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WO2014073580A1 - Procédé de production de polyéther contenant un groupe hydroxyle, procédé de production de polyéther contenant un groupe silyle hydrolysable, et procédé de production de prépolymère d'uréthane - Google Patents

Procédé de production de polyéther contenant un groupe hydroxyle, procédé de production de polyéther contenant un groupe silyle hydrolysable, et procédé de production de prépolymère d'uréthane Download PDF

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Publication number
WO2014073580A1
WO2014073580A1 PCT/JP2013/080037 JP2013080037W WO2014073580A1 WO 2014073580 A1 WO2014073580 A1 WO 2014073580A1 JP 2013080037 W JP2013080037 W JP 2013080037W WO 2014073580 A1 WO2014073580 A1 WO 2014073580A1
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group
hydroxyl group
containing polyether
compound
producing
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English (en)
Japanese (ja)
Inventor
豪明 荒井
知志 鈴木
雄二郎 富塚
田中　英明
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AGC Inc
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Asahi Glass Co Ltd
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Publication of WO2014073580A1 publication Critical patent/WO2014073580A1/fr
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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
    • C08G65/26—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 from cyclic ethers and other compounds
    • C08G65/2642—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 from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4866—Polyethers having a low unsaturation value
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7607—Compounds of C08G18/7614 and of C08G18/7657
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • C08G65/26—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 from cyclic ethers and other compounds
    • C08G65/2603—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 from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • 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
    • C08G65/26—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 from cyclic ethers and other compounds
    • C08G65/2696—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 from cyclic ethers and other compounds characterised by the process or apparatus used
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • 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
    • C08G2190/00—Compositions for sealing or packing joints

Definitions

  • the present invention relates to a method for producing a hydroxyl group-containing polyether.
  • the present invention also relates to a method for producing a hydrolyzable silyl group-containing polyether and a method for producing a urethane prepolymer using the method for producing a hydroxyl group-containing polyether of the present invention.
  • Hydroxyl group-containing polyether obtained by ring-opening addition of a cyclic ether compound to an initiator is used, for example, for reacting with a polyisocyanate compound to produce polyurethane such as polyurethane foam or urethane prepolymer, and hydrolyzable silyl group. It is used for the purpose of producing a hydrolyzable silyl group-containing polyether by reacting the containing compound. Hydroxyl group-containing polyethers and derivatives thereof are widely used for other applications such as surfactants and lubricants.
  • the hydrolyzable silyl group-containing polyether is also referred to as “modified silicone polymer”.
  • the hydroxyl group-containing polyether is generally produced by a method in which an initiator and a catalyst are charged into a reaction vessel, and a cyclic ether compound is successively supplied thereto to cause a ring-opening addition reaction.
  • a high molecular weight hydroxyl group-containing polyether particularly a hydroxyl group-containing polyether having a molecular weight of 15,000 or more is desired. Has been.
  • Alkali catalysts such as KOH are generally used for the production of a hydroxyl group-containing polyether, but there is a tendency that a certain amount of by-products are generated.
  • the molecular weight is 10,000 or more, the amount of by-products It is difficult to produce a high molecular weight body.
  • DMC catalyst double metal cyanide complex catalyst
  • Patent Document 1 discloses a method of producing a high molecular weight polyol having a low total unsaturation by ring-opening addition reaction of a cyclic ether compound with an initiator in the presence of a glyme-based DMC catalyst in the presence of a solvent.
  • the molecular weight of the polyols disclosed in the examples is up to 5,000.
  • a method for producing a high molecular weight hydroxyl group-containing polyether As a method for producing a high molecular weight hydroxyl group-containing polyether, a method in which a cyclic ether compound is subjected to a ring-opening addition reaction with an initiator in the presence of an organic solvent has been proposed.
  • a DMC catalyst is used, and a cyclic ether compound is subjected to ring-opening addition to an initiator in the presence of an organic solvent of 5 parts by weight or less with respect to the obtained hydroxyl group-containing polyether.
  • a method of manufacturing is disclosed.
  • the molecular weight of the hydroxyl group-containing polyether disclosed here is about 10,000, and no example of producing a hydroxyl group-containing polyether of 15,000 or more is described.
  • the present invention relates to a method for producing a hydroxyl group-containing polyether, a method for producing a modified silicone polymer, and a method for producing a urethane prepolymer, which can produce a hydroxyl group-containing polyether having a high molecular weight with a smaller molecular weight distribution.
  • the present invention includes the following [1] to [15].
  • a cyclic ether compound is subjected to a ring-opening addition reaction with an initiator having at least one hydroxyl group per molecule in the presence of a composite metal cyanide complex catalyst and the following polyoxyalkylene compound (Z), and the weight average molecular weight is A method for producing a 5,000 to 500,000 hydroxyl group-containing polyether,
  • the polyoxyalkylene compound (Z) is a compound having a polyoxyalkylene chain derived from an alkylene oxide and having no reactive group capable of undergoing a ring-opening addition reaction, and the weight average molecular weight of which is produced.
  • a method for producing a hydroxyl group-containing polyether which is a polyoxyalkylene compound smaller than the hydroxyl group-containing polyether.
  • the polyoxyalkylene compound (Z) is a hydroxyl group-containing polyoxyalkylene compound (z1) having a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms and having 1 to 3 hydroxyl groups.
  • the method for producing a hydroxyl group-containing polyether according to [3], which is a compound having a molecular weight of 100 to 2000 per terminal group, obtained by converting a hydroxyl group of [6] The method for producing a hydroxyl group-containing polyether according to any one of [3] to [5], wherein all of the terminal groups are methoxy groups.
  • the hydroxyl group-containing polyether has a weight average molecular weight of 15,000 to 500,000
  • the polyoxyalkylene compound (Z) has a hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) having a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms and having 1 to 3 hydroxyl groups.
  • [14] A step of producing a hydroxyl group-containing polyether by the production method according to any one of [1] to [11], The manufacturing method of the urethane prepolymer which has the process of making a polyisocyanate compound react with the obtained hydroxyl-containing polyether.
  • Hydrolysis characterized in that the urethane prepolymer obtained in [14] and having an isocyanate group is reacted with a compound having an active hydrogen-containing group capable of reacting with an isocyanate group and a hydrolyzable silyl group. For producing a reactive silyl group-containing polyether.
  • a hydroxyl group-containing polyether having a high molecular weight and a small molecular weight distribution can be produced.
  • a urethane prepolymer or a modified silicone polymer excellent in workability and physical properties can be produced using a hydroxyl group-containing polyether having a high molecular weight and a small molecular weight distribution.
  • a cyclic ether compound is opened to an initiator having at least one active hydrogen atom per molecule in the presence of a double metal cyanide complex catalyst and a polyoxyalkylene compound (Z).
  • This is a method for producing a hydroxyl group-containing polyether by a cycloaddition reaction.
  • the hydroxyl group-containing polyether in the present specification means polyether monool and polyether polyol.
  • the cyclic ether compound is a compound having a heterocycle composed of a carbon atom and one or two oxygen atoms, and the bond between the carbon atom and the oxygen atom is broken to open the ring.
  • a compound capable of causing a polymerization reaction that is, a ring-opening addition reaction
  • the cyclic ether compound is also referred to as a cyclic ether.
  • Hydroxyl-containing polyether having a polymer chain composed of a structural unit in which the cyclic ether is opened by a ring-opening addition reaction of the cyclic ether to an initiator having a hydroxyl group, and having a hydroxyl group at the terminal Produces.
  • the polyether monool has one hydroxyl group, and the polyether polyol has two or more hydroxyl groups.
  • the polyether chain in this specification refers to a structure in which structural units containing an ether bond are linked in a chain.
  • the ring-opening addition reaction may be simply referred to as polymerization.
  • the number of hydroxyl groups of the hydroxyl group-containing polyether obtained by such polymerization is equal to the number of hydroxyl groups of the initiator.
  • the average number of hydroxyl groups per molecule of the initiator mixture (sometimes simply referred to as the average number of hydroxyl groups) is one molecule of the resulting hydroxyl group-containing polyether.
  • the average number of hydroxyl groups per unit (sometimes simply referred to as the average number of hydroxyl groups).
  • the number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the hydroxyl group-containing polyether are obtained by gel permeation chromatography (GPC) using a polystyrene polymer as a reference. This is the so-called molecular weight in terms of polystyrene.
  • the hydroxyl value (OHV, unit is mgKOH / g) of the hydroxyl group-containing polyether in this specification is a value measured according to JIS K1557 (2007 edition).
  • the weight average molecular weight (Mw) of the hydroxyl group-containing polyether of the present invention is 5,000 to 500,000, preferably 10,000 to 500,000.
  • Mw weight average molecular weight
  • Mw of the hydroxyl group-containing polyether is 5,000 or more, the effect of suppressing the by-product by using the present invention can be sufficiently obtained, and when it is 500,000 or less, the viscosity in use can be kept low. Therefore, it is preferable.
  • the hydroxyl group-containing polyether of the present invention has a weight average molecular weight (Mw) of 15,000 to 500,000, more preferably 20,000 to 300,000, and particularly preferably 25,000 to 100,000.
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution of the hydroxyl group-containing polyether of the present invention is preferably less than 1.20. Since the lower limit of the molecular weight distribution is preferably as small as possible, it becomes difficult to produce.
  • the hydroxyl value of the hydroxyl group-containing polyether obtained by the production method of the present invention is preferably 11 mgKOH / g or less, more preferably 6 mgKOH / g or less, and particularly preferably 4 mgKOH / g or less.
  • the lower limit is preferably 0.22 mgKOH / g or more, more preferably 1 mgKOH / g or more, and further preferably 2 mgKOH / g or more in order to keep the viscosity of the hydroxyl group-containing polyether low.
  • the smaller the molecular weight per hydroxyl group the smaller the molecular weight distribution.
  • DMC catalyst Double metal cyanide complex catalyst
  • M 1 to M 3 are Metal
  • X is a halogen atom
  • L is an organic ligand
  • a, b, c, d, e, f, g, h, i are dependent on the valence of the metal, the coordination number of the organic ligand, etc. Numbers that can vary are shown separately.
  • M 1 or M 3 represents Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Mo (IV), Mo (VI), Al (III), Selected from the group consisting of V (V), Sr (II), W (IV), W (VI), Mn (II), Cr (III), Cu (II), Sn (II), and Pb (II) And at least one metal atom, preferably Zn (II) or Fe (II).
  • the Roman numeral in parentheses following the atomic symbol of the metal represents the valence, and so on.
  • M 1 and M 3 in one molecule may be the same as or different from each other. Preferably they are the same as each other.
  • M 2 is Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), Ni (II), V It is at least one metal atom selected from the group consisting of (IV) and V (V), and is preferably Co (III) or Fe (III).
  • X is a halogen atom.
  • L represents an organic ligand.
  • organic ligand As the organic ligand, alcohol, ether, ketone, ester, amine, amide and the like can be used, and alcohol is more preferable.
  • Preferred organic ligands are water-soluble, and specific examples include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, N, N-dimethylacetamide, One selected from ethylene glycol dimethyl ether (also referred to as glyme), diethylene glycol dimethyl ether (also referred to as diglyme), triethylene glycol dimethyl ether (also referred to as triglyme), ethylene glycol mono-tert-butyl ether, iso-propyl alcohol, and dioxane.
  • ethylene glycol dimethyl ether also referred to as glyme
  • diethylene glycol dimethyl ether also referred to as diglyme
  • triethylene glycol dimethyl ether also
  • Dioxane may be 1,4-dioxane or 1,3-dioxane, and 1,4-dioxane is preferred.
  • Particularly preferred organic ligands are tert-butyl alcohol, tert-pentyl alcohol, ethylene glycol mono-tert-butyl ether, or a combination of tert-butyl alcohol and ethylene glycol mono-tert-butyl ether. When such an organic ligand is used, a particularly high catalytic activity is obtained, which is preferable in terms of narrowing the molecular weight distribution of the hydroxyl group-containing polyether.
  • such a DMC catalyst has the same formula (1) in which M 1 and M 3 are the same as each other, Zn (II) or Fe (II), and M 2 is Co (III) or Fe (III).
  • X is halogen
  • L is tert-butyl alcohol or ethylene glycol mono-tert-butyl ether
  • M 1 and M 3 are Zn (II)
  • M 2 is Co (III)
  • X is Potassium and L in which tert-butyl alcohol is used are particularly preferred because by-products can be reduced.
  • the manufacturing method of a DMC catalyst is not specifically limited, A well-known method can be used suitably.
  • an organic ligand is coordinated to a reaction product obtained by reacting a metal halide salt with a cyanometalate acid and / or an alkali metal cyanometalate in an aqueous solution.
  • a method in which a solid component is separated and the separated solid component is further washed with an organic ligand aqueous solution, or (ii) a metal halide salt, a cyanometallate and / or an alkali metal cyanometa in an organic ligand aqueous solution The reaction product (solid component) obtained by reacting with the rate is separated, and the cake (solid component) obtained by the method of washing the separated solid component with an organic ligand aqueous solution is filtered and further separated.
  • the method of making it dry can be mentioned.
  • the metal constituting the cyano metalate of the alkali metal cyano metalate used in the production of the DMC catalyst corresponds to M 2 in the formula (1).
  • H 3 [Co (CN) 6 ], Na 3 [Co (CN) 6 ], or K 3 [Co (CN 6 ] is preferred, and Na 3 [Co (CN) 6 ] or K 3 [Co (CN) 6 ] is particularly preferred.
  • the amount of the DMC catalyst used in the present invention is set to a required amount or more according to the target molecular weight of the hydroxyl group-containing polyether to be produced.
  • the hydroxyl group-containing polyether is used without removing the DMC catalyst. Therefore, the production efficiency of the hydroxyl group-containing polyether can be increased.
  • the total amount of metals (for example, Zn and Co) derived from the DMC catalyst contained in the hydroxyl group-containing polyether at the end of the polymerization reaction is 1 to 30 ppm with respect to 100 parts by mass of the hydroxyl group-containing polyether. It is preferable that the amount is 10 ppm or less, particularly preferably because excellent storage stability can be obtained when a urethane prepolymer or a hydrolyzable silyl group-containing polyether is obtained. When the total amount of metals derived from the DMC catalyst is 30 ppm or less, removal of the remaining catalyst from the obtained hydroxyl group-containing polyether tends to be unnecessary.
  • the initiator in the present invention is a compound having at least one hydroxyl group in one molecule. Specifically, a compound having 1 to 12 hydroxyl groups and a number average molecular weight (Mn) of 18 to 20,000 is preferable. In addition, when it is comprised only from the molecule
  • the initiator include monovalent compounds such as methanol, ethanol, 2-propanol, n-butanol, iso-butanol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, and oleyl alcohol.
  • Alcohols water; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexane
  • Dihydric alcohols such as diol and 1,4-cyclohexanediol; glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
  • Trihydric or higher polyhydric alcohols such as glucose, sorbitol, dextrose, fructose, sucrose, methylglucoside, trehalose or derivatives thereof; phenols such as bisphenol A, bisphenol F, bisphenol S, novolac, resole, resorcin, Examples include fatty acid triglycerides having a hydroxyl group such as castor oil and castor oil condensate, and condensates thereof. These compounds can be used alone or in combination of two or more.
  • a hydroxyl group-containing polyether or polyoxytetramethylene glycol obtained by polymerizing alkylene oxide with these compounds by a known method can also be used as an initiator.
  • These compounds having a polyether chain preferably have a number average molecular weight (Mn) of 300 to 20,000 and a hydroxyl group number of 1 to 12 per molecule.
  • the hydroxyl value of these compounds is preferably 187 mgKOH / g or less.
  • the compound having a hydroxyl value of 30 mgKOH / g or more higher than the hydroxyl value of the target hydroxyl group-containing polyether is preferable, and a compound having a hydroxyl value of 40 mgKOH / g or more is particularly preferable.
  • the number average molecular weight (Mn) of the initiator is preferably 300 or more, more preferably 300 to 10,000, more preferably 600 in that the time until the polymerization reaction starts in the presence of a DMC catalyst can be easily shortened. ⁇ 5,000 is particularly preferred.
  • an initiator having a number average molecular weight (Mn) of 20,000 or less is used, the viscosity is not too high when the initiator is charged into the reaction vessel, which is preferable.
  • the number average molecular weight (Mn) of the initiator is lower than the number average molecular weight (Mn) of the hydroxyl group-containing polyether obtained by using the initiator.
  • the difference between the number average molecular weight of the initiator and the number average molecular weight of the hydroxyl group-containing polyether obtained by using the initiator is preferably 500 or more, and 1,000 or more. Particularly preferred.
  • the difference in number average molecular weight is 500 or more, the amount of polymerization in the presence of the DMC catalyst increases, so that it is easy to obtain the merit that the amount of by-products can be reduced by polymerization in the presence of the DMC catalyst.
  • the number average molecular weight of the hydroxyl group-containing polyether to be produced is 1.5 times or more and 30 times or less of the number average molecular weight of the initiator used for producing it in relation to the capacity of the stirring tank. Is preferred.
  • the production method of the present invention by introducing the polyoxyalkylene compound (Z) together with the initiator before the reaction for producing the hydroxyl group-containing polyether, it is difficult to be limited by the capacity of the stirring tank, and the number of initiators It is easy to produce a hydroxyl group-containing polyether having an average molecular weight of 30 times or more.
  • the number of hydroxyl groups in the initiator is preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 4.
  • an initiator having a hydroxyl number of not more than the upper limit of the above range is used, the molecular weight distribution of the resulting hydroxyl group-containing polyether tends to be narrow.
  • the average number of hydroxyl groups per molecule is preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 4. preferable.
  • the hydroxyl group number of the hydroxyl group-containing polyether is preferably 2 to 8, particularly preferably 2 to 6.
  • an initiator for producing such a hydroxyl group-containing polyether an initiator having 2 to 8 hydroxyl groups, particularly 2 to 6 is preferred.
  • the average number of hydroxyl groups in the initiator is preferably 1.5 to 8, and more preferably 1.8 to 6.
  • cyclic ether a compound having an epoxy ring, an oxetane ring or an oxolane ring is preferable.
  • a compound having one epoxy ring is preferable.
  • an alkylene oxide is preferable.
  • the compound having one epoxy ring other than alkylene oxide include halogen-containing alkylene oxide, cycloalkene oxide such as cyclopentene oxide and cyclohexene oxide, aryl-substituted alkylene oxide such as styrene oxide, glycidyl compound such as glycidyl alkyl ether and glycidyl alkyl ester, Etc.
  • the compound having an oxetane ring includes oxetane
  • the compound having an oxolane ring includes tetrahydrofuran.
  • an alkylene oxide is preferable, and an alkylene oxide having 2 to 20 carbon atoms is particularly preferable.
  • alkylene oxide used in the present invention include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, and ⁇ -olefin oxide having 5 to 20 carbon atoms. One or more selected from the group consisting of these can be used.
  • alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide are preferable, and ethylene oxide and propylene oxide are particularly preferable.
  • the cyclic ether can be determined depending on the target physical properties of the final product using a hydroxyl group-containing polyether as a raw material. However, in the case of using an adhesive, a sealing agent or the like, it is preferable to use only propylene oxide from the viewpoint of water resistance.
  • the cyclic ether may be used alone or in combination of two or more.
  • a mixture of two or more kinds of cyclic ethers may be subjected to ring-opening addition polymerization to form a random polymer chain, and two or more kinds of cyclic ethers may be separated. May be sequentially subjected to ring-opening addition polymerization to form a block polymer chain. Further, formation of random polymer chains and formation of block polymer chains may be combined.
  • the types of cyclic ethers used in the initial step (a) and the polymerization step (b) may be different.
  • This kind of cyclic ether means not only the kind of cyclic ether but also cyclic ethers having different mixing ratios in the case of a mixture of two or more kinds of cyclic ether compounds.
  • the polyoxyalkylene compound (Z) in the present invention is a compound having a polyoxyalkylene chain derived from an alkylene oxide and having no reactive group capable of undergoing a ring-opening addition reaction with the cyclic ether compound.
  • the polyoxyalkylene compound (Z) converts the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) into an organic group that is inert to the ring-opening addition reaction of a cyclic ether used in the production of the desired hydroxyl group-containing polyether. It is preferable that it is a compound obtained by this.
  • “Converting to an inactive group” means that the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound is converted to a group having no reactive group that the cyclic ether can undergo ring-opening addition.
  • the weight average molecular weight of the hydroxyl group-containing polyoxyalkylene compound (z1) is smaller than the target hydroxyl group-containing polyether.
  • the difference between the molecular weight of the hydroxyl group-containing polyoxyalkylene compound (z1) and the molecular weight of the target hydroxyl group-containing polyether is preferably 5,000 or more, and more preferably 10,000 or more.
  • the hydroxyl group-containing polyoxyalkylene compound means a polyoxyalkylene monool or a polyoxyalkylene polyol.
  • the polyoxyalkylene chain in the hydroxyl group-containing polyoxyalkylene compound (z1) is composed of a chain of oxyalkylene groups formed by a ring-opening addition reaction of alkylene oxide.
  • the polyoxyalkylene compound (Z) has a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms, and the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) having 1 to 3 hydroxyl groups.
  • a compound obtained by converting into an organic group inactive to the ring-opening addition reaction of a cyclic ether used for the production of the target hydroxyl group-containing polyether is preferable.
  • Such inactive organic group conversion methods include conversion to an alkoxy group with an alkyl halide (alkoxylation), monocarboxylic acid (such as acetic acid), monocarboxylic acid anhydride (such as acetic anhydride), acyl halide (salt chloride) Conversion to an acyloxy group (esterification) with a monocarboxylic acid such as acetyl) or a reactive derivative thereof (esterification), urethanization with a monoisocyanate compound, halogenation with phosphorus trichloride, and the like, but is not limited thereto. These methods may use two or more conversion methods in combination.
  • the number of carbon atoms of the alkyl halide, monocarboxylic acid, or monoisocyanate compound used for the conversion is preferably 8 or less.
  • a method of converting a hydroxyl group to an alkoxy group by alkoxylation, or converting a hydroxyl group to an acyloxy group (—O—C (O) —R ′; R ′ is an alkyl group, etc.) by esterification with a monocarboxylic acid or a reactive derivative thereof. is preferred.
  • the conversion method is preferably at least one selected from the group consisting of alkoxylation and esterification in view of the influence during production of the hydroxyl group-containing polyether and production efficiency.
  • each hydroxyl group may be converted into a different inert organic group. In this case, it is preferable that a part of the hydroxyl group is converted into an alkoxy group and the other hydroxyl group is converted into an acyl group and / or an acyloxy group.
  • the total number of moles of esterified terminal hydroxyl groups is 50 mol% or less with respect to the number of moles of alkoxylated terminal hydroxyl groups. From the viewpoint of hydrolysis resistance, it is most preferable to convert all hydroxyl groups of the hydroxyl group-containing polyoxyalkylene compound (z1) into alkoxy groups.
  • the terminal group of the polyoxyalkylene compound (Z) is an alkoxy group (—OR 10 , R 10 is an alkyl group)
  • the number of carbon atoms of the alkoxy group is preferably 1-8. 4 is more preferable, and 1 to 2 is more preferable.
  • the terminal group of the polyoxyalkylene compound (Z) is an acyloxy group
  • the acyloxy group preferably has 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms, and still more preferably 2.
  • the alkoxy group has 8 or less carbon atoms in that the effect of narrowing the molecular weight by producing the hydroxyl group-containing polyether in the presence of the polyoxyalkylene compound (Z) can be sufficiently obtained.
  • the number of carbon atoms of 4 or less is preferable because the oxyalkylene group content in the polyoxyalkylene compound (Z) is high.
  • it is preferable that all of the alkoxy groups present at the terminals of the polyoxyalkylene compound (Z) are methoxy groups because the oxyalkylene group content in the polyoxyalkylene compound is high. The higher the oxyalkylene group content, the better the compatibility with the hydroxyl group-containing polyether.
  • aromatic, alicyclic or aliphatic dicarboxylic acids represented by dioctyl phthalate, diisononyl phthalate, dibutyl phthalate, dioctyl adipate, dioctyl hexahydrophthalate and the like, which are known as plasticizers for general resins
  • An ester compound of an alcohol is not preferred because it may be different from the polyoxyalkylene compound in the possibility of side reactions during production and in polarity with a hydroxyl group-containing polyether. .
  • the conversion rate when converting the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) to the inactive organic group is not necessarily 100%. Specifically, it is preferable to convert 50 mol% or more of the hydroxyl group into an active organic group, more preferably 90 mol% or more, and particularly preferably 95 mol% or more. The higher conversion rate is preferable in that alkylene oxide addition to the unconverted hydroxyl group of the polyoxyalkylene compound (Z) is less likely to occur during the production of the hydroxyl group-containing polyether.
  • the presence of the polyoxyalkylene compound (Z) in the reaction solution when producing a high molecular weight hydroxyl group-containing polyether using a DMC catalyst makes the molecular weight distribution narrower even if the molecular weight is equivalent.
  • a hydroxyl group-containing polyether is obtained.
  • both the hydroxyl group-containing polyether as a reaction product and the polyoxyalkylene compound (Z) have a polyether chain, thereby improving the compatibility of both in the reaction solution. As a result, it is considered that the uniformity of the reaction becomes good and the molecular weight distribution becomes smaller.
  • the polyether chain contained in the hydroxyl group-containing polyether and the polyoxyalkylene chain contained in the polyoxyalkylene compound (Z) are preferably polyether chains derived from the same alkylene oxide. .
  • the terminal having no hydroxyl group in the polyoxyalkylene chain may be an inert organic group such as an alkoxy group or an alkoxycarbonyl group.
  • a polyoxyalkylene monool obtained by polymerizing a cyclic ether with an alkane monool using an alkane monool as an initiator has an alkoxy group, and is similarly obtained by polymerizing a cyclic ether with a monocarboxylic acid.
  • the polyoxyalkylene monool has an acyloxy group.
  • the inactive terminal group of the polyoxyalkylene compound (Z) is a hydroxyl group-containing polyoxyalkylene compound (z1) other than the inactive organic group generated by inactivating the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1). It shall contain the inert organic groups it had. Therefore, the terminal group of the polyoxyalkylene compound (Z) refers to both the inactive organic group possessed by the hydroxyl group-containing polyoxyalkylene compound (z1) and the inert organic group obtained by converting the hydroxyl group. means. Therefore, the number of end groups of the polyoxyalkylene compound (Z) is 2 or more.
  • the hydroxyl group-containing polyoxyalkylene compound (z1) obtained by using a hydroxyl group-containing compound having one or two hydroxyl groups as an initiator is a linear structure compound having one or two hydroxyl groups.
  • the polyoxyalkylene compound (Z) obtained from the hydroxyl group-containing polyoxyalkylene compound (z1) is similarly a compound having a structure. Regardless of the difference in the number of hydroxyl groups in the hydroxyl group-containing polyoxyalkylene compound (z1), the number of terminal groups of these compounds having a linear structure is 2 in the present invention.
  • the resulting hydroxyl group-containing polyoxyalkylene compound (z1) has the same number of end groups as the number of hydroxyl groups in the initiator.
  • the molecular weight per terminal group of the polyoxyalkylene compound (Z) is preferably from 100 to 2,000, more preferably from 100 to 1,000, and even more preferably from 150 to 800.
  • the molecular weight is 100 or more, the volatility of the polyoxyalkylene compound (Z) tends to be sufficiently low. If it is 2,000 or less, the dilution effect is increased. Particularly when the viscosity is 1,000 or less, the viscosity of the reaction solution tends to be sufficiently low.
  • the hydroxyl group-containing polyoxyalkylene compound (z1) used for the synthesis of the polyoxyalkylene compound (Z) is obtained by ring-opening addition of an alkylene oxide having 2 to 4 carbon atoms to an initiator having 1 to 3 hydroxyl groups.
  • the resulting hydroxyl group-containing polyoxyalkylene compound is preferred.
  • the initiator among the compounds that can be used as the initiator of the above-mentioned hydroxyl group-containing polyether, those having no polyoxyalkylene chain and having 1 to 3 hydroxyl groups can be used.
  • the polyoxyalkylene chain is a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms
  • the initiator having 1 to 3 hydroxyl groups can be used as an initiator for synthesizing the hydroxyl group-containing compound (z1), the hydroxyl group-containing polyoxyalkylene compound (z1), or the hydroxyl group-containing polyoxyalkylene compound (z1) itself.
  • the molecular weight of the initiator for synthesizing the hydroxyl group-containing polyoxyalkylene compound (z1) is 18 or more, preferably 32 or more.
  • the upper limit of the molecular weight of the initiator for synthesizing the hydroxyl group-containing polyoxyalkylene compound (z1) is preferably 1,000 or less and more preferably 300 or less because the oxyalkylene group content in the hydroxyl group-containing polyoxyalkylene compound (z1) is high. preferable.
  • the initiator having 1 hydroxyl group examples include methanol, ethanol, 2-propanol, n-butanol, iso-butanol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, and oleyl alcohol.
  • Monohydric alcohols are preferred.
  • an alkoxy group (R 11 O—) derived from the monohydric alcohol is present at the end group of the resulting polyoxyalkylene compound (Z). Exists.
  • the monohydric alcohol (R 11 —OH) as the initiator preferably has 1 to 4 carbon atoms, and more preferably 1.
  • a compound obtained by alkoxylating a terminal hydroxyl group of polyoxyalkylene monool obtained by ring-opening addition of alkylene oxide to an initiator having one hydroxyl group is a compound having alkoxy groups at both ends of one molecule. It becomes.
  • Examples of the initiator having 2 hydroxyl groups include water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4- Dihydric alcohols such as butanediol, 1,6-hexanediol and 1,4-cyclohexanediol are preferred.
  • water, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol having a relatively low molecular weight of the initiator are more preferable, and propylene glycol and dipropylene glycol are particularly preferable in that the ether group content can be increased.
  • the initiator having 3 hydroxyl groups trihydric alcohols such as glycerin and trimethylolpropane are preferable.
  • glycerin having a relatively low molecular weight of the initiator is particularly preferred in that the ether group content can be increased.
  • the initiator having 4 or more hydroxyl groups include tetrahydric or higher polyhydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, diglycerin, polyglycerin; glucose, sorbitol, dextrose, fructose, sucrose, methyl Saccharides such as glucoside and trehalose or derivatives thereof are preferred.
  • the alkylene oxide used for the synthesis of the hydroxyl group-containing polyoxyalkylene compound (z1) is preferably an alkylene oxide having 2 to 4 carbon atoms.
  • the alkylene oxide used in the synthesis of the hydroxyl group-containing polyoxyalkylene compound (z1) is more preferably the same alkylene oxide as the cyclic ether used in the production of the hydroxyl group-containing polyether, specifically, ethylene oxide, propylene oxide, One or more selected from the group consisting of 1,2-butylene oxide and 2,3-butylene oxide are used. Among these, it is preferable to use ethylene oxide and / or propylene oxide in that the oxyalkylene group content can be increased.
  • the hydroxyl group-containing polyether when used as an adhesive or a sealing agent, the hydroxyl group-containing group is contained.
  • the step of obtaining the hydroxyl group-containing polyoxyalkylene compound (z1) by ring-opening addition of alkylene oxide to the initiator can be carried out by a known method.
  • a catalyst is used.
  • a catalyst is not specifically limited, A well-known catalyst can be used suitably.
  • An alkali catalyst such as KOH may be used, and the above-mentioned DMC catalyst may be used.
  • the step of alkoxylating the terminal hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) can be carried out by a known method.
  • the hydroxyl group (—OH) of the hydroxyl group-containing polyoxyalkylene compound (z1) is alcoholated by a known method to form —OM (M is an alkali metal), and then an alkyl halide (R 10 —X: X is a halogen atom) ) Can be substituted with an alkoxy group (—OR 10 ).
  • the halogen atom (X) of the alkyl halide is preferably a chlorine atom (Cl) from the viewpoint of reaction efficiency in the process.
  • the terminal hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) is esterified, it can be similarly performed by a known method.
  • the polyoxyalkylene compound (Z) is preferably used in an amount of 10 to 300 parts by mass with respect to 100 parts by mass of the hydroxyl group-containing polyether to be produced.
  • the amount of hydroxyl group-containing polyether produced corresponds to the total amount of initiator and reacted cyclic ether.
  • the amount of the polyoxyalkylene compound (Z) used is less than 10 parts by mass, the effect of reducing the viscosity of the reaction solution due to the presence of the polyoxyalkylene compound (Z) and the effect of narrowing the molecular weight distribution of the resulting hydroxyl group-containing polyether are obtained.
  • the amount exceeds 300 parts by mass, the proportion of the polyoxyalkylene compound (Z) is too high, and it is difficult to obtain the desired physical properties of the modified silicone polymer or urethane prepolymer produced using the hydroxyl group-containing polyether.
  • the amount is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and still more preferably 15 to 40 parts by mass.
  • the polyoxyalkylene compound (Z) is added to the reaction system at a time until the polymerization step of the hydroxyl group-containing polyether is completed, although it can be added in batches, it is preferable to add the whole amount together with the initiator and the DMC catalyst before starting the reaction.
  • the polyoxyalkylene compound (Z) has a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms, and the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) having 1 to 3 hydroxyl groups is alkoxylated.
  • the compound is preferably a
  • the molecular weight per terminal group of the polyoxyalkylene compound (Z) is preferably from 100 to 1,000, more preferably from 150 to 800.
  • the amount of the polyoxyalkylene compound (Z) used is preferably 10 to 80 parts by weight, more preferably 10 to 50 parts by weight, and further preferably 15 to 40 parts by weight with respect to 100 parts by weight of the hydroxyl group-containing polyether produced. preferable.
  • a preferred method for producing the hydroxyl group-containing polyether of the present invention is a part of a cyclic ether that causes the initiator to undergo a ring-opening addition reaction in a reaction solution containing an initiator and a DMC catalyst (hereinafter sometimes referred to as a cyclic ether for an initial step). )) In an amount of 5 to 20 parts by mass with respect to 100 parts by mass of the initiator contained in the reaction solution, and after the initial step (a), the cyclic ether And a polymerization step (b) in which a polymerization reaction is carried out by additionally supplying.
  • This method is preferably carried out batchwise, but may be a continuous method. Specifically, it can be carried out as follows.
  • the mixing means in the initial step (a) of the production method of the present invention is not particularly limited as long as it is a means capable of sufficiently mixing the DMC catalyst and the initiator (including other components used as necessary).
  • a stirring means is used as the mixing means.
  • Specific examples of the stirring means in the initial step (a) include stirring blades, bubbling with an inert gas such as nitrogen gas, stirring by electromagnetic waves, ultrasonic waves, and the like, but stirring by stirring blades is preferable.
  • the shape and material of the pressure-resistant reaction vessel used in the initial step (a) are not particularly limited, but the material is preferably a heat-resistant glass or metal vessel.
  • an initiator, a DMC catalyst, and preferably a polyoxyalkylene compound (Z) are supplied into a pressure-resistant reaction vessel, and before supplying the cyclic ether for the initial step, the gas phase in the pressure-resistant reaction vessel is nitrogen or polymerized. Substitution with a cyclic ether is preferred. Thereby, oxygen in the reaction solution is removed.
  • the reaction liquid is heated while being stirred, and then heated, and then the initial stage cyclic ether is supplied and reacted in a state where the temperature of the reaction liquid is at a predetermined initial temperature.
  • the initial temperature in this specification refers to the temperature of the reaction liquid at the start of the supply of the cyclic ether for the initial step.
  • the initial temperature of the reaction solution is 120 to 165 ° C, preferably 125 to 150 ° C, particularly preferably 130 to 140 ° C.
  • the initial temperature is not less than the lower limit of the above range, the catalytic activity is remarkably improved, and when it is not more than the upper limit of the above range, there is no fear that the components contained in the reaction solution are thermally decomposed.
  • the temperature of the reaction liquid is increased to the initial temperature while stirring, and the supply of the cyclic ether is started in a state where the temperature of the reaction liquid is maintained. For example, when the reaction liquid reaches a predetermined initial temperature, the heating is stopped, and the supply of cyclic ether is started before the temperature of the reaction liquid starts to drop.
  • the cyclic ether for the initial step is a cyclic ether that is polymerized to an initiator in the production of a hydroxyl group-containing polyether. If the supply amount of the cyclic ether for the initial step is too small, the activation of the DMC catalyst becomes insufficient, and if it is too large, a runaway reaction occurs. Therefore, the amount is 5 to 20 parts by mass with respect to 100 parts by mass of the initiator contained in the reaction solution. 8 to 15 parts by mass is preferable, and 10 to 12 parts by mass is particularly preferable.
  • the cyclic ether for the initial process is supplied in a state where the pressure-resistant reaction vessel is sealed.
  • the internal pressure of the pressure-resistant reaction vessel rises as the unreacted cyclic ether is vaporized.
  • the DMC catalyst is initially activated, a reaction between the cyclic ether and the initiator occurs, and the internal pressure of the pressure-resistant reaction vessel begins to decrease, and at the same time, the temperature of the reaction solution rises due to reaction heat.
  • the internal pressure of the pressure-resistant reaction vessel is reduced to the same level as before the supply, and the temperature of the reaction liquid is not increased by the reaction heat.
  • the initial step (a) in the present specification refers to a step from the start of the supply of the cyclic ether for the initial step to the end of the reaction of the cyclic ether. Completion of the reaction of the cyclic ether for the initial step can be confirmed by a decrease in the internal pressure of the pressure resistant reaction vessel. That is, the end of the initial step (a) refers to the time when the internal pressure of the pressure-resistant reaction vessel is reduced to the same level as before the cyclic ether supply.
  • Polymerization step (b) After completion of the initial step, the cyclic ether is newly supplied to the reaction system, the temperature of the reaction solution is adjusted to a predetermined polymerization temperature, and the polymerization reaction is carried out with stirring to obtain the target hydroxyl group-containing polyether.
  • a pressure-resistant autoclave vessel As the heat-resistant reaction vessel used in the polymerization step (b), a pressure-resistant autoclave vessel is preferably used. The material is not particularly limited.
  • the reaction vessel the vessel used in the initial step (a) can be used as it is.
  • the initial step when the product of the initial step (a) (a compound obtained by reacting a cyclic ether with an initiator) and the cyclic ether are reacted in the presence of a DMC catalyst, the initial step is performed. As in (a), it is preferable to stir the reaction solution.
  • a large blade such as a Max Blend blade or a full zone blade is preferable.
  • dispersers, homomixers, colloid mills, nauter mixers, and the like used for emulsification and dispersion can also be used.
  • These stirring methods may be used in combination. When using a general stirring method using a stirring blade, increase the rotation speed of the stirring blade as much as possible so long as the gas in the gas phase of the reaction vessel is not taken into the reaction liquid and the stirring efficiency does not decrease. It is preferable to do.
  • the polymerization method in the polymerization step (b) is preferably a batch method, but the addition of a mixture containing the cyclic ether and the product of the initial step (a) and the DMC catalyst and the hydroxyl group which is the product of the polymerization step (b) It can also be carried out by a continuous process in which the contained polyether is extracted simultaneously.
  • the use of the polyoxyalkylene compound (Z) can reduce the viscosity of the entire system, and therefore, when the average molecular weight of the initiator is 300 or less, the continuous method is preferable because of high productivity.
  • the temperature of the reaction liquid (polymerization temperature) when the cyclic ether is reacted in the polymerization step (b) is preferably 125 to 180 ° C, particularly preferably 125 to 160 ° C.
  • the polymerization temperature is not less than the lower limit of the above range, an appropriate reaction rate can be obtained, and the remaining amount of unreacted product in the final product can be lowered.
  • the high activity of a DMC catalyst is appropriately maintained as it is below the upper limit of the said range, and molecular weight distribution can be made small.
  • the feed rate of the cyclic ether in the polymerization step (b) is preferably as slow as possible because the molecular weight distribution of the resulting polymer can be narrowed. However, it is preferable to compare these because the production efficiency decreases.
  • a specific supply rate is preferably 1 to 200% by mass / hour with respect to the total mass of the hydroxyl group-containing polyether planned as the final product. The supply rate during the polymerization reaction may be changed gradually.
  • a neutralization method using an organic acid such as lactic acid, succinic acid, adipic acid, or acetic acid or a salt thereof, or an inorganic acid such as sulfuric acid, nitric acid, or hydrochloric acid, or a method that uses a neutralization method and an adsorption method together can be used.
  • the alkali metal catalyst can be similarly deactivated and removed.
  • a composition containing the target hydroxyl group-containing polyether and a polyoxyalkylene compound (Z) is obtained.
  • the composition contains a polyoxyalkylene compound (Z)
  • the viscosity is lowered, and therefore, it is preferable in terms of easy handling when used as a raw material for a urethane prepolymer or a modified silicone polymer.
  • a stabilizer may be added to the composition as necessary in order to prevent deterioration during long-term storage.
  • stabilizer examples include hindered phenolic antioxidants such as BHT (dibutylhydroxyl toluene) and octadecyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.
  • BHT dibutylhydroxyl toluene
  • octadecyl 3,5-di-tert-butyl-4-hydroxyphenyl
  • the polyoxyalkylene compound (Z) is contained in the reaction solution when producing a high molecular weight hydroxyl group-containing polyether using a DMC catalyst, as shown in the Examples below.
  • a hydroxyl group-containing polyether having a narrower molecular weight distribution can be obtained even if the molecular weight is the same.
  • the use of the polyoxyalkylene compound (Z) has a greater effect of reducing the molecular weight distribution than when an organic solvent is used instead of the polyoxyalkylene compound (Z).
  • an ester compound having an aromatic ring is used instead of the polyoxyalkylene compound (Z)
  • the effect of reducing the molecular weight distribution cannot be obtained.
  • the polyoxyalkylene compound (Z) is used in addition to the polyoxyalkylene compound (Z) in addition to the effect of reducing the molecular weight distribution due to the reduced viscosity of the reaction solution. It is thought that having a chain contributes to the reduction of the molecular weight distribution.
  • the hydroxyl group-containing polyether as a reaction product and the polyoxyalkylene compound (Z) both have a polyether chain (polyoxyalkylene chain), thereby improving the compatibility of the two in the reaction solution. As a result, it is considered that the uniformity of the reaction becomes good and the molecular weight distribution becomes smaller.
  • the reaction is not affected when a hydroxyl group-containing polyether is used as a raw material for a urethane prepolymer or a modified silicone polymer.
  • the hydroxyl group-containing polyether obtained by the production method of the present invention can be made into various polyurethane products by reacting with a polyisocyanate compound and optionally a chain extender.
  • the number of hydroxyl groups in the hydroxyl group-containing polyether used for the polyurethane raw material is preferably 2 to 8.
  • the hydroxyl group-containing polyether obtained by the production method of the present invention can be used as a polyol for flexible polyurethane foam. In the production of flexible polyurethane foams, particularly when the hydroxyl group-containing polyether has a high molecular weight and a small molecular weight distribution, good foam appearance, physical properties and vibration characteristics are easily obtained.
  • the hydroxyl group-containing polyether obtained by the production method of the present invention is a functional oil agent such as grease base oil, compressor oil, rolling oil, gear oil, metalworking oil, traction drive oil, engine oil, and drilling oil; Alternatively, it can be used as a surfactant or the like, or as a raw material thereof. In these applications, particularly when the hydroxyl group-containing polyether has a high molecular weight and a small molecular weight distribution, improvement in lubricity, detergency and life can be expected.
  • the hydroxyl group-containing polyether obtained by the production method of the present invention can also be used as a raw material for the modified silicone polymer. Moreover, it can be made to react with polyisocyanate to make a urethane prepolymer.
  • the modified silicone polymer and urethane prepolymer can be produced by the method described below.
  • the modified silicone polymer and the urethane prepolymer can be suitably used as a curing component of the curable composition for a sealing material.
  • the modified silicone polymer and urethane prepolymer constituting the curing component have a high molecular weight and a small molecular weight distribution, the curability is improved particularly including the inside of the sealing material, and the viscosity Therefore, workability is improved. Furthermore, since the molecular weight is uniform, the mechanical properties and durability after curing are excellent.
  • the hydrolyzable silyl group-containing polyether in the present invention has a structure in which the hydrolyzable silyl group represented by the following formula (1) is introduced to the end of the hydroxyl group-containing polyether via a linking group. is there.
  • the modified silicone polymer refers to this hydrolyzable silyl group-containing polyether.
  • Examples of the hydrolyzable group as X in the formula (1) include a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, a ketoximate group, and a hydride group.
  • the number of carbon atoms of the hydrolyzable group having a carbon atom is preferably 6 or less, and particularly preferably 4 or less.
  • X is preferably a lower alkoxy group having 4 or less carbon atoms, particularly preferably a methoxy group, an ethoxy group, a propoxy group or a propenyloxy group.
  • R 1 in formula (1) is preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group. Particularly preferred are methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, phenyl group and the like.
  • the hydrolyzable silyl group-containing polyether in the present invention has a step of producing a hydroxyl group-containing polyether by the production method of the present invention and a step of introducing a hydrolyzable silyl group into the molecular terminal of the hydroxyl group-containing polyether. It can be manufactured by the method.
  • a method for introducing a hydrolyzable silyl group into the molecular terminal of the hydroxyl group-containing polyether a known method can be used. For example, the following methods (i) to (iv) can be used.
  • a hydrolyzable silyl group can be introduced by producing a hydroxyl group-containing polyether, introducing an olefin group at the end thereof, and then reacting the hydrosilyl compound represented by the following formula (2).
  • R 1 , X and a are the same as above.
  • a method for introducing an olefin group into a hydroxyl group-containing polyether for example, a method of reacting a compound having a functional group that reacts with a hydroxyl group and an olefin group with the hydroxyl group of the hydroxyl group-containing polyether can be used.
  • a method in which a hydroxyl group is converted to an alkenyloxy group by alcoholating the hydroxyl group and reacting it with a halogenated alkene for example, allyl chloride
  • a hydroxyl group-containing polyether is produced and reacted with a polyisocyanate group to obtain an isocyanate-terminated urethane prepolymer, and then an active hydrogen-containing group capable of reacting with an isocyanate group such as an amino group.
  • a hydrolyzable silyl group can be introduced by reacting with a compound having a hydrolyzable silyl group represented by the formula (1).
  • a hydrolyzable silyl group can be introduced by reacting a W group of a silicon compound represented by the following formula (4) with an isocyanate group of a urethane prepolymer having an isocyanate group at a terminal, which will be described later.
  • R 1 , X and a are the same as above
  • R 2 is a divalent organic group
  • W is an active hydrogen selected from a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary). It is a containing group.
  • the method for producing a urethane prepolymer of the present invention includes a step of producing a hydroxyl group-containing polyether by the production method of the present invention, and a urethane having an isocyanate group or a hydroxyl group at the terminal by reacting the hydroxyl group-containing polyether with a polyisocyanate compound. A step of obtaining a prepolymer.
  • a urethane prepolymer having an isocyanate group at the terminal is obtained, and by reacting the hydroxyl group in an excess ratio of the hydroxyl group, the terminal has a hydroxyl group.
  • a urethane prepolymer is obtained. This step can be performed using a known method.
  • Hydrolyzable silyl group-containing polyether from the urethane prepolymer by a method comprising a step of producing a urethane prepolymer by the production method of the present invention and a step of introducing a hydrolyzable silyl group into the molecular terminal of the urethane prepolymer.
  • a method comprising a step of producing a urethane prepolymer by the production method of the present invention and a step of introducing a hydrolyzable silyl group into the molecular terminal of the urethane prepolymer.
  • polyisocyanate compound examples include aromatic poly acrylates such as naphthalene-1,5-diisocyanate, polyphenylene polymethylene polyisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate.
  • aromatic poly acrylates such as naphthalene-1,5-diisocyanate, polyphenylene polymethylene polyisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate.
  • Isocyanates Aralkyl polyisocyanates such as xylylene diisocyanate and tetramethylxylylene diisocyanate; Aliphatic polyisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, 2,4,4-trimethyl-hexamethylene diisocyanate An alicyclic polyisocyanate such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate); Urethane modified product obtained from an isocyanate compound, biuret modified compounds, allophanate modified body, carbodiimide modified body, and isocyanurate-modified products thereof.
  • the obtained urethane prepolymer can be used as a raw material for urethane-based sealing materials and as a raw material for cast urethane.
  • the hydroxyl group-containing polyether produced by the method for producing a hydroxyl group-containing polyether of the present invention has a high molecular weight, the molecular weight distribution is smaller than the conventional one and the variation in physical properties is small. Therefore, the urethane prepolymer or the modified silicone polymer is used. Can produce a urethane prepolymer or a modified silicone polymer with excellent properties.
  • the hydroxyl group-containing polyether produced by the method for producing a hydroxyl group-containing polyether of the present invention is reduced in viscosity by the polyoxyalkylene compound (Z), a modified silicone polymer or urethane prepolymer is produced using this.
  • modified silicone polymer or urethane prepolymer having a high molecular weight but a lower viscosity than the conventional one. Therefore, it is possible to obtain a high molecular weight modified silicone polymer or urethane prepolymer having a viscosity suitable for use, which has not been suitable for use because of its high viscosity.
  • the modified silicone polymer is lowered in viscosity, the coating property is improved.
  • the molecular weight of the modified silicone polymer is high, the cured product has excellent mechanical properties such as strength and elongation.
  • Such a modified silicone polymer is particularly suitable for a sealing material.
  • the urethane prepolymer can be used as an adhesive or a sealing agent without being a modified silicone polymer.
  • the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of polyethers such as hydroxyl group-containing polyethers are as follows using a calibration curve prepared using a standard polystyrene sample with a known molecular weight: It is a polystyrene conversion molecular weight obtained by measuring by gel permeation chromatography (GPC) under the conditions described above.
  • GPC gel permeation chromatography
  • the polyol X used in this example was produced by subjecting propylene oxide (hereinafter referred to as PO) to ring-opening addition reaction with propylene glycol using a potassium hydroxide (KOH) catalyst, and further purifying by a known method.
  • Polyoxypropylene diol having an average molecular weight (Mn) of 1,000 and a hydroxyl value of 112 mgKOH / g.
  • an aqueous zinc chloride solution consisting of 10.2 g of zinc chloride and 10 g of ion-exchanged water was prepared in a 500 mL flask and stirred at 300 rpm while keeping the temperature at 40 ° C.
  • the mixture was further stirred for 30 minutes, and then a mixture consisting of 80 g of tert-butyl alcohol (hereinafter abbreviated as TBA), 80 g of ion-exchanged water, and 0.6 g of polyol X was added, and the mixture was stirred at 40 ° C. for 30 minutes. The mixture was further stirred at 60 ° C. for 60 minutes.
  • TBA tert-butyl alcohol
  • the obtained mixture was filtered under pressure (0.25 MPa) using a circular filter plate having a diameter of 125 mm and a quantitative filter paper for fine particles (No. 5C manufactured by ADVANTEC), and the composite metal cyanide complex was obtained in 50 minutes.
  • a solid (cake) containing was obtained.
  • the obtained cake was transferred to a flask, a mixed solution consisting of 36 g of TBA and 84 g of ion-exchanged water was added and stirred for 30 minutes, and then pressure filtration was performed for 15 minutes under the same conditions as above, and the cake was again obtained.
  • the cake was transferred to a flask, and a mixed solution composed of 108 g of TBA and 12 g of ion-exchanged water was added and stirred for 30 minutes to obtain a slurry containing a double metal cyanide complex.
  • the resulting reaction solution was separated into two layers, and the upper aqueous layer containing neutralized salt (NaCl) was removed. Thereafter, 60 g of Kyowad 600S (magnesium silicate-based adsorbent) and 60 g of Kyowado 1000 (hydrotalcite-based adsorbent) (both manufactured by Kyowa Chemical Industry Co., Ltd.) were added as adsorbents for the neutralized salt remaining on the product side. Then, the mixture was heated to 120 ° C., stirred, adsorbed while being degassed under reduced pressure for 2 hours, and then filtered to obtain the desired polyoxyalkylene compound (Z-1). The obtained polyoxyalkylene compound (Z-1) had a polystyrene equivalent molecular weight (number average molecular weight Mn) of 700 and a weight average molecular weight of 742 as measured by GPC.
  • Production Example 2 Production of polyoxyalkylene compound (Z-2)]
  • 670 g of dipropylene glycol was changed to 96 g of methanol
  • 2880 g of propylene oxide was changed to a mixture of 3180 g of propylene oxide and 324 g of ethylene oxide
  • the amount of sodium hydroxide used was changed from 192 g to 104 g
  • methyl chloride was changed from 556 g to 167 g.
  • the desired polyoxyalkylene compound (Z-2) was obtained.
  • the resulting polyoxyalkylene compound (Z-2) had a number average molecular weight Mn of 1200 and a weight average molecular weight of 1270.
  • Initiator (1) Polyoxypropylene diol having a number average molecular weight (Mn) of 5,500 produced using a slurry catalyst (s).
  • Initiator (2) Polyoxypropylene diol having a number average molecular weight (Mn) of 10,000 produced using the slurry catalyst (s).
  • Initiator (3) Polyoxypropylene triol having a number average molecular weight (Mn) of 10,000 obtained by adding propylene oxide to glycerol using a slurry catalyst (s).
  • Example 1 The same pressure resistant reactor (capacity 5 L) as in Production Example 1 was used. First, in a pressure resistant reactor, 800 g of the initiator (1) and 800 g of the polyoxyalkylene compound (Z-2) produced in Production Example 2 (the ratio of the diluent to the total 100 parts by mass of the initiator and the total PO 25 Parts by mass) and the slurry catalyst (s) produced in Reference Example 1 were added to prepare a reaction solution. The amount of the slurry catalyst (s) was 50 ppm as an amount converted to a DMC catalyst. Next, after replacing the inside of the pressure resistant reactor with nitrogen, the reaction solution was heated with stirring. When the temperature reached 130 ° C.
  • the concentration of the slurry catalyst (s) is a concentration based on a total of 100 parts by mass of the initiator used for producing the polyether polyol and the total PO. The same applies to the following examples.
  • the GPC spectrum of the polyether diol thus obtained showed a spectrum which was divided into two spectra: a spectrum due to the polyether diol and a spectrum due to the polyoxyalkylene compound (Z-2).
  • Table 1 shows the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the spectrum derived from the polyether diol, the hydroxyl value, and the main production conditions (the same applies hereinafter).
  • the hydroxyl value is a value (apparent hydroxyl value including polyoxyalkylene compound) measured by the above titration method (JIS K1557) for the obtained reaction product (including polyether diol and polyoxyalkylene compound).
  • Example 1 the type of initiator, the amount of initiator used, the type of polyoxyalkylene compound (Z), the amount of polyoxyalkylene compound (Z) used, the polyoxy to the total of 100 parts by mass of initiator and total PO
  • Example 1 the same procedure as in Example 1 except that the ratio of the alkylene compound (Z), the PO amount supplied in the initial step (PO for initial step), and the PO supply rate and supply amount in the polymerization step were changed as shown in Table 1.
  • a polyether polyol was produced.
  • the amount of the slurry catalyst (s) used is 50 ppm
  • the amount of PO for the initial step is about 10 parts by weight with respect to 100 parts by weight of the initiator
  • the initial step temperature and the polymerization step temperature are 130 ° C. .
  • Example 1 A polyether diol was produced in the same manner as in Example 1 except that the polyoxyalkylene compound (Z) was not used in Example 1. The viscosity was measured after adding the polyoxyalkylene compound (Z-2) to the obtained polyether diol so that the ratio thereof was 20% by mass and mixing the mixture to make it uniform.
  • Example 2 A polyether triol was produced in the same manner as in Example 4 except that the polyoxyalkylene compound (Z) was not used in Example 4. The viscosity was measured after the polyoxyalkylene compound (Z-2) was added to the obtained polyether triol so that the ratio was 20% by mass and mixed uniformly.
  • Example 3 A polyether diol was produced in the same manner as in Example 1 except that 640 g of hexane as an organic solvent was used instead of 800 g of the polyoxyalkylene compound (Z-2) in Example 1. The viscosity was measured after removing hexane with an evaporator, adding the polyoxyalkylene compound (Z-2) so that the ratio was 20% by mass, and mixing the mixture uniformly.
  • Example 4 A polyether diol was produced in the same manner as in Example 1, except that 900 g of tetrahydrofuran (THF) as an organic solvent was used instead of 800 g of the polyoxyalkylene compound (Z-2). The viscosity was measured after removing hexane with an evaporator, adding the polyoxyalkylene compound (Z-2) so that the ratio was 20% by mass, and mixing the mixture uniformly.
  • THF tetrahydrofuran
  • the polyether polyols of Examples 1 to 5 and 17 produced using the specific polyoxyalkylene compound (Z) in the present invention have a high molecular weight and a molecular weight distribution. narrow.
  • Comparative Example 1 in which the polyoxyalkylene compound (Z) was not used, and Comparative Examples 3 and 4 in which an organic solvent was used instead of the polyoxyalkylene compound (Z) were both in Example 1. And the weight average molecular weight is almost the same, but the molecular weight distribution is wide.
  • Comparative Example 2 using an organic solvent instead of the polyoxyalkylene compound (Z) has a broad molecular weight distribution while the weight average molecular weight is almost the same as Example 4.
  • H-type test Surface anodized aluminum was used as the adherend, and an H-type test body was prepared in accordance with JIS A 1439 testing method for building sealing materials, and a tensile property test was performed. Specifically, the prepared H-type specimen was cured at a temperature of 23 ° C. and a humidity of 65% for one week, and further cured at a temperature of 50 ° C. and a humidity of 65% for one week to prepare a cured product of the H-type specimen. .
  • a tensile physical property is measured with a Tensilon tester (H type physical property), the stress (M50, unit: N / mm ⁇ 2 >) when extended 50%, the maximum point tensile stress (unit: N) / Mm 2 ) and maximum point elongation (unit:%) were measured.
  • M50 the higher the flexibility
  • M50 the higher the maximum point tensile stress value
  • Mm 2 the maximum point tensile strength
  • the higher the maximum point elongation value the better the elongation.
  • Example 6 Production of modified silicone polymer (1)
  • 3,000 g of the polyether diol obtained in Example 2 is put into a pressure-resistant reaction vessel (internal volume 5 L (liter)) and dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C.
  • Example 7 Production of modified silicone polymer (2)
  • 3,000 g of the polyether diol obtained in Example 2 was put into a pressure-resistant reaction vessel (internal volume 5 L (liter)) and dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C.
  • a methanol solution containing 1.05 times moles of sodium methoxide with respect to the amount of hydroxyl groups of the polyether diol was added, the methanol was removed by heating under reduced pressure, and the polyether was alcoholated.
  • Example 8 Production of modified silicone polymer (3)
  • 3,000 g of the polyether diol obtained in Example 3 is put into a pressure-resistant reaction vessel (internal volume 5 L (liter)) and dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C.
  • a methanol solution containing 1.05 times moles of sodium methoxide is added to the amount of hydroxyl groups of the polyether diol, the methanol is removed by heating under reduced pressure, and the polyether diol is alcoholated.
  • Example 9 Production of modified silicone polymer (4)
  • 3,000 g of the polyether diol obtained in Example 2 is put into a pressure-resistant reaction vessel (internal volume 5 L (liter)) and dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C.
  • a methanol solution containing 1.05 times moles of sodium methoxide is added to the amount of hydroxyl groups of the polyether diol, the methanol is removed by heating under reduced pressure, and the polyether diol is alcoholated.
  • Example 10 Production of modified silicone polymer (5)
  • 3,000 g of the polyether triol obtained in Example 5 is put into a pressure-resistant reaction vessel (internal volume 5 L (liter)) and dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C.
  • a methanol solution containing 1.05 times moles of sodium methoxide with respect to the amount of hydroxyl group of the polyether triol is added, the methanol is removed by heating under reduced pressure, and the polyether triol is alcoholated.
  • Example 11 Production and evaluation of sealing material
  • Example 12 the modified silicone polymer (1) is changed to the modified silicone polymers (2) to (5), respectively, and a sealing material is prepared in the same manner as in Example 11.
  • a sealing material is prepared in the same manner as in Example 11.
  • Example 16 Production of isocyanate group-terminated prepolymer
  • 400 g of the polyether diol obtained in Example 1 is put into a 1 L glass reaction vessel equipped with a stirring blade.
  • tolylene diisocyanate (a mixture of 2,4-isomer and 2,6-isomer, containing 80% by mass of 2,4-isomer in a reaction vessel.
  • the isocyanate reaction rate n (% relative to the theoretical isocyanate group content n 0 (mass%) was measured. ) The reaction is terminated after confirming that the isocyanate group content n 1 (mass%) is less than or equal to the theoretical isocyanate group content z 0 (0.84 mass%) to obtain an isocyanate group-terminated prepolymer.
  • the obtained isocyanate group-terminated prepolymer is formed into a film having a thickness of about 200 ⁇ m on a release-treated PET film, cured at 25 ° C. for 7 days, and moisture-cured to obtain a cured product. When the physical properties of the obtained cured product are measured, both the elongation and the tensile strength at break are good.
  • TDI used in this example is tolylene diisocyanate
  • 2EHA represents 2-ethylhexyl acrylate
  • KBM903 product name, manufactured by Shin-Etsu Chemical Co., Ltd. is 3-aminopropyltrimethoxysilane.
  • a compound A (a compound having an —NH group and —NH 2 group).
  • a mixture of compounds having 3,000 g of the polyether diol obtained in Example 2 was put into a pressure-resistant reaction vessel (internal volume 5 L (liter)) and dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C. Next, the atmosphere in the reaction vessel is replaced with nitrogen gas, the temperature is lowered to 80 ° C., and 50 ppm of dibutyltin diacetonate is added to the polyether diol as a urethanization catalyst and stirred.
  • TDI-80 product name, manufactured by Nippon Polyurethane Co., Ltd.
  • TDI-80 product name, manufactured by Nippon Polyurethane Co., Ltd.
  • the atmosphere in the reaction vessel was replaced with nitrogen gas, and the prepolymer (p6) was cooled to 50 ° C.
  • Compound A is charged so that the ratio (NCO / NH) of the amino group of the synthesized product (A) calculated from the charged amount to the total number of isocyanate groups of the prepolymer (p6) is 1.05. did.
  • the internal temperature was maintained at 80 ° C.
  • the prepolymer (p6) and the product A were reacted, and an isocyanate peak was observed by FT-IR (Fourier transform infrared spectroscopy). Confirmed disappearance. Then, it cooled to normal temperature and obtained the modified silicone polymer (6) which has a trimethoxysilyl group as a hydrolysable group at the terminal.
  • Example 19 Production and evaluation of sealing material
  • Example 20 Production and evaluation of sealing material
  • a one-component modified silicone sealant was prepared in the same manner as in Example 19 except that the modified silicone polymer (2) was used instead of the modified silicone polymer (6) in Example 19.
  • Table 2 shows the physical properties of the obtained sealing material.
  • the sealing agent produced using the polyether polyol obtained by the production method of the present invention had good elongation properties and strength.
  • the workability during construction was good even at room temperature and at a low temperature of 0 ° C.
  • the hydroxyl group-containing polyether obtained by the production method of the present invention includes a raw material for a synthetic resin such as a flexible polyurethane foam, a thermoplastic polyurethane resin or a thermosetting polyurethane resin, a raw material for a urethane prepolymer, a raw material for a modified silicone polymer, and a surfactant. It can be widely used for lubricants and other applications.
  • the urethane prepolymer can be suitably used as an adhesive, a sealing agent, an adhesive, and a urethane waterproof material.
  • the modified silicone polymer can be suitably used as an adhesive, a sealing agent, and an adhesive.

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Abstract

L'invention concerne un procédé de production d'un polyéther contenant un groupe hydroxyle au moyen duquel il est possible de produire un polyéther contenant un groupe hydroxyle à masse moléculaire élevée et ayant une répartition étroite des poids moléculaires. Un composé éther cyclique est amené par un initiateur possédant au moins un groupe hydroxyle par molécule à subir une réaction d'addition par ouverture de cycle en présence d'un catalyseur composite au complexe de cyanure métallique et d'un composé de polyoxyalkylène (Z), et on obtient ainsi un polyéther contenant un groupe hydroxyle ayant une masse moléculaire moyenne en poids comprise entre 5000 et 500 000. Le composé de polyoxyalkylène (Z) est un composé possédant une chaîne de polyoxyalkylène dérivée d'un oxyde d'alkylène et ne possédant pas de groupes réactifs capables d'une réaction d'addition par ouverture de cycle avec le composé éther cyclique, et est un composé de polyoxyalkylène ayant une masse moléculaire moyenne en poids inférieure à celle du polyéther contenant le groupe hydroxyle.
PCT/JP2013/080037 2012-11-09 2013-11-06 Procédé de production de polyéther contenant un groupe hydroxyle, procédé de production de polyéther contenant un groupe silyle hydrolysable, et procédé de production de prépolymère d'uréthane Ceased WO2014073580A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
JPWO2020066551A1 (ja) * 2018-09-26 2021-08-30 Ａｇｃ株式会社 硬化性組成物並びに硬化物及びシーリング材
WO2024057984A1 (fr) * 2022-09-13 2024-03-21 Ａｇｃ株式会社 Procédé de production de polyéther polyol, procédé de production de polyéther polyol ayant un groupe silicium réactif, et polyéther polyol

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JPH03195727A (ja) * 1989-12-26 1991-08-27 Asahi Glass Co Ltd ポリエーテル類の製造方法
JPH1036500A (ja) * 1996-07-23 1998-02-10 Asahi Glass Co Ltd ポリエーテル類の製造方法
JP2006063335A (ja) * 2004-07-29 2006-03-09 Asahi Glass Co Ltd 室温硬化性組成物
WO2009093599A1 (fr) * 2008-01-25 2009-07-30 Kaneka Corporation Procédé de production d'oxyde de polyalkylène
WO2013157486A1 (fr) * 2012-04-18 2013-10-24 旭硝子株式会社 Procédé de production de polyéther

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JPH03195727A (ja) * 1989-12-26 1991-08-27 Asahi Glass Co Ltd ポリエーテル類の製造方法
JPH1036500A (ja) * 1996-07-23 1998-02-10 Asahi Glass Co Ltd ポリエーテル類の製造方法
JP2006063335A (ja) * 2004-07-29 2006-03-09 Asahi Glass Co Ltd 室温硬化性組成物
WO2009093599A1 (fr) * 2008-01-25 2009-07-30 Kaneka Corporation Procédé de production d'oxyde de polyalkylène
WO2013157486A1 (fr) * 2012-04-18 2013-10-24 旭硝子株式会社 Procédé de production de polyéther

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020066551A1 (ja) * 2018-09-26 2021-08-30 Ａｇｃ株式会社 硬化性組成物並びに硬化物及びシーリング材
JP2024045556A (ja) * 2018-09-26 2024-04-02 Ａｇｃ株式会社 硬化性組成物並びに硬化物及びシーリング材
JP7687463B2 (ja) 2018-09-26 2025-06-03 Ａｇｃ株式会社 硬化性組成物並びに硬化物及びシーリング材
WO2024057984A1 (fr) * 2022-09-13 2024-03-21 Ａｇｃ株式会社 Procédé de production de polyéther polyol, procédé de production de polyéther polyol ayant un groupe silicium réactif, et polyéther polyol

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