WO2009090959A1 - Organogel de polymère, composition de polymère, procédé de fabrication de l'organogel de polymère et procédé de fabrication de la composition de polymère - Google Patents

Organogel de polymère, composition de polymère, procédé de fabrication de l'organogel de polymère et procédé de fabrication de la composition de polymère 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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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.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
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Abstract

L'invention porte sur un organogel polymère qui peut porter une matière organique telle qu'un solvant organique ou une huile comme solvant dans une grande quantité et qui présente une excellente résistance, en particulier une excellente rigidité ; sur une composition de polymère ; sur un procédé pour la fabrication de l'organogel polymère ; et sur un procédé de fabrication de la composition de polymère. De façon spécifique, l'invention porte sur un organogel de polymère incluant : un polymère présentant une structure réticulée tridimensionnelle ; et un milieu organique liquide et un composé phyllosilicate gonflable par l'eau modifié, contenus tous deux dans le polymère, le composé phyllosilicate gonflable par l'eau modifié étant obtenu par modification d'un composé phyllosilicate gonflable par l'eau par l'échange de cation à l'aide d'un composé organique cationique et le polymère étant obtenu par la polymérisation d'un monomère possédant une liaison insaturée polymérisable par addition et d'un monomère possédant au moins deux liaisons insaturées polymérisables par addition et présentant une structure réticulée tridimensionnelle.
PCT/JP2009/050387 2008-01-14 2009-01-14 Organogel de polymère, composition de polymère, procédé de fabrication de l'organogel de polymère et procédé de fabrication de la composition de polymère WO2009090959A1 (fr)

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