DE3025274A1 - VISCOSITY INDEX-IMPROVING POLYMERS OF LUBRICANTS AND METHOD FOR THEIR PRODUCTION - Google Patents

Description

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DR. BERG DIPL.-ING. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAIR

PATENT LAWYERS 3025274

P.O. Box 860245 ■ 8000 Munich 86

Attorney file: 30,990

3 Jun // 1980

EXXON RESEARCH AND ENGINEERING COMPANY FLORHAM PARK, N.J. / UNITED STATES

Viscosity index improver polymeric lubricating oil additives and processes for their preparation

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Γ (089) 988272 Telegrams: Bank accounts: Hypo-Bank Munich 4410122850

988273 BERGSTAPFPATENT Munich (BLZ 70020011) Swift Code: HYPO DE MM

988274. TELEX: Bayet Vetwnsbank Munich 453100 (BLZ 70020270)

9833 10 0524560 BERG d Postscheck Munich 65343-808 (BLZ 70010080)

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Description

The invention relates to stable polymeric dispersing additives for lubricating oils which can also be useful as viscosity index improvers for lubricating oils. In particular, the invention relates to viscosity-stable and turbidity-free solutions of practically saturated polymers which contain ethylene and one or more C ₃ - to C ₂ ga-01efine, preferably propylene, and which in the presence of a free radical initiator with an ethylenically unsaturated dicarboxylic acid material preferably Grafted at elevated temperature and in an inert atmosphere and then reacted with an alkyl hetero-substituted primary alkylene amine, so that multifunctional polymeric reaction products are formed which are characterized by their viscosity-stabilizing effect in mineral oil solutions.

Of ashless dispersants for lubricating oil preparations are known to increase the sludge dispersing ability of these preparations.

One type of dispersant is generally obtained from a hydrocarbon-substituted dicarboxylic acid material, such as an alkenyl succinic acid or its anhydride which is mixed with a nitrogenous material such as e.g. an alkylene polyamine was reacted. It is also known

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that the introduction of carboxylic acid groups in ethylene copolymers e.g. by reacting an oxidized degraded copolymer with maleic anhydride a way to form a derivative represents with an alkylene polyamine and thereby this Copolymers which, when dissolved in mineral oils, have a viscosity index improving Have effect (cf. US Pat. No. 3,316,177), a sludge-dispersing effect is imparted. A procedure to introduce the carboxylic acid groups is the grafting of maleic anhydride onto the polymer by means of a free radical mechanism. US Pat. No. 4,089,794 describes the preparation of oil-soluble, sludge-dispersing Additives for hydrocarbon fuels and lubricating oils described; in doing so, the one induced by free radicals takes place Solution grafting of an ethylenically unsaturated dicarboxylic acid material, such as maleic anhydride, to a practically saturated copolymer of ethylene and at least one other a-01efin at elevated temperature, so that without substantial Polymer degradation a usable precursor polymer is formed, then with a polyfunctional, carboxylic acid reactive material such as a polyamine or a hydroxyamine or mixtures thereof can be implemented, so that multifunctional polymeric imidized derivatives are formed which are particularly useful additives to lubricating oils for the control of Represent engine sludge and deposit.

The invention relates to a grafted ethylene copolymer dispersant, which is generally called the viscosity index

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Mineral oil improver is useful which has useful sludge dispersing and increased viscosity stabilizing effects possesses, and which when dissolved in mineral oil results in a cloud-free solution.

US Pat. No. 4,137,185 states that the reaction of the organic acid anhydrides, for example acetic anhydride, enables the formation of amide derivatives of all primary amino groups of the imidated ethylene copolymer, as a result of which these copolymers obtain a viscosity-stabilizing effect. This reaction can be viewed as a process for improving the viscosity-stabilizing effect of an oil additive concentrate which is a hydrocarbon solvent and 0.1 to 50% by weight, based on the total weight of the concentrate, of an imidized grafted ethylene-C "- to C _2g -α-olefin copolymer Viscosity index improver with molecular weight (M) 700 to 500,000. One step of this process consists of reacting the concentrate with a hydrocarbon-substituted acid anhydride, the hydrocarbon component of which has about 1 to 30 carbon atoms; the acid anhydride is added in an amount of about 0.5 to 2.5 mol per primary amino group of the concentrate and this is added for 0.25 to 8 hours, preferably 0.5 to 3 hours, at a temperature of about 50 ^° C. to 250 ^° C. , preferably 100 ⁰ C to 200 ⁰ C kept. The reaction appears to be an acylation of pendant free primary amino groups, thereby causing a

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Amide structure arises, which has the property of multifunctional Copolymers, to lengthen the chain in solution, are limited and thus the increase in viscosity in oil solutions, which contain these additives inhibits.

It has now been found that in the US Pat. No. 4,137,185 multifunctionalized grafted copolymers described, the viscosity-stabilizing effect can be increased, if 0.5 to 1.5 molar equivalents (based on grafted dicarboxylic acid groups) of a C "- to C" q aliphatic, preferably alkylhe-terosubstituted primary alkyleneamine, e.g. Aminopropyltridecyl alcohol ether, to be reacted with the grafted copolymer. The surprising result is an increased Dispersing effect as well as the emergence of more cloud-free Solutions when dissolved in mineral oil.

The invention relates to a Schmierö preparation, in which at least a viscosity index improving amount of an oil-soluble C_- to C _2Q - alkylheterosubstituierten aminated Alkylenderivats a carboxylgepfropften ethylene polymer viscosity index improver is dissolved, contains from 0.001 to 8 wt% nitrogen, wherein the average per Äthylencopolymermolekül 2 to. 20, preferably 4 to 16, grafted carboxyl groups are present.

The invention leads to an oil additive preparation with improved Viscosity stability and none visually perceptible

Cloudiness. -/8th

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The invention also relates to new grafted aminated ones Ethylene copolymer preparations of the amido-imido, preferably Succinimidoart, as well as lubricants that like these contain copolymers prepared as described here.

Ethylene copolymers

The ethylene copolymers to be grafted contain about 2 to 98, preferably 30 to 80% by weight of ethylene, and also about 2 to 98, preferably 20 to 70% by weight of one or more C "- to C _? g "> preferably C ₃ - to C ^ g- and most preferably C ₃ - to C _g a-01efine, for example propylene. Such copolymers preferably have a degree of crystallinity of less than 25% by weight, determined by means of X-rays and differential scanning calorimetry, and an average molecular weight (M) in the range of about 700 to 500,000, preferably 10,000 to 2,500,000, as determined by vapor phase osmometry (VPO) or membrane osmometry. Ethylene and propylene copolymers are most preferred. Other α-olefins, the Instead of propylene to form the copolymer or together with ethylene and propylene to form a terpolymer, 1-butene, 1-pentene, 1-hexene, 1-octene; also α-olefins with a branched chain, such as 5 -Methylpentene-1 and 6-methylheptene-1, as well as mixtures thereof.

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Terpolymers of ethylene, one of the above, can also be used a-01efine and a non-conjugated diolefin or mixtures such diolefins can be used. The amount of the unconjugated Diolefins is between about 0.5 and 20 mol%, preferably about 1 and 7 mol%, based on the total amount of existing ethylene and α-01efin. Exemplary diolefins are cyclopentadiene, 2-methylene-5-norbornene, non-conjugated Hexadiene, or any other alicyclic or aliphatic non-conjugated diolefin having 6 to 15 carbon atoms per molecule, such as 2-methyl- or ethylnorbornadiene, 2,4-dimethyl-2-octadiene, 3- (2-methyl-1-propane) cyclopentene, Ethylidene norbornene, etc.

These ethylene copolymers, which also include terpolymers, can be prepared with the aid of the known Ziegler-Natta catalyst preparations getting produced.

The polymerization for the production of the ethylene copolymers can be effected by adding 0.1 to 15, for example 5 parts of ethylene, 0.05 to 10, for example 2.5 parts of the higher α-olefin, usually propylene, and 10 to 10,000 parts of hydrogen per million parts of ethylene in 100 parts of an inert liquid solvent that contains a) about 0.0017 to 0.017, for example 0.0086 parts of a main transition metal catalyst, for example VOCl ₃ , and b) about 0.0084 to 0.084, for example 0.042 Contains parts of a cocatalyst, e.g. (C ₂ Hc) ₃ Al ₂ Cl ₃ , at a temperature

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temperature of about 25 ⁰ C and a pressure of H 2 N / cm, and over a period of time sufficient for an optimum conversion, for example 15 to 30 min. All parts are parts by weight.

Ethylenically unsaturated carboxylic acid material

These materials, which are grafted onto the copolymer, have at least one ethylene bond and at least one, preferably two carboxylic acid or carboxylic acid anhydride groups, or one polar group formed by oxidation or hydrolysis can be converted to such carboxyl groups. Maleic anhydride or a derivative thereof is preferred, since it does not appear to be substantially homopolymerized, but rather grafts onto the ethylene copolymer or terpolymer and yields two carboxylic acid functional groups. The preferred materials have the general formula

R ₁ R ₂
CC

I I

O = C C = O

wherein R .. and R "are hydrogen or a halogen and 0 oxygen mean. Suitable examples are also chloromaleic anhydride, itaconic anhydride or the corresponding ones Dicarboxylic acids, such as maleic or fumaric acid or their monoesters.

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Grafting the polymer

The grafting of ethylenically unsaturated carboxylic acid material in solvents such as benzene, induced by free radicals, is known. The grafting takes place at an elevated temperature in the range from about 100 ^° C. to 250 ^° C., preferably 150 ^° C. to 180 ^° C., for example above 160 ^° C., in a solvent, specifically preferably a mineral lubricating oil solution, for example 1 to 50, preferably Contains 5 to 30% by weight of the ethylene polymer (based on the total initial oil solution), and preferably in an inert environment. The grafting is conveniently carried out in the presence of a compound which can decompose at a high temperature and which can give off free radicals at this high temperature.

The free radical initiators which may be used are _f peroxides, hydroperoxides and azo compounds, namely those preferably having a boiling point above about 100 C, which are thermally decomposed within the grafting and release free radicals. Examples of such free radical initiators are azobutyronitrile, 2,5-dimethylhex-3-yn-2,5-bis-tert-butyl peroxide (sold as Lupersol IwO) or its hexane analog, di-tert-butyl peroxide and dicumyl peroxide. The initiator is used in a concentration of about 0.005 to 1%, based on the total weight of the polymer solution.

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The ethylenically unsaturated carboxylic acid material, e.g. maleic anhydride, is used in an amount of about 0.01 to 10%, preferably 0.1 to 2.0%, based on the weight of the total initial oil solution. The carboxylic acid material and the free radical initiator are used in a weight percent ratio from 1.0: 1 to 30: 1, preferably 3.0: 1 to 6: 1, used.

The grafting is preferably carried out in an inert atmosphere, for example under a nitrogen blanket. The grafting can be carried out in the presence of air, but the yield of the desired graft polymer is lower compared to the yield in the case of grafting in an inert atmosphere. The inert environment should be practically free of oxygen. The grafting time is between about 0.1 and 12 hours, preferably 0.5 to 6 hours, most preferably 0.5 to 3 hours. The grafting reaction is carried out up to at least about four times, preferably at least about six times the half-life of the free radical initiator at the reaction temperature used, for example with 2,5-dimethyl-hex-3-yn-2,5-bis (tert-butyl peroxide ) 2 h at 160 ^° C. and 1 h at 170 ^° C.

In the grafting process, the copolymer solution is first heated to the grafting temperature and then is the carboxylic acid material and initiator are added with stirring, although these are also added prior to heating

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can. After the completion of the reaction, the excess becomes Acid material eliminated with an inert gas, e.g. by sparging with nitrogen.

During the grafting step, the maleic anhydride used becomes or other carboxylic acid material grafted onto both the polymer and the reactive solvent. Of the The proportion by weight grafted on the polymer is usually greater than the amount grafted on the oil as the polymer is more reactive with respect to the grafting process. The exact The division between the two substances, however, depends on the polymer and its reactivity, on the type and reactivity of the oil and also depends on the concentration of the polymer in the oil. The division can be carried out empirically with the help of infrared analyzes of the Product are measured, which was separated by dialysis into the oil or polymer fractions, in both the Absorbance of the anhydride peak is measured.

The grafting process is preferably carried out in a lubricating oil, which does not have to be removed after the grafting step, but that as a solvent in the subsequent reaction the graft polymer with the polyfunctional material as well as can be used as a solvent for the end product for the preparation of the concentrate.

The oil grafted with carboxyl, e.g. malexic anhydride groups, becomes primary when reacted with the heterosubstxtuxerten

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Amine also converted to the corresponding derivatives. If desired, the division can be made between the imidized Graft polymer and the imidized graft oil by dialysis in polymer and oil fractions and infrared or nitrogen analysis of the fractions are determined. Unfortunately, the graft oil seems to be a cause of cloudiness, e.g. when it comes through Derivative formation becomes excessively polar.

If the solution grafting step in the presence of a high Temperature decomposable peroxide carried out, then takes place he without degradation of the chain length (molecular weight) of the ethylene-containing polymer. The measurement of molecular weights and degradation can occur by determining the thickening effect of the polymer.

Thickening effect (TE) is defined as the ratio of the weight fraction of a polyisobutylene (oil solution sold by Exxon Chemical Co. as Paratone N) having a Staudinger molecular weight of 20,000 required to produce a solvent-extracted neutral mineral lubricating oil with a viscosity of 150 SUS at 3 7.8 ⁰ C, a viscosity index of 105 and an ASTM pour point of -17.8 at ⁰ C (Solvent 150 Neutral) to thicken to a viscosity of 12.4 mm / s at 98.9 ⁰ C, to the weight of a test copolymer which is needed to thicken the same oil to the same viscosity at the same temperature. TE stands in one

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certain ratio to (M) and is a suitable and useful measure for the formulation of various lubricating oils.

Alkyl heterosubstituted primary alkylene amines

Useful alkyl hetero-substituted primary alkylene amines are characterized by a C _ß - to C _2Q -alkyl group and have a total of 10 to 70 carbon atoms and 1 to 11 nitrogen atoms. Preferably they have the general formula

Y - [(CH ₀ ) - N - 2. - (CH _o ) _e - NH ₉

Z 5 X ZS Z

where s is two to six, t is zero to ten and Y is a substituent selected from:

-N-R (amino group), -S-R (thiol group), -0-R (ether group),

H 0

I Il

-C-C-R (keto group), t

R ¹

-N- (CH ₀ ) _o -NCR (imidazoline group), and

* * I Il

H ₉ CN
² \ /

Il

-OCH ₂ CH ₂ OCH ₂ CH ₂ OCR (Glycolester group),

where N is nitrogen, S is sulfur, O is oxygen, R is a C ₀ - to C ₂₀ ~ alkyl group and R ^{1 is} hydrogen or C ₁ - to C _g -lower alkyl. - / 16

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The following are examples of the amines useful for the invention, which are for the sake of simplicity the meanings given above for Y in the general formula are compiled.

1. Y means an amino group, i.e. -N-R, which is a product

such as, for example, aminopropyloley lamin of the formula C ₁ 0H ₃₁ -NH- (CH ₂ ) -NH ^ results. This type of reactant is easily obtained by cyanoethylation and subsequent reduction of oleylamine. This means that the starting material used is CgH ₁₇ NH ,, (octylamine) to C ^ qH ^ .NH- (eieosylamine) during the cyanoethylation step with acrylonitrile; subsequent reduction can provide useful amines such as aminopropyl-octylamine, aminopropylnonylamine, etc. If the cyanoethylation and the reduction step are repeated with, for example, aminopropyloleylamine, an amine of the formula C ₁₈ H ₃₅ [NH- (CH ₂ ) ₃ ] ₂ NH _{2 is obtained} , and further cyanoethylation and reduction steps increase per step t of the general formula by an integer.

The cyanoethylation with subsequent reduction applies to each of the following categories.

2. Y means a thiol group, i.e. -S-R. The useful primary amines with this group are obtained by cyanoethylation and subsequent reduction of an alkyl mercaptan,

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e.g. CgH ₁₇ SH to C ₂₀ H ^ ₁ SH. With, for example, lauryl mercaptan, this gives aminopropyl lauryl sulfide or stearyl mercaptan, and after two steps, aminopropyl aminopropyl stearyl sulfide.

3. Y is an ether group, ie -0-R. In this case, it is cyanoethylation and reduction of alcohol, for example tridecyl alcohol; all alcohols in the range from 8 to 20 carbon atoms are possible. One such primary amine is aminopropyltri de cy lather C ₁ 3H ₂₇ -O- (CH ₂ KNH ₂ > sold as Armeen EA-13 by the Armak Company Chicago, 111. All C_- to C ₂ Q-alcohols can be cyanoethylated as often as desired are reduced so that the primary [Cg-C ₂ JOC (CH ₂ ) ₃ -Nh] _q _ _{± q} (CH ₂ ) 3NH ₃ amines which can be used for the invention are formed.

H 0

4. Y is a keto group, i.e. -C-C-R, in which, for example

R ¹

R ^{1 represents} a C_H ₁₇ group and R represents a C _g H _Ig group, which is 9-aminopropyl-10-nonadecanone of the formula

0 H

Il ·

C ₉ H ₁₉ -CC- (CH ₂ ) 3NH ₂

^C 8 ^H 17

results, namely by addition of acrylonitrile under basic conditions to 10-nonadecanone (Michael addition) and subsequent reduction of the cyano group.

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5. Y is an imidazoline group, ie -NH- (CH ₀ ) _o -NCR

* ■ * ■ I Il

-, γ

This is actually related to Y = N-R, if R 'water

R ^f
means substance and R is the reaction product of oleic acid and diethylenetriamine, which condenses to form the imidazoline ring. Subsequent cyanoethylation with acrylonitrile and subsequent reduction gives, if the above reaction product is used as an example, aminopropylaminoethyloleylimidazoline of the formula

C _1n H ₁₀ - C - N - (CH_) "-N- (CH ₀ ), NH ₉ . N CH ₀

H ₂

The diversity of the primary amines is evident when the Imidazolinkondensation the C ₇ - to C _ig acids and the appropriate alkylene polyamines are also suitable.

6. Y is a glycol ester group, ie -0- (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -OCR;

(S) this primary amino derivative is available as Kessco glycol ester from Armak Co., Chicago, 111. If R C. H ₃₇ , the primary amine can easily be prepared by cyanoethylation and reduction of diethylene glycol monostearate, which gives aminopropyl diethylene glycol monostearate. Other glycol esters available from Armak Co. are

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Ethylene glycol monostearate and propylene glycol monostearate, the all can be cyanoethylated and reduced to the amines useful for the invention.

Multifunctionalization (imidization) process

The graft polymer can easily be reacted, preferably in solution, with the alkyl heterosubstituted primary alkylene amine and mixtures of such amines by preparing a mixture with the graft polymer for 10 minutes to 30 hours, preferably 10 minutes to 10 hours, usually about 15 minutes Heated to about 100 ^° C. to 250 ^° C. for 3 h. Removal of water ensures that the imidation reaction will proceed to completion. 0.5 to 1.5, preferably 1, molar equivalent of the primary amine is used, based on the content of grafted dicarboxylic acid, for example the content of grafted maleic anhydride. For example, in the case of an ethylene-propylene copolymer with M of about 40,000, ie a thickening effect of about 2.1, and an average of 4 maleic anhydride groups, preferably about 2 to U moles of the primary amine per 1 mole of graft copolymer. It has been found that at least about 0.5 mole equivalent per mole of maleic anhydride grafted results in a solution in oil with improved clarity, although 1 mole equivalent is optimal for clarity (haze free).

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E.g. 0.001 to 50% by weight, preferably 0.005 to 20% by weight of the oil-soluble nitrogen-containing one produced according to the invention Graft polymer, so a lot with a lot of leeway, may be incorporated into a larger amount of an oily material such as lubricating oil or hydrocarbon fuel will. When used in lubricating oil preparations, e.g. lubricating oil for automobile or diesel crankcases the concentrations of the above polymers between about 0.01 and 20% by weight, e.g., 0.1 and 15.0% by weight, preferably 0.25 and 10.0% by weight of the total preparation. The lubricating oils to which the products according to the invention are added can include not only hydrocarbon oils obtained from petroleum, but also synthetic lubricating oils such as esters dibasic acids and complex esters obtained by esterification of monobasic acids, polyglycols, dibasic acids and alcohols are produced.

The imidated graft polymers according to the invention can because of Easier handling can be marketed and / or used in concentrated form, for example with about 10 to 50% by weight, preferably 15 to 49% by weight in oil, for example Mineral lubricating oil.

The above concentrates and lubricating oil preparations can contain other conventional additives such as colorants, pour point depressants, anti-wear agents, Contain antioxidants, other viscosity index improvers, dispersants and the like.

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The process according to the invention and its embodiments are explained in more detail in the following examples. Provided unless otherwise indicated, all parts given in the examples and in the rest of the text are parts by weight. Nitrogen was always determined by means of Kjeldahl analysis.

example 1

Production of ethylene-propylene-succinic anhydride copolymer

100 kg of an oil concentrate of about 15% ethylene-propylene copolymer (2.1 TE) were placed in a 227 l reaction vessel, ^{heated to 121 °} C. under nitrogen and blown through with nitrogen for 1 h. To the stirred reactor contents were added 1.721 kg of maleic anhydride and the temperature increased to 171 ⁰ C. At 171 ⁰ C 0.43 kg Lupersol 130 was added and stirred for a further 1.5 h. Finally, the reaction mixture was sparged with nitrogen for 1.5 hours to remove unreacted maleic anhydride. The product has been diluted with mineral oil to a copolymer content of about 15%.

Example 2

300 g of an oil concentrate of about 15% ethylene-propylene-succinic anhydride copolymer (0.04749 moles of grafted maleic

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Acid anhydride), prepared as described above, was placed in a 1 l four-necked bottle, ^{heated to 170 °} C. under a nitrogen blanket and then gasified vigorously with nitrogen for 1 h. The solution was reacted with 12.2 g (0.04749 mol) Armeen EA-I3 from Armak Company, ie aminopropyl tridecyl ether, C ₁₃ H ₂₇ -O- (CH ₂ ) qNH ₂ and stirred for a further 2 hours. Finally, the solution was diluted with 12 8 g of SIOON oil to a final active ingredient content of 2.5% by weight.

Example 3

This reaction was identical to that of Example 2, but the aminopropyltrxdecyl ether was replaced by 15.0 g (0.04749 mol) Replaced N-aminopropylmorpholine (NAPM).

Example 4

This reaction was identical to that of Example 2, but the Armeen EA-13 was replaced by Duomeen EA-13 from Armak Company, ie aminopropylaminopropyltrxdecyl ether, C ₁₃ H ₂₇ -O- (CH ₃ K-NH ₂ (15.0 g, 0.04749 mol).

Example 5

This reaction was identical to that of Example 2 except that the reaction mixture was made with a 1: 1 mixture of 3.40 g (0.023 mol) NAPM and 6.10 g (0.023 mol) aminopropyltrxdecyl ether aminated.

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252fi

Example 6

This reaction was identical to that of Example 2, however was the reaction mixture with a 1: 1 mixture of 3, MO g (0.023 mol) NAPM and 7.5 g (0.023 mol) bis (aminopropyl) tridecyl ether aminated.

Example 7

This reaction was identical to that of Example 5, but the aminopropyl tridecyl ether was added first and that The reaction mixture was stirred for 30 minutes before NAPM was added. After the addition of NAPM, the reaction mixture was stirred. before it was finally diluted to the final active ingredient content of 10.5% by weight.

Example 8

This reaction was identical to that of Example 6, but the bis (aminopropyl) tridecyl ether was added first and stir the reaction mixture for 30 minutes before adding NAPM became. After the addition of the NAPM, the reaction mixture was stirred for a further 30 minutes before it reached the final content of 10.5% by weight. Active ingredient has been diluted.

Example 9

The products of Examples 2 to 8 was the clarity, ie the lack of _turbidity> in each sample was measured, for which purpose a Model Nephocolorimeter 9 of the Coleman Instrument Corp.,

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Maywood, Illinois was used. The results are shown in Table I, with the lower number being one represents lower haze (greater clarity).

Table I. Cloudiness (nephelus) 33 Example 2 230 3 52 230 5 205 6th 101 7th 156 8th

The results of Table I show that products of the invention (Examples 2 and ¹ O give a bright, clear, stable multifunctional Viskositätsindexverbesserurigskonzentrat while the product NAPM (Example 3) results from a conventional polyamine as an opacified multi-functional viscosity index improvers.

In addition, the correct addition of the polyamine reactants, i.e. first adding the haze-removing and then adding the non-haze-removing polyamines to multifunctional Viscosity index improvement mineral oil solutions with improved clarity, i.e. less turbidity (see Example 5 with example 7 and example 6 with example 8). This indicates

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that the polyamine preferably first with the haze-producing Products, i.e. the grafted oil molecules, and then with the grafted polymer. This is likely on different solubility of the grafted oil and of the grafted copolymer in the mineral oil.

Base resistance test (bench)

The product of Example 4 was examined in a paving inhibition test and the results were compared with those obtained using a commercially available multifunctional healer Viscosity index improver obtained from Lubrizol Corp., Cleveland, Ohio, sold as LZ 3702. This is believed to be a styrene-maleic anhydride copolymer acts, which mit'kürzkettigen alcohols is esterified and aminated with a polyamine.

In the anti-fouling test, each sample consists of 10 g of lubricating oil containing 0.07 g of the additive concentrate (50% active ingredient), for a total of 0.35% by weight of additive in the test sample. The test oil, namely 9.93 g of commercially available lubricating oil with which the additive was mixed, was taken from a taxi after it had driven 3120 km with this lubricating oil. Each of the 10 g samples was ^{soaked overnight at IUO 0} C and then centrifuged to remove the sludge. The supernatant of each sample was heated for 3.5 hours.

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rature change from about 150 C to room temperature with about subjected to two changes per minute. During the warm phase, a gas mixture of about 0.7% by volume SO and 1.4% by volume was NO in air was blown through the test samples, while water vapor was passed through the samples during the cold phase. At the end the test period will be Me wall areas of the flasks in which the samples contained were examined visually for plaque inhibition. The test cycle can be repeated if necessary, to determine the effectiveness of each additive. The deposit on the walls is rated from 1 to 7, with the the higher number denotes the larger amount of covering. It has been found that this test agrees with the topping results, obtained with an MS-VC engine test. The results of the scale inhibition test of the product of Example 4 and LZ 370? are summarized in Table II below:

Table II

Evaluation according to the scale inhibition test, example 4

LZ 3702 5

The results of the paving inhibition test show that the product from Example 4 is the commercially available product in terms of paving inhibition Superior to multifunctional viscosity index improver LZ 3702 is. The products according to the invention make the production of light, clear mineral oil solutions and in particular

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of concentrates of multifunctional viscosity index improvers possible, which are produced in a single derivative formation step and their effectiveness in terms of the pavement inhibition is obviously superior to a commercially available multifunctional viscosity index improver.

Example 11
Engine tests

Duomeen EA-13 from Example 4 was made with NAPM from Example 3 in a 2U0 hour 1H2 crawler tractor single cylinder compressor diesel engine test using ASTM-STP509A conditions and not using a dispersant became. The following results were obtained.

Table III

NAPM Duomeen Weighted Average
of deficiency points 120H 294

Filling the upper

Groove% (TGF) 38 52

The WTD number is the more significant value; the lower the Number, the cleaner the engine is. It can be seen that the Duomeen product is significantly superior as it compares has a significantly lower defect value compared to NAPM. The TGF value shows a slight advantage for NAPM, this is but of lesser significance.

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The two materials were also tested with the L-38 engine compared to a test with a 1-cylinder gasoline engine in which Additives are evaluated for their oil oxidation and bearing corrosion using the Federal Test Method 3405. The supplement value for the piston skirt was 9.7 for Duomeen EA-13 and 7.7 for NAPM. In this test, 10 means a clean one Motor, while 0 indicates a heavily contaminated motor.

In summary, the invention can be described as a preparation which contains an oil-soluble imidized ethylene copolymer with M _n 700 to 500,000 (preferably 1000 to 250,000) and an average of 2 to 20 (preferably 4 to 10) grafted imido fractions per molecule, with 50 to 100 Mol% of the imido components are nitrogen, with C ₀ - to

C ₂₀ alkyl heterosubstituted primary alkyleneamine is substituted. This gives a preparation free of turbidity and having improved viscosity stabilization.

End of description

030062/0957

Claims (1)

DR. BERG BIPL.-ING. STAPF DIPL.-ING. SCHWA3E DR. DR. SANDMAIH P.O. Box 860245 - 8000 Munich 86 Attorney file: 30,990 Claims ΓΙ; Method of making an oil solution of a polymeric J. Viscosity index improver with sludge dispersing properties, wherein maleic anhydride is grafted onto a copolymer in mineral oil solution which contains about 30 to% by weight of ethylene and about 20 to 70% by weight of at least one C ₃ - to C ^ ga olefin, and which has an average molecular weight of about 10,000 to 2,500,000, so that an average of two to twenty maleic anhydride groups are allotted to a copolymer molecule, this mineral oil solution containing about 1 to 50% by weight, based on the total oil solution, of the copolymer, characterized in that part of the maleic anhydride has the polymer and another portion of the maleic anhydride is grafted onto the oil, whereby a graft product is produced, which then with 0.5 to 1.5 molar equivalents, based on converted maleic anhydride, of a C "- to C ₅₀ " alkyl hetero-substituted primary alkyleneamine with a total of 11 to 70 carbon atoms and a total of 1 to 11 nitrogen atoms is implemented . 030062/0957 - _{/ 2} • (089) 988272 telegrams: Bank accounts: Hypo-Bank Munich 4410122850 988273 BERGSTAPFPATENT Munich (BLZ 70020011) Swift Code: HYPO DE MM 988274 TELEX: Bayer Vereinsbank Munich 453100 (bank code 70020270) 983310 0524560 BERG d Postscheck Munich 65343-808 (bank code 70010080) 2. The method according to claim 1, characterized in that the grafting with a free radical initiator at about 100 ⁰ C to 250 ⁰ C is carried out. 3. The method according to claim 1 or 2, characterized in that the C "- to C" _Q - alkyl hetero-substituted alkylene polyamine has the general formula H
I.
Y - [(CH ₂ ) _s - N -] _t - (CH ₂ ) _s - NH ₂ has, wherein s is two to six, t is zero to ten and Y is a substituent selected from HO H 1 Il I -NR, -SR, -0-R, -CCR, -N- (CH ₀ ) ₀ -NCR, ²² II / R ¹ R ^{1 H} 9 ^C _N ^ C i H ₂ 0 ^l It or -OCH ₂ CH ₂ OCH ₂ CH ₂ OCR ^{1 is} selected, in which N is nitrogen, S is sulfur, _{O is oxygen, R is a C g} to C ₂₀ alkyl group and R ^{1 is} hydrogen or C ₁ to C _g alkyl. H. The method according to claim 3, characterized that Y means -0-R. - / 3 030062/0957 5. The method according to any one of the preceding claims, characterized in that the heterosubstituted Alkylenepolyamine is aminopropyl tridecyl ether or bis (aminopropyl) tridecyl ether. 6. The method according to any one of the preceding claims, characterized in that the C _g - to C ₂₀ "alkylheterosubstituted alkylene polyamine is reacted in an amount of less than one molar equivalent per grafted maleic anhydride component, and the remaining maleic anhydride components are then reacted with an alkylene polyamine. 7. The method according to claim 6, characterized that the alkylene polyamine is N-aminopropylmorpholine. 8. oil solution of a viscosity index improver, characterized in that the production was carried out with the method of claims 1 to 7. 9. lubricating oil preparation, characterized in that it has a larger proportion of a Lubricating oil and a viscosity index improving amount the oil solution according to claim 8 contains. 030062/0957