JPH08176429A - Curable composition - Google Patents

Abstract

PURPOSE: To obtain a curable compsn. which is excellent in storage stability and gives a cured item excellent in mechanical strengths by compounding a specific org. polymer having hydrolyzable silicon groups with a polymer obtd. from a polymerizable unsatd. monomer. CONSTITUTION: This compsn. is prepd. by compounding an org. polymer having a hydrolyzable groups represented by the formula (wherein R is a divalent org. group; R<1> is an optionally substd. monovalent 1-20C hydrocarbon group; X is a hydrolyzable group; and a is 1, 2, or 3) and a total content of ionic impurities of 50ppm or lower with a polymer obtd. from a polymerizable unsatd. monomer (e.g. polyacrylonitrile). The former polymer is pref. produced e.g. by polymerizing a cyclic ether onto an initiator using a compound metal cyanide complex as the catalyst to give a hydroxylated polyoxyalkylene polymer, introducing hydrolyzable silicon groups into the molecular terminals of the polyoxyalkylene polymer, and removing ionic impurities contained as insol. salts at a suitable step.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified curable composition, and more particularly to a curable composition having excellent storage stability and a cured product having excellent mechanical properties.

[0002]

2. Description of the Related Art Polyoxyalkylene having at least one hydrolyzable silicon group (silicon-containing group having a hydrolyzable group directly bonded to a silicon atom) in a molecule has a characteristic that a cured product has rubber elasticity. Although it is used for applications such as a living coating composition and a sealing composition, the strength of the cured product is insufficient for applications such as adhesives and waterproofing agents, and there is a practical problem. Further, a curable composition comprising a polymer of a polyoxyalkylene having at least one hydrolyzable silicon group in the molecule and a polymerizable unsaturated group-containing monomer has been proposed, but it has a drawback that the viscosity becomes high. There is a sexual problem.

In order to remedy these drawbacks, the Applicant has disclosed in Japanese Patent Application No. 5-232518 at least obtained using a hydroxyl group-containing polyoxyalkylene polymer prepared using a double metal cyanide complex catalyst. A curable composition composed of a polymer of a polyoxyalkylene having one hydrolyzable silicon group and a polymerizable unsaturated group-containing monomer has been proposed, but it is still insufficient in terms of storage stability.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks and provides a curable composition whose cured product has remarkably excellent mechanical strength and adhesiveness and is excellent in storage stability. For the purpose of providing.

[0005]

That is, the present invention is the following inventions. It is composed of an organic polymer (A) having a hydrolyzable silicon group represented by the following formula (1) and having a total amount of ionic impurities of 50 ppm or less, and a polymer (B) of a polymerizable unsaturated group-containing monomer. Curable composition. A hydrolyzable silicon group represented by the following formula (1), which is a derivative of a hydroxyl group-containing polyoxyalkylene polymer (D) obtained by polymerizing a cyclic ether with an initiator using a complex metal cyanide complex (E) as a catalyst. And has 50 ionic impurities
A curable composition comprising an organic polymer (A) having a content of ppm or less and a polymer (B) of a polymerizable unsaturated group-containing monomer. —R—SiX _a R ¹ _3-a (1) In the formula, R is a divalent organic group, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and X is Hydrolyzable group,
a is 1, 2 or 3.

The organic polymer (A) of the present invention has a hydrolyzable silicon group represented by the formula (1), and the total amount of ionic impurities is 50 ppm or less. In particular, the metal ionic impurities are preferably 30 ppm or less, and more preferably 20 ppm or less. Usually, the polymer having a hydrolyzable silicon group contains metal ionic impurities and the like derived from the catalyst used when producing the polymer and introducing the hydrolyzable silicon group. It was found that the storage stability of the organic polymer (A) and the curable composition of the present invention was improved by reducing the amount of these ionic impurities. Further, it has been found that these ionic impurities remain in the cured product of the curable composition as they are, so that the cured product has a high water absorption rate, which affects the adhesive strength of the product, particularly the water-resistant adhesive strength.
Also in this respect, reduction of the amount of ionic impurities is very important.

Examples of the reducing method include the following methods (I) and (II). In the present invention, the method (I) is particularly preferable because it can effectively reduce ionic impurities.

(I) A method in which the metal ionic impurities contained in the polymer are changed to metal salts essentially insoluble in the polymer, and the metal salts are removed from the polymer. Specifically, by adding a compound capable of reacting with a metal ionic impurity to form a metal salt essentially insoluble in the polymer, water and, if necessary, a nonionic surfactant, and then dehydrating the metal. There is a method of precipitating a salt and then removing the metal salt. The compound capable of forming a metal salt is preferably hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, pyrophosphoric acid, sodium acid pyrophosphate, or the like. The metal salt can be removed by filtration or adsorption.

(II) A method of removing a ionic impurity by adding a solvent to a polymer and then bringing the polymer into contact with an anion exchange resin and / or a cation exchange resin.

The organic polymer (A) is preferably a derivative of the hydroxyl group-containing polyoxyalkylene polymer (D), and the hydrogen atom in the hydroxyl group of the hydroxyl group-containing polyoxyalkylene polymer (D) is replaced by the formula (1). Those obtained are preferred. As described below, the organic polymer (A) is preferably produced by introducing a hydrolytic silicon group into the terminal of the hydroxyl group-containing polyoxyalkylene polymer (D).

The hydroxyl group-containing polyoxyalkylene polymer is usually obtained by polymerizing a cyclic ether with an initiator in the presence of a catalyst. Examples of the catalyst include alkali metal catalysts such as sodium, potassium, and cesium, complex metal cyanide complex catalysts, metal porphyrin complex catalysts, and the like. Examples of cyclic ethers include cyclic ethers such as ethylene oxide, propylene oxide, butylene oxide, and hexylene oxide, and tetrahydrofuran.
These are used alone or in combination.

As the initiator, a compound having 2 to 8 active hydrogen is preferable, and a polyhydroxy compound is preferable,
A polyhydroxy compound having 2 to 4 hydroxyl groups is particularly preferable. Specifically, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, sucrose and these. There is a polyol having a lower molecular weight than the target product obtained by reacting with a cyclic ether. These may be used alone or in combination of two or more. Further, an unsaturated group-containing monohydroxy compound such as allyl alcohol can also be used.

The number of hydroxyl groups of the polymer (D) is preferably 2 or more, and particularly preferably 2 to 4. Particularly preferred polymer (D)
Are polyoxypropylene diols, polyoxypropylene triols and polyoxypropylene tetraols. When used in the following methods (a) and (d), an unsaturated group-terminated polyoxyalkylene monool such as polyoxypropylene glycol monoallyl ether can also be used.

The hydroxyl group-containing polyoxyalkylene preferably has a molecular weight in terms of hydroxyl value of 5,000 or more, and the upper limit is 30,000. Here, the hydroxyl value-converted molecular weight is a molecular weight represented by 56100 × (number of hydroxyl groups per molecule) / hydroxyl value.

The organic polymer (A) has a hydrolyzable silicon group represented by the following formula (1). —R—SiX _a R ¹ _3-a (1) In the formula, R is a divalent organic group, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and X is Hydrolyzable group,
a is 1, 2 or 3. R in the formula (1) is a divalent organic group. R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group. Particularly preferred are methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, phenyl group and the like.

X in the formula (1) is a hydrolyzable group, such as a halogen atom, an alkoxy group, an acyloxy group,
An amide group, an amino group, an aminooxy group, a ketoximate group, an acid amide group, and a hydride group. Of these, the hydrolyzable group having a carbon atom has 6 or less carbon atoms, and particularly 4
The following is preferable. Preferred hydrolyzable groups are lower alkoxy groups having 4 or less carbon atoms, particularly methoxy group, ethoxy group,
A propoxy group etc. can be illustrated. A in the formula (1) is 1,
2 or 3, with 2 or 3 being preferred.

In the present invention, the organic polymer (A) is a derivative of a hydroxyl group-containing polyoxyalkylene polymer (D) obtained by polymerizing a cyclic ether with an initiator using the complex metal cyanide complex (E) as a catalyst. Therefore, it is preferable that the compound has a hydrolyzable silicon group represented by the formula (1) and that the amount of ionic impurities is 50 ppm or less. By using the complex metal cyanide complex (E), a hydroxyl group-containing polyoxyalkylene polymer (D) having a smaller M _w / M _n , a higher molecular weight and a lower viscosity than that obtained by using a conventional alkali metal catalyst is obtained. be able to.

The complex metal cyanide complex (E) is preferably a complex containing zinc hexacyanocobaltate as a main component, and its ether and / or alcohol complex is preferable. As the composition, those essentially described in JP-B-46-27250 can be used. As the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) and the like are preferable, and glyme is particularly preferable from the viewpoint of handling during the production of the complex. As alcohol, JP-A-4-145
The t-butanol described in JP-A-123 is preferred.

When the organic polymer (A) is produced from the hydroxyl group-containing polyoxyalkylene polymer (D) obtained by polymerizing a cyclic ether with an initiator using the complex metal cyanide complex (E) as a catalyst, the organic polymer (A) usually contains metal ions derived from the complex metal cyanide complex (E) and alkali metal ions. These ionic impurities are preferably 50 ppm or less.

Next, the method for producing the organic polymer (A) will be described. The organic polymer (A) in the present invention is produced by introducing a hydrolyzable silicon group into the terminal of the hydroxyl group-containing polyoxyalkylene polymer (D) as described in (a) to (d) below. preferable. Such a compound is liquid at room temperature, and the cured product retains flexibility even at a relatively low temperature, and has desirable properties when used as a sealing material, an adhesive or the like.

(A) A method of reacting a polymer (D) having an unsaturated group introduced at its terminal with a silicon hydride compound represented by the following formula (2). HSiX _a R ¹ _3-a (2) However, in the formula, R ¹ , X, and a are the same as described above.

Here, as a method of introducing an unsaturated group,
After the terminal hydroxyl group OH of the polymer (D) is OM (M is an alkali metal), it is reacted with an unsaturated group-containing halogenated hydrocarbon such as allyl chloride or a functional group capable of reacting with an unsaturated group and a hydroxyl group is added. There is a method of reacting the compound possessed with the polymer (D) to bond them by an ester bond, a urethane bond, a carbonate bond or the like. In this method, when polymerizing a cyclic ether in the production of the polymer (D), a method of introducing an unsaturated group into a side chain by copolymerizing an unsaturated group-containing monoepoxy compound such as allyl glycidyl ether or A hydroxyl group-containing polyoxyalkylene polymer produced by using a terminal-unsaturated group-containing monohydroxy compound as an initiator can also be used.

(B) The following formula (3) is added to the end of the polymer (D).
The method of reacting the compound shown by. R ¹ _3-a SiX _a —R ⁵ —NCO (3) However, in the formula, R ¹ , X, and a are the same as described above, and R ⁵ is a divalent hydrocarbon group having 1 to 17 carbon atoms.

(C) After the end of the polymer (D) is reacted with a polyisocyanate compound such as tolylene diisocyanate to form an isocyanate group terminal, the W group of the silicon compound represented by the following formula (4) is added to the isocyanate group. How to react. R ¹ _3-a —SiX _a —R ⁵ W (4) where R ¹ , R ⁵ , X and a are the same as described above, W is a hydroxyl group, a carboxyl group, a mercapto group and an amino group (1 It is an active hydrogen-containing group selected from primary or secondary).

(D) A method of introducing an unsaturated group into the terminal of the polymer (D) and reacting the unsaturated group with the mercapto group of the silicon compound represented by the formula (4) in which W is a mercapto group.

Removal of ionic impurities is carried out from the above (a) to.
It is preferable to carry out at an appropriate stage such as before or after reacting each silicon compound in each method (d), and the total amount thereof is 50 ppm or less. In particular, the metal ionic impurities contained in the polymer (D) or its terminal unsaturated group-introduced product (C) are essentially unnecessary for the polymer (D) or its terminal unsaturated group-introduced product (C). After forming a metal salt, the ionic impurities contained in the polymer are reduced to 50 ppm or less, and then a hydrolyzable silicon group is introduced into the polymer (D) or a compound with a terminal unsaturated group introduced (C) The method of reacting with the silicon hydride compound of (2) is preferable.

The molecular weight of the organic polymer (A) in the present invention is calculated based on the hydroxyl value-converted valence molecular weight of the polymer (D) as a raw material. The molecular weight is 5,000 to 30,000
Is preferred. If it is less than 5,000, the cured product will be hard and the elongation will be low, and if it exceeds 30,000, flexibility and elongation of the cured product will not be a problem, but the viscosity of the polymer itself will be remarkably increased and the practicality will be lowered. Especially 8000-30
000 is preferable.

The polymer of the polymerizable unsaturated group-containing monomer of the component (B) used in the present invention is obtained by copolymerizing the polymerizable unsaturated group-containing monomer represented by the formula (5) alone or in combination of two or more kinds. To be

CH ₂ = CR ⁶ R ⁷ (5) In the formula, R ⁶ is a hydrogen atom, a halogen atom or a monovalent hydrocarbon group, and R ⁷ is a hydrogen atom, a halogen atom or a monovalent hydrocarbon group. , Phenyl group, carboxyl group, alkoxycarbonyl group, nitrile group, glycidoxy group, alkenyl group,
It is an acyloxy group, an amide group, or a pyridyl group.

Examples of the polymerizable unsaturated group-containing monomer represented by the formula (5) include styrene-based monomers such as styrene and α-methylstyrene, acrylic acid or their esters, acrylic-based monomers such as acrylamide, acrylonitrile, and 2,4. A cyano group-containing monomer such as dicyanobutene-1, a vinyl ester-based monomer such as vinyl acetate,
Isoprene, butadiene, other diene-based monomers,
There are glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, and olefins other than these, unsaturated esters, halogenated olefins, vinyl ethers and the like.

If necessary, a silicon compound represented by the formula (6) can also be used as the polymerizable unsaturated group-containing monomer in the present invention.

Y _3-n -Si (R ⁸ _n ) R ⁹ (6) In the formula, R ⁸ is a monovalent hydrocarbon group or a halogenated hydrocarbon group, and Y is a hydroxyl group, a halogen group or an alkoxy group. , An acyloxy group, an amide group, an amino group, an aminoxy group or a ketoximate group, and n are 0, 1 or 2, and R ⁹ is an organic residue having a polymerizable unsaturated group.

Specific examples of the silicon compound represented by the formula (6) include compounds represented by Chemical formula 1.

[0034]

Embedded image CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₃ Si
_{(CH 3) (OCH 3)} 2 CH 2 = C (CH 3) Si (CH 3) (OCH 3) 2

These polymerizable unsaturated group-containing monomers are
It can be selected as needed. When a cyano group-containing monomer such as acrylonitrile, a styrene-based monomer such as styrene, a cyano group-containing monomer such as glycidyl acrylate, or glycidyl methacrylate is used as a main component, particularly excellent adhesiveness and mechanical properties can be expressed, which is preferable. .

The amount of the polymer (B) of the polymerizable unsaturated group-containing monomer is not particularly limited, and the organic polymer (A) 100
It is preferably used in the range of 0.1 to 100 parts by weight with respect to parts by weight from the viewpoint of workability and the like. The polymerizable unsaturated group-containing monomer is polymerized by the method of polymerizing the polymerizable unsaturated group-containing monomer in the presence of the organic polymer (A), and the presence of the terminal unsaturated group-introduced product (C) of the polymer (D). Examples thereof include a method of polymerizing the polymerizable unsaturated group-containing monomer below and a method of polymerizing the polymerizable unsaturated group-containing monomer in a solvent.

Terminal unsaturated group-introduced product (C) of polymer (D)
Is polyoxyalkylene before introducing the hydrolyzable silicon group in the above-mentioned method for producing the organic polymer (A), and is polyoxyalkylene having an unsaturated group at the end and optionally a hydroxyl group.

The solvent can be appropriately selected depending on the kind of the unsaturated group-containing monomer used for the polymerization. The polymerization initiator used for the polymerization is not limited to the radical generator, and various compounds capable of polymerizing the polymerizable unsaturated group-containing monomer can be used. In some cases, the polymerization can be performed by radiation or heat without using the polymerization initiator. Examples of the polymerization initiator include peroxide-based, azo-based, or redox-based polymerization initiators and metal compound catalysts. Specific examples of polymerization initiators often used include azobisisobutyronitrile, benzoyl peroxide, t-alkylperoxy ester, acetyl peroxide, diisopropyl peroxycarbonate and the like.

The curable composition of the present invention can be obtained by mixing the polymer of the above-mentioned polymerizable unsaturated group-containing monomer with the organic polymer (A). When carried out in the presence of the organic polymer (A), the desired composition can be obtained without newly mixing with the organic polymer (A) after the polymerization of the monomer. When the polymerizable unsaturated group-containing monomer is polymerized in the presence of the terminal unsaturated group-introduced product (C), after the polymerization, the terminal unsaturated group-introduced product (C) is subsequently reacted with a reactive hydrolyzable silicon group. The desired composition can also be obtained by introducing. When the polymerizable unsaturated group-containing monomer is polymerized in a solvent, the desired composition is obtained by distilling part or all of the solvent after mixing with the organic polymer (A).

The polymer of the polymerizable unsaturated group-containing monomer in the composition may be dispersed in the organic polymer (A) in the form of fine particles or may be dissolved uniformly. In consideration of workability such as viscosity, it is preferable that the particles are uniformly dispersed.

From these points, specifically, it is preferable to use a cyano group-containing monomer such as acrylonitrile, a styrene-based monomer such as styrene, or a glycidyl group-containing monomer such as glycidyl methacrylate as the main component.
In particular, when a glycidyl group-containing monomer is selected, excellent adhesion to various substrates can be imparted at the same time.

When curing the cured product of the present invention, a curing accelerating catalyst for accelerating the curing reaction of the hydrolyzable silicon group in the components (A) and (B) may be used. Examples of curing accelerator catalysts include alkyl titanates, organosilicon titanates, bismuth tris-2-ethylhexoate, metal salts of carboxylic acids such as tin octylate and dibutyltin dilaurate, dibutylamine-2-ethylhexanoate. Amine salts such as xoates and the like, as well as other acidic and basic catalysts may be used.

The composition of the present invention may further comprise:
A reinforcing agent, a filler, a plasticizer, an anti-sagging agent, an adhesive agent, etc. may be included. As a reinforcing agent, carbon black, finely divided silica, etc., as a filler, calcium carbonate, talc,
Clay, silica, etc., plasticizers such as dioctyl phthalate, dibutyl phthalate, dioctyl adipate, chlorinated paraffin and petroleum-based plasticizers, and pigments include inorganic pigments such as iron oxide, chromium oxide, titanium oxide and phthalocyanine blue, phthalocyanine. Organic pigments such as green, organic acid-treated calcium carbonate as an anti-sagging agent, hydrogenated castor oil, calcium stearate, zinc stearate, fine powder silica, and the like, aminosilane as an adhesive agent,
An epoxy silane etc. are mentioned.

The curable composition of the present invention comprises a sealing agent,
It can be used as a waterproofing agent, an adhesive, a coating agent and the like. In particular, it is suitable for applications in which the cured product itself requires sufficient strength and high adhesiveness.

[0045]

【Example】

[Production Example 1] Propylene oxide was polymerized using diethylene glycol as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene diol. Sodium hydroxide was added to this to deactivate the catalyst and then neutralized with hydrochloric acid, and the salt precipitated by dehydration was filtered together with the adsorbent to obtain a purified product. Remaining ionic impurities are 20 ppm, of which metal ionic impurities are 10 ppm
Met. Isocyanatopropylmethyldimethoxysilane was added to this to undergo a urethane reaction to convert the hydroxyl groups at both ends into methyldimethoxysilylpropyl groups to obtain a hydrolyzable silicon group-containing polyoxyalkylene (A). The molecular weight of (A) based on the hydroxyl value-converted molecular weight of the raw material polyoxypropylene diol is 11,000, GP
The M _w / M _n by the C method was 1.32.

[Production Example 2] Propylene oxide was polymerized using glycerin as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene triol. A methanol solution of sodium methoxide was added to this to remove methanol, and then allyl chloride was reacted to convert the terminal hydroxyl group into an allyl group. Acidic pyrophosphate, a small amount of water and a nonionic surfactant are added to the reaction product, and the salt is aggregated by dehydration, and then the terminal allyl group-containing polyoxyalkylene (B) purified by filtration with an adsorbent is obtained. Obtained. 12p remaining ionic impurities
pm, of which metal ionic impurities were 6 ppm. The molecular weight of (B) based on the hydroxyl value-converted molecular weight of the raw material polyoxypropylene triol is 17,300, G
The M _w / M _n by the PC method was 1.38.

Production Example 3 (B) obtained in Production Example 2 was reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert an allyl group into a methyldimethoxysilylpropyl group to contain a hydrolyzable silicon group. Polyoxyalkylene (C) was obtained. The molecular weight of (C) was 17,600 based on the hydroxyl group-equivalent molecular weight of polyoxypropylene triol, which is the raw material of (B), and _Mw / _Mn by the GPC method was 1.39.

[Production Example 4] A polyoxypropylene diol having an average molecular weight of 3000 obtained using a KOH catalyst was converted to a terminal sodium with metallic sodium, and then reacted with dibromomethane to increase the molecular weight. The terminal hydroxyl group of the obtained high molecular weight polyoxypropylene diol was terminally allylated in the same manner as in Production Example 2, and the precipitated salt was filtered to obtain a purified product. The residual metal ionic impurities were 150 ppm. In the same manner as in Production Example 3, conversion to a methyldimethoxysilylpropyl group was performed to obtain a hydrolyzable silicon group-containing polyoxyalkylene (D). The molecular weight of (D) based on the hydroxyl group-equivalent molecular weight of the raw material polyoxypropylene diol is 9,700, and M according to the GPC method.
_w / _Mn was 2.8.

Example 1 (A) 1 obtained in Production Example 1
Add 00g to a 300cm ³ 4-necked flask and
While maintaining the temperature at 0 ° C, a mixture of 15 g of methyl methacrylate, 15 g of n-butyl methacrylate and 0.5 g of azobisisobutyronitrile was added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After the reaction is completed, unreacted monomer is heated to 110 ° C and 0.1 mm
It was heated and degassed under reduced pressure for 2 hours to remove it, thereby obtaining a composition comprising a polymer of a polymerizable unsaturated group-containing monomer and a polyoxyalkylene having a hydrolyzable silicon group.

[Example 2] (A) 1 obtained in Production Example 1
Add 00g to a 300cm ³ 4-necked flask and
Glycidyl methacrylate 20 g, acrylonitrile 10 g, azobisisobutyronitrile 0.
6 g of the mixture was added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature.
After the reaction is completed, unreacted monomer is heated to 110 ° C. and 0.1 mmHg.
Then, the mixture was heated and depressurized for 2 hours for degassing to obtain a composition containing a polymer of a polymerizable unsaturated group-containing monomer and a polyoxyalkylene containing a hydrolyzable silicon group.

Example 3 (B) 1 obtained in Production Example 2
Add 00g to a 300cm ³ 4-necked flask and
Glycidyl methacrylate 20 g, acrylonitrile 10 g, azobisisobutyronitrile 0.
6 g of the mixture was added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature.
After the reaction is completed, unreacted monomer is heated to 110 ° C. and 0.1 mmHg.
After heating and degassing under reduced pressure for 2 hours, methyldimethoxysilane is added to this and the silylation reaction is performed to convert the allyl groups at both ends of polyoxyalkylene to methyldimethoxysilylpropyl groups. A composition comprising a polymer of the contained monomer and a polyoxyalkylene containing a hydrolyzable silicon group was obtained.

[Example 4] (C) 1 obtained in Production Example 3
Add 00g to a 300cm ³ 4-necked flask and
Glycidyl methacrylate 20 g, acrylonitrile 10 g, azobisisobutyronitrile 0.
6 g of the mixture was added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature.
After the reaction is completed, unreacted monomer is heated to 110 ° C. and 0.1 mmHg.
Then, the mixture was heated and depressurized for 2 hours for degassing to obtain a composition containing a polymer of a polymerizable unsaturated group-containing monomer and a polyoxyalkylene containing a hydrolyzable silicon group.

Example 5 Production Example 2 in 100 g of toluene
Dissolve 50 g of (B) obtained in step 1, put in a 4-necked flask, and maintain glycidyl methacrylate 70 at 100 ° C.
g, 30 g of acrylonitrile, and 0.6 g of azobisisobutyronitrile while stirring under a nitrogen atmosphere.
It dripped over time. Then, stirring was continued for 0.5 hours at the same temperature. After completion of the reaction, 25 (C) obtained in Production Example 3 was used.
After adding 0 g and mixing with stirring, toluene and unreacted monomer were heated under reduced pressure degassing under heating at 110 ° C. and 0.1 mmHg for 2 hours to distill off, and a polymer of the polymerizable unsaturated group-containing monomer and hydrolysis were obtained. A composition comprising polyoxyalkylene containing a volatile silicon group was obtained.

Comparative Example 1 (D) 1 obtained in Production Example 4
Add 00g to a 300cm ³ 4-necked flask and
While maintaining at 0 ° C, a mixture of 20 g of methyl methacrylate, 10 g of n-butyl methacrylate and 0.6 g of azobisisobutyronitrile was added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After the reaction is completed, unreacted monomer is heated to 110 ° C and 0.1 mm
It was heated under Hg for 2 hours under reduced pressure under reduced pressure to remove it, thereby obtaining a composition comprising a polymer of a polymerizable unsaturated group-containing monomer and a polyoxyalkylene having a hydrolyzable silicon group. The polyoxyalkylene containing hydrolyzable silicon group in the composition had an M _w / M _n of 3.0.

[Comparative Example 2] (D) 1 obtained in Production Example 4
Add 00g to a 300cm ³ 4-necked flask and
Glycidyl methacrylate 20 g, acrylonitrile 10 g, azobisisobutyronitrile 0.
6 g of the mixture was added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature.
After the reaction is completed, unreacted monomer is heated to 110 ° C. and 0.1 mmHg.
Then, the mixture was heated and depressurized for 2 hours for degassing to obtain a composition comprising a polymer of a polymerizable unsaturated group-containing monomer and a polyoxyalkylene having a hydrolyzable silicon group. The polyoxyalkylene containing hydrolyzable silicon group in the composition had an M _w / M _n of 2.9.

Table 1 shows the results of viscosity measurement at 25 ° C. and the storage stability at 25 ° C. of Examples 1 to 5 and Comparative Examples 1 and 2.

[0057]

[Table 1]

Dibutyltin dilaurate was added as a curing catalyst to the curable compositions obtained in Examples 1 to 5 above,
Create a 2mm thick sheet for 7 days at 20 ℃, then 50 ℃
After curing and curing for 7 days, physical properties were measured. The results are shown in Table 2.
Shown in Further, aminosilane and dibutyltin dilaurate were added to the curable compositions obtained in Examples 1 to 5 to measure the tensile shear strength for aluminum (JIS H4000 A1050P). The results are also shown in Table 2.

[0059]

[Table 2]

[0060]

As described above, a derivative of a polyoxyalkylene polymer produced using a double metal cyanide complex catalyst having a hydrolyzable silicon group and having a total amount of ionic impurities of 50 ppm. Some organic polymer (A)
And a curable composition comprising a polymer (B) of a polymerizable unsaturated group-containing monomer have excellent storage stability, and the cured product has excellent mechanical strength.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 33/20 LJM 101/10 LTB (72) Inventor Toshihiko Higuchi 1150 Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa Address: Central Research Laboratory, Asahi Glass Co., Ltd.

Claims (9)

[Claims] 1. An organic polymer (A) having a hydrolyzable silicon group represented by the following formula (1) and having a total amount of ionic impurities of 50 ppm or less, and a polymer of a polymerizable unsaturated group-containing monomer. A curable composition comprising (B). —R—SiX _a R ¹ _3-a (1) In the formula, R is a divalent organic group, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and X is Hydrolyzable group,
a is 1, 2 or 3. 2. The curable composition according to claim 1, wherein the organic polymer (A) is a derivative of a hydroxyl group-containing polyoxyalkylene polymer (D). 3. A derivative of a hydroxyl group-containing polyoxyalkylene polymer (D) obtained by polymerizing a cyclic ether with an initiator using the complex metal cyanide complex (E) as a catalyst, which is represented by the following formula (1). A curable composition comprising an organic polymer (A) having a hydrolyzable silicon group and having an ionic impurity of 50 ppm or less, and a polymer (B) of a polymerizable unsaturated group-containing monomer. —R—SiX _a R ¹ _3-a (1) In the formula, R is a divalent organic group, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and X is Hydrolyzable group,
a is 1, 2 or 3. 4. A metal ionic impurity contained in the organic polymer (A) is changed to a metal salt which is essentially insoluble in the organic polymer (A), and the metal salt is converted from the organic polymer (A). The ionic impurities contained in the organic polymer (A) are reduced to 50 ppm or less by removing the organic polymer (A).
Curable composition. 5. An organic polymer (A), wherein the metal ionic impurities contained in the polymer (D) are converted into metal salts essentially insoluble in the polymer (D), and then the metal salt is added to the polymer (D). An organic polymer obtained by reducing the ionic impurities contained in the polymer (D) to 50 ppm or less by removing the polymer (B), and then introducing a hydrolyzable silicon group into the polymer (D). is there,
The curable composition according to claim 3. 6. The organic polymer (A) essentially contains the metal ionic impurities contained in the terminal unsaturated group-introduced product (C) of the polymer (D) in the terminal unsaturated group-introduced product (C). After the metal salt is insoluble in, the metal salt is removed from the terminal unsaturated group-introduced product (C) to reduce the ionic impurities contained in the terminal unsaturated group-introduced product (C) to 50 ppm or less. The curable composition according to claim 3, which is an organic polymer obtained by reacting a terminal unsaturated group-introduced product (C) with a silicon hydride compound represented by the following formula (2). HSiX _a R ¹ _3-a (2) In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a hydrolyzable group, and a is 1, 2 or 3. 7. The curable composition according to claim 1, which is obtained by polymerizing a polymerizable unsaturated group-containing monomer in the organic polymer (A). 8. An unsaturated group-introduced product (C) of the polymer (D).
In the following, after polymerizing the polymerizable unsaturated group-containing monomer, the terminal unsaturated group-introduced product (C) and the following formula (2)
The curable composition according to any one of claims 1 to 6, which is obtained by reacting with the silicon hydride compound represented by. HSiX _a R ¹ _3-a (2) In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a hydrolyzable group, and a is 1, 2 or 3. 9. A polymer (B) is obtained by polymerizing a polymerizable unsaturated group-containing monomer in a solvent,
Curable composition in any one of Claims 1-6 obtained by mixing with an organic polymer (A), and distilling off a part or all of a solvent after that.