WO2021182118A1 - Polymère organique, composition durcissable, et produit durci - Google Patents

Polymère organique, composition durcissable, et produit durci Download PDF

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WO2021182118A1
WO2021182118A1 PCT/JP2021/007079 JP2021007079W WO2021182118A1 WO 2021182118 A1 WO2021182118 A1 WO 2021182118A1 JP 2021007079 W JP2021007079 W JP 2021007079W WO 2021182118 A1 WO2021182118 A1 WO 2021182118A1
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group
polymer
organic polymer
carbon
reactive silyl
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PCT/JP2021/007079
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Japanese (ja)
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直己 味岡
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株式会社カネカ
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the present invention relates to an organic polymer having a reactive silyl group, a curable composition, and a cured product.
  • An organic polymer having a hydroxyl group or a hydrolyzable group on a silicon atom and a silicon-containing group capable of forming a siloxane bond (hereinafter referred to as "reactive silyl group”) is known as a moisture-reactive polymer. It is contained in many industrial products such as adhesives, sealants, coating materials, paints, and adhesives, and is used in a wide range of fields.
  • a reactive silyl group-containing polymer various polymers having a main chain skeleton such as a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylic acid ester copolymer are known. There is.
  • a method for producing a reactive silyl group-containing polymer for example, an epoxy compound is ring-opened polymerized to synthesize a polyoxyalkylene polymer having a hydroxyl group at the terminal, and then the hydroxyl group is converted into a carbon-carbon double bond. Then, a method of introducing a reactive silyl group into a polymer by carrying out a hydrosilylation reaction between the carbon-carbon double bond and a silane compound is known (see, for example, Patent Document 1). However, the reactive silyl group-containing polymer obtained by this method does not always have sufficient curability, and it is required to improve this.
  • Patent Document 2 discloses a polymer containing a reactive silyl group having improved curability, in which a reactive silyl group is bonded to the polymer skeleton via a sulfide bond.
  • Patent Document 2 by reacting an allyl group-terminated polymer with mercaptomethyltrimethoxysilane in the presence of a radical initiator (thiol-ene reaction), a reactive silyl group is formed into a polymer skeleton via a sulfide bond. It is described to synthesize a bound polymer.
  • a radical initiator thiol-ene reaction
  • the organic polymer synthesized under the production conditions disclosed in Patent Document 2 does not have a sufficiently high tensile strength of the cured product obtained by curing the polymer. It turned out that there was room for improvement in this regard.
  • the present invention provides an organic polymer having a reactive silyl group bonded to a polymer skeleton via a sulfide bond and capable of forming a cured product exhibiting high tensile strength. With the goal.
  • the present invention has the following general formula (1): -S-CH 2- SiR 1 a X 3-a (1)
  • R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
  • X represents a hydroxyl group or a hydrolyzable group.
  • A is 0, 1 or 2.
  • the present invention relates to an organic polymer having a reactive silyl group introduction rate of 60% or more.
  • the polymer skeleton of the organic polymer is a polyoxyalkylene polymer.
  • the present invention is a method for producing the organic polymer.
  • the amount of the mercapto group-containing compound used is 1.2 mol times or more the carbon-carbon double bond.
  • the total amount of the radical initiator used is 0.2 parts by weight or more with respect to 100 parts by weight of the organic polymer having a carbon-carbon double bond.
  • the production method further comprises a step of distilling off volatiles at a temperature of 130 ° C. or higher under reduced pressure after the reaction.
  • the present invention also relates to a curable composition containing the organic polymer and a cured product obtained by curing the curable composition.
  • the present invention relates to an organic polymer having a reactive silyl group.
  • the organic polymer exhibits curability based on the hydrolysis and dehydration condensation reaction of the reactive silyl group.
  • the organic polymer has a polymer skeleton composed of a plurality of repeating units and a terminal structure bonded to the end of the polymer skeleton.
  • the polymer skeleton refers to a polymer main chain composed of a plurality of repeating units.
  • the polymer skeleton of the organic polymer may be linear or branched.
  • the linear polymer skeleton is preferable in that the cured product of the curable composition has high elongation, and the branched-chain polymer skeleton is preferable in that the cured product of the curable composition has high tensile strength.
  • the linear polymer skeleton of the organic polymer is one or two in one molecule in the polymerization method for forming the polymer skeleton. It can be formed by using an initiator having hydroxyl groups, and a branched polymer skeleton can be formed by using an initiator having three or more hydroxyl groups in one molecule.
  • the polymer skeleton is a polymer skeleton composed of only a plurality of repeating units linked to each other, or includes a structure derived from an initiator used at the time of polymerization in addition to the plurality of repeating units. It is preferable that the polymer skeleton is composed of only these.
  • the repeating unit refers to an oxyalkylene unit, for example, an oxyalkylene having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. A unit.
  • the terminal structure refers to a site that does not contain repeating units constituting the polymer skeleton and is bonded to the end of the polymer skeleton.
  • the terminal structure is preferably bonded to an oxyalkylene unit located at the end of the polymer skeleton via an oxygen atom. ..
  • the reactive silyl group contained in the organic polymer is contained in the terminal structure.
  • each terminal structure may contain a reactive silyl group, or the terminal structure containing the reactive silyl group and the terminal structure not containing the reactive silyl group may coexist.
  • the organic polymer has a reactive silyl group in a specific ratio. That is, the reactive silyl group introduction rate is 60% or more. An organic polymer satisfying this condition can form a cured product showing high tensile strength.
  • the reactive silyl group introduction rate is 100 ⁇ the number of moles of the reactive silyl group contained in the organic polymer / (the number of moles of the reactive silyl group contained in the organic polymer + the reactive silyl group is not introduced). It can be expressed by the number of moles of the remaining reactive silyl group-introducable group contained in the organic polymer + the number of moles of the group in which the introduceable group is isomerized).
  • the numerical value of the reactive silyl group introduction rate can be determined based on the integrated value of the signal indicating each group by performing 1 H NMR measurement of the organic polymer.
  • the reactive silyl group introduction rate is 60% or more, but 70% or more is preferable, 80% or more is more preferable, and 90% or more is further preferable, because the organic polymer can exhibit higher tensile strength after curing. , 95% or more is particularly preferable.
  • the upper limit of the reactive silyl group introduction rate is not particularly limited, and may be 100% or less.
  • the reactive silyl group introduction rate is preferably 95% or less, more preferably 90% or less, and more preferably 85%. The following is more preferable, and 80% or less is particularly preferable. 60% or more and 80% or less are particularly preferable in order to exhibit high tensile strength, maintain curability, and further exhibit sufficient flexibility of the cured product.
  • the reactive silyl group contained in the organic polymer has the following general formula (1): -S-CH 2- SiR 1 a X 3-a (1) It is represented by.
  • the condensation reactivity of the reactive silyl group is significantly enhanced by the sulfur atom bonded to the carbon atom adjacent to the silicon atom. Therefore, the organic polymer having a reactive silyl group represented by the general formula (1) exhibits excellent quick-curing property even in a curable composition containing a low-activity silanol condensation catalyst.
  • R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
  • the number of carbon atoms is preferably 1 to 10, more preferably 1 to 8 carbon atoms, further preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.
  • the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include a halogen group such as a chloro group, an alkoxy group such as a methoxy group, and an amino group such as an N, N-diethylamino group. ..
  • It is preferably a substituted or unsubstituted alkyl group, more preferably a methyl group, an ethyl group, a chloromethyl group or a methoxymethyl group, still more preferably a methyl group or a methoxymethyl group, and particularly preferably a methyl group. It is a group.
  • R 1 only one type of group may be used, or two or more types of groups may be used in combination.
  • X represents a hydroxyl group or a hydrolyzable group.
  • Examples of X include hydroxyl groups, hydrogens, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups and the like.
  • the above-mentioned alkoxy group and the like may have a substituent.
  • An alkoxy group is preferable, a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group are more preferable, a methoxy group and an ethoxy group are further preferable, and a methoxy group is particularly preferable, because the hydrolysis property is mild and easy to handle.
  • X only one type of group may be used, or two or more types of groups may be used in combination.
  • a in the general formula (1) is 0, 1 or 2. It is preferably 0 or 1. It is more preferably 1 in terms of the balance between the curability of the organic polymer and the physical properties of the cured product.
  • Examples of -SiR 1 a X 3-a in the general formula (1) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, and a methyldimethoxysilyl group.
  • Methyldiethoxysilyl group dimethoxyethylsilyl group, (chloromethyl) dimethoxysilyl group, (chloromethyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N- Examples thereof include a diethylaminomethyl) dimethoxysilyl group and a (N, N-diethylaminomethyl) diethoxysilyl group.
  • methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N-diethylaminomethyl) ) Dimethoxysilyl group and the like can be mentioned.
  • a trimethoxysilyl group, a (chloromethyl) dimethoxysilyl group, and a (methoxymethyl) dimethoxysilyl group are more preferable.
  • a methyldimethoxysilyl group, a methyldiethoxysilyl group, and a triethoxysilyl group are more preferable. Further, a trimethoxysilyl group, a triethoxysilyl group and a methyldimethoxysilyl group are more preferable because they are easy to produce. Of these, the methyldimethoxysilyl group is most preferable.
  • the number of reactive silyl groups contained in one molecule of the organic polymer is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 1.2 or more on average.
  • the upper limit is preferably 4 or less, and more preferably 3 or less.
  • the terminal structure having a reactive silyl group is not particularly limited, but a typical example is the terminal structure represented by the following general formula (4).
  • R 3 represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms
  • R 4 represents hydrogen or an alkyl group having 1 to 6 carbon atoms.
  • the oxygen at the left end indicates oxygen bound to the polymer skeleton.
  • R 1 , X, and a are the same as those described above for the general formula (1).
  • the R 3 preferably a divalent hydrocarbon group having 1 to 3 carbon atoms, more preferably a divalent hydrocarbon group having 1 to 2 carbon atoms.
  • a hydrocarbon group an alkylene group is preferable, and a methylene group, an ethylene group, a propylene group, and a butylene group can be used. Methylene groups are particularly preferred.
  • the R 4, preferably an alkyl group having hydrogen or a C 1-4, hydrogen or an alkyl group having 1 to 3 carbon atoms is more preferred.
  • the alkyl group include hydrogen, methyl group, ethyl group, propyl group, butyl group and the like.
  • the R 4, a hydrogen, a methyl group, an ethyl group, more preferably a hydrogen, a methyl group is more preferable.
  • a methyl group is preferable as R 4.
  • the main chain structure of the organic polymer may be linear or may have a branched chain.
  • the main chain skeleton of the organic polymer is not particularly limited, and various main chain skeletons can be used. Specific examples of the main chain skeleton include, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer.
  • Polyoxyalkylene-based polymers such as: ethylene-propylene-based copolymers, polyisobutylene, copolymers of isobutylene and isoprene, etc., polychloroprene, polyisoprene, isoprene or butadiene and acrylonitrile and / or styrene and the like.
  • Saturated hydrocarbon-based polymers such as coalesced, polybutadiene, isoprene or butadiene and copolymers of acrylonitrile and styrene, and hydrogenated polyolefin-based polymers obtained by hydrogenating these polyolefin-based polymers; polyester-based weight.
  • (meth) acrylic acid ester-based polymer obtained by radical polymerization of (meth) acrylic acid ester-based monomer such as ethyl (meth) acrylate and butyl (meth) acrylate, as well as (meth) acrylic acid-based monomer and acetic acid.
  • Vinyl-based polymers such as polymers obtained by radical polymerization of monomers such as vinyl, acrylonitrile, and styrene; graft polymers obtained by polymerizing vinyl monomers in the above-mentioned polymers; polysulfide-based polymers; polyamides.
  • Examples thereof include organic polymers such as based polymers; polycarbonate-based polymers; diallyl phthalate-based polymers; Each of the above polymers may be mixed in a block shape, a graft shape, or the like.
  • saturated hydrocarbon-based polymers, polyoxyalkylene-based polymers, and (meth) acrylic acid ester-based polymers have a relatively low glass transition temperature, and the obtained cured product has excellent cold resistance. Therefore, a polyoxyalkylene polymer is more preferable, and polyoxypropylene is particularly preferable.
  • the organic polymer may be a polymer having any one of the above-mentioned main chain skeletons, or a mixture of polymers having different main chain skeletons. Further, the mixture may be a mixture of polymers produced separately from each other, or a mixture produced at the same time so as to have an arbitrary mixed composition.
  • the number average molecular weight of the organic polymer is not particularly limited, but is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and further preferably 3 in terms of polystyrene-equivalent molecular weight in GPC. It is 000 to 30,000.
  • the number average molecular weight is 3,000 or more, the relative amount of the reactive silyl group with respect to the entire polymer is in an appropriate range, which is desirable from the viewpoint of production cost. Further, when the number average molecular weight is 100,000 or less, it is easy to achieve a desired viscosity from the viewpoint of workability.
  • the number average molecular weight can be determined by GPC measurement in terms of polystyrene.
  • the molecular weight distribution (Mw / Mn) of the organic polymer is not particularly limited, but is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, further preferably 1.5 or less, and particularly preferably 1.4 or less.
  • the molecular weight distribution (Mw / Mn) can be calculated from the number average molecular weight and the weight average molecular weight obtained in terms of polystyrene by GPC measurement.
  • the production method is not particularly limited, but for example, the organic polymer introduces a carbon-carbon double bond into the hydroxyl group-containing organic polymer by utilizing the reactivity of the hydroxyl group, and then has a reactive silyl group and a mercapto group. It can be produced by reacting a compound having.
  • the polymer skeleton of the polyoxyalkylene polymer can be formed by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method, whereby a hydroxyl group-terminated polyoxyalkylene polymer can be obtained. ..
  • the specific polymerization method is not particularly limited, but since a hydroxyl group-terminated polymer having a small molecular weight distribution (Mw / Mn) can be obtained, a polymerization method using a composite metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex. Is preferable.
  • the initiator having a hydroxyl group is not particularly limited, and for example, ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, low molecular weight polyoxypropylene triol, allyl alcohol, and low molecular weight polyoxypropylene.
  • examples thereof include organic compounds having one or more hydroxyl groups, such as monoallyl ether and low molecular weight polyoxypropylene monoalkyl ether.
  • the epoxy compound is not particularly limited, and examples thereof include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether. Propylene oxide is preferable.
  • reaction with alkali metal salt In introducing a carbon-carbon double bond into a hydroxyl group-terminated polyoxyalkylene polymer, first, an alkali metal salt is allowed to act on the hydroxyl group-terminated polyoxyalkylene polymer to convert the terminal hydroxyl group into a metaloxy group. It is preferable to do so. Further, a composite metal cyanide complex catalyst can be used instead of the alkali metal salt. As described above, the metaloxy group-terminated polyoxyalkylene polymer is formed.
  • the alkali metal salt is not particularly limited, and examples thereof include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide.
  • Sodium hydroxide, sodium methoxyd, sodium ethoxydo, sodium tert-butoxide, potassium hydroxide, potassium methoxyd, potassium ethoxydo, potassium tert-butoxide are preferable, and sodium methoxyd and sodium tert are preferable because of ease of handling and solubility.
  • -Butoxide is more preferred.
  • Sodium methoxide is particularly preferred in terms of availability, and sodium tert-butoxide is particularly preferred in terms of reactivity.
  • the alkali metal salt may be subjected to the reaction in a state of being dissolved in a solvent.
  • the amount of the alkali metal salt used is not particularly limited, but the molar ratio of the hydroxyl group-terminated polyoxyalkylene polymer to the hydroxyl group is preferably 0.5 or more, more preferably 0.6 or more, and more preferably 0.7 or more. More preferably, 0.8 or more is even more preferable.
  • the molar ratio is preferably 1.2 or less, more preferably 1.1 or less.
  • the alkali metal salt is used to convert the hydroxyl group of the hydroxyl group-terminated polyoxyalkylene polymer into a metal oxy group.
  • water and polyoxyalkylene-based weight are used. It is preferable to remove the substance having a hydroxyl group other than the coalescence from the reaction system in advance. For removal, a known method may be used, and for example, heat evaporation, vacuum evaporation, spray vaporization, thin film evaporation, azeotropic evaporation and the like can be used.
  • the temperature at which the alkali metal salt is allowed to act can be appropriately set by those skilled in the art, but is preferably 50 ° C. or higher and 150 ° C. or lower, and more preferably 110 ° C. or higher and 145 ° C. or lower.
  • the time for allowing the alkali metal salt to act is preferably 10 minutes or more and 5 hours or less, and more preferably 30 minutes or more and 3 hours or less.
  • reaction with electrophile By allowing an electrophile having a carbon-carbon double bond to act on the metaloxy group-terminated polyoxyalkylene-based polymer obtained as described above, a metaloxy group can be formed into a carbon-carbon double bond. It can be converted into a including structure. As a result, a polyoxyalkylene polymer having a carbon-carbon double bond is formed in the terminal structure.
  • the electrophilic agent having a carbon-carbon double bond is a compound that can react with the metaloxy group of the polyoxyalkylene-based polymer to introduce a carbon-carbon double bond into the polyoxyalkylene-based polymer.
  • examples thereof include organic halides having a carbon-carbon double bond.
  • the organic halide having a carbon-carbon double bond reacts with the metaloxy group by a halogen substitution reaction to form an ether bond, and forms a carbon-carbon double bond as a terminal structure of a polyoxyalkylene-based polymer. Structures containing can be introduced.
  • R 3 and R 4 are the same groups as R 3 and R 4 described above for the general formula (4), respectively.
  • Z represents a halogen atom.
  • organic halide having a carbon-carbon double bond are not particularly limited, but are limited to vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, and allyl iodide. , Metallyyl iodide and the like. Allyl chloride and methallyl chloride are preferable from the viewpoint of ease of handling. Further, since the rate of introduction of the reactive silyl group is improved, methallyl chloride, methallyl bromide and methallyl iodide are preferable.
  • the amount of the organic halide having a carbon-carbon double bond added is not particularly limited, but the molar ratio of the organic halide to the hydroxyl group of the polyoxyalkylene polymer is preferably 0.7 or more, preferably 1.0. The above is more preferable. The molar ratio is preferably 5.0 or less, more preferably 2.0 or less.
  • the temperature at which the organic halide having a carbon-carbon double bond is reacted with the metaloxy group-terminated polyoxyalkylene polymer is preferably 50 ° C. or higher and 150 ° C. or lower, more preferably 110 ° C. or higher and 140 ° C. or lower. preferable.
  • the reaction time is preferably 10 minutes or more and 5 hours or more, and more preferably 30 minutes or more and 3 hours or less.
  • the mercapto group-containing compound has the following general formula (2): HS-CH 2- SiR 1 a X 3-a (2) Can be represented by.
  • R 1 , X, and a are the same as those described above for the general formula (1).
  • Specific examples of the mercapto group-containing compound include (mercaptomethyl) methyldimethoxysilane, (mercaptomethyl) trimethoxysilane, (mercaptomethyl) methyldiethoxysilane, and (mercaptomethyl) triethoxysilane.
  • the amount of the mercapto group-containing compound used may be appropriately determined in consideration of the amount of carbon-carbon double bonds of the polyoxyalkylene polymer.
  • the amount of the compound used for the carbon-carbon double bond of the polyoxyalkylene polymer is 0.6 mol times or more, which is preferable from the viewpoint of further increasing the introduction rate of the reactive silyl group. It is 1.0 mol times or more, more preferably 1.2 mol times or more, further preferably 1.5 mol times or more, and particularly preferably more than 1.5 mol times.
  • the upper limit of the amount of the mercapto group-containing compound used is not particularly limited, and is preferably 5 mol times or less, more preferably 3 mol times or less.
  • the addition reaction of the mercapto group to the carbon-carbon double bond may be carried out in the presence of a radical initiator for the purpose of improving the reaction rate or the reaction rate.
  • a radical initiator conventionally known ones can be used. Specific examples thereof include, but are not limited to, an azo-based initiator and a peroxide-based initiator.
  • a catalyst having low activity with respect to the reactive silyl group is preferable, and from this viewpoint, 2,2'-azobis (isobutyronitrile) (AIBN) and 2,2'-azobis (2).
  • Azo-based initiators such as -methylbutyronitrile) (V-59) and 2,2'-azobis (1-methylcyclohexanecarbonitrile) (V-40) are particularly preferred.
  • the radical initiator may be added separately or continuously, instead of being added collectively to the reaction system containing the organic polymer having a carbon-carbon double bond and the mercapto group-containing compound.
  • the reactive silyl group introduction rate of 60% or more can be achieved.
  • the number of additions is preferably 2 times or more, more preferably 3 times or more, and further preferably 4 times or more. It is desirable that each addition be carried out at intervals of, for example, 10 minutes or more, preferably 30 minutes or more.
  • the radical initiator is added continuously, it is desirable that the addition is carried out over a period of, for example, 1 hour or more, preferably 2 hours or more.
  • the radical initiator may be added in a state of being dissolved in an organic solvent.
  • the total amount of the radical initiator used can be appropriately set by those skilled in the art, but from the viewpoint of further increasing the introduction rate of the reactive silyl group, 0.15 parts by weight or more is preferable with respect to 100 parts by weight of the organic polymer, and 0.2. It is more preferably parts by weight or more, more preferably 0.3 parts by weight or more, and particularly preferably 0.4 parts by weight or more. Further, from the viewpoint of suppressing the residue derived from the initiator and controlling the heat of reaction in addition to improving the reactive silyl group introduction rate, the total amount of the radical initiator used is 100 parts by weight of the organic polymer. On the other hand, 0.15 to 10 parts by weight is preferable, 0.2 to 10 parts by weight is more preferable, 0.3 to 5 parts by weight is further preferable, and 0.4 to 3 parts by weight is particularly preferable.
  • the temperature of the addition reaction can be appropriately set by those skilled in the art, but is preferably 50 ° C. or higher and 120 ° C. or lower, and more preferably 70 ° C. or higher and 100 ° C. or lower.
  • the reaction time may be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that the unintended condensation reaction between the polymers does not proceed.
  • the reaction time is preferably 15 minutes or more and 10 hours or less, and more preferably 30 minutes or more and 6 hours or less.
  • ((Meta) acrylic acid ester polymer) When the main chain of the organic polymer is a (meth) acrylic acid ester-based polymer, the method for producing the organic polymer is as follows: (I) A compound having a polymerizable unsaturated group and a reactive functional group (for example, Acrylic acid (2-hydroxyethyl acrylate) is copolymerized with a monomer having a (meth) acrylic structure to obtain a polymer, and then at any position (preferably at the end of the molecular chain) in the obtained polymer.
  • a reactive functional group for example, Acrylic acid (2-hydroxyethyl acrylate
  • a (meth) acrylic structure by a method of introducing a carbon-carbon double bond into the carbon-carbon double bond and then adding the mercapto group-containing compound to the carbon-carbon double bond, or by a living radical polymerization method such as (II) atomic transfer radical polymerization. After polymerizing a monomer having a Examples thereof include a method of adding the mercapto group-containing compound to the heavy bond.
  • the method for producing the organic polymer is an olefin having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene, and isobutylene.
  • a carbon-carbon double bond is introduced at any position (preferably at the end of the molecular chain) of the obtained polymer, and then the carbon-carbon Examples thereof include a method of adding the mercapto group-containing compound to the double bond.
  • the organic polymer of the present invention can be synthesized.
  • the synthesized organic polymer is preferably heated under reduced pressure to distill off unreacted substances or by-products contained in the polymer.
  • a step of distilling off volatile components at a temperature of 100 ° C. or higher under reduced pressure is carried out after the reaction with the mercapto group-containing compound. It is preferable to do so.
  • the temperature is more preferably 110 ° C. or higher, further preferably 120 ° C. or higher, and most preferably 130 ° C. or higher.
  • the present invention can provide a curable composition containing the organic polymer.
  • the curable composition of the present invention preferably contains a silanol condensation catalyst for the purpose of promoting a reaction of hydrolyzing and condensing reactive silyl groups, that is, a curing reaction.
  • silanol condensation catalyst conventionally known ones can be used, and specifically, organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids and the like can be used.
  • organic tin compound examples include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis (butylmaleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis (acetylacetonate), dibutyltin oxide and silicate compounds.
  • dioctyltin diacetate dioctyltin dilaurate
  • dioctyltin bis (ethylmalate) dioctyltin bis (octylmaleate)
  • dioctyltin bis (acetylacetate) Nart dioctyltin compounds are preferable.
  • the curable composition of the present invention does not contain an organic tin compound, but contains a silanol condensation catalyst other than the organic tin compound. Can be done.
  • the curable composition of the present invention can exhibit good curability even if it does not contain an organic tin compound.
  • metal carboxylate salt examples include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, and the like.
  • carboxylic acid group the following carboxylic acids and various metals can be combined.
  • amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine, etc .; pyridine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1, Nitrogen-containing heterocyclic compounds such as 5-diazabicyclo [4,3,0] nonen-5 (DBN); guanidines such as guanidine, phenylguanidine, diphenylguanidine; butylbiguanide, 1-o-tolylbiguanide and 1- Biganides such as phenylbiguanide; ketimine compounds and the like can be mentioned.
  • carboxylic acid examples include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.
  • the alkoxy metal include titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate) and diisopropoxytitanium bis (ethylacetatete), aluminum tris (acetylacetonate), and diisopropoxyaluminum ethylacetate acetate.
  • titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate) and diisopropoxytitanium bis (ethylacetatete), aluminum tris (acetylacetonate), and diisopropoxyaluminum ethylacetate acetate.
  • aluminum compounds such as, and zirconium compounds such as zirconium tetrakis (acetylacetonate).
  • silanol condensation catalysts fluorine anion-containing compounds, photoacid generators and photobase generators can also be used.
  • the silanol condensation catalyst may be used in combination with two or more different catalysts. For example, by using the amine compound and the carboxylic acid in combination, the effect of improving the reactivity may be obtained.
  • the reactive silyl group of the organic polymer of the present invention has high activity, the amount of the curing catalyst can be reduced, a curing catalyst having low activity can be used, or aminosilane which is an amino group-containing silane coupling agent can be used. It can also be used as a curing catalyst. Since aminosilane is usually added as an adhesive-imparting agent, when aminosilane is used as a curing catalyst, a curable composition that does not use a commonly used curing catalyst can be prepared. Therefore, it is preferable not to add another curing catalyst. In particular, when the reactive silyl group contains a trimethoxysilyl group or a methoxymethyldimethoxysilyl group, excellent curability is exhibited even if only aminosilane is used as a curing catalyst.
  • the blending amount of the silanol condensation catalyst is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and 0.01 to 10 parts by weight with respect to 100 parts by weight of the organic polymer of the present invention. Is particularly preferable. If the blending amount of the silanol condensation catalyst is less than 0.001 part by weight, the reaction rate may be insufficient. On the other hand, if the blending amount of the silanol condensation catalyst exceeds 20 parts by weight, the reaction rate is too fast, so that the usable time of the composition is shortened, which tends to deteriorate workability and storage stability.
  • silanol condensation catalysts may exude to the surface of the cured product or contaminate the surface of the cured product after the curable composition has been cured.
  • the amount of the silanol condensation catalyst used may be set to 0.01 to 3.0 parts by weight, the surface condition of the cured product can be kept good while ensuring the curability.
  • a silicon compound an adhesive-imparting agent, a plasticizing agent, a solvent, a diluent, a silicate, a filler, a sagging agent, an antioxidant, a light stabilizer, and ultraviolet rays.
  • an absorbent, a physical property adjusting agent, a tackifier resin, a compound containing an epoxy group, a photocurable substance, an oxygen curable substance, a surface improving agent, an epoxy resin, other resins, a flame retardant, or a foaming agent are added. good.
  • various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the composition or the cured product. Examples of such additives include curability modifiers, radical inhibitors, metal deactivators, ozone deterioration inhibitors, phosphorus peroxide decomposing agents, lubricants, pigments, fungicides and the like. Be done.
  • the curable composition of the present invention can be prepared as a one-component type in which all the compounding components are compounded and sealed in advance and cured by the moisture in the air after construction. Separately, a silanol condensation catalyst is used as a curing agent. It is also possible to prepare a two-component type in which components such as a filler, a plasticizer, and water are blended and the compounding material and the organic polymer composition are mixed before use. From the viewpoint of workability, the one-component type is preferable.
  • the curable composition is a one-component type
  • all the compounding components are pre-blended. Therefore, the moist-containing compounding components are dehydrated and dried in advance before use, or dehydrated by decompression or the like during compounding and kneading. Is preferable.
  • the curable composition of the present invention is an adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a waterproof material, a coating film waterproof material, a molding agent, a vibration isolator, a vibration damping material, and a soundproofing material.
  • the cured product obtained by curing the curable composition of the present invention is excellent in flexibility and adhesiveness, and therefore can be suitably used as a sealing material or an adhesive.
  • the curable composition of the present invention includes electric / electronic component materials such as a solar cell backside sealing material, electrical / electronic components such as an insulating coating material for electric wires / cables, an electrical insulating material for an apparatus, and an acoustic insulating material.
  • electric / electronic component materials such as a solar cell backside sealing material
  • electrical / electronic components such as an insulating coating material for electric wires / cables, an electrical insulating material for an apparatus, and an acoustic insulating material.
  • the curable composition of the present invention is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stones, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing.
  • Adhesives vehicle panel adhesives, electrical / electronic / precision equipment assembly adhesives, leather, textiles, fabrics, paper, board and rubber bonding adhesives, reactive post-bridge pressure sensitive adhesives, direct It can also be used as a glazing sealant, a multi-layer glass sealant, an SSG method sealant, a building working joint sealant, a civil engineering material, and a bridge material. Furthermore, it can also be used as an adhesive material such as an adhesive tape or an adhesive sheet.
  • the number average molecular weight in the examples is the GPC molecular weight measured under the following conditions.
  • Liquid transfer system Tosoh HLC-8220GPC Column: TSKgel SuperH series manufactured by Tosoh Solvent: THF Molecular weight: Polystyrene conversion Measurement temperature: 40 ° C
  • the "reactive silyl group introduction rate" is calculated by measuring 1 H NMR for a polyoxyalkylene-based polymer having a reactive silyl group, and using the integrated value of the signal indicating each group, the formula: 100 ⁇ (reaction). Number of moles of reactive silyl group) / (Number of moles of reactive silyl group and number of moles of group capable of introducing reactive silyl group (allyl group in this example) remaining without introducing reactive silyl group was calculated based on the total number of moles of the isomerized group (1-propenyl group in this example) into which the reactive silyl group can be introduced.
  • Example 1 To a glass reactor equipped with a stirrer, a reflux condenser and a thermometer, 2.5 parts by weight of hexane was added to 100 parts by weight of the polymer (A-1), and azeotropic dehydration was performed at 90 ° C. Hexane was distilled off under reduced pressure and replaced with nitrogen. 5.64 parts by weight of mercaptomethyltrimethoxysilane (1.51 mol times with respect to the terminal allyl group) at 90 ° C., and 0,2'-azobis (2-methylbutyronitrile) as a radical initiator. . 1 part by weight was added and the reaction was started.
  • the obtained reaction product was polyoxypropylene having a number average molecular weight of 15,000 and a (trimethoxysilylmethyl) sulfanyl group at the end, which had a reduced odor peculiar to sulfur compounds.
  • the reactive silyl group introduction rate in the polymer was 94.5%.
  • Example 2 To a glass reactor equipped with a stirrer, a reflux condenser and a thermometer, 2.5 parts by weight of hexane was added to 100 parts by weight of the polymer (A-1), and azeotropic dehydration was performed at 90 ° C. Hexane was distilled off under reduced pressure and replaced with nitrogen. 5.64 parts by weight of mercaptomethyltrimethoxysilane (1.51 mol times with respect to the terminal allyl group) at 90 ° C., and 0,2'-azobis (2-methylbutyronitrile) as a radical initiator. . 1 part by weight was added and the reaction was started.
  • the obtained reaction product was polyoxypropylene having a number average molecular weight of 15,000 and a (trimethoxysilylmethyl) sulfanyl group at the end, which had a reduced odor peculiar to sulfur compounds.
  • the reactive silyl group introduction rate in the polymer was 96.0%.
  • Example 3 To a glass reactor equipped with a stirrer, a reflux condenser and a thermometer, 2.5 parts by weight of hexane was added to 100 parts by weight of the polymer (A-1), and azeotropic dehydration was performed at 90 ° C. Hexane was distilled off under reduced pressure and replaced with nitrogen. 7.48 parts by weight of mercaptomethyltrimethoxysilane (2.00 mol times with respect to the terminal allyl group) at 90 ° C., and 0,2'-azobis (2-methylbutyronitrile) as a radical initiator. . 1 part by weight was added and the reaction was started.
  • the obtained reaction product was polyoxypropylene having a number average molecular weight of 15,000 and a (trimethoxysilylmethyl) sulfanyl group at the end, which had a reduced odor peculiar to sulfur compounds.
  • the reactive silyl group introduction rate in the polymer was more than 99.0%.
  • 100 parts by weight of the obtained polymer and 1 part by weight of 3-aminopropyltrimethoxysilane (A-1110) are weighed in a mini cup, kneaded and stirred, and allowed to stand under constant temperature and humidity conditions of 23 ° C. and 50%. bottom. When the surface of the mixture was touched with a spatula and the time required for the mixture to stop adhering to the spatula was measured as the skinning time, the skinning time was 20 minutes.

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Abstract

Selon la présente invention, un polymère organique comprend un groupe silyle réactif représenté par la formule : -S-CH2-SiR1 aX3-a. (dans cette formule, R1 représente un groupe hydrocarboné substitué ou non substitué comprenant 1 à 20 atomes de carbone, X représente un groupe hydroxyle ou un groupe hydrolysable, et a vaut 0, 1 ou 2 ; lorsque plusieurs R1 ou X sont présents, ceux-ci peuvent respectivement être identiques ou différents). Le rapport d'introduction du groupe silyle réactif est supérieur ou égal à 60 %.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012057281A1 (fr) * 2010-10-27 2012-05-03 セメダイン株式会社 Composition durcissable
WO2016002907A1 (fr) * 2014-07-02 2016-01-07 株式会社カネカ Composition durcissable et objet durci obtenu à partir de celle-ci
JP2017141450A (ja) * 2017-03-09 2017-08-17 信越化学工業株式会社 ポリオキシアルキレン基含有有機ケイ素化合物およびその製造方法
CN107903863A (zh) * 2017-12-11 2018-04-13 浙江工业大学 一种硅烷改性聚醚基胶及其巯基自由基加成制备方法
WO2019039537A1 (fr) * 2017-08-24 2019-02-28 綜研化学株式会社 Polymère à base d'ester alkylique d'acide (méth)acrylique et utilisation associée

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012057281A1 (fr) * 2010-10-27 2012-05-03 セメダイン株式会社 Composition durcissable
WO2016002907A1 (fr) * 2014-07-02 2016-01-07 株式会社カネカ Composition durcissable et objet durci obtenu à partir de celle-ci
JP2017141450A (ja) * 2017-03-09 2017-08-17 信越化学工業株式会社 ポリオキシアルキレン基含有有機ケイ素化合物およびその製造方法
WO2019039537A1 (fr) * 2017-08-24 2019-02-28 綜研化学株式会社 Polymère à base d'ester alkylique d'acide (méth)acrylique et utilisation associée
CN107903863A (zh) * 2017-12-11 2018-04-13 浙江工业大学 一种硅烷改性聚醚基胶及其巯基自由基加成制备方法

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