DE1594652B1 - Aqueous lubricating oil emulsion - Google Patents

Description

and from b) 0.0005 to 0.1 parts by weight per part by weight of the siloxane-oxyalkylene block copolymer added, in which the siloxane block consists of at least 2 siloxane units of the general formula

consists in which R is a monovalent hydrocarbon radical, in particular alkyl or aryl radical, which is optionally substituted with halogen atoms, cyano, amino, amido, carbalkoxy, acyloxy, mercapto or nitro groups, or a divalent hydrocarbon radical, especially alkylene or Arylene radical, where the siloxane block has at least one divalent hydrocarbon radical R and in which b is 1 or 2 or 3, and in which the polyoxyalkylene block consists of at least 2 oxyalkylene units of the formula - R'O - in which R 'is an alkylene radical, the siloxane block is bonded to the polyoxyalkylene block via an alkylene radical R ', characterized in that they additionally contain an emulsified olefin polymer with an average molecular weight of about 1500 to 25,000 in a proportion of 0.001 to 0.1 parts by weight per part by weight of base liquid.

2. Aqueous lubricants according to claim 1, characterized in that they also have a Contain olefin polymer which on average has at least one polar group for every 4 olefin polymer molecules having.

The invention relates to aqueous lubricants containing certain organic silicon compounds.

The usual lubricants consist of a cutting work, for example. The low thermal conductivity the organic base liquid can then cause adverse effects (for example the liquid may volatilize and / or ignite).

There is therefore no lack of attempts to develop lubricants in which water is a part or the represents the entire base fluid because of its low cost, good thermal conductivity and fire safety many of the disadvantages inherent in organic base fluids in the presence of water switch off. The relatively low resistance to stress and abrasion prevention in water could result in such aqueous lubricants by incorporating additives in the same to a certain extent Degree to be overcome. However, previous efforts to use aqueous lubricants have failed not entirely satisfactory because of the properties of these additives. For example It should be mentioned that some additives give the lubricant neither the load resistance nor the Impart abrasion-preventing properties which are required in many fields of application, and that other additives are again unstable and have a corrosive effect. Give other additives the lubricant has poor wetting properties or causes foaming, and again others must be used in excessive amounts in order for them to be effective at all. The object of the invention is to provide additives for aqueous lubricants which Give lubricant better load resistance and its ability to prevent abrasion, to enhance. The additives according to the invention are quite stable and do not cause corrosion; they affect neither the wettability nor the anti-foaming properties of the lubricant and are effective even in relatively small amounts.

The subject of the main patent is an aqueous lubricating oil emulsion consisting of a base liquid in the form of water and a lubricating oil based on a polyoxyalkylene oil, a diester oil, a hydrocarbon oil or an ester oil, which is a block copolymer of siloxane units and oxyalkylene units of a special type identified in more detail below are added.

It has now been found that such an aqueous lubricating oil emulsion has even better use properties if it additionally comprises an emulsified polyolefin with an average molecular weight from about 1500 to 25,000, in a proportion of 0.001 to 0.1 parts by weight each Part by weight of oily base liquid is present. As a preferred weight ratio between the Block copolymer of siloxane and oxyalkylene units and the polyolefin added according to the invention a ratio of about 1: 1 has been found. According to the main patent for aqueous lubricants

organic lubricant base fluid, mostly 60 oils usable siloxane-polyoxyalkylene mixed poly-

a mineral oil containing one or more additives (e.g. antioxidants and corrosion inhibitors) are added. These basic organic fluids are relatively expensive and are poor conductors of heat, which is particularly undesirable is when the lubricant is used in operations where a large Amount of heat generated by friction, like the others, belong to the so-called »block copolymers. Block copolymers are composed of at least two sections or blocks, at least one of which consists of repeating siloxane units or groups, while at least one other section or block from other recurring units or groups, for example oxyalkylene groups. The block-

Copolymers can have a linear, cyclic or formula branched or crosslinked structure.

The siloxane blocks in the siloxane-polyoxyalkylene copolymers contain at least 2 siloxane units of the general formula

R "SiO ₄ _ _b

: HN (C ₄ H ₉ ),

which are derived from the dibutylamine salt of oleic acid by reaction with a siloxane, the silane hydrogen contains, and the remainder of the formula

(D

where R is an optionally substituted monovalent hydrocarbon radical or a divalent hydrocarbon radical and b has the value 1, 2 or 3. R preferably contains 1 to 30 carbon atoms. The radicals R can be identical or different in any siloxane unit or in the entire siloxane block. The value of b can also be the same or different in the various siloxane units in the siloxane block. The siloxane block is bound to the oxyalkylene block via the divalent hydrocarbon radicals R. Each siloxane block contains at least one unit represented by the formula (I) in which at least one R group is a divalent hydrocarbon group. In the siloxane block, the ratio of hydrocarbon radicals to silicon atoms is 1: 1 to 3: 1.

Examples of unsubstituted monovalent hydrocarbon radicals R in formula (I) are the alkenyl groups (e.g. the vinyl and allyl groups), the Cycloalkenyl groups (e.g. the cyclohexenyl group), the alkyl groups (e.g. the methyl, ethyl, isopropyl, Octyl or dodecyl group), the aryl groups (e.g. the phenyl or naphthyl group), the aralkyl groups (e.g. the benzyl or phenylethyl group), the alkaryl groups (e.g. the styryl, tolyl or n-hexylphenyl group) and the cycloalkyl groups (e.g. the cyclohexyl group).

Characteristic examples of substituted monovalent hydrocarbon radicals R in formula (I) are the alkenyl, cycloalkenyl, alkyl, aryl, arylalkyl, alkylaryl or cycloalkyl radicals, the halogen atoms or cyano, amino, amido, salt, ester (e.g. carbalkoxy or acyloxy), sulfur-containing (ζ. Β. Mercapto or SH) or nitro groups can carry as substituents.

This subheading includes B. the following groups:

Tetrafluoroethyl, trifluorovinyl,

Chloromethyl,

y-chloropropyl,

jS-cyanoethyl,

y-cyanopropyl,

Cyanophenyl,

y-aminopropyl,

(5-aminobutyl,

N-jS-aminoethyl-y-aminopropyl,

Aminomethylphenyl,

H ₂ NCOCH ₂ CH ₂ -,

/ I-carbethoxyethyl,

ß-carboxyethyl,

Me O OC (CH ₂ ) ₁₀ -y-Carbpropoxypropyl,

CH ₃ COOCH ₂ CH ₂ -,

CH ₂ = CHCOOCH ₂ CH ₂ -,

/ 5-mercaptoethyl,

y-mercaptopropyl,

Nitrophenyl.

The monovalent silicon-bonded radicals substituted with salt groups include the radicals of

65 obtained by reacting dibutyltin methacrylate with a siloxane containing hydrogen silane. Other monovalent radicals bonded to silicon which are substituted by amino groups are, for example, those of the formula

CH ₃ (CH ₂ ) ₆ CH (CH ₂ ) ₈ CONMe3

(obtainable from Ν, Ν-dimethylolamide by reaction with a siloxane containing hydrogen silane), and

- CH ₂ CH ₂ - CH ₂ NHCOC (Me) = CH ₂

those from N-allylmethylacrylamide by reaction with a siloxane containing hydrogen silane. Such substituents impart to the copolymers additional desirable properties, such as increased lubricity, which relate to the Halogen substituents are decreasing, self-emulsifying properties that can be attributed to the amide groups are, corrosion resistance (thanks to the amino groups), an increased surface effectiveness, which due to the nitrile, carboxyl and ester groups, as well as better dielectric properties, which can be attributed to the nitro groups.

The following are representative of the divalent hydrocarbon groups that can be represented by R in formula (I): alkylene groups (such as methylene, ethylene, propylene, butylene, 2,2-dimethyl-l, 3-propylene and the decylene group), arylene groups (e.g. phenylene and ρ, ρ'-diphenylene groups), the alkarylene groups (e.g. the phenylethylene group) and the alkylene aralkylene groups (e.g. the groups -CH ₂ C ₆ H ₄ CH ₂ CH ₂ - and --CH ₂ C ₆ H ₄ CH ₂ -). A preferred divalent hydrocarbon group is an alkylene group with 2 to 4 carbon atoms. Siloxane groups with divalent hydrocarbon groups as substituents are, for. B. the groups of the following formulation: ·

- CH ₂ CH ₂ SiO ₁₁₅

CH ₃

- CH ₂ CHCH ₂ SiO _{1> 5}
CH ₃

⁵⁵ and

60 o 5

CH ₃

These divalent hydrocarbon groups are bonded to a silicon atom of the siloxane block via a Si - C bond and to an oxygen atom of the oxyalkylene block via a C - O bond.

The siloxane-polyoxyalkylene copolymers have a siloxane block which is represented by the formula (I) may contain siloxane units shown in

which either have the same or different hydrocarbon radicals are bonded to the silicon atoms. In the former case, for example, dimethylsiloxy, Diphenylsiloxy or diethylsiloxy groups, in the second case methylphenylsiloxy, phenylethylmethylsiloxy or ethylvinylsiloxy groups.

The siloxane block in the siloxane-polyoxyalkylene copolymers can have the same or the same siloxane units of various kinds represented by formula (I) provided that at least a unit has one or more divalent hydrocarbon substituents. For example Ethylenmethylsiloxy units only

CH ₃

in which R has the same meaning as in formula (I) and in which e is 0, 1 or 2 and / is 1 or 2 and (e + f) corresponds to the value 1 or 2 or 3.

In addition to the units of the formula (I), the siloxane block can also have tetrafunctional units according to the formula

(RO) "SiO; _"

- C ₂ H ₄ - SiO

in which R is an unsubstituted monovalent hydrocarbon radical according to formula (I) and in which η has the value 0 or 1 to 3. Examples are the groups SiO ₂ , ethoxysiloxy, diethoxysiloxy, triethoxysiloxy and phenoxysiloxy.

The oxyalkylene blocks in the siloxane-polyoxyalkylene copolymers each contain at least 2 oxyalkylene units of the formula

—RO (II)

wherein R 'is an alkylene radical. The alkylene radical R 'in formula (II) preferably contains 2 to 10 carbon atoms, especially 2 to 3 carbon atoms. Examples of units of the formula (II) are as follows

may be contained in the siloxane block, or the siloxane block may contain various types of siloxane units. For example, the block can contain both ethylene methylsiloxy units and diphenylsiloxy units or it can contain ethylene methylsiloxy, diphenylsiloxy and diethylsiloxy units.

The siloxane block can have trifunctional siloxane groups: oxyethyleneoxy-1,4-propylene, oxy-1,3-propylene (e.g. monomethylsiloxane groups, CH ₃ SiO ₁₅ ), pylene, oxy-2,2-dimethyl-1 , 3-propylene and oxydifunctional siloxane units (e.g. dimethylsiloxane 1,10-decylene-.

groups, (GHg) ₂ SiO—), monofunctional siloxane The oxyalkylene blocks in the siloxane-polyoxyalky-

Units (e.g. trimethylsiloxane groups, (CH ₃ J ₃ SiO ₀₃ ) len copolymers can contain one or more oxyalkylene units belonging to different types or combinations of these types of siloxane units with identical or different substituents according to formula (II) As a result of the functionality of the siloxane units, only oxyethylene units or only oxy units, the siloxane block can be predominantly linear propylene units, or also oxyethylene units, or cyclic or also crosslinked. It can also have these structures with oxypropylene units or other combinations. Are 35. different types of oxyalkylene units. different types of siloxane groups present, the oxyalkylene blocks in the siloxane-polyoxyalkylene

so these can alternate, in blocks, in irregular copolymers can have terminal groups moderate distribution or contained in any other of organic chains, for example the Sequence occur. Hydroxyl group, aryloxy groups (e.g. the phenoxy

The siloxane block contained in the siloxane-polyoxyalkylene mixed poly (group), alkoxy groups or alkenyloxy groups (e.g. mers can in addition to the vinyloxyl or allyloxy group). A unit corresponding to formula (I) which terminates the monofunctional siloxane chains also has organic groups which block or terminate the chain ends. Examples of terminal groups on the siloxane 45
block include the hydroxyl group, aryl

single group can serve as a chain-terminating group for more than one oxyalkylene block. For example may be the glycerine oxy group

oxy groups (e.g. the phenoxy group), alkoxy groups (ζ. e.g. the methoxy, ethoxy, propoxy and the butoxy group) and acyloxy groups (e.g.

the acetoxy group).

The siloxane blocks in the siloxane-polyoxyalkylene copolymers contain at least two, preferably a total of 5 to 20 siloxane units corresponding to formula (I). The proportion of the average molecular weight

CH ₂ CHCH ₂ OOO

serve as a chain terminal group for three oxyalkylene chains.

The oxyalkylene blocks in the siloxane-polyoxyalkylene copolymers contain at least two oxides of the copolymers which contain alkylene units corresponding to formula (II) on the siloxane blocks. Each block can be up to 50,000, but preferably 2 to 30 such units are reserved. The preferably between 220 and 20,000. If the proportion of the average molecular weight of the part of the average molecular weight, which falls on the mixed polymer, which is accounted for by the oxyalkylene blocks ent-siloxane blocks, more than 50,000, or contains, can from 88 ( for (C ₂ H ₄ O) ₂ ) vary up to 20,000, the siloxane blocks in total more than 20 siloxane units, however, preferably between 132 and 15,000 units according to formula (I), then the mixed poly- With the proviso that any oxyalkylene block

contains at least two oxyalkylene units corresponding to formula (II), represents the number of oxyalkylene units and the proportion of the average molecular weight of the interpolymer which is based on the oxyalkylene blocks does not apply, is not a critical variable. The copolymers, however, in which the proportion of Oxyalkylene blocks on the average molecular

mers are usually difficult to manufacture.

In addition to the units represented by formula (I), a siloxane block can correspondingly contain siloxane units formula

(Ia)

weight is more than 200,000 or which contain more than 50 oxyalkylene units per block, are less useful because they are too viscous, among other things.

The siloxane-polyoxyalkylene copolymers can be any of siloxane blocks and oxyalkylene blocks relative proportions included. Preferably 5 to 95 parts by weight meet siloxane blocks and 5 to 95 parts by weight Oxyalkylene blocks, in particular 5 to 40 parts by weight of siloxane blocks and 60 to 95 parts by weight Oxyalkylene blocks to 100 parts by weight of copolymer.

The siloxane-polyoxyalkylene copolymers can contain more than one block each, and the Blocks can be in a variety of configurations, such as a linear, cyclic, or branched configuration be arranged. Examples include:

A) mixed polymers which contain at least one unit of the following formula:

(III)

25th

B) mixed polymers which contain at least one unit of the following formula:

03., SiGO (OO) _n CSiO ₃ ^ (IV)

C) mixed polymers which contain at least one unit of the following formula:

(V)

40

45

In the above formulas (III), (IV) and (V) G denotes a monovalent hydrocarbon radical, G 'a divalent hydrocarbon radical, G "an alkylene radical having at least 2 carbon atoms, G'" a hydrogen atom or a monovalent hydrocarbon radical which is not unsaturated aliphatic Has bond, and η is an integer, at least 2, while c in formulas (III) and (IV) is 0, 1 or 2 and in formula (V) 0 or 1. In the formulas, G can represent the same or different radicals, η is preferably an integer from 3 to 30 inclusive, and G "can represent the same or different radicals, ie the group (OG") "can, for example, represent the groups

-, - (OC ₂ H ₄ ) (OC ₃ H ₆ ), -

Is a hydrocarbon radical and b has the value 1 or 2 or 3.

The monovalent hydrocarbon radicals represented by G in formulas (III), (IV) and (V) can be saturated or olefinically unsaturated or have benzene unsaturation. Illustrative Examples of monovalent hydrocarbon radicals represented by G are the linear aliphatic ones Residues (e.g. methyl, ethyl and decyl radicals), the cycloaliphatic Radicals (e.g. cyclohexyl or cyclopentyl radicals), the aryl radicals (e.g. phenyl, tolyl, Xylyl or naphthyl radical), the aralkyl radicals (e.g. the benzyl or the / S-phenylethyl radical) and the unsaturated ones linear aliphatic radicals (e.g. the cyclohexenyl radical).

The radicals included in the definition of “R” in formulas (I) and (Ia) preferably contain G and G '1 to 12 carbon atoms, and those included in the definition of R' according to formula (II) Residues G "2 to 10 carbon atoms. The remainder G '" is then a monovalent hydrocarbon radical, which has no aliphatic unsaturation and preferably contains 1 to 18 carbon atoms.

Characteristic examples of the divalent hydrocarbon radicals in the formulas (III), (IV) and (V) are represented by G ', the alkylene radicals (e.g. the methylene, ethylene, 1,3-propylene, 1,4-butylene or 1,12-dodecylene radical), the Arylene radicals (e.g. the phenylene radical) and the alkarylene radicals (e.g. the phenylethylene radical). Preferably is G 'is an alkylene radical with at least 2 carbon atoms.

Illustrative for alkylene radicals with at least 2C atoms, which are represented by G "in formulas (III, IV, V) are ethylene, 1,2-propylene, 1,3-propylene, 1,6-hexylene, 2-ethylhexylene-1,6 and 1,12-dodecylene.

Examples of the radicals represented by G '"in the formulas (III, IV, V) are the saturated linear ones or chain-branched aliphatic hydrocarbon radicals (e.g. methyl, ethyl, propyl, n-butyl, tert-butyl and decyl radicals), the saturated cycloaliphatic hydrocarbon radicals, the aryl hydrocarbon radicals and the aralkyl hydrocarbon radicals.

The copolymers used in the preparations according to the invention and in particular those which can contain at least one unit corresponding to the formulas (III, (IV) or (V)) also contain at least one unit that corresponds to one of the following formulas:

⁵⁵

mean, in which ρ and q generally mean integers, but they can also be average, non-integer values if the formulas represent mixtures of copolymers. Copolymers of the latter classes can only consist of units according to the formulas (III), (IV) or (V), or they can consist of 1 to 99 mol percent of such units, or consist of 1 to 99 mol percent of units according to formula (I), where R is an unsubstituted monovalent H ₂ NC ₉ H ₂₉ SiO _3. ,

R,

(VI)

H ₂ NC ₁ H ₂₁ HNC ₉ H ₂₉ SiO ₃ ^, (VII)

ROOCC, .H ₂ ; SiO ₃ _ ,, (VIII) R * NCCjH ₂ J-SiO ₃ ^ (K) 209 513/338

O ₂ NQH ₄ SiO ₃ ^,

f RCOOC ₁ H ₂ , SiO ₃ - _h

O R *

(X)

(XI)

(XII)

In the formulas, R is an unsubstituted monovalent hydrocarbon radical as defined above, R "is an unsubstituted monovalent hydrocarbon radical as defined above for R or hydrogen, while g is an integer from 3 to 20, preferably 3, 4 or 5 and h the value O, 1 or 2, i the value 2 or 3 and j the value 2 or 3 or 4. Such copolymers can contain 1 to 99 mol percent of units corresponding to the formulas (III), (IV) or (V) and 1 to 99 mol percent of units of the formulas (VII) to (XII). If appropriate, the copolymers can also contain 1 to 98 mol percent of units of the formulas (III), (IV) or (V), 1 to 98 mol percent of units of the formulas (VII) to (XII) and 1 to 98 mol percent of units corresponding to formula (I), in which R is then an unsubstituted monovalent hydrocarbon radical and b is 1 or 2 or 3.

The organic and inorganic acidic ones formed from the groups of the formulas (VI) and (VII)

ίο salts and those by hydrolysis of the groups according to Formula (XI) formed COOH groups can also be contained in the copolymers, which in the lubricants according to the invention are used.

The following are representatives of the siloxane-polyoxyalkylene block copolymers as they can be used both in the lubricants according to the main patent and in the lubricants according to the invention. In the formulas, Me means methyl (CH ₃ -), Bu butyl (C ₄ H ₉ -), Et means ethyl (CH ₃ CH ₂ -), Φ phenyl (C ₆ H ₅ -), and χ is an integer. If the formula represents a unit of a polymer, this means that the polymer is terminated by terminal block groups of the type described above.

Copolymer I.

Me, SiO

Copolymer 2

Me, SiO

Copolymer 3

Me, SiO

Copolymer 4

Me SiO Me

Γμ LSi

Mel

56

, SiOJ ₂₄ SiMe ₃
(CHa) ₃ (OC ₂ IU ₇ OMe

MeI
SiOj ₂ SiMe ₃

Me 6.3 Me 2 SiO SiO Me I. M8- "37

₅ ^0Bu

Me 7.7 Me 1.4 SiO SiO Me I. Cj. 8 H ₃₇

Mel
SiOJ _4-1 SiMe ₃

(CH ₂ J ₃ (OC ₂ IU ₇ OMe

Me, SiO

Me SiO Me

"Mel SiOJ _3i5 SiMe ₃

(CH ₂ J ₃ (OC ₂ IU ₇ OMe

Copolymer 5

Me Me Me

(Me ₃ SiO) ₂ Si - O - Si - OSiCH ₂ CH ₂ CH ₂ O (C ₃ H ₆ O) ₁₁ H Et ₂ NCH ₂ CH ₂ CH ₂ Me

Copolymer 6

CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ Nh ₂

Me ₃ SiO (Me ₂ SiO) ₄ SiOSiMe ₂

Me CH ₂ CH ₂ (OC ₂ H _{4) 3} O0

11th

Copolymer 7

Me

CH ₂ CHCOOC ₂ H ₅ Φ

Me ₃ SiOSi (Me) OSi (Me ₂ ) OSiCH ₂ CH ₂ CH ₂ (OC ₄ Hg) ₂ OH

Copolymer 8

CH, CH, CH, CN

Me

Me ₃ SiOSi (OSiMe ₂ ) ₄ OSiCH ₂ CH2 (OC ₂ H ₄ ) 3O0 Me Me

Copolymer 9

C ₆ H ₄ NO ₂ Me

Me ₃ SiOSiOSi (Me ₂ ) OSi (02) OSiCH ₂ CH2 (OC2H ₄ ) ₂ OMe C ₂ H ₅ Me

Copolymer 10

CH ₂ CH ₂ OOCCH ₃ Me

C ₂ H ₅

Me

Copolymer 11

CH ₂ CH ₂ CONH ₂ Me

Me ₃ SiOSiOSi (Me ₂ ) OSi (02) OSiCH ₂ CH ₂ CH ₂ (OC ₂ H ₄ ) ₂ OH Me CH ₂ CH ₂ CH ₂ (OO, !!,.) ;, OH

Copolymer 12

Me

MeO (CH ₂ CH ₂ O) ₂ CH ₂ CH ₂ SiO

Copolymer 13

[00 (CH ₂ CH ₂ O) ₃ CH ₂ CH ₂ SiO ₁₁₅ ],

Copolymer 14

Me

Me, SiO

SiO Me

Me SiO

₁₆ SiMe ₃

Copolymer 15

/ Me '

EtSi

SiO (C ₃ H ₆ O) ₂₅₀ (C ₂ H ₄ O) _3-7 Bu

I Me J ₇

Copolymer 16

Me, SiO

Me

- SiO-

3.1

Me "-SiO

Me

SiMe,

17th ^0Bu

Copolymer 17

Me ₃ SiO (Me ₂ SiO) ₂₁

Copolymer 18

Me ₃ SiO (Me ₂ SiO) ₈

Me

QH ₉ (OQH ₄ ) _18iS (OQH ₈ ) _u O (CH ₂ ) ₃ SiO

SiMe,

Me (OQH ₄ Ji ₇ 0 (CH ₂ J ₃ SiO SiMe,

The block copolymers according to the invention substituted monovalent hydrocarbon groups from polysiloxane and oxyalkylene can in particular 25 and an alkali salt of an oxyalkylene polymer

Hi

can be made in two common ways. The first method, known as the metathesis method, is in that a mixture of a siloxane polymer with a silicon-bonded halogen type

prepared and the mixture is heated to a temperature (preferably 80 to 150 ⁰ C), in which the siloxane polymers and the salt react to form the copolymer.

This process can be represented by the following equation:

SILOXANE

( ^l Ϊ
-OSiR ² X

+ (MO) - OXYALKYLENE> SILOXANE- (OSiR ² O) ₁ .- OXYALKYLENE + rMX

where R ^{2 is} a divalent hydrocarbon group, r is a number of at least 1, preferably from 1 to 4, while X stands for a halogen atom, M for an alkali metal and SILOXANE denotes a siloxane block and OXYALKYLENE denotes an oxyalkylene block.

The second method, known as the addition method, is to make a mixture of one An organosiloxane polymer containing a hydrogen siloxy group (i.e., a

HSiO group)

contains, an oxyalkylene polymer with an alkenyloxy group which terminates the chain end, and a platinum catalyst (for example 0.001 to 5.0 percent by weight, based on the reactants, of elemental platinum or chloroplatinic acid). The mixture is brought to a temperature (z. B. preferably 90 to 170 ° C.) at which the siloxane polymer and the oxyalkylene polymer react to form a copolymer.
This process can be represented by the following equation:

OXYALKYLENE - (OR ³ ) _r + HSiO-

SILOXANE

where OXYALKYLENE, SILOXANE and r have the above meaning, OR ^{3 is} an alkenyloxy group (e.g. the vinyloxy or the allyloxy group) and R ^{4 is} an alkylene group with at least two consecutive carbon atoms.

If the block copolymer of polysiloxane and oxyalkylene contains hydrogen atoms, the Silicon bonded, d. H. 2 units represented by the above formula (Ia) so is that Addition method more expedient. If the metathesis process is used, many of them go to silica bonded hydrogen atoms a side reactions, which are caused by the present in the reaction mixture Alkali metal ions are catalyzed.

OXYALKYLENE - [OR ⁴ SiO -] _r SILOXANE

If the copolymer contains unsaturated groups on silicon (e.g. if R in the formulas (I) or (Ia) above alkenyl or cycloalkenyl, such as vinyl or cyclohexenyl means), these are provided Copolymers are preferably made by addition of the oxyalkylene polymer end-blocked with an alkenyloxy group to a monomeric hydrolyzable silane in which the hydrogen is attached to the silicon is bound, whereupon the product of a cohydrolysis or cocondensation with other hydrolyzable Silanes subjugate the hydrogen bonded to silicon and also to silicon contain bound olefinically unsaturated hydrocarbons. You can use the usual, specialist

use known methods. So z. B. the reaction of

CH ₂ = CHCH ₂ (OC ₂ H ₄ ^ OCH ₃

with CH ₃ SiHCl ₂ in the presence of a platinum catalyst with subsequent cohydrolysis of the product with

CH ₂ = CHSi (CH ₃ ) Cl ₂ , CH ₃ SiHCl ₂ and (CHa) ₃ SiCl a copolymer with units of the formulas

[CH ₃ O (C ₂ H ₄ O) ₆ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) O]
[CH ₂ = CHSi (CH ₃ ) O] and [CH ₃ SiHO]

alkyl esters of aliphatic dicarboxylic acids, hydrocarbon lubricating oils and esters of polyalcohols and fatty acids.

Among the silicon-free polyoxyalkylene compounds that are suitable for use as organic lubricant base fluids Suitable in the preparations according to the invention include those corresponding to the formula

G '"(0G") "0G'" (XIII)

IO

end-blocked with [( ₃ ) S] p

Siloxane-polyoxyalkylene copolymers which contain groups from the formulas (VI) to (EX), (XI) and (XII) can also be easily prepared by addition reactions between copolymers with groups according to formula (Ia) and corresponding olefinically unsaturated organic compounds (e.g. N-AHyI-ethylenediamine, allyl cyanide, ethyl acrylate, allyl diethylamine, Ethyl methacrylate, vinyl acetate, trichlorostyrene and acrylic acid amide). In such addition reactions Catalysts that accelerate addition reactions can be used with advantage are known (e.g. platinum, chloroplatinic acid, amines, phosphines, etc.); the procedural conditions correspond to those known for addition reactions.

Siloxane-polyoxyalkylene copolymers with groups according to formulas (VI) to (XII) can also be used easily produced by cohydrolysis and cocondensation of hydrogenalkoxysilanes

[e.g. HSiiOQH ^]

and alkoxysilanes containing the corresponding organofunctional groups

[e.g. O ₂ NC ₆ H ₄ Si (OC ₂ HSy
contain; a siloxane is obtained

[e.g. (HSiO ₁₁₅ UO ₂ NC ₆ H ₄ SiO ₁ , ^]

this then into a siloxane-polyoxyalkylene copolymer

[e.g. (MeO (C ₂ H ₄ O) ₇₁₅ CH ₂ CH ₂ CH ₂ SiO ₁ A

(O ₂ NC ₆ H ₅ SiO ₁₁₅ ) J.

can be converted by treating it with a polyoxyalkylene compound end-blocked by an alkenyloxy group

[e.g. CH ₂ = CHCH ₂ O (C ₂ H ₄ O) ₇₁₅ Me]

implements as described above. The usual methods of cohydrolysis and cocondensation can are used here.

The organic lubricant base fluids which are suitable for use in the various preparations according to the invention include, inter alia, the various customary organic lubricant base fluids. Characteristic representatives of suitable lubricants are silicon-free polyoxyalkylene compounds, Diworin G '", G" and η have the meanings given above. Illustrative of compounds of formula (I) are

I ₉ , CH ₃ (OC ₃ Ho) ₁₂ OC ₄ H ₉ and C ₃ H ₁₇ (OC ₃ H ₆ J ₁₄ OC ₈ H ₁₇ .

A preferred class of compounds according to formula (XIII) are those with a viscosity between 5000 and 12000 cSt at -54 ° C and a viscosity between 2.5 and 3.5 cSt at 154 ° C.

Among the dialkyl esters of aliphatic dicarboxylic acids, which are inorganic for use Lubricant base fluids suitable in the preparations according to the invention include those of formula

R "OOC (C _p H _2p ) COOR" (XIV)

in which R "denotes an alkyl radical having 6 to 10 carbon atoms and ρ an integer from 6 to 10.

Among the hydrocarbon lubricating oils that are suitable for use as organic lubricating base fluids in the preparations according to the invention according to the main patent and according to the present one Additional patents include the paraffinic lubricating oils, the naphthenic lubricating oils, and mixtures such oils. Examples of such hydrocarbon lubricating oils are those having a viscosity in the range of 30 "Saybolt Universal Seconds" at 38 ° C to 100 "Saybolt Universal Seconds" at 99 ° C.

Among the esters of polyalcohols and fatty acids that are suitable for use as organic lubricant base fluids own, include the esters of alcohols such as glycerine, pentaerythritol and trimethylolethane and acids such as oleic acid, stearic acid, coconut fatty acids and valeric acid. to these esters also include those obtained by reacting a polyalcohol with a mixture of Fatty acids have been obtained.

The relative amounts of siloxane-polyoxyalkylene copolymer and base fluid are not decisive for the result and can vary over a wide range, depending on the nature of the to lubricating metals or the base fluid and the copolymers, as well as the temperature and the load conditions under which the preparation is to be used as a lubricant.

In general, about 0.0005 to 0.1, preferably 0.01 to 0.05 parts by weight of the copolymer are applied 1 part by weight of the base fluid (water and any organic lubricating oil) is used. In a similar way Way is also the relationship between the water and the organic lubricating oil that is in the Basic fluid is included in order to improve the result, not a particularly critical size and

209513/338

can vary greatly, depending on economic efficiency or depending on the compatibility of the water with the organic lubricant base liquid and the Compatibility of the mixed polymer with the base liquid. 10 to 200 parts by weight are used of the organic lubricant base liquid per 100 parts by weight of water, preferably 50 to 130 parts by weight Base liquid to 100 parts by weight of water. A shift in the proportions of shares is possible, but mostly not an advantage.

The siloxane-polyoxyalkylene copolymers can be dissolved in the base liquid or to form a Be dispersed in an emulsion or suspension. Likewise, water and organic base liquid can be in Be in the form of a solution or an emulsion; in the latter case either the water is in the organic base liquid or vice versa.

It has been found that in emulsified form the polymer chain can contain the necessary amount Give polarity so that the polymers are emulsifiable and the resulting emulsion is stable.

Emulsion polymerization is generally carried out by converting the starting olefinic material emulsified in water by means of a suitable emulsifier and then the olefin at increased Polymerized under pressure and higher temperature in the presence of a polymerization catalyst. Such Processes for emulsion polymerization are described, inter alia, in the USA patents 2,342,400.2 542,783, 2,592,526 and 2,703,794.

The lubricants according to the invention can contain agents to lower the pour point, preferably methanol or ethylene glycol, in amounts from 1 to 200, more preferably from 1 to 100 parts by weight per 100 parts by weight of water.

In addition to the siloxane-polyoxyalkylene copolymer and the basic fluid can be the

present polyolefins entdem the properties of the various other additives after 20 preparations Hold main patent available lubricating oil emulsions that give them special properties.

keep improving. Suitable polyolefins are those whose molecular weight is between about 1500 and about 25,000, and their melting point is preferably not higher than about 200 ⁰ C. Typical of such polyolefins are the homopolymers and copolymers of α-olefins with 2 to about 12 carbon atoms. Because of their emulsifiability, polyolefins with at least one polar group on average for every 4 polyolefin molecules are preferred.

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

The latter technique is preferred because the pyrolysis of relatively high molecular weight polymers results in a terminal unsaturated vinyl group which is readily available for reaction with an ethylenic unsaturated polar monomers such as maleic anhydride or thioglycolic acid, as described in US Pat U.S. Patents 2,766,214 and 3,144,348. This creates the resulting polyolefin easily emulsifiable.

Another valuable method for the preparation of emulsifiable polymers with a sufficient Number of polar groups consists in the oxidation with or without a catalyst, along the Polymer chains in addition to ketone, aldehyde and hydroxyl groups and carboxyl groups are generated. Other suitable emulsifiable polyolefins are the block copolymers obtained by reacting Ethylene oxide can be formed with polyethylene to form polymers with hydroxyl end groups, as described in U.S. Patent 2,921,920. Also those described in U.S. Patent 2,766,214 Polyolefins, namely the ethylene alcohol telomers reacted with maleic acid, are for purposes suitable for the invention.

The necessary amount of polar groups can also be used in the homo- and copolymers mentioned of α-olefins are introduced by copolymerization of the resulting polyolefins with unsaturated ones Monomers that contain an ethylene bond, such as ethylene acrylate, styrene, bicycloheptene, Vinyl acetate, acrylic acid and the like.

Also the direct polymerization to the above-mentioned olefin polymers or their hydrolysis Such additives include anti-corrosive agents, antioxidants, tarnishing agents and lubricity improving agents, anti-abrasion agents, solubilizing agents, Metal deactivators, additives for extreme pressures, substances to improve the Viscosity index ', agents that lower the pour point, substances that change the viscosity (for example Glycerine), anti-foaming agents, wetting agents, adhesives, cohesive agents, emulsifiers or de-emulsifiers, emulsion breaking agents, slurry dispersants, slurry reducing agents Agents, boil-reducing agents, detergents and swelling-reducing agents. Connections like

can be added as a thickening agent. The abovementioned further additives can be used in quantities from 0.1 to 5 parts by weight, preferably from 0.5 to 2 parts by weight per 100 parts by weight of the base liquid, to be available.

High-pressure additives include graphite, talc, molybdenum sulfide and the alkylamine salts the acidic alkyl esters of phosphoric acid in which the amine salt is at least 25 percent by weight, and the alkyl radicals contain 8 to 18 carbon atoms. Suitable include z. B. Dodecylamine dodecylic acid phosphate, Mixtures of 25 to 95% dodecylamine dodecyl acid phosphate and 75 to 95% Dodecyl dihydrogen phosphate, octylamine dioctyl phosphate, di- (decylamine) dodecyl phosphate, hexadecylamine dodecyl acid phosphate, Octadecylamine dioctadecyl phosphate and mixtures of 2-ethylhexylamine, 2-ethylhexyl acid phosphate and 2-ethylhexyl dihydrogen phosphate equal parts.

Suitable additives for reducing abrasion include the amine salts of long-chain aliphatic acids, neutral aryl phosphates and neutral alkyl aryl phosphates. May be mentioned of this group triethanolamine laurate, the dipropylamine, dibutylamine and diamylamine salts of lauric acid, Triphenyl phosphate, tricresyl phosphate, butyl diphenyl phosphate, phenyl dibutyl phosphate, benzyl dicresyl phosphate, Trixylyl phosphate and diphenyl cresyl phosphate.

Suitable additives for deactivating metals include quinizarine and alizarine.

Among the antioxidants that can be added to the lubricants of the invention are to mention among others:

1. Aromatic compounds which have at least one substituent through which the compound the oxidation becomes more accessible, such as an amino, a hydroxyl or a Alkoxy group, and

2. Dialkyl Selenides.

Examples of the substituted aromatic antioxidants mentioned include primary, secondary and tertiary arylamines, e.g. B. diphenylamine, n-phenyl-a-naphthylamine, N-phenyl-p'-naphthylamine and Ν, Ν'-bis-dinaphthyl-p-phenylenediamine: hydroxyl substituted aromatic compounds including alkyl substituted monophenols, e.g. B. 2,6-di- (tert-butyl) -4-methylphenol and 6-tert-butyl-m-cresol; aryloxy substituted phenols such as

2 - (tert - butyl - 4 - phenoxyphenol; triphenols (e.g. Pyrogallol); Diphenols (e.g. 4 - tert - butylcatechol, 4 - phenylcatechol, 2,5 - di - (tert - butyl) - hydroquinone,

3 - methylcatechol and cyclohexylcatechol), di (hydroxyphenol) alkanes (e.g. bis (2 - hydroxy - 3 - tert-butyl-5-methylphenol) methane), Di-naphthols (e.g. 1,5-dihydroxynaphthylene), hydroxyl-substituted Arylamines (e.g. orthoaminophenol and N - butylp-aminophenol) and aralkoxy-substituted phenols (e.g. hydroquinone monobenzyl ether), as well as dialkoxy-substituted ones aromatic compounds (e.g. hydroquinone dimethyl ether). Preferred aromatic antioxidants are alkyl-substituted monophenols such as 2,6-di- (tert-butyl) -4-methylphenol and secondary ones Arylamines, such as N-phenyl-a-naphthylamine, N-phenyl- / S-naphthylamine and Ν, Ν'-bis-dinaphthyl-p-phenylenediamine. It has been found that aromatic Antioxidants containing amino groups, especially secondary amino groups, are generally more effective than aromatic antioxidants in stabilizing lubricants, which only contain hydroxyl groups as substituents.

Dialkyl selenides, which are suitable as antioxidants, include dihexyl selenide, didodecyl selenide, Hexyldodecyl selenide, di (ethylhexyl) selenide, dioctadecyl selenide and isooctylhexadecyl selenide. In these Compounds contain the alkyl radicals bonded to the selenium atom, preferably 6 to 18 carbon atoms.

Among the anti-corrosion agents that are used in the, according to the invention Preparations that can be used include morpholine, the alkali (Na and K) nitrites, the alkali mercaptobenzothiazoles, among others (e.g. the sodium salt), disalicylpropylenediamine, amino-organic silicon compounds, alkali salts of carboxyorganosiloxanes, alkenylsuccinic acids and their anhydrides, acidic dialkyl phosphates, Sorbitan monooleate, butyl stearate, butyl naphthenate and aluminum stearate.

Aminoorganosilicon compounds that can be added to the preparations according to the invention as corrosion inhibitors include both the aminoorganohydrocarbonoxysilanes and the aminoorganosiloxanes in which the organic radical is a divalent hydrocarbon group with at least 3 carbon atoms and in which the amino group has at least three consecutive carbon atoms of the organic radical Silicon is bonded. Organic amino hydrocarbonoxysilanes suitable as corrosion protection agents include ^ - (aminophenyl) ethyltriethoxysilane, γ - aminopropyltriethoxysilane, N- {ß- aminoethyl) -γ- aminopropyltriethoxysilane and p-aminomethylphenyltriphenoxysilane. Suitable aminoorganosiloxanes include the homopolymers composed of /? - (aminophenyl) -äthylsiloxy-, γ-aminopropylsiloxy, N - (/ S-aminoethyl) -y-aminopropylsiloxy or p-aminomethylphenylsiloxy groups, as well as copolymers of the mentioned Aminoorganosiloxy groups and hydrocarbonsiloxy groups (e.g. methylsiloxy, dimethylsiloxy, trimethylsiloxy and triphenylsiloxy groups). Alkali salts of carboxyorganosiloxanes, which can be added to the agents according to the invention as corrosion inhibitors, include the alkali salts of carboxyalkylsiloxanes in which the carboxyl groups are bonded to silicon via at least two successive carbon atoms of the alkyl radical. Such siloxanes include homopolymers of

KOOCCH ₂ CH ₂ SiO ₁₅ -, KOOCCH ₂ CH ₂ SiO ₁₅ -,
NaOOCCH ₂ CH ₂ SiO _{1 5} -, NaOOCCH ₂ CH ₂ Si (CH ₃ ) O- 'and

LiOOC (CH ₂ ^ Si (C ₆ Hs) ₂ O _0-5 groups,

as well as copolymers of one or more of these units, one or more hydrocarbylsiloxy units and / or one or more alkali metal oxy-substituted tetrafunctional SiI-oxy groups

(e.g. NaOSiO _li5 , (NaO) ₂ SiO, (NaO) ₃ SiO ₀₁₅ ,
KOSiO _{1> 5} and LiOSiO ₁₅ ).

The alkenyl succinic acids and anhydrides useful as corrosion inhibitors in the invention Preparations can be used,

4c are the reaction products of α-olefins such as 1-n-octene, 1-n-pentene and maleic acid or its anhydride. In this anti-corrosion agent the alkenyl radical preferably contains 8 to 12 carbon atoms.

The alkenylsuccinic acids and their anhydrides which can be used as corrosion inhibitors are the reaction products of α-olefins (e.g. 1-octene and 1-pentene) with maleic acid or its anhydride, the alkenyl groups preferably containing 8 to 12 carbon atoms. Examples include the Octenyl succinic acid and pentenyl succinic acid and its anhydrides.

The acidic dialkyl phosphates, which are added to the agents according to the invention as anti-corrosive agents preferably each contain 8 to 12 carbon atoms in the alkyl radical. Illustrative for this are the acidic dioctyl and didecyl phosphates.

The way in which the preparations according to the invention are produced is not decisive d. that is, the components can be in any order in any suitable device are mixed together. Those applicable to the preparation of the usual aqueous lubricants Procedures are also applicable here.

The aqueous lubricating oil emulsions according to the invention are preferably suitable as lubricants in metalworking, especially for own metals. When cutting metals and others

Cutting, shaping and machining methods, these preparations are valuable Auxiliaries, also as hydraulic fluids and as mold release agents for rubber and The emulsions are suitable for plastics, whereby they are applied to the injection molds in a known manner will.

The agents according to the invention were tried out with the aid of the following experiments.

Falex load and abrasion test

The lubricants according to the invention were tested in a Falex apparatus for lubricant testing tested. The jig consisted of a shaft and two steel F-blocks that were so attached were that they could be pressed against the shaft. The shaft and the F blocks were in that the lubricant to be tested is immersed. The shaft was set in rotation, and onto the F-Blocks a load was applied which pressed them against the shaft. The burden has been so long increased until "seizure" occurred, d. H. a blockage between the rotating shaft and the F-Blocks or a drastic increase in abrasion without increasing the load. The load at which These phenomena occur is the "Falex Load" for that Lubricant. The Falex exposure values for various known liquids are the following:

IO

Maintaining a certain load gives a measure of the abrasion on the test shaft. An advance by one notch or one tooth on the load wheel indicates 0.145 μ of wear on the test shaft.

During the test, the shaft and F-block are immersed in the lubricant to be examined.

The experiment consists of the following individual operations:

1. At the beginning of the experiment, leave the wave between the F-blocks for 3 minutes at one Rotate load of 45.4 kg.

2. The load is then increased by 45.4 kg per minute up to 454 kg.

3. When the load of 454 kg is reached, the further increase takes place every minute by 113 kg until blocked or up to a maximum load of 2040 kg.

4. The turning power (torque) and temperature are noted every minute.

5. In each one minute interval, the abrasion is listed on the test shaft as to provide the desired load ™ maintain number of notches (grooves) on the load factor, which had to be adjusted like.

After the end of the experiment, the average The width of the grinding track created on the F-Blocks measured microscopically and the contact pressure calculated from the following formulas:

liquid Load value in kg C ₄ H ₉ (OC ₃ Hg) ₆ OH 181 C ₄ H ₉ (OC ₃ H _{6) 17j7} OH 567 Dimethylpolysiloxane oil <45.4 Petroleum raffinate (viscosity - 44SUS at 99 ° C) <227 Refined paraffin oil (viscosity = 52SUS at 99 ° C) <227

30th

35

40

The amount of abrasion was determined so that the load on the F blocks for a certain time (e.g. 1 hour or 3 hours) constant at e.g. B. held 90.7 or 454 kg. The one through contact with The weight loss in milligrams produced by the F-Blocks on the rotating shaft is then the »Falex abrasion« for the lubricant in question.

The lubricants were rated on a Falex tester. This experimental set-up consists of an exchangeable shaft with a diameter of about 6 mm (mild steel mandrel no. 8), which rotates at 290 rev / min runs between two steel F-blocks. The shaft can be made from SAE 3135 steel with a Rockwell B hardness of 87 (tempered to 8 to 10 RMS) and the two F-Blocks can be made of AISI-C-1137 steel with a Rockwell C hardness of 20 (tempered to 6 to 8 RMS) (method I). With another The shaft can be made from M-2 tool steel with a Rockwell C hardness of 60 (tempered to 12 to 14 RMS) and the two F-Blocks can be made of 440-C stainless steel with a Rockwell-C hardness of 60 (remunerated to 12 to 14 RMS) exist (Method II).

The F-Blocks are arranged so that they are pressed against the shaft by a notched load wheel. Adjustment of the loading wheel during the experiment to ensure a pre-loading when blocked
Bearing load in kg

Bearing load

= Pressure in kg / cm ²

Track length ■ Track width in cm

Track length = 1.25 cm

The invention is explained in more detail using the following examples:

example 1

The behavior of an aqueous emulsion containing about 0.2 weight percent emulsion solids and about 0.2 percent by weight of the copolymer 18 were taken on the Falex apparatus Application of method I assessed. The results are given in Table IV.

Table IV

Designation
tion of the
emulsion Type of emulsion load
at the
To block
in kg Emulsifier
Type A.
no Polyethylene
0.2 percent by weight
Copolymer 18
(Control experiment) > 2040
567 not
Ionic

From the table it can be seen that the combination of an aqueous polyolefin emulsion with a siloxane-oxyalkylene copolymer results in a lubricant with very good loading properties which successfully prevents seizure.

Example 2

The effect of adding a siloxane-oxyalkylene copolymer to an aqueous polyolefin emulsion on the contact pressure was in a Falex apparatus determined using Method II. The results are given in Table V:

Table V

Approved lubricant in water,

containing 0.1 percent by weight

Copolymer 18

load
when blocking

in kg

Medium track width

Contact pressure
in kg / cm ²

0.1 percent by weight additional copolymer 18 567

0.1 weight percent Emulsion F (solids) 1470

0.1 percent by weight Emulsion A (solids)> 2040

0.1 weight percent Emulsion A (solids) ·. 1810

0.1 weight percent Emulsion I (solids) 1250

0.1 percent by weight triethanolamine laurate (soap) 1130

Proof of synergism - (see above)

0.2 percent by weight Emulsion F (solids)

0.2 percent by weight emulsion A (solids)

0.2 percent by weight copolymer 18

0.124

0.04

0.04

0.035

0.053

0.03

1130 0.038 16900 1360 0.04 18300 567 ' 0.124 2810

2810
20400
28100
28100
13400
21100

Characterization of the above emulsions

Emulsion A:

Aqueous, nonionic emulsion of a chemically inert polyethylene of low molecular weight, emulsified with the aid of a polyoxyethylene derivative of an aliphatic compound.

Emulsion F:

Aqueous, nonionic emulsion of cracked high density polyethylene (molecular weight about 2000), modified with about 5 percent by weight maleic anhydride and emulsified with a mixture of nonylphenyl polyethylene glycol ethers with about 4 to 7 moles of ethylene oxide and with morpholine.

Emulsion I:

Aqueous, nonionic emulsion made of low density polyethylene (molecular weight approx 24,000), produced by emulsion polymerization.

The data in the table show that the combination of a siloxane-oxyalkylene copolymer obtained a synergistic increase in contact pressures with a polyolefin in aqueous emulsion can be.

Concentrated mixtures of the basic liquid described above with various large proportions on the described siloxane-polyoxyalkylene copolymers can be stored and shipped easily and at low cost. Such mixtures can then be diluted just before use to give the aqueous lubricant emulsions to obtain according to the invention. The concentrated mixtures can be above 0.1 up to 0.5 or even up to contain 0.7 parts by weight of copolymer per part by weight of base liquid. You can also contain the various additives described above, in amounts from over 0.05 parts to to 0.25 or even up to 0.35 parts by weight per part by weight of base liquid. The dilution of this Mixtures of the aqueous lubricant preparations according to the invention can easily be added perform by having the mixtures with water or with mixtures of water and a organic lubricant base fluid mixed. In addition to the additions already mentioned, their list is not complete, a base (e.g. sodium hydroxide) can be added to the lubricants. added, if necessary or desirable, the pH value above 7 to keep. Also antimicrobial agents such as an aqueous solution of di (phenylmercuri) ammonium propionate in an amount corresponding to about 6 percent by weight of mercury, the invention Lubricants are added. Other bactericidal agents that are also added to the lubricants are chlorophenols, neomycin sulfates, 6-acetoxy-2,4-dimethyl-m-dioxane

and the like. Silicones as antifoam agents can also be added, with z. B. Dimethylpolysiloxane oils with trimethylsiloxy groups as end blocks and a viscosity of 350 to 500 cSt at 25 ° are particularly suitable. Such oils can be mixed with finely divided silica, e.g. B. with 3 percent by weight SiO ₂ , mixed.

209 513/338

Claims (4)

Patent claims: 1. Aqueous lubricants, in particular according to patent 1,719,036, consisting of a) a base liquid in the form of water or of water and up to about 2 parts by weight per part by weight Organic liquid lubricant water, namely 1. a silicon-free polyoxyalkylene compound, 2. a dialkyl ester of an aliphatic dicarboxylic acid, 3. a hydrocarbon lubricating oil and / or 4. an ester of a polyalcohol and a fatty acid,