JPH0733786A - Reactive compound and its production - Google Patents

Abstract

PURPOSE:To obtaina reactive compound the subject compound containing a hydrolyzable group at the end, useful as a coating material, etc., providing a cross-linked polymer by condensation through hydrolysis by reacting a specific mercaptosilane with a prescribed epoxy compound. CONSTITUTION:The objective compound of formula I [A is group of formula II or formula III (R<1> is a 1-6C monofunctional hydrocarbon; R<2> is a 2-8C bifunctional hydrocarbon; R<3> is H or methyl; X is hydrolyzable group; (a) is 0, 1 or 2); R<4> is a monofunctional to tetrafunctional hydrocarbon which may contain ester bond or OH; (b) is 1-41 is obtained by reacting a mercaptosilane of formula IV with an epoxy compound of formula V (B is group of formula VI or formula VII).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel compounds which have not been published in the literature,
In particular, the present invention relates to a compound having a hydrolyzable group at the terminal, which is useful as a coating material, an adhesive, a sealing material or the like, which is hydrolyzed and condensed to form a crosslinked polymer, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, when curing an epoxy compound, a two-pack type using a room temperature curing type curing agent and a one-pack type using a latent curing agent are generally known. There is. Since the two-component type can use a room temperature curing type curing agent, it can be cured at room temperature. However, in order to cure the one-pack type, it is necessary to heat the latent curing agent, and it is not possible to perform room temperature curing.

Attempts have also been made to obtain a one-part room temperature curing type epoxy composition. For example, an epoxy compound added with ketimine as a curing agent, an epoxy compound added with a phosphorous ester as a curing agent,
A freezing method (a two-liquid type is mixed and frozen at about −70 ° C. and then returned to room temperature at the time of use) is known.

However, in the above-mentioned attempt, the storage stability at room temperature is poor and does not result in one liquid, is not applicable to concrete, slate, wood, etc. However, they have not been put to practical use because they have major drawbacks, such as merely theoretically describing the case of
At present, there is a long-awaited need for liquid room temperature curing type epoxy compounds.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is a novel compound which has not been described in the literature, and is particularly hydrolyzed and condensed to form a crosslinked polymer, which is used as a coating material, an adhesive or a sealing material. It is an object of the present invention to provide a compound having a hydrolyzable group at its end, which is useful as a material and the like, and a method for producing the same.

[0006]

The novel compound of the present invention for solving the above-mentioned problems has the general formula (1):

[0007]

[Chemical 11]

Where A is

[0009]

[Chemical 12]

And / or

[0011]

[Chemical 13]

(In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ² is a divalent hydrocarbon group having 2 to 8 carbon atoms, R ³ is hydrogen or a methyl group, and R ⁴ is an ester bond. , A monovalent to tetravalent hydrocarbon group which may contain a hydroxyl group, X is a hydrolyzable group, a
Is 0, 1 or 2, and b is 1 to 4. ) Is a polythioether compound having a hydrolyzable group at the terminal.

In the above general formula (1), the monovalent hydrocarbon group having 1 to 6 carbon atoms represented by R ¹ is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a vinyl group or an allyl group. Examples thereof include alkenyl groups such as and aryl groups such as phenyl groups.

[0014] In the general formula (1), -C divalent hydrocarbon group having 2 to 8 carbon atoms represented by R ² ₂ H ₄ -,
_{-C 3 H 6 -, - C} 6 H 4 -, - CH 2 -CH 2 -C 6 H 4 -
Groups such as

Further, in the above general formula (1), an ester bond represented by R ^{4 or} a hydroxyl group may be contained in 1 to 4
As the valent hydrocarbon group, an aryl group such as phenyl,

[0016]

[Chemical 14]

(In the formula, n is 0 to 16),

[0018] _{-C 4 H 8 -, - C} 6 H 12 -,

[0019]

[Chemical 15]

(In the formula, n is 0 to 16),

[0021] _{-C 6 H 8 -, - C} 8 H 12 -,

[0022]

[Chemical 16]

(In the formula, n is 0 to 16),

And the like.

Further, in the above general formula (1), examples of the hydrolyzable group represented by X include a methoxy group, an ethoxy group, an alkoxy group such as a propoxy group, and the like, and a methylethylketoxime group and the like. May be.

The polythioether compound having a hydrolyzable group at the terminal represented by the general formula (1) is represented by the general formula (2)

[0027]

[Chemical 17]

(Wherein R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ² is a divalent hydrocarbon group having 2 to 8 carbon atoms, X is a hydrolyzable group, a is 0, 1 or 2) and a general formula (3)

[0029]

[Chemical 18]

Where B is

[0031]

[Chemical 19]

And / or

[0033]

[Chemical 20]

(Wherein R ³ is hydrogen or a methyl group, R ⁴ is a monovalent to tetravalent hydrocarbon group which may contain an ester bond or a hydroxyl group, and b is 1 to 4) Obtained by reaction with.

The mercaptosilane used in the above reaction is γ-mercaptopropyltrimethoxysilane, γ
Examples thereof include mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyldimethylmethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-mercaptopropyldimethylethoxysilane.

Examples of the epoxy compound include glycidyl benzoate obtained by the reaction of benzoic acid and epichlorohydrin, diglycidyl phthalate obtained by the reaction of phthalic acid and epichlorohydrin, and triglyceride obtained by the reaction of trimellitic acid and epichlorohydrin. Mellitic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester obtained by reaction of pyromellitic acid and epichlorohydrin, caprylic acid glycidyl ester obtained by reaction of caprylic acid and epichlorohydrin, adipine obtained by reaction of adipic acid and epichlorohydrin Acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester obtained by reaction of hexahydrophthalic acid with epichlorohydrin, linoleic acid and ether Linoleic acid glycidyl ester obtained by reaction with chlorohydrin, tetrahydrophthalic acid diglycidyl ester obtained by reaction of tetrahydrophthalic acid and epichlorohydrin, dimer acid diglycidyl ester obtained by reaction of dimer acid and epichlorohydrin, and hydroxybenzoic acid Examples thereof include hydroxybenzoic acid glycidyl ether / glycidyl ester obtained by reaction with epichlorohydrin.

The reaction between the mercaptosilane and the epoxy compound is carried out by mixing at a compounding ratio such that the stoichiometric molar ratio of mercapto group / epoxy group is 0.8 or more and -10 to -1.
The reaction may be performed within the temperature range of 50 ° C. Excessive mercaptosilane and epoxy compound are distilled off by heating and depressurizing after the reaction is completed. Although this reaction can be carried out without a catalyst, it is preferable to use a catalyst because it requires a high temperature and a long time. As the catalyst, the catalyst used in the reaction between the epoxy compound and the polycarboxylic acid anhydride can be used. These catalysts are from the Handbook of Epox
y Resins (McGraw-Hill Book Company 1967)
ACID-ANHYDRIDE CURING AGENTS FOR EPOXY RESINS
(Chapter 12, page 3, ANHYDRIDE ACCELERATORS), amines, ammonium compounds of amines, organic phosphorus compounds and the like are preferable. As the amines of the catalyst, tertiary amines are preferable, but primary amines and secondary amines
It may be an amine.

Specific examples of the amine-based catalyst include N,
N, N ', N'-tetramethylpropylenediamine,
N, N, N ', N'-tetramethylhexamethylenediamine, N, N-dimethylcyclohexylamine, N, N
-Diethylcyclohexylamine, N, N, N ',
N ", N" -pentamethyldiethylenetriamine,
N, N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, tetramethylguanidine,
Di- (dimethylaminomethyl) -phenol, tris-
(Dimethylaminomethyl) -phenol, triethylenediamine, piperidine, morpholine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dimethylaminoethyl alcohol, diethylaminoethyl alcohol, diethylamine, triethylamine, 1,8-diaza-bicyclo (5,4,0) -undecene-7 and the like.

As ammonium compounds of amines,
Examples thereof include salts of tetraethylammonium halide, benzalkonium halide, 8-diaza-bicyclo (5,4,0) -undecene-7 with phenol, organic acid and mineral acid.

Even if the reaction is carried out in the absence of a solvent, methyl alcohol, ethyl alcohol, toluene, xylene,
It may be carried out in a solvent such as cyclohexane. Further, it is preferable that the water contained in the mercaptosilane, the epoxy compound, the catalyst, the solvent and the like be sufficiently removed in advance with a synthetic zeolite or the like.

The compound of the present invention obtained by the above-mentioned method has a terminal blocked with a hydrolyzable group, and since this compound becomes a crosslinked polymer by hydrolysis condensation, colloidal silica and carbonic acid are added thereto. Fillers such as calcium, carbon black, titanium oxide, colorants such as dyes, plasticizers such as dioctyl phthalate, adhesion promoters such as silane coupling agents, organic tin compounds, titanium compounds, curing catalysts such as amines, Organic acids, organic acid esters, organic zinc compounds, stabilizers such as acetylacetone, fluidity regulators (eg hydrogenated castor oil), leveling agents, methyl alcohol, ethyl alcohol, toluene, xylene, cyclohexane, methyl ethyl ketone, etc. A composition containing a solvent or the like exhibits room temperature curability.
This material is useful as a coating material, an adhesive, and a sealing material. The compound can also be used as a modifier for other resins or resin solutions.

[0042]

EXAMPLES Next, examples of the present invention will be given. Example 1 In a 500 ml flask equipped with a condenser and a thermometer, 182 g of γ-mercaptopropylmethyldimethoxysilane, 198 g of diglycidyl phthalate (trade name: Epomic R508, manufactured by Mitsui Petrochemical Epoxy Co., Ltd.), N, When 1 g of N, N ′, N′-tetramethylhexamethylenediamine was added, the temperature was raised with stirring, the reaction was carried out at 30 ° C. for 6 hours, and then mercaptosilane was detected by gas chromatography, it was not detected. It was judged that the reaction was completed, and 381 g of viscous polymer liquid A was obtained.

This liquid has a viscosity of 7500 cP at 20 ° C. and the chart by the infrared spectrophotometer is shown in FIG.

[0044]

[Chemical 21]

It was confirmed that it is represented by

Example 2 198 g of γ-mercaptopropyltrimethoxysilane and 198 g of diglycidyl phthalate (trade name: Epomic R508, manufactured by Mitsui Petrochemical Epoxy Co., Ltd.) were placed in a 500 ml flask equipped with a condenser and a thermometer. , N, N, N ′, N′-tetramethylhexamethylenediamine (1 g) was added, the temperature was raised with stirring, the reaction was carried out at 30 ° C. for 6 hours, and then mercaptosilane was detected by a gas chromatograph, which was detected. Since it was not present, it was judged that the reaction was completed, and 397 g of viscous polymer liquid B was obtained. Since this liquid has a viscosity of 4850 cP at 20 ° C. and the chart by the infrared spectrophotometer is shown in FIG.

[0047]

[Chemical formula 22]

It was confirmed that it was represented by

Example 3 182 g of γ-mercaptopropylmethyldimethoxysilane and tetrahydrophthalic acid diglycidyl ester (trade name: Epicoat 190P, made by Yuka Shell Epoxy Co., Ltd.) were placed in a 500 ml flask equipped with a condenser and a thermometer. 158 g, N, N, N ', N'-
1 g of tetramethylhexamethylenediamine was added, the temperature was raised with stirring, and the reaction was carried out at 30 ° C. for 6 hours. Then, when mercaptosilane was detected by a gas chromatograph, this was not detected, so it was judged that the reaction was completed. 341 g of a viscous polymer liquid C was obtained.

Since this liquid has a viscosity of 4850 cP at 20 ° C. and the chart by the infrared spectrophotometer is shown in FIG.

[0051]

[Chemical formula 23]

It was confirmed that the product was represented by

Example 4 In a 500 ml flask equipped with a condenser and a thermometer, 198 g of γ-mercaptopropyltrimethoxysilane and tetrahydrophthalic acid diglycidyl ester (trade name: Epicoat 190P, manufactured by Yuka Shell Epoxy Co., Ltd.) were added. 158g, 1g of N, N, N ', N'-tetramethylhexamethylenediamine was added, heated with stirring, reacted at 30 ° C for 6 hours, and then detected by mercaptosilane by gas chromatography. Since it was not done, it was judged that the reaction was completed,
357 g of a viscous polymer liquid D was obtained.

Since this liquid has a viscosity of 2650 cP at 20 ° C. and the chart by the infrared spectrophotometer is shown in FIG.

[0055]

[Chemical formula 24]

It was confirmed that the product was represented by

Example 5 In a 500 ml flask equipped with a condenser and a thermometer, 91 g of γ-mercaptopropylmethyldimethoxysilane and 209 g of dimer acid diglycidyl ester (trade name: Epicoat 871, manufactured by Yuka Shell Epoxy Co., Ltd.) , 1-benzyl-2-methyl-3-dodecylimidazolium chloride was added, the temperature was raised with stirring, the reaction was carried out at 80 ° C. for 6 hours, and then mercaptosilane was detected by a gas chromatograph.
Since this was not detected, it was judged that the reaction had ended, and 300.8 g of viscous polymer liquid E was obtained.

Since this liquid has a viscosity of 3400 cP at 20 ° C. and the chart by the infrared spectrophotometer is shown in FIG.

[0059]

[Chemical 25]

It was confirmed that the product was represented by

Example 6 In a 500 ml flask equipped with a condenser and a thermometer, 99 g of γ-mercaptopropyltrimethoxysilane and 209 g of diglyceride dimer acid (trade name: Epicoat 871, manufactured by Yuka Shell Epoxy Co., Ltd.) , 1-benzyl-2-methyl-3-dodecylimidazolium chloride was added, the temperature was raised with stirring, the reaction was carried out at 80 ° C. for 6 hours, and then mercaptosilane was detected by a gas chromatograph.
Since this was not detected, it was judged that the reaction had ended, and 308.8 g of a viscous polymer liquid F was obtained.

This liquid has a viscosity of 4400 cP at 20 ° C., and the chart by the infrared spectrophotometer is shown in FIG.

[0063]

[Chemical formula 26]

It was confirmed that the product was represented by

Experimental Example 1 The polymer liquids A to F obtained in the above Examples 1 to 6 were cured under the following conditions, and the physical properties of the cured products were evaluated. The results are shown in Table 1.

(Curing conditions) 100 of polymer liquids A to F
Add 2 parts dibutyltin dilaurate to parts by weight,
After leaving for 24 hours at a temperature of 20 ° C and a humidity of 65%,
The presence or absence of tackiness of the cured product was sensory evaluated. As is clear from Table 1, it was confirmed that all of the polymer liquids A to F obtained in each of the above-mentioned examples lose their tackiness and cure when they are stored at room temperature for 1 day.

[0067]

[Table 1]

Experimental Example 2 100 parts by weight of the polymer liquids A to F obtained in Examples 1 to 6, 2 parts of dibutyltin dilaurate and 2 parts of aminosilane (trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.). The composition was evaluated for coating adhesion. The results are shown in Table 2.

(Adhesiveness of coating film) According to JIS K5400 (General test method for coating materials), an adhesiveness test piece of a coating film on a steel plate was prepared using the above composition. The steel plate is 28
A No. 0 sandpaper storm was performed, and a No. 12 bar coater was used to apply the composition. The test piece was allowed to stand for 1 week under conditions of a temperature of 20 ° C. and a humidity of 65% to be cured and cured, and an adhesion test of the coating film was conducted by a cross-cut tape method. As is clear from Table 2, it was confirmed that each of the polymer liquids A to F obtained in each of the above examples had excellent adhesiveness as a coating material.

[0070]

[Table 2]

Experimental Example 3 The same composition as in Experimental Example 1 was used to evaluate the adhesiveness. The results are shown in Table 3.

(Adhesion Test) According to JIS K6850 (Testing method for tensile shearing adhesive strength of adhesive), an adhesive test piece using a steel plate and a Chinese material was prepared using the above composition. This test piece was allowed to stand for 1 week under conditions of a temperature of 20 ° C. and a humidity of 65% to cure and cure, and an adhesion test was conducted.

The steel plate was subjected to No. 180 sandblasting. As is clear from Table 3, it was confirmed that each of the polymer liquids A to F obtained in each of the above Examples had excellent adhesiveness as an adhesive.

[0074]

[Table 3]

[0075]

As described above, according to the present invention, a moisture-curable compound having excellent room temperature curability, adhesiveness and adhesiveness, and a method for synthesizing the same can be obtained. The compound of the present invention is characterized in that its cured product has no tackiness, and is useful as a coating material, an adhesive, a sealing material and the like. Also,
The compound of the present invention has an advantage that it can be easily synthesized on an industrial scale by the synthetic method of the present invention.

[Brief description of drawings]

FIG. 1 is a chart of an infrared spectrophotometer of a liquid obtained in Example 1.

FIG. 2 is a chart of an infrared spectrophotometer for a liquid obtained in Example 2.

FIG. 3 is a chart of an infrared spectrophotometer for a liquid obtained in Example 3.

FIG. 4 is a chart of an infrared spectrophotometer for the liquid obtained in Example 4.

5 is a chart of an infrared spectrophotometer for the liquid obtained in Example 5. FIG.

6 is a chart of an infrared spectrophotometer for the liquid obtained in Example 6. FIG.

Claims (2)

[Claims] 1. A compound represented by the general formula (1): In the formula, A is And / or (In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ² is a divalent hydrocarbon group having 2 to 8 carbon atoms, R ³ is hydrogen or a methyl group, R ⁴ is an ester bond or a hydroxyl group. May include 1
Tetravalent hydrocarbon group, X is a hydrolyzable group, a is 0, 1 or 2, and b is 1 to 4. ) A polythioether compound having a hydrolyzable group at the terminal. 2. A general formula (2): (In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ² is a divalent hydrocarbon group having 2 to 8 carbon atoms, X is a hydrolyzable group, and a is 0, 1 or 2. ) And a mercaptosilane represented by the general formula (3): In the formula, B is And / or (In the formula, R ³ is hydrogen or a methyl group, R ⁴ is an ester bond, a monovalent to tetravalent hydrocarbon group which may contain a hydroxyl group, b
Is 1 to 4. ), Which is obtained by reaction with an epoxy compound represented by the general formula (1) In the formula, A is And / or (In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ² is a divalent hydrocarbon group having 2 to 8 carbon atoms, R ³ is hydrogen or a methyl group, R ⁴ is an ester bond or a hydroxyl group. May include 1
Tetravalent hydrocarbon group, X is a hydrolyzable group, a is 0, 1 or 2, and b is 1 to 4. ] The manufacturing method of the polythioether compound which has a hydrolyzable group at the terminal shown by.