DE2422609A1 - LUBRICATING OIL FORMULATION - Google Patents

Description

Patent assessor Hamburg, May 8th 1974

Dr. Gerhard Schupfner 726 / kr

German Texaco A.G,

2000 Hamburg 76 T 74 028 (D 72,231-F)

Sextuple gate 2

TEXACO DEVELOPMENT CORPORATION

135 East 42nd Street New York, N.Y. 10017

UNITED STATES.

Lubricating oil formulation

Lubricating oil formulations and in particular the so-called used for filling automatic motor vehicle gearboxes. ATF special oils often contain acrylic or methacrylic acid manufactured polymer additives that give them the necessary viscosity / temperature behavior should. These additives are intended to modify the lubricating oil in such a way that that the change in viscosity with temperature is as small as possible. Lubricating oils such containing polymeric additives retain their viscosity at the higher temperatures that are commonly found in engines and power transmissions occur at, but show at

5 0 9849/0814

cold engine to the desired low viscosity. The ability of the hydrocarbon oil to rise in temperature Responding with a minimal drop in viscosity is expressed by its viscosity index (= VI). The more pronounced this ability, the greater the VI. Because of their aforementioned Properties of these polymeric additives are also "thickeners" or "VI improvers" or "VI improvers" called.

Some of the known polymers are multiply effective additives in that they not only improve the VI but also act as a detergent / dispersant and pour point depressant. Multiply effective Additives are particularly desirable for the use of the lubricating oils in engines and automatic transmissions, because today's requirements for these lubricating oils and special oils are so great that the specifications change can only be fulfilled with large proportions of additives. With increasing additive proportions, however, it can easily be a Point can be reached where the main task of lubricating oils or ATF oils is adversely affected. That's why Compounds that can perform several additive functions are in great demand because they meet the requirements of the engine or a gearbox with a lower total amount of additive.

One of the major disadvantages of known multipurpose additives that are used as VI improvers, detergents / dispersants and Pour point improvers work, but consists in that they provide the necessary flowability of lubricating oil formulations at very low temperatures, for example in the range of -4O ° C, cannot adequately guarantee.

It has now been found "" that this disadvantage is eliminated

- 3 509849/0814

If a lubricating oil formulation, which contains a mineral lubricating oil as the main component, is allowed to contain 0.1-10% by weight of monomeric units of dialkylaminoalkyl methacrylate, optionally alkyl- 'substituted styrene, C ^ QC ^^ - alkyl methacrylate and Cjg-C ^ Q-alkyl methacrylate existing copolymer incorporated. These lubricating oil formulation of the invention should contain at least about 75 wt .-% mineral lubricating oil, and the Tetramischpolymerisat should (at 25 ⁰ C in benzene) one intrinsic viscosity from 0.22 to 2.87, preferably 0.68 - 1.2 and possess 4 - 10 Gsw .-% of the N, N-dialkylaminoalkyl methacrylate, about 15 - 25 wt .-% of the optionally alkyl-substituted styrene compound, about 40 - 60 wt .-% of the C ₁ QC ₁ ^ alkyl methacrylate and 20 - 30 % By weight consist of the C ^^ - Cg _{0 -alkyl methacrylate.}

The Tetramischpolymerisat additive of the lubricating oil formulation according to the invention can be prepared, which consists of 4-10 parts by weight of the 5 & dialkylaminoalkyl methacrylate, 15-25 parts by weight of the styrene compound 96, 40 through the usual Mischpolymerisationsverfahren from a monomer mixture - 60 wt, -% of C ₁ QC ₁ ^ and 20-30% by weight of the C ₁ gC ₂ Q-alkyl methacrylate and also about 25-35% by weight of a solvent, preferably a lubricating mineral oil with a viscosity of 110-220 SUS (Saybolt Universal Seconds contains) at 37.8 ⁰ C. The polymerization mixture obtained is flushed with an inert gas, such as pre-purified nitrogen, to a temperature of about 65 - 85 ⁰ C and heated with 0.4 - 0.15 wt -.% Of a polymerization catalyst such as azobisisobutyronitrile or dibenzoyl peroxide and about 0.08 - 0.2% by weight of a chain terminator such as lauryl mercaptan added. The polymerization reaction is usually monitored by periodically sampling the reaction mixture and measuring its index of refraction. The polymerization of the reaction mixture is

5098Λ9 / 0814

continued wisely until the index of refraction does not change by more than 2-9 units in the 4th decimal. Under the preferred working conditions, the polymerization is completed by further Mineral oil in a proportion of 65-75% by weight, based on the polymerization mixture, and polymerization catalyst in a proportion of 0.1-0.15% by weight of the polymerization mixture and the temperature is about Holds between about 95 - 105 ° C for 2-3 hours.

The end product of this polymerization usually consists of a tetrapolymer containing about 38 to 42% by weight Concentrate in lubricating oil. The mixed polymer concentrate is used for the ready-to-use lubricating oil formulations diluted with further lubricating oil or added to a formulation containing mineral oil, so that the content of copolymer in the ready-to-use lubricating oil formulations is about 0.1 to 10 wt .- ^.

Examples of suitable dialkylaminoalkyl methacrylate monomers for preparing the lubricating oil formulations according to the invention are Ν, Ν-dimethylaminoethyl, N, N-diethylaminoethyl, Ν, Ν-dimethylaminopropyl and N, N-diethylaminopropyl methacrylate.

Examples of suitable styrene monomers are styrene, Vinyl toluene, ρ-tert-butyl styrene and p-tert-octyl styrene.

Examples of suitable C ₁ -C 1 ^ alkyl methacrylates are decyl, undecyl, dodecyl, tridecyl and tetradecyl methacrylates and mixtures of these compounds. These mixtures are obtained in the production of alkyl methacrylates if technical alcohol mixtures are used, since these technical alcohols usually represent a homolog mixture in which one alcohol predominates, so that

- 5 509849/0 8 14

a mixture of methacrylic acid esters of these alcohols receives.

The C ₁ g-CpQ alkyl methacrylates include hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl methacrylate and their mixtures.

The lubricating effective mineral oils, which are used in the inventive formulations or in the preparation of the copolymer, naphthenic, paraffinic or mineral oils may gemischtbasische having a viscosity of about 35 - be 1000 SUS at 37.8 ⁰ C.

If the lubricating oil formulations of the invention are to be used for filling automatic motor vehicle gearboxes ("ATF fluid"), the proportion of the tetramix polymer should be about 0.5-5% by weight and the proportion of the lubricating mineral oil about 90-97% by weight. - ·%, respectively, the latter conveniently has a viscosity of 40 - should have 125 SUS at 37.8 ⁰ C and the rest of the ATF fluid from the other commonly used additives is - 150, preferably 50th A preferred base oil for ATF fluids contains about 70-95% by weight of a refined distillate oil and 5-30% by weight of a refined residual fraction which provides the oil with the desired high flash point and lubricity. A preferred residual fraction includes a paraffin-residue which deasphalted with propane, deparaffinized by centrifugation and has a viscosity of less than 250 SUS at 98.9 ⁰ C. A particularly effective base oil blend contains 65% by volume of a furfural refined, acid and clay treated and solvent dewaxed paraffinic distillate that has a viscosity of 100 at 37.8 ° C, a viscosity index of about 100

E09 8.4 9/0814

Has a flash point above 193 ° C and an ASTM pour point of below -12 ⁰ C and 22 vol .-% of an acid-treated naphthenic distillate, which has a viscosity of 60 SUS at 37.8 ° C, a flash point above 149 ⁰ C and an ASTM pour point below -40 ° C and finally 13 vol .-% of a paraffinic residue that has been deasphalted with propane, dewaxed by centrifugation and treated with clay and a viscosity of about 160 SUS at 98.9 ° C, a flash point above 277 ⁰ C and an ASTM pour point of -15 ° C has, contains.

The formulations according to the invention can, in particular when used as ATF liquids, additional Contain additives, such as detergents / dispersants, anti-rust corrosion inhibitors, Antioxidants and friction modifiers. Examples of such additional additives are described in U.S. Patent 3,640,872, e.g., as detergent / dispersant, alkenyl-substituted succinic anhydride derivatives of polyethylene polyamines in which the alkenyl group is a polybutene with a molecular weight of about 1200 and the amine is hexamethylene pentamine, as well Antioxidants such as pheny! Naphthylamine, phenylenediamine, Phenothiazines and diphenylamine, furthermore friction modifiers such as IM-acylsarcosine of the formula

It

RCN-CH ₀ -COOH

, in which R is an aliphatic radical with 12-70 carbon atoms, and anti-rust or corrosion protection agents such as mixtures of hydrolyzed Cg-C _1Q -alkeny / succinic anhydride, phenol, mono- and di-C ^ p-alkyl phosphoric acid esters and compounds, the the life of the friction modifiers

509849/0814

increase, such as zinc di (alkylphenoxypolyalkoxyalkyl) dithiophosphate.

If lubricating oil formulations of the invention are used in internal combustion engines, they are generally about 75-95 wt .-% of a hydrocarbon lubricating base oil, preferably having a viscosity of 95 to 150 SUS at 37.8 ⁰ C and about 1-5 wt 96 of the copolymer, with the remainder consisting of the additives customary for engine lubricating oils. These additional additives belong to the detergents / dispersants, oxidation inhibitors, corrosion inhibitors, defoamers and the like.

Examples of such detergent / dispersant for engine lubricating oils are the ethylene oxide derivatives of inorganic, phosphoric acid-free, steam hydrolyzed reaction products of polyisobutene (molecular weight 700 - 500) and Pp ^ 5 »Overbased calcium salts more alkylaromatic Sulfonic acid having a total base number of at least about 300 and sulfurized normal calcium alkyl phenates. These Additives are described in U.S. Patents 3,087,956, 3,549,534, and 3,537,966.

Examples of suitable antioxidants for motor oils are zinc and cadmium dialkyldithiophosphates and diaryldithiophosphates, the alkylated diphenylamines, sulfurized diphenylamines, unsulfurized and sulfurized alkylphenols and phenates and sterically hindered phenols.

Examples of suitable lubricating oil anti-corrosion agents are zinc dialkyldithiophosphate, zinc diaryldithiophosphate, basic calcium and magnesium sulfonates, calcium barium and magnesium phenolates.

509849/0814

The preparation, composition and properties of the lubricating oil formulations according to the invention and those therein The new copolymers contained therein are further illustrated in the following examples.

example 1

This example explains the production of a concentrate of the copolymer according to the invention in a lubricating oil. The parts given denote parts by weight, unless otherwise noted.

In a 1 liter resin flask, 40 parts of toluene, 10 parts of Ν, Ν-dimethylaminoethyl methacrylate, 100 parts of technical lauryl methacrylate, 50 parts of stearyl methacrylate and 100 parts of technical naphthenbasisches.Schmieröl were added with a viscosity of about 145 SUS at 37.8 ⁰ C. The contents of the resin flask were then flushed with prepurified nitrogen for 40 minutes and then heated to 82 ± 1 ° C. and admixed with 0.4 part of azobisisobutyronitrile and 0.2 part of lauryl mercaptan. The reaction was followed by measuring the refractive index ^{1 of} the polymerization mixture every half hour. After 3.5 hours the reaction was complete, it then the temperature was raised to 100 ⁰ C, and the polymerization mixture was treated with 186 parts of a mineral lubricating oil having a viscosity of about 45 SUS at 37.8 ° C and with a second portion of 0.15 part of azobisisobutyronitrile was added. The temperature of 100 ^° C. was maintained for two hours, and the resulting copolymer concentrate was finally cooled to room temperature and analyzed. It was found to be a 41% by weight copolymer containing lubricating oil solution with a viscosity of about 3100 SUS, the copolymer being a tetrapolymer of dimethylaminomethacrylate, vinyltoluene, dodecyl methacrylate and octadecyl methacrylate in a weight ratio of

509849/0814

Monomers of 1: 4: 10: 5 and the copolymer had an intrinsic viscosity of about 0.85 at 25 ° C in benzene.

The following examples 2 to 4 explain the preparation of the tetramolymers further. Also here are the specified parts are parts by weight, unless otherwise noted.

Example 2

A 1 liter resin flask was charged with 10 parts of N, N-dimethylaminoethyl methacrylate, 40 parts of styrene, 100 parts of technical grade lauryl methacrylate, 50 parts of technical stearyl methacrylate and 100 parts of naphthenic lubricating oil having a viscosity of about -145 SUS at 37-8 ° C. The contents of the resin flask were flushed and the interpolymerization carried out according to the procedure given in Example 1. The product proved to be a 38 wt -.% Copolymer containing lubricating oil solution, wherein the copolymer had an intrinsic viscosity of about 0.69 in benzene at 25 ° C and the weight ratio of its monomer units corresponding to the weight ratio of the employed monomer mixture. .

Example 3

A 1 liter resin flask was filled with 8 parts of N, N-dimethylaminoethyl methacrylate, 40 parts of styrene, 100 parts of technical lauryl methacrylate, 52 parts of technical Stearyl methacrylate and 100 parts of a naphthenic lubricating oil with a viscosity of about 145 SUS 37.8 ° C charged. The contents of the resin flask were flushed and copolymerized according to the procedure of Example 1.

- 10 -

509849 / 08U

The product proved to be a 38 wt .-% copolymer containing lubricating oil solution, wherein the copolymer having an intrinsic Viskösität of about 0.59 in benzene at 25 ⁰ C and the weight ratio of its monomer units corresponded to that of monomers used mixture.

Example 4

A 1 liter resin flask was charged with 8 parts of Ν, Ν-dimethylaminoethyl methacrylate, 44 parts of styrene, 100 parts of technical grade lauryl methacrylate, 48 parts of technical stearyl methacrylate and 100 parts of a naphthenic lubricating oil having a viscosity of about 145 SUS at 37.8 ° C. The contents of the flask were flushed and copolymerized following the procedure of Example 1. The product proved to be a 38 wt -, -% copolymer containing lubricating oil solution, wherein the copolymer had an intrinsic Viskösität of 0.61 in benzene at 25 ⁰ C and the weight ratio of the monomer units corresponded to that of monomers used mixture.

Example 5

This example illustrates the lubricating oil formulations according to the invention and the extraordinary influence of the copolymers contained on the low-temperature flowability of the formulations.

For comparison, three ATF fluids A, B and C used, which were composed as follows:

- 11 509849/0814

Table I. composition

Mineral lubricating oil

ATF-A

86.5

Additional VI improvement 8.5 additive package AI ^c additive package B-II ^d

ATF-B

100

ATF-C

88

Brookfield Visc., Cps at -23.3 ° C at -28.9 ° C at -40 ⁰ C.

Visc., CSt.

at 37.8 "C at 98.9OC

Viscosity index, ASTM pour point, ⁰ C

(SUS)> o,

2270 59200

30.9 (145) 7.72 (51.5)

251 -45.6

30000O ⁺

approx. -18

~ 2700

41000

43.4 (202) 7.89 (52)

167
-42.8 ⁰ C

a) 43 wt .-% solution of a terpolymer of methyl, dodecyl and octadecyl methacrylate in a weight ratio of 25: 50: 25 in one. Mineral lubricating oil with about 100 SUS at 37.8 ⁰ C, wherein the terpolymer has an intrinsic viscosity of 0.68 in benzene at 25 ⁰ C.

b) A 41 wt .-% solution of a Tetrapolymerisats from butyl, dodecyl, Oktadecylmethacrylat 'and dimethylaminoethyl methacrylate in a monomer weight ratio of 21: 50: 25: 4, in a mineral lubricating oil with about 100 SUS at 37.8 ⁰ C wherein the Tetrapolymerisat an intrinsic viscosity of about 0.86 has in benzene at 25 ⁰ C.

509849 / 08U

c) contained about 18% by weight of overbased calcium petroleum sulfonates, 16% by weight barium soaps of fatty acids, 12% by weight overbased zinc salts of alkarylphosphinodithionic acids and 54, wt% mineral oil. "

d) containing about 2 wt .-% alkylated polythiadiazoles, 5 Gevr .-% dioctyldiphenylamine, 21 wt -.% of a reaction product of polyisobutenyl succinic anhydride / polyalkylene oxide condensate having a phosphorsulfidierten hydrocarbon and neutralization with a high molecular weight carboxylic acid and 72 wt .-% mineral oil / Aromatic mixture

The properties of lubricating oil formulations obtained from the three ATF fluids A-C and the above additives on the one hand and the copolymers according to the invention on the other hand, compared. The test results are given in Tables II and III below. the The designation "FISST" in Tables II and III (= Fuel Infective Shear Stability Test) stands for a shear resistance test of the additive, in which the material to be examined is passed through a Die with a diameter of 0.152 mm was pressed. The viscosity was measured before and after the injection, and the amount of viscosity drop is considered proportional to the shear gradient.

In Table II, 618 enter the tests, 621, 664, 665 and 680 lubricating oil formulations according to the invention again, and the comparison of their Brookfield viscosity at -40 ⁰ C to the base fluid shows the beneficial influence of the Tetramischpolymerisate to the low temperature behavior.

- 13 -

509849/0 8 14

Table II

Experiment no.

Base fluid 618 621 664 665

680

Mixed polymer

N, N-dimethylaminoethyl methacrylate

Vinyl toluene

Styrene

Lauryl methacrylate

Octadecyl methacrylate

Intrinsic viscosity I (25 C, benzene)

4th 5 5 4th 4th 21 20th - - - - - 20th 20th 22nd 50 50 50 50 50 25th 25th 25th 26th 24

0.71 0.80 0.69 0.59 0.61

Mixed polymer / lubricating oil concentrate ^ ILC) _.

Copolymer, wt -.%

Mineral oil, ^ 145 SUS at 37.8 ⁰ C) wt -.%

41

59

38

62

38

62

ATF-A + ILC 0 ILC, wt% 30.9 Visc., At
37.8 ° C, cSt. 7.72 at 98.9 ⁰ C, cSt. -45.6 ASTM pour point,
OC *
2270 Brookfield visc.
^cP
at -28.9 C 59200 at -40 ⁰ C

41.1 40.8 37.5 33.4 35.6 8.48 8.25 7.88 7.12 7.62

-49.4 ■ -45.6 -49.4 -49.4 -49.4

3800 3510 2560 2360 2160 25500 24250 12040 13900 10240

509849/0814

Experiment no. reason
fluid
speed - - 0 ATF-A + ILC _ FISST (20 avg
corridors)
Visc. At 37.8 ⁰ C,
cSt. • Visc. At 98.9 ⁰ C,
cSt. ATF-B + ILC ILC, wt% Kin.Visk.,
98.9 C, cSt. Brookfield Visc.,
cP (at -, 40OC)

618 621 664 665

680

30.3 30 27.2 26.1 26.7

6.11 6.17 5.68 5.54 5.72

3.5 3.5 3.5 3.5 3.5

7.14 7.42 6.69 6.38 6.46

46000 42250 35500 38750 32900

Table III

Experiment no.

Mixed polymer

Basic fluid

N, N-dimethylaminoethyl methacrylate

Styrene
Lauryl methacrylate

Oc tade cyl methacrylate

Intrinsic viscosity I (250C, Benzene)

7231 7232 7241 481

25th

482

10 20th 25th 4th 6th 30th 30th 25th 21 19th 60 50 50 50 50

25th

0.55. 0.49 0.55 0.73 0.92

509849708U

Experiment no. reason
fluid
speed 0 Mixed polymer /
Lubricating oil conc
entered (ILC) wt% 4.84 Mixed polymer -
Mineral oil (145 SUS
at 37.8 ⁰ C -15.0 ATF-C + ILC ILC, % by weight Visc., At
98.9 C, cSt. ASTM pour point,
⁰ C

- 15 -

7231 7232 7241 481 482

38 38 38 38 38

62 62 62 62 62

4.3 4.3 4.3 4.3 4.3 6.41 5.59 5.91 7.32 8.00 -17.8 -20.6 -12.2 -45.6 -49.4

Brookfield Visc.,. . ■,

at -40 ⁰ C, cP. 30000O ⁺ 30000O ⁺ 30000O ⁺ 300000 ⁺ 32624 34500 FISST (20 passes)
at 98.9 ° C, cSt. . 5.86 5.90 5.73 5.42 5.88 6.02

In Table III, a comparison of the comparative tests No. 7231, 7232 and 7233 with the inventive tests No. 481 and 482 with regard to the ASTM pour points and the Brookfield viscosity at -4O ⁰ C shows that the claimed weight ratios of the monomer units in the copolymer exert an important influence.

Example 6

This example compares the effect of the tetramic copolymer on the ASTM pour point of one according to the invention Lubricating oil formulation for engines.

- 16 -

5 0984 9/08 U

The base lubricating oil formulation was as follows: Ingredients% by weight

A mineral oil, 130 SUS at 37.8 ⁰ C 78

Mineral oil B, 340 SUS at 37.8 ⁰ C 8

Additive package *) 14

Polysilicon Defoamer 60 ppm

*) Remaining dispersant / inhibitor concentrate for HD engine oils, consisting of ethoxylated, hydrolyzed Polyisobutene / ^ Sc reaction product, with calcium carbonate overbased calcium petroleum sulfate, zinc dialkyldithiophosphate, alkylated diarylamine antioxidant, polysilicon defoamer (750 ppm) and mineral oil solvents

The lubricating oil formulation according to the invention consisted of this base lubricating oil, 9% by weight of the copolymer concentrate (ILC) from Run No. 482 of Example 5, Table III.

The comparison gave the following results: Composition, ASTM pour point, ⁰ ° C

Base oil - 12.2

Base oil + 9 % by weight

ILC (Experiment No. 482) - 40

- 17 -

509 8 4 9/0814

Claims (4)

T Ik 028 claims 1) Lubricating oil formulation, which mainly consists of lubricating oil hydrocarbons and methacrylate copolymers contains as an additive, characterized in that it contains 0.1-10 wt. which consists of the following monomer units: a) a Ν, Ν-dialkylaminoalkyl methacrylate of the formula RO ι u
NAOCC = CHp
ι I *
R ₁ CH ₃ , in which R and R .. alkyl groups with 1- 2 carbon atoms and A is an alkylene radical with 1-5 C atoms, b) a styrene compound of the formula .CH = CH _{2 f} in which R _{2 represents} hydrogen or an alkyl group with 1-10 C atoms, c) an alkyl methacrylate of the formula 0 Il CHo = C - C - OR, - 18 - 50984 9/08 U , in which R, is an alkyl group with 10-14 carbon atoms is and d) an alkyl methacrylate of the formula 0
ü CHp = C - C - OR. I CH ₃ , in which R ^ is an alkyl group with 16-20 carbon atoms means, and that the tetra copolymer in benzene at 25 ^° C. has an intrinsic viscosity of 0.22-2.87 and contains the monomer units a) to d) in the following proportions: a) 4-10, b) 15-25, - c) 40 - 60 "and d) 20-30% by weight. Z) mineral lubricating oil according to claim 1, characterized in that
that R and R ^ methyl groups, A an ethanediyl group, R, a lauryl, R ^ a Are stearyl group and R _{2 is} either hydrogen or a 4-methyl group. 3) mineral lubricating oil according to claim 1 or 2, characterized in that that the proportion of additive Tetramischpolymerisat 0.5-5 wt .-% and the viscosity is of the petroleum hydrocarbon 40-150 SUS (Saybolt Universal Seconds) at 37.8 ⁰ C. 4) Mineral lubricating oil according to one of claims 1 - 3 »characterized in that - 19 - 509849/0814 that the proportion of additive 1. Tetramischpolymerisat-5 wt .-% country the viscosity of the petroleum hydrocarbon, 95 to 150 SUS is at 37.8 ⁰ C. 50 98497 08 U