JPH06329739A - Production of curable composition - Google Patents

Abstract

PURPOSE:To produce a curable composition comprising a polyether compound having a reactive silyl group and having excellent storage stability. CONSTITUTION:The production process comprises polymerizing a polymerizable unsaturated group-containing monomer in the presence of a polyether having a polymerizable unsaturated group in a silylated polyether having a reactive silyl group in the molecule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a modified curable composition, which has particularly excellent mechanical properties and adhesiveness, and has excellent storage stability. It relates to a method for producing a composition.

[0002]

2. Description of the Related Art A polyether compound having at least one reactive silyl group in its molecule has a rubber elasticity as a cured product. Therefore, it can be used for coating compositions, sealing compositions and the like by taking advantage of its characteristics. However, in applications such as adhesives and waterproof materials, the strength and adhesiveness of the cured product are insufficient, so there was a practical problem. For example, when this composition is used as an adhesive, there arises a problem that the shear adhesive strength is insufficient, and when this composition is used as a waterproof material, the strength of the film is insufficient. The problem arises that there is.

However, if an attempt is made to improve the strength of the cured product in order to solve these problems, the cured product generally becomes hard and brittle, and sufficient elongation at break cannot be obtained. Further, depending on the composition, the viscosity becomes extremely high, which is a practical problem.

Therefore, the present inventors have found that in a 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, the polymerizable unsaturated group-containing monomer is used. By uniformly dispersing the polymer of the above in the polyether compound, eliminating the above defects, excellent workability, and a cured product having remarkably excellent mechanical strength and elongation at break, and remarkably excellent adhesiveness We have found a curable composition that provides a cured product having

As one of the methods for producing the above-mentioned curable composition, specifically, the polymerizable unsaturated group-containing monomer is polymerized in a polyether having at least one reactive silyl group in the molecule. A method was proposed (see Japanese Patent Application No. 3-331361). However, the curable composition obtained by this method has insufficient storage stability due to insufficient dispersion stability of the polymer of the polymerizable unsaturated group-containing monomer uniformly dispersed in the polyether having a reactive silyl group. There was a problem.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned disadvantages and has a polymer having a polymerizable unsaturated group-containing monomer excellent in storage stability and at least one reactive silyl group in the molecule. It is an object of the present invention to provide a method for producing a curable composition comprising a polyether compound.

[0007]

The present invention relates to a polyether (b) having a polymerizable unsaturated group in a silyl group-containing polyether (a) containing at least one reactive silyl group in the molecule. A method for producing a curable composition, which comprises polymerizing a polymerizable unsaturated group-containing monomer in the presence thereof.

As the polyether (b) having a polymerizable unsaturated group, it is preferable to use a polyether having at least one reactive silyl group in the molecule or an allyl group at the terminal of the molecule. As the polymerizable unsaturated group-containing monomer, one kind or two or more kinds selected from the group consisting of acrylonitrile, styrene, glycidyl acrylate, and glycidyl methacrylate may be used alone, or a mixture with another polymerizable unsaturated group-containing monomer may be used. Can be used. Furthermore, the molecular weight of the silyl group-containing polyether (a) containing at least one reactive silyl group in the molecule is preferably in the range of 100 to 50,000.

[0009]

According to the present invention, when a polymer of a polymerizable unsaturated group-containing monomer is obtained in a polyether (a) having at least one reactive silyl group in the molecule, a polymer having a polymerizable unsaturated group is used. The presence of ether (b) is intended to achieve the above object.

The polyether (b) having a polymerizable unsaturated group used in the present invention has one or more polymerizable unsaturated groups in one molecule, and the main chain thereof is a polyether chain. It is united. Here, examples of the polymerizable unsaturated group include groups shown below. These polymerizable unsaturated groups may be present at the ends or side chains of the polyether. In the following, φ represents a phenylene group.

[0011]

## STR1 ## _{-OCH 2 CH = CH 2 -OC (} CH 3) = CH 2 -OCH 2 CH 2 CH = CH 2 -OCOCH 2 CH = CH 2 -OCOCH = CH 2 -OCOC (CH 3) = CH 2 -OCH ₂ -φ-CH = CH ₂

As the method for producing the polyether (b),
Method for converting terminal hydroxyl groups of hydroxyl-terminated polyether obtained by ring-opening addition polymerization of monoepoxide to polymerizable unsaturated group, ring-opening addition polymerization of monoepoxide to active hydrogen-containing compound containing polymerizable unsaturated group Method, or in the case of ring-opening addition polymerization of monoepoxide, by copolymerizing a polymerizable unsaturated group-containing monoepoxide such as allyl glycidyl ether, a method of introducing a polymerizable unsaturated group at the side chain or terminal, etc. Can be mentioned. Specifically, there is a method previously proposed by the present inventors (see Japanese Patent Application Laid-Open No. 3-72527).

The polyether (b) may be a polyether having a reactive silyl group as well as a polymerizable unsaturated group in the molecule. The curable composition using this polyether is particularly excellent in mechanical properties.

The above-mentioned reactive silyl group is a group such as a silanol group or a hydrolyzable silyl group that causes condensation and reaction by moisture or a curing agent, and is represented by the general formula (1).

[0015]

## STR2 ## ^{_{X 2-m -SiR 1 m -}} ··· (1)

(In the formula, R ¹ is a monovalent hydrocarbon group or a halogenated hydrocarbon group. X is a hydroxyl group, a halogen group, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminoxy group or a ketoximate group. Degradable group, m is 0,
1 or 2. )

As described above, the polyether having a reactive silyl group together with a polymerizable unsaturated group in the molecule may be, for example, an allyl group terminal, a part of the terminal allyl group of the polyether, or a hydrolyzed group represented by the general formula (2). It is produced by reacting a silicon compound in the presence of a Group VIII transition metal, but is not particularly limited thereto.

[0018]

[Chemical Formula 3] X _3-m -SiR ¹ _m H (2)

(In the formula, R ¹ , X and m are the same as described above.) The polymerizable unsaturated group-containing monomer used in the present invention is a polymerizable unsaturated group-containing monomer represented by the general formula (3) alone or It is a mixture of two or more kinds.

[0020]

[Chemical formula 4] CH ₂ = CR ² R ³ (3)

(In the formula, R ² is a hydrogen atom, a halogen atom or a monovalent hydrocarbon group. R ³ is a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, a carboxyl group, an alkoxycarbonyl group or a glycidyloxycarbonyl group. , Nitrile group, glycidoxy group, alkenyl group, acyloxy group,
Amido group or pyridyl group. )

Examples of the polymerizable unsaturated group-containing monomer represented by the general formula (3) include styrene-based monomers such as styrene and α-methylstyrene; acrylic-based monomers such as acrylic acid, acrylate ester and acrylamide: acrylonitrile, 2 Cyano group-containing monomers such as 4-dicyanobutene-1; vinyl ester-based monomers such as vinyl acetate; isoprene, butadiene, and other diene-based monomers; glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; and olefins other than these. Examples include unsaturated esters, halogenated olefins and vinyl ethers.

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

[0024]

[Chemical Formula 5] Y _3-n -SiR ⁴ _n R ⁵ (4)

(In the formula, R ⁴ is a monovalent hydrocarbon group or a halogenated hydrocarbon group. Y is a hydroxyl group, a halogen group, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminoxy group or a ketoximate group. Decomposable group, R ⁵ is an organic residue having a polymerizable unsaturated group, and n is 0, 1 or 2.)

Specific examples of the silicon compound represented by the general formula (4) include the following compounds.

[0027]

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
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 as a main component. It is preferable because it can exhibit properties and mechanical properties.

The polyether (a) containing at least one reactive silyl group in the molecule used in the present invention is disclosed in JP-A-3-47825, JP-A-3-72527 and JP-A-3-43449. Japanese Laid-Open Patent Publication No. 3-7962
It is proposed in Japanese Patent Publication No.

The reactive silyl group contained in the polyether (a) means the same general formula (5) as the above general formula (1).
Shown in.

[0031]

[Omitted] ^{_{Z 3-P -SiR 6 P -}} ··· (5)

(In the formula, R ⁶ represents a monovalent hydrocarbon group or a halogenated hydrocarbon group. Z represents a hydroxyl group, a halogen group, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminoxy group or a ketoximate group. Hydrolyzable group, p is 0, 1 or 2.)

The polyether having such a reactive silyl group can be obtained, for example, by introducing a reactive silyl group into the polyether by the following method, but the method is not particularly 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 (6) has a hydroxyl group. React with the terminal hydroxyl groups of the polyoxyalkylene compound.

[0035]

## STR00008 ## ^{_{Z 3-P -SiR 6 P -R}} 7 -NCO ··· (6)

(In the formula, R ⁶ , Z and p are the same as above. R ⁷ is a divalent hydrocarbon group or a halogenated hydrocarbon group.) Specific organic silicon compounds may include the following compounds. .

[0037]

Embedded image (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 is reacted with the hydrosilicon compound represented by the general formula (7) in the presence of a Group VIII transition metal.

[0039]

[Chemical Formula 10] Z _3-P -SiR ⁶ _P H (7)

(In the formula, R ⁶ , Z and p 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. The molecular weight of the polyether (a) is preferably 100 to 50,000.

The content of the polymer of the polymerizable unsaturated group-containing monomer is not particularly limited, but in consideration of the viscosity and the physical properties of the curable composition, at least one reactive silyl group is included in the molecule. Polyether (a) 1 containing
It is preferably used in the range of 0.1 to 100 parts by weight with respect to 00 parts by weight. Further, the content of the polyether (b) having a polymerizable unsaturated group varies depending on the concentration of the polymerizable unsaturated group in the polyether (b) and the molecular weight of the polyether (b), but generally the polymerization is performed. The amount is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the monomer containing the unsaturated group.

The polymerization of the polymerizable unsaturated group-containing monomer is specifically carried out by adding a radical-generating polymerization initiator or a polymerizable unsaturated group to the polyether (a) having at least one reactive silyl group in the molecule. A method of adding a monomer and a polyether (b) having a polymerizable unsaturated group and heating with stirring can be applied.

The addition method is not particularly limited,
Polyether (a) having at least one reactive silyl group in the molecule, polymerization initiator, polymerizable unsaturated group-containing monomer, method of collectively mixing polyether (b) having polymerizable unsaturated group, and polymerizable Method of dropping a polymerizable unsaturated group-containing monomer in which a polymerization initiator is dissolved in a polyether (a) having at least one reactive silyl group in a molecule in which a polyether (b) having an unsaturated group is previously dissolved Etc. can be used appropriately.

The polymerization initiator is not limited to the radical generator, and various compounds capable of polymerizing the polymerizable unsaturated group-containing monomer may be used. In some cases, the polymerization initiator may be used. Instead, it can be polymerized by radiation or heat.

Examples of the polymerization initiator include peroxide type, azo type, or redox type polymerization initiators and metal compound catalysts. Specific examples of polymerization initiators often used include azobisisobutyronitrile, benzoyl peroxide, t-alkylperoxy ester, acetyl peroxide, diisopropyl peroxy carbonate and the like.

A solvent may be added during the polymerization.
In this case, the solvent may not be completely distilled off after the polymerization, and may be left if necessary. The polymer of the polymerizable unsaturated group-containing monomer may be uniformly dispersed in the polyether (a) having at least one reactive silyl group in the molecule so as to reduce the viscosity of the curable composition and the cured physical properties. It is preferable from the viewpoint, but when a part or all of the polymer of the polymerizable unsaturated group-containing monomer is uniformly dissolved in the system depending on the composition of the monomer and the addition amount of the polyether (b) having a polymerizable unsaturated group. Is also fully effective.

When curing the cured product of the present invention, a curing accelerating catalyst that accelerates the curing reaction of the reactive silyl group may be used. As a curing acceleration catalyst, an alkyl titanate,
Metal salts of carboxylic acids such as organosilicon titanate, bismuth tris-2-ethylhexoate, tin octylate, dibutyltin dilaurate; amine salts such as dibutylamine-2-ethylhexoate; and other acidic catalysts , A basic catalyst and the like can be used.

If necessary, the composition of the present invention further comprises:
Reinforcing agents, fillers, plasticizers, anti-sagging agents and the like may be included. Reinforcing agents include carbon black and fine powder silica, fillers include calcium carbonate, talc, clay, silica, etc., plasticizers such as dioctyl phthalate, dibutyl phthalate, dioctyl adipate, chlorinated paraffin and petroleum plasticizers. However, the pigment is an inorganic pigment such as iron oxide, chromium oxide, titanium oxide and an organic pigment such as phthalocyanine blue, phthalocyanine green, organic acid-treated calcium carbonate as a sagging inhibitor, hydrogenated castor oil, calcium stearate, zinc stearate, Examples include fine powder silica.

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

[0050]

【Example】

[Production Example 1] Using dipropylene glycol as an initiator, propylene oxide was polymerized under a zinc hexacyanocobaltate catalyst to obtain polypropylene diol.
Allyl chloride was added to this to convert the terminal hydroxyl group into an allyl group to obtain a terminal allyl group-containing polyether compound A having an average molecular weight of 17,000.

[Production Example 2] Using dipropylene glycol as an initiator, propylene oxide was polymerized under a zinc hexacyanocobaltate catalyst to obtain polypropylene diol. Allyl chloride was added to this to convert the terminal hydroxyl group into an allyl group. Then, the obtained terminal allyl group-containing polyoxyalkylene compound is reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert 50% of allyl groups into methyldimethoxysilyl groups, and to give an average molecular weight of 1
7,000 polyether compounds B were obtained.

[Production Example 3] Using dipropylene glycol as an initiator, propylene oxide was polymerized under a zinc hexacyanocobaltate catalyst to obtain polypropylene diol. Allyl chloride was added to this to convert the terminal hydroxyl group into an allyl group. Then, the obtained terminal allyl group-containing polyoxyalkylene compound is reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert 100% of the allyl group into a methyldimethoxysilyl group to obtain a polyether compound C having an average molecular weight of 17,000. It was

[Production Example 4] Using dipropylene glycol as an initiator, propylene oxide was polymerized under a zinc hexacyanocobaltate catalyst to obtain polypropylene diol. Isocyanatopropylmethyldimethoxysilane was added to this to convert 100% of the terminal hydroxyl groups into methyldimethoxysilyl groups, and the average molecular weight was 10,000.
Was obtained.

[Production Example 5] Using glycerin as an initiator, propylene oxide was polymerized under a KOH catalyst to obtain polypropylene triol. Allyl chloride was added to this to convert the terminal hydroxyl group into an allyl group. Then, the obtained terminal allyl group-containing polyoxyalkylene compound is reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert 100% of the allyl group into a methyldimethoxysilyl group to obtain a polyether compound E having an average molecular weight of 5000. It was

[Examples 1 to 5] The unsaturated silyl group-containing polyether compound 1 obtained in Production Examples 1 and 2 was added to 100 g of the reactive silyl group-containing polyether compound obtained in Production Examples 3, 4 and 5.
A mixture of 21 g of glycidyl methacrylate, 9 g of acrylonitrile, and 0.2 g of azobisisobutyronitrile was added dropwise over 2 hours while stirring in a nitrogen atmosphere while keeping 5 g in a four-neck flask. . Then, stirring was continued at the same temperature for 0.5 hours. After completion of the reaction, the unreacted monomer was heated under reduced pressure at 110 ° C. and 0.1 mmHg for 2 hours under reduced pressure to be distilled off to obtain a curable composition of interest. Table 1 shows the types of the unsaturated group-containing polyether compound and the reactive silyl group-containing polyether compound used, and the appearance of the resulting curable composition at 50 ° C. after 7 days.

[Comparative Examples 1 and 2] 4 g of 100 g of the reactive silyl group-containing polyether compound obtained in Production Examples 3, 4 and 5 was used.
A mixture of 21 g of glycidyl methacrylate, 9 g of acrylonitrile and 0.2 g of azobisisobutyronitrile was added dropwise to the flask in a two-necked flask over 2 hours while maintaining the temperature at 100 ° C. Then, stirring was continued at the same temperature for 0.5 hours. After the reaction was completed, the unreacted monomer was heated under reduced pressure at 110 ° C. and 0.1 mmHg for 2 hours under reduced pressure to be distilled off to obtain a target curable composition. Data of this curable composition are shown in Table 1 as 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, and 2
Create a sheet with a thickness of mm for 7 days at 20 ° C and then for 7 days at 50 ° C.
The physical properties were measured after curing by sun curing. The results are shown in Table 2. In addition, dibutyltin dilaurate was added as a curing catalyst to the curable compositions obtained in Examples 1 to 5, and the tensile shear strength for aluminum (JIS H4000 A1050P) was measured. The results are also shown in Table 2.

[0059]

[Table 2]

[0060]

INDUSTRIAL APPLICABILITY The present invention adopts the above constitution, and in the polyether (a) having at least one reactive silyl group in the molecule, the presence of the polyether (b) having a polymerizable unsaturated group. Below, from a polymer of a polymerizable unsaturated group-containing monomer having excellent storage stability by polymerizing a polymerizable unsaturated group-containing monomer, and a polyether compound having at least one reactive silyl group in the molecule. It has become possible to provide a curable composition comprising

Claims (5)

[Claims] 1. A silyl group-containing polyether (a) containing at least one reactive silyl group in the molecule thereof, wherein a polymerizable unsaturated group is present in the presence of the polyether (b) having a polymerizable unsaturated group. A method for producing a curable composition, which comprises polymerizing a contained monomer. 2. The method for producing a curable composition according to claim 1, wherein the polyether (b) having a polymerizable unsaturated group is a polyether having at least one reactive silyl group in the molecule. 3. The method for producing a curable composition according to claim 1, wherein the polyether (b) having a polymerizable unsaturated group is a polyether having an allyl group at the molecular end. 4. The polymerizable unsaturated group-containing monomer is one kind or two or more kinds selected from the group consisting of acrylonitrile, styrene, glycidyl acrylate and glycidyl methacrylate, or a mixture with another polymerizable unsaturated group-containing monomer. The method for producing a curable composition according to claim 1, wherein 5. The polyether (a) containing at least one reactive silyl group in the molecule has a molecular weight of 100-5.
The method for producing a curable composition according to claim 1, which is 0000.