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WO2025063291A1 - Polymère à base de polyoxyalkylène ainsi que procédé de fabrication de celui-ci, et composition durcissable - Google Patents

Polymère à base de polyoxyalkylène ainsi que procédé de fabrication de celui-ci, et composition durcissable Download PDF

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WO2025063291A1
WO2025063291A1 PCT/JP2024/033724 JP2024033724W WO2025063291A1 WO 2025063291 A1 WO2025063291 A1 WO 2025063291A1 JP 2024033724 W JP2024033724 W JP 2024033724W WO 2025063291 A1 WO2025063291 A1 WO 2025063291A1
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polyoxyalkylene polymer
groups
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hydrolyzable silyl
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美伸 大西
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Kaneka Corp
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Kaneka Corp
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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
    • 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 a polyoxyalkylene polymer, a method for producing the polyoxyalkylene polymer, a curable composition containing the polyoxyalkylene polymer, and a cured product of the curable composition.
  • Organic polymers having at least one hydrolyzable silyl group in the molecule can be crosslinked by forming siloxane bonds accompanied by hydrolysis of the silyl group due to moisture or the like, even at room temperature.
  • Polyoxyalkylene polymers having hydrolyzable silyl groups are widely used as such organic polymers. It is known that organic polymers having hydrolyzable silyl groups have the property of giving rubber-like cured products through such crosslinking reactions.
  • the organic polymer having a hydrolyzable silyl group is produced, for example, by subjecting an organic polymer having an allyl group at its terminal to a hydrosilylation reaction with a hydrosilane compound that provides a hydrolyzable silyl group.
  • Karstedt's catalyst platinum divinyldisiloxane complex
  • the present invention therefore aims to provide a polyoxyalkylene polymer having a hydrolyzable silyl group that gives a curable composition with good curability, a method for producing the polyoxyalkylene polymer, a curable composition containing the polyoxyalkylene polymer, and a cured product of the curable composition.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result have found that in a polyoxyalkylene polymer having a hydrolyzable silyl group and a number average molecular weight of more than 3,000, the above problems can be solved by adjusting (N a1 +N a2 )/N t, which is the ratio of the total of the number N a1 of hydrolyzable silyl groups (a1) and the number N a2 of hydrolyzable silyl groups (a2) to the total N t of the number of hydrolyzable silyl groups (a1) of a specific structure, the number of hydrolyzable silyl groups (a2) of a specific structure, the number of 1 - propenyl groups, the number of propyl groups, and the number of allyl groups , to 0.60 or more and 1.00 or less, and adjusting N a2 /N t , which is the ratio of N a2 to N t , to 0.03
  • the present invention provides a polyoxyalkylene polymer having a hydrolyzable silyl group,
  • the number average molecular weight of the polyoxyalkylene polymer is more than 3,000
  • the polyoxyalkylene polymer is represented by the following formula (1): (1) (In formula (1), R 1 is a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, R 2 is a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, and a is 0, 1, or 2.) and a hydrolyzable silyl group (a2) having a Si—H group,
  • (N a1 +N a2 )/N t is a ratio of the total of the number N a1 of the hydrolyzable silyl groups (a1) and the number N a2 of the hydrolyzable silyl groups (a2) to the total N t of the numbers of the hydrolyzable silyl groups (a1), the hydro
  • the present invention provides a polyoxyalkylene polymer having a hydrolyzable silyl group that gives a curable composition with good curability, a method for producing the polyoxyalkylene polymer, a curable composition containing the polyoxyalkylene polymer, and a cured product of the curable composition.
  • the polyoxyalkylene polymer has a hydrolyzable silyl group.
  • the polyoxyalkylene polymer has a number average molecular weight of more than 3,000.
  • the polyoxyalkylene polymer has a hydrolyzable silyl group (a1) represented by the following formula (1) and a hydrolyzable silyl group (a2) having a Si—H group.
  • R 1 is a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms.
  • R 2 is a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms.
  • a is 0, 1, or 2.
  • (N a1 +N a2 )/N t is a ratio of the total of the number N a1 of the hydrolyzable silyl groups (a1) and the number N a2 of the hydrolyzable silyl groups (a2) to the total N t of the numbers of the hydrolyzable silyl groups (a1), the hydrolyzable silyl groups (a2), the 1 -propenyl groups, the propyl groups, and the allyl groups , and is 0.60 or more and 1.00 or less;
  • the ratio of Na2 to Nt , Na2 / Nt is equal to or greater than 0.03 and equal to or less than 1.00.
  • Polyoxyalkylene polymers that satisfy the above conditions provide curable compositions with good curability.
  • the number average molecular weight of the polyoxyalkylene polymer is more than 3000.
  • the number average molecular weight is a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • a cured product of a polyoxyalkylene polymer having such a molecular weight exhibits high modulus and high tensile strength, and therefore a curable composition containing the polyoxyalkylene polymer can be suitably used as an adhesive, a sealing material, an elastic coating agent, a pressure sensitive adhesive, etc.
  • the number average molecular weight of the polyoxyalkylene polymer is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more.
  • the upper limit of the number average molecular weight of the polyoxyalkylene polymer is not particularly limited.
  • the number average molecular weight of the polyoxyalkylene polymer may be, for example, 100,000 or less, and preferably 50,000 or less.
  • the number average molecular weight of the polyoxyalkylene polymer (A) is preferably from 5,000 to 100,000, more preferably from 10,000 to 100,000, further preferably from 10,000 to 50,000, and particularly preferably from 20,000 to 50,000.
  • the number average molecular weight of the polyoxyalkylene polymer is preferably 10,000 or less, more preferably 6,000 or less, and even more preferably 4,000 or less. That is, from the viewpoint of ease of handling of the curable composition, the number average molecular weight of the polyoxyalkylene polymer (A) is preferably more than 3,000 and not more than 10,000, more preferably more than 30,000 and not more than 6,000, and even more preferably more than 3,000 and not more than 4,000.
  • the molecular weight distribution (weight average molecular weight Mw/number average molecular weight Mn) of the polyoxyalkylene polymer is not particularly limited, but it is preferable that the molecular weight distribution is narrow. Specifically, the molecular weight distribution is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, and most preferably 1.3 or less.
  • the weight average molecular weight is also measured by GPC.
  • the polyoxyalkylene polymer has a polyoxyalkylene skeleton.
  • the polyoxyalkylene skeleton is preferably a skeleton composed only of a plurality of oxyalkylene repeating units, or a skeleton composed only of a plurality of oxyalkylene repeating units and units derived from an initiator used in polymerization.
  • the number of carbon atoms in the oxyalkylene repeat unit is preferably 2 to 6, more preferably 2 to 4.
  • the molecular chain structure of the polyoxyalkylene polymer may be either linear or branched.
  • the polyoxyalkylene polymer may contain linear and branched chain molecules.
  • Straight-chain molecules are preferred in that the cured product of the curable composition containing the polyoxyalkylene polymer described below has good elongation. Branched chain molecules are preferred in that the strength of a curable composition containing the polyoxyalkylene polymer described below is good.
  • the linear molecular structure is formed by ring-opening polymerization of a cyclic ether compound using an initiator having one or two hydroxyl groups in one molecule.
  • the branched chain molecular structure is formed by ring-opening polymerization of an alkylene oxide using an initiator having three or more hydroxyl groups in one molecule.
  • the polyoxyalkylene polymer skeleton is not particularly limited. Specific preferred examples of the polyoxyalkylene polymer skeleton include a polyoxyethylene skeleton, a polyoxypropylene skeleton, a polyoxybutylene skeleton, a polyoxytetramethylene skeleton, a polyoxyethylene-polyoxypropylene copolymer skeleton, and a polyoxypropylene-polyoxybutylene copolymer skeleton. Of these skeletons, the polyoxypropylene skeleton is preferred.
  • the polyoxyalkylene polymer may contain only one type of molecule having a polyoxyalkylene skeleton, or may contain a plurality of types of molecules each having a different type of polyoxyalkylene skeleton.
  • the ratio of the mass of oxypropylene repeating units to the mass of the polyoxyalkylene skeleton in the polyoxyalkylene polymer is preferably 50 mass% or more, and more preferably 80 mass% or more.
  • the polyoxyalkylene polymer is amorphous, and the viscosity of the polyoxyalkylene polymer tends to be low.
  • the polyoxyalkylene skeleton in the polyoxyalkylene polymer can be formed by ring-opening polymerization of a cyclic ether compound in the presence of an initiator using a polymerization catalyst according to a conventionally known method.
  • a polyoxyalkylene polymer having a hydroxyl group can be obtained.
  • the above-mentioned polyoxyalkylene polymer having a hydrolyzable silyl group can be obtained by the method described later.
  • Examples of methods for producing polyoxyalkylene polymers include a polymerization method using an alkali catalyst such as KOH, a polymerization method using a transition metal compound-porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound with porphyrin as disclosed in JP-A-61-215623, a polymerization method using a composite metal cyanide complex catalyst as disclosed in JP-B-46-27250, JP-B-59-15336, U.S. Pat. No. 3,278,457, U.S. Pat. No. 3,278,458, U.S. Pat. No. 3,278,459, U.S. Pat. No. 3,427,256, U.S. Pat. No.
  • cyclic ether compound examples include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran.
  • cyclic ether compound only one type may be used, or two or more types may be used in combination.
  • propylene oxide is particularly preferred since it is easy to obtain an amorphous, low-viscosity polyoxyalkylene polymer.
  • the initiator is not particularly limited. Suitable specific examples of initiators include monools such as butanol and propylene glycol monoalkyl ether; glycols such as ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, and triethylene glycol; and polyols having three or more hydroxyl groups such as glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, and sorbitol.
  • monools such as butanol and propylene glycol monoalkyl ether
  • glycols such as ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, and triethylene glycol
  • polyols having three or more hydroxyl groups such as
  • a hydroxyl-terminated polyoxyalkylene polymer having a number average molecular weight of 300 to 4,000 can be used as the initiator.
  • Specific examples of the hydroxyl group-terminated polyoxyalkylene polymer include polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol.
  • the polyoxyalkylene polymer has a hydrolyzable silyl group (a1) represented by the following formula (1) and a hydrolyzable silyl group (a2) having a Si—H group.
  • R 1 is a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms.
  • R 2 is a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms.
  • a is 0, 1, or 2.
  • the polyoxyalkylene polymer usually has a plurality of hydrolyzable silyl groups (a1).
  • the plurality of hydrolyzable silyl groups (a1) in the polyoxyalkylene polymer may be the same group or two or more different groups.
  • the plurality of R 1s when a plurality of R 1s are present, the plurality of R 1s may be the same group or two or more different groups.
  • the plurality of R 2 when a plurality of R 2 are present, the plurality of R 2 may be the same group or two or more different groups.
  • the hydrolyzable silyl group (a1) and the hydrolyzable silyl group (a2) are introduced into the polyoxyalkylene polymer by a hydrosilylation reaction between the polyoxyalkylene polymer having an allyl group and a hydrosilane compound.
  • a hydrosilane compound a compound represented by the following formula (1-1) is used: In formula (1-1), R 1 , R 2 and a are the same as R 1 , R 2 and a in formula (1).
  • HSiR 1 a (OR 2 ) 3-a (1-1)
  • the hydrosilane compound represented by formula (1-1) gives a hydrolyzable silyl group (a1) represented by formula (1) by a hydrosilylation reaction with an allyl group possessed by a polyoxyalkylene polymer.
  • a hydrolyzable silyl group (a2) having a Si—H group is generated.
  • the structure of the hydrolyzable silyl group (a2) is not particularly limited.
  • An example of the structure of the hydrolyzable silyl group (a2) is a structure represented by the following formula (2).
  • R 1 , R 2 and a are the same as R 1 , R 2 and a in formula (1), and n is an integer of 0 or more.
  • the upper limit of n is not particularly limited, and n is usually 10 or less.
  • the group represented by formula (2) is derived from a hydrosilane compound having a structure represented by formula (3) below, which is produced by condensation of two or more molecules of a hydrosilane compound represented by formula (1-1).
  • the group represented by formula (2) is produced by a hydrosilylation reaction between the hydrosilane compound represented by formula (3) and an allyl group in a polyoxyalkylene polymer.
  • n is usually 10 or less.
  • R 1 , R 2 and a are the same as R 1 , R 2 and a in formula (1), and n is an integer of 0 or more.
  • a preferred example of the hydrolyzable silyl group (a2) having a Si—H group is a group represented by the following formula (4):
  • the hydrosilane compound (B) is modified into a hydrosilane compound having a plurality of Si—H groups in one molecule by a disproportionation reaction
  • the modified hydrosilane compound undergoes a hydrosilylation reaction with an allyl group in the polyoxyalkylene polymer (A) to generate a group represented by the following formula (4).
  • R 1 , R 2 and a are the same as R 1 , R 2 and a in formula (1).
  • b is 1 or 2.
  • a+b is 1 or more and 3 or less.
  • the polyoxyalkylene polymer having the hydrolyzable silyl group (a2) having a Si—H group has good curability due to the high reactivity of the Si—H group.
  • the polyoxyalkylene polymer having the hydrolyzable silyl group (a1) and the hydrolyzable silyl group (a2) may have one or more of an allyl group, a 1-propenyl group, and a propyl group.
  • the allyl group is an unreacted allyl group.
  • the 1-propenyl group can be generated by an internal isomerization reaction of the allyl group as a side reaction.
  • the propyl group can be generated by a hydrogenation reaction of the allyl group as a side reaction.
  • the oxygen atom bonded to the trimethylene group is bonded to any position in the polyoxyalkylene skeleton of the polyoxyalkylene polymer.
  • the bonding position of the oxygen atom is not particularly limited, and the oxygen atom may be bonded not only to the terminal of the polyoxyalkylene skeleton, but also to a position other than the terminal of the polyoxyalkylene skeleton.
  • the bonding positions of the oxygen atoms are preferably only at the terminals of the polyoxyalkylene skeleton.
  • R 1 and R 2 each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
  • the hydrocarbon group represented by R 1 and R 2 may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • the hydrocarbon group represented by R 1 and R 2 may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
  • the structure of the aliphatic hydrocarbon group constituting the hydrocarbon group as R 1 and R 2 may be linear, branched, or cyclic, or may be a combination of these structures.
  • the number of carbon atoms in the hydrocarbon group represented by R 1 and R 2 is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, still more preferably 1 to 3, and particularly preferably 1 or 2.
  • the type of the substituent is not particularly limited as long as the desired effect is not impaired.
  • the substituent include halogen atoms such as a chlorine group and a bromo group; alkoxy groups such as a methoxy group and an ethoxy group; and substituted or unsubstituted amino groups such as an amino group, an N-methylamino group, an N-ethylamino group, an N,N-dimethylamino group, and an N,N-diethylamino group.
  • substituent or unsubstituted hydrocarbon group as R 1 and R 2 include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, 2-ethylhexyl group, and n-dodecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; substituted alkyl groups such as chloromethyl group, methoxymethyl group, and N,N-diethylaminomethyl group; alkenyl groups such as vinyl group, isopropenyl group, and allyl group; aryl groups such as phenyl group, toluyl group, naphthalene-1-yl group, and naphthalene-2-yl group; and aralkyl groups such as benzyl group and phenethyl group.
  • alkyl groups and substituted alkyl groups are preferred, with methyl groups, ethyl groups, chloromethyl groups and methoxymethyl groups being more preferred, and methyl groups being particularly preferred.
  • a is 0, 1, or 2. In terms of curability, a is preferably 0 or 1.
  • b is 1 or 2.
  • a+b is 1 or more and 3 or less. Therefore, 3-a-b is 0 or more and 2 or less.
  • Preferred specific examples of the group represented by -SiR 1 a (OR 2 ) 3-a in the group represented by formula (1) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a (chloromethyl)dimethoxysilyl group, a (chloromethyl)diethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilyl group, an (N,N-diethylaminomethyl)dimethoxysilyl group, and an (N,N-diethylaminomethyl)diethoxysilyl group.
  • the group represented by -SiR 1 a (OR 2 ) 3-a is preferably a trimethoxysilyl group, a (chloromethyl)dimethoxysilyl group, or a (methoxymethyl)dimethoxysilyl group, and more preferably a trimethoxysilyl group or a (methoxymethyl)dimethoxysilyl group.
  • the group represented by --SiR 1 a (OR 2 ) 3-a is more preferably a dimethoxymethylsilyl group or a triethoxysilyl group, and particularly preferably a dimethoxymethylsilyl group.
  • the group represented by -SiR 1 a H b (OR 2 ) 3-a-b in the group represented by formula (4) is preferably a group in which one or two of the groups represented by -OR 2 in the group represented by -SiR 1 a (OR 2 ) 3-a in the group represented by formula (1) have been substituted with a hydrogen atom.
  • specific examples of the group represented by -SiR 1 a H b (OR 2 ) 3-a-b in the group represented by formula (4) include a dimethoxyhydrosilyl group, a methoxydihydrosilyl group, a diethoxyhydrosilyl group, a diethoxyhydrosilyl group, a di(2-propenyloxy)hydrosilyl group, a 2-propenyloxydihydrosilyl group, a methoxy(methyl)hydrosilyl group (-SiCH 3 H(OCH 3 )), a methyldihydrosilyl group, an ethoxy(methyl)hydrosilyl group (-SiCH 3 H(OCH 2 CH 3 )), a methoxy(ethyl)hydrosilyl group (-Si(CH 2 CH 3 )H(OCH 3 )), ethyldihydrosilyl group, methoxy(chloromethyl)hydro
  • (N a1 +N a2 ) /N t which is the ratio of the total of the number N a1 of hydrolyzable silyl groups (a1) and the number N a2 of hydrolyzable silyl groups (a2) to the total N t of the numbers of hydrolyzable silyl groups (a1), hydrolyzable silyl groups ( a2 ), 1- propenyl groups, propyl groups, and allyl groups , is 0.60 or more and 1.00 or less. Further, the ratio of Na2 to Nt , Na2 / Nt, is 0.03 or more and 1.00 or less. When (N a1 +N a2 )/N t and N a2 /N t are within the above ranges, the curable composition containing the polyoxyalkylene polymer is cured quickly.
  • N a1 +N a2 )/N t is preferably 0.70 or more and 1.00 or less, more preferably 0.80 or more and 1.00 or less, even more preferably 0.85 or more and 1.00 or less, still more preferably 0.90 or more and 1.00 or less, and most preferably 0.95 or more and 1.00 or less.
  • N a2 /N t is preferably 0.10 or more and 1.00 or less, more preferably 0.20 or more and 1.00 or less, and even more preferably 0.25 or more and 1.00 or less.
  • N a2 /N t may be 0.70 or less, 0.50 or less, 0.40 or less, or 0.30 or less.
  • N a1 /N t and N a2 /N t can be determined by 1 H NMR based on the integral values of the signals corresponding to the hydrolyzable silyl group (a1), the hydrolyzable silyl group (a2), the 1-propenyl group, the propyl group, and the allyl group.
  • 1 H NMR measurement is performed using a sample in which a polyoxyalkylene polymer having a hydrolyzable silyl group is dissolved in deuterated chloroform, the peaks of the hydrolyzable silyl group (a1), the hydrolyzable silyl group (a2), the 1-propenyl group, the propyl group, and the allyl group can be clearly distinguished.
  • a peak derived from two protons is observed at about 0.6 ppm.
  • a peak derived from one proton is observed at about 4.5 ppm.
  • a peak derived from one proton is observed at about 4.5 ppm; however, these peaks can be distinguished from each other because the former is not reduced by removal under reduced pressure, whereas the latter is easily reduced or eliminated by removal under reduced pressure.
  • a peak derived from a 1-propenyl group is observed in the vicinity of 5.9 to 6.3 ppm as multiple peaks derived from one proton.
  • a peak derived from a propyl group is observed in the vicinity of 0.9 ppm as a peak derived from three protons.
  • a peak derived from an allyl group is observed in the vicinity of 5.1 to 5.3 ppm as two peaks derived from two protons. The above ratio can be determined based on the integral values of these peaks.
  • the method for producing the polyoxyalkylene polymer will be described in detail later, but the polyoxyalkylene polymer is produced by a hydrosilylation reaction using a hydrosilylation reaction catalyst.
  • the hydrosilylation catalyst is not particularly limited, and includes metals such as iron, cobalt, nickel, manganese, iridium, palladium, rhodium, and ruthenium, and complexes of the above metals.
  • metals such as iron, cobalt, nickel, manganese, iridium, palladium, rhodium, and ruthenium, and complexes of the above metals.
  • the polyoxyalkylene polymer may contain a hydrosilylation catalyst such as a ruthenium complex used as a catalyst.
  • the polyoxyalkylene polymer described above can be produced by a process comprising hydrosilylation of an allyl group-containing polyoxyalkylene polymer (A) with a hydrosilane compound (B) in the presence of a hydrosilylation reaction catalyst (C).
  • the polyoxyalkylene polymer (A) having an allyl group is prepared using a polyoxyalkylene polymer having a hydroxyl group, which is obtained by ring-opening polymerization of a cyclic ether compound by the method described above.
  • an alkali metal compound is reacted with the hydroxyl group to convert the hydroxyl group into an alkali metal alcoholate.
  • a composite metal cyanide complex catalyst can also be used in place of the alkali metal compound.
  • alkali metal compounds include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide; and alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, sodium tert-butoxide, and potassium tert-butoxide.
  • alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide
  • alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, sodium tert-butoxide, and potassium tert-butoxide.
  • sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred, with sodium methoxide and
  • the amount of the alkali metal compound used is not particularly limited as long as it is possible to introduce a desired amount of allyl groups into the hydroxyl groups of the polyoxyalkylene polymer.
  • the amount of the alkali metal compound used is preferably 0.5 mol or more, more preferably 0.6 mol or more, even more preferably 0.7 mol or more, and even more preferably 0.8 mol or more, per 1.0 mol of hydroxyl groups in the polyoxyalkylene polymer.
  • the amount of the alkali metal compound used is preferably 1.2 mol or less, and more preferably 1.1 mol or less, per 1.0 mol of hydroxyl groups in the polyoxyalkylene polymer.
  • the amount of the alkali metal compound used is preferably 0.5 mol or more and 1.2 mol or less, more preferably 0.6 mol or more and 1.2 mol or less, even more preferably 0.7 mol or more and 1.1 mol or less, and particularly preferably 0.8 mol or more and 1.1 mol or less, per 1.0 mol of hydroxyl groups in the polyoxyalkylene polymer.
  • water and alcohol other than the polyoxyalkylene polymer having hydroxyl groups from the reaction solution containing the polyoxyalkylene polymer and the alkali metal compound.
  • a method for removing water or alcohol various known methods can be used, specifically, a method selected from methods such as thermal evaporation, reduced pressure devolatilization, spray evaporation, thin film evaporation, and azeotropic devolatilization can be used.
  • the temperature at which the hydroxyl groups of the polyoxyalkylene polymer are reacted with the alkali metal compound is not particularly limited as long as the reaction proceeds smoothly.
  • the reaction temperature is preferably 50° C. or higher and 150° C. or lower, and more preferably 110° C. or higher and 145° C. or lower.
  • the reaction time between the hydroxyl groups of the polyoxyalkylene polymer and the alkali metal compound is preferably from 10 minutes to 5 hours, and more preferably from 30 minutes to 3 hours.
  • the polyoxyalkylene polymer after the hydroxyl groups have been converted to alkali metal alcoholates as described above is reacted with an allyl halide to obtain a polyoxyalkylene polymer (A) having allyl groups.
  • allyl halides include allyl chloride, allyl bromide, and allyl iodide. Of these, allyl chloride is preferred due to ease of handling, etc.
  • the amount of the allyl halide used is not particularly limited as long as a desired amount of allyl groups is introduced into the polyoxyalkylene polymer.
  • the amount of allyl halide used is preferably 0.7 mol or more, more preferably 1.0 mol or more, per 1.0 mol of hydroxyl groups contained in the polyoxyalkylene polymer used in the preparation of the alkali metal alcoholated polyoxyalkylene polymer.
  • the amount of allyl halide used is preferably 5.0 mol or less, more preferably 2.0 mol or less, per 1.0 mol of hydroxyl group contained in the polyoxyalkylene polymer used in the preparation of the alkali metal alcoholated polyoxyalkylene polymer.
  • the amount of the allyl halide used is preferably 0.7 mol or more and 5.0 mol or less, and more preferably 1.0 mol or more and 2.0 mol or less, per 1.0 mol of hydroxyl group in the polyoxyalkylene polymer used in the preparation of the alkali metal alcoholated polyoxyalkylene polymer.
  • the reaction temperature between the alkali metal alcoholated polyoxyalkylene polymer and the allyl halide is preferably 50°C or higher and 150°C or lower, more preferably 110°C or higher and 140°C or lower.
  • the reaction time between the alkali metal alcoholated polyoxyalkylene polymer and the allyl halide is preferably from 10 minutes to 5 hours, more preferably from 30 minutes to 3 hours.
  • the polyoxyalkylene polymer having an allyl group (A) obtained as described above is subjected to hydrosilylation with a hydrosilane compound (B) to produce a polyoxyalkylene polymer having a hydrolyzable silyl group.
  • the hydrosilylation is carried out in the presence of a ruthenium complex (C1).
  • the polyoxyalkylene polymer has a hydrolyzable silyl group (a1) represented by the above formula (1) and a hydrolyzable silyl group (a2) having a Si-H group.
  • a compound represented by the following formula (1-1) is used as the hydrosilane compound (B).
  • HSiR 1 a (OR 2 ) 3-a (1-1) The hydrosilane compound (B) represented by the formula (1-1) gives a hydrolyzable silyl group (a1) represented by the formula (1) through a hydrosilylation reaction with an allyl group in the polyoxyalkylene polymer (A). Furthermore, in the hydrosilylation reaction between the hydrosilane compound (B) represented by the formula (1-1) and an allyl group in the polyoxyalkylene polymer (A), a disproportionation reaction of the hydrosilane compound (B) occurs.
  • hydrosilane compound having a plurality of Si—H groups in one molecule produced by the disproportionation reaction further undergoes a hydrosilylation reaction with the allyl group, a hydrolyzable silyl group (a2) represented by the formula (4) is produced.
  • hydrosilylation is carried out in the presence of a hydrosilylation reaction catalyst (C) such as a ruthenium complex (C1), thereby producing a desired amount of hydrolyzable silyl groups (a2) together with hydrolyzable silyl groups (a1).
  • a hydrosilylation reaction catalyst such as a ruthenium complex (C1)
  • hydrosilane compound (B) represented by formula (1-1) include trimethoxysilane, triethoxysilane, triphenoxysilane, tris(2-propenyloxy)silane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, (methoxymethyl)dimethoxysilane, (methoxymethyl)diethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, and diphenoxymethylsilane.
  • trimethoxysilane and dimethoxymethylsilane are particularly preferred as the hydrosilane compound (B).
  • the amount of the hydrosilane compound used is preferably 1.0 mol or more, more preferably 3.0 mol or more, and even more preferably 5.0 mol or more, per 1.0 mol of allyl groups in the polyoxyalkylene polymer (A).
  • the amount of the hydrosilane compound used is preferably 20.0 mol or less, and more preferably 10.0 mol or less, per 1.0 mol of allyl groups in the polyoxyalkylene polymer (A).
  • the amount of the hydrosilane compound used is preferably from 1.0 mol to 20.0 mol, more preferably from 3.0 mol to 20.0 mol, and even more preferably from 5.0 mol to 10.0 mol, per 1.0 mol of allyl groups in the polyoxyalkylene polymer (B).
  • the hydrosilane compound (B) is used in an amount within the above range, a polyoxyalkylene polymer that has a low viscosity and is easy to handle is likely to be obtained.
  • the hydrosilane compound (B) used in the hydrosilylation reaction may be one type or two or more types.
  • hydrosilylation reaction described above is carried out in the presence of a hydrosilylation catalyst (C).
  • a hydrosilylation catalyst There are no particular limitations on the hydrosilylation catalyst, and examples include metals such as iron, cobalt, nickel, manganese, iridium, palladium, rhodium, and ruthenium, as well as complexes thereof.
  • metals such as iron, cobalt, nickel, manganese, iridium, palladium, rhodium, and ruthenium, as well as complexes thereof.
  • ruthenium complex (C1) in particular, it is easy to obtain a polyoxyalkylene polymer having a high content of hydrolyzable silyl groups.
  • the ruthenium complex (C1) is not particularly limited as long as it is a complex that contains a ruthenium atom and effectively promotes the above-mentioned hydrosilylation reaction.
  • the ruthenium complex (C1) is preferably a complex compound having a ligand (C2) derived from the compound (D).
  • Compound (D) has at least one carbon-carbon double bond and at least one electron-withdrawing group in one molecule.
  • the carbon-carbon double bond in compound (D) may be an ethylenic carbon-carbon double bond or an aromatic carbon-carbon double bond.
  • at least one of the electron-withdrawing groups is bonded to a carbon atom that constitutes a carbon-carbon double bond.
  • the ruthenium complex (C1) may have one or more types of ligand (C2).
  • Examples of the electron-withdrawing group contained in the compound (D) include halogen atoms such as a fluoro group, a chloro group, a bromo group, and an iodine group, a cyano group, an aldehyde group, and a nitro group, etc.
  • halogen atoms such as a fluoro group, a chloro group, a bromo group, and an iodine group, a cyano group, an aldehyde group, and a nitro group, etc.
  • the multiple electron-withdrawing groups may be the same or different.
  • Compound (D) has one or more, preferably two or more, more preferably two to four, and even more preferably two or three electron-withdrawing groups in one molecule.
  • the electron-withdrawing group is preferably a halogen atom, more preferably one or more selected from the group consisting of a fluoro group, a bromo group, and an iodo group, more preferably a bromo group or an iodo group, and even more preferably a bromo group.
  • compound (D) preferably has one or more, more preferably two or more, electron-withdrawing groups selected from a fluoro group, a bromo group, and an iodo group in one molecule.
  • Compound (D) preferably has one or more electron-withdrawing groups selected from a bromo group and an iodo group in one molecule.
  • compound (D) may have a fluoro group in addition to a bromo group and/or an iodo group. These electron-withdrawing groups are directly bonded to the carbon atoms constituting the carbon-carbon double bond in compound (D).
  • Compound (D) typically includes a compound having a cyclic skeleton.
  • the cyclic skeleton may be a monocyclic skeleton consisting of only one single ring, such as a cyclooctadiene skeleton, a benzene ring skeleton, or a cyclooctadiene skeleton, a polycyclic skeleton in which two or more single rings are condensed or bonded via a single bond, such as a naphthalene ring skeleton or a biphenyl skeleton, or an aliphatic cyclic skeleton having a bridge, such as a norbornadiene ring.
  • 1,4-dibromobenzene is a compound having a benzene ring skeleton to which a bromo group is bonded as a substituent.
  • compound (D) a compound having a norbornadiene skeleton, a cyclooctadiene skeleton, a benzene ring skeleton, or a benzoquinone skeleton is preferable.
  • a compound having a 2,5-norbornadiene skeleton, a 1,5-cyclooctadiene skeleton, a p-cymene skeleton, a mesitylene skeleton, a benzene ring skeleton, or a benzoquinone skeleton is preferable, and a compound having a benzene ring skeleton or a norbornadiene skeleton is more preferable.
  • the benzene ring skeleton is a skeleton consisting of one benzene ring.
  • the norbornadiene skeleton is a skeleton consisting of one norbornadiene ring.
  • suitable compounds (D) include 2-bromonorbornadiene, 2,3-dibromonorbornadiene, 1,4-dibromobenzene, structural isomers of 1,4-dibromobenzene, 1,3,5-tribromobenzene, structural isomers of 1,3,5-tribromobenzene, 1,2,4,5-tetrabromobenzene, structural isomers of 1,2,4,5-tetrabromobenzene, hexabromobenzene, 1-bromo-3,5 -difluorobenzene, structural isomers of 1-bromo-3,5-difluorobenzene, 1-bromo-3,5-dichlorobenzene, structural isomers of 1-bromo-3,5-dichlorobenzene, 1-bromo-3-chloro-5-fluorobenzene, structural isomers of 1-bromo-3-chloro-5-fluorobenzene, 1,4-d
  • one or more selected from the group consisting of 2,3-dibromonorbornadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, and 1,3,5-tribromobenzene are preferred as compound (D).
  • the ruthenium complex (C1) can be produced by a known production method.
  • raw materials for the ruthenium complex (C1) include anhydrides and hydrates of compounds selected from ruthenium (III) chloride, ruthenium (III) bromide, and ruthenium (III) iodide.
  • the ruthenium complex (C1) can be specifically produced by the following production method. First, the compound (D) is added to an ethanol solution of ruthenium chloride (III) hydrate, and the mixture is heated under reflux. Then, the solid matter in the reaction solution is collected by filtration. The collected solid matter is dried to obtain the ruthenium complex (C1).
  • ruthenium (III) chloride hydrate When ruthenium (III) chloride hydrate is used as a raw material, a reaction liquid to which a basic compound such as sodium carbonate or sodium hydrogen carbonate has been added may be heated under reflux for the purpose of neutralizing hydrogen chloride generated during heating under reflux.
  • ruthenium (III) chloride hydrate is reacted with compound (D), from the viewpoint of the reaction rate, it is preferable to use compound (D) in an amount of 1 molar equivalent or more relative to the starting ruthenium compound.
  • the ruthenium complex (C1) may be a nanoparticle catalyst.
  • the particle size (cumulative median size) of the nanoparticles of the ruthenium complex (C1) is not particularly limited as long as the hydrosilylation reaction proceeds to a desired extent.
  • the particle size is preferably 0.3 nm or more and 200 nm or less.
  • the lower limit of the particle size is preferably 0.5 nm or more, more preferably 1 nm or more.
  • the upper limit of the particle size is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 10 nm or less.
  • the particle size of the nanoparticles of the ruthenium complex (C1) is more preferably from 0.5 nm to 100 nm, even more preferably from 0.5 nm to 50 nm, and particularly preferably from 1 nm to 10 nm.
  • the cumulative median diameter can be measured by a transmission electron microscope (TEM).
  • the ruthenium complex (C1) may contain, in addition to the ligand (C2) derived from the compound (D), a ligand (C2) derived from a compound (D') that does not fall under the category of the compound (D).
  • Compound (D') is a compound capable of coordinating to a ruthenium atom, but does not fall under compound (D).
  • the ligand (C2) derived from the compound (D') include a coordinating organic solvent such as dimethylformamide, a 2,5-norbornadiene ligand, a 1,5-cyclooctadiene ligand, a p-cymene ligand, a mesitylene ligand, a benzene ligand, a carbonyl ligand, an isocyanide ligand, and an arene ligand.
  • a coordinating organic solvent such as dimethylformamide, a 2,5-norbornadiene ligand, a 1,5-cyclooctadiene ligand, a p-cymene ligand, a mesitylene ligand, a benzene ligand, a carbonyl ligand, an isocyanide ligand, and an arene ligand.
  • the ruthenium complex (C1) has both a ligand (C2) derived from the compound (D) and a ligand (C2) derived from the compound (D'), it is preferable that the proportion of the ligand (C2) derived from the compound (D) among all the ligands (C2) contained in the ruthenium complex (C1) is higher, since this allows allyl groups to be converted to hydrolyzable silyl groups (a1) and hydrolyzable silyl groups (a2) with higher selectivity in the hydrosilylation reaction.
  • the ratio of the number of ligands (C2) derived from compound (D) to the total number of ligands (C2) in ruthenium complex (C1) is preferably 1 mol % or more and 100 mol % or less, more preferably 50 mol % or more and 100 mol % or less, even more preferably 70 mol % or more and 100 mol % or less, and particularly preferably 90 mol % or more and 100 mol % or less.
  • the ruthenium complex (C1) contains a phosphorus-containing ligand.
  • a high value of N a2 /N t means that the amount of hydrolyzable silyl group (a2) in the polyoxyalkylene polymer is large.
  • the curability of the curable composition containing the polyoxyalkylene polymer is particularly excellent.
  • the phosphorus-containing ligand is not particularly limited as long as the desired effect is not impaired.
  • the phosphorus-containing ligand is preferably a phosphine ligand.
  • the phosphine ligand is not particularly limited.
  • the phosphine ligand may be a monodentate ligand, a bidentate ligand, or a tridentate ligand.
  • phosphine ligands include tris-1,1,1-(diphenylphosphinomethyl)methane, tris-1,1,1-(diphenylphosphinomethyl)-ethane, tris-1,1,1-(diphenylphosphinomethyl)propane, tris-1,1,1-(diphenylphosphinomethyl)butane, tris-1,1,1-(diphenylphosphinomethyl)2,2-dimethylpropane, tris-1,3,5-(diphenylphosphinomethyl)cyclohexane, tris-1,1,1-(dicyclohexylphosphinomethyl)ethane, tris-1,1,1-(dimethylphosphinomethyl)ethane, tris-1,1,1-(diethylphosphinomethyl)ethane, 1,5,9-triethyl-1,5-9-triphosphacyclododecane, 1,5,9-triethyl
  • tridentate phosphine ligands derived from phosphines such as phenyl-1,5-9-triphosphacyclododecane and bis(2-diphenylphosphinoethyl)phenylphosphine; bidentate phosphine ligands derived from phosphines such as bis-1,2-(diphenylphosphino)ethane, bis-1,3-(diphenylphosphino)propane, bis-1,4-(diphenylphosphino)butane, bis-1,2-(dimethylphosphino)ethane, bis-1,3-(diethylphosphino)-propane, and bis-1,4-(dicyclohexylphosphino)butane; and monodentate phosphine ligands derived from phosphines such as tricyclohexylphosphine, trioctylphosphine, trimethyl
  • the phosphine ligand is preferably a trialkylphosphine ligand or a triarylphosphine ligand, more preferably a triarylphosphine ligand, and particularly preferably a triphenylphosphine ligand.
  • ruthenium complex (C1) having a phosphine ligand is tris(triphenylphosphine)ruthenium(II) dichloride (RuCl 2 (PPh 3 ) 3 ).
  • the amount of compound (D) used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per part by mass of ruthenium complex (C1) having a phosphine ligand.
  • a ruthenium complex (C1) may be produced by reacting a ruthenium compound (C'1) that does not have a ligand (C2) derived from compound (D) with compound (D) in the reaction liquid.
  • the ruthenium compound (C'1) include ruthenium chloride (III), ruthenium bromide (III), and ruthenium iodide (III).
  • the ruthenium compound (C'1) may be a ruthenium complex that does not have a ligand (C2) derived from compound (D) and has a ligand (C2) derived from compound (D') that does not fall under compound (D).
  • the amount of the hydrosilylation catalyst (C) used in the hydrosilylation reaction is preferably 0.01 ppm by mass or more, more preferably 0.1 ppm by mass or more, and even more preferably 1 ppm by mass or more, based on the mass of the allyl group-containing polyoxyalkylene polymer (A).
  • the amount of the hydrosilylation catalyst (C) used in the hydrosilylation reaction is preferably 10 ppm by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less, based on the mass of the allyl group-containing polyoxyalkylene polymer (A).
  • the hydrosilylation reaction may be carried out in the presence or absence of a solvent.
  • a solvent used, the type of the solvent is not particularly limited. A compound that does not react with the raw material or the catalyst is used as the solvent.
  • suitable solvents include hydrocarbon solvents such as hexane, halogenated hydrocarbon solvents such as dichloromethane, etc.
  • a solvent that is sufficiently dehydrated and sufficiently deoxygenated is used for the hydrosilylation reaction.
  • the reaction temperature of the hydrosilylation reaction can be appropriately determined in consideration of the reactivity (reaction rate) and the heat resistance temperature of the reaction vessel, etc.
  • the reaction temperature is preferably 0° C. or higher, more preferably 20° C. or higher, and even more preferably 40° C. or higher.
  • the reaction temperature is preferably 200° C. or lower, more preferably 150° C. or lower. That is, the reaction temperature is preferably 0° C. or higher and 200° C. or lower, more preferably 20° C. or higher and 200° C. or lower, and further preferably 40° C. or higher and 150° C. or lower. The higher the reaction temperature, the shorter the reaction time and the more likely it is that side reactions can be suppressed.
  • the reaction time for the hydrosilylation reaction is not particularly limited as long as the reaction proceeds to the desired extent.
  • the reaction temperature is preferably from 5 minutes to 12 hours, more preferably from 10 minutes to 5 hours.
  • the hydrosilylation reaction is preferably carried out under an atmosphere of an inert gas such as nitrogen or argon.
  • the hydrosilylation is carried out in the presence of compound (D). That is, the hydrosilylation is preferably carried out in the presence of the ruthenium catalyst (C) and the compound (D), in which case the allyl groups in the polyoxyalkylene polymer (B) are easily converted to the hydrolyzable silyl groups (a1) and (a2) with high efficiency.
  • the polyoxyalkylene polymer is washed with water and, if necessary, volatile matter is removed from the polyoxyalkylene polymer by distillation to obtain the polyoxyalkylene polymer.
  • the curable composition contains a polyoxyalkylene polymer having a hydrolyzable silyl group produced by the above-mentioned method.
  • the curable composition also contains a curing catalyst as a component for curing the polyoxyalkylene polymer.
  • the curable composition contains a curing catalyst for the purpose of promoting the reaction of hydrolyzing and condensing the hydrolyzable silyl group, that is, the curing reaction.
  • any conventionally known catalyst can be used as the curing catalyst. Specifically, organic tin compounds, metal carboxylates, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, and mixtures of these can be used as the curing catalyst.
  • organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), reaction products of dibutyltin oxide with silicate compounds, reaction products of dibutyltin oxide with phthalic acid esters, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), dioctyltin distearate, dioctyltin oxide, and reaction products of dioctyltin oxide with silicate compounds. Of these, dioctyltin compounds are preferred due to the growing concern
  • metal carboxylates include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate.
  • carboxylic acids can be combined with various metals to produce metal carboxylates.
  • amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine, piperidine, 4-methylpiperidine, and hexamethyleneimine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; and ketimine compounds.
  • amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine, piperidine, 4-methylpiperidine, and hexamethyleneimine
  • nitrogen-containing heterocyclic compounds such
  • carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.
  • alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), titanium ethylacetoacetate, and diisopropoxytitanium bis(ethylacetoacetate); aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate; and zirconium compounds such as zirconium tetrakis(acetylacetonate).
  • curing catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.
  • Two or more different types of catalysts may be used in combination as the curing catalyst.
  • the reactivity of the curing reaction can be improved by using the aforementioned amine compound in combination with a carboxylic acid, or by using an amine compound in combination with an alkoxy metal.
  • the amount of the curing catalyst used is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 15 parts by mass, and particularly preferably 0.01 to 10 parts by mass, per 100 parts by mass of the polyoxyalkylene polymer.
  • the curing catalyst may seep out onto the surface of the cured product, or the surface of the cured product may be contaminated by the curing catalyst.
  • the curable composition may contain other additives, such as a silicon compound, an adhesion imparting agent, a plasticizer, a solvent, a diluent, a silicate, a filler, an anti-sagging agent, an antioxidant, a light stabilizer, an ultraviolet absorber, a physical property adjusting agent, a tackifying resin, a compound containing an epoxy group, a photocurable substance, an oxygen-curable substance, a surface property improver, an epoxy resin, other resins, a flame retardant, or a foaming agent.
  • various additives may be added to the curable composition as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product.
  • additives examples include a curability regulator, a radical inhibitor, a metal deactivator, an ozone deterioration inhibitor, a phosphorus-based peroxide decomposer, a lubricant, a pigment, and a fungicide.
  • the curable composition may contain various fillers, such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber, and filaments.
  • various fillers such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber, and filaments.
  • the amount of filler used is preferably 1 part by mass or more and 300 parts by mass or less, and more preferably 10 parts by mass or more and 250 parts by mass or less, per 100 parts by mass of polyoxyalkylene polymer.
  • Balloons are hollow spherical fillers. Balloon materials include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran.
  • the amount of balloons used is preferably 0.1 parts by mass or more and 100 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less, per 100 parts by mass of polyoxyalkylene polymer.
  • An adhesion promoter may be added to the curable composition.
  • the adhesion promoter include a silane coupling agent and a reaction product of a silane coupling agent.
  • silane coupling agent examples include amino group-containing silanes such as ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; ⁇ -isocyanatepropyltrimethoxysilane, ⁇ -isocyanatepropyltriethoxysilane, ⁇ -isocyanatepropyltriethoxysilane, and ⁇ -isocyanatepropyltriethoxysilane.
  • amino group-containing silanes such as ⁇ -aminopropyltrimethoxysilane,
  • silanes examples include isocyanate group-containing silanes such as anatopropylmethyldimethoxysilane, ⁇ -isocyanatemethyltrimethoxysilane, and ⁇ -isocyanatemethyldimethoxymethylsilane; mercapto group-containing silanes such as ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, and ⁇ -mercaptopropylmethyldimethoxysilane; and epoxy group-containing silanes such as ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
  • isocyanate group-containing silanes such as anatopropylmethyldimethoxysilane, ⁇ -isocyanatemethyltrimethoxysilane, and ⁇ -isocyanatemethyldimethoxymethylsilane
  • condensates of various silane coupling agents such as a condensate of an amino group-containing silane, a condensate of an amino group-containing silane with another alkoxysilane; a reaction product of an amino group-containing silane with an epoxy group-containing silane, a reaction product of an amino group-containing silane with a (meth)acrylic group-containing silane, and other reaction products of various silane coupling agents, can also be used as adhesion promoters.
  • the adhesion promoter may be used alone or in combination of two or more kinds.
  • the amount of the silane coupling agent used is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer.
  • plasticizer may be added to the curable composition.
  • the plasticizer include phthalate compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl)phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalate compounds such as 1,2-cyclohexanedicarboxylate diisononyl ester; aliphatic polycarboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and acetyl tributyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl
  • Polymer plasticizers can also be used.
  • polymer plasticizers include vinyl polymers, polyester plasticizers, polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more, and polyethers such as derivatives in which the hydroxyl groups of these polyether polyols are converted to ester groups, ether groups, etc., polystyrenes, polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene.
  • the plasticizer may be used alone or in combination of two or more kinds.
  • the polymer plasticizer may or may not have a reactive silyl group.
  • the polymer plasticizer acts as a reactive plasticizer and can prevent the plasticizer from migrating from the cured product.
  • the average number of reactive silyl groups per molecule is preferably 1 or less, more preferably 0.8 or less.
  • a plasticizer having a reactive silyl group, particularly a polyoxyalkylene polymer having a reactive silyl group is used as the plasticizer, it is preferable that the number average molecular weight of the polyoxyalkylene polymer as the plasticizer is lower than the number average molecular weight of the contained polyoxyalkylene polymer.
  • the amount of plasticizer used is preferably 5 parts by mass or more and 150 parts by mass or less, more preferably 10 parts by mass or more and 120 parts by mass or less, and even more preferably 20 parts by mass or more and 100 parts by mass or less, per 100 parts by mass of polyoxyalkylene polymer.
  • solvent or diluent may be added to the curable composition.
  • the solvent or diluent is not particularly limited as long as the desired effect is not impaired.
  • the solvent or diluent aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, and the like can be used.
  • the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and particularly preferably 250°C or higher.
  • the solvent or diluent may be used alone or in combination of two or more kinds.
  • a sagging prevention agent may be added to the curable composition to prevent sagging and improve workability.
  • the sagging prevention agent is not particularly limited. Examples of the sagging prevention agent include polyamide waxes, hydrogenated castor oil derivatives, and metal soaps such as calcium stearate, aluminum stearate, and barium stearate.
  • the anti-sagging agent may be used alone or in combination of two or more kinds.
  • the amount of anti-sagging agent used is preferably 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of polyoxyalkylene polymer.
  • An antioxidant may be added to the curable composition.
  • the use of an antioxidant can improve the weather resistance of the cured product.
  • the antioxidant include hindered phenol compounds, monophenol compounds, bisphenol compounds, and polyphenol compounds.
  • Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, and Irganox 1520 (all manufactured by BASF); SONGNOX 1076 (manufactured by SONGWON), and BHT are exemplified as suitable antioxidants.
  • hindered amine-based light stabilizers such as TINUVIN 622LD, TINUVIN 144, TINUVIN 292, CHIMASSORB 944LD, and CHIMASSORB 119FL (all manufactured by BASF); Adeka STAB LA-57, Adeka STAB LA-62, Adeka STAB LA-67, Adeka STAB LA-63, and Adeka STAB LA-68 (all manufactured by ADEKA CORPORATION); SANOL LS-2626, SANOL LS-1114, and SANOL LS-744 (all manufactured by Sankyo Lifetech Co., Ltd.); and NOCRAC CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) can also be used.
  • Other usable antioxidants include SONGNOX 4120, Naugard 445, and OKABEST CLX 050. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.
  • the amount of antioxidant used is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of polyoxyalkylene polymer.
  • a light stabilizer may be added to the curable composition.
  • the use of a light stabilizer can prevent photooxidation deterioration of the cured product.
  • Examples of light stabilizers include benzotriazole-based compounds, hindered amine-based compounds, and benzoate-based compounds. In particular, hindered amine-based compounds are preferred.
  • the amount of light stabilizer used is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of polyoxyalkylene polymer.
  • the curable composition may contain an ultraviolet absorber, which can improve the surface weather resistance of the cured product.
  • ultraviolet absorbents include benzophenone compounds, benzotriazole compounds, salicylate compounds, substituted acrylonitrile compounds, and metal chelate compounds. Benzotriazole compounds are particularly preferred.
  • Specific preferred examples of the ultraviolet absorber include TINUVIN P, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 327, TINUVIN 328, TINUVIN 329, TINUVIN 571, TINUVIN 1600, and TINUVIN B75 (all manufactured by BASF).
  • the amount of the UV absorber used is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer.
  • a physical property adjuster may be added to the curable composition for the purpose of adjusting the tensile properties of the resulting cured product.
  • the physical property adjuster is not particularly limited. Specific examples of suitable physical property adjusters include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and ⁇ -glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as tris(trimethylsilyl)borate and tris(trieth
  • the physical property adjusting agent may be used alone or in combination of two or more kinds.
  • compounds which upon hydrolysis produce compounds having monovalent silanol groups in the molecule have the effect of lowering the modulus of the cured product without increasing the stickiness of the surface of the cured product.
  • a compound that generates trimethylsilanol is particularly preferable.
  • the compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, and generate silane monool by hydrolysis. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.
  • the amount of the property adjuster used is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.5 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer.
  • Tackifier resin A tackifier resin may be added to the curable composition for the purpose of enhancing adhesion or adhesion to a substrate, or for other reasons.
  • the tackifier resin is not particularly limited.
  • tackifier resins include terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers, hydrogenated styrene block copolymers, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, and DCPD resins.
  • the tackifier resin may be used alone or in combination of two or more kinds.
  • the amount of the tackifier resin used is preferably 2 parts by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, and even more preferably 5 parts by mass or more and 30 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer.
  • the curable composition may contain a compound containing an epoxy group.
  • a compound having an epoxy group can improve the restorability of the cured product.
  • the compound having an epoxy group include epoxy compounds such as epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, and epichlorohydrin derivatives, and mixtures thereof.
  • examples of compounds containing an epoxy group include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxyoctyl stearate, and epoxybutyl stearate.
  • the compound containing an epoxy group is preferably used in an amount of 0.5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the polyoxyalkylene polymer.
  • a photocurable material may be added to the curable composition.
  • a photocurable material When a photocurable material is used, a film of the photocurable material is formed on the surface of the cured product, improving the stickiness and weather resistance of the cured product.
  • Many materials such as organic monomers, oligomers, resins, and compositions containing these are known as photocurable materials.
  • Representative photocurable materials include unsaturated acrylic compounds, which are monomers, oligomers, and mixtures thereof, having one or more acrylic unsaturated groups or having one or more methacrylic unsaturated groups; polyvinyl cinnamates; azido resins, etc.
  • the amount of photocurable substance used is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of polyoxyalkylene polymer.
  • An oxygen-curing substance may be added to the curable composition.
  • the oxygen-curing substance include unsaturated compounds that can react with oxygen in the air.
  • the oxygen-curing substance reacts with oxygen in the air to form a cured film near the surface of the cured product, and exhibits the effect of preventing the surface from becoming sticky and preventing the adhesion of dirt and dust to the surface of the cured product.
  • oxygen-curable substances include drying oils such as tung oil and linseed oil; various alkyd resins obtained by modifying drying oils; acrylic polymers, epoxy resins, or silicone resins modified with drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and C5 to C8 diene polymers obtained by homopolymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene.
  • the oxygen-curing substance may be used alone or in combination of two or more kinds.
  • the amount of oxygen-curable substance used is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of polyoxyalkylene polymer. As described in JP-A-3-160053, it is preferable to use the oxygen-curable substance in combination with a photocurable substance.
  • the curable composition may contain an epoxy resin.
  • the curable composition containing the epoxy resin is preferably used as an adhesive, and is particularly preferably used as an adhesive for exterior wall tiles.
  • Examples of the epoxy resin include bisphenol A type epoxy resin and novolac type epoxy resin.
  • the ratio of epoxy resin to polyoxyalkylene polymer used is preferably within the range of 100/1 to 1/100, in terms of polyoxyalkylene polymer/epoxy resin.
  • a curing agent that cures the epoxy resin may be added to the curable composition together with the epoxy resin.
  • the epoxy resin hardener is not particularly limited, and any commonly used epoxy resin hardener can be used.
  • the amount of hardener used is preferably in the range of 0.1 parts by mass to 300 parts by mass per 100 parts by mass of epoxy resin.
  • the above-described curable composition is cured in a manner appropriate for the intended use of the curable composition to form a cured product.
  • the curable composition can be prepared as a one-component type in which all ingredients are mixed in advance, stored in a sealed container, and cured by moisture in the air after application.
  • a two-component type can be prepared by mixing ingredients such as a curing catalyst, a filler, a plasticizer, and water as a curing agent and mixing the ingredients with a polymer composition containing a polyoxyalkylene polymer before use. From the viewpoint of workability, a one-component type is preferred.
  • the curable composition is of a one-component type, all of the components are mixed in advance. For this reason, it is preferable that the components containing water are dehydrated and dried before use, or dehydrated by reducing pressure or the like during mixing and kneading.
  • the storage stability of the curable composition is further improved by adding an alkoxysilane compound such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldiethoxysilane, and ⁇ -glycidoxypropyltrimethoxysilane to the curable composition.
  • an alkoxysilane compound such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldiethoxysilane, and ⁇ -glycidoxypropyltrimethoxy
  • the curable composition can be used as a building sealant, industrial adhesive, waterproof coating film forming composition, adhesive raw material, etc.
  • the curable composition can also be used as a sealant for buildings, ships, automobiles, roads, etc.
  • the curable composition can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin moldings, either alone or with the aid of a primer. Therefore, the curable composition can also be used as various types of sealing compositions and adhesive compositions.
  • the curable composition can also be used as a contact adhesive in addition to ordinary adhesives.
  • the curable composition is also useful as a food packaging material, a cast rubber material, a material for molding, and a paint.
  • the cured product of the above curable composition exhibits low water absorption. Therefore, the above curable composition and its cured product are particularly suitable for use as waterproof materials such as sealing materials, waterproof adhesives, and waterproof coating films.
  • the present invention includes the following:
  • the polyoxyalkylene polymer is represented by the following formula (1): (1) (In formula (1), R 1 is a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, R 2 is a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, and a is 0, 1, or 2.) and a hydrolyzable silyl group (a2) having a Si—H group,
  • (N a1 +N a2 )/N t is a ratio of the total of the number N a1 of the hydrolyzable silyl groups (a1) and the number N a2 of the hydrolyzable silyl groups (a2) to the total N t of the numbers of the hydrolyzable silyl groups (a1), the hydrolyzable si
  • the hydrolyzable silyl group (a2) is represented by the following formula (4): (4) (In formula (4), R 1 , R 2 , and a are the same as R 1 , R 2 , and a in formula (1), b is 1 or 2, and a+b is 1 or more and 3 or less.)
  • ⁇ 4> The polyoxyalkylene polymer according to any one of ⁇ 1> to ⁇ 3>, wherein N a2 /N t is 0.20 or more and 1.00 or less.
  • ⁇ 5> The polyoxyalkylene polymer according to any one of ⁇ 1> to ⁇ 4>, which contains a ruthenium complex.
  • ⁇ 6> A method for producing a polyoxyalkylene polymer according to any one of ⁇ 1> to ⁇ 5>, comprising hydrosilylation of an allyl group-containing polyoxyalkylene polymer (A) with a hydrosilane compound (B) in the presence of a hydrosilylation catalyst (C).
  • ⁇ 7> The method for producing a polyoxyalkylene polymer according to ⁇ 6>, wherein the hydrosilylation catalyst (C) is a ruthenium complex (C1).
  • the ruthenium complex (C1) has a ligand (C2) derived from the compound (D), Compound (D) has at least one carbon-carbon double bond and at least one electron-withdrawing group in one molecule
  • ⁇ 9> The method for producing a polyoxyalkylene polymer according to ⁇ 8>, wherein the compound (D) has a benzene ring skeleton or a norbornadiene skeleton.
  • the compound (D) has, as an electron-withdrawing group, at least one selected from the group consisting of a fluoro group, a bromo group, and an iodo group.
  • ⁇ 11> The method for producing a polyoxyalkylene polymer according to any one of ⁇ 8> to ⁇ 10>, wherein the compound (D) is one or more selected from the group consisting of 2,3-dibromonorbornadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, and 1,3,5-tribromobenzene.
  • the compound (D) is one or more selected from the group consisting of 2,3-dibromonorbornadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, and 1,3,5-tribromobenzene.
  • ⁇ 12> The hydrosilylation is carried out in the presence of a compound (D), Compound (D) has at least one carbon-carbon double bond and at least one electron-withdrawing group in one molecule,
  • ⁇ 13> The method for producing a polyoxyalkylene polymer according to ⁇ 12>, wherein the compound (D) has a benzene ring skeleton or a norbornadiene skeleton.
  • ⁇ 14> The method for producing a polyoxyalkylene polymer according to ⁇ 12> or ⁇ 13>, wherein the compound (D) has, as an electron-withdrawing group, at least one selected from the group consisting of a fluoro group, a bromo group, and an iodo group.
  • ⁇ 17> The method for producing a polyoxyalkylene polymer according to ⁇ 16>, wherein the phosphorus-containing ligand is a triphenylphosphine ligand.
  • ⁇ 18> The process for producing a polyoxyalkylene polymer according to ⁇ 16> or ⁇ 17>, wherein the ruthenium catalyst (C1) is tris(triphenylphosphine)ruthenium(II) dichloride.
  • C1 is tris(triphenylphosphine)ruthenium(II) dichloride.
  • a curable composition comprising the polyoxyalkylene polymer according to any one of ⁇ 1> to ⁇ 5> and a curing catalyst.
  • ⁇ 20> A cured product of the curable composition according to ⁇ 19>.
  • the number average molecular weight in the examples is a GPC molecular weight measured under the following conditions.
  • Liquid delivery system Tosoh HLC-8420GPC Column: Tosoh TSKgel Super H series Solvent: THF (tetrahydrofuran) Molecular weight: polystyrene equivalent Measurement temperature: 40°C
  • Example 1 To the polymer (A-1) obtained in Synthesis Example 1, 100 ppm by mass of RuCl 2 (PPh 3 ) 3 ) and 260 ppm by mass of 2,3-dibromonorbornadiene were added, based on the mass of the polymer (A-1). 2,3-Dibromonorbornadiene is a compound that has an electron-withdrawing group and can be coordinated to ruthenium. The resulting mixture was stirred at 90° C. for 10 minutes.
  • the obtained polymer (S-1) was subjected to 1 H NMR measurement, and the ratio of the number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2) represented by formula (4), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups to the total was calculated.
  • the skinning time of the resulting polymer (S-1) was measured by the above-mentioned method. The results are shown in Table 1.
  • Example 2 For the purpose of adjusting the ratio of the silyl group (a1) and the silyl group (a2), the polymer (S-1) obtained in Example 1 and the polymer (S-7) obtained in Synthesis Example 2 were mixed to obtain a hydrolyzable silyl group-containing polyoxyalkylene polymer (S-2) of Example 2 and a hydrolyzable silyl group-containing polyoxyalkylene polymer (S-3) of Example 3.
  • the obtained polymer (S-4) was subjected to 1 H NMR measurement, and the ratio of the number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2) represented by formula (4), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups to the total was calculated.
  • the skinning time of the resulting polymer (S-4) was measured by the above-mentioned method. The results are shown in Table 1.
  • Example 5 [RuCl 2 (p-cymene)] n was added to the polymer (A-1) in an amount of 240 ppm by mass relative to the mass of the polymer (A-1).
  • p-Cymene is a p-cymene ligand. The p-cymene ligand does not have an electron-withdrawing group.
  • the resulting mixture was stirred at 90° C. for 10 minutes.
  • 5.0 mol equivalents of dimethoxymethylsilane relative to the allyl group of polymer (A-1) was added to the mixture, and a hydrosilylation reaction between the allyl group of polymer (A-1) and dimethoxymethylsilane was carried out at 90° C.
  • the obtained polymer (S-8) was subjected to 1 H NMR measurement, and the ratio of the number of silyl groups (a1) represented by formula (1), the number of silyl groups (a2) represented by formula (4), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups to the total was calculated.
  • the skinning time of the resulting polymer (S-8) was measured by the above-mentioned method.
  • Table 1 shows the ratios of functional groups in the polyoxyalkylene polymers obtained in the Examples and Comparative Examples.
  • the compounds listed in Table 1 are those that were used in conjunction with the hydrosilylation catalyst.
  • the hydrosilylation catalysts listed in Table 1 are as follows: Cat1: RuCl2 ( PPh3 ) 3
  • Cat 4 Ruthenium complex obtained in Synthesis Example 3
  • the compounds described in Table 1 are as follows.
  • the silyl group a1 in Table 1 is a hydrolyzable silyl group (a1) represented by formula (1).
  • the silyl group a2 in Table 1 is a hydrolyzable silyl group (a2) represented by formula (4). *The functional group ratios in Table 1 are values rounded off to the first decimal place, so the total of the functional group ratios may not amount to 100%.

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Abstract

L'invention fournit un polymère à base de polyoxyalkylène qui possède des groupes silyle hydrolysable, et qui procure une composition durcissable de propriétés de durcissement satisfaisantes. L'invention fournit également un procédé de fabrication de polymère à base de polyoxyalkylène, une composition durcissable contenant le polymère à base de polyoxyalkylène et un objet durci de cette composition durcissable.　Plus précisément, l'invention concerne un polymère à base de polyoxyalkylène qui possède des groupes silyle hydrolysable, et dont la masse moléculaire moyenne en nombre dépasse 3000. （Ｎａ１＋Ｎａ２）／Ｎｔ qui constitue le rapport du total du nombre (Ｎａ１) de groupes silyle hydrolysable (a1) et du nombre (Ｎａ２) de groupes silyle hydrolysable (a2), pour le total (Ｎｔ) du nombre de groupes silyle hydrolysable (a1) de structure spécifique, du nombre de groupes silyle hydrolysable (a2) de structure spécifique, du nombre de groupes 1-propényle, du nombre de groupes propyle et du nombre de groupes allyle, est supérieur ou égal à ０,６０ et inférieur ou égal à １,００. Ｎａ２／Ｎｔ qui constitue le rapport de Ｎａ２ pour Ｎｔ, est supérieur ou égal à ０,０３ et inférieur ou égal à １,００.
PCT/JP2024/033724 2023-09-22 2024-09-20 Polymère à base de polyoxyalkylène ainsi que procédé de fabrication de celui-ci, et composition durcissable Pending WO2025063291A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03200807A (ja) * 1989-02-28 1991-09-02 Kanegafuchi Chem Ind Co Ltd 有機重合体、その製造方法及びそれを用いた硬化性組成物
JP2001059021A (ja) * 1999-08-24 2001-03-06 Japan Science & Technology Corp ルテニウムカルボニル錯体を用いる環状エーテルの開環重合およびそれから得られるシリル化鎖状ポリエーテル
JP2005272733A (ja) * 2004-03-25 2005-10-06 Kaneka Corp 新規な官能基含有ポリオキシアルキレン系重合体及び製造方法
JP2017057384A (ja) * 2015-09-16 2017-03-23 三洋化成工業株式会社 変性ポリエーテル組成物の製造方法
JP2021011456A (ja) * 2019-07-08 2021-02-04 国立研究開発法人産業技術総合研究所 アリルエーテル化合物のヒドロシリル化による有機ケイ素化合物の製造方法
WO2022181545A1 (fr) * 2021-02-24 2022-09-01 株式会社カネカ Procédé de fabrication d'un polymère comprenant un groupe silyle hydrolysable, et polymère, composition durcissable et produit durci
WO2024225205A1 (fr) * 2023-04-24 2024-10-31 株式会社カネカ Polymère de polyoxyalkylène contenant un groupe silyle hydrolysable, composition durcissable et produit durci

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03200807A (ja) * 1989-02-28 1991-09-02 Kanegafuchi Chem Ind Co Ltd 有機重合体、その製造方法及びそれを用いた硬化性組成物
JP2001059021A (ja) * 1999-08-24 2001-03-06 Japan Science & Technology Corp ルテニウムカルボニル錯体を用いる環状エーテルの開環重合およびそれから得られるシリル化鎖状ポリエーテル
JP2005272733A (ja) * 2004-03-25 2005-10-06 Kaneka Corp 新規な官能基含有ポリオキシアルキレン系重合体及び製造方法
JP2017057384A (ja) * 2015-09-16 2017-03-23 三洋化成工業株式会社 変性ポリエーテル組成物の製造方法
JP2021011456A (ja) * 2019-07-08 2021-02-04 国立研究開発法人産業技術総合研究所 アリルエーテル化合物のヒドロシリル化による有機ケイ素化合物の製造方法
WO2022181545A1 (fr) * 2021-02-24 2022-09-01 株式会社カネカ Procédé de fabrication d'un polymère comprenant un groupe silyle hydrolysable, et polymère, composition durcissable et produit durci
WO2024225205A1 (fr) * 2023-04-24 2024-10-31 株式会社カネカ Polymère de polyoxyalkylène contenant un groupe silyle hydrolysable, composition durcissable et produit durci

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