JP2002088148A - Method for producing hydrolyzable silyl group-containing oxyalkylene polymer and curable composition - Google Patents

Abstract

(57) Abstract: A method for producing a hydrolyzable silyl group-containing oxyalkylene polymer having a high molecular weight and a narrow molecular weight distribution. SOLUTION: As an organic ligand, an alkylene oxide is reacted by using a double metal cyanide complex in which a mixture of t-butyl alcohol and another compound is coordinated as a catalyst to have a number average molecular weight of 5,000 to 30,000 and a total degree of unsaturation. 0.02
A method for producing a oxyalkylene polymer containing a polymer by obtaining a polymer having a meq / g or less and converting a terminal hydroxyl group of the polymer into a hydrolyzable silyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition curable in the presence of moisture and a method for producing a hydrolyzable silyl group-containing oxyalkylene polymer as a raw material thereof.

[0002]

2. Description of the Related Art Methods of curing various polymers containing a hydrolyzable silyl group and using them for sealing materials and adhesives are well known and industrially useful. Among such polymers, particularly those having a main chain of polyoxyalkylene are liquid at room temperature, and the cured product retains flexibility even at a relatively low temperature, and is used as a sealing material or an adhesive. In that case, it has preferable characteristics. Also, by using these hydrolyzable silyl group-containing polymers in combination with an epoxy resin or an acrylic resin, a method for improving strength, adhesion and weather resistance is also widely known, and an industrially useful method. It has become. As the hydrolyzable silyl group-containing oxyalkylene polymer, a polymer having a relatively high molecular weight is used because of its excellent properties such as curability, elongation, and strength. As a method for obtaining such a polymer, a polyol having an easily obtainable molecular weight such as a polyoxyalkylene diol having a molecular weight of about 3,000 (hereinafter referred to as an easily obtainable polyol) is used as a raw material, and a polyvalent halogen compound is reacted to increase the molecular weight. Then, a method of introducing an unsaturated group into the molecular terminal and reacting the unsaturated group with a hydrolyzable group-containing silicon hydride compound (JP-A-53-134095, JP-A-55-13)
768 publication) is known. Further, a method of converting the terminal group of an easily available polyol into an unsaturated group, and then increasing the molecular weight by reacting with a polyvalent silicon hydride compound, and further converting the remaining silyl hydride group into a hydrolyzable group silyl group. (JP-A-55-13767, JP-A-55-13)
768, JP-A-59-131625, JP-A-57-158226 and JP-A-58-426.
No. 91) has also been proposed.

However, any of the above-mentioned known methods is a method of obtaining a high molecular weight polymer by using polyoxypropylene glycol having a molecular weight of about 3,000 as a raw material, which is easily available, and increasing the amount thereof. Therefore, the hydrolyzable silyl group-containing polymer as the final product contains a large amount of low-molecular-weight hydrolyzable silyl group-containing organic polymer derived from the readily available polyol as a raw material, and such a low-molecular-weight curable polymer is used. There was a disadvantage that the curability was poor due to the presence of the polymer. On the other hand, using an oxyalkylene polymer having a high molecular weight and a narrow molecular weight distribution obtained by reacting an alkylene oxide with a double metal cyanide complex as a catalyst in the presence of an initiator, a hydrolyzable silyl group-containing oxyalkylene is used. A method for producing a polymer is disclosed in JP-A-3-72527.
No., published in Japanese Unexamined Patent Publication No. The polymer obtained by this method is excellent in curability because it can have a higher molecular weight when compared with the same viscosity because the content of the polymer having a low molecular weight is smaller than that of a conventionally known polymer. It has the characteristic of having a large breaking elongation. However, even when such a curable composition containing a hydrolyzable silyl group-containing oxyalkylene polymer having a narrow molecular weight distribution is used for a sealing material, an adhesive, or the like, there are cases where the curability is still insufficient. Was.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a curable composition which has solved the above-mentioned disadvantages, and has a curable composition having improved curability and a high molecular weight as a raw material. An object of the present invention is to provide a hydrolyzable silyl group-containing oxyalkylene polymer having a narrow molecular weight distribution.

[0005]

That is, the present invention is the following invention. The alkylene oxide is reacted in the presence of an initiator and an alkylene oxide ring-opening polymerization catalyst to give a number average molecular weight of 5,000 to 30,000 and a total degree of unsaturation of 0.0
After obtaining a hydroxyl group-terminated oxyalkylene polymer (polymer (A)) of 2 meq / g or less, the terminal hydroxyl group of the polymer (A) is converted into an unsaturated group, and further, a functional group which undergoes an addition reaction to the unsaturated group. (B) having a group and a hydrolyzable silyl group
And a method for producing a hydrolyzable silyl group-containing oxyalkylene polymer. In the above method for producing a hydrolyzable silyl group-containing oxyalkylene polymer, the alkylene oxide ring-opening polymerization catalyst is a complex metal cyanide in which t-butyl alcohol or t-butyl alcohol is coordinated with another compound as an organic ligand. The production method is a compound complex catalyst. In the above method for producing a hydrolyzable silyl group-containing oxyalkylene polymer, the alkylene oxide ring-opening polymerization catalyst may comprise, as an organic ligand, t-butyl alcohol and a compound represented by the following formula (1), ethanol, s -Butyl alcohol, n-butyl alcohol,
Isobutyl alcohol, t-pentyl alcohol, isopentyl alcohol, N, N-dimethylacetamide,
Ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme),
A production method which is a double metal cyanide complex catalyst in which one or more compounds selected from triethylene glycol dimethyl ether (triglyme), isopropyl alcohol, dioxane, and a polyether having a number average molecular weight of 150 or more are coordinated.

R ¹ -C (CH ₃ ) ₂ (OR ⁰ ) _n OH (1) In the formula (1), R ¹ represents a methyl group or an ethyl group,
R ⁰ is an ethylene group or a group in which a hydrogen atom of the ethylene group is substituted with a methyl group or an ethyl group, and n is an integer of 1 to 3. The method for producing a hydrolyzable silyl group-containing oxyalkylene polymer, wherein the alkylene oxide ring-opening polymerization catalyst is a double metal cyanide complex catalyst obtained by coordinating a zinc hexacyanocobaltate complex with an organic ligand. Method. In the above method for producing a hydrolyzable silyl group-containing oxyalkylene polymer, the viscosity of the hydrolyzable silyl group-containing oxyalkylene polymer may be 5 at 25 ° C.
A production method that is not less than Pa · s. A method for producing a room-temperature curable composition, comprising mixing a filler and a curing catalyst with the hydrolyzable silyl group-containing oxyalkylene polymer.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a hydroxyl-terminated oxyalkylene polymer (polymer (A)) as a raw material of a hydrolyzable silyl group-containing oxyalkylene polymer is used as an initiator and an alkylene oxide ring-opening polymerization catalyst. It is obtained by reacting an alkylene oxide in the presence. As the initiator, an active hydrogen-containing compound can be used, and examples thereof include the following compounds. The following may be used alone or in combination of two or more. Further, a compound having 1 to 4 active hydrogen atoms in one molecule is particularly preferable. water. Monohydric alcohols such as n-butanol. Monohydric unsaturated group-containing alcohols such as allyl alcohol and propenyl alcohol. Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol And polyhydric alcohols such as glycerin, diglycerin, trimethylolpropane, pentaerythritol, glucose, sorbitol, sucrose and methylglycoside. Alkanolamines such as monoethanolamine, diethanolamine and triethanolamine. Phenol compounds such as bisphenol A, bisphenol F, bisphenol S, resorcinol and hydroquinone. Aliphatic amines such as ethylenediamine, diethylenetriamine and hexamethylenediamine. Alternatively, an oxyalkylene polymer having a lower molecular weight than a target product (hydrolyzable silyl group-containing oxyalkylene polymer) obtained by reacting these with an alkylene oxide.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, -Ethylhexylene glycidyl ether, trifluoropropylene oxide and the like. These may be used alone or in combination of two or more. Of these, propylene oxide is preferred.
In the present invention, the alkylene oxide ring-opening polymerization catalyst is preferably a double metal cyanide complex catalyst. The double metal cyanide complex catalyst is produced by coordinating an organic ligand to a reaction product (hereinafter, referred to as a catalyst skeleton) obtained by reacting a metal halide and an alkali metal cyanometalate in water. Are preferred.

As the metal of the metal halide salt, Zn (I
I), Fe (II), Fe (III), Co (II), Ni (II), Mo
(IV), Mo (VI), Al (III), V (V), Sr (II), W (I
V), W (VI), Mn (II), Cr (III), Cu (II), Sn (I
One or more selected from I) and Pb (II)
Preferably, it is used. Especially Zn (II) or Fe (II)
preferable. Cyanometa of alkali metal cyanometallates
The metal constituting the rate is Fe (II), Fe (II)
I), Co (II), Co (III), Cr (II), Cr (III), Mn
(II), Mn (III), Ni (II), V (IV) and V (V)
It is preferable to use one or more selected ones.
Co (III) or Fe (III) is particularly preferred. Catalytic skeleton
The synthesis reaction consists of an aqueous solution of a metal halide salt and an alkali metal salt.
It is preferable to carry out by mixing an aqueous solution of anomalate.
Alkali metal cyanometa
It is more preferable to carry out the reaction by dropping a rate aqueous solution. reaction
The temperature is preferably from 0 ° C to less than 70 ° C, and from 30 ° C to 70 ° C.
It is more preferable that the temperature be lower than 0 ° C. As the catalyst skeleton, Zn₃[F
e (CN)₆]₂, Zn₃[Co (CN)₆] ₂, Fe
[Fe (CN)₆], Fe [Co (CN)₆Is preferred
No. Of these, Zn₃[Co (CN)₆]₂(Sunawa
Or zinc hexacyanocobaltate complex)
No.

Next, a compound which becomes an organic ligand is made to bind to the catalyst skeleton. In the present invention, it is preferable to use t-butyl alcohol or a mixture of t-butyl alcohol and another compound as the organic ligand.
Examples of the compound used in combination with t-butyl alcohol include a compound represented by the following formula (1), ethanol, s-butyl alcohol, n-butyl alcohol, isobutyl alcohol, t-pentyl alcohol, isopentyl alcohol, N , N-dimethylacetamide, glyme, diglyme, triglyme, isopropyl alcohol, dioxane, and one or more compounds selected from polyethers having a number average molecular weight of 150 or more are preferred.

R ¹ -C (CH ₃ ) ₂ (OR ⁰ ) _n OH (1) In the formula (1), R ¹ represents a methyl group or an ethyl group,
R ⁰ is an ethylene group or a group in which a hydrogen atom of the ethylene group is substituted with a methyl group or an ethyl group, and n is an integer of 1 to 3. The compounds represented by the formula (1) include the following compounds. Ethylene glycol mono-t-butyl ether, propylene glycol mono-t-butyl ether, 1,2-butylene glycol mono-t-butyl ether, isobutylene glycol mono-t-butyl ether, ethylene glycol mono-t-pentyl ether, propylene glycol mono-t -Pentyl ether, 1,2-butylene glycol mono-t-pentyl ether, isobutylene glycol mono-t-pentyl ether, diethylene glycol mono-t-butyl ether, dipropylene glycol mono-t-butyl ether, di-1,2-butylene glycol Mono-t-butyl ether, diisobutylene glycol mono-t-butyl ether, diethylene glycol mono-t-pentyl ether, dipropylene glycol mono-t Pentyl ether, di-1,2-butylene glycol mono -t- pentyl ether, di-isobutylene glycol mono -t- pentyl ether, triethylene glycol monobutyl -t- butyl ether, tripropylene glycol monobutyl -t- butyl ether, tri -
1,2-butylene glycol mono-t-butyl ether, triisobutylene glycol mono-t-butyl ether, triethylene glycol mono-t-pentyl ether, tripropylene glycol mono-t-pentyl ether, tri-1,2-butylene glycol mono -T-
Pentyl ether, triisobutylene glycol mono-
t-pentyl ether.

Of these, the compound used in combination with t-butyl alcohol is particularly preferably a compound represented by the formula (1): ethylene glycol mono-t-butyl ether,
Propylene glycol mono-t-butyl ether, ethylene glycol mono-t-pentyl ether, propylene glycol mono-t-pentyl ether, diethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol mono-t-butyl ether, triethylene glycol mono-t-butyl ether Ethylene glycol mono-t-pentyl ether is more preferred. Ethylene glycol mono-t-butyl ether, propylene glycol mono-t-butyl ether, ethylene glycol mono-t-pentyl ether and propylene glycol mono-t-pentyl ether are more preferred, and ethylene glycol mono-t-butyl ether is most preferred. When t-butyl alcohol and another compound are used in combination, the mixing ratio is preferably such that the mass ratio of t-butyl alcohol / other compound is 20 to 95/80 to 5. The double metal cyanide complex catalyst is an organic coordination catalyst containing t-butyl alcohol or a mixture of t-butyl alcohol and another compound with a catalyst skeleton obtained by reacting a metal halide salt with an alkali metal cyanometalate. It is manufactured by heating and stirring in a daughter solution (aging process), followed by filtration, washing and drying by a known method.

In the present invention, the production of the polymer (A) is preferably carried out under the following conditions. The use amount of the catalyst is preferably 1 to 5000 ppm based on the active hydrogen-containing compound,
30 to 2000 ppm is more preferred. As a method of supplying the alkylene oxide, a method of supplying a necessary amount of the alkylene oxide in several steps or a method of continuously supplying the alkylene oxide is used. The reaction of the alkylene oxide may be started from a reduced pressure state or from an atmospheric pressure state. When starting the reaction from atmospheric pressure,
It is desirable to carry out the reaction in the presence of an inert gas such as nitrogen or helium. In the reaction of the alkylene oxide, a solvent may be used. Pentane, hexane,
Examples thereof include aliphatic hydrocarbons such as heptane, ethers such as tetrahydrofuran and dioxane, and aprotic polar solvents such as dimethyl sulfoxide and N, N-dimethylformamide. The produced polymer (A)
Has a number average molecular weight of 5,000 to 30,000 and a total degree of unsaturation of not more than 0.02 meq / g. Number average molecular weight is 800
0-25000 is preferable, and 12000-22000 is especially preferable. The total degree of unsaturation is particularly preferably 0.015 meq / g or less.

In order to convert the terminal hydroxyl group of the polymer (A) into an unsaturated group, for example, a method of converting the terminal hydroxyl group into an alkoxide of an alkali metal or an alkaline earth metal and then reacting the alkoxide with a compound having an unsaturated group can be mentioned. . For conversion to an alkoxide, an alkali metal or alkaline earth metal hydroxide, an alkali metal hydride, and an alkali metal alkoxide can be used. The amount of the alkali metal or alkaline earth metal compound to be used is preferably 0.8 to 1.5 mol, more preferably 0.9 to 1.4 mol, per 1 mol of the terminal hydroxyl group of the polymer (A). 0.95-
1.3 mol is most preferred. After converting the terminal hydroxyl group of the polymer (A) into an alkoxide, it is reacted with an unsaturated group-containing compound to convert it into an oxyalkylene polymer having an unsaturated group at the terminal (hereinafter, referred to as polymer (C)). As the unsaturated group-containing compound, a compound represented by the formula (2) can be used.

CH ₂ ＣC (R ² ) -R ³ -X (2) In the formula (2), R ² is a hydrogen atom or a group having 1 to 1 carbon atoms.
20 substituted or unsubstituted monovalent hydrocarbon groups, R ³ is 2
X is a halogen atom. The carbon number of R ³ is preferably 1 to 10, and more preferably 1. X includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom and a bromine atom are preferred. Equation (2)
Specific examples of the compound represented by, allyl chloride,
Allyl bromide, methallyl chloride, methallyl bromide and the like can be mentioned. Allyl chloride, methallyl chloride and allyl bromide are preferred, and allyl chloride is more preferred from the viewpoint of cost and reactivity. These may be used alone or in combination of two or more.

The amount of the unsaturated group-containing compound used is preferably 0.8 to 1.9 mol, more preferably 0.85 to 1.7 mol, per 1 mol of the terminal hydroxyl group of the polymer (A).
0.9-1.5 mol is most preferred. When the amount is less than 0.8 mol, the unsaturated group content in the unsaturated group-terminated oxyalkylene polymer decreases. On the other hand, if it is more than 1.9 mol, the amount of the unreacted unsaturated group-containing compound increases. When reacting the alkoxide-terminated oxyalkylene polymer with the unsaturated group-containing compound, the reaction temperature is preferably from 20 to 160 ° C.,
-150 ° C is more preferable, and 70-150 ° C is most preferable. In order to prevent coloring of the product, it is preferable to carry out the reaction in the presence of an inert gas such as nitrogen or helium. The reaction time is preferably 1 to 7 hours. After the introduction of the unsaturated group, it is preferable to remove and purify the alkali metal or alkaline earth metal compound used in the reaction, a by-product inorganic salt, and the like by a known method.

Next, a compound (B) having a functional group capable of undergoing an addition reaction to an unsaturated group (hereinafter referred to as an addition reactive group) and a hydrolyzable silyl group to the polymer (C) (hereinafter referred to as a silyl group-introducing agent) (B)) to produce a hydrolyzable silyl group-containing oxyalkylene polymer. The number of addition reaction groups in the silyl group-introducing agent (B) is preferably 2 or less, and 1
Is more preferred. As the silyl group-introducing agent (B), a compound having a structure represented by the following formulas (3) and (4) can be used.

[0018] ^{_{H-SiX a R 4 3-}} a ··· (3) provided that, ^{R 4} in the formula (3) monovalent hydrocarbon groups of the substituted or unsubstituted 1 to 20 carbon atoms, X is a hydroxyl group Or a hydrolyzable group. When two or more Xs are present, Xs may be the same or different. a is 1, 2 or 3.

HS—R ⁵ —SiX _a R ⁴ _3-a (4) wherein R ⁵ in the formula (4) is a divalent hydrocarbon group having 1 to 20 carbon atoms, R ⁴ , X, a is the same as above. As R ⁴ , an alkyl group having 8 or less carbon atoms, a phenyl group, and a fluoroalkyl group are preferable. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and a phenyl group are preferred. X represents a hydroxyl group, a halogen atom, an alkoxy group, an acyloxy group,
Examples include an amide group, an amino group, an aminooxy group, a ketoximate group, a mercapto group, and an alkenyloxy group. A lower alkoxy group having 4 or less carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group is preferable. a is 2
Or 3 is preferred.

Specific examples of the compound represented by the formula (3) include methyldimethoxysilane, trimethoxysilane, triethoxysilane, methyldiacetoxysilane, dimethylchlorosilane, methyldichlorosilane, ethyldichlorosilane, trichlorosilane and the like. No. These compounds may be used alone or in combination of two or more. When reacting the compound represented by the formula (3) with the terminal unsaturated group of the polymer (C), a catalyst such as a platinum-based catalyst, a rhodium-based catalyst, a cobalt-based catalyst, a palladium-based catalyst, and a nickel-based catalyst can be used. . Platinum-based catalysts such as chloroplatinic acid, platinum metal, platinum chloride, and platinum-olefin complexes are preferred. The addition amount of the catalyst is preferably from 10 to 100 ppm, more preferably from 30 to 60 ppm, based on the polymer (C). The reaction temperature is preferably from 30C to 150C, more preferably from 60C to 120C. The reaction time is preferably several hours. Examples of the compound represented by the formula (4) include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane.

When the compound represented by the formula (4) is reacted with the terminal unsaturated group of the polymer (C), the reaction can be started by a radical generator, radiation or heat. Examples of the radical generator include peroxide-based, azo-based, or redox-based compounds and metal compound catalysts, such as 2,2′-azobisisobutyronitrile and 2,2 ′.
-Azobis (2-methylbutyronitrile), benzoyl peroxide, t-butyl peroxide, acetyl peroxide, diisopropylperdioxy carbonate and the like. The amount of the radical generator to be added is preferably 0.01 to 2 g per 100 g of the polymer (C),
0.1-0.8 g is more preferred. Reaction temperature is 20-2
00 ° C is preferred, and 50 to 150 ° C is more preferred. The reaction time is preferably several hours to several tens hours. The ratio of the polymer (C) to the silyl group-introducing agent (B) to be reacted can be arbitrarily changed. The total number of addition reactive groups in the silyl group-introducing agent is preferably equal to or less than the total number of unsaturated groups in the polymer (C). If the number of silyl groups is small, the cured product obtained by curing the hydrolyzable silyl group-containing oxyalkylene polymer becomes flexible. The use ratio of the silyl group-introducing agent can be arbitrarily selected according to the desired physical properties in consideration of the physical properties of the cured product.

The viscosity of the hydrolyzable silyl group-containing oxyalkylene polymer is preferably 30 Pa · s or less, more preferably 25 Pa · s or less, at 25 ° C. for reasons of handling in the production process. 5 Pa · s or more is preferable. The present invention is a method for producing a curable composition, comprising mixing a filler and a curing catalyst with the hydrolyzable silyl group-containing oxyalkylene polymer. The curable composition can further contain additives. less than,
The filler, the curing catalyst and other additives will be described. (Filler) As the filler, a known filler can be used.
Specific examples of the filler include calcium carbonate whose surface is surface-treated with a fatty acid or a resin acid-based organic substance, colloidal calcium carbonate having an average particle diameter of 1 μm or less obtained by further pulverizing the calcium carbonate, and an average particle diameter produced by a precipitation method. 1-3 μm
Light calcium carbonate, calcium carbonate such as heavy calcium carbonate having an average particle size of 1 to 20 μm, fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black, magnesium carbonate, diatomaceous earth, calcined clay, clay , Talc, titanium oxide, bentonite, ferric oxide, zinc oxide, activated zinc flower, organic resin balloons such as shirasu balloon, glass balloon, saran balloon, polyacrylonitrile balloon, wood flour, pulp, cotton chip, mica, walnut flour And powdered fillers such as fir flour, graphite, aluminum fine powder and flint powder, and fibrous fillers such as glass fiber, glass filament, carbon fiber, Kevlar fiber and polyethylene fiber. Even if these fillers are used alone,
Two or more kinds may be used in combination.

The most common of these is calcium carbonate. In this case, it is preferable to use both colloidal calcium carbonate and heavy calcium carbonate. The mixing ratio of colloidal calcium carbonate and heavy calcium carbonate is 1
0: 1 to 1:10 is preferred, and 3: 1 to 1: 3 is more preferred. The amount of the filler used is 1 to 1000 with respect to 100 parts by mass of the hydrolyzable silyl group-containing oxyalkylene polymer.
A mass part is preferable and 50-250 mass parts is more preferable. (Curing catalyst) In order to obtain a practically sufficient curing speed, a curing catalyst is used. Examples of the curing catalyst include the following tin compounds. Divalent tin compounds such as tin 2-ethylhexanoate, tin naphthenate, and tin stearate. Dibutyltin dilaurate, dibutyltin diacetate,
Organic tin carboxylate such as dialkyltin carboxylate and dialkoxytin monocarboxylate such as dibutyltin monoacetate and dibutyltin maleate; tin chelate compounds such as dialkyltin bisacetylacetonate and dialkyltin monoacetylacetonate monoalkoxide; dialkyl Reaction products of tin oxide and ester compounds, reaction products of dialkyltin oxide and alkoxysilane compounds, and tetravalent tin compounds such as dialkyltin dialkylsulfides.

The tin chelate compound includes dibutyltin bisacetylacetonate, dibutyltin bisethylacetoacetate, dibutyltin bismonoacetylacetonate monoalkoxide and the like. The reaction product of the dialkyltin oxide and the ester compound includes dibutyltin oxide and di-2-phthalic acid.
A tin compound which is heated and mixed with a phthalic acid ester such as ethylhexyl or diisononyl phthalate to form a liquid is exemplified. In this case, as the ester compound, tetraethyl silicate or a partially hydrolyzed condensate thereof can be used in addition to an ester of an aliphatic or aromatic carboxylic acid. A compound obtained by reacting or mixing these tin compounds with a low-molecular alkoxysilane or the like can also be used.

The following curing catalysts can be used in addition to the tin compound. Other metal salts, such as bismuth organic carboxylate. Phosphoric acid, p-toluenesulfonic acid, phthalic acid, bis (2-ethylhexyl) phosphate
Acidic compounds such as. Butylamine, hexylamine, octylamine, decylamine, laurylamine, N, N
-Aliphatic monoamines such as dimethyl-octylamine,
Aliphatic polyamine compounds such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, aromatic amine compounds, alkanolamines, 3- (2-aminoethyl) amino-propyltrimethoxysilane and 3-aminopropyl Amine compounds such as aminosilane coupling agents such as trimethoxysilane; A divalent tin compound is preferably used in combination with an amine compound, particularly a primary amine compound, because the effect of accelerating curing is improved. Further, by combining the above acidic compound and a basic compound such as an amine compound, a higher effect promoting effect is exhibited, particularly at a high temperature.
The curing catalyst may be used alone or in combination of two or more. The amount of the curing catalyst used is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the hydrolyzable silyl group-containing oxyalkylene polymer.

(Plasticizer) As the plasticizer, known plasticizers can be used. That is, phthalic esters such as di-2-ethylhexyl phthalate, dibutyl phthalate, butylbenzyl phthalate and isononyl phthalate; aliphatic carboxylic acids such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate and butyl oleate Esters; alcohol esters such as pentaerythritol ester; phosphates such as trioctyl phosphate and tricresyl phosphate; epoxidized soybean oil; 4,5-epoxycyclohexane-1,2-dicarboxylic acid di-2-acid
Epoxy plasticizers such as ethylhexyl ester and benzyl epoxy stearate; chlorinated paraffins; polyester plasticizers such as polyesters obtained by reacting a dibasic acid with a dihydric alcohol; polyoxypropylene glycol, polyoxypropylene triol and the like. Derivatives, for example, polyethers in which hydroxyl groups of polyoxypropylene glycol are sealed with alkyl ethers; polyethers in which hydroxyl groups of polyoxypropylene triol are sealed with allyl compounds; poly-α-methylstyrene, polystyrene, etc. Oligomers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated polybutene, epoxidized polybutadiene, etc. Molecular plasticizers. These plasticizers may be used alone or in combination of two or more. The use amount of the plasticizer is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the hydrolyzable silyl group-containing polyalkylene oxide polymer.

(Adhesiveness-imparting agent) As the adhesiveness-imparting agent,
Examples thereof include silane coupling agents such as (meth) acryloyloxy group-containing silanes, amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, and carboxyl group-containing silanes. Examples of (meth) acryloyloxy group-containing silanes include 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and 3-methacryloyloxypropylmethyldimethoxysilane. Examples of the amino group-containing silanes include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, -(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane,
3-ureidopropyltriethoxysilane, N-[(N
-Vinylbenzyl) -2-aminoethyl] -3-aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane and the like.

Examples of silanes containing a mercapto group include 3-
Examples thereof include mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. Epoxy group-containing silanes include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and the like. Examples of carboxyl group-containing silanes include 2-carboxyethyltriethoxysilane, 2-carboxyethylphenylbis (2-methoxyethoxy) silane, N- (N-carboxylmethyl-2-aminoethyl) -3-aminopropyltrimethoxy Examples include silane. Further, a reaction product obtained by reacting two or more silane coupling agents may be used. Examples of the reactant include a reactant of an amino group-containing silane and an epoxy group-containing silane, a reactant of an amino group-containing silane and a (meth) acryloyloxy group-containing silane, and an epoxy group-containing silane and a mercapto group. Examples of the reaction product include silane-containing silanes and mercapto group-containing silanes. These reactants can be easily obtained by mixing the silane coupling agent and stirring at room temperature to 150 ° C. The reaction time is not particularly limited, but is usually 1 to 8
Any time will do.

The above compounds may be used alone or in combination of two or more. The amount of the silane coupling agent to be used is preferably 0 to 30 parts by mass based on 100 parts by mass of the hydrolyzable silyl group-containing oxyalkylene polymer. Further, an epoxy resin may be added as an adhesion imparting agent. As the epoxy resin, bisphenol A-diglycidyl ether type epoxy resin, bisphenol F-diglycidyl ether type epoxy resin, tetrabromobisphenol A
A flame-retardant epoxy resin such as a glycidyl ether epoxy resin, a novolak epoxy resin, a hydrogenated bisphenol A epoxy resin, a glycidyl ether epoxy resin of a bisphenol A / propylene oxide adduct,
4-glycidyloxy glycidyl benzoate, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl ester epoxy resin such as diglycidyl hexahydrophthalate, m-aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, urethane-modified epoxy resin, Various alicyclic epoxy resins, N,
N-diglycidylaniline, N, N-diglycidyl-o
-Commonly used epoxy resins such as toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ether of polyhydric alcohols such as glycerin, hydantoin type epoxy resins, and epoxidized unsaturated polymers such as petroleum resins. And vinyl polymers containing an epoxy group. The amount of the epoxy resin used is from 0 to 100 based on 100 parts by mass of the hydrolyzable silyl group-containing oxyalkylene polymer.
Parts by weight are preferred.

Further, a curing agent (or a curing catalyst) for the epoxy resin may be used in combination. Specific examples of curing agents for epoxy resins include, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, Amines such as isophoronediamine, 2,4,6-tris (dimethylaminomethyl) phenol or salts thereof, or blocked amines such as ketimine compounds, polyamide resins, imidazoles, dicyandiamides, boron trifluoride complex compounds , Phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecenylsuccinic anhydride, pyromellitic anhydride and other carboxylic anhydrides, phenoxy resins, carboxylic acids, alcohols Oxyalkylene polymers having an average of at least one group capable of reacting with an epoxy group in the molecule (terminal aminated polyoxypropylene glycol, terminal carboxylated polyoxypropylene glycol, etc.), hydroxyl group and carboxyl group at the terminal And liquid terminal functional group-containing polymers such as polybutadiene, hydrogenated polybutadiene, acrylonitrile-butadiene copolymer and acrylic polymer modified with an amino group and the like, and ketimine compounds. The amount of the epoxy resin curing agent used is preferably 0.1 to 300 parts by mass with respect to 100 parts by mass of the epoxy resin.

(Solvent) For the purpose of adjusting the viscosity and improving the storage stability of the composition, a solvent may be added. Examples of the solvent include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, and ethers. Of these, alcohols are preferred because the storage stability of the curable composition of the present invention during long-term storage is improved. Alcohols include those having 1 to 1 carbon atoms.
An alkyl alcohol of 0 is preferred, and methanol, ethanol, isopropanol, isoamyl alcohol and hexyl alcohol are particularly preferred. The amount of the solvent used is preferably 0 to 500 parts by mass based on 100 parts by mass of the hydrolyzable silyl group-containing oxyalkylene polymer.

(Dehydrating Agent) In order to further improve the storage stability of the curable composition, a small amount of a dehydrating agent can be added as long as the curability and flexibility are not adversely affected. Specific examples of the dehydrating agent include alkyl orthoformate such as methyl orthoformate and ethyl orthoformate, alkyl orthoacetate such as methyl orthoacetate and ethyl orthoacetate, methyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, and tetraethoxysilane. Examples include hydrolyzable organic silicon compounds such as silane, and hydrolyzable organic titanium compounds. Vinyl trimethoxysilane and tetraethoxysilane are particularly preferred in view of cost and effect. Such dehydrating agents are particularly effective in products known as one-part formulations, in which a curing catalyst has been added to the formulation and filled into a moisture-proof container.

(Thixotropic agent) A thixotropic agent may be used to improve sagging. Thixotropic agents include organic acid-treated calcium carbonate, hydrogenated castor oil, calcium stearate, zinc stearate, fine powdered silica,
Fatty acid amides and the like are used. The amount of the thixotropic agent used is the amount of the hydrolyzable silyl group-containing oxyalkylene polymer 1
0.1 to 10 parts by mass is preferable with respect to 00 parts by mass,
2 to 6 parts by mass are more preferred. (Anti-aging agent) As the anti-aging agent, generally used antioxidants, ultraviolet absorbers and light stabilizers are appropriately used. Hindered amine, benzotriazole, benzophenone, benzoate, cyanoacrylate, acrylate, hindered phenol, phosphorus, and sulfur compounds can be used as appropriate. It is preferable to use a light stabilizer, an antioxidant, and an ultraviolet absorber in combination. It is particularly effective to combine two or more selected from the group consisting of tertiary and secondary hindered amine light stabilizers, benzotriazole ultraviolet absorbers, hindered phenolic and phosphite antioxidants. The amounts of the antioxidant, the ultraviolet absorber and the light stabilizer used are the hydrolyzable silyl group-containing oxyalkylene polymer 1
The amount is preferably 0.1 to 10 parts by mass with respect to 00 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the weather resistance is small, and if it exceeds 10 parts by mass, there is no great difference in the effect, which is economically disadvantageous.

(Others) An air oxidation-curable compound or a photo-curable compound may be added for the purpose of improving the adhesion and surface tack of the paint over a long period of time. Dry oxidation oils, such as tung oil and linseed oil, as air oxidation-curable compounds,
Various alkyd resins obtained by modifying the compound, acrylic polymers modified with drying oil, silicone resins, polybutadienes, diene polymers such as copolymers and copolymers of diene having 5 to 8 carbon atoms, and Examples include various modified products of the polymer or copolymer (maleization modification, boil oil modification, etc.). As the photocurable compound, a compound containing a (meth) acryloyl group obtained by reacting a hydroxy compound such as a polyhydric alcohol such as trimethylolpropane, polyether polyol, or polyester polyol with acrylic acid or methacrylic acid can be used. . Typically, trimethylolpropane triacrylate is used. An air oxidation curable compound and a photocurable compound may be used in combination. The air oxidation-curable compound is preferably from 0 to 50 parts by mass based on 100 parts by mass of the hydrolyzable silyl group-containing oxyalkylene polymer, and the photocurable compound is based on 100 parts by mass of the hydrolyzable silyl group-containing oxyalkylene polymer. 0 to 50 parts by mass is preferred.

In addition, a compound capable of generating trimethylsilanol by hydrolysis can be added for adjusting physical properties and reducing surface stickiness. This compound has an effect of reducing the modulus of the cured product when a divalent tin compound and a primary amine compound are used as a curing catalyst, and reducing the stickiness of the surface. As the compound generating trimethylsilanol, trimethylsilyl ethers such as aliphatic alcohols and phenols can be generally used, and the stronger the alcohol acid, the slower the curing. The curability can be adjusted by arbitrarily changing the type of alcohol, and trimethylsilyl ethers of a plurality of alcohols can be used simultaneously for the purpose. Also,
Silazanes such as hexamethyldisilazane can also be used.
The amount of the compound that generates trimethylsilanol by hydrolysis is preferably 0 to 50 parts by mass based on 100 parts by mass of the hydrolyzable silyl group-containing oxyalkylene polymer. In addition, inorganic pigments such as iron oxide, chromium oxide, and titanium oxide, and organic pigments such as phthalocyanine blue and phthalocyanine green can be used as the pigment. The use of pigments is effective not only for coloring but also for the purpose of improving weather resistance.

In addition, for the purpose of imparting a design property particularly as a sealing material, by adding fine particles having a color different from the color of the composition to the composition, a surface appearance such as granite or granite can be obtained. It can also be made into a cured product with moisture. It is also optional to add a known flame retardant or fungicide. It is also possible to add a matting agent used for paint applications. The curable composition of the present invention can be obtained by blending a hydrolyzable silyl group-containing oxyalkylene polymer, a filler and a curing catalyst, and optionally blending additives as needed. Further, the curable composition of the present invention further comprises
It may further contain a polymer whose main chain is polyester, polycarbonate, polyacrylate, and polyolefin and contains one or more unsaturated groups in the molecule. When the main chain contains a polyester or polycarbonate polymer, the adhesion to the substrate is improved. When the main chain contains a polymer of polyacrylate, adhesion to a substrate and weather resistance are improved. When the main chain contains a polyolefin polymer, the water resistance is improved. It is also possible to combine a plurality of these. The curable composition of the present invention can be cured by moisture. Curing temperature is 0-35
C is preferable, and 20 to 25C is more preferable. The curable composition of the present invention is a sealing material, a waterproof material,
It can be used for adhesives, coating agents, etc., and is particularly suitable for applications requiring sufficient cohesion of the cured product itself and dynamic followability to adherends.

[0037]

EXAMPLES The present invention will now be described with reference to Examples (Examples 1 to 3 and Examples 7 to 7).
8) and Comparative Examples (Examples 4 to 6), but the present invention is not limited to these. In addition, the number average molecular weight of the hydroxyl group-containing oxyalkylene polymer is a hydroxyl group equivalent molecular weight calculated by a product of a molecular weight per hydroxyl group calculated from the hydroxyl group and an active hydrogen number of the initiator. The hydroxyl value was determined by the method described in JIS K1557. As the molecular weight distribution (Mw / Mn), a value in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent was obtained. Total unsaturation (U
SV) was determined by the method described in JIS K1557. The viscosity of the polymer was measured at 25 ° C. according to the method described in JIS K1557.

<Production of double metal cyanide complex catalyst> In Preparation Examples 1 to 3, 10 g of zinc chloride dissolved in 15 mL of water was used as an aqueous zinc chloride solution, and 4 g of potassium hexacyanocobaltate was used as an aqueous potassium hexacyanocobaltate solution. Dissolved in 80 mL of water was used. (Production Example 1) A potassium hexacyanocobaltate aqueous solution was added dropwise to a zinc chloride aqueous solution at 40 ° C over 30 minutes.
After the dropwise addition, 8 mL of ethylene glycol mono-t-butyl ether (hereinafter, referred to as ETB), 72 mL of t-butyl alcohol (hereinafter, referred to as TBA) and 80 mL of water were added, and the mixture was stirred at 60 ° C. for 1 hour and aged. After aging, the complex was filtered off. 4 mL of ETB and 3 of TBA were added to the obtained complex.
6 mL and 80 mL of water were added, stirred for 30 minutes, washed, and filtered. In addition, 10 mL of ETB and 9 of TBA
After adding 0 mL and stirring for 30 minutes, polyoxypropylene triol having a molecular weight of 1,000 was added and stirred for 30 minutes. Thereafter, the solvent was removed at 120 ° C. to obtain a 7 mass% composite metal cyanide complex catalyst (catalyst A) dispersion dispersed in a polyol.

(Production Example 2) An aqueous solution of potassium hexacyanocobaltate was added dropwise to an aqueous solution of zinc chloride at 40 ° C. over 30 minutes. After completion of the dropwise addition, 24 mL of ETB, 56 mL of TBA, and 80 mL of water were added, and the temperature was raised to 60 ° C. After stirring for 1 hour, the complex was filtered off. E is added to the obtained complex.
12 mL of TB, 28 mL of TBA, and 80 mL of water were added, and the mixture was stirred for 30 minutes and then filtered.
70 mL of L and TBA were added, stirred for 30 minutes, and filtered. After drying under reduced pressure at 50 ° C until the weight becomes constant,
The pulverization was performed to obtain a double metal cyanide complex catalyst (catalyst B).

(Production Example 3) An aqueous solution of potassium hexacyanocobaltate was added dropwise to an aqueous solution of zinc chloride at 40 ° C. over 30 minutes. After dropping, 80 mL glyme and 8 water
After adding 0 mL and stirring at 60 ° C. for 1 hour, the complex was separated by filtration. 80 mL of glyme and 80 mL of water are added to the obtained complex.
Was added, and the mixture was stirred for 30 minutes and filtered off.
After addition of 10 mL of water and 10 mL of water, the mixture was stirred and filtered. 80
After drying at 4 ° C. for 4 hours, the mixture was pulverized to obtain a double metal cyanide complex catalyst (catalyst C).

<Synthesis of oxyalkylene polymer> (Example 1) Propylene oxide (hereinafter referred to as PO) was added to glycerin.
) And a polyoxypropylene triol having a number average molecular weight of 3000 (hereinafter referred to as triol A).
Of the catalyst A in the presence of 22.8 g of the catalyst A dispersion (concentration: 7% by mass) and 6880 g of PO, the number average molecular weight being 20,000, and Mw / Mn = 1.
28, USV = 0.011 meq / g, viscosity 23 Pa.
s of polyoxypropylene triol was obtained. 1000 g of this polyoxypropylene triol was placed in a pressure-resistant container, and a 28% methanol solution of sodium methoxide was added so that the amount of sodium was 1.05 times mol per mol of hydroxyl groups, followed by stirring at 120 ° C. for 30 minutes. After stirring, a methanol removal reaction was performed under reduced pressure, and then 13 g of allyl chloride was added and reacted for 1 hour. Unreacted volatile components were distilled off under reduced pressure, and inorganic salts and the like produced as by-products were removed and purified to obtain an allyloxy-terminated polyoxypropylene polymer. From the quantification of the unsaturated groups, 95% of the hydroxyl groups were converted to allyloxy groups. To 500 g of the obtained allyloxy terminal polyoxypropylene polymer, 50 μL of a xylene solution of divinyltetramethylsiloxane platinum complex (containing 3% by mass of platinum) was added, and the mixture was stirred uniformly.
After adding 7.5 g of methyldimethoxysilane,
The reaction was carried out for a period of time to obtain a pale yellow polyoxypropylene polymer having a terminal methyldimethoxysilyl group (P-1) having a viscosity of 24 Pa · s.

Example 2 Polyoxypropylene diol having a number average molecular weight of about 2,000 (hereinafter referred to as diol B) obtained by reacting PO with dipropylene glycol 97
0 g as an initiator, dispersion of catalyst A (concentration: 7% by mass) 2
By reacting 7030 g of PO in the presence of 2.8 g, the number average molecular weight is 16000, Mw / Mn = 1.17, USV
= 0.009 meq / g and a polyoxypropylene diol having a viscosity of 15.7 Pa · s. An allyl-terminated polyoxypropylene polymer was obtained in the same manner as in Example 1 except that 1000 g of this polyoxypropylene diol was put into a pressure-resistant reactor and 10.5 g of allyl chloride was added. From the quantification of the unsaturated groups, 95% of the hydroxyl groups were converted to allyloxy groups. In the same manner as in Example 1 except that 5.6 g of methyldimethoxysilane was added to 500 g of the allyl-terminated polyoxypropylene polymer, a polyoxypropylene polymer containing a terminal methyldimethoxysilyl group and having a viscosity of 16.5 Pa · s was obtained in the same manner as in Example 1. A combined product (P-2) was obtained.

(Example 3) 1015 g of polyoxypropylene triol (hereinafter referred to as triol C) having a number average molecular weight of about 2000 obtained by reacting PO with glycerin was used as an initiator in the presence of 1.6 g of catalyst B. , 698 of PO
5 g were reacted to obtain a number average molecular weight of 15,000 and Mw / M
Polyoxypropylene triol having n = 1.17, USV = 0.09 meq / g, and viscosity of 14.6 Pa · s was obtained. 1000 g of this polyoxypropylene triol
Was placed in a pressure-resistant reaction vessel, and an allyl-terminated polyoxypropylene polymer was obtained in the same manner as in Example 1 except that 17 g of allyl chloride was added. From the quantification of the unsaturated group, 95
% Had been converted to an allyloxy group. In the same manner as in Example 1 except that 7.8 g of methyldimethoxysilane was added to 500 g of the allyl-terminated polyoxypropylene polymer, a polyoxypropylene polymer having a terminal methyldimethoxysilyl group and having a viscosity of 15.5 Pa · s was obtained in the same manner as in Example 1. Combined (P-
3) was obtained.

(Example 4) Using 863 g of triol A as an initiator and reacting 7137 g of PO in the presence of 1.6 g of catalyst C, a number average molecular weight of 20,000 and Mw / Mn = 1.3
7, USV = 0.032 meq / g, viscosity 19.3P
a · s polyoxypropylene triol was obtained. 1000 g of this polyoxypropylene triol was reacted in the same manner as in Example 1 to obtain a terminally allylated polyether.
From the quantification of the unsaturated group, 95% of the hydroxyl groups were converted to allyl ether. The obtained allyl-terminated polyoxypropylene polymer was reacted in the same manner as in Example 1 to obtain a light yellowish polyoxypropylene polymer having a terminal methyldimethoxysilyl group (C-1) having a viscosity of 22 Pa · s.

(Example 5) Using 840 g of diol B as an initiator and reacting 7160 g of PO in the presence of 1.6 g of catalyst C, a number average molecular weight of 16,000, Mw / Mn = 1.2
5, USV = 0.035 meq / g, viscosity 13.8 Pa
・ S polyoxypropylene diol was obtained. This polyoxypropylene diol was reacted in the same manner as in Example 2 to obtain an allyl-terminated polyoxypropylene polymer. From the quantification of the unsaturated groups, 95% of the hydroxyl groups were converted to allyloxy groups. The obtained allyl-terminated polyoxypropylene polymer was reacted in the same manner as in Example 2 to give a pale yellow viscous 14.5 Pa · s terminal methyldimethoxysilyl group-containing polyoxypropylene polymer (C-2). Obtained.

(Example 6) Using 833 g of triol C as an initiator and reacting 7167 g of PO in the presence of 1.6 g of catalyst C, a number average molecular weight of 15,000 and Mw / Mn =
1.30, USV = 0.027 meq / g, viscosity 12.
6 Pa · s polyoxypropylene triol was obtained.
This polyoxypropylene triol was reacted in the same manner as in Example 3 to obtain an allyl-terminated polyoxypropylene polymer. From the quantification of the unsaturated groups, 95% of the hydroxyl groups were converted to allyloxy groups. The obtained allyl-terminated polyoxypropylene polymer was reacted in the same manner as in Example 3 to give a pale yellow viscous 13.5 Pa · s terminal methyldimethoxysilyl group-containing polyoxypropylene polymer (C-
3) was obtained. In Examples 1 to 6, the catalyst used for producing the hydroxyl-terminated polymer, the number average molecular weight of the hydroxyl-terminated polymer,
And the USV of the hydroxyl-terminated polymer (unit: meq /
g), and the name of the finally obtained polymer and Mw / Mn of the polymer are shown in Table 1.

[0047]

[Table 1]

(Physical Properties and Curability Test) Polymers P-1 to P-1
The following tests were performed on P-3 and C-1 to C-3. (1) Physical properties test 0.5 g of dibutyltin bisacetylacetonate was added to 100 g of each polymer, kneaded well, degassed under reduced pressure, poured into a mold, and subjected to 50 ° C and 65% humidity. After leaving it to stand for one week, it was cured, punched out into a dumbbell-shaped No. 3 test piece described in JIS K6301 (Vulcanized rubber physical test method), measured for physical properties by a tensile test, and subjected to a 50% tensile modulus and rupture. The time elongation was measured. Table 2 shows the results. (2) Curability test Di-2-ethylhexyl phthalate 2 was added to 50 g of each polymer.
0 g was added and mixed, 0.2 g of water and 0.2 g of dibutyltin bisacetylacetonate were added, and the mixture was stirred uniformly.
While measuring the viscosity change with a viscometer, the curing behavior was observed, and the time for gelation was measured. Table 2 shows the results.

[0049]

[Table 2]

In the polymer containing a hydrolyzable silyl group as in the present invention, the more the terminal functional group, that is, the higher the elastic modulus of the cured product, the higher the curing rate under the same conditions. Need to be compared. Therefore, polymers P-1 and C-1, P-2 and C-
2. Comparing the curing speeds of P-3 and C-3, as shown in Table 2, the polymer of the present invention has a characteristic that the curing speed is faster than that of a conventionally known polymer. Understand. (Formulation example) A filler and other generally known additives were added to the polymer of the present invention and kneaded to produce a curable composition. The main raw materials used are as follows.
Colloidal calcium carbonate: manufactured by Takehara Chemical Industry Co., Ltd., trade name Neolite SP-T, heavy calcium carbonate: manufactured by Shiraishi Calcium Industry Co., Ltd., trade name: Whiten SB, fatty acid amide thixotropic agent: Kusumoto Chemical Co., Ltd. ), Trade name Disparon 6500, benzotriazole ultraviolet absorber: Ciba Specialty Chemicals Co., Ltd., trade name Tinuvin 3
27 Hindered amine light stabilizer: Asahi Denka Kogyo Co., Ltd., trade name LA-63P, hindered phenolic antioxidant: Ouchi Shinko Chemical Co., Ltd., trade name Nocrack NS-
6. Epoxy plasticizer: 4,5-epoxycyclohexane-1,2-dicarboxylic acid di-2-ethylhexyl ester, manufactured by Shin Nippon Rika Co., Ltd., trade name: Sansosizer EP
S, hydrogenated castor oil-based thixotropic agent: manufactured by Kusumoto Kasei Co., Ltd.
Product name Dispalon 305, photo-curable compound: Polyacrylate of polyester polyol, Toagosei Co., Ltd.
Manufactured by Aronix M8060, acrylonitrile resin hollow body: manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd., manufactured by Matsumoto Microsphere F-80GCA,

Example 7 100 g of polymer P-1, 100 g of colloidal calcium carbonate, 30 g of heavy calcium carbonate, 5 g of titanium oxide, 30 g of polyoxypropylene triol (molecular weight: 8000), 30 g of fatty acid amide thixotropic agent, 3
-(2-aminoethylamino) propyltrimethoxysilane 1 g, 3-glycidyloxypropyltrimethoxysilane 1 g, benzotriazole-based ultraviolet absorber 1 g,
1 g of a hindered amine light stabilizer, 1 g of a hindered phenol antioxidant, 0.5 g of tetraethyl silicate
g, kneading 0.5 g of vinyltrimethoxysilane, adding 2 g of dibutyltin bisacetylacetonate, and further uniformly mixing to obtain a moisture-curable composition. When the joints between the plates were filled and left to stand in the open air, they hardened into an elastic body.

(Example 8) 90 g of polymer P-1, polymer P
-2 10 g, tung oil 5 g, trimethylolpropane tristrimethylsilyl ether 1 g, phenyltrimethoxysilane 0.3 g, colloidal calcium carbonate 75 g, heavy calcium carbonate 75 g, titanium oxide 5 g, phthalic acid di-2
-25 g of ethylhexyl, 25 g of an epoxy plasticizer, 3 g of tinuvin 305, 5 g of a polyfunctional acrylate compound, 1 g of a benzotriazole ultraviolet absorber, 1 g of a hindered amine light stabilizer, 1 g of a hindered phenol antioxidant, 1 g of an acrylonitrile resin 2,5g hollow body
Was further kneaded, and a mixture of 2 parts of tin 2-ethylhexanoate and 0 and 5 g of laurylamine was added and kneaded to obtain a uniform curable composition. Immediately, the joint between the concrete plates on the outer wall of the building was filled with the curable composition and allowed to stand. As a result, a flexible elastic body was obtained.

[0053]

The polymer obtained by the production method of the present invention has a characteristic that the curing rate is higher than that of a conventionally known polymer. The curable composition using this as a raw material is suitable for sealing materials, adhesives, and the like.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kayoko Sugiyama 3-474-2 Tsukakoshi, Saiwai-ku, Kawasaki-shi, Kanagawa Prefecture F-term in Asahi Glass Co., Ltd. 4H017 AA03 AA31 AB16 AB17 AC01 AC05 AC17 AC19 4J002 CH051 DE106 DE116 DE136 DE236 DJ006 DJ016 DJ036 DJ046 EN027 EZ017 EZ047 EZ057 FD016 FD147 GJ00 4J005 AA02 BB04 BD08

Claims (6)

[Claims] An alkylene oxide is reacted in the presence of an initiator and an alkylene oxide ring-opening polymerization catalyst to obtain a number average molecular weight of 5,000 to 30,000 and a total degree of unsaturation of 0.0.
After obtaining a hydroxyl group-terminated oxyalkylene polymer (polymer (A)) of 2 meq / g or less, the terminal hydroxyl group of the polymer (A) is converted into an unsaturated group, and further, a functional group which undergoes an addition reaction to the unsaturated group. (B) having a group and a hydrolyzable silyl group
And a method for producing a hydrolyzable silyl group-containing oxyalkylene polymer. 2. The method according to claim 1, wherein the alkylene oxide ring-opening polymerization catalyst is a double metal cyanide complex catalyst in which t-butyl alcohol or t-butyl alcohol is coordinated with another compound as an organic ligand. Manufacturing method. 3. An alkylene oxide ring-opening polymerization catalyst comprising, as an organic ligand, t-butyl alcohol and a compound represented by the following formula (1): ethanol, s-butyl alcohol, n-butyl alcohol, isobutyl alcohol. One or more selected from alcohol, t-pentyl alcohol, isopentyl alcohol, N, N-dimethylacetamide, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, isopropyl alcohol, dioxane, and a polyether having a number average molecular weight of 150 or more. 2
The production method according to claim 1, which is a double metal cyanide complex catalyst in which at least one kind of compound is coordinated. R ¹ -C (CH ₃ ) ₂ (OR ⁰ ) _n OH (1) In the formula (1), R ¹ represents a methyl group or an ethyl group,
R ⁰ is an ethylene group or a group in which a hydrogen atom of the ethylene group is substituted with a methyl group or an ethyl group, and n is an integer of 1 to 3. 4. The alkylene oxide ring-opening polymerization catalyst is a double metal cyanide complex catalyst obtained by coordinating an organic ligand to a zinc hexacyanocobaltate complex.
Or the production method according to 3. 5. The hydrolyzable silyl group-containing oxyalkylene polymer has a viscosity of 5 Pa · s or more at 25 ° C.
The method according to claim 1. 6. A room-temperature curable composition comprising a filler and a curing catalyst mixed with the hydrolyzable silyl group-containing oxyalkylene polymer produced by the method according to any one of claims 1 to 5. Production method.