JPH04252228A - Silicone-containing epoxy compound and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title compound useful as a raw material for curable compositions excellent in coating film performance by reaction between a specific ladder-type hydrosilicone compound and allyl glycidyl ether in the presence of a platinum-based catalyst. CONSTITUTION:The objective compound of formula II (R<2> are such that at least one of them in one molecule is of formula III, the other(s) being H) suitable as a raw material for coatings, sealants, adhesives, etc., excellent in weatherability and heat resistance can be obtained by reaction between (A) a ladder-type hydrosilicone compound of formula I (R<1> is lower alkyl; m and n are each 0-100) and (B) allyl glycidyl ether through heating, while agitating, at 50-150 deg.C in the presence of a platinum-based catalyst such as chloroplatinic acid.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone-containing epoxy compound useful as a raw material for paints, coating agents, sealants, adhesives, etc., which have excellent weather resistance and heat resistance, and a method for producing the same.

0002

[Prior Art] Vinyl polymers having an alkoxysilyl group at the end of the molecule or in the side chain are known (Japanese Patent Laid-Open No.
4-36395, JP 54-40893, JP 54-123192). By introducing an alkoxysilyl group to the end or side chain of a vinyl polymer, it not only has the excellent characteristics of vinyl polymers such as high gloss, weather resistance, and discoloration resistance, but also the alkoxysilyl group. It improves adhesion to inorganic materials, and forms a dense network structure through room-temperature crosslinking with moisture, especially atmospheric moisture, resulting in a polymer with excellent solvent resistance, water resistance, heat resistance, high hardness, and weather resistance. It has been known.

0003

[Problem to be solved by the invention] However, recently,
In the construction field, there is a demand for paint raw materials with even better weather resistance for outdoor exterior use.

0004

[Means for solving the problem] The present inventors have developed the following formula 3:
A silicone-containing epoxy compound obtained by reacting a ladder-type hydrosilicone compound represented by the formula with allyl glycidyl ether in the presence of a Group VIII platinum catalyst can be used as a raw material for a curable composition with excellent coating performance. They discovered what they could do and completed the present invention.

[0005]

[Chemical 3]

That is, the present invention provides a silicone-containing epoxy compound represented by the following chemical formula 4, a ladder-type hydrosilicone compound represented by the following chemical formula 5, and allyl glycidyl ether in the presence of a platinum catalyst at 50 to 150°C. This is a method for producing a silicone-containing epoxy compound, which is characterized by a reaction.

[0007]

[C4]

[0008]

[C5]

The silicone-containing epoxy compound shown in formula 4 of the present invention is a new substance. The curable composition in which the silicone-containing epoxy compound shown in formula 4 above, the vinyl polymer having a crosslinking group, the curing accelerating catalyst, etc., of the present invention are oriented, has a cured coating film that has a wide range of weather resistance and heat resistance. improve. The hydrosilicone compound used in the production of the silicone-containing epoxy compound of the present invention is obtained by hydrolyzing trichlorosilane in a solvent such as dioxane by adding water, and then alkoxylating it by adding a lower alcohol such as methanol or ethanol. can get.

The ladder-type hydrosilicone compound used in the present invention is specifically shown in the following formula 6.

[0011]

[C6]

The silicone-containing epoxy compound of the present invention is obtained by adding allyl glycidyl ether to the Si--H group of a ladder-type hydrosilicone compound, but this reaction requires a Group VIII platinum catalyst. Group VIII platinum-based catalysts include simple platinum, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinum-olefin complexes, solid platinum supported on supports such as alumina and silica, rhodium-olefin complexes, etc. Group VIII metal compounds selected from , palladium and nickel are advantageously used. The amount used is usually 1 to 1,000 ppm based on the reactants.

[0013] This hydrosilylation reaction
At a temperature of 0.degree. C., reaction times are achieved in 1 to 5 hours. If the reaction temperature is 50°C or less, the reaction rate becomes slow and it is not practical. Furthermore, if the reaction temperature exceeds 150° C., it is not preferable because some high molecular weight substances will be produced or a gelation reaction will occur. In the present invention, the molar ratio when the ladder-type hydrosilicone compound and allyl glycidyl ether are reacted is as follows:
Although it varies depending on the target reaction product, usually Si-H
0.1 allyl glycidyl ether per mole of group
The range of 5.0 mol is preferred.

In the present invention, in the reaction between the ladder-type hydrosilicone compound and allyl glycidyl ether,
A solvent may also be used. The solvent used is preferably a solvent that dissolves both the ladder-type hydrosilicone compound and allyl glycidyl ether. Usually, organic solvents such as toluene and xylene are used. When using a solvent, 0.1 to 1 part by weight of raw materials used in the reaction.
Preferably, 0 parts by weight is used.

When the silicone-containing epoxy compound of the present invention is exposed to the atmosphere, the alkoxysilyl groups react with moisture in the atmosphere to form a network structure and harden at room temperature. The silicone-containing epoxy compound of the present invention can also be mixed with other compounds having crosslinking groups and cured. Examples of the compound having a crosslinking group include a vinyl polymer having an alkoxysilyl group in a submolecule or in a side chain. In curing the silicone-containing epoxy compound of the present invention, a curing accelerator can also be used. The curing accelerator used is alkyl titanate,
Metal salts of carboxylic acids such as tin octylate and dibutyltin dilaurate, amine salts such as dibutylamine-2-hexoate, and other acidic and basic accelerators are useful. The amount of these curing accelerators added is preferably 0.01 to 10% by weight based on the compound.

The silicone-containing epoxy compound of the present invention can also be cured by mixing it with an epoxy curing agent. An amine compound is usually used as the epoxy curing agent. The silicone-containing epoxy compound of the present invention is useful as a raw material compound for paints, sealants, coating agents, and the like.

[0017] The silicone-containing epoxy compound of the present invention can be blended with various fillers, pigments, etc. depending on the intended use. Fillers and pigments include various silicas, calcium carbonate, magnesium carbonate, titanium oxide,
Various materials such as iron oxide and glass fiber can be used.

[0018]

[Examples] The present invention will be explained below with reference to Examples.

[0019]

[Example 1] In a 300 ml three-necked flask equipped with a thermometer, a stirring rotor, and a cooling tube, 41.6 g (365 mmol) of allyl glycidyl ether and 0.0 g of a 5% isopropanol solution of chloroplatinic acid hexahydrate were placed. 48g, toluene 42
g was added thereto, and the temperature was raised to 85°C while stirring. Next, 20 g of a hydrosilicone compound having the structural formula shown in Chemical formula 7 below.
(Si-H group 243 mmol) was dropped into the flask over 20 minutes. After the dropwise addition was completed, the reaction was continued at 85° C. for an additional 2 hours. The solvent and unreacted allyl glycidyl ether in the reaction solution were removed by vacuum evaporation. 43.0g of liquid material was obtained. As a result of measuring unreacted Si-H groups in the product by an alkaline decomposition method, the reaction rate of Si-H groups was 73.1%. As a result of analysis by infrared absorption spectrum and 1H-NMR, it was confirmed that the product was a compound in which 73.1 mol% of the Si-H groups of the hydrosilicone compound were converted to the following formula 8.

[0020]

[C7]

[0021]

[Chemical formula 8]

[0022]

[Example 2] Using the same apparatus as in Example 1, 30.8 g (270 mmol) of allyl glycidyl ether, 0.3 g of a 5% isopropanol solution of chloroplatinic acid hexahydrate, and 50 g of toluene were added, and while stirring, The temperature was raised to 85°C. Next, 20 g (270 mmol of Si-H) of a hydrosilicone compound having the structural formula shown in Chemical Formula 9 below was dropped into the flask over 20 minutes. After the dropwise addition was completed, the reaction was carried out at 85° C. for 2 hours. As a result of removing the solvent and unreacted allyl glycidyl ether in the reaction solution by vacuum evaporation, 34.2 g of a liquid product was obtained. As a result of structural analysis in the same manner as in Example 1, the product was found to be Si-
It was confirmed that 58% of the H groups were converted into the compound shown in Example 1.

[0023]

[Chemical formula 9]

[0024]

[Example 3] Into the same apparatus as in Example 1, 74.8 g (656 mmol) of allyl glycidyl ether, 0.6 g of a 5% isopropanol solution of chloroplatinic acid hexahydrate, and 95 g of toluene were placed, and the temperature was lowered while stirring. The temperature was raised to 80°C. 20 g (328 mmol of Si--H groups) of a hydrosilicone compound having the structural formula shown in Chemical Formula 10 below was dropped into the flask over 20 minutes. After the dropwise addition was completed, the reaction was carried out at 80° C. for 2 hours. As a result of removing the solvent and unreacted allyl glycidyl ether in the reaction solution by vacuum evaporation, 54.4 g of a liquid product was obtained. As a result of structural analysis similar to Example 1,
The product is Si-H9 of the raw material hydrosilicone compound.
It was confirmed that 5% was the compound converted to Formula 8 shown in Example 1.

[0025]

[Chemical formula 10]

[0026]

[Application example] Silicone-containing epoxy compounds obtained in Examples 1 to 3 and terpolymer of methyl methacrylate/n-butyl acrylate/3-methacryloxypropyltrimethoxysilane (molar ratio 2/1/0.28 ) were mixed in the formulations shown in Table 1, and 2% dibutyltin dilaurate (based on the solid content) was added and mixed, and the mixture was coated on a tin plate to a film thickness of 30 μm. When left at room temperature, each became tack-free in about 30 minutes and was completely cured after 7 days. All had excellent surface gloss.

[0027] Using a sunshine weather meter 2
,000 hours later, the weather resistance (gloss retention rate) was measured. The results are shown in Table 2. From these results, it was confirmed that all the materials had excellent weather resistance.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Effects of the Invention] The silicone-containing epoxy compound of the present invention is useful as a raw material for paints, sealants, etc., which have excellent weather resistance and heat resistance.

[Brief explanation of the drawing]

FIG. 1 shows 1H- of the product obtained in Example 1.
This is an NMR spectrum.

FIG. 2 is an infrared absorption spectrum of the product obtained in Example 1.

Claims (2)

[Claims] 1. A silicone-containing epoxy compound represented by the following formula 1. [Chemical formula 1] 2. A method for producing a silicone-containing epoxy compound, which comprises reacting a ladder-type hydrosilicone compound represented by the following formula 2 with acrylic glycidyl ether at 50 to 150°C in the presence of a platinum catalyst. [Case 2]