.3 g の比率で添加し、撹拌により溶解させたものを溶液Ｐとした。得られた溶液Ｐは約 10.1 mL であり、黄色透明で、特に沈殿物は見られなかった。単量体Ａ－１および単量体Ｂ－２を用い、単量体全体に対して、単量体Ｂ－２を 7.5 モル％混合したものを溶液Ｑとした。溶媒濃度が 75 容量％となるよう溶液Ｐおよび溶液Ｑを混合し十分撹拌したものを溶液Ｒとした。実施例１と同様、溶液Ｒに 0.3 重量％の重合開始剤を添加し十分撹拌したものを原料溶液とした。重合および膨潤処理、ならび膨潤度測定、圧縮破壊歪み測定は実施例１と同様に行なった。
　得られた高分子オルガノゲルは、透明度の高い黄色透明の均一な固体状のゲルであったことから、重合ゲルの状態は合格「○」とした。得られた高分子オルガノゲルの膨潤処理後の膨潤度は約 5 であったことから合格「◎」と判定した。圧縮破壊歪みを測定したところ、50％歪みを加えた場合は破壊しなかったが、75％歪みを加えた場合一部破壊した。このことから合格「○」と判定した。これらの結果から総合評価で合格「○」と判定した。表２に実施概要および結果を併記する。 Example 10
The solvent 5 was used as the organic medium, the modified clay 2 was used as the modified clay, and the solution was added at a ratio of 0.3 g of the modified clay to 10 mL of the solvent and dissolved by stirring to obtain a solution P. The obtained solution P was about 10.1 mL, was yellow and transparent, and no precipitate was observed. Monomer A-1 and monomer B-2 were used, and 7.5 mol% of monomer B-2 was mixed with respect to the whole monomer as solution Q. A solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 75% by volume and stirring them sufficiently. As in Example 1, 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
Since the obtained polymer organogel was a highly transparent yellow transparent uniform solid gel, the state of the polymer gel was set to pass “◯”. Since the degree of swelling after the swelling treatment of the obtained polymer organogel was about 5, it was determined to be a pass “◎”. When compressive fracture strain was measured, it did not break when 50% strain was applied, but partially fractured when 75% strain was applied. From this, it was determined to be a pass “◯”. From these results, it was determined as a pass “◯” in the overall evaluation. Table 2 shows the outline and results.
実施例１１
　有機媒体として溶媒２を用い、変性クレイとして変性クレイ２を用い、溶媒 10 mLに対して変性クレイ 0.5 g の比率で添加し、撹拌により溶解させたものを溶液Ｐとした。得られた溶液Ｐは約 10.3 mL であり、無色透明で、特に沈殿物は見られなかった。単量体Ａ－４および単量体Ｂ－３を用い、単量体全体に対して、単量体Ｂ－３を 5 モル％混合したものを溶液Ｑとした。溶媒濃度が 75 容量％となるよう溶液Ｐおよび溶液Ｑを混合し十分撹拌したものを溶液Ｒとした。実施例１と同様、溶液Ｒに 0.3 重量％の重合開始剤を添加し十分撹拌したものを原料溶液とした。重合および膨潤処理、ならび膨潤度測定、圧縮破壊歪み測定は実施例１と同様に行なった。
　得られた高分子オルガノゲルは、無色透明の固体状のゲルであった。得られた高分子オルガノゲルを、100 mL の溶媒５中に 9 日間浸漬し、その後 150℃で 1 日間熱処理することで溶媒２を除去して、溶媒５を溶媒とする高分子オルガノゲルを得た。得られた高分子オルガノゲルは、実施例２と同様、透明度の高い固体状ゲルであったことから、重合ゲルの状態は合格「○」とした。得られた溶媒５を溶媒とする高分子オルガノゲルの膨潤処理後の膨潤度は約 4 であったことから合格「○」と判定した。圧縮破壊歪みは、75％歪みを加えた場合でも破壊しなかったことから合格「◎」と判定した。これらの結果から総合評価で○と判定した。表２に実施概要および結果を併記する。 Example 11
The solvent 2 was used as the organic medium, the modified clay 2 was used as the modified clay, and 0.5 g of the modified clay was added to 10 mL of the solvent. The obtained solution P was about 10.3 mL, was colorless and transparent, and no precipitate was observed. A solution Q was prepared by using monomer A-4 and monomer B-3 and mixing 5 mol% of monomer B-3 with respect to the whole monomer. A solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 75% by volume and stirring them sufficiently. As in Example 1, 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
The obtained polymer organogel was a colorless and transparent solid gel. The obtained polymer organogel was immersed in 100 mL of solvent 5 for 9 days and then heat treated at 150 ° C. for 1 day to remove solvent 2 to obtain a polymer organogel using solvent 5 as a solvent. Since the obtained polymer organogel was a solid gel with high transparency as in Example 2, the state of the polymer gel was set to pass “◯”. Since the degree of swelling after the swelling treatment of the polymer organogel using the obtained solvent 5 as a solvent was about 4, it was determined to be a pass “◯”. The compressive fracture strain was determined to be acceptable because it did not break even when 75% strain was applied. From these results, it was determined as “good” in the comprehensive evaluation. Table 2 shows the outline and results.
実施例１２
　有機媒体として溶媒２を用い、変性クレイとして変性クレイ１を用い、溶媒 10 mLに対して変性クレイ 0.5 g の比率で添加し、撹拌により溶解させたものを溶液Ｐとした。得られた溶液Ｐは約 10.3 mL であり、無色透明で、特に沈殿物は見られなかった。溶液Ｑは実施例８と同様のものを調整した。溶媒濃度が 75 容量％となるよう溶液Ｐおよび溶液Ｑを混合し十分撹拌したものを溶液Ｒとした。実施例１と同様、溶液Ｒに 0.3 重量％の重合開始剤を添加し十分撹拌したものを原料溶液とした。重合および膨潤処理、ならび膨潤度測定、圧縮破壊歪み測定は実施例１と同様に行なった。
　得られた高分子オルガノゲルは、無色透明の固体状のゲルであった。得られた高分子オルガノゲルを、100 mL の溶媒３中に 13 日間浸漬し、その後 150℃で 1 日間熱処理することで溶媒２を除去して、溶媒３を溶媒とする高分子オルガノゲルを得た。得られた高分子オルガノゲルは、実施例２と同様、透明度の高い固体状ゲルであったことから、重合ゲルの状態は合格「○」とした。得られた溶媒３を溶媒とする高分子オルガノゲルの膨潤処理後の膨潤度は約 4 であったことから合格「○」と判定した。圧縮破壊歪みは、75％歪みを加えた場合でも破壊しなかったことから合格「◎」と判定した。これらの結果から総合評価で○と判定した。表２に実施概要および結果を併記する。 Example 12
The solvent 2 was used as the organic medium, the modified clay 1 was used as the modified clay, and 0.5 g of the modified clay was added to 10 mL of the solvent. The obtained solution P was about 10.3 mL, was colorless and transparent, and no precipitate was observed. Solution Q was the same as in Example 8. A solution R was prepared by mixing the solution P and the solution Q so that the solvent concentration was 75% by volume and stirring them sufficiently. As in Example 1, 0.3% by weight of a polymerization initiator was added to Solution R and sufficiently stirred to obtain a raw material solution. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
The obtained polymer organogel was a colorless and transparent solid gel. The obtained polymer organogel was immersed in 100 mL of solvent 3 for 13 days and then heat treated at 150 ° C. for 1 day to remove solvent 2 to obtain a polymer organogel using solvent 3 as a solvent. Since the obtained polymer organogel was a solid gel with high transparency as in Example 2, the state of the polymer gel was set to pass “◯”. Since the degree of swelling after the swelling treatment of the polymer organogel using the obtained solvent 3 as a solvent was about 4, it was determined to be a pass “◯”. The compressive fracture strain was determined to be acceptable because it did not break even when 75% strain was applied. From these results, it was determined as “good” in the comprehensive evaluation. Table 2 shows the outline and results.
実施例１３
　溶液Ｐは実施例１１と同様のものを調製した。単量体Ａ－６および単量体Ｂ－４を用い、単量体全体に対して単量体Ｂ－４を 5 モル％混合したものを溶液Ｑとした。溶媒濃度が６０容量％になるよう溶液Ｐおよび溶液Ｑを混合し十分撹拌したものを溶液Ｒとした。溶液Ｒに 0.1 重量％の重合開始剤を添加し十分撹拌したものを原料溶液とした。重合および膨潤処理、ならびに膨潤度測定、圧縮破壊歪み測定は実施例１と同様に行なった。
　得られた高分子オルガノゲルは、無色透明の固体状のゲルであった。得られた高分子オルガノゲルを、100 mL の溶媒４中に 9 日間浸漬し、その後 150℃で 1 日間熱処理することで溶媒２を除去して、溶媒４を溶媒とする高分子オルガノゲルを得た。得られた高分子オルガノゲルは、実施例２と同様、透明度の高い固体状ゲルであったことから、重合ゲルの状態は合格「○」とした。得られた溶媒４を溶媒とする高分子オルガノゲルの膨潤処理後の膨潤度は約 1.3 であったことから合格「○」と判定した。圧縮破壊歪みは、75％歪みを加えた場合でも破壊しなかったことから合格「◎」と判定した。これらの結果から総合評価で○と判定した。表２に実施概要および結果を併記する。 Example 13
Solution P was prepared as in Example 11. A solution Q was prepared by using monomer A-6 and monomer B-4 and mixing 5 mol% of monomer B-4 with respect to the whole monomer. Solution R was prepared by mixing solution P and solution Q so that the solvent concentration was 60% by volume and stirring them sufficiently. A solution obtained by adding 0.1 wt% of a polymerization initiator to Solution R and stirring sufficiently was used as a raw material solution. Polymerization and swelling treatment, swelling degree measurement, and compression fracture strain measurement were carried out in the same manner as in Example 1.
The obtained polymer organogel was a colorless and transparent solid gel. The obtained polymer organogel was immersed in 100 mL of solvent 4 for 9 days and then heat-treated at 150 ° C. for 1 day to remove solvent 2 to obtain a polymer organogel using solvent 4 as a solvent. Since the obtained polymer organogel was a solid gel with high transparency as in Example 2, the state of the polymer gel was set to pass “◯”. Since the degree of swelling after the swelling treatment of the polymer organogel using the obtained solvent 4 as a solvent was about 1.3, it was determined to be a pass “◯”. The compressive fracture strain was determined to be acceptable because it did not break even when 75% strain was applied. From these results, it was determined as “good” in the comprehensive evaluation. Table 2 shows the outline and results.
比較例１
　変性クレイを用いなかった以外は実施例４と同様に原料溶液を調整し、重合および膨潤処理を行なった。
　原料溶液 10 mL 中の溶媒濃度は約 80 容量％であり、得られた高分子オルガノゲルは無色透明であったことから、重合ゲルの状態は合格「○」と評価した。
　得られた高分子オルガノゲルの膨潤処理後の膨潤度は約 15 であったことから合格「◎」と判定した。圧縮破壊歪みは、50％歪みを加えた場合に破壊が発生したことから不合格「×」と判定した。なお破壊の状態は非常に脆性的なものであった。これらの結果から総合評価で不合格「×」と判定した。表２に実施概要および結果を併記する。 Comparative Example 1
A raw material solution was prepared in the same manner as in Example 4 except that the modified clay was not used, and polymerization and swelling treatment were performed.
The solvent concentration in 10 mL of the raw material solution was about 80% by volume, and the obtained polymer organogel was colorless and transparent. Therefore, the state of the polymer gel was evaluated as “good”.
Since the degree of swelling of the obtained polymer organogel after the swelling treatment was about 15, it was judged as a pass “◎”. Compressive fracture strain was judged as rejected “x” because fracture occurred when 50% strain was applied. The state of fracture was very brittle. From these results, it was determined as “failed” by comprehensive evaluation. Table 2 shows the outline and results.
比較例２
　変性クレイの代わりに、未変性クレイを用いた以外は実施例４と同様に原料溶液を調製し、重合および膨潤処理を行なった。なお、原料溶液10 mL 中の溶媒濃度は約 80 容量％である。また未変性クレイは、溶媒１中では若干膨潤するようであるが、沈澱してしまった。沈澱が生じたまま重合したところ、底部に未変性クレイが偏析した状態の高分子オルガノゲルが得られた。従って重合ゲルの状態は不合格「×」と評価した。このことから総合評価として不合格「×」と判定した。表２に実施概要および結果を併記する。 Comparative Example 2
A raw material solution was prepared in the same manner as in Example 4 except that unmodified clay was used in place of the modified clay, and polymerization and swelling treatment were performed. The solvent concentration in 10 mL of the raw material solution is about 80% by volume. Further, the unmodified clay seems to swell slightly in the solvent 1, but has precipitated. Polymerization was carried out with precipitation, resulting in a polymer organogel with unmodified clay segregated at the bottom. Therefore, the state of the polymer gel was evaluated as rejected “x”. From this, it was determined as a failure “x” as a comprehensive evaluation. Table 2 shows the outline and results.
比較例３
　単量体Ｂを用いなかった以外は実施例４と同様に原料溶液を調整し、重合を行なった。原料溶液 10 mL 中の溶媒濃度は約 80 容量％である。
　重合後、無色透明な状態ではあったが、固体状ゲルは得られず、粘ちょうな液状であったことから、重合ゲルの状態は不合格「×」と評価した。このことから総合評価として不合格「×」と判定した。表２に実施概要および結果を併記する。 Comparative Example 3
A raw material solution was prepared and polymerized in the same manner as in Example 4 except that the monomer B was not used. The solvent concentration in 10 mL of the raw material solution is about 80% by volume.
After the polymerization, it was in a colorless and transparent state, but a solid gel was not obtained, and it was a viscous liquid. Therefore, the state of the polymer gel was evaluated as rejected “x”. From this, it was determined as a failure “x” as a comprehensive evaluation. Table 2 shows the outline and results.
比較例４
　単量体Ｂとして単量体Ｂ－１を用いた以外は実施例７と同様に原料溶液を調製した。ただし単量体Ｂ－１は原料溶液中でほとんど溶解せず、沈澱した。なお原料溶液 10 mL 中の溶媒濃度は約 75 容量％である。
　単量体Ｂ－１の沈澱が生じている原料溶液を用いて重合を行なったところ、比較例３と同様の粘ちょうな液状物しか得られなかったことから、重合ゲルの状態は不合格「×」と評価した。このことから総合評価として不合格「×」と判定した。表２に実施概要および結果を併記する。 Comparative Example 4
A raw material solution was prepared in the same manner as in Example 7 except that monomer B-1 was used as monomer B. However, monomer B-1 was hardly dissolved in the raw material solution and precipitated. The solvent concentration in 10 mL of the raw material solution is about 75% by volume.
Polymerization was carried out using the raw material solution in which the precipitation of monomer B-1 had occurred. As a result, only a viscous liquid similar to that in Comparative Example 3 was obtained. “×”. From this, it was determined as a failure “x” as a comprehensive evaluation. Table 2 shows the outline and results.
比較例５
　単量体Ａを用いず単量体Ｂのみで調整した溶液Ｑを用いた以外は実施例４と同様に原料溶液を調製し、重合および膨潤処理を行なった。なお原料溶液中の溶媒濃度は約 80 容量％である。
　得られた高分子オルガノゲルは無色透明の固体状物であったことから、重合ゲルの状態は合格「○」と評価した。膨潤処理後の膨潤度は４であったことから合格「○」と判定した。圧縮破壊歪みは、50％歪みを加えた場合に破壊が発生したことから不合格「×」と判定した。なお破壊の状態は非常に脆性的なものであった。これらの結果から総合評価で×と判定した。表２に実施概要および結果を併記する。 Comparative Example 5
A raw material solution was prepared in the same manner as in Example 4 except that the solution Q prepared using only the monomer B without using the monomer A was used, and polymerization and swelling treatment were performed. The solvent concentration in the raw material solution is about 80% by volume.
Since the obtained polymer organogel was a colorless and transparent solid, the state of the polymer gel was evaluated as a pass “◯”. Since the degree of swelling after the swelling treatment was 4, it was determined to be a pass “◯”. Compressive fracture strain was judged as rejected “x” because fracture occurred when 50% strain was applied. The state of fracture was very brittle. From these results, it was determined that the overall evaluation was x. Table 2 shows the outline and results.
比較例６
　単量体Ａとして単量体Ａ－５を用いた以外は実施例７と同様に原料溶液を調整した。ただし単量体Ａ－５は溶媒３に溶解せず、相分離が発生した。なお原料溶液 10 mL 中の溶媒濃度は約 75 容量％である。
　相分離の発生した原料溶液を用いて重合したところ、固体状の高分子オルガノゲルは得られなかった。従って重合ゲルの状態は不合格「×」と評価した。このことから総合評価として不合格「×」と判定した。表２に実施概要および結果を併記する。 Comparative Example 6
A raw material solution was prepared in the same manner as in Example 7 except that monomer A-5 was used as monomer A. However, monomer A-5 did not dissolve in solvent 3 and phase separation occurred. The solvent concentration in 10 mL of the raw material solution is about 75% by volume.
Polymerization was performed using a raw material solution in which phase separation occurred, and no solid polymer organogel was obtained. Therefore, the state of the polymer gel was evaluated as rejected “x”. From this, it was determined as a failure “x” as a comprehensive evaluation. Table 2 shows the outline and results.
比較例７
　有機媒体を全く用いず、実施例４と同様の溶液Ｑ 9.0 mL に変性クレイ１を 1.8 g 添加したものを溶液Ｒ（約 10 mL ）として原料溶液を調製したが、変性クレイ１は原料溶液中にほとんど溶解せず、沈澱が発生した。従って、原料溶液 10 mL 中の溶媒濃度は約 0 容量％である。なお、この原料溶液は実施例４から溶媒分を除いた組成と同等のものである。
　この原料溶液を用いて、実施例と同様に重合を行なったが溶媒を含まないためゲル状物は得られず、底部に変性クレイが偏析した高分子組成物であった。このことから重合ゲルの状態は不合格「×」と評価した。なお上述のように得られた高分子組成物は、実施例１および２で得られた溶媒を乾燥除去した高分子組成物のような均一に変性クレイが微分散した透明な高分子組成物にはならなかった。従って総合評価として不合格「×」と判定した。表２に実施概要および結果を併記する。 Comparative Example 7
The raw material solution was prepared by adding 1.8 g of modified clay 1 to 9.0 mL of the same solution Q 9.0 as in Example 4 without using any organic medium, but the modified clay 1 was added to the raw material solution. Almost did not dissolve, and precipitation occurred. Therefore, the solvent concentration in 10 mL of the raw material solution is about 0% by volume. In addition, this raw material solution is equivalent to the composition obtained by removing the solvent from Example 4.
Using this raw material solution, polymerization was carried out in the same manner as in Example, but no gel was obtained because it did not contain a solvent, and the polymer composition had segregated modified clay at the bottom. From this, the state of the polymer gel was evaluated as rejected “x”. The polymer composition obtained as described above is a transparent polymer composition in which the modified clay is uniformly finely dispersed, such as the polymer composition obtained by drying and removing the solvent obtained in Examples 1 and 2. I didn't. Therefore, it was determined as a failure “x” as a comprehensive evaluation. Table 2 shows the outline and results.
比較例８
　溶媒濃度が 95 容量％になるように調整した以外は実施例４と同様に原料溶液を調整し、重合を行なった。
　しかし、高分子となる単量体Ａおよび単量体Ｂが合計で 5 容量％以下しか存在しなかったためか、固形状の高分子オルガノゲルは得られなかった。従って重合ゲルの状態は不合格「×」と評価した。このことから総合評価で不合格「×」と判定した。表２に実施概要および結果を併記する。 Comparative Example 8
A raw material solution was prepared and polymerized in the same manner as in Example 4 except that the solvent concentration was adjusted to 95% by volume.
However, a solid polymer organogel could not be obtained because the total amount of monomer A and monomer B, which were high polymers, was less than 5% by volume. Therefore, the state of the polymer gel was evaluated as rejected “x”. From this, it was determined as a failure “x” in the comprehensive evaluation. Table 2 shows the outline and results.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本発明により開示される高分子オルガノゲル、高分子組成物およびこれらの製造方法は、有機溶剤や油等の液状の有機物を溶媒として多量に保持することができる膨潤性と、かつ圧縮特性とに優れるので、摺動性が要求される機械部品に好適に利用できる。 The polymer organogel, the polymer composition and the production method thereof disclosed by the present invention are excellent in swelling property and compression property capable of holding a large amount of a liquid organic material such as an organic solvent or oil as a solvent. Therefore, it can be suitably used for machine parts that require slidability.

Claims (14)

  1. 　３次元架橋構造を有する高分子内に、液状の有機媒体と変性水膨潤性層状ケイ酸塩化合物とを含むことを特徴とする高分子オルガノゲル。 A polymer organogel comprising a liquid organic medium and a modified water-swellable layered silicate compound in a polymer having a three-dimensional crosslinked structure.
  2. 　前記変性水膨潤性層状ケイ酸塩化合物は、水膨潤性層状ケイ酸塩化合物を陽イオン交換法によりカチオン性有機化合物を用いて変性した化合物であることを特徴とする請求項１記載の高分子オルガノゲル。 The polymer according to claim 1, wherein the modified water-swellable layered silicate compound is a compound obtained by modifying a water-swellable layered silicate compound with a cationic organic compound by a cation exchange method. Organogel.
  3. 　前記水膨潤性層状ケイ酸塩化合物は、スメクタイト族粘土鉱物であることを特徴とする請求項２記載の高分子オルガノゲル。 3. The polymer organogel according to claim 2, wherein the water-swellable layered silicate compound is a smectite group clay mineral.
  4. 　前記３次元架橋構造を有する高分子は、付加重合性不飽和結合を１つ有する単量体と、少なくとも２つの付加重合性不飽和結合を有する単量体との重合により得られる３次元架橋構造を有する高分子であることを特徴とする請求項１記載の高分子オルガノゲル。 The polymer having a three-dimensional crosslinked structure is a three-dimensional crosslinked structure obtained by polymerization of a monomer having one addition polymerizable unsaturated bond and a monomer having at least two addition polymerizable unsaturated bonds. The polymer organogel according to claim 1, wherein the polymer organogel is characterized by comprising:
  5. 　前記高分子オルガノゲルを該高分子オルガノゲルに含まれる同一の有機媒体に 25℃で 20 日間浸漬したときの膨潤度が 1.2 以上であり、該膨潤度における圧縮破壊歪みが 50％以上であることを特徴とする請求項４記載の高分子オルガノゲル。 When the polymer organogel is immersed in the same organic medium contained in the polymer organogel at 25 ° C. for 20 days, the degree of swelling is not less than 1.2%, and the compression fracture strain at the degree of swelling is not less than 50%. The polymer organogel according to claim 4.
  6. 　請求項１記載の高分子オルガノゲルの製造方法であって、
    　有機媒体に変性水膨潤性層状ケイ酸塩化合物を分散溶解させる溶解工程と、
    　この溶液中で付加重合性不飽和結合を１つ有する単量体と、少なくとも２つの付加重合性不飽和結合を有する単量体とを付加重合により共重合させる重合工程とを含むことを特徴とする高分子オルガノゲルの製造方法。     A method for producing a polymer organogel according to claim 1,
    A dissolution step of dispersing and dissolving the modified water-swellable layered silicate compound in an organic medium;
    A polymerization step in which a monomer having one addition polymerizable unsaturated bond and a monomer having at least two addition polymerizable unsaturated bonds are copolymerized by addition polymerization in this solution, A method for producing a polymer organogel.
  7. 　前記溶解工程は、有機媒体に分散剤を加えることで変性水膨潤性層状ケイ酸塩化合物を分散溶解させる溶解工程であることを特徴とする請求項６記載の高分子オルガノゲルの製造方法。 The method for producing a polymer organogel according to claim 6, wherein the dissolving step is a dissolving step of dispersing and dissolving the modified water-swellable layered silicate compound by adding a dispersant to the organic medium.
  8. 　前記分散剤が有極性液状物質であることを特徴とする請求項７記載の高分子オルガノゲルの製造方法。 The method for producing a polymer organogel according to claim 7, wherein the dispersant is a polar liquid substance.
  9. 　前記重合工程において、前記付加重合性不飽和結合を１つ有する単量体の割合が前記少なくとも２つの付加重合性不飽和結合を有する単量体よりもモル比で多いことを特徴とする請求項６記載の高分子オルガノゲルの製造方法。 The ratio of the monomer having one addition polymerizable unsaturated bond in the polymerization step is larger in molar ratio than the monomer having the at least two addition polymerizable unsaturated bonds. 6. A method for producing a polymer organogel according to 6.
  10. 　前記重合工程において、前記有機媒体の濃度が生成する高分子オルガノゲルを基準として、20.0 容量％ 以上、95.0 容量％ 未満であることを特徴とする請求項６記載の高分子オルガノゲルの製造方法。 The method for producing a polymer organogel according to claim 6, wherein, in the polymerization step, the concentration of the organic medium is 20.0% by volume or more and less than 95.0% by volume based on the polymer organogel produced.
  11. 　前記重合工程を、不活性ガスの雰囲気下で行なうことを特徴とする請求項６記載の高分子オルガノゲルの製造方法。 The method for producing a polymer organogel according to claim 6, wherein the polymerization step is performed in an atmosphere of an inert gas.
  12. 　前記重合工程後に重合時の前記有機媒体とは異なる他の有機媒体中に重合後の高分子オルガノゲルを浸漬することで、３次元架橋構造を有する高分子内に含まれる有機媒体を置換することを特徴とする請求項６記載の高分子オルガノゲルの製造方法。 Substituting the organic medium contained in the polymer having a three-dimensional cross-linking structure by immersing the polymer organogel after polymerization in another organic medium different from the organic medium at the time of polymerization after the polymerization step. The method for producing a polymer organogel according to claim 6.
  13. 　請求項１記載の高分子オルガノゲルを生成できる高分子組成物であって、
    　該高分子組成物は、３次元架橋構造を有する高分子内に変性水膨潤性層状ケイ酸塩化合物が均一に分散されてなることを特徴とする高分子組成物。     A polymer composition capable of producing the polymer organogel according to claim 1,
    The polymer composition is characterized in that a modified water-swellable layered silicate compound is uniformly dispersed in a polymer having a three-dimensional crosslinked structure.
  14. 　有機媒体に変性水膨潤性層状ケイ酸塩化合物を分散溶解させる溶解工程と、
    　この溶液中で付加重合性不飽和結合を１つ有する単量体と、少なくとも２つの付加重合性不飽和結合を有する単量体とを付加重合により共重合させる重合工程と、
    　重合時の前記有機媒体を除去する工程とを含むことを特徴とする、３次元架橋構造を有する高分子内に前記変性水膨潤性層状ケイ酸塩化合物が分散されてなる請求項１３記載の高分子組成物の製造方法。     A dissolution step of dispersing and dissolving the modified water-swellable layered silicate compound in an organic medium;
    A polymerization step in which a monomer having one addition polymerizable unsaturated bond and a monomer having at least two addition polymerizable unsaturated bonds are copolymerized by addition polymerization in this solution;
    14. The method according to claim 13, wherein the modified water-swellable layered silicate compound is dispersed in a polymer having a three-dimensional cross-linked structure, which comprises a step of removing the organic medium during polymerization. A method for producing a molecular composition.
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