DE1545342C3 - Mixtures of lubricants and fuels - Google Patents

Description

CH = CH ₂

in which R ^{1 is} hydrogen, an alkyl radical with up to 18 carbon atoms, an aralkyl radical with up to 18 carbon atoms, an alkyl-substituted aralkyl radical with up to 18 carbon atoms, a dialkylaminoalkyl ^{radical with up to 12 carbon atoms or the furfuryl radical, R 2 in} each case denotes hydrogen or the methyl radical R ³ is hydrogen, an alkyl radical with up to 18 carbon atoms, phenyl, naphthyl, chlorophenyl, chloronaphthyl, an alkylphenyl radical in which the alkyl moiety contains up to 18 carbon atoms, an alkylnaphthyl radical in which the alkyl moiety contains up to 18 carbon atoms, an alkoxyphenyl radical in which the alkyl moiety contains up to 18 carbon atoms, an alkoxynaphthyl radical in which the alkyl moiety contains up to 18 carbon atoms, an aralkyl radical with up to 18 carbon atoms, an alkyl-substituted aralkyl radical with up to 18 carbon atoms or the 2-furyl radical , R ^{4 are} each hydrogen or an alkyl radical with 2 denotes up to 4 carbon atoms, R ⁵ each denotes hydrogen or an alkyl radical having up to 4 carbon atoms, R ² and R ³ together, including the carbon atom to which they are bonded, denote a five to seven-membered saturated ring which can optionally have alkyl substituents, where the total ^{carbon content of R 2} and R ³ together is up to 18 carbon atoms, and R ⁴ and R ⁵ together, including the carbon atom to which they are attached, represent a five- to seven-membered saturated ring which may optionally contain alkyl substituents, where the total ^{carbon content of R 4} and R ⁵ together is up to 18 carbon atoms.

2. Mixture according to claim 1, characterized in that it is at least 0.1 percent by weight of the copolymer as well as a lubricating oil.

3. Mixture according to claim 1, characterized in that it is at least 0.001 percent by weight of the copolymer as well as a hydrocarbon-based fuel.

4. Mixture according to claim 1, characterized in that it contains a copolymer which by using at least 2 percent by weight of that represented by the formula in claim 1 reproduced connection has been received.

5. Mixture according to claim 1, characterized

ίο The invention relates to mixtures such as fuels and lubricants in which specific N-vinyl-2-piperazone polymers are incorporated as an essential component are. The fuel compositions are durable and rust preventive. The lubricant compositions are characterized in that they have detergent properties and one which lowers the pour point Have an effect and that they improve the viscosity. The lubricants perform superbly with regard to the dispersion of sludge.

From U.S. Patent 3,067,163 are oil-soluble Graft copolymers known that by free radical polymerization of at least one by free radical polymerizable monoethylenically unsaturated compound or a mixture of one or more such compounds and a hydrocarbon polymerizable by free radicals, Forming a mixture of polymers and monomers, adding one to this mixture Nitrogen-containing polymerizable monovinylidene compound which is at least 2 different Carries substituents, and continuing the polymerization of this mixture and the added monovinylidene compound, obtained and incorporated into lubricating oils based on mineral oils. In the U.S. Patent 2,944,974, improved mineral oil-based lubricating oil blends are disclosed which have a small amount of an oil-soluble co-polymer (with a high molecular weight)

1. a monovinyl-substituted pyridine such as un-

substituted vinylpyridine and derivatives thereof, with a ring carbon atom lower alkyl group is substituted,

2. a mixture of a stearyl ester of an acrylic acid and a lauryl ester of an acrylic acid and

3. a Q-4 alkyl ester of acrylic acid in an amount from 10 to 60 mole percent of mixture 2, the molar ratio of 1, 2 and 3 varying from 1: 2 to 1:10 and the polymer having an average alkyl chain length of 12-14 C atoms and the copolymer has a molecular weight of 5 · 10 ⁴ to 2.5 · 10 ^e ,

contain.

Neither U.S. Patent 3,067,163 nor U.S. Patent 2,944,974 is that disclosed Compound a heterocyclic compound with more than one nitrogen atom in the ring, as opposed to the structures used according to the invention. However, there is not just one major structural one Difference between the compounds used in these patents and those according to the invention used piperazinone mixtures, but it is also mentioned in the USA patents not suggested a piperazinone as a copolymer component for use as a detergent for Use lubricating oils. The fact is that the insertion of the second nitrogen atom into the hetero-

cyclic ring markedly reduces the oil solubility. For this reason it couldn't be obvious to provide improved sludge dispersing. properties of using a piperazinone. Yet surprisingly, this extremely valuable result was obtained. That was neither from the USA. Patent specification 3,067,163 or in any way indicated by U.S. Patent 2,944,974.

The present compositions are obtained by being in a fuel or in a lubricant of at least one of the polymers of the specific N-vinyl-2-piperazone with the general formula

R ¹

/ R ² R ⁴ - ( \
I-
\ _N / -R ³ R ⁵ -I _n CH = = O CH

R ⁴ means hydrogen, methyl, ethyl, isopropyl or t-butyl.

R ⁵ means hydrogen, methyl, ethyl, isopropyl or t-butyl.

In addition, R ⁴ and R ⁵ together, including the carbon atom to which they are attached, denote pentamethylene, hexamethylene or heptamethylene rings, which in turn may have alkyl substituents, such as. B. methyl, ethyl, butyl, dimethyl or diethyl groups. The limit for R ⁴ and R ⁵ is a total of 18 carbon atoms.

The N-vinyl-2-piperazones are obtained by reacting acetylene with a compound of the following general formula

R ¹

N ^R2

_R 4_ / \ ^ R ³

R ⁵ - _x I = O

r *

incorporated. In this general formula, R ¹ denotes hydrogen, an alkyl group, such as. B. a cycloalkyl group with up to 18 carbon atoms, an aralkyl or alkyl-substituted aralkyl group with up to 18 carbon atoms, a dialkylaminoalkyl group with up to 12 carbon atoms, each of these alkyl groups containing up to 8 carbon atoms, or a furfuryl group. R ² is in each case hydrogen or a methyl group. R ^{3 in} each case denotes hydrogen, an alkyl group, including a cycloalkyl group, with up to 18 carbon atoms, a phenyl, naphthyl or alkyl, chlorine or alkoxy-substituted phenyl or naphthyl group in which the alkyl part contains up to 18 carbon atoms, an aralkyl - or an alkyl-substituted aralkyl group with up to 18 carbon atoms or a 2-furyl group. R ⁴ each denotes hydrogen or an alkyl group with up to 4 carbon atoms and R ⁵ each denotes hydrogen or an alkyl group with up to 4 carbon atoms.

^{R 1} is preferably hydrogen, methyl, ethyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl, octyl, dodecyl, octadecyl, benzyl, phenylethyl, phenylbutyl, phenyloctyl, dimethylbenzyl, dibutylbenzyl, octylbenzyl, amine nonylbenzyl, dimobethylaminoethyl, Dibutylaminoethyl, dipentylaminoethyl or furfuryl.

R ² is hydrogen or methyl. R ³ can be hydrogen, methyl, ethyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl, octyl, decyl, dodecyl, octadecyl, phenyl, naphthyl, chlorophenyl, dichlorophenyl, butylphenyl, dibutylphenyl, octylphenyl, nonylphenyl, methoxyphenyl, t-butoxyphenyl, , Chloronaphthyl, butylnaphthyl, octylnaphthyl, methoxynaphthyl,
Ethoxynaphthyl, benzyl, phenylethyl, phenylbutyl, phenyloctyl, dimethylbenzyl, dibutylbenzyl, octylbenzyl, nonylbenzyl or 2-furyl.

In addition, R ² and R ³ together, including the carbon atom to which they are attached, denote pentamethylene, hexamethylene or heptamethylene rings, which in turn may have alkyl substituents, such as. B. methyl, ethyl, butyl, dimethyl or diethyl groups, R ² and R ³ are limited together to a total of 18 carbon atoms.

N '
H

implements, in which the symbols have the meaning given above.

The reaction between acetylene and 2-piperazone can take place at normal or elevated pressure, such as. B. to about 140 kg / cm ² , can be carried out discontinuously or continuously. It can be carried out in the presence or absence of a solvent, although a solvent is generally preferred, especially if the vinylation is carried out at elevated pressure. Suitable solvents are inert organic compounds, such as. Dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, isopropanol, tetrahydrofuran, dioxane and. The like. There are temperatures between about 100 and 25O ⁰ C, preferably employed between 130 and 220 ⁰ C.

Acetylene and 2-piperazone are in the presence of a strongly basic vinylation catalyst such as z. B. of an alkali metal, an alkali hydroxide and an alkoxide. Typical in this regard are sodium, potassium, sodium methylate, sodium butylate, sodium hydroxide, potassium ethylate, potassium methylate and potassium hydroxide. Sodium metal, potassium metal, sodium methylate and are preferred Potassium methylate is used. The vinylation is generally carried out in such a way that acetylene, preferably in a solvent, in the corresponding 2-piperazone in liquid or molten State, or preferably in a solvent, introduces until the desired vinylation is finished. After the reaction has ended, the N-vinyl-2-piperazones are isolated by distillation, which is described in more detail below.

The above-described N-vinyl-2-piperazone can with one or more, ethylenically unsaturated polymerizable monomers are homopolymerized or copolymerized. Naturally it is necessary for the above purpose that the polymers have sufficient oil solubility, in order to be able to be incorporated into the compositions according to the invention.

Suitable mixed monomers are alkyl and aryl acrylates, in which the alkyl or aryl moiety preferably contains 1 to 18 carbon atoms; Alkyl and

Aryl methacrylates, in which the alkyl or aryl part preferably contains 1 to 18 carbon atoms; Acrylonitrile, Methacrylonitrile, alkylaminoalkyl and dialkylaminoalkyl acrylates and methacrylates, acrylamide and Methacrylamide and its N-alkyl-substituted derivatives, Styrene and alkyl ring-substituted styrenes, a-methylstyrene, Vinyl esters in which the carboxylate moiety contains up to 18 carbon atoms, including the Carbon atom of the carboxyl group; Vinyl alkyl ethers and vinyl alkyl sulfides, in which the alkyl moiety contains no more than 18 carbon atoms, and N-vinyl lactams, preferably having 6 to 20 carbon atoms; Alkyl vinyl sulfones in which the alkyl moiety contains up to about 18 carbon atoms; N-vinylalkylene ureas having 5 to 12 carbon atoms; Olefins such as B. isobutylene, butadiene and isoprene; Dialkyl fumarates of up to 24 carbon atoms; Dialkyl maleates with up to 24 carbon atoms and dialkyl itaconates with up to 24 carbon atoms and vinyl pyridines.

In the above monomers, the alkyl groups can have all possible spatial configurations have such. B. normal, iso- or tertiary configuration. These alkyl groups can be aeylic or be cyclic and alkyl-substituted cyclic Groups, insofar as the total number of carbon atoms corresponds to that specified. In the ring-substituted Styrenes, the substituents can have all possible ring positions, and if the substituents Are alkyl groups, they can have any spatial configuration.

Typical monomers that can be used are '.

Methyl acrylate,

Isopropyl acrylate,

Cyclopentyl acrylate,

2-ethylhexyl acrylate,

Decyl acrylate,

Dodecyl acrylate,

Octadecyl acrylate,

Methyl methacrylate,

t-butyl methacrylate,

Cyclohexyl methacrylate,

Octyl methacrylate,

Undecyl methacrylate,

Dodecyl methacrylate,

Phenyl methacrylate,

Dimethylaminoethyl methacrylate,

Methoxyethoxyethyl methacrylate,

t-butylaminoethyl methacrylate,

t-dodecylaminoethyl acrylate,

Octadecyl methacrylate,

Acrylonitrile,

Methacrylonitrile,

N, N-dibutyl acrylamide,

Acrylamide,

N-methyl acrylamide,

N-t-octyl acrylamide,

Styrene,

p-butyl styrene,

p-octylstyrene,

o-chlorostyrene,

o, p-dipropyl styrene,

p-cyanostyrene,

o-methyl-p-decylstyrene,

Ureido ethyl vinyl ether,

Butyl vinyl sulfide,

Octyl vinyl sulfide,

Octadecyl vinyl sulfide,

Hydroxyethyl vinyl sulfide,

N-vinyl-2-pyrrolidone,
N-vinyl-S-methyW-pyrrolidone,

N-vinyl-4,4-dimethyl-2-pyrrolidone,

N-VinyM-butyM-octyl ^ -pyrrolidone,

N-vinyl-6-methyl-2-piperidone,

N-vinyl-o-octyW-piperidone,
ίο N-vinyl-2-oxohexamethyleneimine,

N-vinyl-5,5-dimethyl-2-oxohexamethyleneimine,

N-vinyl-4-butyl-5-octyl-2-oxohexamethyleneimine, methyl vinyl sulfone,

Isobutyl vinyl sulfone,
t-octyl vinyl sulfone,

Dodecyl vinyl sulfone,

Octadecyl vinyl sulfone,

N-vinyl ethylene urea,

N-vinyl trimethylene urea,
N-vinyl-l ^ -propylene urea,

N-vinylbutylene urea,

N-vinylcarbazole,

Vinyl acetate,

Vinyl stearate,
as dimethyl maleate,

Dioctyl maleate,

Dimethyl itaconate, '

Dibutyl itaconate,

Dihexyl itaconate,
Dimethyl fumarate,

Diethyl fumarate,

Dioctyl fumarate,

Dibutyl fumarate,

Didodecyl fumarate,
Dibutyl maleate,

Dihexyl maleate,

Didecyl maleate,

Diethyl itaconate,

Didodecyl itaconate and
2-methyl-5-vinyl pyridine.

It will be understood that in many instances it will be desirable, and often preferred, one or more of the specific N-vinyl-2-piperazones described above with one or more of the foregoing Mixed polymers combine to produce various modifications and properties of the product achieve. Of course it is for the purposes at hand It is necessary that the interpolymers have sufficient oil solubility, and it is therefore for those skilled in the art it is clear that the mixed monomer is selected to impart this oil solubility.

Typical mixed monomers that give oil solubility, are z. B. Acrylates and methacrylates, in which the alcohol radical contains 6 to 18 carbon atoms, and itaconates, fumarates and maleates in which the alcohol moiety contains 6 to 24 carbon atoms. Particularly valuable in this regard are octyl, nonyl, dodecyl, isodecyl, isononyl, tridecyl, tetradecyl, Octadecyl, phenyl, benzyl, cyclohexyl and alkylphenyl acrylates and methacrylates, itaconates, maleates and fumarates.

Another valuable type of starting material consists of the vinyl esters of monocarboxylic acids.

Here the oil solubility can be regulated by the size of the hydrocarbon content of the acid residue will. If such an ester or a mixture of such esters is used to produce the mixed poly-

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mers used, it is usually desirable that azodiisobutyronitrile,

the average group size at least 8 Koh- azodiisobutyramide,

Ienstoffatome is. Dimethyl, diethyl or dibutylazodiisobutyrate,

Together with the above-mentioned mono- azobis- (a, oc-dimethylvaleronitrile),

mers can be used to achieve the final mixed 5 azobis (a-methylbutyronitrile),

polymeric smaller amounts of other monomers, azobis- (a-methylvaleronitrile),

such as B. acrylic acid, methacrylic acid, or itacone dimethyl or diethylazobis-a-methylvalerate

acid, maleic anhydride, half esters of maleic and the like. acid, fumaric acid or itaconic acid, acrylamide,

N-substituted acrylamides, methacrylamide, N-substituted ίο In connection with a hydroperoxide it is classified Methacrylamides, acrylonitrile, methacrylonitrile, want, but not absolutely necessary, an active vinyl ester of lower monocarboxylic acids, vinyl vator to be used. It works at least in part ethers, vinyl thioethers, vinyl ketones, vinyl chloride and the formation of free radicals at slightly lower levels Vinylidene chloride can be used. Temperatures than when using Hydro-Es it is preferred that the peroxides described above be as specific as possible in the absence of such activators N-vinyl-2-piperazone with an alkyl borrowed.

(C ₁ -C ₁₈ ) methacrylate, alkyl (Cj-C ₁₈ ) acrylate, acrylic Quaternaries are particularly effective as activators

amide, acrylonitrile, DialkyHCi-Ci ^ fumarate, dialkyl ammonium compounds. Typical connections

(C ₁ -C ₁₈ ) maleate, styrene or vinyl ester to be used. are of this type

In most cases, the mixed poly- * ° Benzyltrimethylammonium chloride,

meren of the present invention from a speci- dibenzyldimethylammonium bromide,

fish heterocyclic compound with one or butyldimethylbenzylammonium chloride,

the other of the above-mentioned monomers octyltrimethylammonium chloride,

manufactured, however, it is satisfied for many purposes- dodecyldimethylbenzylammonium chloride,

providing additional monomers as required * 5 nonylbenzyltrimethylammonium chloride,

turn to the desired properties for dodecylbenzyldimethylbenzylammonium chloride,

End product to come. Didodecenyldimethylammonium chloride,

Homopolymers can be used in the benzyldimethyldodecenylammonium chloride according to the invention,

Compositions are used insofar as they are Octylphenoxyäthyldimethylbenzylammonium-

have a sufficient amount of oil. Mixed polymers, 30 chloride

the Diisobuty'lphenoxyäthoxyäthyldimethylbenzyl- in the compositions according to the invention

can be used in terms of percent ammonium chloride

Sets and molecular units vary widely. The pre-octylpyridinium chloride

The valuable properties described above are N-Octyl-N-methylmorpholinium chloride or (

observed when only 0.5 percent by weight of the specific 35 bis-quaternary salts, such as those

fish N-vinyl-2-piperazons m the copolymers _{the quater} nary nitrogen atoms, to an alkylene,

be used. In general, however, it is _{bound to ether or amide-} containing group,

preferred, about 2% or more of the specific. have to use N-vinyl-2-piperazone monomers. as

The upper limit is the use of around 80%. The amount of activator is determined by the hydroper weight percent of N-vinyl-2-piperazone monomers matched in the amount of oxide. Usually there is a lot Mixed polymers provided. proportion of quaternary ammonium between 5 and

The polymerization can be carried out as a block polymerization of 40 percent by weight of the hydroperoxide, The solution polymerization can be carried out when the monomers are liquid in kerosene, Mikeiten or low-melting solids, but 45 mineral oils, diesters, such as. B. di- (2-ethylhexyl) adipate also in solution or suspension or emulsion. At or sebacate, chlorinated hydrocarbons, such as Block and solution polymerizations can z. B. chloroform or ethylene chloride, tributyl phosphate be carried out without a catalyst and phate, dibutylphenyl phosphate, silicate esters or fiüsmit Light and heat are introduced. It will use silicones, benzene, toluene, xylene, but solutions preferred, one or more peroxide or 5 ° benzines, dioxane, diisobutyl ketone, acetonitrile, di-azo initiators to use the free radicals methylformamide, t-butyl alcohol and the like Catalysts between 30 and 150 ° C act on the solubility of the monomers that are used are sam. They can be carried out in amounts from 0.01 to 10, % by weight, preferably 0.01 to 1% by weight. Emulsion polymerization is particularly effective can be used. Typical initiators are 55 with those members of the heterocyclic series,

which have a low solubility in water. To the her-

Benzoyl peroxide, the emulsion can be nonionic or

t-butyl peroxide, cationic emulsifiers can be used, such as

Acetyl peroxide, e.g. B. Dodecyldimethylbenzylammonium chloride, Do-

Caprylic peroxide, 60 decylbenzyltrimethylammonium chloride, cetylpyridi-

t-butyl hydroperoxide, nium chloride, alkylphenoxypolyäthoxyäthanole with

Cumene hydroperoxide, 7 to 18 carbon atoms in the alkyl groups and

t-butyl perbenzoate, 6 to 60 or more ethylene oxide units, such as. B.

Diisopropylbenzene hydroperoxide, heptylphenoxypolyethoxyethanol, octylphenoxy

Triisopropylbenzene hydroperoxide, 65 polyethoxyethanols, methyloctylphenoxypolyethoxy-

Methylcyclohexane hydroperoxide, ethanols, nonylphenoxypolyethoxyethanols, dodecyl

di-t-butyl peroxide, phenoxypolyethoxyethanols and the like, as well as polyethoxy

Methyl ethyl ketone peroxide, ethanol derivatives of methylene-bonded alkylphen

9 10

nolen; sulfur-containing agents, such as ζ. B. Means that are ethylenically unge "with or together with another"

the condensation of 6 to 60 or more moles of ethylene-saturated polymerizable monomers, preferably

oxide with nonyl, dodecyl, tetradecyl, t-dodecyl wise, but not necessarily, in the presence

and the like, mercaptans or with alkylthiophenols with a free radical catalyst.

Alkyl groups with 6 to 15 carbon atoms obtained 5 The initiator and the activator can partly from

will; Ethylene oxide derivatives of long-chain car- time to time or all together at once depending on

carboxylic acids, such as B. lauric, myristic, palmitic, wish can be added. In general, the

Oleic acid and the like, or mixtures of acids, the partial addition is preferred.

be found in tall oil, for example, with 6 to The finished interpolymers can be in a liquid. 60 oxyethylene units per molecule; analogous Ethy- io such as a petroleum or a synthetic lenoxide condensate of long-chain alcohols, such as lubricants, and a concentration. B. octyl, decyl, lauryl or cetyl alcohols occurred with about 10 to 60% of the mixed polymer her-Äthylenoxydderivate of etherified or esterified are made. The volatile solvent and the polyhydroxy compounds with a hydrophobic monomer can be obtained from the mixture of the mixed poly-hydrocarbon chain, such as. B. sorbitol monostearate, 15 mers and the oil or synthetic lubricant containing 6 to 60 ethylene oxide units, etc .; des- be evaporated. The concentrate can be easily ported, stripped and mixed with equal ethylene oxide condensates from long-chain ones,
or branched chain amines, such as. B. Dodecyl- The copolymers can vary greatly in terms of amine, hexadecylamine and octadecylamine, with 6 up to the molecular weight, through changes in 60 oxyethylene groups, block copolymers of 20 the temperature, the reaction time of the catalyst ethylene oxide and propylene oxide with a hydro and the one used special monomers. The phobic propylene oxide, combined with a molecular weight obtained by viscosity measurements or multiple hydrophilic ethylene oxide. can be determined lie in general

In the case of emulsion polymerization, particularly between about 20,000 and 2,000,000 or more, a redox catalyst system is extremely effective. These low molecular weights are particularly desirable, include an organic peroxide such as. B. Benzoyl if the polymers are resistant to shear peroxide, acetyl peroxide, caprylic peroxide and the like., Or should be strong. The high molecular weight polymers are an inorganic peroxide, such as. B. hydrogen- desirable if maximum thickening effect or peroxide, ammonium persulphate, sodium persulphate, Ka- other optimal properties are required. The lium persulfat od. The like. The peroxide catalyst is in 30 Regulation of the molecular weights can be effective in Stan when using a reducing agent, such as methods such. B. by the use of e.g. B. a sulfite, bisulfite, metasulfite or hydrosulfite mercaptans, such as octyl mercaptan, vorgevon ammonium, sodium, potassium or the like.
ned. For the determination of the extent of the mixed poly-

The polymerization can also be initiated by means of energy merization, which can expediently be initiated simply by applying radiation. Suitable sources are used, which consists in the fact that one of high-energy rays are radioactive materials, the mixed polymers from the reaction mixture, beirials and electron accelerators. As radioactive for example by removing a volatile solution materials that deliver gamma rays are means, isolated. Estimating the extent of the isotopes emitted, such as B. Co ⁶⁰ , cleavage products, such as 4 ° formation of the copolymer is particularly useful for z. B. Cs ¹³⁷ , additives for cleavage reactions such. B. Determination of the correct interpolymerization time for radioactive xenon and the like of value One Co ^eo - for a given system of value in which the source is particularly effective. As radioactive material proportions of the initiator, the concentrations of materials that deliver beta rays, Sr ⁹⁰ and the like are set by and the temperatures.
Value. The Van-de-Graaf generator is valuable as electron accelerators that deliver beta 45. A 1-g sample of the mixed polymerization is measured using a resonance transformer and the like. Dosages of the mixed polymerizing mixture are taken in the range from 10,000 to 10,000,000 REP, preferred and dissolved in 5 ecm benzene. The solution obtained is 500,000 to 2,000,000 REP, using a REP mixed with 15 ecm of methanol. The mixed polymer corresponds to the ionization, which is precipitated by the absorption 5 ° and is separated by centrifugation, of 93 ergs, energy per gram of the irradiated sub- The compositions according to the invention are punched, is produced. REP stands for physical obtained by having about 0.001 to 10 Ge X-ray equivalents and is a unit of intensity percent by weight of at least one of the above and time. wrote N-vinyl-2-piperazone polymers in the

The interpolymerization of the monomers in the oil concerned or incorporated into the fuel. For what has been described above, the lubricants according to the invention can be achieved by essentially simultaneously mixing all monomers which are to be used in amounts of 0.1 to 10, preferably 0.2, up to 2.0 percent by weight. In the case of fuels or one of the mixed monomers, the range can in some cases be poly-between 0.001 and 0.1, preferably merized, and then another mixed monomers can be between 0.005 and 0.05 percent by weight
monomeric or other mixed monomers at a later point in time either all at once or in the advantageous combination of a high-grade partial amount. The copolymers effectiveness in terms of dispersing and pure N-vinyl-2-piperazone monomers can be obtained as low properties, the reduction of the cast-graft copolymers, that 65 point and to the improvement of the viscosity,
the polymerization of the oil-solubilizing part. In the following, some tests are described which carry out about 40 to 90% copolymers, which were then carried out to evaluate the valuable N-vinyl-2-piperazone monomer compositions according to the invention, either alone.

11 12

Dispersion test placed in heated oil sump and against a heated plate

sprayed, which is held at 299 ° C for 2 hours.

A method for determining the dispersant weight gain of the plate is determined and

Effect of any polymer is based on that compared to an oil, which the test compound does not

Capacity of the polymer, containing asphaltenes in a 5,

typical mineral oil to disperse. Sundstrand pump test

The asphaltenes are obtained by

a naphthenic oil with air under the influence of a In this test, the distillate fuel oils under-trace iron salt as a catalyst, such as. B. iron naphtha, 1 liter of the fuel oil, the 4 g thenat, is oxidized. The oxidation is preferably io a synthetic sludge, treated with the addition of 175 ⁰ C for 72 hours by passing the rate through. The oil is passed for 1 hour through a stream of air through a naphthenic oil in front of the Sundstrand oil burner pump, which has a sieve. The cooled oxidized oil will have pentane 1600 to 1760 mesh / cm ² . The mud added. In this way a sludge is obtained, deposits are collected and weighed (Nelson, which can be separated by centrifugation. Der 15 Osterhaut and Schwindemann, Ind. Eng . 1892 [1956]).
same freed with pentane. It is then taken up with chlorine The investigated fuels are distillate form and the solution obtained is adjusted to substances whose boiling range is between 24 and 400 ⁰ C, a solids content of about 2% weight per volume This includes gasoline together with nozzle and set. ao diesel fuels and heating oils. The present

If a polymer is to be investigated for its dispersing effect, compounds are particularly valuable for the investigation, so it is in a standard oil, turning in fuels, which up to about 315 ⁰ C such. B. a desolventized neutral boil, ie dissolved for use in normal gasoline oil of 100 SUS. Mixtures and jet fuels can be produced.

that is about 2 to 0.01% or less

Polymer contained in the oil. Mineral oils or synthetic lubricants based on

A sample of 10 ecm of a mixture is used. The mineral oils can have a large viscosity

2 ecm of a standard solution of asphaltenes in the range, for example between 1 and

Treated with chloroform. The sample and the reagent 25 centistokes at 99 ⁰ C is. These oils can

are thoroughly mixed in a test tube, and be naphthenic or paraffinic in nature. she

The test tube is can also consist of oil mixtures in a draft oven at 150 ⁰ C. she

Shut down for 2 hours to dispose of volatile materials. Distillates or mixtures of neutral oils

to drive. The test tube will then be cooled and that and unfinished cylinder oil will be. The lubricants

Examination of the appearance of the specimen. can be solid or gelled and can be used as fats.

If the polymer has a dispersing effect, it can be used if necessary. It is with the oils

the oil appears colored, but clear. from spindle oils or hydraulic oils to oils

Experience has shown that a polymer that is suitable for piston aircraft engines. This includes oils for not at least a dispersing effect on machines with spark ignition and compression concentrations of under about 2% in the pre-ignition with S.A.E. grades from 5 to 50. Others The standing test shows that the cleanliness of Ma- 40 types of lubricants are also not included, as machine parts improved in machine tests. z. B. hydraulic and automatic transmission

API Service MS Sequence V-A-Test ^ SS synthetic lubricants include esters, such as

In this test, the sludge dispersing z. B. dioctyl, dinonyl or isodecyl adipates, azelates

Properties of a lubricant at low and 45 or sebacates, polyethers and silicones. For hydraulic

rated at medium operating temperatures. In general, phosphate esters are used as the basic

cylinder oil testing machine is used among those in ASTM material.

Special Technical Publication No. 315, issued on the compositions of the invention from the American Society for Testing and Materials, a transmission or 1916, Race Street, Philadelphia 3, Pa., Described 50 hydraulic fluid, gear oil, or grease conditions put into operation. be turned.

The machine can be switched on at any time during the process

be assessed during the course of the test. The seven parts, one or more other additions, such as B. Antioxidant

be assessed for residues (CRC assessment, medium, anti-foam, anti-rust, anti-

10 = clean) are rocker arms, rocker arm cover plate, 55 abrasives, high-performance detergents, the casting

Valve cover, time-out switch cover, agents reducing the thrust point, improvements to the

cover plate, pushrod chamber and oil pan. Viscosity index agents or others

™ ^. ,, Additives are used. For example, can

_{Plate coking test emes odef several of the Dithio} ph _OS p _ha te, such as B.

This test is used in the Fifth World report 60 zinc, barium or nickel dialkyldithiophosphates, Petroleum Congress (1959) in an article by sulfurized oils, e.g. B. Sulphurized Spennazetöl and R. M. J ο lie, “Laboratory Screening Test for Lubricated Terpenes, Alkylphenol Sulphides, Alkylarylcating Oil, Detergents and Dispersants ". sulfonates, petroleum sulfonates with or without alkali, A sample of a compound to be tested is presented in e.g. Calcium, barium or strontium petroleum Coming from Central America, from solvent 65 sulfonates, polymers and copolymers of alkyl agents Freed neutral oil from 170 SUS dissolved in acrylates, methacrylates, itaconates or fumarates 1% of a thermally unstable zinc dialkyldithio- or vinylcarboxylate and mixtures thereof, mixed phosphate contains. The mixture is converted into a polymer of acrylic acid esters and polar mono-

13 14

vinylidene compounds, such as ζ. B. N-vinyl-2-pyrrolidone, razon, S-dodecyl-S ^ -tetramethylene-l-vinyl ^ -pipera-

Vinylpyridines, aminoalkyl acrylates or other methzone or 4-octadecyl-1-vinyl-2-piperazone instead

acrylates or polyethylene glycol acrylic acid esters, poly des 3,3-dimethyl-4-dodecyl-l-vinyl-2-piperazon yer-

butenes, alkylphenol alkylene oxide condensates, alkenyl turns,

succinic anhydrides, various silicones and 5. .

Alkyl or aryl phosphates, such as. B. Tricresylphos- B e ι s ρ ι e 1 i

phate, can be used. 4,4'-Me- It is a mixture of 50 parts of toluene, 50 parts

⁺ ethylene-bis-2,6-di-tert-butylphenol, trialkylphenols, vinyl laurate, 10 parts of vinyl acetate, 3 parts of 3,3-di-

tri- (diinethylaminomethyl) -phenol, phenothiazine, methyl-1-vinyl-2-piperazon. It will be on

Naphthylamine, N'-sec-Butyl-NjN-dimethyl-p-pheny- io 70 ⁰ C heated while nitrogen over the surface

Lenediamine, alkaline earth alkylphenolates, alkaline earth metal alloys. 0.2 parts are then added to the mixture

late, calcium phenyl stearate, alkylamines, especially azodiisobutyronitrile. After 8 hours

C ₁₂ - to Ca ^ alkylamines, cyclic amines, alkyl and heat a viscous solution of the polymer

Arylamidazoline and Alkenyl Succinic Anhydrides, which hold as a stabilizing oil additive from

which is around 15 with amines and then with boron compounds.

were set, such as B. boron oxide, boron halide and the Sundstrand pump test was used in one

Borate esters. Content of 0.01 g of the above copolymer

In addition to the copolymers according to the invention in 100 ecm of oil, the weight of the sludge at 42 mg can also be determined as an agent lowering the pouring point, while 210 mg was obtained for an oil and a viscosity index-improving agent ao that contained no additive,
can be added, but instead of such valuable polymers with additives, a copolymer of the present invention can be used, which is not only a dispersible and 4-benzyl-l-vinyl-2-piperazon instead of 3,3-digiting effect, but also one or both of these methyl-l-vinyl-2-piperazon obtained,
has other, above-mentioned effects. A mixed as _R. . .
polymeric one of the esters described above, e 1 s ρ 1 e 1
A 500 ecm three-necked round-bottomed flask will contain atoms of matter, particularly cetyl or stearyl with a gas inlet tube, a condenser and a group, along with smaller groups such as e.g. B. provided semicircular glass stirrer. The system of myristyl, lauryl or octyl groups, sets the pouring 30 is filled with nitrogen, and the oil bath surrounding the reaction point of the oils, which have a waxy pouring point, piston is kept at 99 ⁰ C, and at the same time improves the relationship Dem Flask is fed a mixture that varies from temperature to viscosity. Viscous improvements 46.0 parts lauryl myristyl methacrylate, 4.0 parts
Sity index can be effected by the selection of the substitu- l-vinyl-3,3-dimethyl-2-piperazone, 3.0 parts toluene ducks, and such improvements consisted of 35 and 0.1 part azobisisobutyronitrile. This can be achieved without lowering the pour point, if this is lauryl myristyl methacrylate, the methacrylate ester, is desired. obtained from a commercial alcohol,

A turbo-prop lubricant can be obtained whose composition is 4% decanol, 66.4% by mixing the copolymers of the present dodecanol, 27.2% tetradecanol and 2.4% hexadecinvention with di-2-ethylhexyl sebacate and a Ge 40 canol existed. The reaction mixture is mixed at 88 ⁰ C mixed polyesters. The mixture is heated through, this point in time is set equal to zero. The condensation of 2-ethyl-1,3-hexanediol and sebacin exothermic development leaves the temperature acidic to 93 ° C. to give the polyesters with 2-ethylhexanol, with an increase. The reaction mixture is cooled to 80 to 85 ⁰ C on average about 3 glycol units per molecule, and this temperature range is available during are obtained. 45 of the polymerization is maintained. Additions of

This composition can also antioxidant 0.01 part azo-bis-isobutyronitrile in 5.0 parts toluene

agents, stabilizers or other valuable additives are added after 2.67, 3.33, 4.67 and 5.33 hours.

sets included. taken. 25.0 parts of toluene are added to the

The polymers are added to the fuel or lubricant mixture after 6 hours, and so is the bath

medium according to standard procedures in the preceding 50 is removed after 6.50 hours. The implementation is

given amounts incorporated. then completed. The toluene solution obtained is

In the case of the information in the explanatory notes below, 42.8% of the mixed polymer is equivalent to a poly it is all parts by weight. mers yield of 83.7% corresponds.

. -J ₁ The toluene solution of the mixed polymer is

B e 1 s ρ 1 e 1 1 _{55 tra} i _em viscous oil (100 SSlJ) diluted, and that

It is a mixture of 15 parts of hexadecylmeth- toluene from the solution at 125 ⁰ C during a

acrylate, 5 parts S ^ -DimethyM-dodecyl-l-vinyl ^ -pi- hour stripped at 10 mm Hg. The solution obtained

perazon and 0.02 part azodiisobutyronitrile. contains 25% of the mixed polymer in oil and has a

The mixture under nitrogen for 24 hours The viscosity of 165.3 centistokes at 99 ⁰ C.

70 ⁰ C heated. The viscous oil obtained is an additive. Analysis of the copolymer for nitrogen shows that

valuable for stabilizing heating and lubricating oils. about 96% of the nitrogen-containing monomer in the

The Sundstrand pump test showed that the polymers were in.

It was found that 0.06% of the copolymer in 100 cc of oil had a weight of sludge containing 0.2% asphaltenes in an oil test mixture of 27% mg while 65 150 ° C dispersed.
in the case of oil without addition, 210 mg were obtained. During a Sundstrand pump test,

Similar polymers are produced in the same way with a content of 0.04 g of the above mixed poly-

obtained by determining 3,3-dimethyl-1-vinyl-2-pipe meren in 100 ecm of oil 16 mg of sludge, while

15 16

A rend of 210 mg was found for an oil containing 1 part phenothiazine and 1 part tricresyl phosphate

contained no additives. mixed into 96 parts of di-2-ethyl sebacate. The liquid one

In the plate coking test, a Ge material was subjected to corrosion and resistance at 175 ° C

blend containing 1% of the above polymer, Federal Test Method oxidation resistance

to a deposit of 23 mg. The same oil examined without 5 No. 5308 that for the aircraft turbine

Additions resulted in a deposit of 322 mg. Engine Lubricating Oil Specification MIL-L-7808 ge

4 parts of the above copolymer are required. The oxidation tubes have a clear one

with part of a commercial zinc dialkyldithio appearance compared to an analogous test

phosphate in 95 parts of a Mid-Continent, with solder the mixed polymer of the previous example

solvent extracted neutral oil from 170 SUS io was not used.

mixed in. The viscosity of this mixture is 4 parts of the copolymer of this example

7.31 centistokes at 99 ° C and 45.74 centistokes in 5 parts of a commercially available automatic transmission

38 ⁰ C. The viscosity index is 127. This mission liquid additive Lubrizol 280 in 91 parts

Lubricant is used in the Sequence VA engine test of a base oil of 4.0 centistokes at 99 ⁰ C and one

evaluated. The value for a viscosity index of 95 mixed in after 100 hours. The received

total retained sludge is 65.3 solution has a viscosity of 7.5 centistokes at

(70.0 = clean). A test with an oil without additives at 99 ° C. This oil is made under the conditions of

leads to a value of 48.1 after 100 hours. Federal Test Method No. 5308 tested ^{at 149 ° C.}

The ASTM pour point of this lubricant is After 300 hours, the paper stain shows

-40 ⁰ C. oil which does not contain the copolymers, has 90 test in that the sludge is still dispersed in the oil.

a pour point of -18 ° C. A similar test with a liquid that has a

4 parts of the interpolymer of this example are used in place of non-dispersing viscosity modifiers

with 0.7 parts of 4,4-methylene-bis- (2,6-di-t-butylphenol), of the copolymer of the above example,

1.0 part of tricresyl phosphate and 0.30 part of sulphate, negative in 72 hours,

rated spermacet oil in 94 parts of a mid-continent, »5

solvent extracted neutral oil with example

170 SUS mixed. The viscosity of this mixture becomes a 500 ecm, three neck, round bottom flask

is 7.21 centistokes at 99 ° C and 44.85 centi- with a gas inlet tube, a condenser, and a

stokes at 38 ° C. The viscosity index is 127. Semicircular glass stirrer provided. The system

1 part of the toluene solution of the copolymer of this 30 is filled with nitrogen, and the reaction

For example, it is mixed with di-2-ethyl sebacate and the oil bath surrounding the flask is kept at 105.degree.

Toluene is made from this solution at 125 ° C while In the flask is a mixture of 46.0 parts

Stripped for 1 hour at 10 mm Hg. The obtained lauryl myristyl methacrylate, 3.0 parts of toluene and solution consists of 30% of the mixed polymer in 0.1 part of azo-bis-isobutyronitrile. The Reakdem diester and has a viscosity of 598.3 centi- 35 tion mixture is heated to 80 ° C, this time stokes at 99 ⁰ C. 2 parts of the copolymer in the same 0 is set, and the exothermic development diesters with 1 part Phenothiazine and 1 part will soon raise the temperature to 95 ° C. The mixture of tricresyl phosphate in 96 parts of di-2-ethyl sebacate is cooled to 80 to 85 ° C. and mixed at this temperature. The liquid material is maintained at 175 ° C. during the polymerization, according to the method described in Federal Test Method No. 5308 Parts of 1-vinyl-3,3-dimethyl-2-pipe-Turbine Engine Lubricating Oil Specification MIL-razon, 0.05 parts of azo-bis-isobutyronitrile and 1.5 parts of L-7808 is examined. The Oxidations- Ien given toluene. The addition of 0.01 parts of azo tubes has a clear appearance compared to bis-isobutyronitrile in 5.0 parts of toluene, according to 2.67, a test in which the oil without the copolymer is 45 3.33, 4.00, 4 , 67 and 5.35 hours. 25.0 parts of toluene are added to the reaction mixture

4 parts of the copolymer of this example are added after 6.0 hours and the bath is after

removed with 5 parts of a commercial automatic 6.50 hours after the implementation as

Transmission fluid additive Lubrizol 280, is considered completed in. The obtained toluene

91 parts of a base oil of 4.0 centistokes at 99 ° C 50 solution contains 45.1% of the copolymer, which is a

with a viscosity index of 95 mixed in. The polymer yield of 88.4% corresponds to

The solution obtained has a viscosity of 7.5 centigrade. The toluene solution of the copolymer is mixed with

stokes at 99 ⁰ C. The material is diluted under the neutral oil of 100 SUS viscosity, and

Conditions of Federal Test Method No. 5308 when the toluene is released from the solution at 125 ° C during

Tested at 149 ° C. After 300 hours the paper shows an hour stripped at 10 mm Hg. The received

stain test that the sludge in the liquid material contains 25% of the interpolymer in oil and solution

is still dispersed. A similar test with one has a viscosity of 202.9 centistokes at 99 ⁰ C.

Liquid containing a non-dispersing Vislcosi- It was found that 0.06% of the interpolymer

Activity modifier instead of the 0.2% asphaltene according to the invention in an oil test mixture at 150 ° C

Contains mixed polymers, turns out to disperse after 72 hours 60.

as negative. In the Sundstrand pump test, one

1 part of the toluene solution of the copolymer this content of 0.04 g of the above copolymer

Example is diluted with di-2-ethyl sebacate, and in 100 ecm of oil sludge weighing 15 mg

the toluene is determined from the solution at 125 ° C. for 1 hour, while the oil is 210 mg without addition

long stripped at 10 mm Hg. The solution obtained led to 65 sludge.

consists of 30% of the interpolymer in the diester. A mixture resulted in the plate coking test

and has a viscosity of 598.3 centistokes at 99 ° C. with a content of 1% of the above mixed

2 parts of the copolymer in diester solution become polymeric to a deposit of 53 mg. That

the same oil used without additive resulted in a deposit of 322 mg.

4 parts of the above copolymer are mixed with about 1 part of commercially available zinc dialkyldithiophosphate in 95 parts of a mid-content, solvent extracted neutral oil of 170 SUS incorporated. The viscosity of this mixture was 7.37 centistokes at 99 ° C and 46.36 centistokes at 38 ° C with a viscosity index of 126. The ASTM pour point this lubricant was -40 ° C.

Example 5

A reaction vessel comes with an Allihn condenser and a nitrogen inlet pipe. A mixture of 4.76 parts of lauryl acrylate, 0.25 part of 1-vinyl-2-piperazone, 0.005 part of azobisisobutyronitrile and 1.25 parts of toluene were added. The nitrogen inlet tube is inserted into the monomer mixture; the vessel is filled with nitrogen and immersed in an oil bath kept at 100 to 105 ° C. This point in time is set equal to 0. Additions of 0.002 part of azobisisobutyronitrile in 0.25 part of toluene are after 2.00, 3.00, 4.00, 5.00 and 6.00 hours. The polymerization is carried out by cooling the reaction mixture to room temperature stopped and restarted the following day at bath temperatures of 100 to 105 ° C. After 6.17 hours, 0.05 part of azobisisobutyronitrile is added to the mixture. Additions of 0.002 parts of initiator are also taken after 8.17, 9.17, 10.17, 11.17 and 12.17 hours. The polymerization is considered complete after 13.00 hours. The obtained toluene solution contains 68.6% of the copolymer, which corresponds to a polymer yield of 80.6%. A part of Toluene solution of the copolymer is diluted with a neutral viscous oil of 100 SUS, and that Toluene is stripped from the solution at 125 ° C for one hour at 10 mm Hg. The solution obtained contains 25% of the interpolymer in oil and has a viscosity of 456.9 centistokes at 99 ° C.

In the Sundstrand-Pumpen test, at a content of 0.04 g of the above copolymer a sludge of 47 mg was found in 100 ecm oil, while 210 mg was found in an oil that contained no copolymer.

In the plate coking test, a mixture containing 1% of the above copolymer contained, a deposit of 26 mg was found. The same oil with no additive resulted in a deposit of 322 mg.

4 parts of the above copolymer are mixed with 1 part of a commercially available zinc dialkyldithiophosphate in 95 parts of a mid-continent, solvent-extracted neutral oil of 170 SUS. The viscosity of this mixture was 8.43 centistokes at 99 ° C and 52.76 centistokes at 38 ° C, a viscosity index of 132. The ASTM pour point of the lubricant is at -29 ⁰ C.

Example 6

Following the procedure of Example 3, 25 parts of cetostearyl methacrylate and 23 parts of n-butyl methacrylate are obtained and 2 parts of 1-vinyl-2-piperazone mixed with 3 parts of toluene and 0.1 part of azobisisobutyronitrile. That Cetyl stearyl methacrylate is the methacrylate ester obtained from a commercial alcohol, which contains 2% tetradecanol, 30% hexadecanol and 68% octadecanol. This monomer mixture is introduced into the polymerization vessel heated to 88 to 90 ° C. for 100 minutes. All in all 0.05 parts of azobisisobutyronitrile and 25 parts of toluene are added during the course of the copolymerization used. 25 parts of toluene are added to the reaction mixture after 6.00 hours, and heating is set after 6.5 hours. The analysis of the batch showed 44% of mixed polymer.

ίο This mixed polymer is made into a neutral oil by 100 SUS was introduced by mixing an equal weight of the oil with the toluene solution and then stirring and heated to 125 ° C under reduced pressure until the pressure is 10 mm Hg. In the system will Air is admitted and sufficient oil is added to increase the copolymer concentration 25% reduction.

In the Sundstrand-Pumpen test, at a content of 0.04 g of the above copolymer

in 100 ecm of oil a sludge of 20 mg weight is determined, while oil without addition had a residue of 210 mg.

In the plate coking test, a mixture containing 1% of the above according to the invention resulted Interpolymers to a deposit of 46 mg. The same oil with no added resulted in one Deposit of 322 mg.

6 parts of the above copolymer are mixed with 1 part of a commercially available zinc dialkyldithiophosphate in 93 parts of a mid-continent, solvent extracted neutral oil of 170 SUS mixed in. The viscosity of this mixture was 11.24 centistokes at 99 ° C and 61.61 centistokes 38 ° C with a viscosity index of 140. The ASTM pour point of this lubricant is -32 ° C.

Example 7

Put into a clean, weighed container:
9.78 parts of cetostearyl methacrylate with a purity of 93% as determined by gas-liquid chromatography, which corresponds to 9.10 parts of 100% methacrylate ester;
30.8 parts of isodecyl methacrylate with a purity of 96% determined by gas-liquid chromatography, which corresponds to 19.97 parts of 100% polymerizable methacrylate;
2.83 parts of n-butyl methacrylate with a purity of 99% determined by gas-liquid chromatography, corresponding to 2.80 parts of 100% butyl methacrylate;

3.15 parts of 1-vinyl-3,3-dimethyl-2-piperazone;
3.5 parts light mineral oil;
0.175 part of diisopropylbenzene hydroperoxide solution (with an active ingredient content of 50%, as is commercially available);
0.026 part of lauryl mercaptan.

In a pure polymerization vessel equipped with a thermometer, a dropping funnel, an inlet for

Nitrogen and an electrically heated oil bath were provided, 0.035 parts of an n-butanol solution are added (25% tert-octylphenoxyethoxyethylbenzyldimethylammonium chloride monohydrate), Added 12.36 parts of the above monomeric mixture and 1.75 parts of a light mineral oil. This is done under nitrogen Feed heated to 100 ° C. The copolymerization and one start within 10 minutes exothermic conversion takes place, so that the temperature

19 20

temperature rises to 120 ° C. After 20 minutes this has a viscosity index of 132. The ASTM casting

remaining monomeric mixture during 110 mi- point of this lubricant is -29 ° C.
Grooves introduced into the polymerization vessel, wherein

a temperature of 115 to 120 ° C is maintained. Example 9
During the next 4 ¹ _{y 2} hours 5

the total of 0.245 parts of a 50% solution of The process described in Example 3 is followed

Diisopropylbenzene hydroperoxide, 0.049 part of a turn to polymerize a monomeric mixture,

25% solution of tert-Octylphenoxyäthoxyäthyl- that from 25.0 parts of cetylstearyl methacrylate, 11.5 parts

benzyldimethylammonium chloride monohydrate and n-butyl methacrylate, 11.5 parts of styrene and 2 parts

48.5 parts of a mineral oil are supplied. Further Lauryl- io l-Vinyl-2-piperazon consists. The cetostearyl meth

Quantities of mercaptan up to 0.036 parts are the same. Acrylate is a methacrylic acid ester that consists of a

if commercial alcohol is obtained in the polymerization circuit during this time, which from

run introduced. 2% tetradecanol, 30% hexadecanol and 68% octa-

After 6.5 hours a vacuum is applied and there is decanol. The addition of azobisisobutyro-

the mixture for half an hour at 120 ° C 15 nitrile is in the course of the copolymerization in

held when 10 mm mg is reached. The ab- partial amounts made so that a total of 0.05 and

Striped mixture contains 39.5% solids as mixed 50 parts of toluene are added. The heating will

polymer. At 99 ° C its viscosity ax, 681Cen- is broken off after 8 hours. The solution obtained

tistokes. contained 40% interpolymer.

The Sundstrand Pump test was performed at a temperature of 20. The copolymer is converted into a neutral oil of

Content of 0.04 g of the above copolymer 100 SUS. 1 part of the toluene solution is with

in 100 ecm of oil a sludge weight of 28 mg is diluted with the neutral oil of 100 SUS, and that

telt, while 210 mg was determined for an oil, volatile material will come out of the solution under heating

which did not contain any mixed polymer. and stirring stripped, with the solution finally

In the plate coking test, a mixture gave 25 for half an hour at 125 ^° C. and 10 mm Hg

is held with a content of 1% of the above invention. The solution obtained consists of 25%

according to copolymers a deposit of 33 mg. of the mixed polymer in oil.

The same oil with no additive resulted in a deposit

of 322 mg. Content of 0.04 g of the above copolymer

6 parts of the above product are determined at 3 ° in 100 ecm of oil 22 mg of sludge, while the 1 part of a commercially available zinc dialkyldithiophos oil without addition left 210 mg of residue,
phats in 93 parts of a Mid Continent, solvent extracted neutral oil of 170 SUS an example 10
mixed. The viscosity of this mixture was

10.92 centistokes at 99 ⁰ C and 67.15 centistokes at 35 by following the procedure of Example 3 42 parts

38 ° C with a viscosity index of 139. The ASTM diisodecyl itaconate with 8 parts of 1-vinyl-2-piperazone

Pour point of this lubricant is at -29 ⁰ C. using 1.5 parts of benzoyl peroxide and

5 parts of toluene copolymerized ⁰ C at HO. For example 8 benzoyl peroxide are added during the

40 during the interpolymerization in partial quantities so

After that described in Example 3 above, taken that a total of 0.05 and 50 parts of toluene

Process will be fed a copolymer of 6.7 parts. The heating will be after 24 hours

Dilauryl fumarate, 2.5 parts of vinyl acetate and 0.8 part canceled; the solution obtained contains 42.7%

l-vinyl-2-piperazon produced. The interpolymer interpolymer. The toluene solution is neutral with

sation is mixed in toluene at 90 ⁰ C using 45 oil from 100 SUS, and the volatile material

a total of 0.05 parts of azobisisobutyronitrile superiors is stripped at 125 ⁰ C and 5 mm Hg. The get-

took. The yield of the copolymer is tene concentrate is adjusted so that it is 25% of the

81%. This mixed polymer is contained in that in Example 3 mixed polymers. When treating a

described neutral oil with 100 SUS entered, oil mixture with 0.25% of the copolymer at 38 ° C

before it is tested. 50 0.2% asphaltenes are easily dispersed.

In the Sundstrand pump test, one. ,

Content of 0.04 g of the above copolymer Example 11

63 mg of sludge are obtained in 100 ecm of oil while following the procedure of Example 3

Oil without addition has a residue of 210 mg. 4.75 parts of vinyl laurate and 0.25 parts of 1-vinyl-2-pipe-

In the plate coking test using a mixture yields 55 razon in the presence of toluene

with a content of 1% of the above invention of azodiisobutyronitrile as a catalyst mischpoly-

according to copolymers a deposit of 83 mg. merized. A total of 0.025 parts of azo dizo

The same oil with no addition resulted in a deposit of butyronitrile and 10.8 parts of toluene used in one

of 322 mg. Polymerization temperature from 100 to 103 ⁰ C and

6 parts of the above product are used with a duration of 11% hours. It is formed

1 part of a commercially available zinc dialkyldithiophos 10.6 parts solution containing 37.5% copolymer,

phats in 93 parts of a mid-continent, with solution dispersed after stripping the copolymer

Medium extracted neutral oil with 170 SUS one- this in a neutral oil of 100 SUS with one

mixes. The viscosity of this mixture was 9.39 CEN content of 0.125% of the copolymer, 0.2% tistokes at 99 ° C and 60.83 centistokes at 38 ⁰ C, at 65 asphaltenes in an oil test mixture at 15O ⁰ C.

Claims (1)

Patent claims: 1. Lubricant and fuel mixtures containing 0.001 to 10 percent by weight of an oil-soluble Copolymers consisting of at least one ethylenically unsaturated monomer and at least a compound of the general formula draws that it contains a copolymer, which by using a monomer with containing a vinyl ester.