DE2046782A1 - Soap-filled dimethyldiphenylpoly siloxane grease - Google Patents

Description

Dr. rer. near Horst pupil

PATENT ADVOCATE

6 Frankfurf / Main 1, September 21, 1970 Nidcfastraße 52 Dr.Fu / ro

Telephone (0611) 237220 Postscheck-Account: 282420 Frankfurt / M. Bank account: 523/3108 Deutsche Bank AG, Frankfurt / M.

16O5-8SI-942

GENERAL ELECTRIC COMPANY, 1 River Road Schenectady, N.Y., U.S.A.

Soap-filled dimethyldiphenylpolysiloxane grease

The present invention relates to a relatively narrow range of polyethers having the following formula:

(D

CH.

In the formula, A denotes an alkyl radical having 1 to 14 carbon atoms which can contain up to one hydroxyl group, η is a number from 4 to 2000 with an average of 20 to

109 8 15/1762

The compounds can be added to dispersions of lithium soaps of higher fatty acids in organopolysiloxane fluids containing 5 to 50% phenyl and tetrachlorophenyl substituents.

The organopolysiloxane fluids have the formula:

(2) R _a ^Rl b ^Si0 4-ab

in which R is a monovalent alkyl radical, preferably methyl W , R 'is a phenyl or tetrachlorophenyl radical, b is a number from 0.05 to 0.5, the sum of a and b is 2.002 to 2.2. The liquids can have viscosities of 10 to 500 centistokes at 25 ° C.

When you consider certain polyethers and those corresponding to formula (2) If liquids are used, soap clumps will form, which cannot be dispersed during the subsequent grinding. However, if the polyethers according to the invention are used According to formula (1), the polyethers contribute when the first soap crystals form to wet them and to the Orienting liquid fibers so that they accumulate additional layers of liquid and t layers of soap can. The result is a soft but stable fat that looks very good and has good mixing and evaporation properties owns. In the absence of the special polyethers described, it is impossible to use the fat compositions in the same way marry.

It is therefore an aim of the present invention in manufacture to propose a polyether processing aid for fats, the mixing of higher fatty acid lithium soaps with organopolysiloxane fluids containing significant amounts of phenyl or tetrachlorophenyl substituents.

In accordance with the present invention, a particular group of polyethers can be used for blending higher fatty acid lithium soaps with organopolysiloxane fluids containing 5 to 50 percent phenyl or tetrachlorophenyl substituents. The polyethers have the formula

(D

CH

in which A is an alkyl substituent having 1 to 14 carbon atoms which can contain up to one hydroxyl group, η can be in the individual molecules are between 4 and 2000, but is on average as it is used in the mixture 20 to 40.

The alkyl radicals A have 1 to 14 carbon atoms and comprise e.g. methyl, ethyl, butyl, hexyte, decyl and dodecyl residues, preferably straight-chain alkyl radicals of this chain length. Up to one hydrogen substituent can be replaced by a hydroxyl group. As stated, the one is repetitive Polyether unit is a secondary propylene oxide unit and the average number of ether units in the chain is 20 to 40. However, the polyethers used are generally mixtures and individual molecules in the mixture can have η values between 4 and 2000.

The polyether is used in an amount of 0.5 to 3 parts per 100 parts of the organopolysiloxane fluid. Preferably, the amount of the polyether of formula (1) is 1 1/2 to 3 parts per 100 parts of the organopolysiloxane liquid. If more than 3 % is used, several undesirable properties arise in the fat, such as an excessive odor.

; α ^r )

Less than 1/2 part per 100 parts of the organopolysiloxane fluid are too small an amount to adequately wet the higher fatty acid lithium soap ..

The organopolysiloxane fluids used in accordance with the present invention are known compounds. These liquids have the formula

(2)

where R is a lower alkyl radical, preferably methyl, R 'can be a phenyl or tetrachlorophenyl radical, b is a number from 0.05 to 0.5, the sum of a and b is 2.002 to 2.2. The viscosity of the fluid in question

ο about

measured at 25 C, it can be between 10 and 500 centistokes.

The term "organopolysiloxane fluids" of the formula (2) includes numerous types and compounds, e.g. trimethylsiloxane units, Dimethylsiloxane units, methylphenylsiloxane units, Monomethylsiloxane units. The only requirement is that the ratio of the various siloxane units P is selected according to the formula (1).

The preferred liquid is made from recurring or sprinkled Units of the following formula formed:

CH,
(A) - Si 0,

and

10 :. ': ■', / ι 7 6 ο

^C 6 ^H 5

(B) Si O

6 5

or, in other words, dimethylsiloxane and diphenylsiloxane units. The particular arrangement of these units in the polymer chain of the liquid is not critical. The ends of the chain of the polymers are mainly trimethylsiloxy units.

The fat thickeners used in the mixture are known "Compounds and include the lithium soaps of higher fatty acids with 10 to 22 carbon atoms outside the Carboxyl group. The term "fat" as used here includes fat-like materials, the consistency of which is from. Completely flowing material to non-flowing solid substances. The consistency of the fats of the present invention depends on the amount of thickener used, the type of thickener and the polysiloxane liquid used away. For example, lithium soaps of higher fatty acids with 10 to 22 carbon atoms are used as thickeners use outside the carboxyl group, such as lauric acid, myristic acid, palmitic acid and stearic acid. Preferred The soaps used are lithium stearate and lithium myristate.

The amount of lithium soap used in the grease according to the invention is not very critical. It has been found, however, that the amount of thickener is normally from about 8 to 40 parts, preferably 20 to 25 parts based on 100 parts of the organopolysiloxane fluid should be.

In addition to the components mentioned above, additives that are usually used in silicone greases can also be added to the

1 ü '- ·, 1 1 7 6 2

Mixtures of the present invention may be present. Examples of such additives include antioxidants such as Amines, ζ · .Β. N-phenyl-alpha-naphthylamine, corrosion inhibitors, κ.Β. Zinc naphthenate and extreme pressure additives such as selenium disulfide and molybdenum disulfide.

Furthermore, as already mentioned, a small amount of a base should be present. The amount should be enough to make a weak maintain alkaline reaction. A suitable base for this is lithium hydroxide.

^ According to a preferred method for producing the inventive The polysiloxane liquid, the lithium soap thickener, the polyether dispersant and a small amount of a finely ground base such as lithium hydroxide heated to 204 to 260 C. Following the heating, the Pett mixture is cooled to room temperature and then marry.

The following examples illustrate the invention but no limitation.

example 1

In this example, the use of a polyether corresponding to formula (1) with that of a polyether not covered by the formula falling polyether. The following Table I contains the trade names of the compounds used. Following Table I, the structure of these compounds is explained. In each case a lot of 100 parts of dirnethyldiphenylpolysiloxane liquid used, wherein about 10 weight percent of the diphenylsiloxane group liquid duration. The viscosity at 25 ° C was about 100 to 125 centistokes. There were 40 parts per 100 parts of the liquid Lithium stearate and 5 parts of the processing aid (polyether) are used.

10:. / ι 7 κ?

In each case the components were einschliesslieh about 0.1% lithium hydroxide, based on the Dimethylsiloxydiphenylsiloxyflüssigkeit, thoroughly mixed and heated to about 232 ⁰ C. The mixture was then slowly cooled (about 2.4 ° C per minute) to 176 ° C, at which point about 1.5 % N-phenyl-alphanaphthylamine based on the polysiloxane fluid and an additional amount (140 parts) of the polysiloxane fluid were added with continued stirring. The slow cooling was continued and 0.6 % finely divided lithium hydroxide, based on the total amount of organopolysoxane liquid, was added at 93 ° C. With continued stirring, the fat was cooled to room temperature. The fat formed was milled three times with a Morehouse mill. Mixture 7 was extremely easy to process and produced little clumping due to lithium stearate conglomerates, while the other blends produced significant lithium sextene clumping when processed.

Table I.

attempt
No. Additive
Surname Fat appearance
before ver
grind %
Chatting out
(Bleed) % Verdamr: .. g
(24 hours
at 200 ⁰ C) 1 no addition bad 6.2 0.8 2 Pluracol V5 bad 0.0 1.4 3 PEG 750 pretty good 0.0 2.0 4th WL 660 pretty good 0.0 1.3 5 Carbowax 400 bad 0.0 3.5 β HB 2000 very bad - - 7th LB 1145 very good 0.2 0.9

The above substances have the following structure:

- / '5762

Attempt:
2

HO (C ₂ H ₄ O) ₂₄ (C ₃ H ₆ O) ₈ CH,

CH ₂ (OC

C - CH ₂ (OC ₃ H ₆ ) ₈ (OC ₂ H ₄ ) ₂₄ OH CH ₂ (OC ₃ H ₆ )

CH _x

CH

CH _x

CH-

OJCH ₂ -C

where η has an average value of 28.

From the table it can be seen that only experiment 7 according to the invention runs. It was the only attempt where the pettos look was acceptable prior to marriage, and so with it indicated that the lithium soap was desirably dispersed and wetted by the organopolysiloxane. Farther this experiment resulted in the only mixture whose outflow (fluid) and evaporation compared to that no polyether did not increase significantly. Even though

Au ^ ™ ·
a slight sweating (bleed) is observed, remains that

10:

; / 1 7 β 2

Difference between the polyether according to the invention achieved effect and the basic mixture 1 very clearly.

In addition, there were other problems when using the polyethers from the other attempts. For example, if the additive des Experiment 2 was used, there were large ones due to the presence of large soap lumps during the grinding process Difficulty pumping and handling the grease. On the other hand, after Experiment 7, the mixture could with conventional grease machines can be easily pumped and ground. There was also a remarkable improvement the fat structure.

Example 2

Another grease according to the invention was prepared using 100 parts of dimethylsiloxyphenylsiloxy-organopolysiloxane containing 40 % diphenylsiloxy units and having a viscosity of about 150 to 200 centistokes at 25 ° C. In the same way as described in Example 1, 30 parts of lithium stearate, 4 parts of the polyether used in Experiment 7 and about 0.1 part of finely divided lithium hydroxide were added. On cooling, a further 100 parts of the organopolysiloxane liquid and 2 parts of N-phenyl-alpha-naphthylamine and later a further 0.1 part of finely divided lithium hydroxide were added. The processing was extremely easy in all stages. Very few clumps formed

Example 3

To an amount of 100 parts of an organopolysiloxane consisting of dimethylsiloxy units and Methyltetrachlorphenylsiloxyeinheiten, 20 parts of lithium myristate, 1 ¹ ml of a polyether of the formula

10/176

(D)

CH-

35

and OjI part of lithium hydroxide was added. The number "35" in the above polyether formula means an average number of propylene oxide units, and not the number of propylene oxide units in each molecule of the polyether. The organopolysiloxane fluid had a viscosity of about 50 centistokes as measured at 25 ° C. It contained about 10 % tetrachlorophenyl units, so that b in the formula (2) is about O ₃ I, while R is a methyl radical and R ^{1 is} a tetrachlorophenyl radical. As the mixture cooled, another 100 parts of the polysiloxane liquid and 0.1 part of lithium hydroxide were added. Grinding is easy and the fat formed does not contain any noticeable lumps.

A special processing aid was thus shown, in particular a polyether formed au.s repeating polypropylene oxide units with an alkoxy and a hydroxyl end group for use in organopolysiloxanes containing phenyl or tetrachlorophenyl groups. While such a processing aid is not required if the phenyl group content is higher than described, are formed in experiments in the absence of the processing aid in the disclosed mixtures containing phenyl and tetrachlorophenyl substituents Compounds and lithium soaps of higher fatty acids cause significant amounts of clumping that the processing of the fats impossible with standard machines. In addition, through Use of the special polyethers to like the appearance of the fats

From "■

their switching properties (bleed) and evaporation are also decisive improved.

10

Claims (6)

Claims 1. A fat mashing consisting essentially of: (1) 100 parts of an organopolysiloxane liquid with the Average formula ^R a ^Rl b ^Si0 4-ab where R is a lower alkyl substituent, R ^{1 is a} phenyl or tetraehlorphenyl radical and b is a number from 0.05 to 0.5 and the sum of a and b is between 2.002 and 2 _S 2, (2) 8 to 40 parts of a lithium soap with a fatty acid 10 to 22 carbon atoms not belonging to a carboxyl group, (3) 0.5 to 3 parts of a polyether of the formula CH- wherein A is an alkyl substituent of 1 to 14 carbon atoms with up to one hydroxyl substituent means, and (4) a base in an amount sufficient to remove the fat to keep alkaline. 1782 20A6782 2. Fat mixture according to claim 1, characterized in that the polysiloxane liquid consists of dimethylsiloxy units and diphenylsiloxy units. 3. Pett mix according to claim 1 or 2, characterized characterized by having a polyether of the formula CH- -H in which η means 28 is used. 4. Fat mixture according to claims 1 to 3, characterized in that R 'is a phenyl radical and R is a methyl radical. 5. Fat mixture according to claims i to 3, characterized in that R ^{1 is} a tetrachlorophenyl radical and R is a methyl radical. 6. fat mixture according to claims 1 to 5, characterized in that the polyether in an amount of 1.5 to 3 % is used. 10 '!. , f 1 7 6 2