JP2811143B2 - Fluorine-containing organosilicon compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorine-containing organosilicon compound, and more particularly to a polymerizable cyclotrisiloxane having a fluorine-containing substituent and useful as a raw material for silicone oils, silicone elastomers and the like.

[0002]

2. Description of the Related Art Conventionally, organosilicon compounds having a cyclic siloxane skeleton, such as hexamethylcyclotrisiloxane, are known, and chain-like siloxane polymers obtained by ring-opening polymerization of these compounds can be used in various silicone oils and silicone elastomers. Widely used as a raw material.

[0003] At present, silicone oils and silicone elastomers having excellent heat resistance, chemical resistance, weather resistance and surface energy properties are required. From such a viewpoint, organosilicon having a cyclic siloxane skeleton as a raw material thereof has been demanded. Research on compounds has also been performed.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel organosilicon compound having a cyclic siloxane skeleton, and particularly to heat resistance, chemical resistance, weather resistance and surface energy characteristics. An object of the present invention is to provide a novel organosilicon compound useful as a raw material for excellent various silicone oils and silicone elastomers.

[0005]

Means for Solving the Problems To solve the above problems, the present invention provides a compound represented by the following general formula (1):

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, each is an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.) A fluorine-containing organosilicon compound represented by the formula:

In the general formula (1), R ¹ , R ² , R ³ , R
⁴ and R ⁵ may be the same or different and each is an alkyl group having 1 to 6 carbon atoms, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group.

Further, by appropriately selecting n of the fluorine-containing substituent of the compound represented by the above general formula (1), the heat resistance, chemical resistance, weather resistance, surface energy properties, etc. of the siloxane polymer to be produced can be used. Can be changed according to

Production Method The fluorine-containing organosilicon compound of the present invention is, for example, a compound represented by the following general formula:
(2):

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined above), and a cyclotrisiloxane having a Si—H group represented by the general formula (3):

Embedded image (Wherein n is as defined above), and can be synthesized by an addition reaction with a vinyl group-containing organic compound represented by the formula (1) in the presence of a conventionally known catalyst.

As a catalyst in this reaction, for example,
Platinum-based catalysts, palladium catalysts and rhodium catalysts can be mentioned. Among them, particularly preferred are platinum-based catalysts. Specifically, for example, platinum black, alumina, a carrier such as silica on which solid platinum is supported, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum chloride Platinum and platinum compounds such as a complex of an acid and an olefin and a complex of platinum and a vinyl siloxane are exemplified. The amount of the catalyst to be used is generally in the range of 1.0 to 2.0 mol, preferably 1.1 to 1.0 mol, per 1 mol of the cyclosiloxane represented by the general formula (2).
In the range of 3 moles.

[0010] The reaction temperature of the above addition reaction is usually 50 to 150 ° C, preferably 70 to 100 ° C.

[0011]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Example 1 Internal volume equipped with stirrer, cooling pipe, thermometer, dropping funnel
In a 100 ml three-necked flask, the following formula (4):

Embedded image (In the formula, Me is a methyl group.) 7.6 g of cyclotrisiloxane represented by the formula is charged, and the flask is heated to 75 to 80 ° C. and fully stirred while being modified with 2-ethylhexanol having a platinum concentration of 2%. 0.04 g of a platinum catalyst was added, and the following formula (5)
:

Embedded image 35.0 g of a vinyl-containing fluorine-containing organic compound represented by
Dropped over minutes. After the addition, the mixture in the flask was further stirred for 1 hour, and the mixture was distilled under reduced pressure.
22 g of a compound were obtained as a fraction at a temperature of 2 ° C./2 mmHg.
%).

Next, the obtained compound is subjected to elemental analysis.
When the IR spectrum and the NMR spectrum were measured, the following results were obtained.

Elemental analysis C H Si F Calculated value ^* (%): 25.68 2.06 7.83 51.22 Actual value (%): 25.41 2.18 7.64 51.29 (* as C ₂₃ H ₂₂ O ₈ F ₂₉ N ₁ Si ₃ )

FIG. 1 shows an IR spectrum . (Characteristic ^{absorption) 1020cm -1: (Si-O} ) 1000~1400cm -1: (CF) 1540,3320cm -1: (NH) 1700cm -1: (C = O)

¹ H-NMR spectrum TMS standard δ (ppm) 0.03 to 0.37 (-Si-CH ₃ , bs, 15H) 0.40 to 0.87 (-Si-CH _2- , m, 2H) 1.37 to 2.03 (C- (CH ₂ -C, m, 2H) 3.03 to 3.70 (N-CH _2- , m, 2H) 7.37 to 7.93 (NH, m, 1H)

[0016] · ¹⁹ F-NMR spectrum CF ₃ COOH standard φ (ppm) -2.71 (-CF ( C F 3), 12F) -4.25 (CF 3 CF 2 C F 2 -, 5F) -5.05 (-CF ( CF ₃ ) C F _2- , 6F) -51.94 (CF ₃ C F ₂ CF _2- , 2F) -54.14 (-C F (CF ₃ ) CO-, 1F) -66.81 (-C F (CF ₃ ) CF _2- , 3F)

From the above results, the obtained compound is represented by the following formula:
(6):

Embedded image It was confirmed that the compound was a fluorine-containing organosilicon compound represented by the formula:

Example 2 The same flask as in Example 1 was charged with 20.8 g of the cyclotrisiloxane represented by the above formula (4),
While heating to 80 ° C. and stirring sufficiently, 0.1 g of a 2-ethylhexanol-modified platinum catalyst having a platinum concentration of 2% was added thereto.

Embedded image 36.9 g of a vinyl-containing fluorine-containing organic compound represented by
Dropped over minutes. After the completion of the dropwise addition, the mixture in the flask was stirred for 1 hour, and the mixture was distilled under reduced pressure.
26.3 g of the compound was obtained as a fraction of 3 mmHg (yield 46
%).

Next, the obtained compound is subjected to elemental analysis.
In addition, the following results were obtained by measuring the IR spectrum and the NMR spectrum.

Elemental analysis C H Si F Calculated value ^* (%): 29.12 3.84 14.59 36.18 Actual value (%): 28.95 3.93 14.66 36.12 (as C ₁₄ H ₂₂ O ₅ F ₁₁ N ₁ Si ₃ )

IR spectrum is shown in FIG. (Characteristic ^{absorption) 1020cm -1: (Si-O} ) 1000~1400cm -1: (CF) 1540,3320cm -1: (NH) 1700cm -1: (C = O)

¹ H-NMR spectrum TMS standard δ (ppm) 0.03 to 0.33 (-Si-CH ₃ , bs, 15H) 0.37 to 0.83 (-SiCH _2- , m, 2H) 1.33 to 2.00 (C-CH ₂ -C, m, 2H) 2.97 to 3.63 (N-CH _2- , m, 2H) 7.23 to 7.67 (NH, m, 1H)

[0023] · ¹⁹ F-NMR spectrum CF ₃ COOH standard φ (ppm) -5.03 (-CF ( C F 3) -, 3F) -7.15 (C F 3 CF 2 C F 2 -, 5F) -53.01 (CF ₃ C F ₂ CF _2- , 2F) −55.57 (C F (CF ₃ )-, 1F)

The compound obtained from the above results has the following formula
(8):

Embedded image It was confirmed that the compound was an organosilicon compound represented by the formula:

[0025]

The fluorinated organosilicon compound of the present invention comprises
Alkaline catalyst such as KOH, (n C ₄ H ₉ ) ₄ POH or H ₂ SO
_4. Ring-opening polymerization is easily carried out by an acid catalyst such as CF ₃ SO ₃ H to form a chain siloxane polymer. This siloxane polymer can be subjected to an equilibration reaction in the same manner as conventional hexamethylcyclotrisiloxane, and various oils,
Useful as a raw material for rubber.

In particular, since the fluorine-containing organosilicon compound of the present invention has a substituent containing a large number of fluorine atoms, the resulting siloxane polymer has heat resistance, chemical resistance, weather resistance, water repellency, oil repellency, mold release. The properties and the like can be further improved as compared with the conventional ones, and these properties can be changed according to the intended use by appropriately setting the degree of polymerization of the fluorine-containing group. Therefore, such a siloxane polymer is particularly useful as a water repellent, an oil repellent, a release agent, and the like.

[Brief description of the drawings]

FIG. 1 is an IR chart of the fluorine-containing organosilicon compound of the present invention synthesized in Example 1.

FIG. 2 is an IR chart of the fluorine-containing organosilicon compound of the present invention synthesized in Example 2.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshiyuki Ishii 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside the Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (56) References JP-A-4-316584 ( JP, A) JP-A-4-243886 (JP, A) JP-A-60-163887 (JP, A) JP-A-64-71887 (JP, A) JP-A-2-127498 (JP, A) Hei 5-331292 (JP, A) JP-B 36-7014 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/21 CA (STN) CAOLD (STN) REGISTRY ( STN) WPIDS (STN)

Claims (1)

(57) [Claims] [Claim 1] General formula (1): (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, each is an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.) A fluorine-containing organosilicon compound represented by the formula: