DE1210843B - Process for the preparation of organosilicon compounds - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C07f

German KL: 12o - 26/03

Number: 1 210 843

File number: G 37883IV b / 12 ο

Filing date: June 4, 1963

Opening day: February 17, 1966

The invention relates to a process for the preparation of organosilicon compounds in general formula

ZO-

Si-O

* 7

R.
ZO-Si-Y

II

in which R and Z are as defined above and Y is a halogen atom or a hydroxyl group is, either alone or together with a compound of the general formula

Y-Si-Y R

III

hydrolysed and, if appropriate, condensed in a manner known per se, and if Y means a halogen atom in one of the reactants, worked in the presence of an HCl acceptor will.

Media such as these are preferably used in a projection arrangement in U.S. Patent 2,943,147.

A projection arrangement according to the United States patent cited above uses a deformable medium which has a high resistance and which is responsive to an electron beam which is speed modulatable. In general, one such device shown in FIG. 1 'of the drawing is shown an evacuated glass housing 10, which contains an electron gun 11 for generating an electron beam 13, which in a rectangular grid over the surface method for the production of
Organosilicon compounds

in which R is a methyl or phenyl radical, Z is a biphenylyl, naphthyl or phenoxyphenyl radical and η is an integer from 2 to 4, which is characterized in that a compound of the general formula

Applicant:

General Electric Company,

Schenectady, N. Y. (V. St. A.)

Representative:

Dipl.-Chem. Dr. rer. nat. G. Ratzei,

Patent attorney,

Mannheim, Seckenheimer Str. 36 a

Named as inventor:

James Gordon Murray,

Frederick Frank Holub, Scotia, N.Y .;

Matthew Joseph Smith, Schenectady, N. Y.

(V. St. A.)

Claimed priority:

V. St. v. America June 5, 1962 (200 074)

a transparent deformable medium 15 is deflected, which is in part 17 of the transparent Container is located; an enlarged view of this part of the assembly is shown in FIG. 2 shown. Of the Beam 13 is preferably speed modulated by a television signal, which acts on the deflection means (not shown) in the electron gun 11. The deformable Medium 15 has a central region 19 of reduced thickness in accordance with FIG the raster area of the beam 13, which is generated by the electrons of the beam 13, which from a conductive coating 21 on the inner surface of the container 17 are attracted. These Electrons also cause deformations in the surface of the deformable medium 15, wherein the amplitudes of which are a function of the number of times the beam 13 reaches the various locations on the surface of the medium 15 are electrons emitted. These deformations are used to To refract light from a light source 23 in an optical arrangement, as shown in the drawing is, wherein a lens 24 is present, which the light source 23 on the surface of the medium 15 by means of a rod and slot arrangement 25 on the surface of the medium 15. Another

609 908/341

Lens 29 forms the slits of arrangement 25 the bars of another bar and slot arrangement 31 in the absence of deformations in the Surface of the deformable medium. However, every deforming phase bends the light, so that this passes through the slots of the system 31 with an intensity which corresponds to the amplitudes corresponds to the deformations. The light which passes through the assembly 29 is through a projection lens 33 imaged on a screen 35 after being deflected by the mirror 37 became.

If a deformable medium, which belongs to the prior art, in the one in the drawing is used, the mean charge density exerts a force on the medium. 15 from which the surface tension of the superfluous medium outside the grid area overcomes and reduces the portion 19 of the medium 15 to a thickness of zero; under such conditions but no deformations can be formed, d. i.e. the arrangement is unusable for so long until the medium is replaced again.

U.S. Patent 2,943,147 states that that when the medium decreases in resistance with decreasing thickness, the portion 19 falls below the pressure of the charges does not decrease to a thickness of zero, but retains a thickness whose value a function of the magnitude of the charge density on the surface of the medium 15 is with decrease The resistance becomes the time constant for current to dissipate from the surface of the deformable Medium 15 to the coating 21 arranged underneath, resulting in an enlargement of the Current dissipation results, which reduces the charge density on the surface of the medium, whereby the Pressure is reduced somewhat. Eventually a state of equilibrium is reached in which the pressure the charges on the surface of the medium equals the pressure of the surface tension on the excess Medium that is around the grid is. In this state of equilibrium, then maintain the thickness. The charge density on the surface of the medium is due to the current dissipation never drop to zero, as the charge is continuously passed through the electrons of the Beam 13 is supplemented.

The deformable compounds described in the aforementioned U.S. Patent as a suitable medium are required to be transparent, to be able to withstand electron bombardment without significant decomposition, to be kept at the operating temperature which is between about 25 and 150 ⁰ C, one. Have a viscosity of approximately 100 to 50,000 cSt and that they do not degrade the conductive coating.

The medium must also have a resistance which is on the order of approximately ¹⁴ to 10 ^µ ohm-cm, with the mean resistance at the stable thickness being approximately approximately 10 ¹¹ ohm-cm.

However, it has been found that the known deformable liquids are not as stable as this is desirable because under the influence of an electron beam they tend to have a larger To get viscosity and since the viscosity with continuous use in the above Projection arrangement increases to a point where the formation of gel particles begins to eventually the deformable medium gels; of course this means that the device does not longer can be used with this particular deformable medium.

It has now surprisingly been found that a group of organic compounds, the Formula I given above correspond exceptionally well as deformable media in the above-described Projection arrangement are suitable. It doesn't just produce sharp, visible images Get good light intensity with these fluids, but these fluids stand out also characterized by an exceptionally low vapor pressure and by a much greater resistance to radiation, which is why they are in the presence of a Electron beam, which is used in the aforementioned projection arrangement for use, essential are more stable.

The organosilicon compounds produced according to the invention, which are in the projection arrangement described above can be used for longer periods of time to achieve a surprising and progressive effect remain used continuously without a significant change in the deformable Medium takes place, whereby the life of the projection arrangement is extended to a great extent will.

The surprising technical effect of the process products according to the present invention is further demonstrated in the following test report:

Comparative tests were carried out on the use of the following compounds as deformable ones Media carried out in projection arrangements:

1. [QHsSitCH ^ feO

2. [naphthyl-Si (CH3> _{2] 2} 0

3. [Biphenylyl Si (CH3) ₂ ] 2O

The connection denoted by the number 1 represents a deformable medium of the prior art represent, the compounds marked with the numbers 2 and 3 are deformable media, according to of the present invention.

The stability of these deformable media, which is crucial here, is thereby measured that one determines the amount of gas, which with an irradiation of a certain strength and certain Duration is developed. Compounds 1 to 3 were each exposed to the same irradiation, with the following results:

link

2
3

Amount of evolved gas in parts of the flower

0.22

0.052

0.059

From this result, it can be seen that conjugated aromatic substituents such as biphenylyl and naphthyl, a much greater resistance to radiation of the organosilicon compounds condition as a single phenyl group. From the table just given it can be seen that the stability of compounds 2 and 3 a

A multiple of that of the prior art compound 1.

The following examples illustrate the invention Preparation of a number of organosilicon compounds falling under the general formula I fall:

It should be noted that where the biphenylyl or phenoxyphenyl radical in the The compound used as a deformable medium is present, the phenyl radicals of the biphenylyl group and the phenoxy radical of the phenoxyphenyl group in both the ortho, meta and para positions with respect to the junction in the biphenylyl or phenoxyphenyl radical, as in formula I. shown can stand. The biphenylyl bonds are therefore with

indicated; the phenoxyphenyl bonds can be represented as follows:

The naphthyl radical can be bonded either in the a or ^ position.

example 1

1,3-di- (o-phenylphenoxy) -l, 3-diphenyl-1,3-dimethyldisiloxane

C ₆ H ₅ C ₆ H ₅

O - Si - O - Si - O
CH ₃ CH ₃

First, o-phenylphenoxyphenylmethylchlorosilane was prepared by adding a solution of 85.1 g of o-phenylphenol in benzene (180 ml of solution) within 40 minutes to a stirred mixture of 95.6 g of phenylmethyldichlorosilane in 250 ml of benzene and 39.6 g dry pyridine at 0 to 10 ⁰ C was given. The mixture was stirred for an additional 2 hours and then filtered. The filter cake was washed with benzene and the washing liquid was added to the filtrate, followed by removal of the benzene by distillation. The residue was then distilled under reduced pressure, giving 113 g of a product which boiled at 149 to 156 ° C./0.1 torr and was identified as o-phenylphenoxyphenylmethylchlorosilane. About 65 g of this chlorosilane were dissolved in 100 ml of benzene and 1.8 g of water (an amount sufficient to completely hydrolyze the silicon-bonded chlorine atoms) in 15.8 ml of pyridine were added within 2 hours at 20 to 30 ^° C. . The mixture was stirred for 18 hours, filtered off and the filter cake washed with benzene. The washing liquid and the filtrate were combined and fractionally distilled for the purpose of removing the benzene, a residue being obtained which passed over at 250 to 260 ° C./0.1 Torr. This compound was identified by being found to contain 77.0% carbon, 5.9% hydrogen and 9.7% silicon; the theoretical values are 76.72% carbon, 5.67% hydrogen and 9.44% silicon.

Example 2
C ₆ H ₅ C ₆ H ₅ C ₆ H ₅

O - Si - O - Si - O - Si - O

CH ₃

CH ₃

CH ₃

11.1 g of diphenylsilanediol were added in small portions within 20 minutes to 33.7 g of o-phenylphenoxyphenylmethylchlorosilane, which was prepared according to Example 1 and was dissolved in 100 ml of benzene and 10 ml of pyridine; the temperature was kept at about 20 to 30 ^{° C. during this addition.} After the resulting mixture was allowed to stand with stirring for about 18 hours, the product was filtered off, benzene was removed from the filtrate by distillation, and the residue was then fractionally distilled under reduced pressure to give a product having a boiling point of 273 to 276 ° C / 0.05 torr. The compound contains 75.9% carbon, 5.9% hydrogen and 10.2% silicon; the theoretical values are 75.71% carbon, 5.95% hydrogen, 10.62% silicon.

Example 3

1,5-di (o-phenylphenoxy) -1,5-diphenyl-1,3,3,5-tetramethyltrisiloxane

C ₆ H:

β ti ₅

C ₆ H ₅ C ₆ H ₅

Ο —Si —Ο —Si —Ο —Si —O
CH ₃ CH ₃ CH ₃

The o-biphenylyloxyphenylmethylchlorosilane required as an intermediate compound was prepared according to Example 1. It was then hydrolyzed by the fact that 130 g of this compound to a mixture of 100 g sodium bicarbonate and 400 ml of acetone was added thereto at -15 to -20 ⁰ C. This addition was carried out over 15 minutes and stirring of the mixture was continued for an additional hour at the same temperature. The resulting mixture was filtered off and the acetone removed under reduced pressure at room temperature. The resulting mixture was then heated at 0.5 torr and room temperature

constricted. The o-biphenylyloxymethylphenylsilanol was added ^{at 0 to 10 °} C. to a solution of 25.8 g of dimethyldichlorosilane and 31.6 g of pyridine in 200 ml of benzene within 45 minutes. The mixture was stirred for approximately 8 hours and then warmed to room temperature. The benzene was removed and the product subjected to fractional distillation under reduced pressure, whereby a liquid having Kp. _O o8 = 251-274 ° C and nf = 1.5876 was incurred. It was then stirred with solid sodium bicarbonate to remove small amounts of unreacted chlorosilanes; then the sodium bicarbonate was removed and the product subjected to fractional distillation to obtain a compound with Kp.o, os = 248-266 ⁰ C and nf = 1.5901 was incurred. The compound had ^{a viscosity of 900 cSt at 25 °} C. and contains 73.5% carbon, 6.3% hydrogen, 11.4% silicon and has a molecular weight of 613; the theoretical values are 71.8% carbon, 6.0% hydrogen and 12.6% silicon; the theoretical molecular weight is 669.

Example 4

1,3-di- (m-phenoxyphenoxy) -l, 3-diphenyl-1,3-dimethyldisiloxane

C ₆ H ₅ C ₆ H ₅
O - Si - O - Si - O
CH ₃ CH ₃

The chloromethylphenyldisiloxane "of the formula

C ₆ H ₅ C ₆ H ₅
Cl-Si-O-Si-Cl

CH ₃

CH ₃

was prepared by 18 g of water was added to a stirring solution contained in 709 g of methylphenyldichlorosilane in the same weight amount of diethyl ether at 10 ⁰ C within 3 hours. The ether was evaporated and the product was distilled under reduced pressure, the aforementioned chlorosiloxane passing over at 120 to 121.5 ° C / 0.02 Torr. - About 65.4 g of this chloromethylphenyldisiloxane were added dropwise to a reaction vessel over the course of 2 hours, which contained 88.4 g of m-phenoxyphenol and 34.8 g of pyridine in 200 ml of benzene as a solvent. After the mixture of ingredients was refluxed for 2 hours, the pyridine hydrochloride was filtered off and washed with benzene. The solvent was removed from the filtrate and distillation was carried out under reduced pressure to give 102.0 g of the above-identified compound. Bp 0.01 = 265 to 268 ° C, nf = 1.5943. The analysis of this

bond indicated that it contained 72.8% carbon and 5.6% hydrogen and had a molecular weight owned by 618; the theoretical values are 72.79% carbon and 5.47% hydrogen; the theoretical molecular weight is 627.

Example5

1,3-Di-0? -naphthyloxy) -l, 1,3,3-tetraphenyldisiloxane

C ₆ H ₅

C ₆ H ₅

O - Si - O - Si - O
C ₆ H ₅ C ₆ H ₅

is prepared analogously to the procedures described above, by, is reacted at about 0 ⁰ C at first 1 mol / S-naphthol with 1 mole of diphenyldichlorosilane in pyridine, which serves as a hydrogen halide, wherein jS-Naphthyloxydiphenylchlorsilan is obtained. This chlorosilane was then hydrolyzed with water in a manner known per se to give the compound indicated above.

Example 6

1,5-di- (a-naphthyloxy) -1,5-diphenyl-1,5,3,5-tetramethyltrisiloxane

C ₆ H ₅ CH ₃ C ₆ H ₅
O-Si-O-Si-O-Si-O
CH ₃ CH ₃ CH ₃

First was the a-naphthyloxyphenylmethylchlorosilane prepared according to Example 1, with a-naphthol now being used instead of o-phenylphenol became. The thus obtained α-naphthyloxyphenylmethylchlorosilane is used in a similar manner hydrolyzed as in Example 3, the a-naphthyloxymethylphenylsilanol is obtained. This silanol was then again, similar to Example 3, added to dimethylchlorosilane, the the same molar concentrations and the same conditions were observed.

In addition to the above-mentioned use, the polysiloxanes of the formula I can also be used as hydraulic and dielectric fluids are applied when thermal stability and Radiation resistance are required. Furthermore, the aforementioned compounds are because of their radiation resistance also useful for application forms in space.

The compounds of the formula can be used as deformable medium in the aforementioned projection arrangement with other suitable ones and preparations useful as a deformable medium are mixed. So can this Compounds with other organopolysiloxanes as described in U.S. Patents 2,258,221 and 2,258,222 are to be mixed; they can also be used in the U.S. Patent 2,943,147 to modify organopolysiloxanes disclosed.

Claims (1)

Claim: 10 Process for the production of organosilicon compounds the general formula ZO-- Si-O --Z in which R is a methyl or phenyl radical, Z is a biphenylyl, naphthyl or phenoxyphenyl radical and η is an integer from 2 to 4, characterized in that a compound of the general formula ZO-Si-Y
R. II in which R and Z are as defined above and Y is a halogen atom or a hydroxyl group is, either alone or together with a compound of the general formula Y-Si-Y
R. III hydrolysed and, if appropriate, condensed in a manner known per se, in which case, when Y in one of the reactants is a halogen atom, in the presence of one HCl acceptor is worked. 1 sheet of drawings 609 508/341 2.66 ® Bundesdruckerei Berlin