JPH0395190A - Production of alpha,omega-dichloroorganopolysiloxane - Google Patents

Abstract

PURPOSE:To obtain the subject polysiloxane having a definite and uniform siloxane chain length and useful as an intermediate for silicones by reacting dihydrogen organopolysiloxane with carbon tetrachloride in the presence of a metal chloride. CONSTITUTION:The objective polysiloxane of formula II is produced by reacting an alpha,omega-dihydrogen organopolysiloxane of formula I (R<1> and R<2> are H, alkyl, alkenyl, aryl or halogenoalkyl; (n) is 3-10) with preferably 100-500mol% (based on the compound of formula I) of carbon tetrachloride in the presence of preferably 0.01-10mol% (based on the compound of formula I) of a metal chloride (preferably palladium chloride) preferably at 10-40 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides an α. The present invention relates to a method for producing ω-dichloroorganoborisiloxane.

[Prior Art] α,ω-dichloroorganoborisiloxanes, in which cosiloxanes have chlorine atoms at both ends, are useful silicone intermediates widely used in the silicone industry. As a method for producing this α,ω-dichloroorganopolysiloxane, for example, a method of obtaining an oligomer by partially hydrolyzing and condensing dichlorosilane (J. Am.
hem. Soc. , 68, 358 (1946))
, a method of disproportionation of cyclic silicone and dichlorosilane using an appropriate acid/base catalyst (U.S. Pat. No. 3,101,
No. 361 and US Pat. No. 3,642,851) are known.

[Problems to be Solved by the Invention] However, since all of these methods involve equilibration reactions, the obtained α. The ω-dichloroorganoborisiloxane had a distribution in the siloxane liquid length. Therefore, α with a specific siloxane chain length. In order to obtain ω-dichloroorganoborisiloxane, it is necessary to use a roundabout method of fractionally distilling these quasi-compounds, and there is a problem in that it can only be obtained in an extremely low yield.

Therefore, α. ω
- As a method for synthesizing dichloroorganopolysiloxane, a method in which thionyl chloride is applied to a cyclic silicone has been reported (US Pat. No. 3,646,090). However, this method has problems in that thionyl chloride is complicated to handle and harmful sulfur dioxide is produced as a by-product.

Therefore, by a simple reaction operation, α having a specific siloxane chain length can be obtained without producing harmful substances as by-products. There has been a demand for the development of a method that can produce ω-dichloroorganopolysiloxane in high yield.

[Means for Solving the Problems] Under these circumstances, the present inventors have conducted extensive research to solve the above problems, and as a result, we have developed an α,ω-dihyde-diene organoborisiloxane having a certain siloxane chain length. We have completed the present invention by discovering that this objective can be achieved by substituting hydrogen atoms at both ends with chlorine atoms under reaction conditions that do not break bonds.

The present invention is shown by the following reaction formula.

(II) (In the formula, R1 and R2 represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a halogenoalkyl group, which may be the same or different, and n represents an integer of 3 to 10.) α. This invention provides a method for producing α,ω-dichloroorganoborisiloxane (■), which comprises reacting ω-dihydrodieneorganopolysiloxane (1) with carbon tetrachloride in the presence of a metal chloride. be.

The amount of carbon tetrachloride used in the production method of the present invention is
50 to 1000 mol %, especially 100 to 50 mol % based on I)
0 mol% is preferred.

As metal chlorides, chlorides of transition metals such as chromium, manganese, iron, cobalt, nickel, copper, palladium, platinum, and mercury; rare earth metals such as lanthanum; and non-transition metals such as tin, antimony, and lead are used. Palladium chloride is particularly preferred. The amount of metal chloride used is α. 0.0 for ω-dihydride diene organoborisiloxane (1)
01-10 mol%, particularly 0.01-10 mol% is preferred.

The reaction temperature ranges from O'C to the reflux temperature of the reaction solution, especially 10C.
A range of 40°C to 40°C is preferred.

After the reaction is completed, insoluble matter is filtered if necessary, and the filtrate is distilled to obtain α,ω-dichloroorganoborisiloxane (n).

α used in the production method of the present invention. The ω-dihydride diene organoborisiloxane (1) is produced, for example, by reacting a cyclic silicone (■), a chlorosilane (IV), and water in the presence of an inorganic solid compound according to the following reaction formula.

R2 R2 R2 (1) (In the formula, R', R2 and n have the same meanings as above) In the cyclic silicone (III) used in this reaction, the alkyl group represented by R1 and R2 has 1 carbon number.
~6, alkenyl groups include those with 2 to 6 carbon atoms, aryl groups include phenyl groups, and halogenoalkyl groups include carbon atoms substituted with 1 to 3 chlorine, bromine, or fluorine atoms. An alkyl group of number 1 to 6 is preferred. Specific examples include hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, hexaphenylcyclotrisiloxane, trimethyltrivinylcyclotrisiloxane, trimethyltriphenylcyclotrisiloxane, octamethylcyclotetrasiloxane, and tetramethylcyclotetrasiloxane. , octaethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, tetra(trifluorobrovir)tetramethylcyclotetrasiloxane, decamethylcyclobentasiloxane, dodeca Examples include methylcyclohexasiloxane.

Examples of the chlorosilane (IV) include dimethylchlorosilane, diethylchlorosilane, diphenylchlorosilane, and divinylchlorosilane. The amount of chlorosilane (IV) to be used is preferably about 2 to 10 times the mole, particularly 2 to 4 times, and more preferably about 3 times the mole of the cyclic silicone (I[I).

In addition, inorganic solid compounds used as catalysts include:
Those that are insoluble and uniformly dispersed in the reaction solution are preferred, such as silica gel, titanium dioxide, silica/alumina, and the like. Among these, silica gel is particularly preferably used.

The amount of inorganic solid compound used is cyclic silicone (III)
The amount is appropriately selected depending on the reactivity of the silicone and chlorosilane (rV), but it is preferably in the range of 1 to 50% by weight based on the cyclic silicone (III).

Furthermore, water is used in stoichiometric excess as raw flll1. That is, 1 to 5 for cyclic silicone (III)
The amount used is preferably in the range of 00 times the mole, particularly 5 to 20 times the mole.

A reaction solvent may or may not be used, but when hexamethylcyclotrisiloxane, which is solid at room temperature, is used as the cyclic silicone, it is preferably used to facilitate the reaction. Examples of the solvent used include hydrocarbon solvents that are immiscible with water, such as pentane, hexane, hebutane, benzene, and toluene.

This reaction is preferably carried out by adding chlorosilane (rV) to a mixture of the cyclic silicone (■), the inorganic solid compound, and water. The reaction time is cyclic silicone (
Although it varies depending on the reactivity of III), the reaction is usually completed in 1 to 5 hours at room temperature after addition of chlorosilane (IV). The resulting reaction solution is distilled under normal pressure, preferably under reduced pressure to separate unreacted cyclic silicone and chlorosilane, thereby obtaining αω-dihydrogenorganopolysiloxane (I).

Also, α obtained in this way. By repeating the process of converting ω-dihydrodiene organopolysiloxane into silane diol and reacting with chlorosilane (IV) to extend the siloxane unit by two, a longer chain α.
It is also possible to obtain ω-dihydride diene organopolysiloxane (1). Since cyclic silicones with n'=7 or more are difficult to obtain, this method is effective when the object is a chain.

[Examples] Hereinafter, the present invention will be explained in more detail by giving examples, but the present invention is not limited thereto.

Production Example 1 In an IA flask equipped with a dropping funnel, 100 g of hexamethylcyclotrisiloxane, 100 g of hexane, and 81 g of water were added.
and silica gel (Merck Kieselgel 60, 250)
~400 mesh) 5.0 g was charged. The flask was cooled with water, and 127.7 g of dimethylsiloxane was added dropwise over 30 minutes while stirring thoroughly. 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 filter, it was transferred to a separating funnel and washed twice with 200 ml of water, once with 200 ml of saturated aqueous sodium bicarbonate solution, and twice with 200 mQ of water. After completely removing water in the solution by azeotroping with benzene, it was distilled under reduced pressure to obtain 137.3 g of 1.9-dihydrodiene decamethylpentasiloxane (yield 85.5%). All of the methylcyclotrisiloxane had reacted.

b. p, 57°C 70.5mmHg MS: 355 (M”-1), 341 (M”-1
5) IR: 2128cm-'(SL-H)"
SL-NMR (heavy benzene, TMS standard. δppm)
:-6.73 (1.9-Si) -19.78 (37-Si) -21.57 (5-Si) 'H-NMR (heavy benzene, CsHs δ=7.15 standard. δppm): 0.16 (s, 18H) 0.18 (d 3Hz 128) 4.96 ~ 5.00 (bs, 21{) Production Example 2 Using octamethylcyclotel/lasiloxane as the cyclic silicone, Production Example 1 In almost the same way as 1.11-
Dihydrogendodecamethylhexasiloxane was obtained.

b. p. 81'C/0.16mmHgMS:
429 (M”-1), 415 (M”-15)! R
: 2128cm-'(Si-H)"Si-NMR
(Heavy benzene, TMS standard, δI) pr[l): -6
．． 74(1.11-Si) -19.81(3.9-Si) -2 1. 62 (5.7-Si)'H-NM
R (heavy benzene, C, H. δ=7.15 standard, δppm
) 0.18 (s. 12H) 0.19 (d, 2.1Hz, 12B) 0.21 (s.
, 12H) 5.00 (sept, 2.7Hz, 2H) Production Example 3 Production Example 4 4.96 (sept, 2.7Hz, 2H) Using decamethylcyclobentasiloxane as the cyclic silicone. ′! 1.13-dihydride dienetetramethylhebutasiloxane was obtained in substantially the same manner as in Preparation Example 1.

b. p. 107℃/2. OmmHgMS: 4
89(M"-15) I R: 2128cm-'(Si-H)"SL
-NMR (heavy benzene, TMS standard, δppm): -
6.75(1.13-Si) -19.83(3.11-SL) -21.64(5.7 9-Si) 'H-NMR (Heavy benzene, TMS group/$1δp
pm) :0.16(s, 12H) 0.19(d, 2.71{z, 12H) 0.20(
s. 12H) 0.21(s, 6H) 1.15-dihydrodiene hexadecamethylocucsiloxane was obtained in substantially the same manner as in Production Example 1, using dodecamethylocucsiloxane as the cyclic silicone.

b. p, 105℃70.14mmHgMS:
563(M"-15) I R: 2132cm-'(Si-H)"St
-NMR (heavy benzene, TMS standard, δppm)
: -6.68 (1.15-SL) -19.76 (3.13-Si) -21.58 (5.11-SL) -21.60 (7.9-Si) 'H -NMR ( Heavy benzene.C.H6 δ=7.1
5 criteria. δppmIO. 1? (s, 12H) 0.19 (d, 2.8Hz. 12H) Production Example 5 0.21 (s, 12H) 0.22 (s, 12H) 4.97 (sept, 2.8Hz, 2H) Production Example 6 0.16(s.12H) 0.18(d,2.7Hz.12H) 0.20(s.18}1) 0.21(s,12H) 4.95(Sept,2.7}1z , 2}1) 117-dihydeoctadecamethylnonasiloxane was obtained in substantially the same manner as in Production Example 1 using tetradecamethylsiloxane as the cyclic silicone.

b. p. 109°C/0, 14mm HgM
S: 637 (M"-15) IR: 2128cm-'(SL-H)"Si
-NMR (heavy benzene, TMS standard. δpptn)
:-6.68(1.17-Si)'H-NMR (heavy benzene, ctos δ=7.
15 standard, δppQl): Using hexadelytic methylcyclooctasiloxane as the cyclic silicone, Production Example 1
1,19-dihyde dieneicosamethyldecasiloxane was obtained in substantially the same manner as above.

b. p 136℃/0.014mmHgMS:
711 (M”-15) I R: 2134cm-” (Si-H)”SL
-NMR (heavy benzene, TMS standard. δppm): -
6.65 (1.19-Si) "I{-NMR (heavy benzene.CmHs δ=7.15
Standard, δppm): 0.17 (s, 12}!) 0.19 (d, 3Hz, 12H) 0.21 (s. 12H) 0.23 (s, 24H) 4.99 (Sept, 3} 1z , 2H) Example 1 84 strips of carbon tetrachloride and 0.15 g of palladium chloride were placed in a 200 ml flask purged with argon. While cooling with water and thoroughly stirring, 30 g of 1,9-dihydrodiene decamethylbentasiloxane was added dropwise over 1 hour. After the dropwise addition was completed, the temperature was returned to room temperature and stirring was continued for 2 hours. Next, the precipitated palladium metal was filtered, and carbon tetrachloride was distilled off from the obtained filtrate. The obtained liquid was distilled under reduced pressure to obtain 1,9-dichlorodecamethylpentasiloxane 2
7 g was obtained (yield 75.3%).

b. p. 72℃70.22mmHgMS:
El 409 (M"-15); CI 442 (l
J"+NH4)IR: 465cm-' (Si
-CQ)"Si-NMR (heavy benzene, TMS standard, δ
ppm) :3.87(1.9-Si) -18.83(3.7-Si) -20.97(5-SL) 'H-NMR (Heavy benzene, CaHs δ=7.1
5 criteria. δppm) 0.13 (s, 18H) 0.32 (s, 12H) Example 2 Example except that 100 mR of carbon tetrachloride, 0.16 g of palladium chloride, and 20 g of 1l1-dihydrogendomethylhexasiloxane were used. Similarly to 1, l,1
1-dichlorododemethylhexasiloxane 18.
9 g was obtained (yield 81%).

b. p. 94℃/0.1n+mHgMS:
El 483 (Mゝ-15), Cl 516 (M”
+NH. )IR: 466cm-' (Si
-CI2)”Si-NMR (heavy benzene, TMS standard.
δppm) :3.87(1.11-Si) -18.83(3.9-Si) -20.97(5.7-Si) 1}1 -NMR (Heavy benzene, C.H, δ= '!．
15 standard, δppm): 0.13 (s, 121{) 0.14 (s, !2H) 0.33 (s, 12H) Example 3 Earthworks [warm carbon ditetrachloride 100ml2, palladium chloride 0. 14g
18.1 g of 1,13-dichlorotetrademethylhebutasiloxane was obtained in the same manner as in Example 1 except that 20 g of 113-dihydrodienetetrademethylhebutasiloxane was used (yield: 80%). ).

b. p, 102℃/0.13mmHgMS:
El 557 (M”-15), CI 590 (M
”+NH4)I R: 466cm-' (S
t-CI2)" SL-NMR (1 benzene, TMS standard, δppm): 3.92 (1.13-Si) -18.83 (3.11-Si) -21.05 (5.9-Si) -21.41(7-Si)'H-NMR (heavy benzene, C8H. δ=7.15 standard, δppm) 0.20 (s, 30H) 0.32 (s, 121) Example 4 1,15 -dichlorohexadecamethyloctasiloxa carbon tetrachloride 52 ml2, palladium chloride 0.09
25 g of 1,15-dichlorohexadecamethyloctasiloxane was obtained in the same manner as in Example 1, except that 30 g of 1,15-dichlorohexadecamethyloctasiloxane was used (yield: 745%).

b. p. 121°C 70.2 mml {gMS:
El 631 (M“-15), Cl 666 (M
”+NH4)IR: 465cm-' (St
-Cfl)"Si-NMR (heavy benzene, TMS standard. δppm): 3.89 (1.15-Si) -18.83 (3.13-Si) -21.05 (5.11-Si) - 21.41 (7.9-SL) 'H-NMR (heavy benzene, CaHs δ=7.15 standard, δppm) 0.19 (s, 12H) 0.20 (bs 24H) 0.35 (s, 12 }1) Example 5 Carbon tetrachloride 50ml!, Palladium chloride 0.054g
and 117-dihydride, except that 10 g of octadecamethylnonasiloxane was used,
117-dichlorooctadecamethylnonasiloxane9.
4 g was obtained (85% yield).

b. p, 116℃/2.4X 10-'mn+l{
gMS: EI 705 (M"-15), Cl
740 (M"+NH.)I R: 466
cm-'(SL-CQ)"Si-NMR (heavy benzene, TMS standard, δppm): 3.97 (1.17-S
L) -18.76 (3.15-SL) -20.99 (5.13-SL) -21.38 (7.11-Si) -21.44 (9-Si) 'H -NMR (Heavyweight Benzene, C, H, δ=7.15
standard. δppm): 0.20 (bs, 42H) 0.35 (s. 12H) Example 6 Carbon tetrachloride 23.4 mffi, palladium chloride 0.
11.8 g of 1.19-dichloroeicosamethyldecasiloxane was obtained in the same manner as in Example 1 except that 16.7 g of 042 g and 1.19-dihydrogeneicosamethyldecasiloxane were used (yield 63 .1%).

MS: El 749 (M"-15). CI
814(M”+NH4)IR: 465c
m-'(SL-Cll)"Si-NMR (heavy benzene, TMS standard. δppm): 3.79 (1.19-
SL) -18.89(3.17-Si) -21.13(5.15-Si) -21.52(7.13-Si) -21.59(9.11-Si) "H-NMR (fflbenzene, C, }Ia δ=
7.15 Standards. δm)pm) 0.20(s, 24H) 0.21(s, 12}1) 0.22(s, 12H) 0.35(s, 12H) [Effects of the Invention] As described above, the present invention According to α., which has no distribution in chain length and is useful as a silicone intermediate. ω-Dichloroorganoborisiloxane can be obtained in high yield through simple reaction operations.

that's all b. p 150℃70.02cmHg

Claims (2)

[Claims] (1) The following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 and R^2 may be the same or different, a hydrogen atom, an alkyl group, an alkenyl group, aryl group or halogenoalkyl group, n is an integer of 3 to 10) is reacted with carbon tetrachloride in the presence of a metal chloride. The following general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1, R^2 and n have the same meanings as above) α, ω- Method for producing dichloroorganopolysiloxane. (2) The manufacturing method according to claim 1, wherein the metal chloride is palladium chloride.