Grease Compositions

The invention described herein may be manufactured or used by or for the Government of the United States for all governmental purpos- es without the payment of any royalty.

Technical Field

This invention relates to grease compositions having superior performance properties. In one aspect, it relates to poly (metal) phosphinates) that are particularly useful for thickening silicone fluids.

Background Art

In the past, inorganic polymers have been added to various fluids to obtain grease compositions. For example, as disclosed in U.S. patent no. 3,332,873, greases are made from phosphate esters by the addition of certain doubly bridged inorganic polymers coordinated with two unidentate ligands. According to U.S. patent no. 3,331,774, a diester liquid is converted to a grease by the addition of similar inorganic polymers consisting of doubly bridged chromium atoms coor¬ dinated with a hydroxyl group and a water molecule. U.S. patent no. 3,331,775 discloses that silicone fluids are converted to greases by adding a relatively low molecular weight doubly bridged chromium phosphinate polymer. And in U.S. patent no. 3,522,178, it is reveal¬ ed that grease compositions can be obtained by using triply bridged chromium atoms where the bridging groups are the anions of phosphinic acids.

In general, silicones show a weak response to the usual lubricity additives and oiliness agents. Also, silicones do not respond well to antiwear and extreme pressure agents, and the few additives that do show some response have an inadequate thermal stability. To ob- tain silicone greases with good properties, an additive is required that can function as a thickener and provide other properties as well without detracting from such characteristics as thermal stability, consistency, thickener-fluid compatability, drop point, and fluid

separation at elevated temperatures.

It is an object of this invention, therefore, to provide a thick¬ ening agent for silicone fluid that fulfills the above-mentioned re¬ quirements. Another object of the invention is to provide a grease composi¬ tion based on a silicone fluid that possesses good antiwear and ex¬ treme pressure properties.

Other objects and advantages of the invention will become appar¬ ent to those skilled in the art upon consideration of the accompany- ing disclosure.

Disclosure of Invention

The present invention resides in a grease composition based on a silicone fluid thickened with a poly (metal phosphinate) containing at least one XP(R)(H)X group, where X is oxygen or sulfur, and R is an alkyl or aryl radical. The poly (metal phosphinates) function as thickeners for silicone fluids to provide a grease having good anti- wear and extreme pressure properties. The effectiveness of the pres¬ ent poly (metal phosphinates) is attributed to the presence of the hydrogen atom attached to the phosphorus atom in the XP(R)(H)X group. Silicon fluids thickened with other poly (metal phosphinates) , which do not contain such a group, do not possess the outstanding proper¬ ties of the instant grease compositions.

The poly (metal phosphinates) used as thickeners in the grease composition of this invention can be represented by the following formulas:

(1) [XP(R )X] _c [XP(R)(H)X] _d or

(2) M^0 ₄ (0H) _χ [XP(R)(H)X] ₈ _ _χ , wherein M is trivalent chromium or iron, ' is tetravalent titanium, zirconium or hafnium, X is oxygen or sulfur, R is alkyl or aryl, R' is alkyl, R' ' is aryl, a and b are each zero, 1 or 2 and the sum of a and b is 2, c is zero, 1 or 2 and d is equal to 3-c, and x ranges from zero to 7.9. The R, R ¹ and R' ' radicals generally contain about 1 to 12 carbon atoms. Examples of such radicals include methyl, ethyl , t-butyl , hexyl , octyl , decyl , dodecyl , phenyl , tolyl , xylyl , naphthyl , and the like. From the foregoing, it will be understood that so long as the poly (metal phosphinate contains a XP(R)(H)X

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group other phosphinate groups may be present that do not have a hy¬ drogen atom attached to the phosphorus atom.

The poly (metal phosphinate) according to formula (1) above is synthesized by initially preparing a polymeric chromium (or iron) bis (phosphinate) in accordance with the procedure described by H. D. Gilman et al in Inorganic Syntheses, XVI, 89-92 (1976). As disclosed in this publication, a solution of a phosphinic acid and potassium carbonate in water-tetrahydrofuran is added with stirring to a solu¬ tion of a soluble simple chromium salt, such as chromium chloride, in water-tetrahydrofuran. The resulting mixture is brought to a boil and the tetrahydrofuran is allowed to evaporate. After most of the tetrahydrofuran has evaporated, additional water is added. Boiling is continued until a precipitate is formed that can be readily ground with a spatula. The precipitate is then separated, thoroughly washed with water, and then allowed to dry. The water-containing polymer obtained is then heated under a vacuum to constant weight, thereby converting it to a hydroxobis (phosphinate) polymer. The bisphos- phinate polymer is then reacted in a low boiling solvent, such as chloroform, with a hydrophosphinic acid having the formula R(H)P(X) XH, where R and X are as indicated hereinabove, resulting in the for¬ mation of a gel in the solvent. After standing for 15 to 60 minutes, the gel forms a viscous solution of the thickening agent of this in¬ vention. A hydrophosphinic acid may be used in preparing the bis- phosphinate in which case a polymer according to formula (1) is ob- tained in which c is equal to zero and d is equal to 3. Alternative¬ ly, a phosphinic acid having the formula R'R 'P(X)XH where R', R" , a, b and X are as indicated above, may be utilized alone or in admix¬ ture with a hydrophosphinic acid in preparing the bisphosphinate in which case a polymer a-cording to formula (1) is obtained in which c is 1 or 2 and d is 2 or 1.

When preparing a grease composition using a poly [chromium (or iron) phosphinate] of formula (1) as the thickener, the viscous solu¬ tion mentioned in-the preceding paragraph is added to the silicone fluid. The resulting mixture is then stirred while heating to a tem- perature of about 120°C whereby the solvent is evaporated and a grease is formed. The grease is then cured by heating at a tempera¬ ture ranging from about 150 to 250°C for a period of about 1 to 2

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hours. In general, the amount of thickener utilized is that which is sufficient to thicken the silicone fluid to a grease-like consistency. The amount utilized usually ranges from about 5 to 20 weight percent, preferably about 5 to 15 weight percent, based upon the weight of the grease composition.

The poly (metal phosphinates) according to formula (2) above are synthesized directly in the silicone fluid to be thickened to a grease composition. Initially, zirconium oxychloride (ZrOCl ₂ .8H ₂ 0) , or the corresponding titanium or hafnium compound, is dissolved in distilled water and then hydrolyzed with an ammonium hydroxide solution. After washing with distilled water, the wet hydrolyzed solid [Zr0(0H) ₂ 'XH ₂ 0] is then reacted at a temperature between about 80 and 110°C with a hydrophosphinic acid having the formula R(H)P(X)XH, where R and X are as indicated above, dispersed in the silicone fluid to be thickened. The reaction mixture is continuously stirred for a period of about 60 minutes while being maintained at a temperature of about 110°C. Dur¬ ing this heating period, any water separating from the reaction mix¬ ture is decanted off. The poly (metal phosphinate) that forms thick¬ ens the silicone fluid to a grease-like consistency. The grease is cured by heating at a temperature ranging from about 150 to 250°C for a period of about 1 to 2 hours.

The composition of the thickener can be varied by controlling the mole ratio fo zirconium oxychloride to hydrophosphinic acid. It is often preferred to utilize equimolar amounts in which case the poly (metal phosphinate) has the formula M ₄ 0 ₄ (0H) ₄ [0P(R)(H)0] ₄ , where M' and R are as defined above. In general, the amount of thickener that is formed in the silicone fluid is that which is sufficient to thick¬ en the fluid to a grease-like consistency. The amount usually ranges from about 20 to 35 percent by weight, preferably about 25 to 30 weight percent, based upon the weight of the grease composition.

The silicone fluids used as a base oil in forming the grease com¬ position of this invention are well known, commercially available products. The fluid is preferably a liquid polyorganosiloxane having a high phenyl content and diphenylmethylsilyl end groups. The poly- organosiloxanes can be produced by hydrolyzing and polymerizing a mixture of diphenylmethylchlorosilane, dimethyldichlorosilane and di- phenyldichlorosilane in a ratio of 1:1:1 according to procedures

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known to those skilled in the art. While the polyorganosiloxanes are generally a misture of polymers, a general formula representing the polymer mixture by an ideal molecule is as follows:

CH ₃ (C ₆ H ₅ ) ₂ Si0[(CH3) ₂ Si0] _χ [CC ₆ H ₅ ) ₂ Si0] _y Si(C ₆ H ₅ ) ₂ CH ₃₁ where x and y can be from 1 to 10 and higher. Other silicone fluids, such as poly (methylphenyls loxane) (Dow Corning 550 lubricant) can also be used.

A more complete understanding of the invention can be obtained by referring to the following illustrative examples which are not intend- ed, however, to be unduly limitative of the invention.

Example I

Preparation of Cr[0P(Me)(Ph)0] ₂ [0P(Ph)(H)0] - High Phenyl Content

Polysiloxane Grease ^—

A mixture of 7.58 g (0.02 mole) of Cr[0P( e)(Ph)0] ₂ 0H polymer (prepared by the procedure described in Inorganic Syntheses, XVI, 89 (1976)) and 2.85 g (0.02 mole) of Ph(H)P(0)0H was suspended in 60 ml of CHC , resulting in the formation of a gel, which after 20 minutes became a viscous solution. The solution was added to 163 g of high a phenyl content polysiloxane. The resulting mixture was agitated with a Z-blade stirrer and heated slowly to 120°C in an oil bath. As the solvent evaporated during heating, the solution became viscous and subsequently formed a grease. The oil bath was raised to 170°C and held at this temperature for 30 minutes. The grease was transferred to a beaker and cured at 200°C for 90 minutes followed by milling several times on a three-roll mill. The extreme pressure and other physical properties of the grease are set forth in Table I herein¬ after.

Example II

Preparation of Cr[0P(Me)(Ph)0], - High Phenyl Content Polysiloxane Grease

In a control run, a grease was prepared using Cr[0P(Me)(Ph)0] ₃ polymer as the thickener for high phenyl content polysiloxane. The polymer was prepared by the procedure described in Inorganic Synthe¬ sis, XVI, 89 (1976), using methylphenylphosphinic acid. The same conditions as described in Example I were followed in preparing the

grease except that it was cured at 250°C for 2 hours before mill ng. Extreme pressure and other properties of the grease are listed here¬ inafter in Table I.

TABLE I

Cr[0P(Me)(Ph)0] ₉ Cr[0P(Me)(PH)0] ₃ [0P(Ph)(H)0] ^ά Thickened

Base"> Thickened Grease Grease

Fluid Example II Example I

Wt Percent of Fluid 100 94 94

Wt Percent Thickener 6 6

Penetration (ASTM D 1403) .

Unworked ( _. Conv.to 346 347 D 217)

Worked (Conv. to D 331 347 217)

Drop Point (ASTM D >500 >500 566), °F

Oil Separation (FTMS 791-321)

Wt % after 30 hrs at 6.4 16.0

400°F

Oxidation Stability (ASTM D 942) Psig 0 ₂ pressure drop in 600 hrs, 210°F

Extreme Pressure Pro¬ perties (ASTM D 2596)

Wel d point , kg (AISI- C-52100 steel ) 126 250 160

(1 ) High phenyl content polysiloxane (MCO 66-21 ) ; 100°F viscosi ty , 240 cs ; pour point, +25°F.

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Exa ple III

Preparation of Zr _| 0 ₄ (0H) _| [0P(P )(H)0] _/| - High Phenyl Content Polysi¬ loxane Grease ^—

Zirconium oxychloride (ArOCl ₂ -8H ₂ 0) in the amount of 64.6 g (0.2 mole) was dissolved in distilled water (300 ml) and then hydrolyzed with 400 g IN NH ₄ 0H solution. The wet hydrolyzed solid [Zr0(0H) ₂ ^« xH ₂ 0] after being washed several times with distilled water was reacted with 28.2 g (0.2 mole) Ph(H)P(0)0H dispersed in 124 g high phenyl content polysiloxane between 80 and 110°C. The reaction mixture was continuously stirred for 60 minutes in a 110°C oil bath. During this heating period, a small amount of water separated from the reaction product and was decanted off. The thickened product was heated at 150°C to a constant weight and then milled several times on a three- roll mill. Evaluation data on the grease are shown hereinafter in Table II.

Example IV

Preparation of Zr ₄ 0 ₄ (0H).[0P(Me)(Ph)0 - High Phenyl Content Polysi¬ loxane Grease „ ^{— ~~}

In a control run, Zr,0 ₄ (0H) ₄ [0P(Me)(Ph)0 - high phenyl content polysiloxane grease was prepared. Except for using methylphenylphos¬ phinic acid instead of phenylhydrophosphinic acid, the same procedure as described in Example III was followed. Evaluation data are shown hereinafter in Table II.

TABLE II

Zr ₄ 0 ₄ (0H) ₄ - ^Z> W ^0H) ₄ - [0P(Ph)(H)0] ₄ [0P(Me)(Ph)0] ₄

Thickened Thickened

Base") Grease Grease Fluid Example III Example IV

Weight % of Fluid 100 70 70

Weight % of Thickener 30 30

Penetration (ASTM D 1403)

Unworked (Conv. to D 217) 256 275

Worked (Conv. to D 217) 279 282

Drop Point (ASTM D 566), °F >464 >464

Oil Separation

Wt % after 30 hrs at 400 °F 3.0 2.8

Oxidation Stability (ASTM D 942) #

Psig 0 ₂ pressure drop after 600 hrs at 212°F

Extreme Pressure Proper¬ ties (ASTM D 2596)

Weld Point, kg 126 250 282

Wear Prevention Charac¬ teristics (ASTM D 2266)

40 kg load, 1200 rpm, 167°F and 1 hr

Scar diameter, mm 3.75 1.91 2.44

(1 ) High phenyl content polysi loxane (MCO 66-21 ) ; 100°F viscosi ty , 240 cs ; pour point, +25°F.

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The data in Table I show the effect on certain properties of Cr [OP(Me)(Ph)0] ₃ -polys loxane grease after replacing one of the OP(Me) (Ph)0 groups with a 0P(Ph)(H)0 group. Thus, the date demonstrate that the grease containing a poly (chromium phosphinate) having a OP (Ph)(H)0 group possessed superior extreme pressure and oil separation properties. As shown by the data in Table II, the greases thickened with a poly (zirconium phosphinate) containing 0P(Ph)(H)0 groups pro¬ vided a significant improvement on wear scar diameter as compared to a grease thickened with a poly-(zirconium phosphinate) which did not contain such a group. It is thus seen that the poly (metal phosphin- ates containing at least one XP(R)(H)X group, where X is oxygen or sulfur and R is alkyl or aryl, are effective grease thickeners for silicone fluids.

As will be evident to those skilled in the are, modifications of the present invention can be made in view of the foregoing disclosure without departing from the spirit and scope of the invention.

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