JPH0459783A - 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 agents, 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 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, the two Rs may be the same or different from each other, and Rf is perfluoroalkyl having 1 to 10 carbon atoms. is a group, expressed as . As understood from the general formula (1), the fluorine-containing organosilicon compound of the present invention is a novel compound that has not been described in any literature.

The fluorine-containing organosilicon compound of the present invention represented by the above general formula (1) has the following general formula [11], where Rf and R are Rf and R in the above general formula (1). A hydrosilane represented by, which is a group corresponding to , and the following general formula (I[[),
CHzCHzRf CHz=CHSt C1 (III) In the formula, Rf and R are as described above. It is produced by addition reaction of vinylsilane represented by: in the presence of a catalyst.

In the general formulas [■] and (I[[), the groups Rf and R are the groups Rf and R in the general formula (1), respectively.
is a group corresponding to .

That is, the group Rf is a perfluoroalkyl group having 1 to 10 carbon atoms, preferably -CF3, C4F?
.

C6F+3, CsF+s, etc.

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.

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 in terms of platinum group metal.
00 ppm, preferably in the range of 0.5 to 200 pp+n.

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 toluene, xylene, benzene, n-hexane, cyclohexane, etc. The reaction 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.

F... A The fluorine-containing organosilicon compound of the present invention thus obtained 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.

CH2CHICF3 C1 (zcHzcFs[ Cj! Si CHzCHz St CfC
H, CH.

C.I.

Hs CJCHzCiF+3 CB, CB, C, F, I CHzCIlzCsF+t CHzCHzCaF+
tCI St CHtCHz Si CIC
Hs CHs 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. A 5-membered ring monomer is synthesized by hydrolyzing an elementary organosilicon compound and cranking with an alkali metal hydroxide, and by polymerizing the monomer, a polysil having a perfluoroalkyl group in the side chain is produced. Ethylene siloxane polymers can be synthesized. Since this polymer has a high fluorine content, it is particularly useful as a material that can be used for solvent-resistant silethylene siloxane rubber, mold release agents, and the like.

(Example) 613 g of trifluoropropylvinylmethylchlorosilane was placed in a 21-four-bottle flask equipped with a back cover, soil cooling tube, stirring bar, thermometer, and dropping funnel.
(3.03 mol) and 0.1 g of a 1% isopropanol solution of chloroplatinic acid were charged and heated to 80°C.

Next, 535 g (3.03 mol) of trifluoropropylmethylsilane was added dropwise into the flask 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 was 102-103°C/3+llmHg, and the melting point was 39°.
1017 g of C fraction (yield: 89%) was obtained. Regarding this fraction, 'H-NMR, infrared absorption spectrum,'
``When we conducted analysis using F-NMR and elemental analysis, we obtained the following results.

'H-NMR; Internal standard C41Cl in CCl2a
sδ (ppm) 0, 50 (s, Si CHs, 6H
)0.88 (s, St CHgCH2S
ir 4H) 1, 08 (t, st C
Hz, 4H)2,18 (t, CF3
-CHz, 4H) Infrared absorption spectrum; shown in FIG.

C-F peak 1000-1400cm-'”F
NMR; CFsCOOH standard CF3-7.0p
pm Elemental analysis: From the above analysis results, it was confirmed that the above fraction was a compound represented by the following structural formula.

Real m As vinyl silane, the following formula: ChzCHzCaP* CHgCH2 CII I used the one represented by .

In addition, as hydrosilane, the following formula, cutcnzcapq H-5i-CII C.B.

I used the one represented by .

i.e. 3j with cooling tube, stirring bar, thermometer and dropping funnel! In a four-necked flask, 823 g (2.34 mol) of the vinylsilane and 0.085 g of a 1% isopropanol solution of chloroplatinic acid were added.
and heated to 80°C.

Then in this flask, CH.

H3 763 g (2.34 mol) of the above hydrosilane was added dropwise through a dropping funnel over 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, 1069 g (yield: 67%) of a fraction with a boiling point of 121-b was obtained. Regarding this fraction, 'H-NMR, infrared absorption spectrum,
When analyzed by F-NMR and elemental analysis,
The following results were obtained.

'H-NMRHCC1a, internal standard CHCf.

δ (ppm) 0, 50 (s, St CHs, 6B) 0.
90 (s, Si CHlCHl Sit
48) 1,07 (t, Si-CI□ 48)
2,13 (t, cp, CHz+4H) infrared absorption spectrum; shown in FIG.

C-F peak 1000-1400c+a-yam”F
-NMR; CF3COOH standard abc CF3-CFz-CFz-CFz-CH2-CHl-5
ia: b: C: d: Elemental analysis; 51.20 ppm 49.37 ppm 41,17 ppm 6.92 ppm 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 shows the infrared absorption spectrum of the fluorine-containing organosilicon compound obtained in Example 1, and FIG. 2 shows the infrared absorption spectrum of the fluorine-containing organosilicon compound obtained in Example 2. It is a figure showing an absorption spectrum.

Claims (1)

[Claims] (1) The following general formula [I], ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] In the formula, R is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and the two R's are mutually A fluorine-containing organic compound represented by the following, which may be the same or different, and Rf is a perfluoroalkyl group having 1 to 10 carbon atoms.