Organosilicon compound

Abstract

To provide a new organosilicon compound useful as an alkoxysilylating agent for an organopolysiloxane.SOLUTION: An organosilicon compound represented by the following general formula (1): (In the formula, R1 and R3 are substituted or unsubstituted monovalent hydrocarbons having 1 to 20 carbon atoms, and R1 and R3 may be the same or different.). R2 is a substituted or unsubstituted C1-C20 divalent group which may contain at least one atom selected from N, O and Si. X is a hydrolyzable group. N is a number of 1 to 3, and m is a number of 2 or more. ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel organosilicon compound, and in particular to a novel organosilicon compound useful as an alkoxysilylating agent, a curing agent, a scavenger, or other storage stability imparting agent. [Background technology]

[0002] Various types of room-temperature-curable silicone compositions are known, which cure at room temperature upon contact with moisture in the air. Among these, compositions that release alcohol upon curing have no unpleasant odor and are less likely to cause chemical cracking in the resin, making them suitable for use in sealing, bonding, and coating electrical and electronic devices.

[0003] Examples of alkoxysilylating agents that introduce alkoxy groups into organopolysiloxanes include various alkoxysilanes, such as methoxysilanes, ethoxysilanes, and nitrogen-containing silylating agents such as those described in JP-A-5-345888 (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 5-345888 Summary of the Invention [Problem to be solved by the invention]

[0005] However, these alkoxysilylating agents have low reactivity, and therefore, there is a demand for more reactive alkoxysilylating agents. Therefore, an object of the present invention is to provide a novel organosilicon compound that is useful as an alkoxysilylating agent for organopolysiloxanes. [Means for solving the problem]

[0006] As a result of investigations conducted by the present inventors to achieve the above object, they discovered that an organosilicon compound represented by the following formula (1) is highly reactive and useful as an alkoxysilylating agent, which led to the completion of the present invention. Accordingly, the present invention provides novel organosilicon compounds represented by the following formula: [1] An organosilicon compound represented by the following general formula (1): [ka] (In the formula, R 1 and R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 1 and R 3 may be the same or different. 2 is a substituted or unsubstituted divalent group having 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, and a silicon atom. X is a hydrolyzable group. n is a number from 1 to 3, and m is a number of 2 or more. [2] The organosilicon compound according to [1], wherein the hydrolyzable group represented by X in the general formula (1) is an alkoxy group. [3] The organosilicon compound according to [1] or [2], wherein m in the general formula (1) is a number from 2 to 10. [Effects of the Invention]

[0007] The novel organosilicon compounds of the present invention react efficiently with alcohols or silanols and are useful as storage stability imparting agents such as alkoxysilylating agents, curing agents, and scavengers for organopolysiloxanes such as dihydroxydimethylpolysiloxanes, and can be used in dealcohol-curable room-temperature curable silicone rubber compositions.

[0008] Furthermore, because the novel organosilicon compounds of the present invention are cyclic, they are more reactive than conventional alkoxysilylating agents, and are expected to shorten the production time of the composition. [Brief explanation of the drawings]

[0009] [Figure 1] 1 shows the 1H-NMR chart of the organosilicon compound obtained in Example 1. [Figure 2] 1H-NMR chart of the organosilicon compound obtained in Example 3 is shown. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below.

[0011] In the general formula (1), R 1 and R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 1 and R 3 may be the same or different. R 1 and R 3 Specific examples of R include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, tolyl, xylyl, naphthyl, and biphenylyl; aralkyl groups such as benzyl, phenylethyl, phenylpropyl, and methylbenzyl; and groups in which some or all of the hydrogen atoms bonded to carbon atoms of these groups have been substituted with halogen atoms such as fluorine, chlorine, and bromine, or with cyano groups, such as chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl, and 3,3,4,4,5,5,6,6,6-nonafluorohexyl. 1 and R 3are preferably an unsubstituted or substituted alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a chloromethyl group, a bromoethyl group, a 3,3,3-trifluoropropyl group, or a cyanoethyl group; and an unsubstituted or substituted phenyl group, such as a phenyl group, a chlorophenyl group, or a fluorophenyl group.

[0012] In the above general formula (1), R 2 R is a substituted or unsubstituted divalent group having 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, and a silicon atom. 2 is preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain at least one divalent group selected from a carbonyl group, an ether bond, an amino group, and a diorganosiloxy group, more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, even more preferably a substituted or unsubstituted divalent hydrocarbon group having 2 to 15 carbon atoms, and particularly preferably a substituted or unsubstituted divalent hydrocarbon group having 2 to 10 carbon atoms. Examples of divalent hydrocarbon groups having 1 to 20 carbon atoms include alkylene groups having 1 to 20 carbon atoms and alkenylene groups having 2 to 20 carbon atoms, with alkylene groups and alkenylene groups having 2 to 15 carbon atoms being preferred, alkylene groups and alkenylene groups having 2 to 10 carbon atoms being more preferred, and unbranched chain alkylene groups or alkenylene groups having 3 or more carbon atoms being preferred. Examples of such divalent hydrocarbon groups having 1 to 20 carbon atoms include methylene groups, ethylene groups, trimethylene groups, tetramethylene groups, -(CH2) y an alkylene group represented by the formula - (y is a number from 5 to 20, preferably a number from 5 to 10); a vinylene group, a propenylene group, a -(CH z and alkenylene groups represented by CH═CH— (z is a number from 2 to 18, preferably a number from 2 to 8). Some or all of the hydrogen atoms of these divalent hydrocarbon groups having 1 to 20 carbon atoms may be substituted with halogen atoms such as fluorine atoms and chlorine atoms. Also, R 2may be a group obtained by combining the divalent hydrocarbon group having 1 to 20 carbon atoms with at least one group selected from a carbonyl group, an ether bond, an amino group, and a diorganosiloxy group (i.e., a group in which at least one carbon atom of the divalent hydrocarbon group having 1 to 20 carbon atoms is substituted with at least one group selected from a carbonyl group, an ether bond, an amino group, and a diorganosiloxy group). The organic group bonded to the silicon atom of the diorganosiloxy group is the above-mentioned R 1 and R 3 Examples of the diorganosiloxy group include the same groups as the substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms exemplified above. Examples of the diorganosiloxy group include dialkylsiloxy groups such as dimethylsiloxy group and diethylsiloxy group; diarylsiloxy groups such as diphenylsiloxy group; and alkylarylsiloxy groups such as methylphenylsiloxy group.

[0013] In the above general formula (1), X is a hydrolyzable group, and specific examples thereof include alkoxy groups having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; ketoxime groups such as a methylethylketoxime group; alkenyloxy groups having 2 to 6 carbon atoms, such as an isopropenoxy group or a cyclopentanoxy group; acyloxy groups such as an acetoxy group; dialkylaminooxy groups such as a dimethylaminooxy group; and alkoxysiloxy groups such as a trimethoxysiloxy group, among which an alkoxy group is preferred.

[0014] In the above general formula (1), n ​​is a number of 1 to 3, with 2 or 3 being preferred. In the above general formula (1), m is a number of 2 or more, preferably a number of 2 to 10, and more preferably 3 or 4.

[0015] The organosilicon compound of the present invention represented by the above general formula (1) is, for example, [I] an addition reaction step by hydrosilylation between an organohydrogensilane having a silicon-bonded hydrogen atom represented by general formula (2) and a compound having an aliphatic unsaturated monovalent hydrocarbon group such as an alkenyl group or an alkynyl group on the silicon atom of a cyclic silazane represented by general formula (3); [II] An addition reaction step by hydrosilylation reaction between an organosilane having an aliphatic unsaturated monovalent hydrocarbon group such as an alkenyl group or an alkynyl group represented by general formula (4) and a compound having a hydrogen atom on the silicon atom of a cyclic silazane represented by general formula (5). It can be easily produced by a method including the steps of: Hereinafter, organohydrogensilanes having silicon-bonded hydrogen atoms of general formula (2) and organosilanes having an aliphatic unsaturated monovalent hydrocarbon group of general formula (4) may be referred to simply as "organosilanes." Furthermore, compounds having an aliphatic unsaturated monovalent hydrocarbon group on the silicon atom of a cyclic silazane of general formula (3) and compounds having a hydrogen atom on the silicon atom of a cyclic silazane of general formula (5) may be referred to simply as "cyclic silazanes."

[0016] [ka] [ka] (In the formula, R 1 and R 3 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R 1 and R 3 may be the same or different. 4 is a single bond or a substituted or unsubstituted divalent hydrocarbon group having 1 to 18 carbon atoms, which may contain at least one group selected from a carbonyl group, an ether bond, an amino group, and a diorganosiloxy group. X is a hydrolyzable group. n is a number from 1 to 3, and m is a number of 2 or more, preferably 3 or 4. In addition, the bond containing a dashed line in formulas (3) and (4) represents a carbon-carbon double bond or a carbon-carbon triple bond, and the bond containing a dashed line in formulas (11) and (12) represents a carbon-carbon single bond or a carbon-carbon double bond. R in formulas (2) to (5), (11) and (12) 1 , R 3Examples of R and X are the same as those exemplified in the above formula (1), and as in the above formula (1), n ​​and m in formulas (2) to (5), (11) and (12) are preferably 2 or 3, and m is preferably a number from 2 to 10, more preferably 3 or 4. R in formulas (3), (4), (11) and (12) 4 Among these, the divalent hydrocarbon group having 1 to 18 carbon atoms includes R 2 Among the groups exemplified as R, the same groups as the divalent hydrocarbon groups having 1 to 18 carbon atoms can be mentioned. 4 is preferably a single bond or an alkylene group having 1 to 8 carbon atoms.

[0017] The hydrosilylation reactions represented by [I] and [II] above are preferably carried out using a platinum group metal catalyst commonly used in hydrosilylation reactions. Examples of platinum group metal catalysts include platinum, palladium, rhodium, and ruthenium catalysts. Of these, platinum-based catalysts are preferred. The amount of platinum group metal catalyst used may be a catalytic amount, and is, for example, preferably 0.1 to 1,000 ppm, more preferably 0.5 to 100 ppm, calculated as the mass of platinum group metal relative to the mass of organopolysiloxane (cyclic silazane).

[0018] This reaction may be carried out in the presence of a solvent such as toluene or xylene, provided that it does not adversely affect the addition reaction. The hydrosilylation reactions represented by [I] and [II] above may be carried out according to a conventional method, and the reaction temperature is not particularly limited, but is preferably from room temperature (23° C.) to 200° C., more preferably from 40 to 110° C., and even more preferably from 40 to 90° C. The reaction time is also not particularly limited, but is preferably from 1 to 60 hours, more preferably from 1 to 30 hours, and even more preferably from 1 to 20 hours. From the viewpoint of efficiently obtaining a product, the quantitative ratio of the cyclic silazane to the organosilane is preferably such that 1.0 to 10.0 mol, and more preferably 1.0 to 3.0 mol, of aliphatic unsaturated monovalent hydrocarbon groups bonded to silicon atoms in the cyclic silazane or organosilane per 1 mol of hydrogen atoms (hydrosilyl groups) bonded to silicon atoms in the cyclic silazane or organosilane.

[0019] Examples of the compound represented by the formula (1) obtained in this manner include, but are not limited to, those represented by the following formulas: [ka]

[0020] The organosilicon compounds of the present invention react efficiently with alcohols or silanols, and are therefore useful as storage stability imparting agents such as alkoxysilylating agents, curing agents, and scavengers for organopolysiloxanes such as dihydroxydimethylpolysiloxane. Furthermore, when the organosilicon compounds of the present invention are used as additives in dealcohol-curable room-temperature curable silicone rubber compositions, the reactivity is higher than that of conventional alkoxysilylating agents, and the production time for the composition can be shortened. [Example]

[0021] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. [Example 1] A 300 mL recovery flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 50.0 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane and 0.47 g of a 0.5 mass% toluene solution of chloroplatinic acid (HPtCl6·6H2O), and the temperature was raised to 80°C. 84.3 g of trimethoxysilane was added dropwise, and the mixture was stirred for 6 hours. Subsequently, low-boiling components were distilled off, yielding 113.4 g of product. 1The 1 H-NMR spectrum was measured, and it was confirmed that the raw material peaks had disappeared and that the obtained compound was the desired organosilicon compound represented by the following formula (13). [ka]

[0022] This compound 1 The H-NMR spectrum data is shown in Figure 1. 1 In the H-NMR spectrum, the peaks derived from the hydrogen atoms labeled a to e in the structural formula of the compound shown in FIG. 1 are labeled a to e.

[0023] [Example 2] A 500 mL recovery flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 100 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane, 200 g of toluene, and 0.23 g of a 0.5% by mass toluene solution of chloroplatinic acid (HPtCl6·6H2O), and the temperature was raised to 80°C. 157 g of trimethoxysilane was added dropwise, and the mixture was stirred for 4 hours. Subsequently, low-boiling components were distilled off, yielding 236 g of product. 1 The 1 H-NMR spectrum was measured, and it was confirmed that the raw material peaks had disappeared and that the obtained compound was the desired organosilicon compound represented by the above formula (13). In Example 2, a solvent (toluene) was used in the reaction, but there was no significant difference in yield compared to Example 1, and the target organosilicon compound was obtained.

[0024] [Example 3] A 500 mL recovery flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 74.5 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane and 0.11 g of a 0.5 mass% toluene solution of chloroplatinic acid (HPtCl6·6H2O), and the temperature was raised to 80°C. 154.0 g of triethoxysilane was added dropwise, and the mixture was stirred for 5 hours. Subsequently, low-boiling components were distilled off, yielding 212.0 g of product. 1The 1 H-NMR spectrum was measured, and it was confirmed that the raw material peaks had disappeared and that the obtained compound was the desired organosilicon compound represented by the following formula (14). [ka]

[0025] The organosilicon compound represented by formula (14) 1 The H-NMR spectrum data is shown in Figure 2. 1 In the 1 H-NMR spectrum, the peaks derived from the hydrogen atoms labeled af in the structural formula of the compound shown in FIG. 2 are labeled af.

Claims

1. An organosilicon compound represented by the following general formula (1): 【Chemistry 1】 (In the formula, R 1 and R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 1 and R 3 may be the same or different. 2 is a substituted or unsubstituted divalent group having 1 to 20 carbon atoms which may contain at least one atom selected from a nitrogen atom, an oxygen atom, and a silicon atom; X is a hydrolyzable group; n is a number from 1 to 3, and m is a number of 2 or more.

2. 2. The organosilicon compound according to claim 1, wherein the hydrolyzable group represented by X in general formula (1) is an alkoxy group.

3. 2. The organosilicon compound according to claim 1, wherein m in general formula (1) is a number from 2 to 10.

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