Method for producing polyoxypropylene polymer

Abstract

Provided is a method for producing a polyoxypropylene polymer with which it is possible to achieve a high average molecular weight in a short polymerization time. This method is a method for producing a polyoxypropylene polymer having a number average molecular weight of 30,000-70,000 (inclusive). The polymerization is carried out by additionally oxidizing propylene over time in a reaction system comprising a hydroxyl group-containing initiator and a composite metal cyanide complex catalyst. The polymerization temperature is set to 120-160 DEG C, the moisture content in the propylene oxide is 200 ppm or less, and the ratio (X / Y) of the designed molecular weight (X) to the time (Y) (minute) required to add the propylene oxide is 95-130.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for producing a polyoxypropylene polymer. BACKGROUND

[0002] Polyoxypropylene polymers are widely used for applications such as sealing materials, adhesives, paints, and the like. As a method for producing the same, a method in which ring-opening polymerization of propylene oxide is performed in the presence of a hydroxyl group-containing initiator and a polymerization catalyst is known.

[0003] In the polymerization reaction, as the polymerization catalyst, a complex metal cyanide complex catalyst (also referred to as a DMC catalyst) exhibits high activity, and thus is often used. As one example thereof, a zinc hexacyanocobaltate complex can be given.

[0004] For example, in Patent Literature 1, a method in which, in order to produce a polyoxyalkylene polymer having low viscosity, polymerization of alkylene oxide is performed in the presence of a complex metal cyanide complex catalyst while supplying alkylene oxide at a given rate is disclosed.

[0005] PRIOR ART DOCUMENTS

[0006] PATENT LITERATURE

[0007] Patent Literature 1: Japanese Patent No. 4277541 SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] When attempting to produce a polymer having a high average molecular weight as a polyoxypropylene polymer, there is a tendency that the reaction time required for the polymerization reaction becomes long.

[0010] If the polymerization time is shortened in order to improve the productivity of the polymer, the average molecular weight or the viscosity of the polymer decreases, and it is difficult to obtain a polyoxypropylene polymer having a desired average molecular weight or viscosity.

[0011] In view of the above-described circumstances, an object of the present application is to provide a method for producing a polyoxypropylene polymer having a high average molecular weight with a shorter polymerization time.

[0012] MEANS FOR SOLVING THE PROBLEMS

[0013] The present application was completed as a result of finding that, when propylene oxide is polymerized in the presence of a hydroxyl group-containing initiator and a complex metal cyanide complex catalyst, by controlling the ratio of the designed molecular weight to the time required for the addition of propylene oxide within a given range in addition to setting the temperature of the reaction system and the moisture content in propylene oxide within given ranges, respectively, a polyoxypropylene polymer having a high average molecular weight can be produced with a shorter polymerization reaction, and thus the present application was completed.

[0014] That is, the present application relates to a method of producing a polyoxypropylene polymer having a number average molecular weight of 30,000 or more and 70,000 or less as measured by gel permeation chromatography, the method comprising a step of performing polymerization of propylene oxide by adding propylene oxide over time to a reaction system containing a hydroxyl group-containing initiator and a complex metal cyanide complex catalyst,

[0015] The above polymerization is performed in a range set to 120 to 160°C,

[0016] The moisture content in the above propylene oxide is 200 ppm or less,

[0017] The ratio (X / Y) of the designed molecular weight X relative to the time Y (minutes) required for the addition of the above propylene oxide is 95 to 130.

[0018] Effects of the Invention

[0019] According to the present application, it is possible to provide a method of producing a polyoxypropylene polymer having a high average molecular weight in a short polymerization time. DETAILED DESCRIPTION

[0020] The embodiments of the present application will be described in detail below.

[0021] The present embodiment relates to a method of producing a polyoxypropylene polymer, which includes a step of performing polymerization of propylene oxide by adding propylene oxide over time to a reaction system containing a hydroxyl group-containing initiator and a complex metal cyanide complex catalyst.

[0022] The present embodiment aims to produce a high molecular weight polyoxypropylene polymer having a number average molecular weight of 30,000 or more and 70,000 or less. In producing a polyoxypropylene polymer having such a high molecular weight, it is desirable to continuously or intermittently add propylene oxide as a monomer to a reaction system over time. According to the present embodiment, the time for reacting by adding such propylene oxide can be shortened.

[0023] The number average molecular weight of the produced polyoxypropylene polymer is not particularly limited as long as it is in the range of 30,000 or more and 70,000 or less. From the viewpoint of ease of handling of the polymer, the upper limit is preferably 70,000 or less, and can be 60,000 or less, 50,000 or less, or 40,000 or less. The number average molecular weight is a value determined by gel permeation chromatography (GPC) and converted to polystyrene.

[0024] The molecular weight distribution (Mw / Mn) of the polyoxypropylene-based polymer produced is not particularly limited, and is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, further preferably 1.5 or less, particularly preferably 1.4 or less. In addition, from the viewpoint of improving the durability, elongation, and other mechanical properties of the cured product, it is preferably 1.3 or less, particularly preferably 1.2 or less. The molecular weight distribution (Mw / Mn) can be calculated from the number average molecular weight and the weight average molecular weight determined by GPC, converted to polystyrene.

[0025] The viscosity of the polyoxypropylene-based polymer produced is not particularly limited, and the viscosity determined at 23°C is preferably 40 Pa-s or more, more preferably 50 Pa-s or more, further preferably 60 Pa-s or more, particularly preferably 80 Pa-s or more, most preferably 90 Pa-s or more. According to the present embodiment, a polyoxypropylene-based polymer having such a high viscosity can be produced in a short time.

[0026] The propylene oxide used as the monomer is a substance having a high water absorption, and thus generally contains water as an impurity. However, when the moisture content of the propylene oxide becomes high, there is a tendency for the average molecular weight of the polyoxypropylene-based polymer obtained to decrease. Therefore, when producing a polyoxypropylene-based polymer having a high molecular weight with high productivity, it is preferable to use propylene oxide having a low moisture content. Specifically, the moisture content of the propylene oxide is preferably 200 ppm or less. More preferably, it is 150 ppm or less, further preferably 130 ppm or less, particularly preferably 100 ppm or less.

[0027] From the viewpoint of polymerizing the polyoxypropylene-based polymer to a high molecular weight, the moisture content of the propylene oxide is preferably low. However, there are difficulties in industrially using propylene oxide having an extremely low moisture content. From the viewpoint of ease of industrial use, the moisture content of the propylene oxide is preferably 20 ppm or more, more preferably 40 ppm or more, further preferably 50 ppm or more. According to the present embodiment, even when propylene oxide containing a certain amount of moisture is used, a polyoxypropylene-based polymer having a high molecular weight can be produced with good productivity.

[0028] As the propylene oxide having a moisture content as described above, commercially available products can be used, provided that the moisture content is within the range described above. In addition, propylene oxide having a reduced moisture content can be used by appropriately performing known drying or dehydration operations, and the like, on commercially available products containing a large amount of moisture.

[0029] As the hydroxyl group-containing initiator, there are no particular limitations, and examples that can be given include: monohydric alcohols such as methanol, ethanol, 1-propanol, 2-propanol, n-butanol, isobutanol, sec-butanol, t-butanol, 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; dihydric or higher alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, methylallyl alcohol, hydrogenated bisphenol A, neopentyl glycol, polybutylene glycol, diethylene glycol, triethylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene triol, polyoxypropylene tetraol, dipropylene glycol, glycerol, trimethylolmethane, trimethylolpropane, and pentaerythritol; and various polymers having a hydroxyl group. One of these can be used alone, or two or more of these can be used in combination. In the case where a variety of polymers having a hydroxyl group are used as the initiator, the same kind of polymer having a different molecular weight can be used in combination.

[0030] As the hydroxyl group-containing initiator, polyoxypropylene glycol, polyoxypropylene triol is preferably used. Of these, a compound having two hydroxyl groups in one molecule is more preferable because a polyoxypropylene polymer having a high molecular weight can be obtained, and polyoxypropylene glycol is preferably used.

[0031] The hydroxyl value of the hydroxyl group-containing initiator is not particularly limited, and is generally preferably around 0.1 to 10 mmol / g. The upper limit is more preferably 3 mmol / g or less, and further preferably 2 mmol / g or less.

[0032] In the case where polyoxypropylene glycol or polyoxypropylene triol is used as the hydroxyl group-containing initiator, the molecular weight X' of the hydroxyl group-containing initiator is preferably around 500 to 20,000, more preferably 1,000 to 15,000, and further preferably 1,500 to 12,000. The molecular weight X' of the hydroxyl group-containing initiator is defined by the following formula (2).

[0033] Molecular weight X' = (n x 1,000) / a (2)

[0034] In formula (2), a is the hydroxyl value (mmol / g) of the above-described hydroxyl group-containing initiator, and can be obtained by the measurement method of JIS K 1557-1. n is the number of hydroxyl groups contained in one molecule of the above-described hydroxyl group-containing initiator.

[0035] In the present embodiment, a complex metal cyanide complex catalyst is used as the polymerization catalyst. Thereby, a polyoxypropylene polymer having a high molecular weight and a small molecular weight distribution (Mw / Mn) can be obtained.

[0036] As the above-mentioned complex metal cyanide complex, a conventionally known compound can be used without particular limitation. Among them, a complex metal cyanide complex in which an organic ligand is coordinated to a catalyst skeleton is preferred.

[0037] As the catalyst skeleton of the complex metal cyanide complex, Zn3[Fe(CN)6]2, Zn3[Co(CN)6]2, Fe[Fe(CN)6], Fe[Co(CN)6], and the like can be mentioned. A zinc hexacyanocobaltate complex represented by Zn3[Co(CN)6]2is particularly preferred.

[0038] As the organic ligand, an alcohol, an ether can be used. Among these, alcohols such as t-butyl alcohol, ethanol, sec-butyl alcohol, n-butyl alcohol, isobutyl alcohol, t-amyl alcohol, isoamyl alcohol, isopropyl alcohol, and ethers such as glyme, diglyme, triglyme, dioxane, and polyethers having a number average molecular weight of 150 to 5000 can be mentioned. Among these, an ether-based organic solvent is preferred, and glyme is particularly preferred.

[0039] The amount of use of the complex metal cyanide complex is not particularly limited, and generally, 50 mass ppm or more, more preferably 80 mass ppm or more, and further preferably 100 mass ppm or more relative to the obtained polymer is preferred. Thereby, a polyoxypropylene polymer having a small molecular weight distribution (Mw / Mn) can be obtained.

[0040] The polymerization reaction of propylene oxide is preferably performed in the presence of an organic solvent. As the organic solvent, an organic solvent having no active hydrogen and having no activity for polymerization can be used without particular limitation. Polar compounds such as benzene, monochlorobenzene, toluene, ethylbenzene, styrene, o / m / p-xylene, heterocyclic compounds such as tetrahydrofuran, dioxane, furan, pyran, chain ethers such as butyl ethyl ether, and the like can be mentioned. The above-mentioned organic solvent can be used alone or in combination of two or more. Among them, a heterocyclic compound, a chain ether, more preferably tetrahydrofuran, dioxane, butyl ethyl ether, and particularly preferably tetrahydrofuran is preferred.

[0041] In the polymerization of propylene oxide, first, a reaction system containing a hydroxyl group-containing initiator and a complex metal cyanide complex catalyst is prepared. The reaction system can contain a small amount of propylene oxide, the above-mentioned organic solvent. The reaction system containing a small amount of propylene oxide is preferably heated to a temperature of, for example, about 50 to 110°C to activate the complex metal cyanide complex catalyst.

[0042] Next, by performing the polymerization reaction in the range of 120 to 160°C, a polyoxypropylene polymer of high molecular weight can be produced in a short polymerization time. The above temperature can 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. By performing the polymerization reaction in the given temperature range, even if the polymerization reaction is performed for a short time, the catalyst activity does not decrease until the end, and the internal pressure of the reaction vessel can be suppressed from rising, and thus is preferable in terms of safety.

[0043] While maintaining the temperature of the reaction system in such a temperature range, the polymerization is performed by adding propylene oxide to the reaction system over time. The method of adding propylene oxide can be continuous or intermittent as long as it is performed over time. It is desirable that propylene oxide be added at a certain supply rate.

[0044] As described later, the time Y required for the addition of propylene oxide is set in a manner that relates to the design molecular weight X, and thus the specific value thereof is not particularly limited, and is generally preferably around 300 to 1000 minutes. The upper limit is more preferably 800 minutes or less, and further preferably 600 minutes or less.

[0045] In the present embodiment, the design molecular weight X of the polyoxypropylene polymer is set. The design molecular weight X is a theoretical value calculated from the hydroxyl value of the used hydroxyl group-containing initiator, the number of hydroxyl groups in one molecule, the used amount thereof, and the total used amount of propylene oxide, and is different from the number average molecular weight obtained by measuring the actually produced polymer, the average molecular weight targeted.

[0046] Specifically, the design molecular weight X can be calculated as a value obtained by dividing the total weight of the initiator and propylene oxide by the number of moles of the initiator corresponding to each 1 hydroxyl group, from the following formula (1).

[0047] Design molecular weight X = (b + c) / (a x b / (m x 1000))... (1)

[0048] In formula (1), a is the hydroxyl value (mmol / g) of the above hydroxyl group-containing initiator, and can be calculated by the measurement method of JIS K 1557-1. b is the weight (g) of the above hydroxyl group-containing initiator, and c is the total weight (g) of propylene oxide used in the above polymerization, and m is the number of hydroxyl groups contained in one molecule of the above hydroxyl group-containing initiator. The total weight of propylene oxide represented by c is the value obtained by adding the initial weight of propylene oxide contained in the initial reaction system and the weight of the added propylene oxide.

[0049] In the case where two or more initiators are used in combination, the design molecular weight X can be determined as a value obtained by dividing the total weight of all the initiators and the propylene oxide by the total number of moles corresponding to each hydroxyl group of the respective initiators. Specifically, in the case where n initiators are used, the above formula (1) can be modified as follows.

[0050] Design molecular weight X = ((b1 + b2 +... + bn) + c) / ((a1 x b1 / (m1 x 1000)) + (a2 x b2 / (m2 x 1000)) +... + (an x bn / (man x 1000))... (1) n n n n

[0051] In formula (1), a n is the hydroxyl value (mmol / g) of the nth hydroxyl group-containing initiator. b n is the weight (g) of the nth hydroxyl group-containing initiator. c is the total weight (g) of the propylene oxide used in the above polymerization, and m n is the number of hydroxyl groups contained in one molecule of the nth hydroxyl group-containing initiator.

[0052] As described below, the design molecular weight X is set in relation to the time Y required for the addition of the propylene oxide, and is not particularly limited in its specific value, and is preferably about 40,000 to about 120,000, and further preferably about 50,000 to about 100,000.

[0053] In the present embodiment, the ratio (X / Y) of the design molecular weight X to the time Y (minutes) required for the addition of the propylene oxide is set to be within the range of 95 to 130. In this way, by setting the design molecular weight corresponding to the addition time within a given range, a polyoxypropylene polymer having a high molecular weight can be produced in a short polymerization time. When X / Y is less than 95, the molecular weight of the polyoxypropylene polymer is not high enough. In the present embodiment, the value of X / Y can be, for example, 100 to 130, 100 to 125, 105 to 130, 105 to 125, 110 to 130, or 110 to 125, or the like.

[0054] The polymerization reaction is preferably performed under an atmosphere of a non-reactive gas such as nitrogen or argon. After the addition of the propylene oxide is completed, the polymerization reaction is continued for, for example, about 10 minutes to about 1 hour, and then the unreacted propylene oxide and the organic solvent are distilled off, whereby a polyoxypropylene polymer can be obtained. In addition, by washing with water or an organic solvent, metal impurities from the polymerization catalyst can be removed.

[0055] Based on the above-described polymerization reaction, a polyoxypropylene polymer having a high average molecular weight as a target can be efficiently produced in a short polymerization time. ​​​​

[0056] <Hydrolyzable silyl group-containing polyoxypropylene polymer>

[0057] The polyoxypropylene polymer obtained according to the present embodiment has a hydroxyl group at the terminal of the main chain. By utilizing this hydroxyl group, a hydrolyzable silyl group can be introduced in one step or two or more steps, and thus a hydrolyzable silyl group-containing polyoxypropylene polymer can be produced.

[0058] The hydrolyzable silyl group refers to a silyl group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and which can form a crosslink by forming a siloxane bond. Specifically, it can be represented by the following formula.

[0059] -SiR 1 b R 2 3-b (3)

[0060] In the above formula, R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. R 2 represents a hydroxyl group or a hydrolyzable group. b represents 0, 1, or 2, and is preferably 0 or 1.

[0061] R 1 The number of carbon atoms of the hydrocarbon group represented by R 1 is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3. As specific examples of R 2 , for example, 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, and the like can be given. Among these, from the viewpoint of hydrolysis stability and ease of handling, an alkoxy group such as a methoxy group and an ethoxy group is more preferable, and a methoxy group and an ethoxy group are particularly preferable.

[0062] As R 2 , for example, 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, and the like can be given. Among these, from the viewpoint of hydrolysis stability and ease of handling, an alkoxy group such as a methoxy group and an ethoxy group is more preferable, and a methoxy group and an ethoxy group are particularly preferable.

[0063] As specific examples of the above hydrolyzable silyl group, a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetyloxy silyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a (chloromethyl)dimethoxysilyl group, a (chloromethyl)diethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilyl group, a (N,N-diethylaminomethyl)dimethoxysilyl group, a (N,N-diethylaminomethyl)diethoxysilyl group, and the like can be given.

[0064] The specific production method of the hydrolyzable silyl group-containing polyoxypropylene polymer is not particularly limited, and as an example, a method in which a urethanization reaction is performed between the isocyanate group of a hydrolyzable silyl group-containing isocyanate compound and the hydroxyl group of a polyoxypropylene polymer can be given. In the obtained hydrolyzable silyl group-containing polyoxypropylene polymer, the polymer skeleton and the hydrolyzable silyl group are bonded via a urethane bond.

[0065] The above-mentioned hydrolyzable silyl group-containing isocyanate compound is a compound having an isocyanate group and a hydrolyzable silyl group in the same molecule, and is not particularly limited, and examples that can be given include: (isocyanatomethyl)trimethoxysilane, (isocyanatomethyl)triethoxysilane, (isocyanatomethyl)dimethoxymethylsilane, (isocyanatomethyl)diethoxymethylsilane, (3-isocyanatopropyl)trimethoxysilane, (3-isocyanatopropyl)dimethoxymethylsilane, (3-isocyanatopropyl)triethoxysilane, (3-isocyanatopropyl)diethoxymethylsilane, and the like.

[0066] The urethanization reaction can also be performed without using a urethanization catalyst, but in order to improve the reaction speed and the reaction rate, it can be performed in the presence of a urethanization catalyst. As such a urethanization catalyst, a conventionally known urethanization catalyst such as the catalyst listed in Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963 can be used. Specifically, examples that can be given include: organotin compounds, bismuth compounds, and basic catalysts such as organic amines, but are not limited to these.

[0067] As another example of the production of the hydrolyzable silyl group-containing polyoxypropylene polymer, a method in which the hydroxyl group of a polyoxypropylene polymer is reacted with an alkali metal salt, then reacted with a halide containing a carbon-carbon unsaturated bond, the hydroxyl group of the polyoxypropylene polymer is converted into a group containing a carbon-carbon unsaturated bond, and then a hydrolyzable silyl group-containing hydrosilane compound is subjected to a hydrosilylation reaction with the group containing a carbon-carbon unsaturated bond, and the group containing a carbon-carbon unsaturated bond is converted into a hydrolyzable silyl group can be given. The hydrolyzable silyl group-containing polyoxypropylene polymer thus obtained generally does not contain a urethane bond.

[0068] Specific examples of the above-mentioned alkali metal salt are not particularly limited, and examples that can be given include: sodium hydroxide, sodium alcoholate, potassium hydroxide, potassium alcoholate, lithium hydroxide, lithium alcoholate, cesium hydroxide, cesium alcoholate, and the like.

[0069] As specific examples of the halide containing carbon-carbon unsaturated bond, there are no particular limitations, and examples that can be given include chloroethylene, allyl chloride, methylallyl chloride, bromoethylene, allyl bromide, methylallyl bromide, iodoethylene, allyl iodide, and methylallyl iodide, and the like. From the viewpoint of ease of handling, allyl chloride and methylallyl chloride are preferred.

[0070] In addition, with respect to the polyoxypropylene polymer after reaction with the alkali metal salt, first, it is reacted with an epoxy compound having a carbon-carbon unsaturated bond (for example, allyl glycidyl ether), and then, reacted with the above-mentioned halide containing carbon-carbon unsaturated bond, whereby a polyoxypropylene polymer having two or more carbon-carbon unsaturated bonds at one terminal can also be formed.

[0071] As specific examples of the above-mentioned hydrolyzable silyl hydrosilane compound, there are no particular limitations, and examples that can be given include halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, bis(methoxymethyl)chlorosilane, and the like; alkoxysilanes such as 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)dimethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyl]dimethylsilane, [(chloromethyl)diethoxysilyl]dimethylsilane, [(methoxymethyl)dimethoxysilyl]dimethylsilane, [(methoxymethyl)diethoxysilyl]dimethylsilane, [(diethylaminomethyl)dimethoxysilyl]dimethylsilane, [(3,3,3-trifluoropropyl)dimethoxysilyl]dimethylsilane, and the like; acyloxysilanes such as diacetoxy-methylsilane, diacetoxyphenylsilane, and the like; ketoximosilanes such as bis(dimethylketoximo)methylsilane, bis(cyclohexylketoximo)methylsilane, and the like; isopropenoxysilanes (depropanedione type) such as triisopropenoxysilane, (chloromethyl)diisopropenoxysilane, (methoxymethyl)diisopropenoxysilane, and the like.

[0072] To promote the reaction, the hydrosilylation reaction is preferably performed in the presence of a hydrosilylation catalyst. As the hydrosilylation catalyst, metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, complexes thereof, and the like can be used. Specifically, catalysts in which platinum is supported on a carrier such as alumina, silica, and carbon black; chloroplatinic acid; chloroplatinic acid complexes formed from chloroplatinic acid and an alcohol, an aldehyde, or a ketone, and the like; platinum-olefin complexes [for example, Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2]; platinum-vinylsiloxane complexes [for example, Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4]; platinum-phosphine complexes [for example, Ph(PPh3)4, Pt(PBu3)4]; platinum-phosphite complexes [for example, Pt{P(OPh)3}4]; ruthenium complexes to which 2,3-dibromonorbomadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,3,5-tribromobenzene, 1,4-diiodobenzene, or hexabromobenzene, and the like are coordinated, and the like can be used. From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid, platinum vinylsiloxane complexes, and the like are preferred, and from the viewpoint of improving the silyl group introduction rate, ruthenium complexes are preferred.

[0073] <Curable composition containing a hydrolyzable silyl group-containing polyoxypropylene polymer>

[0074] The hydrolyzable silyl group-containing polyoxypropylene polymer produced by the above method can be included in a curable composition. The curable composition can use only one kind of polyoxypropylene polymer, or two or more kinds in combination.

[0075] A curing catalyst, a silicon compound, an adhesive, a plasticizer, a solvent, a diluent, a silicate, a filler, an anti-sag agent, an antioxidant, a light stabilizer, an ultraviolet absorber, a property adjuster, a tackifying resin, an epoxy group-containing compound, a photocurable substance, an oxygen-curable substance, a surface property modifier, an epoxy resin, another resin, a flame retardant, a blowing agent, and the like can be added to the curable composition containing the hydrolyzable silyl group-containing polyoxypropylene polymer.

[0076] In addition, various additives can be added to the above curable composition as needed in order to adjust the respective properties of the composition or the cured product. As examples of such additives, for example, a curing adjuster, a radical inhibitor, a metal deactivator, an ozone deterioration preventive, a phosphorus peroxide decomposer, a lubricant, a pigment, and a mildew preventive, and the like can be given.

[0077] <<Use>>

[0078] The above-mentioned curable composition can be used as an adhesive, a sealing material for buildings / ships / automobiles / highways, etc., a bonding agent, a waterproofing material, a coating waterproofing material, a mold release agent ), a vibration-damping material, a shock-absorbing material, a soundproofing material, a foaming material, a paint, and a spray-on material. The cured product obtained by curing the above-mentioned curable composition is excellent in flexibility and adhesiveness, and thus can be suitably used as a sealing material or a bonding agent.

[0079] In addition, the above-mentioned curable composition can be used for electrical / electronic component materials such as a solar cell back surface encapsulant, electrical / electronic components such as an electrical insulation material for electrical / electronic devices, an acoustic insulation material, an elastic adhesive, an adhesive, a contact-type adhesive, a spray-type sealing material, a crack repair material, a tile laying adhesive, a bituminous waterproofing material adhesive, a powder paint, a casting material, a medical rubber material, a medical adhesive, a medical adhesive sheet, a medical device sealing material, a dental impression material, a food packaging material, a sealing material for joints of exterior materials such as an extrusion-molded sheet, a paint, a non-slip coating material, a cushioning material, a primer, an electroconductive material for electromagnetic wave shielding, a thermal conductive material, a hot melt material, an electrical / electronic adhesive, a film, a gasket, a concrete reinforcing material, a temporary fixing adhesive, various molding materials, and a sealing material for rust / waterproofing of wired glass, laminated glass end faces (cut portions), an automotive component, a large vehicle component such as a truck / bus, a train vehicle component, an aircraft component, a ship component, a motor component, various mechanical components, and a liquid sealant used in various applications. In the case of an automobile, it can be used in a wide variety of applications such as adhesive bonding of various types of plastic cover plates, trim panels, flanges, bumpers, window installations, interior members, and exterior members, and the like. Furthermore, since it can adhere to a wide range of substrates such as glass, ceramics, wood, metal, resin molded articles, and the like, either alone or with the aid of a primer, it can be used as a sealing composition and an adhesive composition of various types. In addition, the composition of the present embodiment can also be used as an interior panel adhesive, an exterior panel adhesive, a tile laying adhesive, a stone laying adhesive, a ceiling finishing adhesive, a floor finishing adhesive, a wall finishing adhesive, a vehicle panel adhesive, an electrical / electronic / precision instrument assembly adhesive, an adhesive for bonding leather, fiber products, cloth, paper, boards, and rubber, a reactive post-crosslinking pressure-sensitive adhesive, a direct glazing sealing material, a sealing material for multi-layer glass, a sealing material for SSG work, a working joint sealing material for buildings, a civil engineering material, a bridge material. In addition, it can also be used as an adhesive material such as a tape, an adhesive sheet, and the like.

[0080] Preferred modes in the present disclosure are exemplified in each of the following items, but the present invention is not limited to the following items.

[0081] [Item 1]

[0082] A method for producing a polyoxypropylene polymer having a number average molecular weight of 30,000 or more and 70,000 or less as measured by gel permeation chromatography, the method comprising:

[0083] a step of polymerizing the propylene oxide by adding the propylene oxide over time to a reaction system containing a hydroxyl group-containing initiator and a complex metal cyanide complex catalyst,

[0084] the polymerization is performed in a range set to 120 to 160°C,

[0085] the moisture content in the propylene oxide is 200 ppm or less,

[0086] the ratio (X / Y) of the designed molecular weight X relative to the time Y (minutes) required for the addition of the propylene oxide is 95 to 130.

[0087] [Item 2]

[0088] The production method according to item 1, wherein

[0089] the moisture content in the propylene oxide is 40 ppm or more.

[0090] [Item 3]

[0091] The production method according to item 1 or 2, wherein

[0092] the hydroxyl group-containing initiator has two hydroxyl groups in one molecule.

[0093] [Item 4]

[0094] The production method according to item 1 to 3, wherein

[0095] the complex metal cyanide complex catalyst contains an ether-based organic solvent as a ligand.

[0096] [Item 5]

[0097] The production method according to item 1 to 4, wherein

[0098] the polyoxypropylene polymer has a viscosity of 40 Pa-s or more at 23°C.

[0099] Examples

[0100] The following examples illustrate the present application in more detail, but the present application is not limited to these examples.

[0101] (Number average molecular weight, weight average molecular weight)

[0102] The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer were GPC molecular weights measured under the following conditions.

[0103] Liquid delivery system: HLC-8420 GPC manufactured by Tosoh Corporation

[0104] Column: TSK-GEL H type manufactured by Tosoh Corporation

[0105] Solvent: THF (tetrahydrofuran)

[0106] Molecular weight: polystyrene conversion

[0107] Measurement temperature: 40°C

[0108] (PO moisture content)

[0109] The moisture content in propylene oxide (PO moisture content) was a value measured using a Karl Fischer moisture meter (Model MKH-700) manufactured by Kyoto Electronic Industrial Co., Ltd.

[0110] (Example 1)

[0111] A zinc hexacyanocobaltate ethylene glycol dimethyl ether complex catalyst 0.50 g as a complex metal cyanide complex catalyst, tetrahydrofuran (THF) 90 g, a polyoxypropylene glycol having 2 hydroxyl groups in 1 molecule (hydroxyl value 0.179 mmol / g) 360 g as an initiator, a polyoxypropylene glycol having 2 hydroxyl groups in 1 molecule (hydroxyl value 0.676 mmol / g) 166 g, and propylene oxide (PO) 60 g were added to a reaction vessel, and the catalyst was activated by heating to 95°C while stirring with a stirrer.

[0112] Next, the internal temperature of the reaction vessel was maintained at 135°C, and 3741 g of propylene oxide, the water content of which was measured in advance, was added over 480 minutes. The moisture content of the added propylene oxide used was 60 ppm.

[0113] After the polymerization reaction was completed, the polymerization reaction was continued for 30 minutes, and then unreacted PO and THF were removed, to obtain a polyoxypropylene-based polymer.

[0114] The number average molecular weight and the weight average molecular weight of the obtained polymer measured by gel permeation chromatography, and the value of the molecular weight distribution calculated from the number average molecular weight and the weight average molecular weight are shown in Table 1.

[0115] In addition, the viscosity of the obtained polymer was measured using an E-type viscometer (manufactured by Tokimec, Inc., product name: RE-85U type) at a temperature of 23°C and a rotor No. 4 (3° x R14). JS14000 (manufactured by Japan Grease Co., Ltd.) was used as a standard solution for calibration. The viscosity values of the obtained polymers are shown in Table 1.

[0116] (Examples 2 to 3, Comparative Examples 1 to 5, Reference Example 1)

[0117] The conditions shown in Table 1 were changed, and otherwise, the same operations as in Example 1 were performed to obtain a polyoxypropylene polymer.

[0118] The number average molecular weight, weight average molecular weight, molecular weight distribution, and viscosity values of the obtained polymers were measured in the same manner as in Example 1, and are shown in Table 1.

[0119]

[0120] The following was found from Table 1. In Reference Example 1, the polymerization was performed by adding propylene oxide for a long time of 1080 minutes, and a polyoxypropylene polymer having a desired average molecular weight or viscosity was produced.

[0121] In each of Examples and Comparative Examples, the time Y required for the addition of propylene oxide was shortened to about half that of Reference Example 1, and examples of polymerization in a short time were attempted.

[0122] In Comparative Example 1, the average molecular weight and viscosity of the polymer produced were greatly decreased compared to those in Reference Example 1. In Comparative Example 2, although the design molecular weight X was set to a value greater than those in Comparative Example 1 and Reference Example 1, the average molecular weight and viscosity of the polymer produced were decreased compared to those in Comparative Example 1.

[0123] In Comparative Example 3, although the reaction temperature was set to a value higher than those in Comparative Examples 1 and 2, the value of X / Y was not sufficiently large, and the average molecular weight and viscosity of the polymer were further decreased.

[0124] In Comparative Example 4, the design molecular weight X was set to a value greater than those in Comparative Examples 1 to 3, and the time Y required for the addition of propylene oxide was set to be slightly longer, and the value of X / Y was the same level as that in Comparative Example 1. As a result, the average molecular weight and viscosity of the polymer were lower than those in Reference Example 1.

[0125] In Comparative Example 5, propylene oxide having a high moisture content was used, and the average molecular weight and viscosity of the polymer were greatly decreased.

[0126] In Examples 1 to 3 in which the reaction temperature and the PO water content were set in given ranges while the X / Y was controlled in a given range, relative to these Comparative Examples, the values of the average molecular weight and the viscosity of the polymer were improved compared to those of the respective Comparative Examples, and values close to those of Reference Example 1 were able to be achieved. That is, it was known that in Examples 1 to 3, a polyoxypropylene polymer having values of the average molecular weight and the viscosity on the same level as those of Reference Example 1 was able to be produced with a reaction time that was substantially shorter than that of Reference Example 1.

Claims

1. A method for producing a polyoxypropylene polymer having a number average molecular weight of 30,000 or more and 70,000 or less as measured by gel permeation chromatography, the method comprising: a step of conducting polymerization of propylene oxide by adding propylene oxide over time to a reaction system containing a hydroxyl group-containing initiator and a complex metal cyanide complex catalyst, the polymerization is conducted at a temperature in the range of 120 to 160°C, a moisture content in the propylene oxide is 200 ppm or less, a ratio (X / Y) of a designed molecular weight X to a time Y (minutes) required for the addition of the propylene oxide is 95 to 130.

2. The production method according to claim 1, wherein, the moisture content in the propylene oxide is 40 ppm or more.

3. The production method according to claim 1 or 2, wherein, the hydroxyl group-containing initiator has two hydroxyl groups in one molecule.

4. The production method according to claim 1 or 2, wherein, the complex metal cyanide complex catalyst contains an ether-based organic solvent as a ligand.

5. The production method according to claim 1 or 2, wherein, the polyoxypropylene polymer has a viscosity of 40 Pa-s or more at 23°C. ​

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