JP3150576B2 - Organic silicon compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel organosilicon compound, and more particularly, to an organosilicon compound suitable for producing a silane-modified polymer.

[0002]

2. Description of the Related Art Conventionally, various cured films such as a protective film and a resist material are known. The curing of these cured films is performed by a crosslinking reaction. In this case, since the reaction of adding the alkenyl group directly bonded to the silicon atom and the hydrogen atom directly bonded to the silicon atom can proceed at room temperature, using the above addition reaction as a crosslinking reaction requires
This is particularly effective when heat curing is not desired. Thus, the present inventors have conducted intensive studies on introducing an alkenyl-containing silyl group as a crosslinkable group of a curable polymer, and found that a novel organic silicon suitable for introducing a silylphenyl group into a polymer terminal. The compounds have been found and have reached the present invention.

[0003]

Accordingly, the first aspect of the present invention is as follows.
It is an object of the present invention to provide a novel organosilicon compound suitable for introducing a silylphenyl group into a polymer terminal. A second object of the present invention is to provide a novel compound suitable for imparting room temperature curability to various polymers by introducing a silylphenyl group having an unsaturated group at the terminal of the polymer.

[0004]

The above objects of the present invention have been attained by an organosilicon compound represented by the following formula (3).

Embedded image Wherein R 1 in Chemical Formula 3 is a hydrogen atom or a group represented by Chemical Formula 4, and R ^{2 to} R ⁵ are a substituted or unsubstituted monovalent hydrocarbon group;

Embedded image However, R ^{6 to} R ⁸ in Chemical Formula 4 are substituted or unsubstituted monovalent hydrocarbon groups.

Specific examples of the novel organosilicon compound of the present invention include compounds represented by the following chemical formulas (5) and (6).

Embedded image

Embedded image Here, Me and Ph in the formula represent a methyl group and a phenyl group, respectively.

The novel organosilicon compound shown in Chemical Formula 5 is a specific example in which R ^{1 in} Chemical Formula 3 is a hydrogen atom, and the compound shown in Chemical Formula 6 is ^This is a specific example when ¹ is represented by Chemical Formula 4. Specific examples of the substituted or unsubstituted monovalent hydrocarbon group represented by R ^{2 to} R ⁸ include an alkyl group such as a methyl group, an ethyl group and a propyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group, and an allyl group. Examples include alkenyl groups such as groups, aryl groups such as phenyl groups and tolyl groups, and groups in which the hydrogen atoms of these groups are partially substituted with halogen atoms and the like. Requires that at least one of R ^{3 to} R ^{6 be} an alkenyl group.

The organosilicon compound of the present invention is prepared by reacting a silylated metahaloaniline derivative having the general formula represented by the following formula (7) or (8) with magnesium to prepare a Grignard reagent, and then triorganochlorosilane. And an organosilyl group can be introduced by reacting

[0008]

Embedded image From the compound represented by Chemical formula 7, a derivative in which R ¹ is a group represented by Chemical formula 4 is obtained.

By hydrolyzing a novel compound obtained from the compound represented by the above formula 7, a novel organosilicon compound of the present invention wherein R ¹ is a hydrogen atom can be synthesized. The solvent used in this reaction may be an ether-based solvent, but is preferably a cyclic ether such as THF. Further, the reaction temperature is preferably from 40 to 70 ° C.

[0010]

The novel organosilicon compound of the present invention is useful as a compound for introducing a reactive silyl group into a polymer terminal. Further, a polymer obtained by introducing a vinylsilyl group into a terminal by using the compound of the present invention can obtain a cured product by a hydrosilylation reaction of a siloxane having a hydrosilyl group with a platinum catalyst. The cured product takes a form of resin, elastomer, gel or the like depending on the molecular weight of the obtained polymer, and is useful as an adhesive, a gel, a sealing material, a coating material, a release agent, and the like.

[0011]

Next, embodiments of the present invention will be specifically described. A curable fluorine-containing amide compound can be obtained by using the compound of the present invention as represented by the following chemical formula (9).

Embedded image Table However, wherein R ^2, R ³ and R ⁴ are the same as R ^2, R ³ and R ⁴ in 3 of, a substituted or unsubstituted monovalent hydrocarbon group, Q is the following formula 10 Rf is a divalent perfluoroalkylene group or a divalent perfluoropolyether group, and b is an integer of 0 or more.

[0012]

Embedded image However, R ¹³ may have one or more oxygen atoms, nitrogen atoms and silicon atoms interposed therebetween during the bonding. A substituted or unsubstituted divalent hydrocarbon group, R ¹⁴ and R ¹⁵ may be substituted. Or an unsubstituted divalent hydrocarbon group.

The fluorine-containing amide compound obtained by the above chemical formula 9 can be an elastomer or a resin having a low surface energy by increasing the fluorine content, and is a rubber having heat resistance, solvent resistance and chemical resistance. Material for material,
Alternatively, it is effective as a material for a release agent. The cured product obtained by further adding the following components (a) and (b) to the above-mentioned fluorinated amide compound and curing is not only excellent in solvent resistance and chemical resistance, but also has low moisture permeability and low surface energy, so that it is released. Excellent in water resistance and water repellency.

(A) one molecule has one perfluorooxyalkyl group, monovalent perfluoroalkyl group, divalent perfluorooxyalkylene group or divalent perfluoroalkylene group, and two or more A fluorine-containing organohydrogensiloxane having a hydrosilyl group. (B) Catalytic amount of platinum group compound In this case, the amount of the component (a) is such that the hydrosilyl (Si-H) group is 0.5 to 5 mol per 1 mol of the aliphatic unsaturated group in the composition. It is preferred that the amount be

[0015]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Embodiment 1 FIG. 24.0 g of magnesium powder, 400 g of tetrahydrofuran and 0.06 g of iodine were charged into a 1-liter four-neck separable flask equipped with a stirrer, a thermometer, a Dim funnel, and a dropping funnel. 78.8 g was added dropwise to prepare a Grignard reagent. After aging at 60 ° C. for 2 hours, 30.1 g of vinyldimethylchlorosilane was added dropwise from a dropping funnel. After aging at 60 ° C. for 2 hours, the generated magnesium salt was filtered, and the filtrate was distilled under reduced pressure. The boiling point was 124 to 127 ° C./3 mmHg, and the refractive index was 1.4864 (25 ° C.). 63.1 g of the compound (yield: 78.6%) was obtained.

Embedded image

The structural formula of the above compound is the following ¹ H-NM
It was confirmed by R, IR and the elemental analysis shown in Table 1. ¹ H-NMR δ 0.12 (s, N-Si-CH ₃ , 18H) δ 0.42 (s, C-Si-CH ₃ , 6H) δ 5.4 to 6.4 (m, Si-CH = CH ₂₎ , 3H) δ 6.7 to 7.3 (m, arom., 4H)

IR (see FIG. 1) 1590 cm ^-1 arom. 1650cm ^-1 ν _{c = c}

[0019]

[Table 1]

[0020]

EXAMPLE 2 78.7 g of silylated metabromoaniline was replaced with 213.6 g of silylated metachloroaniline, and the amount of vinyldimethylchlorosilane used was 120.5 g.
The reaction was carried out in exactly the same manner as in Example 1, except that
Boiling point: 101 to 102 ° C./1 mmHg, refractive index: 1.5
116 (25 ° C.), a compound 19 represented by the following formula
1.3 g (yield: 72.7%) was obtained.

Embedded image

The structural formula of the above compound is the following ¹ H-NM
It was confirmed by R, IR and the elemental analysis shown in Table 2. ¹ H-NMR δ 0.20 (s, N-Si-CH ₃ , 9H) δ 0.31 (s, C-Si-CH ₃ , 6H) δ 2.81 (s, N-CH ₃ , 3H) δ 5.4 ６6.2 (m, Si—CH ＝ CH ₂ , 3H) δ 6.5 to 7.2 (m, arom., 4H)

IR (see FIG. 2) 1595 cm ^-1 arom. 1650cm ^-1 ν _{c = c}

[0023]

[Table 2]

Embodiment 3 FIG. Compound 10 obtained in Example 2
After 1.8 g was mixed with 100 g of water and hydrolyzed, the upper layer was separated and distilled under reduced pressure to give a boiling point of 99 to 10.
0 ° C / 1mmHg, refractive index 1.5425 (25 ° C)
And 65.1 g of the compound represented by the following formula (yield: 8)
8%).

Embedded image

The structural formula of the above compound is the following ¹ H-NM
It was confirmed by R, IR and the elemental analysis shown in Table 3. ¹ H-NMR δ 0.31 (s, Si—CH ₃ , 6H) δ 2.67 (s, N—CH ₃ , 3H) δ 3.33 (s, NH, 1H) δ 5.4 to 6.1 ( _{m, Si-CH = CH 2} , 3H) δ6.2~7.2 (m, arom., 4H)

IR (see FIG. 3) 1595 cm ^-1 arom. 1650cm ^-1 ν _{c = c} 3300-3500cm ^-1 ν _NH

[0027]

[Table 3]

[Brief description of the drawings]

FIG. 1 is an IR spectrum of the compound obtained in Example 1.

FIG. 2 is an IR spectrum of the compound obtained in Example 2.

FIG. 3 is an IR spectrum of the compound obtained in Example 3.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Yasushi Yamamoto 1-10 Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory Inside (56) References British Patent 1153132 (GB, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C07F 7/10 C08G 77/20 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. An organosilicon compound represented by the following chemical formula 1. Embedded image Wherein R 1 in Chemical Formula 1 is a hydrogen atom or a group represented by Chemical Formula ² , and R ^{2 to} R ⁵ are a substituted or unsubstituted monovalent hydrocarbon group; However, R ^{6 to} R ⁸ in Chemical Formula 2 are substituted or unsubstituted monovalent hydrocarbon groups. 2. At least one of R ^{3 to} R ^{5 in} Chemical formula 1.
The organosilicon compound according to claim 1, wherein the two groups are alkenyl groups.