DE2339510A1 - OIL-SOLUBLE LUBRICANTS - Google Patents

Description

233951Q

• PATENT ADVOCATE

DR ".!. 'MAAS

S MONKS 40

SCHtj33SWEIM £ R STR. 29 »

Ta. 3592201/205

Wt / My. - *

Standard Oil Company, Chicago, Illinois / USA

oil soluble lubricants

The invention relates to bifunctional lubricant additives, which have good V, I «improving properties and dispersion properties. The invention Lubricant additives are made by Mannich condensation of an oxidized, long chain, high molecular weight, amorphous Copolymers of essentially ethylene and propylene having a number average molecular weight of at least about 10,000 and at least 140 side methyl groups per 1,000 chains of carbon atoms with a reactant that Formaldehyde there, and a primary or secondary amine or polyamine, with the reactants in molar ratios from about 1: 2: 2 to about 1:20:20 be used.

Lubricant breakdown in high speed engines causes varnish, sludge and coke build-up on the inner surfaces of the engines, thereby accelerating wear and engine efficiency reduced. To prevent these harmful products from settling on the surfaces of the engines, it is good

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• known that lubricating oil additives are incorporated, which have dispersion and / or detergent properties.

The ongoing search for and the need for available ones ash-free dispersion and / or detergent additives for Motor oils are well known. Since the positive crankcase ventilation (PCV) system was developed, a still greater need for improved additives of this kind.

It is well known that lubricating oils tend to thin at elevated temperatures while they tend to thin at low temperatures Temperatures become thick, and therefore it is generally necessary to add additives to such lubricating oils as ~ about the relationship between viscosity and temperature to improve. For example, in the case of crankcase lubricating oil in cold machines, it is desirable that the oil does not become so thick that it becomes difficult to start the engine, while when the engine is hot it is required .is that the oil remains sufficiently viscous that an oil film is present between moving parts.

Various products have been developed to provide the dispersing and / or detergent function. Neutral and overbased organometallic compounds such as alkaline earth salts of sulfonic acids and hydrocarbon PpSc reaction products were for. the first addition means for this purpose. The disadvantages, what they showed in operation included the formation of undesirable thermal metal ash decomposition products. Other suggested additives are amine salts, amides, imides and amidines of polybutenyl-substituted polycarboxylic acids. Mixtures of soil were also used as additives. alkali sulfonates and Mannich condensation products of alkyl-substituted hydroxyaromatic compounds with low molecular weight, amines containing at least one substitutable hydrogen on nitrogen, and Aldehydes suggested. Furthermore, alkaline earth salts were sol-

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• cher ^: Mannich condensation products proposed.

Mannich condensation products that differ from alkyl-substituted ones hydroxyaromatic compounds with relatively low molecular weight alkyl substituents, i.e. 2 to 20 carbon atoms in the alkyl substituent, are in U.S. Patents 2,403,453, 2,353,491, 2,363,134, 2,459,112,

2 984 550 and 3 036 003. In the US patent

3,368,972 are used as dispersion and / or detergent additives for lubricating oils with high molecular weight Mannich condensation products of high molecular weight alkyl-substituted hydroxyaromatic compounds in which the alkyl substituent is a Molecular weight in the range of 600 Us 3000, an amine and an aldehyde are described. However, such condensation products do not show any bifunctional properties, i.e. they do not show a better dispersibility "and the viscosity index improving properties at the same time,

Ashless dispersants are disclosed in U.S. Patent 3,544,520 described, which are prepared by adding an olefin polymer having a molecular weight of about 200 'to 2000 such as polybutene or polypropylene in the presence a catalyst such as manganese (II) carbonate and that oxidized polymer then condensed with formaldehyde and polyalkylene polyamine. Such condensation products are as Ashless dispersants are effective, but they do not impart any V.!. improving properties to the lubricating oils.

Additives that. Lubricating oils have sludge inhibiting and detergent properties lend, are produced by oxidized, degraded copolymers of propylene and Reacts ethylene with a molecular weight of at least about 1000 with maleic anhydride and the acidic intermediate neutralized with an alkylene polyamine, as described in

4Ü98Ö8 / QS88

'of U.S. Patent 3,316,177.

A product has now been found which is prepared as described above and which is useful as a lubricant additive and improves both dispersants and V.I. Possesses properties. The known lubricants which are described in the cited patents show this bifunctional properties are not.

According to the invention, a bifunctional additive is produced by simultaneously at a temperature of about 121 to 177 ⁰ C (250 to 350 ⁰ F) an oxidized copolymer (as described below) of ethylene and propylene with a reactant that gives formaldehyde, and an aliphatic amine or polyamine and recovering the resulting reaction product, the reactants being used in molar ratios from 1: 2: 2 to about 1:20:20.

When preparing the additive according to the invention, it is desirable to have the Mannich condensation in the presence a non-reactive, organic solvent or diluent such as an aromatic hydrocarbon solvent, for example benzene, xylene, toluene etc., or an aliphatic hydrocarbon solvent, for example, hexane * to carry out. A Low viscosity hydrocarbon oil is particularly suitable as a solvent or diluent such as a solvent extracted SAE SW mineral oil. The use of a solvent or diluent Is particularly advantageous for mixing the reaction participants and controlling the reaction temperatures to facilitateβ

The copolymer

The term "copolymer" "as used in the present application

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Application and is used in the claims, means amorphous copolymers derived mainly from ethylene and propylene. Such copolymers can, however, also contain small amounts, for example up to 10% _t based on the molar amounts of monomeric ethylene and propylene units in the copolymer, polymerized units which are derived from other olefin monomers. Such other olefin monomers include olefins of the formula RCH = CK ^ ,, wherein R is _a: aliphatisehe or cycloaliphatic group having 2 to 20 carbon atoms, for example butene-1, hexene-1, 4-methyl-1-pentene, decene-1, Vinylidene norbornene, 5-methylene-2-norbornene, etc. Other olefin monomers containing a variety of double bonds can be used, particularly diolefins containing from about 4 to about 25 carbon atoms, for example 1,4-butadiene, 1,3-hexadiene , 1,4-pentadiene, 2-methyl-1,5-hexadiene, 1,7-octadiene, etc.

Suitable ethylene-propylene copolymers containing from about 30 to about 65, preferably from about 35 to _{v is} about 45 mol% of propylene and having a number average molecular weight of at least about 20,000, ie, from about 20,000 to about 200,000 or more, and preferably from about 25,000 to about 40,000 and they contain at least 150 side methyl groups / 10000 chains · carbon atoms, (· = carbon atoms in the chain).

A particularly suitable ethylene-propylene-co-polymer is one with the following properties:
Number average molecular weight
% (molar.) propylene monomer

Side methyl groups / 1000 chains carbon atoms Inherent viscosity Gardner Viscose! Did Mooney »Viscosity

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25,000 - 35 000 38-42 160-170 1.7 - 2.0 (A) U-V (B) 20 - 35 (C)

(A) 0.1 g copolymer in 100 ecm decalin at 135 ° C

(B) 8.0% copolymer in toluene at 25 ^° C

(C) ASTM "D-1646 _N

Processes for making these copolymers are well known and such processes are described in many U.S. patents, for example, et al., in U.S. patents

2 700 633, 2 726 231, 2 792 288, 2 933 480, 3 .0DO 866,

3,063,973, 3,093,621 and others.

Oxidation of the * copolymer

The oxidation can be achieved by treating the copolymer, under suitable temperature conditions and at atmospheres or elevated pressure with an oxidizing agent such as air or free oxygen or any material containing oxygen contains and is able to give up or release oxygen under the oxidizing conditions, treated. If desired, the oxidation in the presence of known oxidation catalysts such as in the presence of platinum or a metal of the platinum group and compounds containing metals such as copper, iron, cobalt, cadmium, manganese, vanadium, etc. included. The oxidation can be carried out by methods such as those described in US patents 2 982 728, 3 316 177, 3 153 025, 3 365 499 and 3 544 520 are described.

In general, the oxidation can be carried out over a wide range of temperatures, depending on the oxidizing agents used. For example, for example, SO ,, · temperatures in the range of 4.4 were mixed with an active .Oxydationsmittel used to 204 ⁰ C (-40 to 400 ⁰ F), while the less active oxidizing agents, for example in air, temperatures in the range of 38 were used to 427 ° C (100 to 800 ⁰ F). Depending on the desired speed, the oxidation can be carried out at subatmospheric, atmospheric or superatmospheric pressures,

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and in the presence or absence of oxidation catalysts. The temperature and pressure conditions, the oxygen content of the oxidizing agent, the rate at which the oxidizing agent is introduced, the catalyst used., when present, etc. are easily regulated and selected by those skilled in the art to obtain the optimal ones desired Get results.

An oxidation method of a copolymer is explained in detail below. To a copolymer of ethylene and propylene (1 part by weight) with a number average molecular weight of approximately 28,000, a solvent-extracted SAE 5 ^W mineral oil (9 parts) is added in an open reaction vessel. The mixture is slowly stirred and heated to a temperature of 182 ⁰ C (36O ° F) in an inert gas atmosphere until the rubbery polymer has dissolved in the solvent. At a temperature of 182 ⁰ C (36O ⁰ F) the mixture is rapidly in a. Stirred atmosphere containing 50% air and 50% nitrogen in order to cause or activate the oxidation of the copolymer. A 50:50 air to nitrogen ratio is used to eliminate the possibility of an explosive mixture forming. The reaction in the manner described was carried out for between 2.5 and 4.0 hours. Under such oxidizing conditions approximately 5 to 50 oxygen atoms / molecule of copolymer are introduced.

The amine reactant

Primary or secondary aliphatic amines and diamines of the general formula H ₂ N (CH ₂ Y _- NH ₂ 'where y is an integer from 3 to 10, these amines and diamines up to contain about 10 carbon atoms in the alkyl group. In addition, one can use polyalkylene-polyamines of the general formula HN- (AN) _V H-

I ^X

"H 409808/0888

den, wherein A is a divalent alkylene group of about 2 to about 6 carbon atoms and. χ an integer of 1 to about 10. Examples of suitable amines are: methylamine, dibutylamine, cyclohexylamine, propylamine, decylamine, Ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, Tetraethylene pentamine, tripropylene tetramine, tetrapropylene pentamine and other polyalkylene polyamines in which the alkylene groups suitably contain up to about "10 carbon atoms."

The aldehyde reactant

Examples of aldehydes suitable for the present invention are aliphatic aldehydes such as Formaldehyde, acetaldehyde, b-hydroxybutyraldehyde. It is preferred Formaldehyde or a compound that gives formaldehyde such as para-formaldehyde and formalin.

The chemical composition of the reaction products according to the invention cannot be specified exactly by chemical structural formulas. It is believed that in the case of oxidation of the copolymers mainly ketones are formed, It however, it is known that minor amounts of aldehydes, acids and perhaps esters are also present could be. In view of the complex nature of the oxidized reaction product, the exact composition of a Such a product cannot be listed by the chemical formula, but can only be specified by a manufacturing process can be specified.

The invention described in the present application "Reaction products are effective bifunctional dispersants and, if necessary, improving additives in oily or oil-containing lubricant compositions when used in amounts of from about 0.1 to about 10% will. Suitable lubricant base oils are mineral

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<51e, ^r that is, petroleum oils, synthetic lubricating oils such as those obtained by the polymerisation of hydrocarbons, and other well-known synthetic lubricating oils and lubricating oils of animal or vegetable origin. Suitable oil base concentrates containing greater than 10%, ie from about 10 to about 75% or more, of the additive of the present invention, alone or in conjunction with other well known additives, can be mixed with lubricating oils in the amounts required for the particular conditions , or they can be used to make a finished product containing from about 0.1 to about 10% bifunctional additive of the invention.

The following examples explain the invention without limiting it restrict.

At game 1, 1 ■

Part A - Making the Copolymer ?

An amorphous ethylene-propylene copolymer is prepared by solution polymerization using a Ziegler-Natta type catalyst, vanadium oxytrichloride solution together with ethylaluminum sesquichloride solution. Dry n-heptane (1200 ml) is at 30 ⁰ C (86 ⁰ F) and 2.11 atü (30 psig) with a gas mixture containing 50 Μο3, -% ethylene, 35 mole% propylene and 15 mole% hydrogen contains, saturated. The gas mixture is introduced at a rate of 100 l / h, circulated through the heptane and then withdrawn from the system. After the saturation has ended, the catalyst components in heptane solution are started to be added. The vanadium quytrichloride solution (0.370 wt.%) Is introduced into the olefin mixture at a rate of 13 ml / h and the ethyl aluminum sesquichloride solution (0.459 wt.%) Is introduced at a rate of 60 ml / h. The molar ratio of A1 / V was 8.06 / After the polymerization had started, the introduction of propylene and

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des-ethylene adjusted so that for the greater reactivity the latter is compensated. The average propylene / ethylene ratio, expressed by weight, is 2.3 ("determined by periodic gas chromatographic Analyzes). After 1.25 hours, the polymerization is terminated by replacing the gas mixture with nitrogen and the addition of the catalyst stops »The reaction mixture is then washed twice with methanol to deactivate and remove the catalyst. The yield is based on the amount of vanadium catalyst used, 1680 g polymer / g

The copolymer obtained has a number average molecular weight (M _n ) of 28 O00 (determined by vapor pressure osmometry), 159 side methyl groups / 1000 chains of carbon atoms (determined by infrared spectroscopy) and an inherent viscosity of 2.28 dl / g (measured in Decalin at 135 ^° C and 0.1 g / 100 ml) ..

Part B - Oxidation of the Copolymer

A solution of 70 g of the copolymer obtained in Part A, above, in 1000 g of heptane is heated to 121 ⁰ C (25O ° F), while one by blowing nitrogen, to remove the heptane. 280 g of SAE 5W mineral oil are gradually added as the heptane is removed and the viscous oil copolymer mixture is ^{heated to 221 °} C. (430 ^° F.) with vigorous stirring. You then stop blowing with nitrogen and allow atmospheric oxygen to flow into the reaction vessel. After 0.5 hours, thermal or oxidative degradation lower the viscosity of the mixture to such an extent that a starkeg stirring can be carried out only at an optimum oxidation temperature of 154 ⁰ C (310 ⁰ F). Stirring is continued at this temperature for a total of 2.5 hours. The conversion, determined by chromatography on silica gel, is 100 %.

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• Part * C - condensation of the oxidized copolymer with a "Aldehyde and an amine

900 g of benzene are added to 665 g of the oil solution of the oxidized copolymer from part B above (20% active oxidized copolymer) and the solution is heated to 49 ° C. (120 ° C.). Solid paraformaldehyde _(0? 69 g, .9 * 52 wt.%, Based on the oxidized copolymer) was then added, "and the mixture is heated to a temperature of 60.0 ⁰ C (14O ° F) in the course of 0 , heated for 5 hours. hexamethylenediamine (2,66- g, 2.0% wt., based on the oxidized copolymer) was then added and the solution .If vigorously at reflux for 3 hours at 79 ⁰ C (176 ⁰ F) .

The resulting condensation product is then ^{heated to 149 0} C (300 ⁰ F), blowing nitrogen through it for 1 hour in order to remove the benzene solvent. The activity of the solvent-free product was adjusted to 1396 by adding SAE 5W-Ö1. ■

The condensation product obtained was crystal clear and had a color of 6.70 (ASTM color scale) and contained 0.06% Nitrogen and 0.1% oxygen.

Example 2 Part A - Oxidation of the Copolymer

A solution of 70 g of the copolymer, obtained in Part A of Example 1 above, in 1000 g of heptane was ^{heated at 121 °} C. (250 ^° F) while nitrogen was blown through the reaction mixture to remove the heptane. 63Ο g SAE 5W-I4ineralöl, which was extracted with a solvent were gradually added as the heptane was removed and the viscous oil polymer mixture was heated to a temperature of 182 ° C (36O ⁰ F) under vigorous stirring and nitrogen sparging warmed up. These conditions were applied for 0.5 hours

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to remove the last traces of heptane solvent. Purge with pure nitrogen was then stopped and a gas atmosphere of 50% air and 50% nitrogen was introduced. The mixture was heated at 182 ⁰ C (360 ⁰ F) was under vigorous stirring are 3 hours, "The conversion, determined by silica gel chromatography 100%. The carbonyl content of the oxidized product, as determined by the infrared absorption band at 5.8 / u, was 7.5 absorption units (cell thickness 0.005 cm = 0.002 inch). The oxygen analysis of the product showed $ 0.89> oxygen.

Part B -. Condensation product of oxidized copolymer with aldehyde and amine

200 g of the oxidized copolymers obtained as described in Part A above (10% active oxidized copolymer in a SAE SW-mineral oil diluent), were (F ⁰ 320) heated under a nitrogen atmosphere .on 160 C. Solid paraformaldehyde (0.38 g, .1 _# 9 wt.% _F based on the oxidized copolymer) "and molten anhydrous hexamethylene diamine (1.5 g, 7.5 wt.%, Based on the oxidized copolymer) were were simultaneously added to the stirred reaction mixture which was maintained at a temperature of 160 ⁰ C (32O ⁰ F) under nitrogen. the mixture was heated at this temperature for 2 hours, wherein the Mannich condensation took place under formation of water during this time. '

Towards the end of the 2 hour reaction time, 11 nitrogen was passed through the condensation product formed 0.5 hours to remove any residual volatile by-products. The reaction product was filtered and, a crystal clear product was obtained with the following properties:

% active condensation product 10.0

% Nitrogen 0.185

% Oxygen "* 0.45

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; Color (ASTM) 7.0

Viscosity (SSU at 98.9 ° C = 210 ° F) 3200

Example 3

Part A - Oxidation of the copolymer

A solution. 115 g g.des in Part A of Example 1 obtained above Copolymeren.in 1745 heptane was heated to 121 ° C (250 ⁰ F) under a stream of nitrogen to remove the heptane. A solvent extracted SAE 5W mineral oil (770 g) was gradually added as the heptane was removed. After complete removal of the heptane by heating at 177 ° C (35O ⁰ F) under a nitrogen stream to obtain 885 g of an oil-copolymer, the copolymer contained T3%.

The oxidation of the copolymer successes by heating the above mixture to 204 ⁰ C (400 ⁰ F) and the nitrogen removed by blowing air to diffuse into the reaction vessel was allowed ·. Kan increased the agitation speed at this point so that the viscous liquid came into close contact with the air. After a reaction time of 0.5 hours in this way, oxidation of the copolymer and the associated degradation have taken place and a decrease in viscosity in the reaction medium was obtained. The stirring speed and the reaction temperature were gradually decreased, while the desired gas-liquid contact was maintained, until a temperature of 154 ^° C. (310 ^° F.) was reached. The reaction temperature ensures the desired balance between an appropriate rate of oxidation and the undesirable excessive polymer degradation. After a total reaction time of 2.5 hours, silica gel chromatography indicated that the recovered product contained 17% active oxidized products, which corresponds to a theoretical conversion of the copolymer to the oxygenated products (this allows a typical 5-6% oxidation of the diluent oil) , '-

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Part: B - Condensation product of the oxidized copolymer with aldehyde and amine

To 885 g of the oxidized copolymer product, which had been obtained in part A above, were added 900 g of benzene and increased the reaction temperature to 49 ⁰ C (120 ⁰ F), under nitrogen, wherein the nitrogen at a rate von28dnr ⁵ (i, OCFH) was introduced. Powdered, anhydrous paraformaldehyde (0.62 g, OjO2O7 mol) was added all at once! And the temperature rose over the course of 0.5 hour at 60 ⁰ C (14O ° F). The melted, anhydrous hexamethylenediamine (2.4 g, 0.0207'MoI) was added all at once and the resulting. Mixture was rapidly increased to the reflux temperature of benzene (78 ⁰ C = ⁰ I76 F). The molar ratios of the reactants were 1: 4: 4.

While maintaining a nitrogen atmosphere, the benzene and water (formed as a by-product in the condensation reaction) were distilled off from the reaction mass. After 1 hour at a moderate distillation rate, the distillate in the receiving vessel was clear, indicating that there was no remaining water. The Mannich condensation was believed to have ended at this point. The remaining benzene was removed by increasing the temperature to 16O ° C (320 ⁰ F) and nitrogen initiated in an amount of 168 dnr (6CFH) in the Reaktipnsgefäß. Man. heated at the same temperature for an additional hour and allowed nitrogen through the reaction mixture to remove the last traces of volatile impurities. 99.4% (880 g) of a turbidity-free Mannich condensation product with the following properties were obtained:

. Activity. . 13%

Nitrogen, 0.063% (calculated)

0.058% (found)

Viscosity (SSU at 98.9 ⁰ C =

21O ⁰ F) 2100

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' Example 4

1625 g of a solution of 130 g of the oxidized ethylene-propylene copolymer, obtained in Part A of Example 3 above, and 1495 grams of a solvent extracted SAE SW mineral oil were mixed with 1200 ecm of benzene and described for the Mannich condensation as in Part B of Example 3 prepared. In this example the molar ratio of oxidized copolymer, para-forraaldehyde and hexamethylenediamine was however, 1: 8.6: 8.6 based as in Example 3 above of the oxidized copolymer having a number average molecular weight von-22,200. The reaction conditions and procedures for carrying out the Mannich condensation were the same as described in Part B of Example 3 above. A 99.5% yield of a clear Mannich condensation product was obtained with the following characteristics:

Activity 8.0? »

Nitrogen 0.086% (calculated),

0.0845 ^ (found)

- Viscosity (SUU at 98.9 ⁰ C =

210 ° F) 1125

Example 5-

A copolymer of 55 mol% ethylene. 35-mol-1 propylene and 10 mol-So 1-decene were prepared as described in Part A above of Example 1 and then _{oxidized as described in Part B 1} of Example 1. The oxidized copolymer was then reacted with para-formaldehyde and hexamethylenediamine under Mannich condensation conditions as described in Part C of Example 1 above using the reactants in molar ratios of 1: 4: 4. The Mannich condensation product obtained showed an activity of 13% and contained 0.0655 nitrogen.

The V.!. Improving properties of the inventive Mannich condensation products are indicated by the values listed in Table I below, in which the

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the following oil samples were used: - -.

Sample A - 150 neutral base oil

Sample B- Rrobe A plus 1.1? 6 pure (i.e. undiluted Mannich condensation product from Example 1, Part C.

Sample C - Sample A plus 1.5% pure oxidized polyisobutylene (number averaging molecular weight 'weight 1500), Mannich condensation product

Sample D <* Sample A plus 1.5% pure oxidized

- Ethylene-Propylene-Copolyraer '(fcahlennittle- ■ : ■ res molecular weight 2000), Mannieh-Kon- " · Densation product

Table 1 Sample SSU viscosity at about 9 ⁰ C (210 ⁰ F) Vl.

- "A '" '43, 5 108

B 57.5 '142

C 45.0 110

D '46.0 110

From the above values it can be seen that the Kannieh condensation products of the invention are highly effective in imparting the desired V, I, property to a low Vl base oil stock _fl

The effectiveness of the additives according to the invention is shown by the so-called "Spot Dispersancy" test. In this test , a measured amount of the additive to be investigated is mixed with a measured volume of Qetvie housing lubricating oil formulations which are combined in one Ford sequence VC engine test was used during 192 hours (double the time, based on die'Standard · "trial time), this Zusajiimensetzung is at about 149 ⁰ C (509 F), v / erv hile about 16 hours / ärint and stirred and Then an aliquot is put on blotting paper * A comparative experiment is carried out at the same time by running a second sample for 16 hours , the 192-3-hour Word. at

149 ⁰ C (30O ⁰ F) and then heated auftrug an aliquot on blotting paper. At the same time, a commercially available ashless dispersant is mixed in the same manner as described above for comparison. The deposits on the blotting paper are determined to determine the average diameter of the outer ring of oil (Do) and the average diameter of the inner ring of mud (Da). The Da / Do ratio is a measure of the detergent dispersion property of the additive.

In the following Table II the dispersion properties of the additive according to the invention are compared with a technical 'Dispersion additive compared. The following samples were used in this experiment:

Sample A - comparative oil - no dispersant

Sample B - comparative oil plus 1.0% Mannich condensation product from Example 3, Part B above

Sample C - reference oil plus 1.0? O technical dispersant VI additive ■

Table II

S; sample ■ ° / o Dispersionsvermöp

■ ■ A 45

B 93

C 66

From the above V / erten it can be seen that the invention Mannich condensation products are very highly effective dispersants and are the best commercially available Dispersant V.Iο additives are superior.

Lubricating oil compositions containing the Mannich condensation products of the invention are included in the Ford MS Sequence VC test described in SAE Technical Report J 183a, "Engine Oil Performance and Engine Services Classification "is checked. The information described in this technical report

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25.1% (Vol.) 60.0% Il 1.2% Il 1.2% Il 0.5% Il 12.0% Il

Sharp level tests are in SAE report J 304 and in ASTM

STP 315 described. The following oil compositions were used in these experiments: Sample A: -, - _a ^ r-

SAE 5-oil extracted with solvent 49.8% (vol.)

with solvent, extracted SAE 10-01 $ 36.8 "

Zinc dialkyl dithiophasphate 1.2 % "

high purity. Magne.s, iumsulfonät ,,, ^. . 1.2% "

Mannich product, example 3, part B 11.0% "

(13% active, 1.4% (vol.) Active ingredients) '·

Sample B:

SAE 5-oil extracted with solvent, SAE 10-01 extracted with solvent

'' Zinc dialkyl dithiophosphate high purity magnesium sulfonate

Means to lower the pour point Mannich product, mixture of example 3, Part B and Example 4 (10% active, 1.2% (vol.) Active ingredients)

Sample C:

SAE 5-Ö1 30.0% (vol.) extracted with solvent

SAE 10-01 extracted with solvent 56.93% (vol.) Zinc dialkyl dithiophosphate 1.1% »

high purity magnesium sulfonate 2.0% "

technical means to improve the V.I. 5.2% "

Silicone antifoam agent '■' 500 ppm

commercially available ashless dispersant (42% active, 2.0% (vol.) Active ingredients) 4.77% (vol.)

The results obtained in these experiments are shown in Table III below.

Table III

Sample mud engine ratings

Covering or varnish Belap; on the piston

A 8.4 8.5 7.3

B 9.5 8.6 ". 7.5. C 9.0 8.5 8.2

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7339510

From ^r to the results listed in Tables I, II "and III above shows" that the erfindüngsgemäß ·· produced Mannich condensation products have a unique combination of good properties, namely a strong dispersant effectiveness and excellent VI "properties, -. '. -. - ....- ■■

Unless otherwise specified, the percentages are expressed by weight * ■ /

Claims (1)

, · ■ - 20 - 7339510 : Claims Λ "'Λ' Öllosliches condensation product, characterized in that it is produced by out at a high temperature of about 121 to about 1-77 ° C (250 to 35O ⁰ F) an oxidized amorphous copolymer of high molecular weight. In essentially ethylene and propylene, the copolymer having a number average molecular weight of at least about 10,000 and containing at least 140 side methyl groups / 1000 chains of carbon atoms, with a reactant providing formaldehyde at the specified reaction temperature and a primary or secondary aliphatic amine such as one Alkylamine with about 2 to about 12 carbon atoms, an aliphatic diamine of the general formula HpN (CHp) NHp, where y is an integer from about 3 to about 10, or a polyalkylene polyamine of the general formula HN- (AN) -H, where A is a divalent alkylene group with -H about 2 to about 6 carbon atoms and χ is an integer 'from "1 to about 10, where the Reactants in molar ratios from about 1: 2: 2 to "about 1:20:20" can be used. 2. Oil-soluble condensation product according to claim 1, wherein the copolymer contains essentially ethylene and from about 30 to about 65 moles-50 propylene. 3. Oil-soluble condensation product according to claim 1, wherein the copolymer is essentially ethylene, from about 30 to about 65 mole percent propylene, and up to about • 20 mole percent of a third olefinic monomer such as one Monomers of the general formula RCH = CHp, where R is an aliphatic or is a cycloaliphatic group having 2 to about 20 carbon atoms, or a diolefinic monomer with about 4 to about 25 carbon atoms 409808 / Ö8ÖÖ '4. : Oil-soluble condensation product according to claim 3, wherein 1-decene is used as the third olefinic monomer. 5. Oil-soluble 'condensation product according to claim 1, in which one uses para-formaldehyde as a reaction participant that supplies formaldehyde, and in which one is used as aliphatic Diamine hexamethylenediamine used. 6. Oil-soluble condensation product according to claim 1, wherein the reactant, the formaldehyde, is used, para-formaldehyde and, as polyalkylene-polyamine, tetraethylene pentamine used. 7. The oil-soluble condensation product of claim 1, wherein the copolymer consists essentially of ethylene and about 38 Ms contains 42 mol% propylene and wherein the copolymer has a number average molecular weight from about 25,000 to about 35,000 and from about 160 to about 170 side methyl groups / 1000 chains of carbon atoms contains and where one uses para-formaldehyde as the reactant that supplies formaldehyde and as the aliphatic Diamine Hexamethylenediamine is used, and the reactants are in molar ratios of approximately 1: 14.5: 14.5 can be used. 8. A lubricant composition containing a major part of a usually liquid, oil-like lubricant and from about 0.1 to about 10% of the oil soluble condensation product according to claim 1. 9 «· · Lubricant composition containing a main part a 'usually liquid, oil-like lubricant and from about 0.1 to about 10% of the oil soluble condensation product of claim 2. 409808/0888 7339510 10.. ' A lubricant composition containing a major part of a usually liquid, oil-like lubricant and from about 0.1 to about 10% of the oil soluble condensation product of claim 3. 11. A lubricant composition containing a major part of a usually liquid, oil-like lubricant and from about 0.1 to about 10% of the oil soluble The condensation product of claim 4. 12. Lubricant composition containing a major part of a usually liquid, oil-like lubricant and from about 0.1 to about 10% of the oil soluble The condensation product of claim 6. 13. An additive concentrate for lubricating oils containing a lubricating oil containing from about 10 to about 75% of the oil-soluble condensation product of claim 1. 409806/0888