JP2652888B2 - Method for producing α-chloro-ω-hydrogen organopolysiloxane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an α-chloro-
The present invention relates to a method for producing an ω-hydrogen organopolysiloxane.

[Background Art] α-Chloro-ω-hydrogenorganopolysiloxane in which one end of siloxane is a chlorine atom and the other end is a hydrogen atom is a compound expected to be useful in the silicone industry. Nevertheless, only a few compounds have been synthesized. That is, 1-
Chloro-3-hydrogendisiloxane, 1-chloro-5-hydrogentrisiloxane, 1-chloro-7
-Hydrogentetrasiloxane and 1-chloro-13
Hydrogen heptasiloxanes are only described in the literature.

[Problems to be Solved by the Invention] Accordingly, an object of the present invention is to provide a method for producing a novel α-chloro-ω-hydrogen organopolysiloxane useful as a silicone intermediate.

[Means for Solving the Problems] Under these circumstances, the present inventors have conducted intensive studies and as a result, have found that α, ω-dihydrogen organopolysiloxane having a constant siloxane chain length can be converted into a reaction condition that does not break siloxane bonds. Then, it was found that α-chloro-ω-hydrogen organopolysiloxane can be obtained by substituting a hydrogen atom at one end with a chlorine atom, and completed the present invention.

That is, the present invention provides an invention relating to a method for producing α-chloro-ω-hydrogenorganopolysiloxane (I) represented by the following reaction formula.

(Wherein, R ¹ and R ² may be the same or different, and
An alkyl group, an alkenyl group, an aryl group or a halogenoalkyl group, and n represents an integer of 3 to 10. That is, using α, ω-dihydrogenorganopolysiloxane (II) as a raw material, “Bull. Chem. .Jpn., 40,
2214 (1967) ", by reacting with a radical initiator in carbon tetrachloride.
-Hydrogen organopolysiloxane (I) is produced.

In the present invention, alkyl groups represented by R ¹ and R ² in formulas (II) and (I) have 1 to 6 carbon atoms, alkenyl groups have 2 to 6 carbon atoms, and aryl groups have Is a phenyl group, and as a halogenoalkyl group is 1 to
An alkyl group having 1 to 6 carbon atoms substituted by three chlorine, bromine or fluorine atoms is preferred.

The amount of carbon tetrachloride used in the production method of the present invention is preferably 32.9 to 33.7% (molar ratio) based on 1 mol of α, ω-dihydrogen organopolysiloxane (II).

Examples of the radical initiator include benzoyl peroxide,
Although t-butyl peroxide, azobisisobutyronitrile, etc. are used, benzoyl peroxide is particularly preferred. The amount of the radical initiator used is preferably from 0.1 to 10 mol%, particularly preferably from 1 to 4 mol%, based on the α, ω-dihydrogenorganopolysiloxane (II).

The reaction temperature is preferably from room temperature to the reflux temperature of the reaction solution, and particularly preferably from 50 ° C to 120 ° C in order to promptly advance the reaction.

After the completion of the reaction, the insolubles are filtered if necessary, and the filtrate is distilled to obtain α-chloro-ω-hydrogenorganopolysiloxane (I).

Among the α-chloro-ω-hydrogen organopolysiloxanes (I) obtained by the production method of the present invention, n
Are 3, 4, 6, 7 and 8 are novel compounds not described in the literature.

The α, ω-dihydrogen organopolysiloxane (II) used in the production method of the present invention may be, for example, cyclic silicone (III) or chlorosilane (I) according to the following reaction formula.
V) and water in the presence of an inorganic solid compound.

(Wherein R ¹ , R ² and n have the same meanings as described above) Examples of the cyclic silicone (III) used in this reaction include hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, and hexaphenylcyclotrisiloxane. , Trimethyltrivinylcyclotrisiloxane, trimethyltriphenylcyclotrisiloxane,
Octamethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, tetra (trifluoropropyl) tetramethylcyclotetra Examples include siloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like.

Examples of chlorosilane (IV) include dimethylchlorosilane, diethylchlorosilane, diphenylchlorosilane, divinylchlorosilane and the like. The amount of the chlorosilane (IV) to be used is preferably 2 to 10 times, especially 2 to 4 times, and more preferably about 3 times the mol of the cyclic silicone (III).

As the inorganic solid compound used as the catalyst, those which are insoluble and uniformly dispersed in the reaction solution are preferable, and examples thereof include silica gel, titanium dioxide, and silica / alumina. Of these, silica gel is particularly preferably used. The amount of the inorganic solid compound used is appropriately selected depending on the reactivity between the cyclic silicone (III) and the chlorosilane (IV), but may be in the range of 1 to 50% by weight based on the cyclic silicone (III). preferable.

Furthermore, water is in principle used in stoichiometric excess.
That is, the amount used is preferably 1 to 500 times, especially 5 to 20 times the mole of the cyclic silicone (III).

The reaction solvent may or may not be used. However, when hexamethylcyclotrisiloxane which is solid at normal temperature is used as the cyclic silicone, it is preferably used for smoothly proceeding the reaction. As the solvent used, pentane,
Hydrocarbon solvents that do not mix with water, such as hexane, heptane, benzene, and toluene, may be mentioned.

This reaction is preferably performed by adding chlorosilane (IV) to a mixture of the cyclic silicone (III), the inorganic solid compound and water. The reaction time varies depending on the reactivity of the cyclic silicone (III), but is usually completed within 1 to 5 hours at room temperature after the addition of chlorosilane (IV).
The resulting reaction solution is distilled under normal pressure, preferably under reduced pressure, to separate unreacted cyclic silicone and chlorosilane, whereby α, ω-dihydrogen organopolysiloxane (II) is obtained.

Further, the α, ω-dihydrogen organopolysiloxane thus obtained is converted into silanediol, and the process of reacting chlorosilane (IV) to extend two siloxane units is repeated to obtain a longer-chain α. ,
ω-dihydrogen organopolysiloxane (II) can also be obtained. Since it is difficult to obtain a cyclic silicone having n = 7 or more, this method is effective when the target substance has a long chain.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Production Example 1 Synthesis of 1,9-dihydrogendecamethylpentasiloxane [in the general formula (II), R ¹ = R ² = CH ₃ , n = 3]: Hexamethylcyclotriethyl was added to a flask equipped with a dropping funnel. 100 g of siloxane, 100 g of hexane, 81 g of water and 5.0 g of silica gel (Kieselgel 60, 250 to 400 mesh manufactured by Merck) were charged. The flask was ice-cooled, and 127.7 g of dimethylchlorosilane was added dropwise over 30 minutes while sufficiently stirring. After 30 minutes, the flask was returned to room temperature and stirring was continued. After 1 hour, stirring was stopped and the silica gel was filtered. After distilling off excess dimethylchlorosilane from the obtained filtrate, the solution was transferred to a separating funnel and 200 ml twice with 200 ml of water.
Was washed once with a saturated aqueous solution of sodium hydrogencarbonate and then twice with 200 ml of water. After water in the solution was completely removed by azeotropy with benzene, the solution was distilled under reduced pressure to obtain 137.3 g of 1,9-dihydrogendecamethylpentasiloxane (yield 8).
5.5%). All of the starting hexamethylcyclotrisiloxane had reacted.

bp 57 ° C / 0.5 mmHg MS: 355 (M ⁺ -1), 341 (M ⁺ -15) IR: 2128 cm ^-1 (Si-H) ²⁹ Si-NMR (heavy benzene, TMS standard, δ ppm): -6.73 ( 1,9-Si) -19.78 (3,7-Si) -21.57 (5-Si) ¹ H-NMR (heavy benzene, C ₆ H ₆ δ = 7.15 standard, δ ppm): 0.16 (s, 18H) 0.18 ( d, 3 Hz, 12H) 4.96 to 5.00 (bs, 2H) Production Example 2 Production of 1,11-dihydrogendecamethylhexasiloxane [in the general formula (II), R ¹ = R ² = CH ₃ , n = 4] Synthesis: Using octamethylcyclotetrasiloxane as the cyclic silicone, 1,11-dihydrogendecamethylhexasiloxane was obtained in substantially the same manner as in Production Example 1.

bp 81 ° C / 0.16 mmHg MS: 429 (M ⁺ -1), 415 (M ⁺ -15) IR: 2128 cm ^-1 (Si-H) ²⁹ Si-NMR (heavy benzene, TMS standard, δ ppm): -6.74 ( 1,11-Si) -19.81 (3,9-Si) -21.62 (5,7-Si) ¹ H-NMR (heavy benzene, C ₆ H ₆ δ = 7.15 standard, δ ppm): 0.18 (s, 12H) 0.19 (d, 2.7 Hz, 12H) 0.21 (s, 12H) 5.00 (sept, 2.7 Hz, 2H) Production Example 3 1,15-dihydrogenhexadecamethyloctasiloxane [In the general formula (II), R ¹ = Synthesis of R ² CHCH ₃ , n = 6]: Using dodecamethylcyclohexasiloxane as the cyclic silicone, 1,15-dihydrogenhexadecamethyloctasiloxane was obtained in substantially the same manner as in Production Example 1.

bp 105 ℃ / 0.14mmHg MS: 563 (M + -15) IR: 2132cm -1 (Si-H) 29 Si-NMR ( heavy benzene, TMS standard, δppm): -6.68 (1,15- Si) -19.76 (3,13-Si) -21.58 (5,11-Si) -21.60 (7,9-Si) ¹ H-NMR (heavy benzene, C ₆ H ₆ δ = 7.15 standard, δ ppm): 0.17 (s, 12H ) 0.19 (d, 2.8 Hz, 12H) 0.21 (s, 12H) 0.22 (s, 12H) 4.97 (sept, 2.8 Hz, 2H) Production Example 4 1,17-dihydrogenoctadecamethylnonasiloxane [general formula ( In II), the synthesis of R ¹ = R ² = CH ₃ , n = 7]: Using tetradecamethylcycloheptasiloxane as the cyclic silicone, 1,17-
Dihydrogen octadecamethyl nonasiloxane was obtained.

bp 109 ℃ / 0.14mmHg MS: 637 (M + -15) IR: 2128cm -1 (Si-H) 29 Si-NMR ( heavy benzene, TMS standard, [delta] ppm): ¹ H-NMR (Heavy benzene, C ₆ H ₆ δ = 7.15 standard, δ ppm): 0.16 (s, 12H) 0.18 (d, 2.7 Hz, 12H) 0.20 (s, 18H) 0.21 (s, 12H) 4.95 (Sept , 2.7 Hz, 2H) Production Example 5 Synthesis of 1,19-dihydrogeneicosamethyldecasiloxane [In the general formula (II), R ¹ = R ² = CH ₃ , n =
8]: Hexadecamethylcyclooctasiloxane was used as the cyclic silicone, and 1,19-
Dihydrogen eicosamethyldecasiloxane was obtained.

bp 136 ° C./0.014 mmHg MS: 711 (M ⁺ −15) IR: 2134 cm ⁻¹ (Si-H) ²⁹ Si-NMR (heavy benzene, TMS standard, δ ppm): ¹ H-NMR (deuterated benzene, C ₆ H ₆ δ = 7.15 standard, δ ppm): 0.17 (s, 12H) 0.19 (d, 3 Hz, 12H) 0.21 (s, 12H) 0.23 (s, 24H) 4.99 (Sept, 3 Hz, 2H) Example 1 1-chloro-9-hydrogendecamethylpentasiloxane [in the general formula (I), R ¹ = R ² = CH ₃ , n = 3]
Synthesis of: 1,9-dihydrogendecamethylpentasiloxane 2
6.7 g, carbon tetrachloride 3.8 g and benzoyl peroxide 0.606 g,
It was charged into a 50 ml flask purged with argon. 90 ℃
After reacting for 2 hours, the by-product crystals of benzoic acid were filtered, and the filtrate was distilled under reduced pressure to obtain 7.1 g of 1-chloro-9-hydrogendecamethylpentasiloxane (yield 24.5).
%).

bp 85 ° C / 2mmHg MS: EI 389 (M ⁺ -1), 375 (M ⁺ -15), CI 408 (M ⁺
+ NH ₄ ) IR: 466 cm ^-1 (Si-Cl), 2128 cm ^-1 (Si-H) ²⁹ Si-NMR (heavy benzene, TMS standard, δ ppm): ¹ H-NMR (Heavy benzene, C ₆ H ₆ δ = 7.15 standard, δ ppm): Example 2 1-chloro-11-hydrogendecamethylhexasiloxane [In the general formula (I), R ¹ RR ² CHCH ₃ , n =
Synthesis of 4]: 1-chloro-11-hydrogendecamethyl was performed in the same manner as in Example 1 except that 50 g of 1,11-dihydrogendecamethylhexasiloxane, 6.0 g of carbon tetrachloride and 1 g of benzoyl peroxide were used. 12.7 g of hexasiloxane was obtained (yield: 24%).

bp 82 ° C / 0.2 mmHg MS: EI 463 (M ⁺ -1), 449 (M ⁺ -15), CI 482 (M ⁺
+ NH ₄ ) IR: 466 cm ^-1 (Si-Cl), 2128 cm ^-1 (Si-H) ²⁹ Si-NMR (heavy benzene, TMS standard, δ ppm): ¹ H-NMR (deuterated benzene, C ₆ H ₆ δ = 7.15 standard, δ ppm): 0.15 (s, 6H) 0.18 (bs, 24H) 0.34 (s, 6H) 4.96 (bs, 1H) Example 3 1-chloro -15-hydrogen hexadecamethyloctasiloxane [in the general formula (I), R ¹ = R ² = CH ₃ , n
= 6]: 1,15-dihydrogenhexadecamethyloctasiloxane 30 g, carbon tetrachloride 2.7 g and benzoyl peroxide 0.42 g
Was used in the same manner as in Example 1 except that 1-chloro-15-
Hydrogen hexadecamethyloctasiloxane 8.95
g was obtained (28.2% yield).

bp 113 ° C./0.18 mmHg MS: EI 523 (M ⁺ -15), CI 556 (M ⁺ + NH ₄ ) IR: 465 cm ^-1 (Si-Cl), 2128 cm ^-1 (Si-H) ²⁹ Si-NMR (heavy Benzene, TMS standard, δppm): ¹ H-NMR (Heavy benzene, C ₆ H ₆ δ = 7.15 standard, δ ppm): Example 4 1-Chloro-17-hydrogenoctadecamethylnonasiloxane [in the general formula (I), R ¹ = R ² = CH ₃ , n =
Synthesis of 7]: 38.5 g of 1,17-dihydrogenoctadecamethylnonasiloxane, 3.0 g of carbon tetrachloride and 0.48 g of benzoyl peroxide
Except that 1-chloro-17- was used in the same manner as in Example 1.
6.0 g of hydrogen octadecamethylnonasiloxane was obtained (15.6% yield).

^{bp 116 ℃ / 2 × 10 -5} mmHg MS: EI 671 (M + -15), CI 704 (M + + NH 4) IR: 466cm -1 (Si-Cl), 2132cm -1 (Si-H) 29 Si -NMR (Heavy benzene, TMS standard, δppm): ¹ H-NMR (Heavy benzene, C ₆ H ₆ δ = 7.15 standard, δ ppm): Example 5 Synthesis of 1-chloro-19-hydrogeneicosamethyldecasiloxane [In the general formula (I), R ¹ RR ² CHCH ₃ ,
n = 8]: 1-chloro-19-hydrogen was prepared in the same manner as in Example 1 except that 42.1 g of 1,19-dihydrogen eicosamethyldecasiloxane, 3.0 g of carbon tetrachloride and 0.47 g of benzoyl peroxide were used. 7.3 g of Geneicosamethyldecasiloxane was obtained (yield 17.1%).

bp 118 ° C./1.5×10 ⁻⁵ mmHg MS: EI 745 (M ⁺ −15), CI 778 (M ⁺ + NH ₄ ) IR: 466 cm ⁻¹ (Si-Cl), 2132 cm ⁻¹ (Si-H) ²⁹ Si -NMR (Heavy benzene, TMS standard, δppm): ¹ H-NMR (Heavy benzene, C ₆ H ₆ δ = 7.15 standard, δ ppm): [Effects of the Invention] As described above, according to the present invention, a novel method for producing a novel α-chloro-ω-hydrogenorganopolysiloxane having no distribution in chain length, which is useful as a silicone intermediate, is provided.

 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-58-4792 (JP, A) JP-A-3-95190 (JP, A) JP-A-3-135985 (JP, A) Journal of Organometallic Chemistr y, Vol. 44 No. 1P. 107-109 (1972) Journal of the American Chemical Society, Vol. 100 No. 20 p. 6362−6367 (1978)

Claims (2)

(57) [Claims] 1. The following general formula (II) (Wherein, R ¹ and R ² may be the same or different, and
An alkyl group, an alkenyl group, an aryl group, or a halogenoalkyl group, and n represents an integer of 3 to 10.) The α, ω-dihydrogen organopolysiloxane represented by the following formula: 32.9-33.7 relative to dihydrogen organopolysiloxane
% (Molar ratio) of carbon tetrachloride. (Wherein, R ¹ , R ² and n have the same meanings as described above), a process for producing an α-chloro-ω-hydrogen organopolysiloxane represented by the following formula: 2. The method according to claim 1, wherein the radical initiator is benzoyl peroxide.