CS225044B1 - The preparation of organo-siliceous esters - Google Patents

Description

The invention relates to a process for the preparation of organosilicon esters from phenyltriehlorsilane, polyesters of ethylene glycol ethers and monovalent alcohols suitable for the lubrication technique.

The preparation of the new esters is based on the available raw materials, a technological process without the use of solvents and hydrogen chloride acceptors.

Process for the preparation of organosilicon esters of theoretical composition corresponding to the formula ^C 6 ^H 5 ^c 6 ^H 5

R, 0

-Si-OCH ₂ CH ₂ O (CH ₂ CH ₂ O) _m O

-Si-OR,

STEED.

wherein R 1 to R 4 is an alkyl having a carbon number of 8 to 20, m is 0 to 5 and n is 1 to 20, the reaction of phenyltriehlorsilane and the corresponding alcohols consists in reacting phenyltrichlorosilane with said alcohols at 15 to 160 ° C. After completion of the reaction, nitrogen is bubbled through the reaction mixture, and after completion of the bubbling, a solution of sodium hydroxide in the alcohol used is added and the volatiles are distilled off.

The process is practically waste-free, since the release of dry hydrogen chloride can be returned to the production of silicones and the distilled front parts to the production of esters.

Modern lubricants for lubrication technology are mostly mixtures of substances, in order to achieve optimum properties, so far there is no known liquid that could itself meet the demanding requirements of lubrication technology.

The esters obtained are useful in the clear temperature range, have an excellent viscosity dependence on temperature, are readily miscible with mineral, diester, polyol ester and siloxane oils and have excellent dissolution additives. When tested for corrosive oxidation stability at 175 ° C from the presence of metals such as me3, steel, Al alloy, Mg alloy, and air bubbling for 72 h, they are virtually non-shock and corrosive.

The effect of not BSR rubber at 120 ° C in terms of bulk, mass e hardness is substantially weaker than that of diester e polyolester oils e is comparable to that of petroleum motor oils.

Reflectance of these new esters at 80% rel. The moisture content of 90 h did not exceed 0.20% by weight and is about the same as for diester or polyolester oils.

The esters intermediate strength tested on a 4-ball machine at 1420 rpm, at 20 ° C and at 200 ° C for 1 minute compared to the dloctylsebecety is significantly better in terms of the critical load in N, ie the following load at the area of the balls swung sharply.

These new esters, because of their excellent properties, can be used as capsule oils or hydraulic fluids, or as components thereof and for longer in the preparation of greases.

The following examples illustrate the preparation procedure.

Example 1

To a 6 L four-necked Keller flask equipped with a stirrer, thermometer, reflux condenser, admission funnel, heating bath, β manometer drain line, 1,200 g of 2-ethylhexanol and 186 g of ethylene glycol was charged and allowed to stir for 1 h. 270 g of phenyltrichlorosilane and finally 560 g of 2-ethylhexanol. The admission was controlled according to the pressure of the escaping hydrogen chloride and the heating was increased to rise to 100-120 ° C at the end of the admission. After the addition of the alcohol, a nitrogen stream was introduced to the bottom of the flask via a tube and with stirring and heating of the flask at 110-120 ° C, the acidity of the flask was reduced by about 1 hour to about 0.2 mg KOH / g. After determining the acidity, a calculated amount of saturated sodium hydroxide solution was added to the flask with stirring. The contents of the flask, having an acid number of 0.01 to 0.02 mg KOH / g, were transferred to a vacuum distillation apparatus and the volatiles were distilled off at 1500 Pe to a boiling point of 50 ° C. The distillation residue after filtering through the paper was clear and colorless, weighed 2094 g, n ² 1,4 1.4760, pour point -69 ° C, flash point 203 ° C, viscosity at 100 ° C 4.95 mm ² . with"'. at 50 ° C 1536 mm ² . s ”', at -40 ° C 6 358 mm ² . with an acid number of 0.03 mg KOH / g.

The ester obtained was subjected to further distillation at a pressure of 30 Pa to a boiling point of 220 ° C.

The condensate obtained had a freezing point of -70 ° C, a viscosity at ¹⁰⁰ ° C of 4.51 mm ² . s ”', at 50 ° C 3 1 λ

13,81 mra. distillation residue (460 g), pour point -55 ° C, flash point 229 ° C, n ²⁵ 1.4836, viscosity at .00 ° C 7.28 mm ² . s '', at 50 ° C 25.15 mm ² . s ^-1 , at -40 ° C 18 016 mm ² . with"'.

Example 2

Νθ of the apparatus and procedure of Example 1 were charged with 1,200 g of 2-ethylhexanol and 3.8 g of diethylene glycol ether, allowing 1,270 g of phenyltrichlosilane and finally 560 g of 2-ethylhexanol.

After ester neutralization, the front portions were distilled off at 2000 Pa to the reflux temperature

140 ° C β after filtration distillation residue (2 325 g) was clear, colorless, acid No 0.05 mg KOH / g, flash point 196 ° C, pour point -68 ° C, viscosity at, 00 ° C 4 , 31 mm ² . s ^-1 , at 50. ° C 12.81 mm ² . s ”, at -40 ° C 5 529 mm ² . s '', viscosity index, 64.

3

On the apparatus and procedure of Example 1, 400 g of 2-ethylhexenol and 106 g of diethylene glycol ether were introduced, 422 g of phenyltrichlorosilane were finally admitted, and finally 85 g of 2-ethylthioxenol. After ester neutralization, the front portions were distilled off at 2000 Pa to a temperature of 245 ° C. After replacing the receiver, it was distilled at 23 Pa for a longer temperature of 220 ° C. 34 g of condensate were obtained which was clear, colorless and had an acid number of 0.03 mg KOH / g,

1.4715, flash point 201 ° C, pour point below -70 ° C, viscosity at 100 ° C 3J7 mo ² . s ^- 'at 50 ° C 8.93 mm ^2nd s- ¹ , at -40 ° C 2 595 mm ² . s ^- '. The distillation residue after filtration was clear, slightly yellow, acid 0.02 mg KOH / g, n = 1.4832, flash point 215 ° C, pour point -55 ° C, viscosity at 100 ° C 7.78 mm ² . s ^- 'at 50 ° C 26.44 mm ^2nd

, at -40 ° C 23 283 viscosity index 187.

Example

300 g of 2-ethylhexanol and 317 g of diethylene glycol ether, 740 g of phenyltrichlorosilane and finally 285 g of 2-ethylhexanol were introduced on the apparatus and procedure of Example 1.

After ester neutralization, the front portions were distilled off at 2000 Pa to a boiling point of 245 ° C. The filtration residue (800 g) was clear, colorless, with an acid of 0.04 mg KOH / g, a freezing point at -20 ° C of 6 300 mm ² and 242 ° C.

57 ° C, viscosity at 00, viscosity index 184, flash point 203

C 13.16 mm. s, at 50 ° C 50.57 mm ⁴ -1 ° C;

390 g of 2-ethylhexanol, 3.8 g of diethylene glycol ether and 960 g of a mixture composed of 85% decanol and 15% dodecenol were added to the apparatus and procedure of Example 1, respectively, 270 g of phenyltrichlorosilane and finally 585 g of 2-ethylhexanol. After ester neutralization, the front portions were distilled off at a pressure of 1400 Pa to a boiling point of 210 ° C. The distillation residue was clear, slightly yellowish after filtration, having an acid number of 0.03 mg KOH / g, n ² ^ 1.4760, flash point 193 ° C, combustion temperature 243 ° C, pour point -61 ° C, viscosity at 100 ° C 4.98 mm ² . s ¹ , at 50 ° C 15.15 mm ² . ^s1 , at -20 ° C 586 mm ² . s- ¹ , at -40 ° C 4834 mm ² . . s ^-1 , viscosity index, 79.

Example 6

On the apparatus and procedure of Example 1, 1,200 g of 2-ethylhexanol and 450 g of triethyleliglycol ether were added, 1,270 g of phenyltrichlorosilane was added, and finally 560 g of 2-ethylhexanol. After ester neutralization, the front portions were distilled off at a pressure of 1800 Pa to a boiling point of 140 ° C. The filtration residue (2,444 g) was clear, colorless and had an acid value of 0.02 mg KOH / g, a flash point of 218 ° C, a freezing point of -6 ° C, a viscosity of 100 ° C of 6.99 mm ² . and, at 50 ° C, 21.87 mm ² . s ”\ at -40 ° C 12 093 mm. with a viscosity index of 208.

Example 7

400 g of 2-ethylhexanol and 300 g of triethylene glycol ether, 529 g of phenyltrichlorosilane and finally 86 g of 2-ethylhexanol were introduced on the apparatus and procedure of Example 1. After ester neutralization, the front portions were distilled off at a pressure of 200 Pa to a boiling point of 240 ° C. After replacing the receiver, it was distilled at 30 Pa for a further boiling point of 218 ° C.

70 g of a clear, colorless condensate with an acid number of 0.04 mg KOH / g, 1.4690, viscosities at 00 ° C of 3.43 mm ^{2 were obtained} . s', at 50 ° C 9.30 mm ² . s '', at -40 ° C 2 305 mm ² . with a viscosity index of 170, a flash point of 98 ° C, a pour point below -70 ° C.

The distillation residue after filtration (765 g) was clear, slightly yellowish, had an acid number of 0.03 g KOH / g, n ^ 1.4892, a flash point of 244 ° C, a freezing point of -40 ° C, a viscosity at 100 ° C. 63, 4 nm ² . at 50 ®C 249 aa ² . s- ¹ , at -20 ° C 29 427 mm ² . and “ ¹ , viscosity index 252.

Example 8

400 g of 2-ethylhexanol and 150 g of triethylene glycol were added to the apparatus and procedure of Example 1, 422 g of phenyltrichlorosilene were added, and finally 185 g of 2-ethylhexanol.

After ester neutralization, the front portions were distilled off at 2000 Pa to a boiling point of 250 ° C. After replacing the receiver, it was distilled at 26 Pa for a further boiling point of 215 ° C. 332 g of a clear colorless condensate were obtained with an acid number of 0.02 mg KOH / g, n ² 1,4 1.4690, a viscosity at 100 ° C of 3.43 mm ² . s ^- 'at 50 ° C 9.43 mm ^2nd s ¹ , at -40 ° C 2 264 mra ² . with ^-1 , flash point 197 ° C, pour point below -70 ° C.

The distillation residue after filtration (410 g) was clear, pale yellow, having an acid value in the skins at 100 ° C of 19.18 mm ² . s ^- 'at 50 ° C 9.43 mm ^2nd s', at -20 ° C 6, flash point 237 ° C, pour point -48 ° C, viscosity index 209.

Claims (1)

SUBJECT OF THE INVENTION 0.04 mg KOH / g, 812 mm ² . s ¹ , Process for preparing organosilicon esters of theoretical composition corresponding to the formula RjO. ^C 6 ^H 5 -Si-OCH ₂ CH ₂ O (CH ₂ CH ₂ O) _f ^C 6 ^H 5 Si-OR, ^LR 2 OR, wherein R1 to R1 is an alkyl having a carbon number of 8 to 20, m is 0 to 5 and en is 1 to 20, the reaction of phenyltrichlorosilene 8 with the corresponding alcohols, characterized in that phenyltriohorsilene is reacted with said alcohols at After completion of the reaction, nitrogen is bubbled through the reaction mixture, and after completion of the bubbling ee, a solution of sodium hydroxide in the alcohol used is added and the volatiles are distilled off. Severography, n Price 2,40 Kčs