DE1248657B - Process for the preparation of vinyl acetylenesiloxanes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

int. Cl .:

C07 F 7/08 /

C07f

Number:
File number:
Registration date:
Display day:

German class: 12 ο - 26/03

1,248,657
J28528IVb / 12o
July 6, 1965
August 31, 1967

~ Λμ ~ αΛ ^ \ (

Method of manufacture
of vinyl acetylenesiloxanes

The invention relates to a process for the production of vinylacetylenesiloxanes, which can be used to obtain new types of organosilicon monomers and polymers for the production of resins, paints, Coatings, rubbers, elastomers, adhesives and other materials are suitable.

The production of vinyl acetylenesiloxanes by dehydrogenation of vinyl acetylenesilanols is known. This process has the major disadvantages that, firstly, only symmetrical disiloxanes and, secondly, its raw material base is limited because the vinylacetylenesilanols are difficult to access are.

The object on which the invention is based is to eliminate these disadvantages Development of a process for the production of vinylacetylenesiloxanes from easily accessible raw materials. According to the invention, this object was achieved by using vinylacetylene magnesium bromide with diorganosiloxanediols and the resulting ao compounds are reacted with organochlorosilanes.

In both reaction stages, the reactants are preferably in an equimolar ratio

used. The reaction stages follow the y

Scheme:

(CH ₂ = CH - C ξ C) - MgBr + HO (SiR ₂ O) ^ H > (CH ₂ = CH - C ξ C - SiR ₂ O) - MgBr

+ R '"SiCl ₄ _".

Applicant:

Irkutsky Institute Organicheskoi Khimii

SO AN SSSR, Irkutsk (Soviet Union)

Representative:

Dipl.-Chem. L. Zellentin, patent attorney,

Ludwigshafen / Rhine, Rubensstr. 30th

Named as inventor:

Mikhail F. Shostakovsky, Moscow;

Nikolai V. Komarov,

Jury V. Maroshin, Irkutsk;

Anastasia D. Lebedeva, Kustanaiskaya

(Soviet Union)

where R and R 'are hydrogen and / or organic radicals and η are the numbers 1, 2 or 3. The end product which precipitates out of the reaction mixture is purified by vacuum distillation.

The process according to the invention is illustrated in the following examples.

example 1

Pentamethyl (vinylethinyl) disiloxane (CH ₂ = CH - C = C) - Si (CH ₃ ) ₂ - O - Si (CH ₃ ) ₃

Magnesium bromovinylacetylene, which was prepared from 24.3 g (1 gram atom) of magnesium, 109 g (1 mol) of ethyl bromide and 52 g (1 mol) of vinyl acetylene in 250 ml of ethyl ether, is added to 59 g (0.8 mol) of dimethylsiloxanediol. The mixture is heated on the water bath for 12 to 18 hours, then cooled with ice water and treated with 108.5 g (1 mol) of trimethylchlorosilane with stirring. To allow the reaction to subside, the mixture is heated for a further 5 to 10 hours, then the precipitate is filtered off and this (CH ₂ = CH - C = C - SiR ₂ OV "SiR'n

washed with ether. The ether extract is combined with the filtrate and distilled.

The yield is 62.5 g (40%), bp. ₁₆ - 52 ° C, "o ⁰ = 1.4424, Z) ₄ ²⁰ = 0.8381, MR 62.69 (for C ₉ H ₁₈ O ₂ S calculated MR 60.73).

Example 2
1,1,2,3,3 - pentamethyl -1,3 - bis - (vinyläthinyl) - trisiloxane,

(CH ₂ = CH - C ξ C)

Si (CH ₃ ) ₂ —O — SiH (CH ₃ )

Lo- Si (CHg) ₂ - (C = C - CH = CH ₂ )

This compound is prepared according to Example 1 from 24.3 g (1 gram atom) of magnesium, 109 g (1 mol) of ethyl bromide, 52 g (1 mole) vinyl acetylene, 59 g (0.8 mole) dimethylsiloxane diol and 57.5 g (0.5 mole) methyldichlorosilane obtained in 300 ml of ether.

The yield is 44 g (36%), b.p. _{1) 6} = 80 to 8I ⁰ C, rfS = 1.4629, Z) ₄ ²⁰ = 0.9107, MR 89.07 (for C ₁₃ H ₂₂ Si ₃ O ₂ calculated MR 87.31).

709 639/578

Example 3

Tetramethyl-1,2-bis (vinylethhinyl) disiloxane
(CH ₂ -CH-C = C) - Si (CHg) ₂ - O - Si (CH ₃ ) ₂

'- (Cs C - CH: CH ₂ )

This compound is made from 4.86 g (0.2 gram atom) of magnesium, 21.8 g (0.2 mol) of ethyl bromide, 10.5 g (0.2 mol) of vinyl acetylene, 11.8 g (0.16 mol) of dimethylsiloxane diol and 28.8 g (0.2 mol) of dimethyl (vinylethhinyl) chlorosilane obtain.

The yield is 8.9 g (41.5%), b.p. ₅ = 84 ° C, V ² S = ■ 1.4732, D ₄ ²⁰ = 0.8915, MR 73.69 (for C ₁₂ H ₁₈ Si ₂ O calculates MR 72.54).

Example 4
Hexamethyl-1,3-bis (vinylethhinyl) -trisiloxane
(CH ₂ = CH - C s C) - Si (CHs) ₂ - O - Si (CH ₃ ),

O - Si (CH ₃ ), - (C = CH = CH ₂ ) This compound is made in the same way from 24.3 g (1 gram atom) magnesium, 109 g (1 mol) ethyl bromide, 52 g (1 mol) vinyl acetylene, 59 g (0.8 mol) of dimethylsiloxanediol and 64.5 g (0.5 mol) of dimethyldichlorosilane in 250 ml of ether.

The yield is 29.62 mg (24%), b.p. ₈ = 99 ⁰ C, n ² ₀ ^D = 1.4616, D ₄ ²⁰ = 0.9192, MR 92.23 (for Ci ₄ H ₂₄ Si ₃ O ₂ calculated MR 91.18).

Claims (2)

Patent claims: 1. A process for the preparation of vinylacetylenesiloxanes, characterized in that that one reacts vinylacetylenemagnesium bromide with diorganosiloxanediols and the obtained Reacts compounds with organochlorosilanes. 2. The method according to claim 1, characterized in that the reactants in both stages used in an approximately equimolar ratio.