JPH0615618B2 - Fluorine-containing polysilethylene siloxane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel polysilethylene siloxane which has not been published in the literature.

(Prior Art) Dimethylpolysiloxane is excellent in heat resistance, cold resistance, and weather resistance, and also has excellent properties such as rubber elasticity, releasability, and electrical characteristics. As a main component of various rubber materials and coating materials, It is used in a wide range of fields such as building materials, transportation equipment, home appliances, and office machines. Such characteristics of dimethylpolysiloxane are derived from the fact that the bond energy of the siloxane bond, which is the main chain, is large, it has ionic bondability, and the intermolecular cohesive force of siloxane molecules is small.

(Problems to be Solved by the Invention) However, dimethylpolysiloxane is liable to cause cleavage of the main chain due to ionic reagents such as acids and alkalis, mechanical strength characteristics are unsatisfactory, and swelling easily to organic materials. Has the drawback of.

To remedy this drawback, fluorosilicones with triflopropyl groups in the side chains have been developed (US Pat. No. 3,
179,619), the problem of swelling property with respect to organic solvents has been improved to some extent, but the swelling property with respect to polar solvents has not been improved to a satisfactory degree, and resistance to acid, alkali, etc., and mechanical strength The problem is still unsolved.

Therefore, an object of the present invention is to provide a novel fluorine-containing polysiloxane compound in which the above-mentioned drawbacks of dimethylpolysiloxane are eliminated.

(Means for Achieving the Object) The polysilethylene siloxane of the present invention has the following general formula [I]: In the formula, R represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, plural Rs may be the same or different from each other, Rf is a perfluoroalkylethyl group, and n is It is an integer from 10 to 1,000 and is represented by.

That is, the present invention improves mechanical strength and resistance to chemicals such as acid and alkali by introducing a silethylene bond into the siloxane main chain, and also introduces one perfluoroalkylethyl group into the side chain. Thus, the swelling property with respect to an organic solvent, machine oil, etc. is reduced, and further, the mold releasability and the water / oil repellency are improved.

In the above general formula [I], the group R has 1 to 8 carbon atoms.
The monovalent hydrocarbon group is preferably a lower alkyl group having 8 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group, an allyl group, an isopropenoxy group. Examples thereof include an alkenyl group such as, an aryl group such as a phenyl group and a tolyl group, an aralkyl group such as a benzol group, and a 2-phenylethyl group. The plurality of Rs may be the same group or different groups. In the present invention, the most preferred R is a lower alkyl group, especially a methyl group.

The group Rf is a perfluoroalkylethyl group, specifically, a group represented by the following formula, —CH ₂ CH ₂ C _m F _{2m + 1} , in which m is 1 to 10. It is preferably an integer. Examples of such a perfluoroalkylethyl group include CH ₃ CH ₂ CH ₂ —, (CF ₃ CFCH ₂ CH ₂ —,
C ₄ F ₉ CH ₂ CH ₂ −, C ₆ F ₁₂ CH ₂ CH ₂ −, C ₈ F ₁₇ CH ₂ CH ₂ −, C ₁₀
F ₂₁ CH ₂ CH ₂ − and the like can be mentioned.

Further, in the general formula [I], n is an integer of 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 to 500,000 at 25 ° C.
It is in the range of cSt, preferably 1000 to 100,000 cSt, which is preferable as a liquid polymer.

Production Method The polysilethylene siloxane of the present invention can be synthesized by various methods, but typically, the following general formula [II], In the formula, R and Rf are as described above, a method of synthesizing by dichlorosilane represented by, and the following formula [III], In the formula, R and Rf are as described above, and a method of synthesizing the 5-membered cyclic silethylene siloxane represented by by ring-opening polymerization can be mentioned.

This ring-opening polymerization is generally carried out in the presence of a polymerization catalyst at 10
It is performed by heating to a temperature of ~ 200 ° C. As the polymerization catalyst used, lithium, potassium, hydroxides of alkali metals such as sodium and silanolates are preferably used,
In addition to these, an acid catalyst, an alkali catalyst, etc. which are commonly used for ring-opening polymerization of dimethylpolysiloxane can also be used. Such a polymerization catalyst varies depending on its type,
Generally, it is preferable to use 0.001 to 5 parts by weight per 100 parts by weight of 5-membered cyclic silethylene siloxane.

Polysilethylene Siloxane The thus obtained polysilethylene siloxane of the present invention has a silethylene bond and a siloxane bond in the main chain and has silanol groups at both ends, as represented by the above general formula [I]. Have This polysilethylene siloxane is a liquid polymer which is excellent in chemical resistance, water repellency, electrical characteristics and the like, and is extremely useful as a main component of an elastomer having high strength and high elongation. For example, a rubber cured product having the above-mentioned properties can be obtained by curing the polysilethylene siloxane of the present invention by a crosslinking reaction applied to a usual silicone compound.

Such a polymer is extremely useful as a highly functional rubber material or a raw material for a coating material.

(Example) Example 1 A 300 ml four-necked flask equipped with a cooling tube, a stirring blade and a thermometer was charged with the following formula, The cyclic siloxane represented by 72.6 g (0.3 mol) 5 g of acetonitrile and 54 mg (0.003 mol) of pure water were charged, and the mixture was heated to 90 ° C. with stirring.

Next, when potassium-silanolate was added to this mixed solution in an amount such that the Si / K ratio (atomic ratio) was 5,000, heat was generated after 3 minutes, the internal temperature rose to 110 ° C, and The reflux became violent, and then the viscosity gradually increased. After aging at 90 ° C for 3 hours, 1 g of tetrachloroethane was added as a neutralizing agent, and further aging at 90 ° C for 3 hours.

Next, it was cooled to room temperature, the reaction solution was pressurized, and the solution was vacuum stripped at 100 ° C. for 3 hours at 3 mmHg by an evaporator to obtain 68 g of an oily substance.

About this oil, GPC, OH group determination, ¹ H-NMR, ¹⁹ F-
When analyzed by NMR, the following results were obtained.

GPC; Measuring instrument Tosoh Corp. HLC-8020 Measuring conditions Column: G2500 + G4000 (1 each) Solvent: Freon-113 Flow rate: 1 ml / min Detector: Differential refractometer Temperature: 35 ° C The chart is shown in Fig. 1. .

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

OH group quantification; 4.13 × 10 ^-5 mol / g ¹ H-NMR; internal standard CHCl ₃ δ (ppm) 0.10 (s, Si-CH ₃ , 9H) 0.45 (s, Si-CH ₂ CH _{2 in} CCl ₄ -Si, 4H) 0.80 (t, Si-CH 2, 2H) 2.11 (t, CF 3 -CH 2, 2H) 19 F-NMR; CF 3 COOH 8.81ppm CF 3 from -CH ₂ above results, the oil Is the following formula, It was confirmed that the polymer was represented by

Example 2 A 300 ml four-necked flask equipped with a cooling tube, a stirring blade and a thermometer was charged with the following formula, The cyclic siloxane represented by 118.4 g (0.2 mol) acetonitrile 10 g and pure water 36 mg (0.002 mol) were charged, and the mixture was heated to 90 ° C. with stirring.

Next, to this mixture was added lithium-silanolate in an amount such that the Si / Li ratio was 4,000, then Example 1
The same operation as above was performed to obtain 108 g of a viscous oily substance.

When this oil was analyzed by GPC, OH group quantification, infrared spectrum, ¹ H-NMR and ¹⁹ F-NMR, the following results were obtained.

GPC; Measuring instrument Tosoh Corp. HLC-8020 Measuring conditions Column: G2500 + G4000 (1 each) Solvent: Freon-113 Flow rate: 1 ml / min Detector: Differential refractometer Temperature: 35 ° C The chart is shown in Fig. 2. .

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

OH group determination; 1.10 × 10 ^-5 mol / g ¹ H-NMR; internal standard CHCl ₃ δ (ppm) 0.22 (s, Si-CH ₃ , 9H) 0.63 (s, Si-CH ₂ CH _{2 in} CCl ₄ shows a chart in Figure 3; -Si, 4H) 0.88 (t , Si-CH 2, 2H) 2.12 (t, CF 2 -CH 2, 2H) IR absorption spectrum.

CF: 1130 to 1260 cm ^{-1 19} F-NMR; CF ₃ COOH standard a: −49.42 ppm b: −47.77 ppm c: −39.87 ppm d: −5.32 ppm From the above results, the above oil was It was confirmed that the polymer was represented by

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

[Brief description of drawings]

1 is a diagram showing a GPC chart 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. It is a figure which shows the infrared absorption spectrum of the polymer synthesize | combined in Example 2.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenichi Fukuda, Kenichi Fukuda 2-13-1, Isobe, Annaka City, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Hideji Suganuma Annaka, Gunma Prefecture 2-13-1 Ichiisobu Shin-Etsu Chemical Co., Ltd. Silicon Silicon Electronic Materials Research Laboratory (56) Reference JP-A-58-92594 (JP, A) JP-B-46-37743 (JP, B1) US Patent 3041363 (US, A)

Claims (1)

[Claims] 1. The following general formula [I]: In the formula, R represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, plural Rs may be the same or different from each other, Rf is a perfluoroalkylethyl group, and n is A fluorine-containing polysilethylene siloxane represented by the formula, which is an integer of 10 to 1,000.