US3457173A - Aqueous lubricants containing siloxane-polyoxyalkylene compositions - Google Patents

Description

US. Cl. 25246.3 12 Claims ABSTRACT OF THE DISCLOSURE The method of lubricating metal surfaces by applying an aqueous siloxane-polyoxyalkylene block copolymer. The aqueous lubricant may also contain an olefin polymer emulsion.

This application is a continuation of US. Ser. No. 514,104- filed Dec. 12, 1965 which is a continuation in part of US. Ser. No. 227,700 filed Oct. 2, 1962 and issued as US. Patent No. 3,234,252.

This invention relates to aqueous lubricant compositions containing certain organosilicon compounds.

Conventional lubricants are generally composed of an organic lubricant base fluid (e.g. a petroleum oil) to which may have been added one or more additives (e.g. anti-oxidants and corrosion inhibitors). Such organic base fluids are relatively costly and possess poor heat transfer properties which are particularly undesirable when the fluid is employed in a lubricant in operations where a great deal of heat is generated by friction (e.g. in cutting operations). In such operations the inability of the organic base fluid to dissipate the heat may have deleterious effects (eg. the fluid may volatilize and/or ignite).

Consequently, efforts have been made to develop lubricants wherein water comprises part or all of the base fluid since the inexpensiveness, good heat transfer properties and non-flammability of water obviates many of the disadvantages inherent in organic base fluids. The relatively poor load carrying and anti-wear properties of water have been overcome to some extent in aqueous lubricants by incorporating therein additives. However, prior efforts to develop aqueous lubricants have not been entirely satisfactory because of the properties of these additives. For example, some additives do not impart load carrying or anti-Wear properties to the lubricant that are adequate for the demands of many applications. Other additives are unstable or corrosive. Moreover, some conventional additives impart poor wetting properties to the lubricant or promote foaming and some additives must be employed in excessively large amounts to be effective.

It is an object of this invention to provide additives for aqueous lubricants that impart improved load carrying and anti-wear properties to the lubricant, that are relatively stable and non-corrosive, that do not impair the Wetting and anti-foaming properties to the lubricant and that can be employed effectively in relatively small amounts.

This invention is based on the discovery that copolymers composed of a siloxane moiety linked to a polyoxyalkylene moiety by a silicon to carbon bond can be em ployed as additives in aqueous lubricant compositions to achieve the aforementioned objects of this invention. It has also been discovered that the performance of the aqueous lubricant compositions can be further enhanced 3,457,173 Patented July 22, 1969 by the incorporation therein of a polyolefin in emulsified form.

The lubricant compositions of the present invention comprise an aqueous base fluid, a siloxane-oxyalkylene copolymer present in an amount in the range fo from about 0.0005 to about 0.1 part by weight, based on one part by weight of the base fluid. Optionally the compositions can also contain, in emulsified form, a polyolefin having molecular weight in the range from about 1,500 to about 25,000, present in an amount in the range from about 0.001 to about 0.1 part by weight per one part by weight of base fluid. When the polyolefin is present in the composition, it is preferred that the weight ratio of the siloXane-oxyalkylene copolymer to the polyolefin is about 1:1.

The base fluid for the lubricant compositions of this invention can be water or a water-organic fluid lubricant admixture. The organic fluid lubricant can be 1) a silicon-free polyoxyalkylene compound, (2) a dialkyl ester of an aliphatic dicarboxylic acid, (3) a hydrocarbon lubricating oil, (4) an ester of a polyhydric alcohol with a fatty acid or mixtures of the foregoing. Where the base fluid is a Water-organic fluid lubricant admixture, the weight ratio of water to the organic fluid lubricant preferably ranges from about 10:1 to about 1:2, respectively. The weight ratio of water to the organic fluid lubricant in the admixture should not be lower than about 1:2, i.e., the base fluid can contain water and up to about 2 parts by weight of the organic fluid lubricant per one part by weight water.

The siloxane-polyoxyalkylene copolymers that are useful in the compositions of this invention are of the class that are known as block copolymers. Block copolymers are composed of at least two sections or blocks, at least one section or block composed of one type of recurring units or groups (e.g., siloxane groups as in the copolymers useful in this invention) and at least one other section or block composed of a different type of recurring units or groups (e.g., oxyalkylene groups as in the copolymers useful in this invention). Block copolymers can have linear, cyclic or branched (crosslinked) structures.

The siloxane blocks in the siloxane-polyoxyalkylene copolymers employed in the compositions of this invention contain at least two siloxane groups that are represented by the formula:

4-b R Si (I) wherein R is a substituted or unsubstituted monovalent hydrocarbon group or a divalent hydrocarbon group and b has a value from 1 to 3 inclusive. Preferably, R contains from one to about thirty carbon atoms. The groups represented by R can be the same or different in any given siloxane group or throughout the siloxane block, and the value of b in the various siloxane groups in the siloxane block can be the same or different. The divalent hydrocarbon groups represented by R link the siloxane block to the oxyalkylene block. Each siloxane block contains at least one group represented by Formula 1 wherein at least one group represented by R is a divalent hydrocarbon group. The siloxane block has a ratio of hydrocarbon groups to silicon atoms from 1:1 to 3:1.

Illustrative of the unsubstituted monovalent hydrocarbon groups that are presented by R in Formula 1 are the alkenyl groups (for example, the vinyl and the allyl group); the cycloalkenyl groups (for example, the cyclohexenyl group); the alkyl groups (for example, the methyl, ethyl, isopropyl, octyl and dodecyl groups); the aryl groups (for example, the phenyl and naphthyl groups); the aralkyl groups (for example, the benzyl and the phenylethyl groups); the alkaryl groups (for example, the styryl, tolyl and n-hexylphenyl groups), and the cycloalkyl groups (for example, the cyclohexyl group). Illustrative of the substituted monovalent hydrocarbon groups that are represented by R in Formula 1 are the alkenyl, cycloalkenyl, alkyl, aryl, aralkyl, alkaryl and cycloalkyl groups having haogeu, cyano, amino, amido, salt, ester, (e.g. carbalkoxy or acyloxy), sulfur-containing (e.g. mercapto, SH) or nitro groups as substituent-s. Such R groups include the tetrafluoroethyl, trifluorovinyl, chloromethyl, gamma chloropropyl, beta cyanoethyl, gamma-cyanopropyl, cyanophenyl, gamma-amino propyl, delta aminobutyl, N betaaaminoethyl-gamma-aminopropyl, aminomethylphenyl, H NCOCH CH betacarbethoxyethyl, beta-carboxyethyl, MeOOC(CH gamma carbopropoxypropyl, CH COOCH CH CH =CHCOOCH CH beta mercaptoethyl, gamma-mercaptopropyl,

Cl C H SCH CH gamma nitropropyl and nitrophenyl groups. The monovalent silicon-bonded salt groups include the groups having the formulae:

cHawHmivHwHmoooH-HNwmai (derived from the dibutyl amine salt of oleic acid by reaction with a siloxane containing silanic hydrogen) and (derived from dibutyl tin methacrylate by reaction with a siloxane containing silanic hydrogen). Other monovalent silicon-bonded amide groups include those having the formulae:

C H3 (CHDtH (CH2) BCONMe;

(derived from N,N dimethyl oleamide by reaction with a siloxane containing silanic hydrogen) and (derived from N-allyl methylacrylamide by reaction with a siloxane containing silanic hydrogen). Such substituent groups can be used to impart additional desirable properties to the copolymers [c.g. increased lubricity (imparted by halogens), self-emulsifying properties (imparted by amide groups), anti-corrosion (imparted by amino groups), increased surface activity (imparted by CN, COOH and ester groups), and higher dielectric properties (imparted by N groups)].

Illustrative of the divalent hydrocarbon groups represented by R in Formula 1 are the alkylene groups (such as the methylene, ethylene, propylene, butylene, 2,2 dimethyl 1,3 propylene and decylene groups), the arylene groups (such as the phenylene and p,pdiphenylene groups), the alkarylene groups (such as the phenylethylene group) and the alkylene-aralkylene groups (such as the CH C H CH CH group and the -CH C H CH group). Preferably, the divalent hydrocarbon group is an alkylene group containing from two to four successive carbon atoms. Siloxane groups containing divalent hydrocarbon groups as substituents are illustrated by groups having the formulae:

3 (EH3 -CH2CHzSiOr.5, CH3CHCH2SiO1.5 and --CH2CHzSi0 5" These divalent hydrocarbon groups are linked to a silicon atom of the siloxane block by a silicon-to-carbon bond and to an oxygen atom of the oxyalkylene block by a carbon-to-oxygen bond.

The siloxane block in the siloxane-polyoxyalkylene copolymers useful in the compositions of this invention can contain siloxane groups that are represented by Formula 1 wherein either the same hydrocarbon groups are attached to the silicon atoms (e.g., the dimethylsiloxy, diphenylsiloxy and diethylsiloxy groups) or different hydrocarbon groups are attached to the silicon atoms (e.g., the methylphenylsiloxy, phenylethylmethylsiloxy and ethylvinylsiloxy groups).

The siloxane block in the siloxane-polyoxyalkylene copolymers useful in the compositions of this invention can contain one or more types of siloxane groups that are represented by Formula 1 provided that at least one group has at least one divalent hydrocarbon substituent. By way of illustration, only ethylenemethylsiloxy groups CH CzH4-Sii0 can be present in the siloxane block or the siloxane block can contain more than one type of siloxane yroup, e.g., the block can contain both ethylenemethylsiloxy groups and diphenylsiloxy groups, or the block can contain ethylenemethylsiloxy groups, diphenylsiloxy groups and diethylsiloxy groups.

The siloxane block contained in the siloxane-polyoxyalkylene copolymers useful in the compositions of this invention can contain tri-functional siloxane groups (e.g., mouomethylsiloxane groups, CH SiO difunctional siloxane groups [e.g., dimethylsiloxane groups, (CH SiO], monofunctional siloxane groups [e.g., trimethylsiloxane groups, (CH SiO or combinations of these types of siloxane groups having the same or different substituents. Due to the functionality of the siloxane groups, the siloxane block can be predominantly linear or cyclic or crosslinked or it can have combinations of these structures. When different types of siloxane groups, are present they can be alternating, in blocks, randomly distributed or in any other sequence.

The siloxane block contained in the siloxanepolyoxyalkylene copolymers useful in the compositions of this invention can contain organic end-blocking or chain terminating organic groups, in addition to the monofunotional siloxane chain terminating groups encompassed by Formula 1. By way of illustration, the siloxane block can contain such organic end-blocking groups as the hydroxyl group, the aryloxy groups (such as the phenoXy group), the alkoxy groups (such as the methoxy, ethoxy, propoxy and butoxy groups), the acyloxy groups (such as the acetoxy group), and the like.

The siloxane blocks in the siloxane-polyoxyalkylene copolymers useful in the compositions of this invention contain at least two siloxane groups that are represented by Formula 1. Preferably, the siloxane blocks contain a total of from five to twenty siloxane groups that are represented by Formula 1. That part of the average molecular weight of the copolymer that is attributable to the siloxane blocks can be as high as 50,000 but preferably it is from 220 to 20,000. If that part of the average molecular Weight of the copolymer that is attributable to the siloxane blocks exceeds 50,000 or if the siloxane blocks contain a total of more than twenty siloxane groups that are represented by Formula. 1, the copolymers are usually difficult to produce.

A siloxane block can contain, in addition to the groups represented by Formula 1, siloxane groups represented by the formula:

wherein R has the meaning defined in Formula 1, e has a value from 0 to 2, f has a value from 1 to 2 and (e-H) has a value from 1 to 3, inclusive.

The siloxane block can also contain, in addition to the groups represented by Formula 1, tetrafunctional groups represented by the formula:

wherein R is an unsubstituted monovalent hydrocarbon group as defined for Formula 1 and n has a value from to 3 inclusive. Illustrative of such groups are the SiO ethoxysiloxy, diethoxysiloxy, triethoxysiloxy and phenoxysiloxy groups.

The oxyalkylene blocks in the siloxane-polyoxyalkylene copolymers employed in the compositions of this invention each contain at least two oxyalkylene groups that are represented by the formula:

wherein R is an alkylene group. Preferably, the alkylene group represented by R in Formula 2 contains from two to about ten carbon atoms, and most preferably from two to three carbon atoms. Illustrative of the oxyalkylene groups that are represented by Formula 2 are the oxyethylene oxy-1,2-propylene, oxy-1,3-propylene, oxy-2,2- dimethyl-1,3-propylene, oxy-1,l0-decylene groups and the like.

The oxyalkylene blocks in the siloxane-polyoxyalkylene copolymers useful in the compositions of this invention can contain one or more of the various types of oxyalkylene groups represented by Formula 2. By way of illustration, the oxyalkylene blocks can contain only oxyethylene groups or only oxypropylene groups or both oxyethylene and oxypropylene groups, or combinations of the various types of oxyalkylene groups represented by Formula 2.

The oxyalkylene blocks in the siloxane-polyoxyalkylene copolymers employed in the compositions of this invention can contain organic end-blocking or chain terminating groups. By way of illustration, the oxyalkylene blocks can contain such end-blocking groups as the hydroxy group, the aryloxy group (such as the phenoxy group), the alkoxy groups (such as the methoxy, ethoxy, propoxy and butoxy groups), alkenyloxy groups (such as the vinyloxy and the allyloxy groups). Also, a single group can serve as an end-blocking group for more than one oxyalkylene block. For example, the glyceroxy group,

CHzCllHcHz Ill can serve as an end-blocking group for three oxyalkylene chains.

The oxyalkylene blocks in the siloxane-polyoxyalkylene copolymers useful in the compositions of this invention each contain at least two oxyalkylene groups that are represented by Formula 2. Preferably, each block contains from two to thirty of such groups. That part of the average molecular weight of the copolymer that is attributable to the oxyalkylene blocks can vary from 88 [for (C H O) to 20,000, but preferably it is from 132 to 15,000. Provided that each oxyalkylene block contains at least two oxyalkylene groups represented by Formula 2, the number of oxyalkylene groups and that part of the average molecular weight of the copolymer that is attributable to the oxyalkylene blocks is not critical, but those copolymers in which that part of the average molecular weight that is attributable to the oxyalkylene blocks exceeds 200,000 or that contain more than fifty oxyalkylene groups per block are less useful, e.g., they are too viscuos for convenient use in the formulations of this invention.

The siloxane-polyoxyalkylene copolymers useful in the compositions of this invention can contain siloxane blocks and oxyalkylene blocks in any relative amount. In order to possess desirable properties, the copolymer should contain from 5 parts by Weight to 95 parts by weight of siloxane blocks and from 5 parts by weight to 95 parts by weight of oxyalkylene blocks per 100 parts by weight of the copolymer. Preferably, the copolymers contain 5 parts by Weight to 40 parts by weight of the siloxane blocks and from 60 parts by weight to 95 parts by weight of 2 (3) B. Copolymers that contain at least one unit that is represented by the formula:

Clle l o o siG'o(G"0).G'sio C. Copolymers that contain at least one unit that is represented by the formula:

In the above Formulas 3, 4 and 5, G is a monovalent hydrocarbon radical, G is a divalent hydrocarbon radical, G" is an alkylene radical containing at least two carbon atoms, G is a hydrogen atom or a monovalent hydrocarbon radical free of aliphatic unsaturation and n has a value of at least tWo and c has a value from 0 to 2 in Formulas 3 and 4 and a value from 0 to 1 in Formula 5. In Formulas 3, 4 and 5, G can represent the same different radicals, n preferably has a value from 3 to 30 inclusive and G can represent the same or different radicals, i.e., the group (OG) can represent, for example, the groups! -(OC2H4) (OC2H4)(OC3H (OC H (OC H where p and q are integers having a value of at least one in any given molecule but may have average fractional values Where the formulae represent mixtures of copolymers. Copolymers of the latter classes can consist only of units represented by Formulae 3, 4 or 5 or they can consist of from 1 to 99 mole-percent of such units and from 1 to 99 molepercent of units represented by Formula 1 wherein R is an unsubstituted monovalent hydrocarbon group and b has a value from 1 to 3 inclusive.

The monovalent hydrocarbon radicals represented by G in Formulas 3, 4 and 5 can be saturated or olefinically unsaturated or can contain benzenoid unsaturation. Ilustrative of the monovalent hydrocarbon radicals represented by G are the linear aliphatic radicals (e.g., the methyl, ethyl and decyl radicals), the cycloaliphatic radicals (e.g., the cyclohexyl and the cyclopentyl radicals), the aryl radicals (e.g. the phenyl, tolyl, Xylyl and naphthyl radicals), the aralkyl radicals (e.g., the benzyl and beta-phenylethyl radicals), and the unsaturated linear aliphatic radicals (e.g., the cyclohexenyl radical).

Preferably, the G and G groups [included in the definition of R in Formulas 1 and l-a above] contain from one to about twelve carbon atoms and the G group [included in the definition of R in Formula 2 above] contain from two to about ten carbon atoms. When the G group is a monovalent hydrocarbon radical free of aliphatic unsaturation it preferably contains from one to about eighteen carbon atoms.

Illustrative of the divalent hydrocarbon radicals represented by G in Formulas 3, 4 and 5 are the alkylene radicals (e.g., the methylene, ethylene, 1,3-propylene, 1,4-butylene and 1,12-dodecylene radicals), the arylene radicals (e.g., the phenylene radical) and the alkarylene radicals (e.g., the phenylethylene radicals). In Formulas 3, 4 and 5, G is preferably an alkylene radical containing at least tWo carbon atoms.

Illustrative of the alkylene radicals containing at least two carbon atoms represented by G" in Formulas 3, 4 and 5 are ethylene, 1,2-propylene, 1,3-propylene, 1,6- hexylene, 2-ethylheXylene-1,6 and 1,12-dodecylene radicals.

Illustrative of the radicals represented by G" in Formulas 3, 4 and 5 are the saturated linear or branched chain aliphatic hydrocarbon radicals (e.g., the methyl, ethyl, propyl, n-butyl, tert-butyl and decyl radicals), the saturated cycloaliphatic hydrocarbon radicals (e.g., the cyclopentyl and cyclohexyl radicals), the aryl hydrocarbon radicals (e.g., the phenyl, tolyl, naphthyl and xylyl radicals), and the aralkyl hydrocarbon radicals (e.g., the benzyl and beta-phenylethyl radicals).

The copolymers employed in the compositions of this invention, particularly those containing at least one unit represented by Formulae 3, 4 r 5, can also contain at least one of the units represented by the formulae:

wherein R is an unsubstituted monovalent hydrocarbon group as defined above, R" is an unsubstituted monovalent hydrocarbon group as defined for R above, or hydrogen, g has a value from 3 to (or even up to 20) inclusive, It has a value from O to 2 inclusive, i has a value from 2 to 3 inclusive, and f has a value from 2 to 4 inclusive. Such copolymers can contain from 1 to 99 molepercent of units represented by Formulae 3, 4 or 5 and from 1 to 99 mole-percent of units represented by Formulae 6, 7, 8, 9, 10, 11, or 12. Alternatively such copolymers can contain from 1 to 98 mole-percent of units represented by Formulae 3, 4 or 5; from 1 to 98 mole-percent of units represented by Formulae 6, 7, 8, 9, 10, 11, or 12; and from 1 to 98 mole-percent of units represented by Formula 1 wherein R is an unsubstituted monovalent hydrocarbon group and b has a value from 1 to 3 inelusive.

The organic and inorganic acid salt groups produced from the groups represented by Formulae 6 and 7 and the -COOH groups produced by hydrolyzing the groups represented by Formula 11 can also be present in the copolymers employed in the compositions of this invention.

The following are representativeof the siloXane-polyoxyalkylene block copolymers useful in the compositions of this invention. In the formulas, Me represents methyl (CI-I Bu represents butyl (C H Et represents Me (Me LIB SIQ SIO S10 Me SID/I63 COPOLYMER II Me Me Me IVIBaSiO [SID] S10 SIC] MC 5,: I i z SiMe COPOLYMER III Me Me Me Mfmsio SIC] SiO SIC] Me 1.7 l 4,1 SiMe;

(CH2)a(O C2 4) "0M6 COPOLYMER IV 13.5 SiMe Me Me MiQaSiO [SID] Me a COPOLYMER VI C H 0 HzC HzNHCHnCHzNHa MeSiO (MezSiO) 4310 SIMS;

Me CH2CHz(O CzHOsOqS COPOLYMER VII Me C HalHCOOOzHMfi l\!I63SiOSi (M6) 0 Si (M02) O 510 HzCHzC Hz O C 4H8 2OII COPOLYMER VIII 0 H: C H; C H C N Me IMeSiOSK O SiMez) AOS IC Hz C Hz (0 (321103 0d:

llile Me COPOLYMER DQ C uHtN O 7; M13 LIQaSiOSi O SIQIB O SI(2)O fi l C H20 H: (O C 2H4)2OM6 ('1 lire COPOLYMER X CHZCHZO 0C CH3 Me LIBSIO Sio S KMez) O 51(4):)0i011z0 HKO 0 3H) 206M COPOLYMER XI OHzCHzGONH: 1H9 IVIBBSIOSIOSKMBZ) 0 SK 0 Z) 0 SIICHQC HIGH1( O 0211]): OH

ll le CH2GH2CH2(OC:H4)2OH COPOLYMER XII 1W0 [M (CHaCHzOhCHzC Has iolt COPOLYMER XIII [45 O (0117CHzOhCHzCHzSiOmh 9 COPOLYMER XIV SIiO M SiMes COPOLYMER XVI COPOLYMER XVII I Me SiO(MegSiO)z [C iHrKO CrHr) 18.5 C3110) 1.10 (CH2)aSli O] SiMea In the examples presented below, the specific copolymers appearing above are identified for brevity as Copolymer I, Copolymer 11, etc.

The polysiloxane-oxyalkylene block copolymers that are useful in the compositions of this invention can in general be prepared by two convenient methods. The first method, known as the metathesis process, involves forming a mixture of a siloxane polymer containing a siliconbonded, halogen-substituted monovalent hydrocarbon group and an alkali metal salt of an oxyalkylene polymer and heating the mixture to a temperature sufliciently elevated (e.g. preferably from 80 C. to 150 C.) to cause the siloxane polymer and the salt to react to produce the copolymer. This process can be illustrated by the following equation:

I SILOXANE-(OSIiR X) (MO)-OXYALKYI.ENE

SILOXANE- (O SiR O) FOXYALKYLENE rMX wherein R is a divalent hydrocarbon group, r is an integer that has a value of at least 1 and preferably 1 to about 4, X is a halogen atom, M is an alkali metal, SILOXANE denotes a siloxane block and OXYALKYL- ENE denotes an oxyalkylene block.

The second method, known as the addition process, involves forming a mixture of an organo-siloxane polymer containing a hydrogen-siloxy group (i.e., a

HSIF

group), an oxyalkylene polymer containing an alkenyloxy end-blocking or chain terminating group and a platinum catalyst (e.g. from 0.001 to 5.0 weight-percent based on the reactants of elemental platinum or chloroplatinic acid) and heating the mixture to a temperature sufficiently elevated (e.g. preferably from 90 C. to 170 C.) to cause the siloxane polymer and the oxyalkylene polymer to react to produce the copolyrner.

This process can be illustrated by the following equation:

OXYALKYLENE[O RSi 0-], SILOXANE wherein OXYALKYLENE, SILOXANE and r have the meaning defined for Formula 7, OR is an alkenyloxy group (such as the vinyloxy and the allyloxy groups) and R is an alkylene group containing at least two successive carbon atoms.

When the polysiloXane-oxyalkylene block copolymer contains silicon-bonded hydrogen atoms, i.e., contains two units represented by Formula 1-a hereinabove, the addition process is preferable. If the metathesis process is used, many of the silicon-bonded hydrogen atoms will undergo side reactions that are catalyzed by the alkali metal ions present in the reaction mixture.

When the copolymer useful in this invention contains olefinically unsaturated groups attached to silicon (for example, when R in Formulas 1 or 1-a above, is alkenyl or cycloalkenyl such as vinyl or cyclohexenyl) it is preferable to prepare these copolymers by addition of the alkenyloxy-end-blocked oxyalkylene polymer to a monomeric, hydrolyzable silane containing silicon-bonded hydrogen, followed by co-hydrolysis or co-condensation with other hydrolyzable silanes containing silicon-bonded hydrogen and silicon-bonded olefinically unsaturated hydrocarbon groups using conventional techniques known to those versed in the art. For example, reaction of with CH SiHCl in the presence of a platinum catalyst followed by cohydrolysis of the product with CH CHSi(CH )Cl CH SiHCl and (CH SiCl gives a copolymer of this invention containing units have the formulas [CH O (C H O) CH CH CH Si (CH O] and [CH SiHO], end-blocked with [(CH SiO] groups.

Siloxane-polyoxyal'kylene copolymers containing groups represented by Formulae 6 to 9, 11 and 12 are also readily prepared by addition reactions between copolymers containing groups represented by Formula l-a and suitable olefinically unsaturated organic compounds (e.g. N-allyl ethylene diamine, allyl cyanide, ethyl acrylate, allyl diethyl amine, ethyl methacrylate, vinyl acetate, trichlorostyrene and the amide of acrylic acid). In such addition reactions, known catalysts for addition reactions (e.g. platinum, chloroplatinic acid, amines, phosphines, etc.) can be advantageously employed and the process conditions conventionally employed in known addition reactions are applicable.

siloxane-polyoxyalkylene copolymers containing groups represented by Formulae 6 to 12 are also readily produced by the cohydrolysis and cocondensation of hydrogen alkoxysilanes [e.g. HSi(OC H and alkoxysilanes containing the appropriate organofunctional groups to produce a siloxane [e.g. (SiO (O NC H SiO which can then be converted to a siloxane-polyoxyalkylene copolyrner by reaction with a suitable alkenyloxy end-blocked polyoxyalkylene compound in accordance with the abovedescribed addition process. Conventional cohydrolysis and cocondensation procedures can 'be used in this method.

The organic lubricant base fluids that are suitable for use in the various compositions of this invention include the various conventional organic lubricant base fluids. Typical of suitable lubricants are silicon-free polyoxyalkyl ene compounds, dialkyl esters of aliphatic dicarboxylic acids, hydrocarbon lubricating oils and esters of polyhydric alcohols and fatty acids.

Among the silicon-free polyoxyalkylene compounds that are suitable for use as organic lubricant base fluids in the compositions of this invention are those represented by the formula:

GIH(OGII)nOGIII wherein G'", G" and n have the above-defined meanings. Illustrative of the compounds represented by Formula 1 are 4 9( a s)1o 4 9 a( s s)12 4 s and C3H1'7(OC3H5)14OC8H17. A preferred class of compounds represented by Formula 13 are those having a viscosity between 5000 and 12,000 centistokes at -65 F. and a viscosity between 2.5 and 3.5 centistokes at 310 F.

Among the dialkyl esters of aliphatic dicarboxylic acids that are suitable for use as organic lubricant base fluids in the compositions of this invention are those represented by the formula:

R"OOC(C H )COOR" wherein R" is an alkyl group containing from 6 to carbon atoms inclusive and p has a value from 6 to 10 inclusive. Illustrative of the compounds represented by Formula are C H OOC(CH COOC H ethylhexyl)sebacate and C H OOC(CH COOC H Among the hydrocarbon lubricating oils: that are suitable for use as organic lubricant base fluids in the compositions of this invention are the paraffini-c lubricating oils, naphthenic lubricating oils and mixtures of such oils. Illustrative of such hydrocarbon lubricating oils are those having viscosities which range from 30 Saybolt Universal Seconds at 100 F. to 100 Saybolt Universal Seconds at 210 F.

Among the esters of polyhydric alcohols and fatty acids that are suitable for use as organic lubricant base fluids in the compositions of this invention are the esters of alcohols such as glycerol, pentaerythritol and trimethylolethane and acids such as olcic acid, stearic acid, coconut fatty acids and Valerie acid. Such esters include those produced by reacting a polyhdric alcohol with a mixture of fatty acids.

The relative amount of the siloxane-polyoxyalkylene copolymer and the base fluid employed in the compositions of this invention for best results is not narrowly critical and can vary over a wide range depending upon such factors as the type of metals to be lubricated by the composition, the type of organic fluid lubricant, the type of copolymer, the temperature and load conditions under which the composition is to be used as a lubricant and similar factors. In general, from about 0.0005 to about 0.1 part by weight of the copolymer per one part by weight of the base fluid (i.e. the water and any organic fluid lubricant) are employed; but from about 0.01 to about 0.05 part by weight of the copolymer per one part by Weight of the base fluid are preferred. Similarly, the relative amount of Water and any organic fluid lubricant present in the base fluid for best results is not narrowly critical and it can vary widely depending upon such factors as the compatibility of the water and the organic fluid lubricant, economic conditions, the compatibility of the copolymer with the base fluid and the like. In general from 10 to 200 parts by weight of the organic fluid lubricant per 100 parts by weight of Water are desirable but from 50 to 130 parts by weight of the organic fluid lubricant per 100 parts by weight of water are preferred. The relative amounts of the copolymer, water and organic fluid lubricant other than those mentioned above can be employed but no commensurate advantage is gained thereby.

The siloxane-polyoxyalkylene copolymers employed in the compositions of this invention can be dissolved in the base fluid to form a solution or dispersed in the base fluid to form an emulsion or a suspension. Similarly, the water and the organic fluid lubricant can be in the form of a solution or an emulsion (i.e. either a water in organic fluid emulsion or an organic fluid in water emulsion).

The polyolefins, when present in an emulsified form, further enhance the properties of the lubricating compositions of this invention. A suitable polyolefin is one having molecular weight in the range from about 1,500 to about 25,000 and a melting point which preferably does not exceed about 200 C. Typical of such polyolefins are the homopolymers and copolymers of an alpha olefin containing from about 2 to about 12 carbon atoms. Because of their emulsifiability, polyoleflns containing on the average at least one polar group for every four polyolefin molecules are preferred.

The polyolefins may be obtained within the aforementioned molecular weight range by direct polymerization, emulsion polymerization, or by the pyrolysis of a higher molecular Weight polyolefin.

The latter technique is preferred since the pyrolysis of the relatively higher molecular weight polymers creates terminal vinyl unsaturation which is readily available for reaction with an ethylenically unsaturated polar monomer such as maleic anhydride or thioglycolic acid, as taught by US. Patents 2,766,214 and 3,144,348, thereby rendering the resulting polyolefin readily emulsifiable.

Another valuable technique for the preparation of emulsifiable polymers having a suflicient number of polar groups is by oxidation, with or without a catalyst, so as to create pendant carboxylic groups on the polymer chain along with ketone, aldehyde, and hydroxyl groups. Other suitable emulsifiable polyoleflns are the block copolymers formed by reacting ethylene oxide with polyethylene so as to produce hydroxyl terminated polymers in accordance with the teachings of US. Patent 2,921,920. Also suitable polyolefins are the ethylene-alcohol telomers reacted with maleic acid as taught by US. Patent 2,7 66,- 214.

Similarly, the requisite amount of polar groups can be introduced into the aforementioned homopolymers and copolymers of alpha olefins by the copolymerization of the resulting polyolefins with unsaturated monomers containing the ethylene linkage such as ethylene acrylate, styrene, bicycloheptene, vinyl acetate, acrylic acid, and the like.

In addition, the direct polymerization to and/or hydrolysis of the olefin polymers mentioned above can impart the necessary amount of polarity to the polymer chain to make the polymers emulsifiable and the resulting emulsion stable.

Emulsion polymerization is generally carried out by emulsifying the olefin starting material in water by means of a suitable emulsifier and thereafter polymerizing the olefin at elevated pressures and temperatures in the presence of a polymerization catalyst. Illustrative emulsion polymerization processes are set forth in US. Patents 2,342,400; 2,542,783; 2,592,526; and 2,703,794.

The compositions of this invention can also contain freezing point depressants (preferably methanol or ethylene glycol) in an amount from 0.01 to about 2 parts by weight (per one part by weight of water in the composition). Preferably the freezing point depressant is present in an amount from about 0.01 to about 1 part by weight (per one part by Weight of water in the composition).

In addition, the compositions of this invention can contain, various other additives so as to impart particular properties to the lubricant compositions. Among such additives are corrosion inhibitors, anti-oxidants, blooming agents, oiliness agents, anti-wear agents, solubilizers, metal deactivators, extreme pressure additives, viscosity index improvers, pour point depressants, viscosity moditiers (e.g. glycerol), anti-foam agents, metal dcactivators, wetting agents, adhesive agents, cohesive agents, emulsifying agents, deemulsifying agents, break-in agents, sludge dispersants, anti-sludge agents, anti-coking agents, detergents, extreme pressure additives and swelling agents (where the composition comes into contact with rubber). Compounds such as (MEO OMe can be added as thickeners. The compositions of this invention can, if desired, contain the above-mentioned additional additives in amounts from about 0.001 to about .05 part by weight (per one part by weight of the base fluid) of each such additive. From about 0.005 to about 0.02 part by Weight (per one part by weight of the base fluid) of each such additive are preferred. These additives can be omitted entirely in may applications.

Suitable additional extreme pressure additives include graphite, talc, molybdenum sulfide, alkylamine salts of acid alkyl esters of phosphoric acid in which the amine salt constitutes at least 25 percent by weight, the alkyl groups here referred to containing from 8 to 18 carbon atoms each. Suitable additives coming within this group are dodecylamine dodecyl acid phosphate, blends made up of from 25 to 95 percent of dodecylamine dodecyl acid phosphate and from 75 to 95 percent of dodecyl dihydrogen phosphate, octylamine dioctyl phosphate, di (decylamine) dodecyl phosphate, hexadecylamine dodecyl acid phosphate, octadecylamine dioctadecyl phosphate, and blends containing 2-ethyl-hexylamine, 2-ethylhexyl acid phosphate and 2-ethylhexyldihydrogen phosphate in equal proportions. Suitable anti-wear additives include the amine salts of long chain aliphatic acids, neutral aryl phosphates and neutral alkyl aryl phosphates. Representative additives coming Within this grouping are triethanolamine laurate, the dipropylamine, dibutylamine, and diamylamine salts of lauric acid, triphenyl phosphate, tricresyl phosphate, butyl diphenyl phosphate, phenyl dibutyl phosphate, bensyl dicresyl phosphate, trixylyl phosphate and diphenyl cresyl phosphate. Suitable metal deactivator additives include quinizarin and alizarin.

The antioxidants that are useful in the compositions of this invention include 1) aromatic compounds that contain at least one substituent group that causes the compound to be susceptible to oxidation, (such as an amino, a hydroxyl or an alkoxy group) and (2) dialkyl selenides.

Illustrative of these aromatic antioxidants are such substituted aromatic compounds as primary, secondary and tertiary aryl amines (for example, diphenyl amine, n-phenyl-alpha-naphthyl-amine, N-phenyl-beta-naphthylamine and N,N' bis dinaphthyl-para phenylene diamine); hydroxy-substituted aromatic compounds including alkyl-substituted monohydric phenols (for example 2,6di(tert-butyl)4-methyl phenol and G-tert-butylmeta-cresol), aryloxy-substituted phenols (for example 2-(tert-butyl)4-phenoxy phenol), trihydric phenols (for example pyrogallol), dihydric phenols (for example 4- tert-butyl catechol, 4-phenyl catechol, 2.5-di(tert-butyl) hydroquinone, 3-methyl catechol and cyclohexyl catechol), di(hydroxyphenol)alkanes [for example bis-(2- hydroxy-3-tert-butyl-5-methyl phenol) methane], dihydric naphthols (for example, 1,5-dihydroxynaphthylene), hydroxyl-substituted aryl amines (for example ortho-aminophenol, and N-butyl-para-aminophenol) and aralkoxysubstituted phenols (for example hydroquinone monobenzyl ether); and dialkoxy-substituted aromatic compounds (for example, hydroquinone dirnethyl ether). The preferred aromatic antioxidants are the alkyl-substituted monohydric phenols such as 2,6-di(tert-butyl)4- methyl phenol and secondary aryl amines, such as N- phenyl-alpha-naphthylamine, N-phenyl beta-naphthylamine and N,N'-bis-dinaphthyl-para-phenylene diamine. In general, it was found that aromatic antioxidants containing amino groups, especially secondary amine groups, were more effective in stabilizing the compositions of this invention than aromatic antioxidants containing only hydroxyl groups as substituents.

The dialkyl selenides that are useful in the compositions of this invention as anti-oxidants include dihexyl selenide, didodecyl selenide, hexyl dodecyl selenide, di(2- ethylhexyl) selenide, dioctadecyl selenide, isooctyl hexadecyl selenide, and the like. In these compounds each alkyl group attached to the selenium atom preferably contains from 6 to 18 carbon atoms.

The corrosion inhibitors that are useful in the compositions of this invention include morpholine, the alkali metal nitrites (e.g. potassium nitrite and sodium nitrite), the alkali metal mercaptobenzothiazoles (e.g. the sodium salt of mercaptobenzothiazole), disalicylalpropylenediamine, amino-organosilicon compounds, alkali metal salts of carboxyorganosiloxanes, alkenylsuccinic acids, alkeuylsuccinic acid anhydrides, dialkyl acid phosphates, sorbitan mono-oleate, butyl stearate, butyl naphthenate and aluminum stearate.

Amino-organosilicon compounds that are useful as corrosion inhibitors in the compositions of this invention include both the amino-organo (hydrocarbonoxy) silanes and the amino-organosiloxanes wherein the organo group is a divalent hydrocarbon group containing at least three carbon atoms and wherein the amino group is connected to silicon through at least three successive carbon atoms of the organo group. Suitable amino-organo(hydrocarbonoxy)silane corrosion inhibitors include beta(aminophenyl)ethyltriethoxysilane, gammaaminopropyltriethoxysilane, N (beta aminoethyl)gamma-aminopropyltriethoxysilane and p-aminomethylphenyltriphenoxysilane. Suitable amino-organosiloxane corrosion inhibitors include homopolymers composed of beta (aminophenyl)ethylsiloxy, gamma aminopropylsiloxy N (beta aminoethyl)gamma aminopropylsiloxy or p-amino-methylphenylsiloxy groups as well as copolymers composed of one or more of the aforementioned amino-organosiloxy groups and one or more hydrocarbonsiloxy groups (eg methylsiloxy, dimethylsiloxy, trimethylsiloxy and triphenylsiloxy groups).

The alkali metal salts of carboxy-organosiloxanes that are useful as corrosion inhibitors in the compositions of this invention include alkali metal salts of carboxyalkylsiloxanes wherein the carboxy group is linked to silicon through at least two successive carbon atoms of the alkyl group. Such siloxanes include homopolymers composed of KOOCCHgCHzSiO KOOCCH CH SiO 5 NaOOCCH CH Si (CH O and LiOOC (CH Si a 5 2 0.5

groups as well as copolymers composed of one or more of these groups and one or more hydrocarbonsiloxy groups and/or one or more alkali metal-oxy substituted tetrafunctional siloxy groups [c.g. NaOSiO (NaO) SiO, (NaO) SiO KOSiO and LiOSi0 The alkeuyl succinic acids and anhydrides that are useful as corrosion inhibitors in the compositions of this invention are the reaction products of alpha-olefins (e.g. l-octene and l-pentene) and maleic acid or its anhydride. In these corrosion inhibitors the alkenyl group preferably contains from 8 to 12 carbon atoms. Illustrative of these corrosion inhibitors are octenyl succinic acid and its .anhydride and pentenyl succinic acid and its anhydride.

The dialkyl acid phosphates that are useful as corrosion inhibitors in the compositions of this invention preferably contain from 8 to 12 carbon atoms in each .alkyl group. Illustrative of such acid phosphates are dioctyl acid phosphate, didecyl acid phosphate and dilauryl acid phosphate.

The manner in which the compositions of this invention are produced is in no way critical. That is, the components of the compositions can be mixed in any convenient sequence and in any suitable apparatus. The techniques applicable to producing conventional aqueous lubricant compositions can be employed in producing the compositions of this invention.

The compositions of this invention are particularly suitable as lubricants for metal, especially as lubricants for ferrous metals, in metal cutting, forming and machining operations. In addition, these compositions are useful as hydraulic fluids, and as mold release agents for rubber and plastics. In the latter application, the compositions are applied to the molds in the usual manner for treating molds with conventional mold release agents.

3,457,173 I 15 re The following test was conducted on compositions of For comparison purposes, the results of Falex Wear this invention to evaluate them as lubricants. Tests using copolymer-free (Blank) aqueous lubricant compositions are also shown on Table '11. These blank compositions are illustrative of conventional aqueous lubricant compositions.

Falex load and wear test In this test the lubricant is evaluated in a Falex Lubricant Test Machine. The machine consists of a steel shaft All of the compositions tested contained 1.0 part of and two steel V-blocks that are positioned so that they morpholine and 1.0 part of potassium nitrite as corcan be forced against the shaft, The haft and the V- rosion 1nhibitors and 1.0 part of the dibutyl amine salt of blocks are immersed in the lubricant to be tested. The lauric acid as an additional lubricity-imparting additive. shaft is rotated and a load is applied to the V-blocks, 10 All parts are parts by Weight.

TABLE II Ethylene Copolymer K Wear Test Glye Polyoxy- Composition Water 1 Anti-freeze 1 alkylene 1 2 Type Amount Time (hrs.) Load (lbs.) Wear (mgs) 45.5 32.0 18.4 111 1. 3 200 14 45.5 32.0 13.4 V 1.0 1 1,000 45.5 32.9 18.4 In 1.0 1 1,000 13 35.0 40.7 18.4 III 1.0 1 1,000 35 45. 32. 9 1s. 4 None 3 200 22 45. 5 32. 9 1s. 4 None 1 1, 000 175 55. 3 40. 7 0. 0 1. 0 1 1, 000 55.3 40.7 0.0 III 1.0 1 1,000 10 55.3 40.7 0.0 III 1.0 1 2,000 24 50. 0 41. 0 0. 0 None 1 1, 000 32 1 All amounts indicated as parts by weight. 2 Having the average formula: HO(CHgCH O) (C3HO),,H, having a viscosity of 90,000 Saybolt Universal seconds at 100 F. and having a weight ratio of -CH2CH2O- to -C3HO- groups of 3:1. forcing them against the shaft. The load is increased until 25 EXAMPLE III failure occurs (i.e. seizure between the rotating shaft and the V-blocks or a radical increase in wear with no increase in load). The load at which failure occurs is the Falex Load value for the lubricant. The Falex Load values for various known fluids were determined as Several aqueous lubricant compositions of this invention were tested in the Falex Load Test at two temperatures. The compositions tested and the test temperatures are shown in Table III. The parts are parts by weight.

follows: TABLE III Fluid: Falex load (pounds) Copolymer Pam gg g C H (OC H OH 400 Composition yp Parts Water Fluid 1 Temp.,I 4 9( 3 0) 17.7 1250 1 8 3 r 77 Dimethylpolysiloxane oil 100 1 14 3 A refined petroleum oil having a viscosity of 1 30 a 122 about 44 SUS at 210 F. 500 1 99 0.0 A refined parafiinic hydrocarbon oil having a 5 0 0 97 viscosity of about 52 SUS at 210 F. 500 a l 1 5 II 1 99 0 0 The amount of wear was ascertamed by keeping the i 118 load on the V-blOCkS constant (e.g. at 200 lbs. 01' 1000 1 A mixture of 2 parts di-2-ethylhexyl sebacate and 1 part of a commercially available hydrocarbon lubricating oil that ha a viscosity of f a fixed Perlod of m'zne 1 or 3 hrs) The 44 Saybolt Universal Seconds at 210 F. and has an SAE viscosityof 10W. loss in weight of the rotating shaft caused by contact with the V-blocks is the Falex Wear value for the lubri- Failure seiizllm or P loss of the rubbing cant The loss of weight is measured in milligrams D faces by wear d1d not occur 1n any of the tests which were The following examples illustrate the present inven terminated at a load of 400 pounds in each of the lower tion: temperature tests and at a load of 800 pounds in each EXAMPLE I of the h1gher temperature tests. When pure water was tested, excessive wear occurred at a 200' pound load when Several aqueous lubricant compositions of this inventhe test temperature was 86 F. at a 250 pound load when tion were produced by simply mixing the indicated co the test temperature was 250 F. polymers with water or, in one case, with aqueous ethylene glycol. The compositions gave the following results EXAMPLE IV on the Falex load test: Copolymer V can be produced by reacting One mole 55 of allyl diethyl amine with one mole of a olymer having TABLE I P the formula Amount Failure (30- Load Me Me Me Copolymer polymer 1 (lbs.) 1

1 0 24 00 fi fi s uOGsHonOH ,0 1.0 3, 200 H M 5.0 1,500 3 E :23 81?, 8 The reaction is convemently conducted at a temperature 11 and W 1.0 4,9 of 100 C. employing 100 parts per million based on the H and IV fig Qggg weight of reactants of platinum in the form of chloro- 0.7 24,500 platinic acid as a catalyst and employing xylene as a i: g 2 it 238 Solvent. 4 2 0 li EXAMPLE v l Parts by weight per 100 parts by weight of water. No failure to this load at which time the testwas stopped. Copolymer VI can be produced by reacting one mole equa weig mixture H 4 equal amounts of water and ethylene glycol used in this run 0 of allyl ethylene dlamme with one mole of a Polymer having the formula EXAMPLE H H l The Falex Wear Test results with several aqueous Measiomegsiohsiosmeg lubricant compositions of this invention are shown in Table IL Me CH CHKOCQHQBOxfi 17 The reaction is conveniently conducted at a temperature of 110 C. employing 100 parts per million based on the weight of the reactants of platinum in the form of chloroplatinic acid as a catalyst and employing toluene as a solvent under reflux conditions.

EXAMPLE VI Copolymer VIII can be produced by reacting one mole of allyl cyanide with one mole of a polymer having the formula Me i l Me Si OSIi (OSiMez)iofiiCH CHfloCzHmOo Me Me The reaction is conveniently conducted at a temperature of 125 C. employing two hundred parts per million (based on the weight of the reactants) of platinum in the form of chloroplatinic acid as a catalyst and employing xylene as a solvent.

EXAMPLE VII Copolymer IX is readily prepared by equilibrating the appropriate methylsiloxanes, nitrophenyl(ethyl)siloxanes and methylhydrogensiloxanes in the presence of an acid catalyst to produce a polymer having silanic hydrogen and then reacting the latter polymer with the appropriate vinyl end-blocked oxyalkylene polymer according to the addition process described hereinabove to produce copolymer IX. Similarly, Copolymers V, VII, VIII, X and XI, as well as other copolymers having organofunctional substituents, can be produced by analogous two-step processes involving first the equilibration of the appropriate hydrocarbonsiloxanes, organofunctional siloxanes and hydrogensiloxanes to produce an Si-H containing siloxane which can then be reacted by an addition reaction with an alkenyl ether of an oxyalkylene polymer to produce the copolymer.

Copolymers containing organofunctional groups can also be prepared by equilibrating the appropriate hydrocarbonsiloxanes, chlorohydrocarbonsiloxanes and organofunctional siloxanes to produce a polymer that can be reacted through the halohydrocarbon groups therein with alkali metal salts of oxyalkylene polymers in accordance with the metathesis procedure described hereinabove.

EXAMPLE VIII Copolymer X can be produced by reacting one mole of vinyl acetate with one mole of a polymer having the formula i t McSiOSliOSKMez) OSi( 2)OSiCHzCH2(O OaHthOMe C2H Me The reaction is conveiently conducted at a temperature of 100 C. employing 50 parts per million (based on the weight of reactants) of platinum in the form of chloroplatinic acid as a catalyst and employing toluene as a solvent.

EXAMPLE IX Copolymer XI can be produced by reacting one mole of the amide of acrylic acid with one mole of a polymer having the formula The reaction is conveniently conducted at a temperature of 200 C. employing 250 parts per million (based on the weight of reactants) of platinum in the form of chlo roplatinic acid as a catalyst.

The evaluation of the following lubricating composttions was carried out using a Falex Tester where the test equipment comprises a replaceable At-inch diameter shaft (No. 8 soft steel pin) which is revolved at 290 r.p.m. between two steel V-blocks. The shaft can be machined from SAE 3135 steel having a Rockwell B hardness of 87 to a 8-10 RMS finish, and the two V-blocks can be machined from AISI C-1137 steel having a Rockwell C hardness of 20 to a 6-8 RMS finish (Method I). In the alternative, the shaft can be machined from M-2 tool steel having a Rockwell C hardness of 60 to a 12-14 RMS finish, and the two V-blocks can be machined from 440C stainless steel having a Rockwell C hardness of 60 to a 12-14 RMS finish (Method II).

The V-blocks are positioned so that they can be forced against the shaft by a notched loading wheel. The adjustment of the loading wheel during the test in order to maintain a predetermined load is indicative of the wear on the test shaft. The adjustment of each notch or tooth on the loading wheel indicates 0.000057 inch of wear of the test shaft.

During a test both the shaft and the V-blocks are immersed in the lubricant to be tested.

The operational steps during the test are as follows:

(1) the test is commenced by revolving the shaft between the V-blocks for 3 minutes at lb. load;

(2) the load is then increased each minute in 100 lb. in-

crements up to 1000 lbs.;

(3) after 1000 lbs. load is reached, further loading is done in 250 lb. increments each minute until seizure of a maximum load of 4500 lbs. is attained;

(4) torque and temperature are recorded each minute;

and

(5) during each one minute interval the wear on the test shaft is noted and recorded as the number of notches on the loading Wheel that have to be adjusted in order to maintain the desired load.

After the test the average scar width on the V-blocks is measured microscopically and the contact pressure in pounds per square inch calculated from the following:

gauge load seizure F2 bearing load, lbs. scar length, in. scar width, in.

=bearing load, lbs.

pounds per sq. inch scar length=0.5 inch EXAMPLE X sented in Table IV below.

TABLE IV Identification of Seizure Emulsifier Emulsion Type of Emulsion load, lbs. Type Carboxylated SBR 3,000

. Polyethylene 4,500 Nonionio.

0.2 wt. percent; Copolymer 1, 250

XVIII control.

The foregoing data indicate that the combination of an aqueous polyolefin emulsion with a siloXane-oxyalkylene copolymer provides a lubricating composition having very good load carrying and anti-weld properties.

EXAMPLE XI The effect of the addition of a siloxane-oxyalkylene copolymer to an aqueous polyolefin emulsion on contact pressures was determined in a Falex Tester employing Method II. The test results are reported in Table V below.

TABLE V Gage Avg Lubricant Tested 111 Water Load, Scar Contact Containing 0.1 wt. percent lbs, at Width, lrcssure, Gopolymer XVIII Seizure inches p.s.i.

0.1 wt. percent Additional Oopolymer XVIII l, 250 049 40, 000 0.1 wt. percent Emulsion F solids- 3,250 016 200,000 0.1wt. percent Emulsion A solids 4, 500 016 400, 000 D 4, 000 014 400, 000 0.1 wt. percent Emulsion I solids 2, 750 021 100, 000 0.1 wt. percent triethanolaniine luuratc (soap) 2, 500 012 300, 000

Proof of synergism0omparo with above 0.2 wt. percent Emulsion F solids 2, 500 015 240, 000 0.2 wt. percent Emulsion A solids 3, 000 016 260, 000 0.2 wt. percent Copolymer XVIII... l, 250 040 40, 000

Characterization of the above emulsions Emulsion A.-An aqueous, non-ionic emulsion of chemically inert, low molecular weight polyethylene emulsified by a polyoxyethylene derivative of an aliphatic compound.

Emulsion F.An aqueous, non-ionic emulsion of cracked, high-density polyethylene (molecular weight: about 2000) modified with about weight percent maleic anhydride and emulsified with a mixture of nonylphenyl polyethylene glycol ethers containing about 4 and about 7 moles of ethylene oxide and with morpholine.

Emulsion I.An aqueous, non-ionic emulsion of lowdensity, polyethylene (molecular weight: about 24,000) prepared by emulsion polymerization.

Emulsion P.An aqueous styrene-butadiene latex.

The foregoing data demonstrate that a synergetic increase in contact pressures can be obtained by the combination of a siloxane-oxyalkylene copolymer with a polyolefin in an aqueous emulsion.

Concentrated admixtures containing an above-described base fluid and relatively large amounts of the above-described siloxane-polyoxyalkylene copolymers can be conveniently and economically stored and shipped. Such admixtures can then be readily diluted just prior to use to produce the aqueous lubricant compositions of this invention described above. The concentrated admixtures can contain from over 0.1 part up to 0.5 or even as high as 0.7 part by weight of the copolymer per one part by weight of the base fluid. These admixtures can also contain the various additional additives described above in amounts from over 0.5 part to up to 0.25 or even as high as 0.35 part by Weight per one part by weight of the base fluid. Dilution of such admixtures to form aqueous lubricant compositions of this invention is readily accomplished by mixing the admixtures with water or with mixtures of water and an organic lubricant base fluid.

It should be understood that the various above-mentioned additional additives which may be present in the aqueous lubricant composition of this invention are not an exhaustive list of such materials. By way of illustration, a base (e.g. sodium hydroxide) can be added to the composition of this invention when necessary or desirable in order to maintain the pH of the composition above 7. As a further illustration, anti-microbacterial agents such as an aqueous solution containing di(phenyl mercuric) ammonium propionate in an amount providing about 6 wt. percent of mercury can be added to the compositions of this invention. Other bactericidal agents that can be employed are the chlorophenols, the neornycin sulfates, 6-acetoxy-2,4-dimethyl-n-dioxane, and the like. As a further illustration, silicone anti-foam agents can be added to the composition. Illustrative of the suitable types of silicone anti-foam agents are trimethylsiloxy-endblocked dimethylpolysiloxane oils having a viscosity from 350 to 500 centistokes at 25 C. Such oils can be mixed with finely divided silica, e.g. about 3 wt. percent silica.

The foregoing discussion and the examples are intended as illustrative of the present invention. Other variations and modifications within the spirit and scope of this invention will readily present themselves to the skilled artisan.

What is claimed is:

1. A method for lubricating two metal surfaces in moveable contact with each other which method comprises applying to the surfaces a composition comprising an aqueous base fluid and from about 0.0005 to about 0.1 part by weight per one part by weight base fluid of a siloxane-oxyalkylene copolymer having:

(a) at least one siloxane block containing at least two siloxane groups represented by the formula:

Rbsl O2 wherein R is a member of the group consisting of a monovalent hydrocarbon group, halosubstituted monovalent hydrocarbon group, cyano-substituted monovalent hydrocarbon group, amino-substituted monovalent hydrocarbon group, carbalkoxy-substituted monovalent hydrocarbon group, acyloxy-substituted monovalent hydrocarbon group, mercapto-substituted monovalent hydrocarbon group, nitro-substituted monovalent hydrocarbon group, and a divalent hydrocarbon group, and b has a value from 1 to 3, inclusive, and the siloxane block has at least one divalent hydrocarbon group represented by R; and

(b) at least one polyoxyalkylene block containing at least two oxyalkylene groups represented by the formula:

wherein R is an alkylene group, each siloxane block being linked to each polyoxyalkylene block by the divalent hydrocarbon group represented by R; said aqueous base fluid containing water and up to about 2 parts by weight per one part by weight Water of an organic fluid lubricant which is a member of the group consisting of a silicon-free polyoxyalkylene compound, a dialkyl ester of an aliphatic dicarboxylic acid, a hydrocarbon lubricating oil, and an ester of polyhydric alcohol with a fatty acid.

2. The method of claim 1 wherein the compositions also contain an olefin polymer in emulsified form having an average molecular weight from about 1,500 to about 25,000 and being present in an amount in the range from about 0.001 to about 0.1 part by weight per one part by weight of the base fluid.

3. The method of claim 2 wherein the base fluid is water.

4. The method of claim 1 wherein the siloxane polyoxyalkylene block copolymer is present in an amount from about 0.001 to about 0.05 part by Weight per one part by weight of the base fluid.

5. The method of claim 1 wherein R is a monovalent hydrocarbon group or a divalent hydrocarbon group.

6. A lubricant composition comprising:

(A) an aqueous base fluid containing Water and up to about 2 parts by weight per one part by weight water of an organic fluid lubricant which is a member of the group consisting of a silicon-free polyoxyalkylene compound, a dialkyl ester of an aliphatic dicarboxylic acid, a hydrocarbon lubricating oil and an ester of polyhydric alcohol with a fatty acid;

(B) from about 0.0005 to about 0.1 part by weight per one part by weight base fluid of a siloxaneoxyalkylene copolymer having:

(a) at least one siloxane block containing at least two siloxane groups represented by the formula;

RbSiO wherein R is a member of the group consisting of a monovalent hydrocarbon group, halo-substituted monovalent hydrocarbon group, cyanosubstituted monovalent hydrocarbon group, aminosubstituted monovalent hydrocarbon group, amide-substituted monovalent hydrocarbon group, carbalkoxy-substituted monovalent hydrocarbon group, acyloxy-substituted monovalent hydrocarbon group, mercapto-substituted monovalent hydrocarbon group, nitro-substituted monovalent hydrocarbon group, and a divalent hydrocarbon group, and b has a value from 1 to 3, inclusive, and the siloxane block has at least one divalent hydrocarbon group represented by R; and

(b) at least one polyoxyalkylene block containing at least two oxyalkylene groups represented by the formula:

wherein R is an alkylene group, each siloxane block being linked to a polyoxyalkylene block by the divalent hydrocarbon group represented by R, and

(C) an olefin polymer in emulsified form having an average molecular weight in the range from about 1,500 to about 25,000 and being present in an amount in the range from about 0.001 to about 0.1 part by weight per one part by weight of the base fluid.

7. The composition of claim 6 wherein the siloxanepolyoxyalkylene block copolymer is present in an amount of from about 0.001 to about 0.05 part by weight per one part by weight of the base fluid and wherein R is a monovalent hydrocarbon group or a divalent hydrocarbon group. i

8. A composition as defined in claim 6 consisting essentially of (A) water, (B) from about 0.001 to about 0.1 part by weight per one part by weight water of an olefin polymer in emulsified form having an average molecular weight in the range of from about 1,500 to about 25,000, and (C) from about 0.0005 to about 0.1 part by weight per one part by weight water of a siloxane-polyoxyalkylene copolymer as defined in claim 6 wherein R is a monovalent hydrocarbon group or a divalent hydrocarbon group.

9. The composition of claim 8 wherein the olefin polymer contains on the average of at least one polar group for every four olefin polymer molecules.

10. An admixture consisting essentially of:

(A) an aqueous base fluid containing water and up to about 2 parts by weight per one part by weight water of an organic fluid lubricant which is a member of the group consisting of a silicon-free polyoxyalkylene compound, a dialkyl ester of an aliphatic dicarboxylic acid, a hydrocarbon lubricating oil, and an ester of polyhydric alcohol with a fatty acid;

(B) a siloxane-oxyalkylene block copolymer having:

(a) at least one siloxane block containing at least two siloxane groups represented by the formula:

RbSiO wherein R is a member of the group consisting of a monovalent hydrocarbon group, halo-substituted monovalent hydrocarbon group, cyanosubstituted monovalent hydrocarbon group, amino-substituted monovalent hydrocarbon group, amide-substituted monovalent hydrocarbon group, carbalkoxy-substituted monovalent hydrocarbon group, acyloxy-substituted monovalent hydrocarbon group, mercapto-substituted monovalent hydrocarbon group, nitro-substituted monovalent hydrocarbon group and a divalent hydrocarbon group, and b has a value from 1 to 3, inclusive, and the siloxane block has at least one divalent hydrocarbon group represented by R; and

(b) at least one polyoxyalkylene block containing at least two oxyalkylene groups represented by the formula:

wherein R is an alkylene group, each siloxane block being linked to a polyoxyalkylene block by the divalent hydrocarbon group represented by R in an amount from over 0.1 to 0.7 part by weight per part by weight of the aqueous base fluid, and

(C) an olefin polymer having an average molecular weight in the range from about 1,500 to about 25,000 in an amount from over 0.05 part up to 0.35 part 1l ly weight per part by weight of the aqueous base 11. An admixture as defined in claim 10 consisting essentially of:

(A) water,

(B) a siloxane-oxyalkylene block copolymer as defined in claim 10 wherein R is a monovalent hydrocarbon group or a divalent hydrocarbon group, said block copolymer being present in an amount from over 0.1 to 0.7 part by weight per part by weight of the water, and

(C) an ethylene polymer having an average molecular weight in the range from about 1,500 to about 25,000 in an amount from over 0.05 part up to 0.35 part by weight per part by weight of the water.

12. The admixture of claim 11 wherein the ethylene polymer contains on the average of at least one polar group for every four ethylene polymer molecules.

References Cited UNITED STATES PATENTS 3,234,252 2/1966 Pater 252-493 X 3,256,211 6/1966 Bailey et al 252-493 X 3,280,160 10/1966 Bailey 260-4482 3,299,112 1/1967 Bailey 260-4482 2,122,826 7/1938 Van Peski 252-55 2,142,980 1/1939 Huijser et a1 2 2-5 2,561,178 7/1951 Burkhard 252-496 2,846,458 8/1958 Haluska 252-496 2,868,824 1/1959 Haluska 252-496 2,941,944 6/1960 Ervine 252-495 2,965,596 12/1960 Sharf 260-296 3,198,820 8/1965 Pines et al. 260-448.2

FOREIGN PATENTS 718,179 11/1954 Great Britain. 785,780 11/1957 Great Britain.

DANIEL E. WYMAN, Primary Examiner W. CANNON, Assistant Examiner US. Cl. X.R.