JPH0762219A - Curing composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing a specific polyether and a polymer of a polymerizable unsaturated group-containing monomer, excellent in fluidity and mechanical strength and adhesion of a cured product and useful as waterproof agents, adhesives, etc. CONSTITUTION:This composition contains (A) a silyl group-containing polyether, having a reactive silyl group obtained by converting terminal hydroxyl groups of a polyether monool or polyether polyol produced by using a composite metallic cyanide complex catalyst into a reactive silyl group-containing organic group, preferably a silyl group-containing polyether having preferably <=1.5 ratio (MW/MN) and (B) a polymer of a polymerizable unsaturated group-containing monomer such as acrylonitrile, styrene or glycidyl (meth)acrylate. Furthermore, the component (B) is preferably a polymer obtained by polymerizing a polymerizable unsaturated group-containing monomer in the component (A) and is blended in an amount of preferably 0.1-100 pts.wt. based on 100 pts.wt. component (A).

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 remarkably excellent mechanical properties and excellent workability.

[0002]

2. Description of the Related Art Polyether compounds having at least one reactive silyl group in the molecule have been used for coating compositions, sealing compositions, etc. by taking advantage of the fact that cured products have rubber elasticity. In particular, the strength of the cured product is insufficient for applications such as adhesives and waterproofing agents, which poses a practical problem. For example, when it is used as an adhesive, there arises a problem that the shear adhesive strength is insufficient, and when it is used as a waterproofing agent, there is a problem that the strength of the film is insufficient. In order to solve these problems, a curable composition comprising a polymer of a polyether compound having at least one reactive silyl group in the molecule and a polymerizable unsaturated group-containing monomer has been proposed. However, there is a problem in that work efficiency is high.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a curable composition which solves the above-mentioned drawbacks and has a cured product having remarkably excellent mechanical strength and adhesiveness and excellent workability. The purpose is to do.

[0004]

The present invention relates to a composition comprising a polyether compound having at least one reactive silyl group in a molecule and a polymer of a polymerizable unsaturated group-containing monomer, and the compound as a polyether compound. It has at least one reactive silyl group obtained by converting at least one terminal hydroxyl group of a polyether monool or polyether polyol produced using a metal cyanide complex catalyst into a reactive silyl group-containing organic group. It was made based on the finding that a curable composition having a remarkably excellent mechanical strength and adhesiveness and having excellent workability can be obtained by using the silyl group-containing polyether (a). It is a thing.

That is, at least one of the terminal hydroxyl groups of the polyether monool or polyether polyol produced by using the double metal cyanide complex catalyst is converted to the reactive silyl group-containing organic group. A curable composition comprising a silyl group-containing polyether (a) having a reactive silyl group and a polymer (b) of a polymerizable unsaturated group-containing monomer.

The polyether (a) in the present invention is subjected to ring-opening polymerization of a monoepoxide having 3 or more carbon atoms in the presence of an initiator by using a double metal cyanide complex as a catalyst for ring-opening polymerization of monoepoxide. It is obtained by converting a part or all of the hydroxyl groups at the molecular ends into hydrolyzable silyl groups. The double metal cyanide complex produces extremely less unsaturated monool, and is particularly excellent as a catalyst for producing a high molecular weight polyoxyalkylene compound. This catalyst is known and is described, for example, in the following US patent specifications. USP. 3278457, USP. 3278458, U
SP. 3278459 USP. 3427256, US
P. 3427334, USP. 3427335, US
P. 3829505, USP. 3941849

This catalyst is represented, for example, by the following formula (1). M ¹ _a [M ² (CN) _b ] (H ₂ O) _d (R ¹ ) _e (M ¹ X) _f・ ・ ・ (1)

Here, M ¹ is Fe (II), Fe (III),
Co (II), Co (III), Cr (II), Cr (III)
, M ² is Zn (II), Fe (II), Fe (III), C
o (II), Ni (II), Mo (VI), etc., R ¹ is an ether or other ligand, and X is an anion such as halogen. a, b, c, d, e and f represent integers depending on the valence, coordination number, etc. of the metal.

Examples of the monoepoxide having 3 or more carbon atoms used in the present invention include aliphatic alkylene oxides such as propylene oxide, 1.2-butylene oxide and epichlorohydrin, and aromatic alkylene oxides such as styrene oxide. Among them, aliphatic alkylene oxide is preferable, and propylene oxide is particularly preferable. It is also possible to use a small amount of ethylene oxide together with this.

The initiator used in the present invention includes polyhydric alcohols, polyhydric phenols, polyhydric active hydrogen-containing compounds such as polycarboxylic acids, and unsaturated group-containing activities such as unsaturated alcohols, unsaturated phenols and unsaturated carboxylic acids. A hydrogen-containing compound or the like can be used.

In the present invention, a ring-opening polymerization of a monoepoxide having 3 or more carbon atoms is carried out by using a complex metal complex catalyst for these initiators to produce a polyoxyalkylene compound having a hydroxyl group or an unsaturated group at the terminal. .

Next, the terminal hydroxyl group or terminal unsaturated group is converted into a hydrolyzable silyl group in order to introduce at least one hydrolyzable silyl group into the molecule. As this method, for example, the following methods can be specifically exemplified, but the method is not limited to these methods.

(A) A specific organosilicon compound having at least one, preferably only one isocyanate group and at least one hydrolyzable silyl group in the molecule as represented by the general formula (2) has a hydroxyl group. React with the terminal hydroxyl groups of the polyoxyalkylene compound.

X _3-m -SiR ² _m -R ³ -NCO (2) (wherein R ² is a monovalent hydrocarbon group or a halogenated hydrocarbon group. X is a hydroxyl group, a halogen group or an alkoxy group. , An acyloxy group, an amido group, an amino group, an aminoxy group or a ketoximate group, etc. m is 0, 1 or 2. R ³ is a divalent hydrocarbon group or a halogenated hydrocarbon group.)

The following compounds can be shown as specific organic silicon compounds. _{(C 2 H 5 O) 3} Si (CH 2) 3 NCO (CH 3 O) 3 Si (CH 2) 3 NCO (CH 3 O) 2 (CH 3) Si (CH 2) 3 NCO (CH 3 O) ₃ SiNCO (CH ₃ O) ₂ Si (NCO) ₂

(B) A terminal unsaturated group obtained by reacting a terminal unsaturated group-containing isocyanate compound or a terminal unsaturated group-containing halogen compound with a terminal hydroxyl group of a polyoxyalkylene compound or a polyoxyalkylene compound derived from an initiator. The terminal unsaturated group and the hydrosilicon compound represented by the general formula (3) are reacted in the presence of a Group VIII transition metal.

X _3-m -SiR ² _m H (3) (wherein R ² , X and m are the same as above).

Specific examples include allyl isocyanate as the terminal unsaturated group-containing isocyanate compound and allyl chloride as the terminal unsaturated group-containing halogen compound.
In addition to the above methods, the methods described in JP-A-5-194678 and the like can be mentioned.

The M _w / M _N of the polyether (a) thus obtained is preferably 1.5 or less in consideration of viscosity and the like.

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 general formula (4) alone or in combination of two or more kinds. can get.

CH ₂ ═C (R ⁴ ) (R ⁵ ) ... (4) (wherein R ⁴ is a hydrogen atom, a halogen atom or a monovalent hydrocarbon group, and R ⁵ is a hydrogen atom, a halogen atom or 1 Valent hydrocarbon group, carboxyl group, alkoxycarbonyl group,
It represents a nitrile group, a glycidoxy group, an alkenyl group, an acyloxy group, an amide group or a pyridyl group. )

Examples of the polymerizable unsaturated group-containing monomer represented by the formula (4) 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 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, the silicon compound represented by the general formula (5) can also be used as the polymerizable unsaturated group-containing monomer in the present invention.

Y _3-n -Si (R ⁶ _n ) R ⁷ (5) (wherein R ⁶ is a monovalent hydrocarbon group or a halogenated hydrocarbon group. 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, etc., n is 0, 1 or 2. R ⁷ represents an organic residue having a polymerizable unsaturated group.)

Specific examples of the silicon compound represented by the formula (5) include compounds represented by Chemical formula 1.

[0026]

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

These polymerizable unsaturated group-containing monomers are
Although it can be appropriately selected as necessary, particularly excellent adhesion is obtained when a cyano group-containing monomer such as acrylonitrile, a cyano group-containing monomer such as glycidyl acrylate or glycidyl methacrylate, or a styrene-based monomer such as styrene is used. It is preferable because it can exhibit properties and mechanical properties.

The amount of the polymer of the polymerizable unsaturated group-containing monomer is not particularly limited, but the polyether (a) 1
It is preferably used in the range of 0.1 to 100 parts by weight with respect to 00 parts by weight from the viewpoint of workability and the like. The polymerizable unsaturated group-containing monomer is polymerized by a method of polymerizing the polymerizable unsaturated group-containing monomer in the presence of the polyether (a), a method of polymerizing the polymerizable unsaturated group-containing monomer in a solvent, and a reactive silyl group. Examples thereof include a method of polymerizing a polymerizable unsaturated group-containing monomer in the presence of a polyether (b) having a functional group capable of introducing a group.

The polyether (b) having a functional group capable of introducing a reactive silyl group is a polyether compound before introducing the reactive silyl group in the above-mentioned method for producing the polyether (a), It is a polyether having a hydroxyl group or an unsaturated group at the terminal.

The solvent can be appropriately selected according to the kind of 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 the polymerization initiator often used include azobisisobutyronitrile, benzoyl peroxide, t-alkylperoxy ester, acetyl peroxide, diisopropyl peroxycarbonate and the like.

The curable composition of the present invention is obtained by mixing the polymer of the above-mentioned polymerizable unsaturated group-containing monomer and the polyether (a) containing at least one reactive silyl group in the molecule. However, when the polymerization of the polymerizable unsaturated group-containing monomer is carried out in the presence of the polyether (a), a new polyether (a) is added after the polymerization of the monomer.
The desired composition can be obtained without mixing with. When the polymerizable unsaturated group-containing monomer is polymerized in the presence of the polyether (b), the desired composition can also be obtained by introducing a reactive silyl group into the polyether (b) after the polymerization. can get. When the polymerizable unsaturated group-containing monomer is polymerized in a solvent, the desired composition is obtained by distilling off part or all of the solvent after mixing with the polyether (a).

In the composition, the polymer of the polymerizable unsaturated group-containing monomer is evenly dispersed in the form of fine particles in the polyether (a) containing at least one reactive silyl group in the molecule. Moreover, although it may be dissolved uniformly,
Considering workability such as viscosity of the composition, it is preferable that the composition is uniformly dispersed.

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

In curing the cured product of the present invention, a curing accelerating catalyst which accelerates the curing reaction of the reactive silyl group in the components (A) and (B) may be used. Examples of curing accelerator catalysts are metal titanates, organosilicon titanates, metal salts of carboxylic acids such as bismuth tris 2-ethylhexoate, tin octylate and dibutyltin dilaurate: dibutylamine-2-ethylhexoate. Amine salts such as: and other acidic and basic catalysts may be used.

The composition of the present invention may further contain a reinforcing agent, a filler, a plasticizer, an anti-sagging agent, an adhesive agent, etc., if necessary. Carbon black, fine powder silica, etc. as the reinforcing agent, calcium carbonate, talc, clay, silica, etc. as the filler, and dioctyl phthalate, dibutyl phthalate, dioctyl adipate, chlorinated paraffin and petroleum plasticizers as the plasticizer. However, as the pigment, inorganic pigments such as iron oxide, chromium oxide, and titanium oxide, and organic pigments such as phthalocyanine blue and phthalocyanine green, organic acid-treated calcium carbonate as a sagging inhibitor, hydrogenated castor oil, calcium stearate, zinc stearate, Fine powder silica, etc., aminosilane as an adhesive,
An epoxy silane etc. are mentioned.

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

[0037]

【Example】

[Production Example 1] Polypropylene diol was obtained by polymerizing propylene oxide with zinc hexacyanocobaltate catalyst using diethylene glycol as an initiator. Isocyanatopropylmethyldimethoxysilane was added to this to undergo a urethane reaction to convert the hydroxyl groups at both ends into methyldimethoxysilyl groups. The number average molecular weight of the obtained reactive silyl group-containing polyether was 10,000, and the molecular weight distribution (M _W / M _N ) was 1.30.

[Production Example 2] Polypropylene triol was obtained by polymerizing propylene oxide with zinc hexacyanocobaltate catalyst using glycerin as an initiator. Allyl chloride was added to this to convert the hydroxyl groups at both ends into allyl groups. The number average molecular weight of the obtained terminal allyl group-containing polyether 17,000, molecular weight distribution (M _W / M
_N ) was 1.40.

[Production Example 3] The allyl group-containing polyether obtained in Production Example 2 was reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert the allyl group into a methyldimethoxysilyl group. The number average molecular weight of the obtained reactive silyl group-containing polyether was 17,300, and the molecular weight distribution (M _W / M _N ) was 1.40.

[Production Example 4] Polypropylene diol having an average molecular weight of 3000 obtained using a KOH catalyst was subjected to terminal sodium conversion with sodium metal, and then reacted with dibromomethane to increase the molecular weight. The terminal hydroxyl groups of the obtained high molecular weight polypropylene diol were converted into methyldimethoxysilyl groups by the same method as in Production Example 2. The number average molecular weight of the obtained reactive silyl group-containing polyether compound was 10,000, and the molecular weight distribution (M _W / M _N ) was 2.5.

Example 1 100 g of the reactive silyl group-containing polyether obtained in Preparation Example 1 was placed in a 300 ml four-necked flask, and methylmethacrylate 10 g, n-butyl methacrylate 20 g, and azo were kept at 110 ° C. A mixture of 0.6 g of bisisobutyronitrile 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 completion of the reaction, unreacted monomer is removed by depressurizing by heating under reduced pressure by heating at 110 ° C. and 0.1 mmHg for 2 hours to contain a polymer of a polymerizable unsaturated group-containing monomer and at least one reactive silyl group in the molecule. A composition A consisting of polyether was obtained.

Example 2 100 g of the reactive silyl group-containing polyether obtained in Preparation Example 1 was placed in a 300 ml four-necked flask and 21 g of glycidyl methacrylate, 9 g of acrylonitrile and azobisisobutyrate were kept at 110 ° C. A mixture of 0.6 g of ronitrile was added dropwise over 2 hours with stirring under a nitrogen atmosphere. After that, at the same temperature, 0.
Stirring was continued for 5 hours. After the reaction is completed, the unreacted monomer is changed to 11
A composition B comprising a polymer of a polymerizable unsaturated group-containing monomer and a polyether having at least one reactive silyl group in the molecule, which is removed by degassing under reduced pressure by heating at 0 ° C. and 0.1 mmHg for 2 hours. Got

Example 3 100 g of the polyether having terminal allyl groups obtained in Production Example 2 was placed in a 300 ml four-necked flask and, while maintaining at 110 ° C., 21 g of glycidyl methacrylate, 9 g of acrylonitrile and azobisisobutyro. A mixture of 0.6 g of nitrile was added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then 0.5 at the same temperature
Stirring was continued for hours. After the reaction is completed, 110
Removed by degassing under reduced pressure while heating at 0.1 mmHg for 2 hours.
Subsequently, methyldimethoxysilane was added to this to carry out a silylation reaction to convert allyl groups at both ends of the polyether into methyldimethoxysilyl groups, and to obtain a polymer of unsaturated group-containing monomers and at least one reactive silyl group in the molecule. A composition C consisting of a group-containing polyether was obtained.

Example 4 100 g of the reactive silyl group-containing polyether obtained in Preparation Example 3 was placed in a 300 ml four-necked flask and 21 g of glycidyl methacrylate, 9 g of acrylonitrile and azobisisobutyrate were kept at 110 ° C. A mixture of 0.6 g of ronitrile was added dropwise over 2 hours with stirring under a nitrogen atmosphere. After that, at the same temperature, 0.
Stirring was continued for 5 hours. After the reaction is completed, the unreacted monomer is changed to 11
A composition D comprising a polymer of a polymerizable unsaturated group-containing monomer and a polyether having at least one reactive silyl group in the molecule, which is removed by degassing under reduced pressure by heating at 0 ° C. and 0.1 mmHg for 2 hours. Got

Example 5 Production Example 2 in 100 g of toluene
50 g of the polyether containing terminal allyl group obtained in (3) was dissolved, placed in a 4-neck flask, and 70 g of glycidyl methacrylate and 30 g of acrylonitrile while maintaining at 100 ° C.
A mixture of 0.6 g of azobisisobutyronitrile was added dropwise over 2 hours while stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After completion of the reaction, Production Example 3
250 g of the reactive silyl group-containing polyether obtained in
After adding and stirring and mixing, toluene and unreacted monomers were stirred and heated at 110 ° C. and 0.1 mmHg for 2 hours under reduced pressure degassing, and then distilled off to form a polymer of the polymerizable unsaturated group-containing monomer and the molecule. A composition E consisting of a polyether containing at least one reactive silyl group was obtained.

Comparative Example 1 100 g of the reactive silyl group-containing polyether obtained in Production Example 4 was placed in a 300-ml four-necked flask, and methylmethacrylate 10 g, n-butyl methacrylate 20 g, and azo were kept at 110 ° C. A mixture of 0.6 g of bisisobutyronitrile 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 completion of the reaction, unreacted monomers are heated and degassed under reduced pressure for 2 hours at 110 ° C. and 0.1 mmHg for 2 hours to remove a polymer of the polymerizable unsaturated group-containing monomer and M _W.
A composition F consisting of a polyether having a / _MN of 2.5 and containing at least one reactive silyl group in the molecule was obtained.

COMPARATIVE EXAMPLE 2 100 g of the reactive silyl group-containing polyether obtained in Production Example 4 was placed in a 300 ml four-necked flask and 21 g of glycidyl methacrylate, 9 g of acrylonitrile, and azobisisobutyrate were kept at 110 ° C. A mixture of 0.6 g of ronitrile was added dropwise over 2 hours with stirring under a nitrogen atmosphere. After that, at the same temperature, 0.
Stirring was continued for 5 hours. After the reaction is completed, the unreacted monomer is changed to 11
It was heated at 0 ° C. and 0.1 mmHg for 2 hours under reduced pressure degassing and removed to obtain a polymer of a polymerizable unsaturated group-containing monomer, and M _W / M
_A composition G consisting of a polyether having _N of 2.5 and containing at least one reactive silyl group in the molecule was obtained.

Table 1 shows the viscosity measurement results and workability of Examples 1 to 5 and Comparative Examples 1 and 2.

[0049]

[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, the physical properties were measured. The results are shown in Table 2. 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.

[0051]

[Table 2]

[0052]

As described above, at least one of the terminal hydroxyl groups of the polyether monool or polyether polyol produced by using the double metal cyanide complex catalyst is converted into the reactive silyl group-containing organic group. The resulting curable composition comprising a polymer of a silyl group-containing polyether (a) having at least one reactive silyl group and a polymerizable unsaturated group-containing monomer has a cured product with remarkably excellent mechanical strength, It has been revealed by the present invention that it has adhesiveness, low viscosity and excellent workability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 33/20 LJP 101/00 LTA // C08G 65/32 NQH

Claims (6)

[Claims] 1. A method of converting at least one terminal hydroxyl group of a polyether monool or polyether polyol produced by using a complex metal cyanide complex catalyst into a reactive silyl group-containing organic group. A silyl group-containing polyether (a) having a reactive silyl group,
And a curable composition comprising a polymer (b) of a polymerizable unsaturated group-containing monomer. 2. The polyether (a) has a M _W / M _N of 1.5.
The curable composition of claim 1, which is: 3. The polymer (b) of the polymerizable unsaturated group-containing monomer is a polymer obtained by polymerizing the polymerizable unsaturated group-containing monomer in the polyether (a). Curable composition. 4. A polyether (c) having a functional group capable of introducing a reactive silyl group, which comprises a polyether monool or a polyether polyol produced by using a double metal cyanide complex catalyst as a main chain, The curable composition according to claim 1, which is obtained by polymerizing the polymerizable unsaturated group-containing monomer and subsequently introducing a reactive silyl group into the polyether (c). 5. After obtaining a polymer (b) by polymerizing a polymerizable unsaturated group-containing monomer in a solvent,
The curable composition according to claim 1, obtained by mixing with the polyether (a) and then distilling off part or all of the solvent. 6. The polymerizable unsaturated group-containing monomer polymer (b) is obtained by polymerizing at least one polymerizable unsaturated group-containing monomer selected from the group consisting of acrylonitrile, styrene, glycidyl acrylate and glycidyl methacrylate. Alternatively, the curable composition according to claim 1, which is a polymer obtained by copolymerizing with another polymerizable unsaturated group-containing monomer.