DE2810248A1 - OIL SOLUBLE PRODUCT AND ITS USES - Google Patents

Description

L 747 C (J / MK / or) _{March 9, 1g78}

K 4245 GEW

SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ B.V. The Hague, Netherlands

"Oil-soluble product and its use"

claimed priority:

Mar. 11, 1977 - V.St.A. - No. 776 797 and 776 573

The newer engines place increased demands on the lubricants to be used. So far, various additives have been used added to lubricating oils to improve properties such as viscosity index and dispersibility. Considerable cost savings are achieved by using a single additive, but using several the properties of the lubricant are improved. When trying to improve more than one property of the lubricant, however, care must be taken that other properties are not impaired. Thus, according to US Pat. No. 3,687,905 and 3,864,268 copolymers of ethylene and propylene first oxi-

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dated and then degraded with an amine before the reaction. However, this process creates spots for the oxidati ven degradation introduced,

Significantly, there are known methods of manufacture of dispersants does not always affect the manufacture

of dispersants with viscosity index improving self-usable.
shafts / Thus, according to US Pat. No. 3,172,892, a polymer with a relatively low molecular weight (about 50 carbon atoms) is reacted with maleic anhydride and an ethylene amine to form a dispersant. The mechanism of the reaction relies on the presence of a single double bond at the end of the olefin polymer. If the polymer has only 50 carbon atoms, this single terminal double bond means that there are enough places responsible for good dispersibility. However, if the polymer has more than 500 carbon atoms, as is necessary for an additive with viscosity index-improving properties, the single terminal double bond is not sufficient and difficult modification processes have to be used in order to achieve a corresponding dispersibility.

In addition, it is important that the polymer used as a dispersant and viscosity index improver has a sufficient large number of suitable sites for dispersing Has an effect. Therefore, additives such as those described in US Pat. No. 3,454,607, which are made from monocarbon

/ Connections
acid-forming / have not been produced

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always suitable.

The object of the invention was therefore to provide an ashless, oil-soluble To provide additives for lubricating oils that are not oxidatively degraded prior to modification, of which Manufacturing process does not depend on the presence of double bonds in the polymer chain and has good dispersibility and has a good viscosity-improving effect.

The invention thus provides an oil-soluble product which is characterized in that it is produced by reacting

a) an amorphous copolymer of essentially ethylene and

(Number average) propylene with an average molecular weight M / of about

with ⁿ

70,000 to about 300,000 / a 0 ( , ß-unsaturated dicarboxylic acid, its anhydride or ester and

b) Reacting the resulting product with an Amiη

1 to 18 carbon atoms and 1 to 8 nitrogen atoms and / or an alkane polyol with at least 2 hydroxyl groups has been received.

The reaction takes place both in stage a) and in stage b / preferably at about 150 to about 250 ° C., in step a) for about 1 to about 24 hours.

The ethylene-propylene copolymer can also be used with chlorine and the (X, ß-unsaturated dicarboxylic acid component before the Reacting with the amine or the polyol. · This

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Chlorination is radical and does not depend on the presence of double bonds in the polymer backbone. The chlorination can be carried out before or at the same time as the addition of the Dicarboxylic acid component in the presence of radical initiators, such as azo-bis-isobutyronitrile, tert-buty! Hydroperoxide or dibenzoyl peroxide, or by UV irradiation. These initiators are not absolutely necessary; the radical one Chlorination can be carried out at temperatures above 30 ° C. in the presence of a solvent.

The amount of chlorine used is expediently about 1 to about 20 percent by weight, preferably about 5 to about Percentage by weight, based on the ethylene-propylene copolymer. The chlorination takes place at a temperature from about 0 to about 100 ° C., preferably about 25 to about 60 ° C. for about 10 minutes to about 2 hours.

The amorphous copolymers used as the starting material exist consisting essentially of ethylene and propylene, but they can contain small amounts of those derived from other olefin monomers polymerized units, e.g. up to 10% based on the molar amounts of monomers. Ethylene and propylene units in the copolymer. Examples of such other olefin monomers are olefins of general Formula RCH = CH-, in which R is an aliphatic or cycloaliphatic

is a table radical with 2 to 20 carbon atoms /, e.g. butene-1,

Hexene-1, 4-methyl-1-pentene and decene-1.

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Ethylene-propylene copolymers suitable as starting material contain about 30 to about 65, preferably about 35 to about 45 mol percent propylene and have an average molecular weight M of about 70,000 to about 300,000, preferably about 80,000 to about 200,000. The copolymer preferably contains at least 150 methyl groups per 1000 carbon atoms in the chain. Production processes for these copolymers are known per se (cf. US Pat. No. 3,864,268).

The ethylene-propylene copolymer comes first with the dicarboxylic acid component at a temperature of about 150 to about 250 ° C, preferably about 180 to 230 ° C, for about 1 to 24 hours, preferably about 8 to 16 hours, reacted.

Suitable dicarboxylic acid components are maleic acid, Maleic anhydride, maleic acid dimethyl ester and diethyl ester, itaconic acid, itaconic acid dimethyl ester, methyl maleic anhydride and citraconic anhydride. Maleic anhydride is preferred.

It is important for the oil-soluble product according to the invention, that the carboxyl groups along the main chain of the ethylene-propylene copolymers are bound and not only to the terminal double bond, as in known products of the Case is. In known processes, not enough carboxyl groups are bound to the polymer chain, so that the Product does not have sufficient dispersibility.

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In the production of the oil-soluble product according to the invention can be olefin-free as solvent in preparation stage a) - Petroleum hydrocarbons, aromatic and halogenated hydrocarbons be used. Preferred solvents are a lubricating oil base oil or trichlorobenzene. A concentration of approximately 1 to 10 percent by weight is required for production stage a) of the copolymer in the solvent is suitable.

In preparation stage a) the amount of dicarboxylic acid component is about 5 to about 25 percent by weight, preferably about 8 to * 15 percent by weight, based on the ethylene-propylene copolymer.

The polymer modified in this way is then used in step b) of the production process with a saturated straight-chain or branched amine having 1 to 18 carbon atoms or one

e.g.
Alkane polyol implemented. The succinic acid imide or ester groups formed are responsible for the dispersing function of the additive.

Aliphatic primary or secondary amines with 1 up to 8 nitrogen atoms, preferably mono- or diamines, such as ethylamine, butylamine, sec-butylamine or diethylamine, and higher polyamines, e.g. alkylene polyamines, each containing 2 nitrogen atoms are linked by alkylene groups of 2 to 4 carbon atoms. Polyamines of the formula

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in which η is 2 to 4 and m is 0 to 6 are particularly suitable. Specific examples of such polyamines are tetraethylene pentamine, Tripropylenetetramine, N-aminoalkylpiperazines, such as N- (2-aminoethy1) piperazine or N, N'-di- (2-aminoethyl-piperazine. Tetraethylene pentamine and commercially available polyamine mixtures are preferred.

Are suitable as alkane polyols for the preparation stage b) Alkane polyols with at least 2, preferably at least 4 hydroxyl groups, such as trihydroxyalkanes, e.g. ethylene glycol, propylene glycol, Polymethylene glycol, trihydroxybutanes, -pentanes, -hexanes, -heptanes, -octanes, -nonanes and -dodecanes, as well as tetrahydroxyalkanes, pentahydroxyalkanes and hexahydroxyalkanes, also sugar alcohols, such as erythritol, pentaerythritol, tetrite, pentite, Hexites, mannitol, sorbitol and glucose. Pentaerythritol and mannitol, in particular pentaerythritol, are preferred.

The molar ratio of amine or polyol to dicarboxylic acid component is expediently about 0.1: 1 to about 2: 1, preferably about 0.5: 1 to about 2: 1, in particular about 1: 1. This reaction is conveniently carried out at a temperature of 150 to 250 ° C. and for a period of about 1 to 20 hours.

In the manufacturing process, all stages are preferably absent carried out by oxygen, since the end product can be much more unstable to oxidation if it is in Presence of oxygen has been established. Nitrogen is very suitable as a protective gas.

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If there is an excess of amine or polyol in the production process it is sometimes desirable to remove it. This can be achieved by first adding a volume of heptane corresponding to the volume of the dissolved end product, then a corresponding volume of methanol is added. It is formed two separate phases, the lower one mainly contains methanol and the unreacted polyamine or polyol, the upper one the Heptane, the solvent and the end product. After the lower phase has been separated off, the upper phase becomes the volatile Components distilled off. The excess polyol can also be distilled off under reduced pressure or with a Strip off gas.

Does the copolymer used as the starting material have a sufficient low molecular weight, e.g., about 70,000 to about 300,000, the final product has sufficiently good viscosity index improvers Properties. However, one can also start from a copolymer which has a higher molecular weight, e.g. about 300,000 to about 1,000,000. However, the product produced must then be subjected to a shear action in order to reduce the molecular weight to reduce to the desired value. This can be achieved by adding a solvent to the product adds, e.g. heptane, to reduce viscosity, and then the solution through a diesel injector at high pressures

• over ₂
pumps, e.g. at / about 70 kg / cm. But you can also use shear mixers and pumps, for example a gear pump. The molecular weight of the resulting polymer can thus be controlled

lieren that you pass the solution different times through the nozzle or

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the shear device pumps. When shearing, not only the molecular weight of the manufactured product is reduced to the desired one Decreased value, but also the molecular weight vertexlung is within narrower limits, as larger molecules are more easily sheared than small ones. This narrow molecular weight distribution is favorable for the stability in the engine. Preferably the ratio of M / M is from about 1 to about 4, where M

Vr Ii W

is the weight average and M is the number average.

The oil-soluble product according to the invention can be lubricating oil mixtures, e.g. oils for motor vehicle crankcases, in concentrations of about 0.1 to 15 percent by weight, preferably about 0.1 to 3 percent by weight, based on the total mixture. The product according to the invention can not only

. Mineral lubricating oils are added rather

also synthetic oils. Not only hydrocarbons but also other oils, such as dibasic ones, are suitable as synthetic lubricating oils Acid esters, e.g. di-2-ethylhexyl sebacate, carbonic acid ester, Phosphate esters, halogenated hydrocarbons, polysilicones, polyglycols, glycol esters, e.g. C ^ oxo acid diesters of Tetraethylene glycol. Gasoline or a fuel, e.g. diesel oil , or No. 2 fuel oil, are generally about 0.001 to 0.5 percent by weight, based on the total mixture, the inventive Oil-soluble product added. For easier handling you can also produce concentrates that have a lower Amount, e.g. 5 to 45 percent by weight, of the oil-soluble product in a larger amount of hydrocarbon as a diluent, e.g. 95 to 55 percent by weight mineral lubricating oil, given

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if included with other additives.

These lubricant mixtures or concentrates can also contain other conventional additives, such as colorants, Pour point lowering, wear-preventing agents, e.g. Trlcresylphosphat, ZinkdialkyIdithiophosphate with 3 to 8 carbon atoms, antioxidants such as phenyl-of-naphthylamine or tert-octylphenol sulfide, bisphenols such as 4,4'-methylenebis (3,6-di-tert-butylphenol), viscosity index improvers, such as a copolymer of ethylene and a higher Olefin, polymethyl acrylate, polyisobutylene or alkyl fumarate-vinyl acetate copolymers, as well as other ashless dispersants or detergents such as overbased sulfonates.

The examples illustrate the invention.

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example 1

A practically saturated (0.04 raVal • Unsaturated bonds per gram of polymer, determined by ozone titration) Ethylene-propylene copolymer with an average Molecular weight M of about 121,000 and M of about 202,000 containing about 62 mole percent ethylene was used.

415 g of this polymer are ground into crumbs and dissolved in 7.4 liters of lubricating base oil. This solution is 33.2 g Maleic anhydride was added and the mixture was heated to 225 ° C. for 8 hours. Unreacted maleic anhydride is then reduced under reduced Distilled pressure.

After cooling to 140 ⁰ C, the mixture with 52 g of tetraethylenepentamine is added, heated for 1 hour at 160 C, then for 2 hours at 180 to 190 ° C. After cooling, the mixture is diluted with an appropriate volume of heptane and pumped through a homogenizer until the viscosity of the heptane-free solution has decreased by about 30%.

The sheared solution is then filtered and washed with methanol, the volatile components are stripped off. The end product consists of 6200 g of an oil solution that is 6.7 percent by weight contains active material.

The dispersibility of the product is assessed with the stain dispersion test certainly. 1 part of a 2 percent by weight polymer solution in 100 parts of neutral oil is mixed with 2 parts

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used oil containing sludge and mixed overnight heated to 150 ° C. Stains are made on filter paper, "the ratio of the diameters of Schlairan stain to oil stain becomes measured after 24 hours. Less than about 50% is a bad value; a good value is 60% or more. The inventive oil soluble product has a value of 64%. Unmodified starting material gives a value of about 30%.

A fully alloyed oil containing 2% of the oil-soluble product of the present invention and a commercially available one Contains a combination of detergent and inhibitor, has the required viscosity of a 10 W / 50 standard oil.

Example 2

The ethylene-propylene copolymer is first reacted with chlorine, then with maleic anhydride and tetraethylene pentamine.

About 20 g of the copolymer are dissolved in 380 g of carbon tetrachloride dissolved and with a solution of 1 g of chlorine in .13 ml of carbon tetrachloride added at room temperature. The mixture is heated to 50 ° C for 1 hour, then the unreacted chlorine becomes and the hydrogen chloride formed is stripped with a stream of nitrogen.

After stripping, the mixture is mixed with 350 g of a standard lubricating base oil added, the carbon tetrachloride is distilled off. 2 g of recrystallized maleic anhydride

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add, the mixture is heated to 180 to 200 ° C. for 2 hours. Excess maleic anhydride is released under reduced pressure removed.

After cooling to 120 ° C., the mixture is mixed with 2.5 g of tetraethylene pentamine added, 1 hour to 160 ° C, then 2 hours 190 C heated. The solution is cooled and diluted with an appropriate volume of heptane. A nitrogen atmosphere is maintained during all manufacturing stages at high temperature.

After diluting with heptane, the solution is pumped through a homogenizer three times to reduce the molecular weight and narrow the molecular weight distribution. The solution is then filtered and washed with methanol. The volatile components are stripped.

The end product has good dispersibility in the stain dispersion test a value of 67% is obtained.

A 2 percent by weight solution of the oil-soluble according to the invention Product increases the kinematic viscosity at 99 ° C of a lubricating base oil from 4 cSt to 16 cSt.

Example 3

The procedure of Example 2 is repeated, with the difference that that an ethylene-propylene copolymer with a mean

Molecular weight M of about 96,000 and M of about 72,000 and

η w _Λ

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and an ethylene content of about 65 mole percent is used. A value of about 61% is obtained in the stain dispersion test.

Example 4

TO g of the ethylene-propylene copolymer from Example 1 are dissolved in 190 g of trichlorobenzene and at room temperature with a Solution of 270 mg of chlorine in 4 ml of carbon tetrachloride was added. The mixture is heated to 50 ° C. for 1 hour. Not implemented Chlorine and the hydrogen chloride formed are stripped off with nitrogen.

After stripping, the mixture is mixed with 800 mg of maleic anhydride added and heated to 180 ° C. for 2 hours under nitrogen protection. Unreacted maleic anhydride is reduced Distilled pressure. After the addition of 900 mg of pentaerythritol, the temperature is increased to 2OO to 20S ° C. for 4 hours. Towards the end of this time, the water formed in the reaction is removed under reduced pressure. Till this point in time the reaction under nitrogen protection.

The trichlorobenzene is distilled off under reduced pressure and replaced by a lubricating base oil. Unreacted pentaerythritol is removed this way. The oil solution is diluted with an appropriate volume of heptane, filtered and washed with methanol. The volatile components are stripped off. The product has a value in the stain dispersion test of 61%.

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2 percent by weight of this product according to the invention in one conventional mineral lubricating base oils increase the kinematic viscosity at 99 ° C from 4 cSt for the base oil alone to 17 cSt for the lubricating oil provided with the additive. This increase in viscosity shows that the product according to the invention as viscosity index improver is suitable.

.S

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Claims (13)

Claims 1. · Oil-soluble product, characterized in that it is characterized by Implementation of a) an amorphous copolymer of essentially ethylene and (Number average) propylene with an average molecular weight M / of about 70,000 to about 3OO,000 with a ° (, ß-unsaturated dicarboxylic acid, their anhydride or ester and b) Reacting the resulting product with an amine with 1 to 18 carbon atoms and 1 to 8 nitrogen atoms and / or an alkane polyol having at least 2 hydroxyl groups. 2. Oil-soluble product according to claim 1, characterized in that that it is made by reacting an ethylene-propylene copolymer that in stage a) before or simultaneously with the C <, ß-unsaturated dicarboxylic acid component reacted with chlorine has been obtained. 3. Oil-soluble product according to claim 1 and 2, characterized in that that it is obtained by reacting at a temperature of about 150 to 25O ° C both in stage a) and in stage b) has been. 4. Oil-soluble product according to claim 1 to 3, characterized in that that it is obtained by reacting about 5 to 25 percent by weight of the dicarboxylic acid component, based on the ethylene-propylene copolymer has been. ' '809837/0918 originally inspected a, 5. Oil-soluble product according to claim 1 to 4, characterized in that it has been obtained by reacting a copolymer, the ethylene, about 30 to 65 mol percent propylene and up to 10 mol percent of a 0 <-olefin of the formula RCH = CH ₂ , in the R is an aliphatic or cycloaliphatic radical with up to 20 carbon atoms. 6. Oil-soluble product according to claim 1 to 5, characterized in that that there is maleic anhydride as the dicarboxylic acid component contains. 7. Oil-soluble product according to claim 1 to 6, characterized in that that it is made by reacting it with an amine of the formula in which η is 2 to 4 and m is 0 to 6, has been obtained. 8. Oil-soluble product according to claim 1 to 7, characterized in that that it contains tetraethylene pentamine as an amine component. 9. Oil-soluble product according to claim 1 to 6, characterized in that that it contains pentaerythritol as the alkane polyol component. 10. Oil-soluble product according to claim 1 to 9, characterized in that with
draws that it is by reacting / an amine or polyol 809837/0918 in a relative amount to the dicarboxylic acid component corresponding to a molar ratio of about 0.5: 1 to about 2; 1 has been obtained. 11. Oil-soluble product according to claim 1, characterized in that that it consists of a copolymer with an average molecular weight M_ of about 300,000 to about 1,000,000 as the starting material and treating the reaction product from step b) by repeated. Shear to reduce molecular weight to about 70,000 to about 300,000 and the ratio from M / M to 1 to 4 has been obtained. w η 12. Use of the oil-soluble product according to claim 1 to in lubricant mixtures. 13. Embodiment according to claim 12, characterized in that the lubricant mixture contains a lubricating oil and a small amount of the oil-soluble product as the main amount. 8 0 9 8 3 7/0918