DE2258966A1 - LUBRICATING OIL MIXTURES - Google Patents

Description

SHELL INTERNATIONAL RESEAROH MAATSOHAPPIJ N-Y. The Hague, Netherlands

¹¹ lubricating oil mixtures "

Priority; ^ - December. 1971 * V.St.A · N; r. 2; Q4 668

The invention relates to a lubricating oil mixture. Preferably concerns they are a lubricating oil mixture for use in internal combustion engines.

The specialty of the lubricant preparation was because of the always strerigsr The increasing demands of the automotive industry become more and more complex in the course of their development. One of the main for- ' It is an economical petroleum-based lubricant to make available that over a wide range of operating conditions, in particular over a large Temperature range, can be used. At the same time, the lubricant mixtures must also have the ability to oxidize

309823/0980

transfer stability , surface activity, anti-wear and corrosion- inhibiting effect both during use and during storage. The automotive industry '

Lubricants are required whose SAE viscosity grades are below those prevailing during use and storage Conditions remain constant over a significant period of time.

By "multi-grade lubricants ¹¹ lubricants are understood, the viscosity at -17" 8 and +98.9 ^0C certain provisions, such as SAE, J3OOa for engine oils, corresponding to that shown in the following, the SAE Handbook 1969 extracted table.

Viscosity at SAK -17.8 ⁰ C, Poiae

Oil classification

Viscosity at SAE 98.9 ⁰ C,

Oil classifi- Seyboldt Univerzierung sal seconds

5 W. 12th maximum 10 W. 12 - 20th W. 24 - - 24th - 96

20 30 40 50

45 - 58 58 - 70 70 - 85 85 - 110

According to the above table must, for example, a SAB 10W / 50 oil at -17.8 ⁰ C toiee a viscosity of 12 bit and 24 at 98.9 ⁰ C a viscosity 85-110 Seyboldt Universal seconds have.

Eb a number of multigrade oils ^, such as SAB 10W / 30- and SAE 20W / 40 oils, but with a few

309823/0980

previously not possible to use multigrade oils with a larger Work area, such as SAE 10W / 50 to manufacture the one have low oil consumption and high shear stability. From an industrial point of view, such oil approaches must be economical are in the realm of the possible, be able to be produced on an industrial scale, they must be in view of the starting material used Versatile and preferably resistant to degradation when exposed to high shear stress.

Many polymer additives are mainly used as thickeners, Agents for improving the viscosity index (VI) and as pour point lowering agents have been used. The possibility of use However, almost all of these..additions will go through their sensitivity to shear stress is limited. This is not surprising because most of these polymers Are relatively high molecular weight materials and - accordingly, are easily degraded under shear stress. On the other hand, polymers with relatively low molecular weight, at least so far, than relatively ineffective when used as a thickener or viscosity index improver in lubricants

Automotive engines.
proven for /, although they may have sufficient shear stability.

A number of styrene-diene copolymers are based on the The possibility of their use in lubricants has been investigated. U.S. Patent 3,554,911 teaches use, for example of hydrogenated edom-butadiene-styrene copolymers

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as viscosity index improvers which should be stable to shear. However, these connections have proven to be like next- ^; is shown to be relatively ineffective,

especially with regard to their response to additional j

Pour point depressants and also regarding theirs
Effect on the viscosity index. The USA patent ■} 3 509 056 describes the use of styrene-olefin copolymers prepared with Ziegler catalysts as

Lubricating oil additives. These, however, have proven to be thickeners and
Viscosity index improvers proved to be surprisingly ineffective. A number of block polymers of the stereospecific type produced in stages, such as those by

Mixed polymerization of oc-methylstyrene and ethylene produced

ι th, have been investigated. For reasons that have not yet been clarified

I carries out the stereospecific or the random mixed polymerisation \

tion, as in the case of random interpolymerization of styrene

-and butadiene, to unsatisfactory compositions (cf.

U.S. Patent 3,290,414). i

Styrene hydrated! As explained in US Pat. No. 3,419,365, certain block copolymers of the structure / butadiene have been used as pour point depressants or as stabilizers "against thermal degradation in petroleum fuels". However, they are in concentrations as fuel additives
γόη fractions of a percentage have been used that are not _; sufficient to influence the thickness of the oil or its viscosity index to a significant degree. In addition, as will be shown below, block copolymers containing hydrogenated polybutadiene blocks show practically no

L.

309823/0980

ORIGINAL INSPECTED

Action on additionally contained pour point depressants, especially with low 1,2-content.

It is an object of the present invention to provide improved multigrade lubricants which have a lower oil consumption due to the volatility of the oil than with conventional viscosity index improvers have produced multigrade lubricating oils with the same viscosity. Other objects of the invention are from the following more detailed description of the invention.

The invention accordingly relates to a lubricating oil mixture which

a) from a mineral lubricating oil "with a viscosity index of at least 85. ■

b) from a small amount of a pour point depressant, and

c) from 0.1 to 10 percent by weight of a block copolymer:

i consists, the block copolymer consisting of;

1) a single polymer block unit A with an average molecular weight from about 10,000 to about 55,000,

the-at least 75 percent of condensed alkenyl arene units exists whose aromatic unsaturated bonds are saturated to a maximum of 5 percent by hydrogenation

are and

Average ^

2) a single Pplymerisatblockeinheit B with a / mole-.

kulargjewicht from about 20,000 to about 100,000, which consists of consists of a polyisoprene block, the olefinic dop-

309 823/098 0 ORIGINAL INSPECTED

pel bonds saturated by hydrogenation to at least 95 percent have been, Z Z 003 00 composed, with the block units A and B in one Weight ratio of 0.45: 1 to 0.8: 1 and

optionally further polymer block units contained in the copolymer C together have an average molecular weight of not more than 7,500 and are composed of alkenyl arene polymer block units, from polymer block units from conjugated dienes and / or from mixed polymer block units consist of alkenylarenes and conjugated dienes, the degree of hydrogenation in each case according to that for the block units A and B applicable limit values is limited.

It has been found that the block polymers with the aforementioned Limits in combination with a hydrocarbon lubricant containing a pour point depressant with a high viscosity index have excellent physical properties unlike any other polymer Thickeners were found. The block copolymer preferably has the simple structure A-B. How however Already explained above, it can deviate from this have the structure A-B-C, in which C the aforementioned polymer block is of relatively low molecular weight. Blocks A and B are preferably each homopolymer. Also is A is preferably a substantially aromatic polymer block which is, for example, less than 5 percent hydrogenated during in the polymer block B at least 99 percent of the original olefinic double bonds are saturated.

ORIGINAL INSPECTED 309 823/0980

To the monoalkenylarenes, especially the <o6-alkenylarenes, include styrene and methylstyrene, such as «· -Methylstyrene, Vinyltoluene and other styrenes with a methyl group on the benzene ring. If appropriate, mixtures of these alkenyl arenes can also be used be used.

The conjugated diene used as the starting material to make B block is polyisoprene. Preferably, the Polyisoprene block about at least 80 percent and especially about at least 88 percent 1,4 structure in either cis or trans configuration.

The block copolymer can, using lithium-based initiators, in particular alkyllithium, such as Butyllithium or amyllithium, can be prepared by conventional methods. The polymerization is usually carried out in Solution in an inert solvent, e.g. in cyclohexane or alkanes, such as butanes or pentanes and their mixtures, carried out. The first monomer to be polymerized (which is either which can be monoalkenyl arene or isoprene) is injected into the system and contacted with the polymerization initiator, which is added in such an amount that the polymerization is up to. a predetermined average molecular weight runs. After the desired molecular weight has been reached and the monomer has been depleted, the second Monomers are injected into the living polymer system and the block polymerization is carried out, which results in the living block copolymer Poly (alkenyl arene) polyisoprene, whose re-

ORIQIMAL INSPECTED 309823/0980

ability to act then, ζ.B. by adding methanol, destroyed will.

The starting material is then e.g. similar to that in the USA patent 3,595,942 described method is selectively hydrogenated, whereby the in the inventive lubricating oil mixtures Block copolymers used are formed. The hydrogenation is preferably carried out in the same solvent carried out in which the polymer was produced, wherein a catalyst made from the reaction product of alkyl aluminum and nickel or cobalt carboxylate or alkoxide is used will. The reaction product is preferably obtained from the reaction of triethylaluminum and nickel octoate used as a catalyst.

The temperatures and pressures used in the hydrogenation stage are regulated according to US Pat. No. 3,595,942 and thereby practically complete hydrogenation of the polyisoprene block brought about without the monoalkenyl

arene polymer block is hydrogenated appreciably.

The polymer can after the hydrogenation of its solvent separated and dispersed in lubricating oil. This can be done, for example, by adding a lubricating oil to the solution of the hydrogenated Polymer and subsequent evaporation of the relatively volatile solvent take place.

Concentrates of the hydrogenated block copolymer in lubricating oil can be conveniently prepared. Contain such concentrates

3 O 9 B? 3 / O 9 8 O * «*""■

expediently up to about 20 percent by weight of the hydrogenated block copolymer and depending on the molecular weight of the polymer preferably from about 2.5 to 15 percent by weight.

Molecular weights of the block copolymer in the present description and claims mean the number average molecular weights, as determined e.g. by tritium counting methods or by measuring the osmotic pressure.

The manufacture vgu. Block copolymers by anionic Polymerization in solution results in contrast to the broad distribution that occurs when using Ziegler polymerization catalysts obtained, to the desired relatively very narrow molecular weight distribution ^ polymers with broader Molecular weight distributions (Ziegler) contain a substantial proportion of high molecular weight fractions and show an extraordinarily strong degradation under shear stress on.

The molecular weights of the block polymer A are preferably from about 25,000 to 50,000 and that of the block polymer B between about 35,000 and about 80,000. In particular the weight ratio of A: B is from 0.5: 1 to 0.7 ι 1.

The currently used Pourpo i.nb-depressants are mainly because of their Pourpoirifc-degrading effect aftfiEjebiU, although many of the means also use a viscosity index

; μ / ι) 9Β0 ^bad

Improving agents or thickeners can be used. However, since they are used as pour point lowering agents in smaller amounts of, for example, 0.1 to 2.5 percent by weight and preferably from 0.15 to 0.7 percent by weight, their concentration is usually not sufficient to achieve other properties of the oil in addition to the pour point to influence in a significant way. Since the abovementioned block copolymers have practically no effective pour point-lowering effect, it is essential, however, that the oil contains such pour point-lowering agents. On the other hand, it is characteristic of the aforementioned block copolymers that they strongly rely on added pour point depressants, such as (mixed) polymers of acrylic esters and / or nitrogen-containing acrylic esters, preferably copolymers of a vinyl _{pyridine or vinyl pyrrolidone and Cg, Q} -alkyl (meth) acrylates or copolymers of Co, ₀ -alkyl (meth) acrylates with a high molecular weight react. The term "acrylic ester" denotes esters of the acrylic acid series, such as acrylic and methacrylic acid.

The aforementioned nitrogen-containing acrylic acid ester polymers can be prepared by any suitable method, as described, for example, in US Pat. No. 3,215,632. Such nitrogen-containing acrylate polymers include the copolymers of vinyl pyridine, and G ,, -, ^ - alkyl methacrylates Lchtsbere I day with a mw of I from 400 to 2,000,000 and preferably from 200 000 to OSO 000, such as (1) copolymer

BATH ORIGINAL

M) ') ■';"»: .i / 0 ⁽ J 8 0

from 25 percent by weight of 2-methyl-5-vinylpyridine and 75 percent by weight of stearyl methacrylate with a molecular weight of 200,000; 2) the copolymer of 30 percent by weight of stearyl methacrylate, 51 percent by weight of lauryl methacrylate, 14 weight percent methyl methacrylate and 5 weight percent 2-methyl-5-vinylpyridine with a molecular weight of 600,000;

3) the copolymer of 14 percent by weight of methyl methacrylate, 54 percent by weight of lauryl methacrylate, 27 percent by weight of stearyl methacrylate and 5 percent by weight of 2-methyl-5-vinylpyridine with a molecular weight of 830,000;

4) the copolymer of lauryl methacrylate, stearyl methacrylate and 2-methyl-5-vinylpyridine in a weight ratio of van 60: 35: 5 with a molecular weight of 810,000 j

5) the copolymer of 2-methyl-5-vinylpyridine, lauryl methacrylate and stearyl methacrylate in a weight ratio of 7.5 ί 58: 34.5 with a molecular weight of 31,000.

There are also 6) N-vinylpyrrolidone-alkyl acrylate mixed. polymers and 7) Ν, Ν-dimethylaminoethyl acrylate-alkyl acrylate copolymers. ·

As the oil component of the lubricating oil mixture according to the invention, a lubricating oil which is especially suitable for the production of multigrade lubricants is used, although a single-grade lubricating oil can also be added to the mixture as an oil component *. In particular, the inventive mixture of block copolymers, pour point lowering agents and lubricating oil is suitable for the use of paraffin-containing lubricating oil fractions, as they are in Mid-Continent oils, West Texas

309 8 23/09 80 BATHROOM _{0 RfGiNAL}

Ellenburger crude oils, crude oils from East Texas, Oklahoma, Pennsylvania, California and the like can be found which, in contrast to asphalt-based crudes, can be referred to as paraffin-based crude oils, naphthenic-based crude oils, or mixed-base crude oils. Although crude oils of any viscosity can be used as the basis for the mixtures according to the invention, preferably crude oils with a high viscosity index (HVI) 100 neutral, HVI 250 neutral (the viscosities are about 100 and about 250 Seyboldt, universal seconds at 3718 ⁰ C) and HVI -Brightstock (BS), as well as mixtures of the aforementioned oils, are used. In the present description, the general designation HVI- (Jl also includes oils with a very high viscosity index (VHVI), such as those obtained by hydrocracking oils of low quality, e.g. oils with a low viscosity index (LVI). For special purposes, more volatile These neutral oils are produced by means of well-known refining processes, such as distillation, dewaxing, deasphalting, dearomatization, the process used in each case largely depending on the crude oil used. Typical properties of these HVI oils are summarized below:

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Properties of the base oils

HVI

HVI

HVI

HVI

description 80 N 100 N 250U 150 BS 100 N Viscosity
indices at 98.9 ° C (SUS) 38.0 '39.8 50.0 157 38.6 Viscosity
indices at 37.8 ⁰ C (SUS) 82 107 265 2775 82.7 VI 103 93 93 95 126 Pour point ( ⁰ G) -20.6 -6.7 -6.7 -9, 4th -17.8 Flash point ( ⁰ C) 182.2 207.2 221.1 301, 7th 204.4 $ Aromatics through
UV measurement 15th 11 14th 27-40 5 Weight percent
sulfur 0.05 0.09 0.05 0, 16 0.0

The present invention is based in part on the discovery that the block polymers defined above only in hydrocarbon lubricating oils with a viscosity index of at least 85 and preferably of at least 90 (according to ASTM D2270-64) come into effect. The values given below demonstrate how critical the present invention is in this relationship is by showing that the inventive Block copolymers have little or no effect on the viscosity index of low and medium oils Have viscosity index or the viscosity index of such oils even belittle it. - -. . ...

309823/0980

A primary aspect of the present invention is to discover the unique utility of these mixtures for Manufacture of multigrade lubricants with large Lubricating area and with relatively low oil consumption when using them. It is common knowledge that oil consumption is directly related to the relative volatility of the base lubricating oil. When using most thickeners, Viscosity index improvers, like most pour point depressants, have an essential approach to produce a SAE 10W / 50 lubricant that contains a significant proportion of relatively highly volatile oils, such as 80 neutral or even lighter oils. This works out the fundamental fact that most polymers change the viscosity / temperature curve only insignificantly. However, as is shown by FIG. I of this description, it is due to the use of the block copolymers according to the invention Surprisingly possible, a unique viscosity / temperature curve between -47.8 and 98.9 ° C to obtain. In practice, this means that multigrade oils such as SAE 10W / 30, 10W / 40 and iOW / 50 oils by means of the Additional mixture using relatively heavier oils, e.g. fractions with one viscosity of at least about 95 Seyboldt Universal seconds at 37 | 8 ° C, as with HVI-100 or heavier oils, as the base oil component can be produced and therefore more volatile lubricating oils are no longer used as an oil component got to. This leads to the second economically important consequence that a single mixture of relatively heavy

ORIGINAL INSPECTiD 309823/0980

Lubricating oil feedstocks used in the manufacture of a range of Multigrade oils can be stocked simply by changing the concentration of the block copolymer can be produced. It is so by means of the present invention possible to simplify both the requirement for lubricant production and the oil consumption in the engine to reduce.

As can be seen from the examples below, others have to a certain extent at temperatures between 37 j8 and 98.9 ° C polymer types suitable as oil thickeners or viscosity index improvers the unique and strong Effect on the viscosity / temperature curve between -17i8 and 98.9 ° C, as determined by the specific inventive Block copolymers is effected, not on »The surprisingly low viscosities of the SAE-iOW / 50 lubricant mixtures according to the invention at -17.8 C are unique and cannot be achieved with other polymers.

The examples further show that the molecular weights of the / Blocks and the weight ratios of the two blocks even in the case of the polystyrene-hydrogenated polyisoprene structure Polymers must move within the limits described above, if the BlockmischpOlymerisat should be able to give the lubricant a substantial increase in its viscosity index.

The present invention not only provides multigrade lubricant mixtures with a large lubrication area available

_L

309 823/0980

but also leads to mixtures with a relatively low ash content of e.g. less than about 1 percent by weight sulphated ashes, which are particularly suitable for gasoline engines.

The base mixture described above can be used as such are, however, is preferably due to the presence of further additives in addition to the block copolymer and the Pour point lowering agent to achieve the required stability, surface-active effect, dispersibility, Anti-wear and anti-corrosion properties of modern times Lubricants modified in accordance with the increasingly stringent requirements of the automotive industry.

Such further additives are e.g. polymeric succinic acid derivatives, used as detergents and dispersants such as 1) succinic acid imide of mono- (polyisobutylene ^ succinic anhydride and tetraethylene pentamine, the polyisobutylene radical having a molecular weight of about 1000 having; 2) the amine derivative of polyisobutyl monocarboxylic acid and tetraethylene pentamine with a molecular weight of about 1000; 3) the succinic acid imide of mono- (polypropylene) succinic anhydride and diethylenetriamine, the polypropylene group having a molecular weight of 800 to 1500} 4) the diimide of mono- (polyisobutylene) succinic anhydride and tetraethylene pentamine with a molecular weight of the polyisobutylene radical from 800 to 1500.

The particular in the inventive lubricant

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Mixtures used dispersants are oil-soluble mixtures, by reaction under esterification conditions of

A) at least one acylating agent from a substituted Polycarboxylic acid with an average of at least about 30 aliphatic Carbon atoms per substituent with

B) at least one polyhydric alcohol in at least equivalent Amount to the acylating agent can be obtained from the substituted carboxylic acid, thereby forming an ester containing first reaction mixture is formed, which is then intimately with

C) about 0.025 to 0.15 equivalents of at least one hydroxy-substituted primary amine per equivalent of (A) is contacted. These reaction products and their manufacture are described in U.S. Patent 3,576,743. In particular, the reaction component (A) is characterized in that that it is a practically saturated acylating agent that is obtained by reacting an olefinically unsaturated Carboxylic acid reactants of the formula:

R ₀ -

or of the corresponding carboxylic acid halide, anhydride and ester, in which R is characterized by the presence of at least one covalent olefinic carbon-carbon double bond and η represents an integer from 2 to 6, with an olefinically unsaturated or containing at least 30 aliphatic carbon atoms chlorinated hydrocarbon has been produced at temperatures of 100 to 300 ⁰ C, with the proviso that the aforementioned acylating agent has polar substituents up to 10 percent by weight of the

3 Ό 9823/0980 ORIGINAL INSPECTED

Hydrocarbon portion of the acylating agent without the carboxylic acid groups ". The use of such Detergents lead to a considerable reduction (e.g. from 15 to 50 percent) in the ash content compared to use of other otherwise effective and satisfactory detergents such as succinic imides of mono- (polyolefin) succinic anhydride high molecular weight and polyalkylene polyamines.

Overbased alkaline earth petroleum sulfonates can also be used will. The highly basic alkaline earth metal - (magnesium, Calcium and / or barium) petroleum sulfonate can by means of suitable Methods such as described in British Patent 790,471 can be prepared. The basic Calciuraerdölsulfonate (Molecular weight 300 to 800) are preferably used. Other sulfonic acids in the molecular weight range from 350 to 800, which are derived from olefinic polymers, alky! aromatic compounds, such as of alkylated benzene or alkylated naphthalene ,, derive, can also be used for Preparation of the basic salts can be used. Similar alkaline earth metal alkyl phenates and alkyl salicylates are also suitable.

In addition, dithiophosphates can be used as additional additives, e.g. calcium, zinc and lead salts of alkyl thiophosphates as well their thio derivatives are added. The full esters of pentavalent phosphoric acids, such as triphfmyl, tricresyl, Trilauryl and tristearyl-o-phosphates can be used.

0 9 8 2 3/980 ° R'G <nal inspected

Anti-foaming agents, such as silicone polymers, e.g. the Dimethyl silicone polymer can also be used.

If necessary, the oil mixtures according to the invention can through Addition of small amounts (0.01 to 2 and preferably 0.1 to 1 percent) of phenolic antioxidants, arylamines and dialkyl sulfides with regard to their oxidation stability and wear prevention can be improved. Anti-wear Agents are e.g. esters of metal salts of organic phosphites, phosphates and phosphonates and their thio derivatives.

A preferred lubricant mixture according to the invention has the following composition:

Components by weight

Block copolymer 0.1-10 pour point depressant 0.1-5 Oil soluble metal

thiophosphate - 0.01-0.3

Ashless detergent 0.1-8.5

Overbased alkaline earth

metal alkaryl sulfonate

(Basis: sulphated ash) 0.05 - 3.5

Oil rest

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example 1

Reaction of various block polymers to pour point depressants.

The base oil of the mixture is lower in this example, a iow-base oil (viscosity 47 SUS at 98.9 ⁰ C) containing a sufficient amount of acrylic pour point depressant at its pour point to -28.9 ⁰ C. The viscosity index of the base oil (with the acrylic additive) is 117 (sample A in Table I). The acrylic pour point lowering agent is a copolymer of cetyl methacrylate (50 percent by weight), lauryl methacrylate (25 percent by weight) and octyl methacrylate (25 percent by weight) and is in a Amount of 0.17 percent by weight based on the oil is used.

The tested block polymers are given in Table I. The column "polymer" indicates the type of blocks and the gap « "Molecular Weight" indicates the molecular weight of each block.

When testing the polymers of Table I in the base oil without further additional components show no pour point-lowering effect. The polymers must therefore be used together with a pour point depressant in order to to obtain a low temperature lubricant mixture.

In the test tests shown in Table I, in each case Such an amount of polymer is used that the viscosity of the oil blend is increased from 47 to 65 SUS at 98.9 ° C. Table I summarizes the er.hAltfiJifi.DiWer.te..together

309823/0980

! Table I.

sample Polymer molecular
weight
χ 10 "" ⁵ Poly-
merisat-
focus
tration
in weight # Pour point
⁰ G VI A. none - --- -28.9 117 B. Polystyrene hydrogenation
tes polyisoprene 28-44 1.2 -28.9 171 C. Polystyrene hydrogenation
tes polybutadiene 23-53 1.0 -6.7 147 D. ■ Hydrogenated PoIv-

styrene hydrogenated polybutadiene, 23-53

E Hydrogenated polystyrene-hydrogenated polyisoprene 21-107

Hydrogenated polybutadiene-polystyrene hydrogenated Polybutadiene 61-140-61

G polystyrene (styrene / hydrogenated butadiene handom copolymer)

H hydrogenated poly-styrene-hydrogenated Polyisoprene hydrogenated polystyrene 13-70-13

1.4 +3.9 146

1.0 +3.9 147

1.4 -9.4 160

19- (35/10) 1.5 +3.9 102

1.3 -34.4 * 147

As can be seen from the values above, only that delivers
Polymer with the structure polystyrene-hydrogenated polyisoprene (sample B) 'satisfactory results. All other polymers have poor properties in this regard; . ·

Ί 0 9 M 2 ') / 0 ¹ J 8 U

BATH ORIGINAL

The 2-block polymer with the structure hydrogenated polystyrene hydrogenated Polyisoprene (sample E) whose A: B ratio is outside the range prescribed according to the invention, 2.B .. only has a mediocre effect on the viscosity index. All hydrogenated polybutadiene blocks (manufactured by containing about 40 percent 1,2-addition) (samples C, D, F, and G) Samples have considerably higher pour points than the base oil with the additives but without the block copolymer. Further values show that this pour point problem is caused by random interpolymerization of styrene with the butadiene block or by using a higher 1,2 content (about 70 percent) can be dissolved in the butadiene block. However, the two agents have an adverse effect on thickening ability of the polymer and accordingly either make higher polymer concentrations to achieve the desired thickening of the oil or polymers with higher molecular weights are required.

Example 2 Comparison of the polymers.

In order to determine which type of polymer leads to the best possible combination of properties in the lubricating oil mixture, a series of polymers are mixed in a 100 HVI Neutral Mid- Continent oil that contains 0.2 percent by weight of a copolymer of 2-methyl-5-vinylpyridine (5 percent by weight). Contains lauryl methacrylate (60 percent by weight) and stearyl methacrylate (35 percent by weight) alij Pourpo Ltit nutritional agents,

BATHROOM OR _{1 GINAL}

existing oil mixture checked. The oil with the pour point depressant is gedickt with the -erforderlichen for the increase in viscosity of the oil from 45 to 75 SUS at 98.9 ⁰ C amount of polymer. The values obtained are summarized in Table II below:

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Polymer I. - 24th II viscosity
at
- 17.8 C
(Poise) 2258966 none Molecu *
1arge
weight
χ 10 " ⁵ Tabel 9.6 hydrogenated
Polyisoprene _ V.l. 18th Per
be Polystyrene
hydrogenated
Polyisoprene 88 Con-
Zen-
t ra
tion
(Weight #) 117 Dismantling
lust through
Scherbean
verdict
(Sonic)
{$> at
98.9 ⁰ C) A. Polystyrene
hydrogenated
Polyisoprene 21-21 - 169 B. 19-51 1.95 180 7th C. 4.0 60 7th D. 2.6 10

Polystyrene hydrogenated

Polyisoprene 21-107 1.75 95 14.2

Polystyrene hydrogenated polyisoprene 28-44 1.85 180 .11.9

Polystyrene hydrogenated polyisoprene 19-51 1.70

.Polystyrene Hydrogenated Polybutadiene 16-47 4.0 121 21.0

hydrogenated polystyrene hydrogenated (butadiene / Styrene) copolymer 20- (25/25) 4.6 161 24.0

Ethylene / propylene miscopolymer i sat

1.2 173 14.8

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The above comparison shows some important points to ^1: The ethylene / propylene random copolymer (Sample J) has a low 'shear stability. The ethylene / propylene copolymer used here was used for the investigation because of its relatively good flow properties at low temperatures. In general, ethylene / propylene random copolymers are very good

• poor flow properties at low temperatures. The hydrogenated block polymer (sample I) containing a styrene / butadiene random copolymer block has a poor thickening effect, does not meet expectations with regard to its effect on the viscosity index and has a relatively high viscosity ^{at −17 »8 ° C.}

—The-one-hydrogenated polybutadiene block (manufactured by 72 percent 1,2-addition) containing block copolymer (sample H) shows practically no effect with respect to a Viscosity index improvement. The samples with the structure polystyrene-hydrogenated polyisoprene (samples C through G) show a significant effect of the molecular weight and the ge

—Weight ratio of the two blocks on thickening effect and the viscosity index: If the weight ratio of polystyrene to hydrogenated polyisoprene is too low (Samples ■ D and E) there is a strongly negative effect on the viscosity index. If the weight ratio of polystyrene to hydrogenated polyisoprene (sample C) is too high, the polymer has a slight thickening effect on »There is, however, a Equilibrium between the two types of block and the molecular weights are within the limits according to the invention

309823/0 980 ORIGiNAL INSPECTED

(samples F and G), the lubricating oil mixture has a high
Thickening effect of the polymer and a high viscosity index improvement effect.

Example 3
Rheological properties depending on the base oil

BLe viscosity indices of a block copolymer (the same polymer as in Sample P, Table II of Example 2), 0.2 percent by weight of a pour point lowering agent
(the same as in Example 2) and four lubricating oils with lubricating oil mixtures each containing different viscosity indices are determined

309823/0980

• Polymeric
sat concentrate
tration
(Wt. ^) - fabeile III 2258966 O 1.0 viscosity
at 98.9 ° C
(SUS) Viscosity at
37.8 ° C
(SUS) Uasis oil 2.0 38.2 106 V.l. IVI 10OW 3.0 45.6 214 6th LVI 100N 0 55.4 564 70 LVI 100N 2.0 73.5 1698 19th LVI 100N 3.0 38.2 100 negative MVI 100N O 59.2 638 38 MVI 100N 1.0 98.2 2092 35 MVI 100N 2.0 • 39.2 98 33 HVI 100N 3.0 48.8 182 100 HVI 100N 0 75.9 423 150 HVI 100N 1.0 163.9 1246 176 HVI 100N 2.0 38.7 84 186 VHVI 100N 3.0 48.8 158 129 VHVI 100N 80.2 399 184 VHVI 100N 212.0 1447 205 VHVI 100N 200+

309823/0980

As can be seen from the values in Table III, the present invention is suitable for the use of lubricating oils with high and very high viscosity index, as the block polymers have the structure of polystyrene-hydrogenated polyisoprene show either no effect or even a harmful effect when using oils with low and medium viscosity index.

Other block copolymers, for example a 3-block copolymer of the structure: hydrogenated polystyrene-hydrogenated polyisoprene-hydrogenated polystyrene, have about the same effect on lubricants with any viscosity index and show ]

the above critical behavior does not. Such 3-block copolymers, however, require the addition of a relatively light lubricating oil (80N) _{1 to} meet the viscosity ^requirement; Changes of a multi-range lubricant with a wide lubricating range, such as that of an SAE 10W / 50 (see polymer K in: Table IV and Figure I), to correspond. "\

Example4,

Requirements for the base oil for the production of multigrade oils.

"The main objective is, as described above, to produce a multigrade oil with relatively low volatility. Figure I shows the effect of different types of polymer ^: with regard to the base oils that can be used for multigrade oils Additive combination

309 8 23/0980 originally inspected

existing base mixture added. At a certain viscosity at 98.9 ⁰ C can be used a so heavier oil for a given multigrade oil, the lower the measured at 17.8 ⁰ C cold crank simulator viscosity. It is readily apparent from FIG. I that there are two types of polymer, namely the polymers containing polystyrene and the polymers containing hydrogenated polystyrene or no styrene. It can also be seen that the polystyrene-containing polymers in FIG. I have a steeper curve and thus better behavior. In this figure! Logarithm of the viscosity is applied at 98f9 ° C to the viscosity at -17 "8 ⁰ C. The letters refer to the polymers from Table IV. The dashed lines represent the desired course of the curve.

These values are based on real polymer concentrations in SAE iOW / 50 engine oils and in such oils usable base oil mixtures transfer. The results are given in Table IV. It can be seen from these values that only the polymer having the structure of polystyrene hydrogenated polyisoprene to make an acceptable SAE i0W / 50 lubricant can be used. The ethylene / propylene random mixed poly merisat is for use as a SAE 1OW / 50 lubricant too sensitive to shear stress under normal stress. With the exception of the polymers with the structure polystyrene-hydrogenated polyisoprene is used for production SAE 1OW / 5O lubricants require the use of significant amounts of HVI 80 oils in a mixture or of higher amounts of polymer

309823/0980 original imcpected

necessary. The use of 80-neutral oil leads to high oil consumption in operation. If large amounts of polymer are used, the lubricant mixture is economically disadvantageous compared to active-coated polymers. Using the present block copolymers, the base oil can consist essentially of groups having a viscosity of at least 95 SUS at 37.8 ⁰ C. The inventive approach mixture preferably has a viscosity of less than 24 poise at -17.8 ⁰ C and more than 58, preferably more than 85 SUS at 98.9 ⁰ C.

ORJGfNAL INSPECTED

309823/0980

IV

Per
be Polymer Moletai
lar-
weight
χ 10 ~ ³ Concentration
tion Relationship
nis from
HVI
80/100 N -Behavior
nis from
HVI
, 100/250 Έ A. Hydrogenated poly
isoprene 41 U.N
possible B. Hydrogenated poly
isoprene 98 2.4 10/90 C. Hydrogenated poly
isoprene 125 2.1 25/75 D. Polystyrene-halo
Poly is embarrassed
isoprene 29-51 1.9 75/25 E. Polys "^ yrol-halo-
embarrassed poly
isoprene 32-54 1.7 - 75/25 I ¹ Polystyrene haLo-
embarrassed poly
isoprene 38-70 1.5 72/28 G Polystyrene halo-
embarrassed poly
isoprene -40-69 1.8 77/23 H Hydrogenated poly
styrene hydrogenated
Polyisoprene 21-107 2.7 ; 25/75 I.
J
K
L.
M. Hydrogenated poly
styrene hydrogenated
Polyisoprene 38-70
as before 40-69
Hydrogenated poly
styrene hydrogenated
Polyi soprene — hydrogenated
tes polystyrene 13-70-13
Ethylene / propylene
Random mixed poly
merisat
Polymethacrylate. {_ 3.1
3.2
2.8
1.5
.6.8 10/90
10/90
25/75
.35 / 65 70/30

309823/0980

From this comparison it can be seen that only the block copolymer with the structure of polystyrene is hydrogenated Polyisoprene is suitable. 'It knows' namely

1) even at relatively low concentrations corresponding effect on,

2) it does not require highly volatile (80 neutral) oils, and 3) lubricating oils can be used over a certain viscosity range (e.g. 3AE 10W / 30, 10W / 40 and 10W / 50) by changing the Polymer concentration can be produced from the same base oil.

Example 5 Effect of the partial hydrogenation of the aromatic block.

About the possibility of minor hydrogenation of the aromatic block to be tested, the following comparison is made: A polymer with the structure polystyrene (molecular weight 32 OOO) -hydrogenated polyisoprene (molecular weight 55,000) manufactured. The polystyrene block of two further polymer samples is partially up to 5 percent or up to 12 percent hydrogenated. The three polymers are made in a mixture of 75 percent HVI-100N, 25 percent HVI 250 N and 0.2 percent of the Pour point depressant used in Example 2 as Viscosity index improvers tested. It will be the get the following results:

309823/0980

Table V

Degree of saturation the aromatic double bonds,

Polymer concentration

viscosity

at
98.9 G

(SUS)

O O O 5 5 5

12 12 12

1> 5 74.4 166 2.0 105.5 172 2.5 163.8 177 1.5 71.9 152 2.0 99.2 153 2.5 142.7 158 1.5 62.6 145 2.0 72.3 127 2.5 89.5 121

Surprisingly, it can be seen from these values that even a slight hydrogenation of the aromatic double bonds uses the polymer as a viscosity index improver makes it less suitable · * ■ "

Example 6 Behavior of the finished SAE 1OW / 50 engine oil.

The following is an inventive approach for a SAE iOW / 5O lubricating oil shown:

30982 3/0980

Ingredient weight percent

HVI 100 neutral oil (Mid-Continent) 65.66

HVI 250 neutral oil "" 21.89

Polystyrene hydrogenated polyisoprene

(Molecular weight 29,000-51,000) 1.95

Zinc dialkyldithiophosphate 2.00

Polyisobutylene succinic acid imide

(0.34 ⁰ A total nitrogen content,
Basic nitrogen content: none) 7.00

Overbased Ca petroleum sulfonate

(1400 % excess basicity
as CaCO ₅ ) 1.00

Mixed polymer of 2-methyl-5-

vinyl pyridine (5 percent by weight),
Lauryl methacrylate (60 wt. $) And
Stearyl methacrylate (35 wt. ^)
(Molecular weight 810,000) 0.50

Dimethyl silicone 0.0010

This approach has the following typical characteristics

309823/0980

. "Tested oil

Viscosity "at 98.9 ° C, SUS 108.8

Viscosity at 37.8 ⁰ C, SUS 756.0

Viscosity at ⁰ C -17.8

(cold crankcase simulator), poise 21.2

Viscosity index 174

Pour point, ⁰ C -34.4

Flash point, ⁰ C 207.2

Sulphated ash, weight percent 0.89

Zinc, weight percent 0.18

Phosphorus, weight percent 0.15

Calcium, weight percent 0.17

The above approach was subjected to a series of test tests ^: mass ASTM-SE, which provide standard values for the requirements of the automotive industry (cf. ASTM Special technical publication No. 315-E, engine test tests of the addition to Technical Report J183 of the SAE- Handbooks, 1971) «

The most important results of the tests, all with the The above approach are summarized below: '·

3 09823/0980

Sequence III C

This is an oxidation thickening test for Simulation of the conditions in the engine of a motor vehicle pulling a trailer at 112.6 km / hour.

SE requirement tested oil

Average sludge (10 = clean)

Medium deposit on the piston skirt (10 = clean)

Medium deposit on the ring web (10 = clean)

Increase in viscosity at 37.8 G, ° ß> after 40 hours after 64 hours

Average wear of the cam disks and valve tappets, inch maximum value , inch 9.0 min.
9.5 min.

6.0

400 max.
Completely

0.0010
0.0020

9.8 9.8

8.3

18th

0.0006 0.0013

309823/0980

BAD ORlGiMAL

Sequence V C

It is a matter of checking the sludge and the deposits at low temperatures, which determines the effect of the oil build-up on the cleanliness of the engine.

Average sludge (10 = clean)

Medium deposits (10 = clean)

Medium deposit on the piston skirt (10 ~ clean)

Clogging of the oil strainer, fo

Clogging of the oil sealing ring, %

Plague eating the piston rings

SE requirement tested oil

8.5 min.

8.0 min.

8.2 min.

Max.

Max.

9.6

8.7

8.7

no plague eating no plague eating

L-38

This is a high temperature corrosion test of copper-lead plain bearings under operating conditions.

Weight loss of the plain bearing, mg after 40 hours

Max.

12.2

309823/0980

Sequence II B

This test is used to determine the anti-rust properties of the oil build-up carried out under dynamic operating conditions.

SB requirement tested oil

Medium rusting of the engine

(10 = clean) 8.9 min. 8.9

The summary of the behavior of the above approach and / The results of the engine test tests show that the SAE i0W / 50 approach due to the unique polystyrene-hydrogenated polyisoprene thickener enables the use of a base oil with low volatility and low oil consumption in operation leads. The low temperature properties are enhanced by the Vinylpyridine-methacrylate copolymer improves and the dithiophosphate has an anti-oxidation and anti-wear protection effect achieved. The addition of overbased calcium sulfonate and ashless dispersant (polybutylene succinic acid imide) results in less rust formation and greater engine cleanliness. The Gesarat approach points typically only 0.8 percent by weight sulfated ash.

As can be seen from the engine test results, the above approach provides excellent sludge, deposit and wear control, as demonstrated by the Sequence III C, V C and L-38 tests. The value of rust formation in the Sequence II B test shows that

309823/0980

BATH ORIGINAL

■ - '. 2258SS6

Sufficient rust protection even with heavy loads on the engine is guaranteed.

Except those obtained from laboratory engine test tests Results that ensure excellent operating behavior, the oil also meets the current requirements for shear stability, i.e. that it is after

a) 1 609 simulated kilometers in a Ford j5O2-CID shear stability test (17 hours, 96.5 km / hour), ~

b) 10 hours in the L-38 engine test within the SAE 10W / 50 viscosity range remains.

An additional advantage of the present invention lies in the facilitation of the hot start, which is made possible by the use of, for example, a 10W / 50 oil according to the invention. In motor vehicles, hot start problems occur fairly frequently, for example after a short stop at a gas station after a fast drive on a motorway. A comparison is made between the SAE 10W / 50-Ö1 of Example 6 and an SAE 10W / 30-Ö1 according to US Pat. No. 3,438,897. The tests are carried out in a 1972 Cheveile motor vehicle with a 307-CID V-8 engine and the speed of the crankshaft is determined as a puncture of the cooling temperature in the cooling jacket on the cylinder wall inventive SAE 1QY // 5O-oil can be started with a higher by at least 5.6 ⁰ C temperature than when using the Km / 30-ÖIS according to the aforementioned United States Patent.

309823 / 0980- ORIGINAL BATHROOM

Example?

To the usability of ^ block polymers with terminal Determine polystyrene blocks on a central hydrogenated rubber block in mixtures according to the invention, the tendency of such polymers to gel in lubricating oils is tested.

The above-described polymers of the structure polystyrene-hydrogenated Polybutadiene-polystyrene with the molecular weights of the blocks given below are in an HVI 100 Neutral lubricating oil dispersed at a concentration of 2 percent by weight and observed at room temperature.

sample Molecular weights of the
Blocks χ 10 ~ ⁵ Gelation at '
Room temperature » A. 3-53-4 no ; B. 5-25-5 no C. 10-50-10 gelled

The above results show that 3-block S-EP-S copolymers are suitable according to the invention as long as the additional polystyrene block has a sufficiently low molecular weight that gelation does not take place. However, if both polystyrene blocks are small enough not to allow gelation to take place, then they are outside the best possible range molecular weight range according to the invention, - ..j

309823/0980 ^, ".,

BATH ORIGINAL

and the polymer exhibits the unique properties of The above-described polymer of the structure polystyrene-hydrogenated polyisoprene does not.

Example 8

Rust protection properties of the following according to the invention

oil attachment:

Weight percent

100 HVI neutral oil '.65,24

250 HVI ». 21.75

Block copolymer 1.85

Zinc dialkyldxthiophosphate 1.5

Polyisobutylene succinic acid imide

of trimethylolaminomethane 7.00

Overbased Magnesium Sulphonates 2.16

Vinyl pyridine acrylate

Mixed polymer 0.50

Dimethyl silicone. 0.001

Total - sulfated ash. 1.0

The above SAE i0W / 50 approach is used in the test Sequence II B and gives a value for the rusting of the engine of 9.0. The above approach is essentially from the same ingredients as the batch from Example 6, but using different concentrations be and the calcium sulfonafce by magnesium sulfonate (800 percent overbased) are replaced.

BATH ORIGINAL 309823/0 98 0

34, O 29 O H, O

Example 9

Cleanliness of a diesel engine when using the following oil formulation according to the invention:

Weight percent

100 HVI neutral oil 250 HVI » 150 HVI Brightstοck

Polystyrene hydrogenated polyisoprene

Block copolymer 0.8

Tetraethylene pentamine derivative of

Polyisobutylene 6.0

Zinc diaryldithiophosphate 3.4

Overbased calcium salicylate 11.7, acrylate polymer 0.1

Iso-octylphenoxytetraethoxylethanol 1.0

liquid silicone +0.001 total - sulfated ash 1.8

The above SAE 20W / 4O approach is 240 hours according to the Caterpillar 1-G test trial tested. Excellent results with a very low carbon deposit in the upper piston groove (2 percent) and a very low deposit coating, will get. The behavior is practically that of an SAE 30 oil with the same additives, but without the block copolymer, identical. A comparable oil containing a polymethacrylate polymer leads to poorer values regarding the cleanliness of the engine with a carbon deposit in the upper piston groove of 25 percent.

309823/098 0 ^BAD ORiQtNAL

Claims (15)

Claims: 1 »Lubricating oil mixture, consisting of a) a mineral lubricating oil with a viscosity index of at least 85, ■. b) a small amount of a pour point depressant, and c) 0.1 to 10 percent by weight of a block copolymer consisting of 1) a single polymer block unit A with a Average molecular weight from about 10,000 to about . 55,000, at least 75 percent of which condensed, Alkenyl arene units, the aromatic un- ■ saturated bonds to a maximum of 5 percent by hydrle, tion are saturated, and '; 2) a single polymer.! Sat block unit B with a j . Average molecular weight of about 20,000 to about \ 100,000, which consists of a polyisoprene block whose: olefinic double bonds have been saturated by hydrogenation to at least 95 percent, the block units A and B in a weight ratio of 0.45: 1 to 0 ,8th ; 1 are present, and where optionally further polymer block units C contained in the copolymer together have an average molecular weight of not more than 7,500 and are composed of alkenyl arene polymer block units. ' 309823/0980 BAD original Polymer block units made from conjugated dienes and ybder from mixed polymer block units from alkenylarenes and conjugated dienes, their degree of hydrogenation is limited according to the limit values applicable to block units A and B » 2. Mixture according to claim 1, characterized in that it contains a block copolymer with the structure A-B. 3. Mixture according to claim 1 or 2, characterized in that that it is a block copolymer with practically homopolymers Contains block units A and B. 4. Mixture according to claim 1 to 3, characterized in that that it contains a block copolymer with an aromatic block unit A. 5. Mixture according to claim 1 to 4 »characterized in that that it contains a block copolymer with a block unit B which is at least 99 percent saturated. 6. Mixture according to claim 1 to 5 »characterized in that that it is a block copolymer with a block unit A . contains in which the alkenyl arenas are styrene units. 7 Mixture according to Claim 1 to 6, characterized in that . that it contains a block copolymer with a block unit B of which at least 80 percent has a 1,4-structure. BATH ORIGINAL 309823/0 980 8. Mixture according to claim. 1 to 7, characterized in that that it is a block copolymer with a block unit A and an average molecular weight of 25,000 to 50 and a block unit B having an average molecular weight of 35,000 to 80,000. 9 · Mixture according to claim 1 to 8, characterized in that the block copolymer contains the block units A and B in a weight ratio of 0.5: 1 to 0.7 J 1 contains. 10. Mixture according to claim 1 to 9, characterized in that it is a pour point depressant in one concentration contains from 0.1 to 2.5 percent by weight. · 11. Mixture according to claim 1 to 10, characterized in that it is a (copolymer an acrylic acid ester and / or a nitrogen-containing acrylic acid ester. 12. Mixture according to claim 1 to 11, characterized in that it is a copolymer of vinyl pyridine or a vinyl pyrrolidone and C _{8 -Z 0} alkyl (meth) acrylates or a copolymer of as pour point lowering agent ^{Contains C} 8 ^ rv-alkyl-CmetlO-acrylates. 13 »Mixture according to claim 1 to 12, characterized in that it has a viscosity of less than 24 poise ^{at -17.8 0} G and of over 85 SUS ^{at 98.9 0 C '.} ""'"" BAD ORIO ^- (MAL 309 823/0980 14. Mixture according to claim 1 to 13, characterized in that that it contains a base oil with a viscosity index of at least 90. That it contains 15. The mixture of claim 1 to 14, characterized in essentially consisting of fractions having a viscosity of at least 95 SUS at 37.8 ⁰ C base oil. BATH ORIGINAL 309823/0930