DE1262484B - Lubricant based on alkanediol diorthosilicic acid (polyoxyalkylene glycol ether) esters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Int. Cl .:

ClOm

GERMAN

PATENT OFFICE

EDITORIAL

German class: 23 c -1/01

Number:
File number:
Registration date:
Display day:

1262484
R38336IVC / 23C
July 10, 1964
March 7, 1968

The silicic acid esters previously described as lubricants are resistant to hydrolytic attack not very stable. They are not viscous enough for important lubrication tasks; their viscosity is on average below 3 cSt at 98.9 ° C, and they show such considerable volatility that high evaporation losses arise.

Although the lubricity of silicic acid esters is better than that of other organosilicon compounds has not yet satisfied its pressure-absorbing capacity.

The invention is based on the object of developing silicic acid esters with a high molecular weight, which combine the good properties of high-molecular substances with a low low-temperature viscosity.

It has been found that lubricants meet these requirements if the diorthosilicic acid ester general formula

Lubricant based on alkanediol

diorthosilicic acid (polyoxyalkylene glycol ether) -

ester

Applicant:

Ruhrchemie Aktiengesellschaft,

4200 Oberhausen-Holten

Named as inventor:

Dr. Herbert Göthel, 4200 Oberhausen-Sterkrade; Dr. Hans Feichtinger, 4220 Dinslaken;

Dr. Heinz Noeske,

4200 Oberhausen-Sterkrade-Nord

wherein A radicals of alkanediols with 2 to 24 carbon atoms, R polyoxyalkylene glycol ether radicals with 1 to 4 ether oxygen atoms and R 'alkyl radicals with are more than 3 carbon atoms, μ is 0 to 4, where R and R 'can be the same or different, alone or in a mixture with up to 50% other known lubricants and additives. Diorthosilicic acid esters of the general formula are particularly suitable

R R

O O

ROSiOAOSiOR

O O

R R

and A (OSi) ₂ (OR) ₃ (ORO ₃

wherein A, R and R 'have the meaning given above.

The esters according to the invention with R and R 'substituents of 8 or more carbon atoms are water-resistant, in particular in the case of steric shielding of the SiOC bond. The boiling points are above 470 ° C at 260 Torr and about 200 ⁰ C at 0.015 Torr. Isononadecandiol-diorthokieselsäureester this type boiling above 535 ° C at 760 mm Hg or about 26O ⁰ C at 0.015 Torr.

Diorthosilicic acid esters according to the invention have not yet been described. You can choose any customary processes in a manner analogous to the previously known diorthosilicic acid esters be e.g. B. by reacting stoichiometric mixtures of the corresponding alcohols and ether alcohols with gaseous silicon tetrachloride according to German patent 1142 855. Their manufacture is not the subject of the protection request.

In order to demonstrate the advantages of the esters according to the invention, the properties are various in the table Esters according to the invention compared with those of known diorthosilicic acid esters of corresponding molar size.

For comparison there are the following known esters that have a formula

A (OSi) ₂ (ORO ₈
correspond.

I Ethylene glycol diorthosilicic acid hexa-iso-decyl-

ester,
II 2,2-dimethyl-1,3-propanediol diorthosilicic acid

hexa-iso-decyl ester,
V isononadecanediol - diorthosilicic acid - hexa-

(3,5,5-trimethyl-hexyl) ester,
VIII Ethylene glycol diorthosilicic acid hexa-iso-tridecyl ester.

Opposed to them are the esters according to the invention

III Ethylene glycol - diorthosilicic acid - hexa - (diethylene glycol n-butyl ether) ester,

IV 2,2-dimethyl-1,3-propanediol diorthosilicic acid hexa- (diethylene glycol n-butyl ether) ester,

VI Ethylene glycol diorthosilicic acid tri- (diethylene

glycol-n-butyl-ether) -tri- (iso-tridecyl) -ester,
VII 2,2-dimethyl-1,3-propanediol-diorthosilicic acid tri - (diethylene glycol - η - butyl - ether) - tri - (iso - tridecyl) ester,
IX Isononadecanediol - diorthosilicic acid - tri - (di-

Ethylene glycol n-butyl ether) tri- (iso-decyl) ester,
X Isononadecanediol - diorthosilicic acid - hexa - (diethylene glycol n-butyl ether) ester.

809 517/639

1-ä ο

O t / i ^?

¹ S §

.-ä po ο es Tf m φ μ ρ s η harmful effect on the viscosity temperature

3 4

OxO-C ₁₀ H ₂₁ , OxO-C ₁₃ H ₂₇ , OxO-C ₁₉ H ₃₈

oooo ° § ° §oo ° residues of alcohols produced by hydroformylation o "o" ο "©" ο "©" ο "ο" (Oxo synthesis) and subsequent hydrogenation of S £ Si η SSS trimer propylene, tetramer propylene and oleic acid er-5 were holding.

^The viscosity-temperature behavior and the

«Si vo

coN «si vor rH rt ve o Tf Tf

vo. vp C-C- "? * ■> ^ 7 ^ 7 Height of the viscosity indices of the invention

¹ .., .. '''''''' Ester is of the chain length and structure of the A-, R-

~ and R 'groups, as can be seen from the data of the

on t ~ - '- 00 «o - Tf vo 00 in ^ h c- ίο table emerges.

C— <o ο 00 ■ * vo ir \ cn vo vo ~. , _T,. , ·. · ,,,. . ,. .,,. «..

r-irH (Nr-i ^ HrHr-I, -1 -> rH When comparing ethanediol diorthosilicic acid esters with 2,2-dimethyl-1,3-propanediol esters with each

_ooo oo because the same R or R 'groups show that

"μ II § IR § - the ethanediol diorthosilicic acid esters have a higher ⁰⁰ " * Pi cn cn ¹ S viscosity index (cf. the well-known esters I.

and II as well as the esters according to the invention III and IV

5 ^ 1 cQ ^ Ιτίνο Tft ^ cn as well as III and VII). As the chain length of the ^> h c- Tf c- es> n substituents (A, R and R ') the viscosity index drops

from (compare the esters II with IV, VI with VII, VIII with IX

S _n vo _n oo _n Tf _n o _n es o _n Tf o _n 20 and X). The viscosity-temperature behavior of the- '

£ 3 S "Ω" S cn cn "es" vo es τ? "Like ester according to the invention is somewhat lower than the one with shorter A, R and R 'links, over-

ο cn ο 00 o \ c- τ? However, t- meets the well-known synthetic lubricant """ö""TT ff

Tf "cn" cn "vö" Tf "o" vo cT fabrics.

. 25 The influence of the oxyalkylene ether residues is

o S .oh SSS SSS behavior. Äthandiöl - ^ - Dimethyl-l ^ -propanediol-

ri -π- r-ir-i r-ir-irH r-ir-irH ^^ Isononadecanediol - diorthosilicic acid - hexa - (di-

vo vo ο ο vo cn cn vo cn ο Ethylene glycol n-butyl ether) esters have viscosity

indices of 208, 185 and 167. The values correspond

_r , -j approximately those of the respective hexa-n-hexyl ester.

ffi Concerning the vaporizability or the

öj boiling point behave the esters with diethylene glycol

W n-butyl ether groups (R groups) roughly like those with

; · J = ^ ₅ ■ 35 isodecyl groups.

W The decrease in viscosity indices caused by the

Q Incorporation of alkyl groups with a higher carbon number

3 sä - W s 5 sa occurs, is caused by the oxy-

g ο η? ^ k ^ L jl g alkylene ether residues (e.g. diethylene glycol n-butyl ether

OtS- (j U * U * U * U * 40 remainders as R groups) compensated. The inventive

g g Hj? g g g g possess esters with oxyalkylene ether residues

OO UOOOO therefore the advantages of the known esters with alkyl

groups with more than 8 carbon atoms, namely

low volatility and increased water tolerance

ϊύ K WK WK ⁴⁵ ^ ^e ^ » ^unc * ^na ^ ^{en to} the advantage of an excellent

Ü "<Jü" tS Ό Ό Viscosity-temperature behavior, as it is the silica

Pi α ά α ö ö acid esters with alkyl groups below 8 carbon

\ \ LL LL atoms is peculiar to. the

^ g · Q ~ 'S S "S" ^unc * ^ ^e I ^sonona decanediol diorthosilicic acid ester

ffl "trT irT W bf b? ⁵ ° ¹ ^ diethylene glycol n-butyl ether groups (R) and

U ₁ U ₁ UU U ₁ U _{1 have} oxotridecyl and oxodecyl as R 'groups

ffi 'ffl ¹ in? K * ffi "W Viscosity indices which are higher than those of the

Ö- w ö- ö / Si w known dibasic carboxylic acid esters, polyglycols,

Phosphate esters and other synthetic oils.
~ 55 As the molecular weight increases, the viscosity of the ester generally increases at the comparison temperature of 98.9 ° C. Esters with branched A-

C ₀ , c groups, as with those from neopentyl glycols

Κ W W, on the other hand, is less viscous than those with the smallest

^ ^ s; co ^ «ο α, ^6o alkylene bridge, namely ethanediol diorthodieselic acid

_M öf _N KW ₀₄ M «KW ester (see the table).

W ö W Si r ^ ffiö. Kf? ^ Are the R groups of the esters according to the invention

^^ ^ i ^ i i H, H, ^ όό Oxyalkylenätherreste, z. B. diethylene glycol-n-butyl-UU UU OUU UOO ether residues, the toughness falls compared to the

65 corresponding esters. The humiliation works

have a very beneficial effect on the low-temperature viscosities that

^l ~ ¹ '-' Ηίί ^^ - g BXX can be measured at -40 and -54 ° C. Ethanediol

> and 2,2-dimethyl-1,3-propanediol diorthosilicic acid

hexa- (diethylene glycol-n-butyl ether) ester (III and IV) have at -54 ⁰ C viscosities that are far below the limit of 13000 cSt, the via for dibasic Carbonsäureester serving as aircraft gas turbine oils, in the range 3 cSt ^{must be at 98.9 0} C (see specification Mil-L-7808 D *). The same applies to the isononadecanediol diorthosilicic acid hexa- (diethylene glycol n-butyl ether) ester (X), the viscosity of which at -4O ⁰ C is also well below the limit of 1300 oCSt. The specification is D. Eng for this ester with the viscosity of about 7.5 cSt at 98.9 ⁰ C. RD 2487 ** decisive.

The alkanediol diorthosilicic acid hexa-oxyalkylene ether esters according to the invention with molecular weights below 900, such as ethanediol and 2,2-dimethyl-1,3-propanediol diorthosilicic acid hexa (diethylene glycol butyl ether) esters, have very good properties low cold viscosities at -40 and -54 ⁰ C. They are at -54 ° C below 250OcSt. Their viscosity indices are high at 209 and 180. ao

As a benchmark for the load-bearing capacity of the lubricating film or the pressure absorption capacity of the various Ester is used for the welding value, which in the four-ball

* Military Specification Lubricating Oil, Aircraft Turbine

Engine, Synthetic Base dated November 9, 1959.
** Directiorale of Engine Research and Development Material Specif, dated May 16, 1960.

See Gunderson-Hart, Reinhold Publishing Corp., 1962, pp. 155/156.

apparatus (VELA) according to Boerlage (Lexikon der Schmiertechnik, G. Voegtle Franckh'sche Publishing House Stuttgart 1964). The first number means the highest possible load in kilograms, which the tested oil film can withstand for 1 minute without change, while the second is the one Denotes the load at which the balls are welded together.

The esters according to the invention can also be mixed with mineral lubricating oils, dicarboxylic acid esters, phosphoric acid esters, Organosilicon compounds of other structure are mixed. It can be common to them Oxidation inhibitors and active ingredients are added.

Claims (1)

Claim: Use of diorthosilicic acid esters of the general formula A (OSi) ₂ (OR) ₆ - "(OR% wherein A is radicals of alkanediols having 2 to 24 carbon atoms, R is polyoxyalkylene glycol ether radicals with 1 to 4 ether oxygen atoms and R 'alkyl radicals with more than 3 carbon atoms, η is 0 to 4, where R and R 'are identical or different can be, alone or in a mixture with up to 50% other known lubricants and additives as lubricants. 809 517/639 2.68 © Bundesdruckerei Berlin