JPH0465431A - Fluorine-containing polysilethylene siloxane - 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 polysilethylene siloxane that has not been described in any literature.

(Prior art) Dimethylpolysiloxane has excellent heat resistance, cold resistance, and weather resistance, as well as excellent properties such as rubber elasticity, mold release properties, and electrical properties, and is used as the main component of various rubber materials, coating materials, etc. It is used in a wide range of fields such as building materials, transportation equipment, home appliances, and office equipment.

Such characteristics of dimethylpolysiloxane originate from the fact that the siloxane bond in the main chain has a large bond energy, has ionic bonding properties, and the intermolecular cohesive force of the siloxane molecules is small.

(Problems to be Solved by the Invention) However, dimethylpolysiloxane is susceptible to cleavage of its main chain by ionic reagents such as acids and alkalis, has unsatisfactory mechanical strength characteristics, and swells in organic solvents. It has disadvantages such as being easy to use.

In order to improve this drawback, fluorosilicone having a triflopropyl group in the side chain was developed (U.S. Pat.
, 179, 619), the problem of swelling in organic solvents has been improved to some extent, but swelling in polar solvents in particular has not been improved to a satisfactory degree.
The problems of resistance to alkali and mechanical strength are still unsolved.

Accordingly, an object of the present invention is to provide a new fluorine-containing polysiloxane compound that eliminates the above-mentioned drawbacks of dimethylpolysiloxane.

(Means for achieving the object) The polysilethylene siloxane of the present invention has the following general formula (
1), in the formula, R represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, the plurality of R's may be the same or different groups, Rf is a perfluoroalkylethyl group, n is an integer from 10 to 1,000.

That is, the present invention improves mechanical strength and resistance to chemicals such as acids and alkalis by introducing a silethylene bond into the siloxane main chain, and also introduces two perfluoroalkylethyl groups into the side chain. This reduces the swelling property against organic solvents, machine oil, etc., and also improves the mold releasability and
This product succeeded in improving water and oil repellency.

In the above general formula (1), the group R has 1 to 8 carbon atoms.
A monovalent hydrocarbon group, preferably a lower alkyl group having 8 or less carbon atoms such as a methyl group, ethyl group, or propyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group, an allyl group, or an isopropenoxy group. Alkenyl groups such as phenyl groups, aryl groups such as tolyl groups, benzyl groups,
Examples include aralkyl groups such as 2-phenylethyl group. These plural R's may be the same group or different groups. In the present invention, the most preferred R is a lower alkyl group, particularly a methyl group.

Further, the group Rf is a perfluoroalkylethyl group,
Specifically, it is a group represented by the following formula, CHzCHtC-Pt-++, where m is preferably an integer of 1 to 10. Such perfluoroalkylethyl groups include, for example, CFiCHtCHz (CFs)
zcFc[zcHz, CJqCHzCHz,
CaF+zCHzC)It-CsF+tCHzCHz
-9C+. F! +cHzcHz-, etc. can be mentioned.

Furthermore, in the general formula (1), n is an integer from 10 to 1,000, and in relation to such a value of n, the polysilethylene siloxane of the present invention has a viscosity of 25°C at 25°C.
5-500,000 cSt, preferably i,o
It is in the range of oo to 100.0OOcSt, and is preferable as a liquid polymer.

Production method The polysilethylene siloxane of the present invention can be synthesized by various methods, but is typically expressed by the following general formula [■], where R and Rf are as described above. A method of synthesizing dichlorosilane by hydrolyzing it,
and a method of synthesis by ring-opening polymerization of a 5-membered cyclic silethylene siloxane represented by the following formula (I[), where R and Rf are as described above.

This ring-opening polymerization is generally carried out in the presence of a polymerization catalyst.
It is carried out by heating to a temperature of 0 to 200°C. As the polymerization catalyst to be used, hydroxides and syralates of alkali metals such as lithium, potassium, and sodium are preferably used, and in addition, acid catalysts and alkali catalysts commonly used for ring-opening polymerization of dimethylpolysiloxane are used. etc. can also be used. Although the polymerization catalyst varies depending on its type, it is generally preferable to use it in a proportion of o, ooi to 5 parts by weight per 100 parts by weight of the 5-membered cyclic silethylene siloxane.

The polysilethylene siloxane of the present invention thus obtained has a silethylene bond and a siloxane bond in the main chain, and a silanol group at both ends, as represented by the general formula (I). have. This polysilethylene siloxane is a liquid polymer that is excellent in properties such as chemical resistance, water repellency, and electrical properties, and is extremely useful as a main component of elastomers with high strength and high elongation. For example, a cured rubber product having the above characteristics can be obtained by curing the polysilethylene siloxane of the present invention by a crosslinking reaction applied to ordinary silicone compounds.

Such polymers are extremely useful as highly functional rubber materials or as materials for coating materials.

(Example) 97.2 g (0.3 mol) of a cyclic siloxane represented by the following formula, 10 g of acetonitrile, and 54 μg of pure water ( 0,003 mol) and heated to 90°C while stirring.

Next, in this mixed solution, the Si/to ratio (atomic ratio) is 5.0.
When potassium syralate was added in an amount such that 0.00 was added, heat was generated after 5 minutes, the internal temperature rose to 105°C, the reflux of acetonitrile became intense, and the viscosity gradually increased thereafter. After aging at 90″C for 3 hours,
1 g of tetrachloroethane was added as a neutralizing agent, and the mixture was further aged at 90°C for 3 hours.

Next, it was cooled to room temperature, the reaction solution was heated in a pressurized oven, and the oven solution was stripped using an evaporator under reduced pressure at 100° C. and 3 g of F for 2 hours to obtain 91 g of an oily substance.

GPC analysis of this oil showed a monodisperse pattern. In addition, analysis by Go quantitative analysis, infrared absorption spectrum, and 'tl-NMR1'' F-NMR gave the following results.

OH group determination; 3.01X10-'mol/g'H-NMR; Internal standard CHC123 in CCl a
δ (ppm) 0.07 (s, 5i-CH3,6H) 0.43
(S, 5i-CB, CH, -5i + 4H)0.
81 (t, 5i-CHz, 4B) 2.02
(t, cpff-co!, 4B) Infrared absorption spectrum; A chart is shown in FIG.

C-F: 1000~l100CII-'”F-NM
R; CF3COOH standard 8.82pP@Ch-CL From the above results, it was confirmed that the above oil was a polymer represented by the following formula.

Urasenran I 124.8 g (0.2 mol) of cyclic siloxane represented by the following formula, 12 g (0.2 mol) of acetonitrile, and 28.8 ■ (0.0 , 016 mol) and heated to 90°C while stirring.

Next, in this mixed liquid, the S i / Li ratio is 4.0
Adding an amount of lithium syralate such that 00,
Next, the same operation as in Example 1 was performed to obtain 116 g of a viscous oily substance.

When this oil was analyzed by GPC, OH group amount infrared absorption spectrum, 'II-NMR, and 'F-NMR, the following results were obtained.

G.P.C.

Measuring equipment HLC-8020 manufactured by Tosoh ■ Measurement conditions Column: G2500 + G4000 (one each) Solvent: Freon-113 Flow rate: 1 d/sin Detector: Differential refractometer Temperature: 35°C The chart is shown in FIG.

As is clear from this chart, a monodisperse pattern was shown.

OH group weight 1.25 x 10-S mol/g heavy H-NMR; internal standard CHCfsδ in CCN 4
(ppn+) 0.23 (s, 5i-C1h, 68)0-
61 (5,h-CBzCFIz-SI 1 4H)
0.91 (t, 5i-CR1,4H)2.12
(t, CF!-CI!, 4EI) Infrared absorption spectrum; a chart is shown in FIG.

C-F: 1000-1100CI+-'” F-NMR
; CF, C0OH standard abc CFs-CFz-CFg"Ch-CI'1zC)It-
Si3a: -49,56ppm B: 47.80ppm C: -39,70ppm A: -5,37ppm From the above results, the above oil has the following formula, CHi
It was confirmed that it was a polymer represented by C1(3).

(Effects of the Invention) According to the present invention, a novel fluorine-containing polysilethylene siloxane capable of forming a cured rubber product having excellent resistance to acids, alkalis, etc. and excellent mechanical strength. A compound was obtained.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the infrared absorption spectrum of the polymer synthesized in Example 1, FIG. 2 is a diagram showing a GPC chart of the polymer synthesized in Example 2, and FIG. 3 is a diagram showing the infrared absorption spectrum of the polymer synthesized in Example 2. FIG. 3 is a diagram showing an infrared absorption spectrum of a polymer synthesized in Example 2. Figure 2

Claims (1)

[Claims] (1) The following general formula [I], ▲Mathematical formula, chemical formula, table, etc.▼[I] In the formula, R represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, and multiple R's are the same as each other. A fluorine-containing polysilethylene siloxane represented by the following formula: Rf is a perfluoroalkylethyl group, and n is an integer from 10 to 1,000.