JPH0459785A - Fluorine-containing organosilicon compounds - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel fluorine-containing organosilicon compound that has not been described in any literature.

(Prior art) Polysiloxane, which has fluorine atoms in its molecules, is useful as a material for rubber materials with excellent solvent and chemical resistance, and can also be used as a material for mold release, water and oil repellents, etc. Known to be useful.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a novel fluorine-containing organosilicon compound that is particularly useful as a raw material for producing the above-mentioned strong fluorine-containing polysiloxane.

(Means for achieving the object) The fluorine-containing organosilicon compound of the present invention has the following general formula (1
), in the formula, R is a -valent hydrocarbon group having 1 to 8 carbon atoms, and multiple R's may be the same or different from each other, and R is a perfluoroalkyl group having 1 to 10 carbon atoms. , expressed as . As understood from the general formula (I), the fluorine-containing organosilicon compound of the present invention is a novel compound that has not been described in any literature.

The above general formula (I
) The fluorine-containing organosilicon compound of the present invention represented by
The following general formula (II), H-3i-Cj! In the formula, R is, as described above, a hydrosilane represented by and the following general formula (III),
CHzCHJf C1h=CHSt C12(In) In the formula, Rf and R are as described above. It is produced by carrying out an addition reaction with a vinylsilane represented by the following in the presence of a catalyst.

In the general formulas (II) and (III), the groups Rf and R correspond to the groups Rf and R in the general formula (1), respectively.

That is, the group Rf is a perfluoroalkyl group having 1 to 10 carbon atoms, preferably a group such as CFs, C4F9°-, F1a + CaF22, and the like.

The group R is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and specifically includes a lower alkyl group having 8 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, etc. Cycloalkyl groups, vinyl groups, allyl groups, propenyl groups, alkenyl groups such as butenyl groups, aryl groups such as phenyl groups, tolyl groups, naphthyl groups, benzyl groups,
Examples include aralkyl groups such as 2-phenylethyl group. In the present invention, an alkyl group is preferred, and a methyl group is most preferred.

Note that the vinylsilane represented by the general formula (I[) can be synthesized, for example, by reacting a vinyl Grignard reagent such as vinylmagnesium bromide with a dichlorosilane having a perfluoroalkylethyl group.

Examples of catalysts used in the addition reaction between hydrosilane and vinylsilane include platinum group metal catalysts, such as chloroplatinic acid, alcohol-modified chloroplatinic acid (U.S. Pat. No. 3,220,972) ), complexes of chloroplatinic acid and olefins (U.S. Pat. Nos. 3.159.601 and 3.159.66)
No. 2, No. 3.775.452), platinum black or palladium supported on a carrier such as alumina, silica, carbon, rhodium-olefin complex, etc. can be suitably used. Among these catalysts, complex type catalysts in particular are preferably used after being dissolved in an alcohol-based, ketone-based, ether-based, or hydrocarbon-based solvent. In addition, the amount of these platinum group metal catalysts used is generally 0.1 to 5% relative to the total amount of hydrosilane and vinylsilane, calculated as platinum group metal.
00 ppm+*, particularly preferably in the range of 0.5 to 200 ppm.

The reaction between hydrosilane and vinylsilane can be carried out without a solvent, but if necessary, it can also be carried out using an inert solvent such as benzene, toluene, xylene, n-hexane, cyclohexane, etc. The temperature is preferably in the range of 60 to 150°C, particularly 80 to 120°C.

After the reaction is completed, the desired fluorine-containing organosilicon compound can be obtained by purification means known per se, such as distillation.

The fluorine-containing organosilicon compound of the present invention obtained in this manner has a molecular structure represented by the above-mentioned general formula (1). Representative examples of the fluorine-containing organosilicon compound of the present invention are shown below.

CHi　　　　　　　　　　L；H CH.

CH2GHzCaF.

It is particularly useful as a material that can be used for solvent-resistant silethylene siloxane rubber, mold release agents, etc.

(Examples) Reference Example: The fluorine-containing organosilicon compound of the present invention can be used for various purposes, but is particularly useful as a raw material for producing polysilethylene siloxane having excellent solvent resistance. For example, by hydrolyzing the fluorine-containing organosilicon compound of the present invention and performing cranking using an alkali metal hydroxide to synthesize a 5-membered ring monomer, and polymerizing the monomer, perfluoroalkyl is added to the side chain. Polysilethylene siloxane polymers having groups can be synthesized. Because this polymer has a high fluorine content, heptadecafluorodecylmethyldichlorosilane 2525
g.

Then, 2500 g of tetrahydrofuran was charged, and then 2489 g of a tetrahydrofuran solution of vinyl magnesium bromide prepared in advance (
4.5 mol of vinylmagnesium bromide) was added dropwise through a dropping funnel over a period of 2 hours.

After the dropwise addition, the reaction mixture was heated and stirred at 60°C for 3 hours, and then analyzed by gas chromatography. The peak of the raw material heptadecafluorodecylmethyldichlorosilane (A) and the peak of heptadecafluorodecyl vinylmethylchlorosilane (B) were detected. ) and hebutadecafluorodecyldivinylmethylsilane (C) overlapped at 8.6% each.
, confirmed at a rate of 11.8%.

This reaction mixture was placed in a suction furnace, salts were removed, and the furnace liquid was distilled under reduced pressure to obtain a boiling point of 1O5 to 110"C/7m.
Fraction of sHg (A; 32.3χ, B+C; 66.2
χ) 1819 g was obtained.

1527 g of the fraction obtained in the above reference example and 0.1 g of a 1% isopropanol solution of chloroplatinic acid were charged into a 32-four-bottle flask equipped with a cooling tube, a stirring bar, a temperature needle, and a dropping funnel. , heated to 80°C.

Then in this flask, 261g dimethylchlorosilane was added dropwise from the dropping funnel over a period of 2 hours.

After the dropwise addition was completed, heating and stirring was further performed at a temperature of 80° C. for 1 hour. By distilling the reaction mixture under reduced pressure, the boiling point is 158-160°C/8ml/g, and the melting point is 38-40°C.
515 g of a fraction (yield 72.0%) was obtained. Regarding this fraction, 'H-NMR, infrared absorption spectrum,
When analyzed by F-NMR and elemental analysis,
The following results were obtained.

'H-NMR; CCj! In a, internal standard CHCj!
! .

δ (ppm) 0.55 (s, Si CHs, 6H) 0.5
7 (s, Si CHs, 3H) 1.01 (
s, Si CH2CHz St, 4H) 1.2
2 (t, St -CHg, 21) 2.36
(t, CFz-CHz+2H) Infrared absorption spectrum; shown in FIG.

C-F peak 1130-1280cm+-'”F-N
MRHCFsCOOH standard d: -40,15 pps e: -5,71 ppm Elemental analysis; From the above analysis results, it was confirmed that the above fraction was a compound represented by the following structural formula.

(Effects of the Invention) According to the present invention, a novel fluorine-containing organosilicon compound is provided which is extremely useful as a raw material for producing polysilethylene siloxane having excellent solvent resistance.

[Brief explanation of drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of the fluorine-containing organosilicon compound obtained in Example 1.

Claims (1)

[Claims] (1) The following general formula [I], ▲Mathematical formula, chemical formula, table, etc.▼[I] In the formula, R is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and multiple R's are the same as each other. A fluorine-containing organic compound represented by the following, wherein Rf is a perfluoroalkyl group having 1 to 10 carbon atoms.