Process for producing polyoxypropylene polymer

Abstract

To provide a method for producing a polyoxypropylene-based polymer, by which the polyoxypropylene-based polymer having a large molecular weight and exhibiting a low viscosity due to a narrow molecular weight distribution can be produced without using a large amount of water.SOLUTION: The polyoxypropylene-based polymer having a design molecular weight value X (g / mol) of 12,000g / mol or more and 30,000g / mol or less is obtained by setting the internal temperature of a reaction vessel charged with an initiator, a double metal cyanide complex catalyst, and propylene oxide to 90 °C or higher and 110 °C or lower. Activating the double metal cyanide complex catalyst, and after adjusting the internal temperature of the reaction vessel to a temperature of at least 90 °C and at most 110 °C, carrying out polymerization by additionally adding propylene oxide to the reaction vessel over Y minutes under a condition of at least 120 °C and at most 160 °C, wherein the value of X / Y is at least 35 and at most 67.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polyoxypropylene polymer. [Background technology]

[0002] Industrially produced reactive silicon-terminated polyethers are widely used in a variety of applications, such as sealants, adhesives, paints, etc. Reactive silicon-terminated polyethers are usually produced by introducing reactive silicon groups into the molecular chain terminals of polyethers such as polyoxypropylene polymers using various methods. For this reason, polyethers such as polyoxypropylene polymers are important as raw materials for reactive silicon-terminated polyethers.

[0003] As a method for producing a polyoxypropylene polymer, for example, a method has been proposed in which propylene oxide is polymerized in the presence of a composite metal cyanide complex catalyst and an initiator so as to satisfy the following formulas (1) to (3) (see Patent Document 1). Reaction ratio = equivalent molecular weight of polyether poly(mono)ol / equivalent molecular weight of initiator (1) X = alkylene oxide supply time / reaction ratio (2) X≧equivalent molecular weight of polyether poly(mono)ol / 3000 (3) [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2023-009929 Summary of the Invention [Problem to be solved by the invention]

[0005] When considering the application of reactive silicon-terminated polyethers to industrial applications, particularly construction, the use of polymers with relatively high molecular weights (greater than 10,000) can achieve desirable physical properties, such as high elongation. However, polymers with higher weight-average molecular weights tend to have higher viscosity (i.e., larger molecular weight distributions (Mw / Mn)). This makes it difficult to increase the rate of monomer addition during the polymerization reaction during production, resulting in long production times. Furthermore, polymers with large molecular weight distributions (Mw / Mn) have the problem of being difficult to handle on-site due to their high viscosity. For these reasons, there is a demand for reactive silicon-terminated polyethers that have low viscosity while still possessing desirable physical properties such as high elongation. Narrowing the molecular weight distribution of reactive silicon-terminated polyethers is an effective way to lower the viscosity of high-molecular-weight reactive silicon-terminated polyethers. In other words, reactive silicon-terminated polyethers with high molecular weights and narrow molecular weight distributions combine desirable physical properties such as high elongation with low viscosity, and are suitable for use as components of sealants.

[0006] The present invention has been made in view of the above problems, and relates to a method for producing a polyoxypropylene polymer, which can produce a polyoxypropylene polymer having a large molecular weight and a narrow molecular weight distribution and therefore a low viscosity. [Means for solving the problem]

[0007] Specifically, the present invention relates to the following: A method for producing a polyoxypropylene polymer having a design molecular weight value X (g / mol) of 12,000 g / mol or more and 30,000 g / mol or less, comprising: activating the composite metal cyanide complex catalyst by setting the internal temperature of a reaction vessel containing the initiator, the composite metal cyanide complex catalyst, and propylene oxide to 90°C or higher and 110°C or lower; After raising the internal temperature of the reaction vessel to a temperature of 90°C or higher and 110°C or lower, propylene oxide is additionally added to the reaction vessel over Y minutes under the condition of 120°C or higher and 160°C or lower to carry out polymerization. Including, The manufacturing method, wherein the value of X / Y is 35 or more and 67 or less. [Effects of the Invention]

[0008] According to the present invention, there is provided a method for producing a polyoxypropylene polymer, which can produce a polyoxypropylene polymer having a large molecular weight and a narrow molecular weight distribution and therefore a low viscosity in a shorter time than conventional methods. Furthermore, even when a double metal cyanide complex catalyst containing an ether solvent as an organic ligand is used, a polyoxypropylene polymer having a low viscosity can be produced in a shorter time than conventional methods. DETAILED DESCRIPTION OF THE INVENTION

[0009] <Method for producing polyoxypropylene polymer> The method for producing a polyoxypropylene polymer is a method for producing a polyoxypropylene polymer having a design molecular weight value X (g / mol) of 12,000 g / mol or more and 30,000 g / mol or less by polymerizing propylene oxide in the presence of an initiator and a composite metal cyanide complex catalyst. In the above production method, the polymerization of propylene oxide can be carried out at an internal temperature of the reaction vessel in the range of 120° C. to 160° C. The internal temperature may be, for example, 125 to 160° C., 125 to 150° C., 125 to 140° C., 130 to 160° C., 130 to 150° C., or 130 to 140° C.

[0010] The above manufacturing method is activating the composite metal cyanide complex catalyst by setting the internal temperature of a reaction vessel containing the initiator, the composite metal cyanide complex catalyst, and propylene oxide to 90°C or higher and 110°C or lower; After the internal temperature of the reaction vessel is increased to 90°C or higher and 110°C or lower, propylene oxide is additionally added to the reaction vessel over Y minutes under conditions of 120°C or higher and 160°C or lower, thereby carrying out polymerization.

[0011] The designed molecular weight X of the polyoxypropylene polymer is 12,000 g / mol or more and 30,000 g / mol or less. The designed molecular weight X (g / mol) is calculated by dividing the total weight of the initiator and propylene oxide by the number of moles of the initiator per hydroxyl group. Specifically, the designed molecular weight X is calculated using the following formula (1): Design molecular weight X=(b+c) / (a×b / (n×1000))...(1) In formula (1), a is the hydroxyl value (mmol / g) of the initiator, b is the weight (g) of the initiator, c is the weight (g) of propylene oxide, and n is the number of hydroxyl groups contained in one molecule of the initiator. It is calculated as follows. When two or more types of initiators are used in combination, the design molecular weight X (g / mol) is calculated by dividing the total weight of all initiators and propylene oxide by the total number of moles per hydroxyl group for each initiator. Specifically, when m types of initiators are used, the design molecular weight X is calculated using the following formula (1'): Design molecular weight In formula (1'), am is the hydroxyl value (mmol / g) of the mth hydroxyl-containing initiator. bm is the weight (g) of the mth hydroxyl-containing initiator. c is the total weight of propylene oxide. dm is the number of hydroxyl groups contained in one molecule of the mth hydroxyl-containing initiator. m is an integer of 2 or more.

[0012] According to the above-described production method, a polyoxypropylene polymer having a high molecular weight and a narrow molecular weight distribution and therefore a low viscosity can be produced.

[0013] As the initiator, any initiator that has been conventionally used in the production of polyoxypropylene polymers can be used without any particular limitation. Specific examples of the initiator include monohydric alcohols such as methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, and 2,2-dimethyl-1-propanol; ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, 1,4-butanediol, hexamethylene glycol, methallyl alcohol, hydrogenated bisphenol A, neopentyl glycol, polybutadiene diol, diethylene glycol (HO-CHCH-O-CHCH-OH), triethylene glycol (HO Examples of initiators include dihydric or higher alcohols such as -CH2CH2-(O-CH2CH2)2-OH), polyoxyethylene glycol (a linear polymer of ethylene oxide having hydroxyl groups at both ends), dipropylene glycol (HO-CH2C(CH3)HO-CH2C(CH3)H-OH), polyoxypropylene glycol (a linear polymer of propylene oxide having hydroxyl groups at both ends), polyoxypropylene triol (a polymer of propylene oxide having three hydroxyl groups obtained by adding propylene oxide to a trihydric alcohol), polyoxypropylene tetraol (a polymer of propylene oxide having four hydroxyl groups obtained by adding propylene oxide to a tetrahydric alcohol), glycerin, trimethylolmethane, trimethylolpropane, and pentaerythritol; and various polymers having hydroxyl groups. As the initiator, only one of these may be used, or two or more may be used in combination. When various polymers having hydroxyl groups are used as initiators, polymers of the same type but with different molecular weights may be used in combination. Among the above initiators, it is preferable to use polyoxypropylene glycol and / or polyoxypropylene triol.

[0014] Usually, when producing a polyoxypropylene polymer, the designed molecular weight X of the polyoxyalkylene polymer and the type of initiator are determined. Once the type of initiator is determined, the hydroxyl value (mmol / g) a of the initiator is determined by the measurement method of JIS K 1557. Next, once b, which is the weight (g) of the initiator, is determined, c, which is the weight (g) of propylene oxide, can be calculated based on formula (1).

[0015] As described above, the designed molecular weight X of the polyoxyalkylene polymer is 12,000 g / mol or more and 30,000 g / mol or less. For example, when priority is given to low viscosity of the polyoxypropylene polymer, the designed molecular weight X is preferably 12,000 g / mol or more and 20,000 g / mol or less, and more preferably 12,000 g / mol or more and 18,000 g / mol or less. Furthermore, when priority is given to high elongation of the polyoxypropylene polymer, the designed molecular weight X is preferably 20,000 g / mol or more and 30,000 g / mol or less, and more preferably 22,000 g / mol or more and 30,000 g / mol or less.

[0016] The catalyst used is a double metal cyanide complex catalyst, which usually has an organic ligand. As the composite metal cyanide catalyst, any composite metal cyanide catalyst that has been conventionally used in the production of polyoxyalkylene polymers can be used without any particular limitation. As the composite metal cyanide catalyst, for example, the composite metal cyanide catalyst described in WO 2013 / 157486 can be used.

[0017] Examples of organic ligands that the composite metal cyanide complex may have include alcohols such as tert-butyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-pentyl alcohol, and isopentyl alcohol; amides such as N,N-dimethylacetamide; and ether solvents. Among these organic ligands, ether solvents are preferred, and ether solvents having no hydroxyl group are more preferred. Examples of ether solvents having no hydroxyl group include tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, 1,3-dioxane, and 1,4-dioxane.

[0018] When producing a polyoxypropylene polymer, first, the internal temperature of a reaction vessel containing the initiator, propylene oxide, and catalyst described above is set to 90°C or higher and 110°C or lower to activate the composite metal cyanide complex catalyst. The time for which propylene oxide is maintained at a temperature in the range of 90° C. to 110° C. is not particularly limited as long as the desired effect is not impaired. Before additional propylene oxide is added to the reaction vessel to start polymerization, the internal temperature of the reaction vessel is preferably maintained at a temperature in the range of 90° C. to 110° C. for 30 minutes to 120 minutes, more preferably 45 minutes to 90 minutes.

[0019] The amount of the catalyst used is preferably 30 ppm by mass or more and 150 ppm by mass or less, more preferably 50 ppm by mass or more and 120 ppm by mass or less, relative to the mass of the polyoxypropylene polymer.

[0020] The polymerization reaction of propylene oxide can be carried out in the presence or absence of a solvent, and is preferably carried out in the presence of a solvent. An organic solvent is usually used as the solvent. The organic solvent is not particularly limited as long as it does not contain active hydrogen and is inactive in polymerization. Specific examples of organic solvents include aromatic compounds such as benzene, monochlorobenzene, toluene, ethylbenzene, styrene, o-xylene, m-xylene, and p-xylene; heterocyclic compounds such as tetrahydrofuran, dioxane, furan, and pyran; and polar compounds such as chain ethers such as butyl ethyl ether. One organic solvent may be used alone, or two or more organic solvents may be used in combination. Among the above organic solvents, heterocyclic compounds and chain ethers are preferred, with tetrahydrofuran, dioxane, and butyl ethyl ether being more preferred, and tetrahydrofuran being particularly preferred.

[0021] The amount of propylene oxide at the start of polymerization is not particularly limited, and is preferably from 1 to 5% by mass, more preferably from 1 to 3% by mass, relative to the mass of the polyoxypropylene polymer.

[0022] The amount of the initiator used is preferably 4% by mass or more and 50% by mass or less, and more preferably 4% by mass or more and 30% by mass or less, based on the mass of the polyoxypropylene polymer.

[0023] The internal temperature of a reaction vessel containing an initiator, a composite metal cyanide complex catalyst, and propylene oxide is raised to 90°C or higher and 110°C or lower to activate the composite metal cyanide complex catalyst, and then propylene oxide is polymerized by adding additional propylene oxide to the reaction vessel over Y minutes at a temperature of 120°C or higher and 160°C or lower. The polymerization reaction system may contain the organic solvent described above. In the above-mentioned method for producing a polyoxypropylene polymer, the time when the additional addition of propylene oxide to the reaction vessel is started at a temperature of 120°C or higher and 160°C or lower is defined as the time when polymerization is initiated. After the start of polymerization, propylene oxide is additionally added to the reaction vessel over Y minutes. The additional addition of propylene oxide to the reaction vessel at 120°C or higher and 160°C or lower is carried out so that the value of (design molecular weight X) / (time Y required for additional addition of propylene oxide) is 35 or higher and 67 or lower. As long as the polymerization reaction is carried out within this numerical range, a polyoxypropylene-based polymer exhibiting low viscosity can be produced in a shorter time than conventional methods. If a higher viscosity of the produced polyoxypropylene polymer is acceptable, the value of the time Y required for additional addition of propylene oxide may be reduced. Therefore, the value of X / Y may be, for example, 37 to 67, 39 to 67, 41 to 67, 43 to 67, 45 to 67, 47 to 67, or 49 to 67.

[0024] The addition of propylene oxide to the reaction vessel is preferably started when the internal temperature of the reaction vessel is 120° C. or higher and 160° C. or lower. However, the addition of propylene oxide to the reaction vessel may be started when the internal temperature of the reaction vessel is lower than 120° C.

[0025] The feed rate of propylene oxide when adding propylene oxide to the reactor may be constant or may vary. Propylene oxide may be added to the reaction vessel continuously or intermittently, preferably continuously.

[0026] The time Y required for the additional addition of propylene oxide to the polymerization reaction system is preferably 180 minutes or more and 850 minutes or less, more preferably 180 minutes or more and 800 minutes or less, or may be 180 minutes or more and 500 minutes or less, or 180 minutes or more and 400 minutes or less.

[0027] After the predetermined amount of propylene oxide has been added to the polymerization reaction system, the polymerization reaction may be continued at a temperature of 120°C or higher and 160°C or lower. The reaction time after the addition of a predetermined amount of propylene oxide to the polymerization reaction system is, for example, preferably 15 minutes or more and 90 minutes or less, and more preferably 30 minutes or more and 60 minutes or less.

[0028] The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon. After the addition of propylene oxide is completed, the polymerization reaction is continued for, for example, about 10 minutes to 1 hour, and then the unreacted propylene oxide and the organic solvent are distilled off to obtain a polyoxypropylene polymer. Furthermore, metal impurities derived from the polymerization catalyst can be removed by washing with water or an organic solvent.

[0029] <Hydrolyzable Silyl Group-Containing Polyoxypropylene Polymer> The polyoxypropylene polymer obtained by the above method has two or more hydroxyl groups at the terminals of the main chain. By utilizing the two or more hydroxyl groups present at the terminals of the main chain, hydrolyzable silyl groups can be introduced into two or more terminals of the main chain of the polyoxypropylene polymer in one step or two or more steps. This allows the production of a polyoxypropylene polymer containing hydrolyzable silyl groups.

[0030] The hydrolyzable silyl group is a silyl group that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can form a crosslink by forming a siloxane bond. Specifically, the hydrolyzable silyl group is represented by the following formula (2): -SiR 1 b R 2 3-b (2) In formula (2), R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 2 represents a hydroxyl group or a hydrolyzable group. b represents 0, 1, or 2, preferably 0 or 1. When b is 2, two R 1 When b is 0 or 1, a plurality of R 2 may be the same or different.

[0031] R 1 The number of carbon atoms in the substituted or unsubstituted hydrocarbon group represented by the formula (I) is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The number of carbon atoms in the substituted or unsubstituted hydrocarbon group includes the number of carbon atoms in the substituent. R 1 Specific examples of R include a methyl group, an ethyl group, a chloromethyl group, a methoxymethyl group, and an N,N-diethylaminomethyl group. 1 is preferably a methyl group or an ethyl group.

[0032] R 2 Examples of the alkyl group include a hydroxyl group, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, alkoxy groups such as a methoxy group and an ethoxy group are more preferred, and a methoxy group and an ethoxy group are particularly preferred, because they are mildly hydrolyzable and easy to handle.

[0033] Specific examples of the hydrolyzable silyl group include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl 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.

[0034] The specific method for producing the hydrolyzable silyl group-containing polyoxypropylene polymer is not particularly limited, but an example of the production method is a method in which a hydroxyl group of the polyoxypropylene polymer is reacted with an isocyanate group of a hydrolyzable silyl group-containing isocyanate compound to bond the hydrolyzable silyl group to the terminal of the polyoxypropylene polymer via a urethane bond.

[0035] The hydrolyzable silyl group-containing isocyanate compound is not particularly limited as long as it is a compound having an isocyanate group and a hydrolyzable silyl group in the same molecule. Specific examples of the hydrolyzable silyl group-containing isocyanate compound include (isocyanatemethyl)trimethoxysilane, (isocyanatemethyl)triethoxysilane, (isocyanatemethyl)dimethoxymethylsilane, (isocyanatemethyl)diethoxymethylsilane, (3-isocyanatepropyl)trimethoxysilane, (3-isocyanatepropyl)dimethoxymethylsilane, (3-isocyanatepropyl)triethoxysilane, and (3-isocyanatepropyl)diethoxymethylsilane.

[0036] The urethanization reaction may be carried out in the presence or absence of a urethanization catalyst, and is preferably carried out in the presence of a urethanization catalyst for the purpose of improving the reaction rate and reaction rate. Examples of the urethanization catalyst include conventionally known urethanization catalysts such as those listed in "Polyurethanes: Chemistry and Technology," Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963. Specific examples of the urethanization catalyst include organic tin compounds, bismuth compounds, and basic catalysts such as organic amines. The urethanization catalyst is not limited to these.

[0037] Another example of a method for producing a hydrolyzable silyl group-containing polyoxypropylene polymer is the following method. In this method, first, the hydroxyl groups of the polyoxypropylene polymer are reacted with an alkali metal salt to form an alkali metal alcoholate. Then, the alkali metal alcoholate is reacted with a carbon-carbon unsaturated bond-containing halide to convert the terminal hydroxyl groups of the polyoxypropylene polymer to carbon-carbon unsaturated bond-containing groups. Next, a hydrolyzable silyl group-containing hydrosilane compound is added to the carbon-carbon unsaturated bond in the carbon-carbon unsaturated bond-containing group by a hydrosilylation reaction, thereby introducing hydrolyzable silyl groups into the terminals of the polyoxypropylene polymer. The hydrolyzable silyl group-containing polyoxypropylene polymer obtained by this method usually does not contain a urethane bond.

[0038] The alkali metal salt is not particularly limited, and specific examples of the alkali metal salt include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide.

[0039] The carbon-carbon unsaturated bond-containing halide is not particularly limited. Specific examples of the carbon-carbon unsaturated bond-containing halide include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. From the viewpoint of ease of handling, allyl chloride and methallyl chloride are preferred.

[0040] Alternatively, a polyoxypropylene-based polymer having two or more carbon-carbon unsaturated bonds at one end can be formed by first reacting the polyoxypropylene-based polymer after the reaction with the alkali metal salt with an epoxy compound having a carbon-carbon unsaturated bond (e.g., allyl glycidyl ether), and then reacting the resulting polymer with the above-mentioned carbon-carbon unsaturated bond-containing halide.

[0041] Specific examples of hydrolyzable silyl group-containing hydrosilane compounds include halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, and bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, Dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxysilane, (methoxymethyl)dimethoxysilane, bis(methoxymethyl)methoxysilane, (methoxymethyl)diethoxysilane, (ethoxymethyl)diethoxysilane, (3,3,3-trifluoropropyl (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(methoxymethyl)diethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, and [(3,3,3-trifluoro alkoxysilanes such as [(propyl)dimethoxysilyloxy]dimethylsilane; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; and isopropenyloxysilanes (deacetone type) such as triisopropenyloxysilane, (chloromethyl)diisopropenyloxysilane, and (methoxymethyl)diisopropenyloxysilane.

[0042] The hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst to promote the reaction. Examples of the hydrosilylation catalyst include metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, as well as complexes of these metals. Specific examples of platinum-containing catalysts include catalysts in which platinum is supported on a support such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes composed of chloroplatinic acid and alcohols, aldehydes, or ketones; platinum-olefin complexes [e.g., Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2]; platinum-vinylsiloxane complexes [e.g., Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4]; and platinum-phosphine complexes [e.g., Examples of suitable catalysts include platinum-phosphite complexes [e.g., Pt{P(OPh)}] (where Ph is a phenyl group and Me is a methyl group); and ruthenium complexes in which ruthenium is coordinated with 2,3-dibromonorbornadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,3,5-tribromobenzene, 1,4-diiodobenzene, or hexabromobenzene. Platinum catalysts such as chloroplatinic acid and platinum-vinylsiloxane complexes are preferred in terms of reaction efficiency, while ruthenium complexes are preferred in terms of improving the silyl group introduction rate.

[0043] <Curable composition containing hydrolyzable silyl group-containing polyoxypropylene polymer> The hydrolyzable silyl group-containing polyoxypropylene polymer can be preferably blended in a curable composition. The curable composition may contain only one type of polyoxypropylene polymer, or may contain two or more types of polyoxypropylene polymer.

[0044] The curable composition containing the hydrolyzable silyl group-containing polyoxypropylene polymer may contain a curing catalyst, a silicon compound, an adhesion promoter, 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 adjuster, 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, a foaming agent, and the like.

[0045] Various additives may be added to the curable composition as needed for the purpose of adjusting the physical properties of the curable composition or the cured product. Examples of the additives include a curability adjuster, a radical inhibitor, a metal deactivator, an antiozonant, a phosphorus-based peroxide decomposer, a lubricant, a pigment, and an antifungal agent.

[0046] ≪Applications≫ The curable composition can be used as a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a waterproofing material, a waterproof coating material, a mold release agent, an anti-vibration material, a vibration-damping material, a sound-proofing material, a foam material, a paint, and a spray material. The cured product obtained by curing the curable composition has excellent flexibility and adhesiveness, and can therefore be suitably used as a sealant or adhesive.

[0047] The curable composition can be used in a wide range of applications, including electrical and electronic component materials such as solar cell backside sealing materials; electrical insulating materials for electrical and electronic components or devices such as insulating coating materials for electric wires and cables; acoustic insulating materials; elastic adhesives; binders; contact adhesives; spray-type sealants; crack repair materials; tiling adhesives; adhesives for asphalt waterproofing materials; powder coatings; casting materials; medical rubber materials; medical adhesives; medical adhesive sheets; medical device sealants; dental impression materials; food packaging materials; and joint sealants for exterior materials such as sizing boards. It can be used for a wide variety of applications, such as coating materials, anti-slip coating materials, buffer materials, primers, conductive materials for electromagnetic wave shielding, thermally conductive materials, hot melt materials, potting agents for electrical and electronic applications, film-forming materials, gaskets, concrete reinforcing materials, temporary fixing adhesives, various molding materials, anti-rust and waterproof sealants for the edges (cut parts) of wired glass and laminated glass, automotive parts, and liquid sealants used in the manufacture of large vehicle parts such as trucks and buses, train car parts, aircraft parts, marine parts, electrical parts, and various machine parts. Taking automobiles as an example, the curable compositions described above can be used in a wide variety of applications, such as adhesive attachment of plastic covers, trim, flanges, bumpers, window attachments, interior components, and exterior components. The curable compositions described above, alone or with the aid of a primer, can adhere to a wide range of substrates, such as glass, porcelain, wood, metal, and resin moldings, and therefore can also be used as various types of sealing and adhesive compositions. In addition, the above-mentioned curable composition can also be used as an adhesive for interior panels; an adhesive for exterior panels; an adhesive for tiling; an adhesive for stone cladding; an adhesive for ceiling finishing; an adhesive for floor finishing; an adhesive for wall finishing; an adhesive for vehicle panels; an adhesive for assembling electrical, electronic, and precision equipment; an adhesive for bonding leather, textile products, fabrics, paper, boards, and rubber; a reactive post-crosslinking pressure-sensitive adhesive; a sealant for direct glazing; a sealant for double-glazing glass; a sealant for the SSG construction method; a sealant for working joints in buildings; a civil engineering material; and a bridge material. Furthermore, the curable composition can also be used as an adhesive material for adhesive tapes, adhesive sheets, and the like. [Example]

[0048] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.

[0049] (molecular weight distribution) The molecular weight distribution of the polymer is a value calculated from the number average molecular weight and weight average molecular weight measured under the following conditions. Liquid delivery system: Tosoh HLC-8420GPC Column: Tosoh TSK-GEL H type Solvent: THF (tetrahydrofuran) Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0050] Example 1 A reaction vessel was charged with 76 ppm by mass of zinc hexacyanocobaltate ethylene glycol dimethyl ether complex catalyst as a composite metal cyanide complex catalyst relative to the mass of the polyoxypropylene polymer, 2.5 phr of tetrahydrofuran (THF) relative to the mass of the polyoxypropylene polymer, 1076 g of polyoxypropylene glycol as an initiator, and 113 g of propylene oxide (PO). After charging, the internal temperature of the reaction vessel was heated to 95°C to activate the catalyst.

[0051] Next, the internal temperature of the reaction vessel was raised to 135°C, and at the same temperature, the addition of propylene oxide (PO) to the reaction vessel was started to initiate polymerization. Over a period of 300 minutes from the start of the reaction, 3311 g of propylene oxide (PO) was added to the reaction vessel at a uniform rate, and a polymerization reaction was carried out at 135°C. The polymerization reaction was continued for an additional 30 minutes to obtain a polyoxypropylene polymer. The molecular weight distribution of the resulting polymer was calculated from the number average molecular weight and weight average molecular weight measured by gel permeation chromatography. In addition, 0.5 mL of the obtained polymer was sampled, and the viscosity was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: RE-85U type) at a measurement temperature of 23°C with rotor No. 4 (3° x R14). JS14000 (manufactured by Nippon Grease Co., Ltd.) was used as the calibration standard solution. The viscosity values ​​of the obtained polymer are shown in Table 1.

[0052] (Examples 2 to 6, Comparative Examples 1 and 2) A polyoxypropylene polymer was obtained in the same manner as in Example 1, except that the conditions were changed to those shown in Table 1 below. The molecular weight distribution of the resulting polymer was calculated from the number average molecular weight and weight average molecular weight measured by gel permeation chromatography. The viscosity of the resulting polymer was measured in the same manner as in Example 1. The results of the viscosity measurements are shown in Table 1.

[0053] In Tables 1 and 2, the initiators used in the examples and comparative examples are as follows. I1: Polyoxypropylene glycol (hydroxyl value 0.676 mmol / g) I2: Polyoxypropylene glycol (hydroxyl value 0.998 mmol / g) I3: Polyoxypropylene triol (hydroxyl value 0.989 mmol / g)

[0054] In Tables 1 and 2, the composite metal cyanide catalysts used in the examples and comparative examples are as follows: C1: Ethylene glycol dimethyl ether-coordinated double metal cyanide catalyst C2: tert-Butyl alcohol-coordinated double metal cyanide catalyst

[0055] [Table 1]

[0056] (Example 7, Example 8, Comparative Example 3, and Comparative Example 4) A polyoxypropylene polymer was obtained in the same manner as in Example 1, except that the conditions were changed to those shown in Table 1 below. The molecular weight distribution of the resulting polymer was calculated from the number average molecular weight and weight average molecular weight measured by gel permeation chromatography. Table 2 shows the molecular weight distribution. The viscosity of the resulting polymer was measured in the same manner as in Example 1. The results of the viscosity measurements are shown in Table 2.

[0057] [Table 2]

[0058] Tables 1 and 2 show that the methods of the examples that satisfy the above-mentioned predetermined conditions can produce polyoxypropylene polymers that have a high molecular weight and a narrow molecular weight distribution, and therefore a low viscosity.

Claims

1. A method for producing a polyoxypropylene polymer having a design molecular weight value X (g / mol) of 12,000 g / mol or more and 30,000 g / mol or less, comprising: activating the composite metal cyanide complex catalyst by setting the internal temperature of a reaction vessel containing the initiator, the composite metal cyanide complex catalyst, and propylene oxide to 90°C or higher and 110°C or lower; After the internal temperature of the reaction vessel is set to a temperature of 90°C or higher and 110°C or lower, propylene oxide is additionally added to the reaction vessel over a period of Y minutes under the condition of 120°C or higher and 160°C or lower, thereby carrying out polymerization. Including, The manufacturing method, wherein the value of X / Y is 35 or more and 67 or less.

2. The method of claim 1 , wherein the double metal cyanide complex catalyst comprises an ether solvent as an organic ligand.

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