SK281687B6 - An additive and the process of its production - Google Patents

Abstract

An additive for lubricating oils of internal combustion engines containing the imide- and/or ester and/or ester-amide, derivatives of the reaction product of an unsaturated polyisobutylene and some unsaturated reactive dicarboxylic acids and/or their anhydride comprising the reaction product of a polyisobutylene of a number average molecular weight 800 - 30 000 and an unsaturated reactive dicarboxylic acid and/or its anhydride, preferably maleic anhydride containing 1.6 - 6.0 SA - derivative per polyisobutylene chain on the average having a concentration of molecules containing more than one SA - derivative more than 25 weight percent and the polyisobutylene is grafted or reacted with an SA containing copolymer formed from a more reactive, low molecular weight comonomer of a molecular weight less than 500, containing olefinic double bond or from a mixture of such comonomers and from unsaturated reactive dicarboxylic acid and/or their anhydride, preferably maleic anhydride using the molar ratio 1.2 - 5.5 : 0.1 - 3.5 : 1 = MAH : comonomer : polyisobutylene, and in which the widening of the molecular weight distribution is less than 70 percent, referred to the starting polyisobutylene, while the SA groups of the copolymer linked to the polyisobutylene are reacted, in a 0.7 - 5.5 ratio, with compound containing at least bifunctional amine and/or hydroxyl groups. The invention disclosed the process of preparation of the additive.

Description

The invention relates to a ashless detergent and dispersant (DD) additive based on graft polyolefin and polysuccinic anhydride, which increases both viscosity and viscosity index, and which can advantageously be used to improve the properties of lubricating oils and their manufacturing process.

BACKGROUND OF THE INVENTION

Ashless imide and ester type additives synthesized from alkenyl succinic acid derivatives have been used for over thirty years to improve the detergent and dispersant properties of motor oils. Due to their polar and often basic character, these additives limit the formation and surface deposition of insoluble acidic impurities formed during engine operation. This significantly increases engine life and oil life.

Various so-called modified derivatives containing sulfur, boron, halogen, molybdenum, copper and the like. have good anticorrosion and wear resistance in addition to their DD effect, while derivatives containing high molecular weight (Mn> 2000) polymer side chains contribute to improving the viscosity and viscosity index.

These alkenyl succinic acid derivatives are usually admixed in lubricating oils together with other metal-containing DD additives, VI additives, antioxidants, anti-corrosion and anti-wear components, friction modifiers and foaming inhibitors using advantageous interactions.

Over the past decade, oil additive manufacturers have focused their research on improving DD efficacy and beneficial side effects. According to engine test results, this can be achieved either by increasing the molecular weight of the intermediates and the end product, or by forming polysuccinimides, polyesters, polyester amides bonded through their polar groups (e.g., U.S. Patent No. 4,234,435).

The synthesis of these additives is based on the finding that in the first stage of the synthesis of succinimides, when polyolefins and maleic anhydride (MAH) react under specific conditions, more than one MAH is bound to the polyolefin molecule or alternatively so-called olefin-MAH copolymers are formed. If the thus formed intermediates with more than two carboxyl groups are reacted with amines, polyamines, alcohols, polyalcohols, alkanolamines or mixtures thereof of different compositions, then higher molecular weight end products of the type of polyimides, polyamides, polyesters, polyesteramides and the like are obtained. (U.S. Patent 4,234,45).

Despite the high DD effect, these ashless additives have only a low base number due to the blocking of their basic amino and imino groups and cause less damage to the fluorine-containing elastomer engine seals compared to traditional succinicides.

Due to their higher DD effect and significant increase in viscosity and viscosity index (VI), these ashless additives increase the performance of engine oils and have also proven useful in replacing a portion of traditional additives used to improve flow properties to reduce engine oil cost. Various methods of synthesizing alkenyl succinic anhydride-type intermediates are recommended in published procedures.

According to U.S. Pat. Nos. 4,234,435 and EP 0 208 560, the molar ratio of succinic anhydride (SA): polyisobutylene (PIB, Mn = 1300-5000) can be increased above 1.05 by one or more stages of chlorine catalyst addition and by raising the temperature up to 160-220 ° C. . A significant disadvantage of this process is that hazardous chlorine is formed in the polyolefin molecule during the addition reaction, which remains in the final product in an amount of 0.001 to 0.5% by weight, based on the additive.

Processes in which the addition of polyisobutylene-MAH is carried out at high temperature (over 190 ° C) without the use of a catalyst have also been described. SA / PIB molar condensation ratios greater than 1 were achieved using a highly reactive (α-olefin content of more than 70%) polyisobutylene feedstock and a large excess of MAH. The disadvantages of this method are the need for more expensive feedstock, higher reaction temperature and long reaction times (e.g., European Patent No. 0 271 937).

The low temperature procedure was described in PCT no. WO 90/03359, wherein the polyisobutylene maleate anhydride copolymer was prepared using a free radical initiator and an aromatic or chlorinated hydrocarbon solvent. In a PIB-MAH copolymer with an alternating structure, the average number of PIB-MAH units ranges from 1.1 to 20. If this type of intermediates is used for the acylation reaction, the end products may have a broad molecular weight range (Mn = 10,000 to 150,000).

EP 0 400 866 includes an oil-soluble composition which is used as a multi-effect viscosity enhancing additive to an oily composition comprising adduct A) a high molecular weight ethylene copolymer substituted with a carboxylic acid comprising the reaction product (i) of an ethylene copolymer having an average molecular weight of at least 15,000; (ii) a mono unsaturated carboxylic acid; and B) at least one polyamine comprising one primary amino group and at least one secondary amino group.

Further, EP 0 400 866 includes an embodiment of said composition comprising reaction product A), B) and C ₅₀ to C ₄₀ O hydrocarbyl substituted with carboxylic acid containing 1 to 2 carboxylic acid groups or anhydride group.

EP 0 002 286 generally describes an oil-soluble graft copolymer suitable for use as an additive to lubricating oils and liquid hydrocarbon fuels. The copolymer comprises a substantially linear saturated, elastic, olefinic and graft polymerized polymer. The copolymerized units of the monomer system comprise maleic acid and / or maleic anhydride and one or more other monomers copolymerizable with maleic acid or maleic anhydride. Said copolymerized units are reacted with a polyamino compound containing one primary or secondary amino group or one primary amido group.

According to EP 0 002 286 a suitable polymer backbone includes ethylene / propylene copolymers, ethylene / propylene / diene modified terpolymers, hydrogenated styrene / butadiene copolymers, styrene / isoprene copolymers and atactic polypropylene.

This document deals with the molecular weight selection of the polymer backbone. Manipulating low molecular weight starting polymeric materials is problematic because these materials are semi-liquid or have a cold flow at ambient temperature (about 20 ° C) and are therefore often complicated and uneconomical.

It is necessary to control the molecular weight during copolymerization. Although the use of a low molecular weight starter polymer could avoid the need for subsequent degradation of the copolymer product, the difficulties in handling and manufacturing such starter polymers also undermine this advantage.

According to European patents EP 0 400 866 and EP 0 002 286, maleic anhydride and other unsaturated comonomer or comonomers are grafted to traditional viscosity index improving ethylene propylene copolymers, with a number average molecular weight higher than 10000, preferably 100000 to 200000 based on the viscosity average molecular weight using hydrocarbons or other solvents in the presence of a free radical initiator. The copolymer thus prepared was then reacted with amines, polyamines, etc. to obtain a viscosity index improving additive with a dispersing effect. The use of polymers with an average molecular weight below 30000 and a viscosity average molecular weight below 100000 is considered disadvantageous for this purpose. According to the arguments presented in these patents, hydrocarbon polymers with a number average molecular weight below 30000 have been difficult to process due to their unfavorable flow properties. at low temperatures.

The previously published methods for the advantageous synthesis of high molecular weight polyfunctional succinimides have both technological and structural limitations. According to the preferred examples, patented for the synthesis of polyisobutylene-based succinimides, the use of polyisobutylenes with an average molecular weight Mn = 1300 to 2500 can be considered typical and beneficial. As is known, increasing the average molecular weight of the polyisobutylene feedstock above the Mn = 2500 limit considerable problems due to the high viscosity of the raw material. In addition, experience has shown that as a result of the use of these raw materials, a significant disadvantageous increase in cold viscosity and a decrease in the number of polar nitrogen-containing groups per unit mass of the additive can be expected and the effect of DD associated therewith.

Succinimide derivatives obtained by seeding with ethylene-propylene copolymers have been produced and used to obtain a further effect of DD in addition to their main function of increasing viscosity and viscosity index (EP 400866, EP 002286). With this type of additive, the optimum viscosity and viscosity index enhancement effect is in the range of molecular weights Mn = 15000 to 200000. Successful use of olefin copolymers with a number average molecular weight of less than 15000 has not been reported so far, apparently due to the loss of flow enhancing effect.

SUMMARY OF THE INVENTION

Surprisingly, however, it has been found that, using our invention, it is possible to synthesize polyisobutylene-based succinimide additives with significant properties increasing DD, viscosity and viscosity index even in the molecular weight range deemed unfavorable to both polyisobutylene and ethylene-propylene copolymers.

Our invention is based on the finding that the above-mentioned synthesis disadvantages based on grafting hydrocarbon polymers, limiting the average molecular weight of the feedstock, can be overcome by appropriate control of the grafting reaction. The recommended procedure is a convenient synthesis of these intermediates from lower average molecular weight polyolefins and, moreover, intermediates obtained from polyisobutylenes or, in particular, from their so-called highly reactive homologues containing higher olefins, are suitable for preparing additives with a new molecular structure having viscosity enhancing effects. and a viscosity index, a more advantageous anti-friction effect, and at the same time having better compatibility with sealing materials compared to other known ashless dispersants with a molecular weight of less than 15,000.

The invention relates to an additive in solution in an oil and its preparation for use in lubricating oils of internal combustion engines comprising an imide and / or ester and / or esteramide derivative of a reaction product of a polyolefin, preferably polyisobutylene, and some unsaturated reactive dicarboxylic acid and / or an anhydride thereof comprising a reaction product of a polyolefin having a number average molecular weight of 800 to 15,000, and an unsaturated reactive dicarboxylic acid and / or an anhydride thereof, preferably maleic anhydride, containing an average of 1.6 to 6.0 SA derivatives per polyolefin chain, the concentration of molecules containing more than one SA-derivative is more than 25% by weight of the additive and the polyolefin is grafted or reacted with a more reactive low molecular weight copolymer containing a low degree of polymerization, formed from a comonomer suitable for copolymerization containing an olefinic double bond zbu, or a mixture thereof, and from an unsaturated reactive dicarboxylic acid and / or anhydride thereof, preferably maleic anhydride, using a molar ratio of MAH: comonomer: polyolefin of 1.2 to 5.5: 0.1 to 3.5: 1, wherein the distribution distribution the molecular weight is less than 70 relative to the starting polyolefin, while the SA groups of the grafted copolymer are reacted in a molar ratio of 0.7 to 5.5 with compounds containing at least bifunctional amine and / or hydroxyl groups.

Further, the invention relates to the preparation of an additive for use in said lubricating oil, wherein the polyolefin, preferably polyisobutylene having an average molecular weight greater than 800, reacts with an unsaturated dicarboxylic acid and / or its anhydride, preferably maleic anhydride, and a more reactive comonomer with a lower molecular weight. a copolymerizable linkage or comonomer mixtures and / or a pre-prepared low polymerization copolymer of an unsaturated dicarboxylic acid and / or its anhydride and comonomer and / or comonomers, using a maleic anhydride: comonomer: polyolefin molar ratio of 1.2 to 5, 5: 0.1 to 3.5: 1 in a solvent or without a solvent, preferably at a solvent concentration of 15 to 75% by weight, based on the reaction mixture ensuring a homogeneous phase, in the presence of a radical initiator in an amount of 5 to 25% by weight (b) to an unsaturated dicarboxylic acid or its anhydride, at a pressure of 1 to 15.102 kPa and in an inert and / or hydrocarbon atmosphere at 80 to 180 ° C for 1 to 16 hours, the concentration of unreacted dicarboxylic acid and / or anhydride and comonomer and / or comonomers maintained below 5% by weight; the intermediate obtained in which the increase in the number average molecular weight of the components, measured by GPC, is less than 2.5 times the molecular weight of the starting polyolefin, the molecular weight distribution extension is less than 70%, based on the starting polyolefin, diluted with base oil as necessary and in the presence of a filter aid, it is worked up, filtered and reacted with compounds containing one or more at least bifunctional amine and / or hydroxyl groups, while the molar ratio of the compounds carrying succinic anhydride groups and the amine and / or hydroxyl groups is 0.7 to 5, 5 and the acylation is carried out in the presence or absence of a catalyst in an amount of 0.01 to 2% by weight at a pressure of 0.05 to 600 kPa at a temperature of 120 to 235 ° C for 2 to 15 h and optionally modified, diluted and filtered.

Furthermore, the scope of the invention also covers the intermediate used for the production of the additive and its preparation. As polyolefins, homo- and / or copolymers of α-olefins, such as ethylene, propylene, 1-butene, isobutylene or other olefins and diolefins, such as 1,3-butadiene, with a number average molecular weight of between 800 and 15000 are generally used. Polyisobutylenes with a number average molecular weight of between 1300 and 8000 have proved to be the most preferred.

Today, this type of polyisobutylenes, especially with an average molecular weight above 5000, has some limited applications such as viscosity-improving additives and viscosity index. Despite their good thermal oxidation properties and shear stability, their wide application is limited as they increase the low temperature viscosity of oils more than any other type of viscosity index improving polymers. For this reason they cannot be used alone in the production of modern universal motor oils. The process of the invention dramatically reduces and, in preferred cases, removes these disadvantages of PIB-based viscosity index improving additives. Inoculation of the polar side chain to the PIB backbone produces a combined polymer structure with good thermal and chemical stability as well as the viscosity-enhancing effect characteristic of polyisobutylenes, and at the same time the cold viscosity-increasing effect is significantly reduced due to the decrease in polymer solubility.

Low molecular weight reactive, polar and apolar monomers such as ethylene, propylene, 1-butene, 1,3-butadiene, isobutylene, C5.20 α-olefins, styrene, acrylic acid, methacrylic acid, acrylates and comonomers are used as comonomers. methacrylates prepared from alcohols C1-20 acrylonitrile or mixtures thereof.

The polyolefin-polysuccinic acid derivatives prepared from a polyolefin, preferably polyisobutylene, an unsaturated dicarboxylic acid and / or an anhydride thereof, and from a comonomer or a comonomer mixture, have the general formula (1)

-r-CH-C8 ™ 11 C - m, - / \ / \ | 0 ° 0 r.

where

R is a polyolefin group, preferably polyisobutylene (M = 800-15000), n is an integer of 1 to 4, preferably 1, m is an integer of 0 to 5, preferably 1, p is an integer of 1 to 15, preferably 2 to 6,

Y is f!

ľ ¹ '

-C-CH 1

COOil _η

CH, -CH 1

CN and / or a group containing less than 30 carbon atoms, formed from another olefin or diolefin or a mixture thereof,

X is hydrogen or a saturated or unsaturated group formed from Y and

R 1 and R ₂ are hydrogen or C 1-6. _Two of the most suitable are the alkyl derivatives in which the number of the succinic anhydride (SA) groups linked to one polyolefin molecule, an average of between 1.6 and 6, preferably between approximately 1.8 and 4, and the concentration of molecules containing more than one SA group the concentration of free maleic acid is less than 0.3% by weight and the increase in the number average molecular weight of the components determined by GPC is less than 2.5 times the molar mass of the starting polyolefin. The intermediate formed by said long apolar polyolefin chain and the shorter, strongly polar, statistical or alternating copolymer chain is particularly suitable for the preparation of imide and / or ester, and / or amide, and / or esteramide derivatives having a high dispersing effect, wherein derivatives occurring in one The polyolefin chain may be identical or different.

Multifunctional, usually polar chain end groups also ensure that, when suitable at least bifunctional base reagents are used in the acylation reaction, chain polymer additives of the crosslinked type are formed under preferred conditions in addition to conventional crosslinked polymers.

The additive prepared according to the invention may contain components with different average molecular weights in which the average number of molecules bound by carboxyl groups is 2 to 100.

The additive prepared according to the invention preferably exists in solution in oil. In this oil solution, the oil concentration is at least 10% by weight, preferably between 30 and 80% by weight. Any type of refined oil, lubricating oil or base oil can be used for this purpose.

In the preparation process of the invention, maleic anhydride and the comonomer or comonomers containing the olefinic double bond or their copolymers are grafted to the starting polyolefins. During the reaction, the double bonds of maleic anhydride and the comonomer or comonomers are activated by a free radical initiator and, as a result of subsequent binding to polyolefins and / or by binding statistical or alternating copolymers formed from maleic anhydride and comonomer, a polymer chain comprising several SA groups is formed.

The first step of the additive synthesis, i. j. the reaction of the polyolefin and the unsaturated dicarboxylic acid and / or anhydride thereof, preferably maleic anhydride, and the comonomer or comonomers is carried out in a homogeneous solution at an energy-efficient low temperature with a suitable weight ratio corresponding to the molar ratio of reactants with different reactivities under more favorable conditions. to polyolefin, occasionally in the presence of compounds controlling the structure of polar groups containing side chains.

The reaction of the polyolefin and the unsaturated dicarboxylic acid and / or anhydride thereof, preferably maleic anhydride, and the comonomer or comonomers was carried out in a solvent containing components also boiling in the range of 110-250 ° C, in which the reactants and intermediates were readily soluble at 20-75 % by weight, preferably 35 to 60% by weight, based on the reaction mixture, in a temperature range of 80 to 180 ° C, preferably between 120 and 160 ° C, for 1 to 16 h using

286 molar ratio of maleic anhydride: comonomer: polyolefin 1,2 to 5,5: 0,1 to 3,5: 1 and using 5 to 25% by weight of peroxide, based on the amount of maleic anhydride or another type of initiator such as azobisisobutyronitrile or cumene hydroperoxide or, optionally, compounds or mixtures thereof controlling the monomer incorporation ratio in a ratio of 0.01 to 5% by weight, based on the amount of maleic anhydride, at a pressure of 1 to 15.10 kPa, preferably 1 to 5.102 kPa, in an inert atmosphere such as nitrogen and / or gaseous hydrocarbon.

It has been found that it is possible to achieve a high average SA / polyolefin molar ratio while keeping the formation of an oil insoluble by-product at a minimum level when using such a solvent or solvent mixture where the proportion of components boiling below 250 ° C is at least 3% by weight. . In order to reduce the concentrations of oil-insoluble by-products, the concentration of the comonomer or comonomers in the reaction mixture during the addition should be less than 5% by weight. These conditions can be maintained if the rate of addition of the MAH, comonomer or comonomers and the radical initiator decomposing in the temperature range of 80 to 180 ° C is set to appropriate values. For this purpose, the radical initiator, the MAH and the comonomer or comonomers are added in two or more portions or in a continuous manner. As the initiator, organic peroxides, hydroperoxides or azo compounds such as dibenzoyl peroxide, di-tert-butyl peroxide, azobisisobutyrodinitrile, azodicarboxamide or a mixture thereof can be used.

The compounds to inhibit unwanted side reactions such as decarboxylation, resin formation, or to control the MAH: comonomer incorporation ratio may be carboxylic acids of 1 to 20 carbons, dicarboxylic acids or anhydrides, hydroxycarboxylic acids, ketones, ethers, esters, alcohols, water or mixtures thereof and derivatives thereof. Preferably, isobutyl alcohol, isopropyl alcohol, monobutyl succinate may be used. If necessary, these additives are used in a concentration of 0.01 to 5% by weight, based on the amount of maleic anhydride. During the decomposition of these compounds or radical initiators, highly reactive substances may be formed which may be involved in addition and polymerization reactions taking place in the reaction mixture.

The reaction products were identified by their ¹³ C and 1 H NMR spectra using deuterated chloroform as solvent. It has been observed that, under the experimental conditions used in the invention, the monomers added to the reaction mixture mostly bound to the α-double bond of the polyisobutylenes. This is demonstrated by the disappearance of the ³ C peaks at 114.5 and 143.6 ppm, characteristic of the terminal double bonds of the polyisobutylenes, as well as the peak in the 1 H spectrum at 4.3 ppm and the ¹³ C peak at 136.6, typical of maleic anhydride, and peaks characteristic of comonomer double bonds. Experiments with maleic anhydride enriched in the &^lt; ³ &^gt; C isotope have demonstrated the existence of linkages characteristic of incorporation into the comonomer groups constituting the grafted copolymer chains.

From the colorless to light brown intermediate prepared according to the invention, the solvent can be regenerated by stripping the components with a boiling point below 250 ° C and the residual heavier fraction can be diluted to 20 to 60% by weight with refined oil, preferably refined oil of 2-15 mm viscosity. ² / s, at 100 ° C.

The intermediate solution may be filtered with or without the addition of a filter aid or filtration aid at a concentration of 0.5 to 5% by weight.

If the intermediate prepared according to the invention is reacted in a second, so-called acylation step, with polyamines, polyalcohols, alkanolamines containing at least two reactive groups and / or mixtures thereof, and / or derivatives thereof using a hydrocarbon and / or refined oil as solvent at 120 ° C. to 235 ° C in an inert atmosphere, for example nitrogen gas, at a pressure of 0.05 to 6.10 ² kPa in the presence of a catalyst in a concentration of 0.01 to 2% by weight, then a mixture of an additive based on polysuccinimide and / or polyamide is obtained; a polyester, and / or a polyesteramide (e.g., a polysuccinimide of formula (II)), where one or more components with significantly different molecular weights may be formed depending on the reactants used and molar ratios. In the formula (II)

(J 1.11 (II.b) ‘(II c) or another bifunctional diolefin, or

R a polyolefin, preferably a polyisobutylene group (molar mass 800 to 15000),

At least a bifunctional group derived from polyalkylene polyamines and / or polyalcohols, and / or polyalkanolamines, or other conventional nitrogen-containing and / or hydroxyl-containing components,

Y 'group

CM, _rH | J ^CH } CN

-CH-C-. -CH-CU-. <. _C H,. _CH . _C 'ik i ^ i! I, II ¹ Ί ro! in ₁ j a group formed from olefin or mixtures or a monofunctional group obtained by converting said groups,

Z is hydrogen or -NH- (CH ₂ CH ₂ NH) -H, or OR 1, R 1; and R ₂ each C 1. _{A 20-} alkyl group, a, b, c, d, e, and f integers of 0 to 5, preferably 1, q, m, n zero, 1 or an integer greater than 1, provided that:

the sum of m and n is an integer greater than 1, the proportion of molecules containing groups (II.b) and / or (II.c.) in the product is greater than 25% by weight and the compounds of structures (II.a), (II.b) and (II.c) can be linked to each other into any sequence.

The important characteristic of the additive prepared according to the invention is due to the new structure of the intermediate. In this intermediate, probably the reactive groups SA and others are located adjacent to each other at the end of the long polyolefin chain. Consequently, the growth of the macromolecule is not sterically restricted by multiple or chain condensations, as is the case with other intermediates where the SA groups are randomly distributed either at the end or between the polyolefin chains.

As the multifunctional polyamide component, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, a cyclic polyamine such as piperazine, diethyleneaminopiperazine or mixtures thereof may be used; as polyalcohol, for example, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, trimethylolpropane or pentaerythritol may be used, such as amino alcohol, for example ethanolamine, diethanolamine, triethanolamine or mixtures and derivatives thereof.

SK 281687 Β6

Since it is possible to vary the molar fraction of different polymers with different molecular weights in a wide range in the additive, the need to produce different motor oils can be easily met by modifying the preparation process easily. In our experience, additives have been found to be particularly advantageous where the ratio of higher molecular weight and lower molecular weight was in the range of 0.01 to 5% by weight.

The average molecular weight of the lower average molecular weight polymer is less than six times the number average molecular weight of the polyolefin used as feedstock. Experimental acylation conditions must be chosen to promote the formation of multiple bonds in the amide, imide and ester forming condensation reactions, i. j. to produce compounds characterized by a polyamide, polyimide and polyester structure or combinations thereof. This can be achieved by maintaining the molar ratio of the succinic anhydride group of the intermediate to the acylated component in the range of 0.7 to 5.5: 1, preferably in the range of 1.7 to 5.5: 1.

4.5: 1.

A reaction time of 2 to 15 hours and, if desired, conventional acid or base catalysts in a concentration range of 0.1 to 2% by weight is used to provide the desired degree of conversion in the acylation.

As the catalyst, acidic or basic compounds such as petroleum sulfonic acid, p-toluenesulfonic acid, sulfuric acid, potassium hydroxide, triethanolamine, ethanolamine or ion exchange resin, preferably in the form of hydrogen ions, can be used in the acylation reaction.

In the formation of polyester, which is one of the possible versions of acylation, it is particularly advantageous to use petroleum sulfonic acid, which has hitherto been proposed as a catalyst only in the preparation of low molecular weight (M _n &_lt; 3500) alkenyl succinates (patent HU 205.778).

After the acylation reaction, unreacted acid can be removed if necessary. In order to promote other beneficial side effects, such as anti-corrosion effect, wear reduction or antioxidant effect, a structure-modifying step may be included as the final step. In this process, the modifying compound is added at a concentration of 0.1 to 8% by weight, based on the reaction mixture, which is then stirred for 0.5 to 10 hours at 80 to 230 ° C under an inert atmosphere.

Conventional modifying chemicals such as sulfur, active sulfur containing compounds, phosphorous sulfide, boric acid or a derivative thereof, zinc compounds such as zinc dialkyl dithiophosphate, copper compounds including organic copper salts or complexes, molybdenum dioxide, organic acids, for example, fatty acids, glycolic acids, malic acid, fumaric acid, amides, alkenylsuccinimide, mixtures thereof or derivatives thereof.

Upon completion of the acylation and optional modification reactions, volatile reagents from the reaction mixture can be removed by stripping in vacuo at 160 to 210 ° C, after which the reaction product is diluted with refined oil and can be filtered using or without filter aid if necessary.

The different components of the final product with different average molecular weights have characteristic differences, with additives containing low molecular weight components at a higher concentration having a greater ability to neutralize acids and a sediment removal effect, while products containing higher molecular weight components at a higher concentration have a significant effect in stabilizing dispersion, viscosity and viscosity index as well as anti-wear effect.

In the products of the invention, the components are characterized by a number average molecular weight calculated as follows:

_ ^Ση Μ H, “----- Ln _t where

M _n is the number average molecular weight, n, is the number of moles of the i-th polymer molecule,

M i is the molar mass of the i-th polymer molecule, i is a positive integer.

The degree of polydispersity characterizing the molecular weight distribution is the ratio of the weight average and the number average molecular weight. The weight average molecular weight is calculated from the equation:

SrijMj ² M _{w =} ----- En _t M _t where

M _w is the weight average molecular weight and the other symbols have the meaning given above. Polydispersity is calculated from the equation:

R, a =

W ».

The extension of the molecular weight distribution (Δα) is:

Δα '------. Wherein a _PIB is the polydispersity of the polyolefin feedstock and a is the polydispersity of the reaction product.

DETAILED DESCRIPTION OF THE INVENTION

Examples are provided to illustrate the invention, but do not limit its scope.

Example A

1125 g (0.5 mol) of polyisobutylene (Mn = 2250) and 1450 g of xylene are weighed into a 3 dm ³ pressure-resistant stirred tank reactor equipped with a thermometer, inert gas inlet and a condenser coupled to the condensate collector. with stirring in an inert atmosphere at 76 ± 4 ° C, 98.6 g (1 mol) of maleic anhydride and 2.8 g of dibenzoyl peroxide are added at a rate of 0.7 g / h and a total of 28 g of isobutylene in four 7 g portions. After the addition was complete, the reaction mixture was stirred for 1 hour under the above conditions. Xylene and other unreacted lighter components can be removed by distillation at 140 ° C at 15 kPa for 1.5 h. To the intermediate is added 1200 g of refined lubricating oil (viscosity

3.5 mm ² / s at 100 ° C, viscosity index 95, pour point -22 ° C). After homogenization at 135-150 ° C and clarification, the mixture is filtered in the presence of 3.5% by weight of filter aid. The acid number of the yellow-brown viscous oily intermediate is 43.0 mg

SK 281687 Β6

KOH / g, its maleic anhydride content is 1.5 mg / g and contains on average 1.7 succinic anhydride groups, based on the PIB molecule. The SA / PIB succession ratio is calculated from the equation:

E »E

SR = ------------------- 112,2.10 ´ - 98,6.E where

SR is the suction ratio SA / PIB, E is the acid number of the intermediate (mg KOH / g), is the number average molecular weight of PIB.

Example B

In the reaction vessel described in Example A, 1125 g (0.5 mol) of polyisobutylene having a number average molecular weight Mn = 2250, 950 g of base oil SAE-30 (viscosity 9.5 mm ² / s at 100 ° C) are charged and 110 g of solvent MOL Rt. High aromatics content (commercial name AROMATOL) and mixed. The mixture is stirred under an inert atmosphere at atmospheric pressure and 135 ± 6 ° C and 118.3 g of MAH, 76 g of octyl methacrylate and 9.6 g of di-tert-butyl peroxide are added in 4 equal portions over 4 h. The reaction mixture is then stirred with additional Aromatol and the other lighter components are removed by boiling at 155 ° C and 12 kPa. 250 g of refined oil SN-150 / A (manufactured by MOL Rt.) Were added to the intermediate at 120 ° C. The intermediate thus obtained is initially clarified with 2% by weight of filter aid and filtered at 110 ° C in the presence of 1% of filtration aid. The acid number of the diluted and filtered intermediate is 39.7 mg KOH / g, the maleic anhydride content 2.8 mg / g and contains on average 1.6 succinic anhydride groups based on the PIB molecule. The increase in average molecular weight is less than 60% and the proportion of compounds containing more than one succinic anhydride group per molecule is greater than 55%.

Example C

1200 g (0.15 mol) of polyisobutylene (Mn = 8000) and 500 g of xylene were weighed into the reaction vessel described in Example A and mixed. The mixture was then heated to 115 ° C and added in 6 equal portions over 3 h

59.2 g (0.6 mol) of maleic anhydride, 12.0 g of azobisisobutyronitrile and 24.0 g of styrene. After the addition was complete, the reaction mixture was heated to 180 ° C and stirred for an additional 6 h. Unreacted maleic anhydride was removed at 195 ° C and 10 kPa pressure, then the product was mixed with 1150 g of refined lubricating oil of Example A, and the resulting mixture was filtered in the presence of 3% by weight of filter aid. The acid number of the filtered and diluted intermediate is 23.9 mg KOH / g, the maleic anhydride content is 1.3 mg / g and contains on average 3.3 succinic anhydride groups based on the PIB molecule. The increase in average molecular weight and molar mass distribution is less than 20% and the proportion of compounds containing more than one SA group per molecule is 42% by weight.

Example D

To the reaction vessel described in Example A was added 1200 g (0.5 mol) of polypropylene and a 9: 1 weight blend of SN 150 / A base oil (a commercial product of MOL Rt.) And kerosene. The mixture is heated to 80 ± 4 ° C and 98.6 g (1 mol) of maleic anhydride and 4.2 g of dibenzoyl peroxide are added with stirring, the mixture is stirred for 2 h and the temperature is raised to 160 ° C, 33 g of isobutylene are added. as an initiator

11.4 g of di-tert-butyl peroxide, 43.3 g of maleic anhydride, 6.5 g of monobutyl succinate, 33 g of styrene in 2 equal portions per hour and 88.7 g of maleic anhydride in 5 equal portions over 6 h.

Unreacted lighter components were removed at 200 ° C at 10 kPa for 1.5 h. The product was then diluted with 1060 g of the base oil of Example B and the resulting mixture was filtered in the presence of 4% by weight of filter aid; the acid number of the filtered and diluted intermediate was 60.1 mg KOH / g, the maleic anhydride content was 2.1 mg / g, the average SA: PIB suction ratio was 2.4, the proportion of components containing more than one SA per molecule was 64%, the increase the average molecular weight was less than 60% and the measured extension of the molecular weight distribution was 68%.

Example E

0.08 mol of polyisobutylene (Mn = 15000), 600 g of xylene, 0.4 g of cumene hydroperoxide and a 1: 1 mixture of fumaric acid and maleic anhydride were added to the reaction vessel described in Example A and the mixture was placed under an inert atmosphere at 6 bar. stirred and heated to 180 ± 5 ° C for 2.5 h. The reaction mixture was then cooled to 150 ± 4 ° C and 9 g of acrylic acid and 1.8 g of di-tert-butyl peroxide and 12.8 g of said acid mixture were added with stirring over 6 hours in 6 portions so that before each addition of acrylic acid 0.5 g of isobutyl alcohol was also added to the mixture. After 2 hours of distillation at 165 ° C and 15 kPa pressure, 1000 g of the oil described in Example A were added, after 2 filter aid and filter enhancement material, and the mixture was filtered. The acid number of the filtered and diluted intermediate was 9.3 mg KOH / g, maleic anhydride content 1.7%, average dicarboxylic acid-polyisobutyl- condensation ratio. The proportion of compounds containing more than one group derived from dicarboxylic acid was 47%. the increase in the average molecular weight and the extension of the molecular weight distribution was less than 10%.

Example F

500 g of water-saturated xylene and 28.5 g of isobutylene were weighed into the reaction vessel described in Example A, and the mixture was heated to 130 ± 5 ° C for 2 h, and 0.75 mol (73.95 mol) was added at 130 ° C. g) maleic anhydride and continuously 14 g of di-tert-butyl peroxide initiator, 3 g of monobutyl succinate were added dropwise over half an hour, after about 0.25 h in 4 equal portions of 98.6 g of maleic anhydride and 60 g of styrene and 6 equal portions. 27 g di-tert-butyl peroxide initiator. Before the addition of the last two parts of the initiator, 0.5 mol of polyisobutylene (Mn = 2250) and 0.5 mol (43.3 g) of maleic anhydride were added to the reaction mixture, and the reaction mixture was heated to 140 ± 5 ° C and stirred for 1 hour. h. Unreacted lighter components were removed by boiling for 1.5 h at 175 ° C and 15 kPa. The product so obtained was diluted with 1200 g of the base oil of Example B and filtered in the presence of 2% by weight of a filtration improving material. The saponification number of the filtered and diluted intermediate was 78.8 mg KOH / g, the maleic anhydride content was 1.9 mg KOH / g, the average SA: PIB suction ratio was 3.1, the average molecular weight increase was less than 30%, the molecular weight distribution expanded the proportion of components containing more than one succinic anhydride group per molecule was 65%.

Example G

800 g of SN 150 / A base oil and 200 g of water-saturated xylene were weighed into the reaction vessel described in Example A. 10 g of "C ₄ -fraction" (petroleum pyrolysis product, commercial product TVK Rt.) Were bubbled through the mixture. the mixture was heated to 90 ± 3 ° C at a rate of 50 ° C / h; 0.5 mol (49.3 g) of maleic anhydride and 12 g of dibenzoyl peroxide were added in 3 equal portions over a period of 2 h, the temperature of the reaction mixture was raised to 140 ± 5 ° C and 70 g of styrene was added continuously over 4 h. 9 g (15 mol) of maleic anhydride and 14 g of di-tert-butyl peroxide. To the oily xylene solution of the low molecular weight copolymer was added 1125 g (0.5 mol) of polyisobutylene and the reaction mixture was then heated to 140 + 5 ° C and 10 g of di-tert-butylperoxide was added with stirring for 1 h. , 5 h. Untreated lighter components of the mixture were removed by boiling as in Example A and the obtained intermediate, further diluted with 300 g of SN 150 / A oil, was suitable for further use without filtration and further processing. Its acid value was 72.4 mg KOH / g, maleic anhydride content 1.8, average SA: P1B succination ratio was 3.3, average molecular weight increase was less than 35%, molecular weight distribution expanded to 45%, the proportion of ingredients containing more than one succinic anhydride group per molecule was 73%.

Example H (reference)

1125 g (0.5 mol) of polyisobutylene and 500 g of xylene were weighed into the reaction vessel described in Example A. The mixture was heated to 135 ± 5 ° C and 111.0 g (1.1 mol) of maleic anhydride was added under stirring in 5 portions with stirring in 7 equal portions of 9 g di-tert-butyl peroxide initiator. The lighter components of the mixture were removed as in Example A, and the resulting intermediate was diluted with 1300 g of the oil shown in Example B; its acid number after clarification and filtration was 31.6 mg KOH / g, free maleic anhydride content 3.2 mg / g, increase in average molecular weight less than 15%, expanded molecular weight distribution was 45%, average molar ratio SA: PIB was 1.3 and the proportion of components containing more than one succinic anhydride group per molecule was 35%.

Example I

To the reaction vessel described in Example A was added 950 g (1 mole) of polyisobutylene and, under stirring in an inert atmosphere at 180 ± 10 ° C, 270 g of an isobutylene-styrene mixture (4: 5 weight ratio) over 5 h in 5 equal portions.

246.5 g (2.5 mol) of maleic anhydride and 28 g of di-tert-butyl peroxide in 7 h. After the first hour of the reaction, but before all the maleic anhydride was added, 1 g of isopropyl alcohol was also added dropwise to the reaction mixture. The slightly unreacted components of the mixture were removed as in Example B and the obtained intermediate was diluted with 1300 g of the base oil shown in Example B. Its acid number after clarification and filtration again according to Example B was 87.6 mg / g, free maleic anhydride content 3.0 mg The average SA: PIB suction ratio was 1.5, the molecular weight increase was 60%, the molecular weight distribution was less than 68%, the proportion of components containing more than one succinic anhydride group was 47%.

Example J (reference)

1300 g (1 mol) of polyisobutylene and 350 g of xylene were weighed into the reaction vessel described in Example A, and the mixture was heated to 145 ° C with stirring under an inert atmosphere at 145 ° C and added at 4 and 4 hr. 7 parts of 197.2 g (2 mol) of maleic anhydride and 11.9 g of cumene hydroperoxide and 6.8 g of di-tert-butyl peroxide. Unreacted lighter components were removed by boiling for 1 h at 150 ° C and 15 kPa. The intermediate mixture thus obtained was diluted with 1150 g of the oil of Example A and was filtered in the presence of 3% by weight of a filter improving material. The saponification number of the filtered and diluted intermediate was 70.3 mg KOH / g, the maleic anhydride content was 2.5 mg / g, the average number of succinic anhydride groups bound per PIB molecule was 1.6. The proportion of components containing more than 3 succinic anhydride groups per molecule was 34%, the increase in average molecular weight was 550%, the extension of the molecular weight distribution was 85%, based on the polyisobuiylene feedstock used.

Example 1

783.3 g of the acylating agent described in Example A was weighed at 65 ° C into a stirred tank reactor equipped with reagent feed, cooler, sampler, nitrogen discharge valve, thermometer, and pressure gauge, when 14 was added to the mixture. 2 g of tetraethylenepentamine and 0.1% by weight of triethanolamine as catalyst. The reaction mixture was then heated to 175-180 ° C with stirring under an inert atmosphere and then the acylation reaction was continued for 5 h under these conditions. Then, 3.1 g of diethylenetriamine was added to the reaction mixture, and the reaction mixture was stirred at 190 ° C for 1 hour at 50, 30 and 10 kPa pressure. The nitrogen content of the final product was 0.8%, the ratio of the higher molecular weight to the lower molecular weight polymer was 0.6.

Example 2

84.7 g of the acylating agent described in Example B and S g of triethylenetetramine and 22.4 g of triethanolamine were weighed into the stirred tank reactor described in Example 1 at 60 ° C. The reaction mixture was then heated to 175-180 ° C with stirring under an inert atmosphere and then the acylation reaction was continued for 6 h under these conditions. In the last four hours of the acylation reaction, a pressure of 300 kPa was applied for 3 h and a further 1 h pressure of 10 kPa. After filtering in the presence of 1% by weight of filter aid, the nitrogen content of the product obtained was 0.40% by weight, the ratio of higher to lower molecular weight polymer being 0.5.

Example 3

To the stirred tank reactor described in Example 1, 938.9 g of the intermediate of Example C was weighed at room temperature, and then 10.3 g of diethylenetetramine was added at 140 ° C. The acylation reaction was carried out for 4 h with stirring under an inert atmosphere at 50 kPa while raising the temperature to 190 ° C at a rate of 20 ° C / h. After filtering at 120 ° C in the presence of 1% by weight of filter aid, the nitrogen content of the product obtained was 0.4% by weight and the ratio of the higher and lower molecular components was 2.3.

Example 4

To the stirred tank reactor described in Example 1, 746.8 g of the intermediate of Example D, 0.2% by weight of malic acid catalyst was added in two portions at room temperature and 130 ° C, and

12.3 g of glycerol, whereupon acylation was carried out for 4 hours under an inert atmosphere at 210 ° C and 400 kPa and 3.5 hours at 10 kPa. Then the reaction mixture was cooled to 120 ° C, 3.1 g of diethylenetriamine were added, then the mixture was stirred at 155 ° C at 65 kPa for 1 h and at 185 ° C at 10 kPa for 2 h. After filtering in the presence of 1% by weight of the filter aid, the nitrogen content of the product obtained was 0.1% by weight and the ratio of the higher and lower molecular components was 0.2.

Example 5

To the stirred tank reactor described in Example 1 was weighed 844.5 g of the intermediate of Example E. While stirring under an inert atmosphere, 1.24 g of diethylenetriamine was added at room temperature, followed by 2.27 g of tetraethylenepentamine at 70 ° C and the reaction was carried out for 2 hours. h at 130 ° C. An additional 0.6 g of diethylenetriamine and 1.1 g of tetraethylenepentamine were then added dropwise to the reaction mixture. The reaction was carried out at atmospheric pressure at 190 ° C for 4 h and the mixture was filtered at 120 ° C in the presence of 1% by weight of filter aid. The nitrogen content of the product obtained was 0.2% by weight and the ratio of the higher and lower molecular components was 0.1.

Example 6

To the stirred tank reactor described in Example 1 was weighed 711.9 g of the intermediate of Example F, and in the presence of 0.2% by weight of petroleum sulfonic acid catalyst, 6.0 g of ethylenediamine was added to the mixture at room temperature and atmospheric pressure. the temperature was raised to 190 ° C and the pressure to 15-10 kPa and the acylation reaction was carried out for 6 h. 11.3 g of tetraethylenepentamine were added to the reaction mixture, and the reactants were stirred at 215 ° C and 10 mbar for 2 h. After filtering at 120 ° C in the presence of 1% by weight of filter aid, the nitrogen content of the product obtained was 0.9% by weight, the ratio of the higher to lower molecular components being 1.25.

Example 7

774.9 g of the acylating agent used in Example G were weighed into the mixing tank reactor described in Example 1 and 8.76 g of triethylenetetramine was weighed in an inert atmosphere at atmospheric pressure and 9.49 g of diethanolamine were stirred with stirring. After the acylation reaction was carried out at 175 ° C at 50 kPa for 4 h, the reaction was carried out for 10 min. 25 g of monosuccinimide derivative (KOMAD-303, MOL Rt.) was added dropwise at 120 ° C. The reaction was continued for 3 h at 170 ° C and 2.102 kPa and for a further 1.5 h at 15 kPa. The nitrogen content of the product obtained was 0.54% by weight and the ratio of the higher molecular weight to the lower molecular weight polymer was 0.7.

Example 8 (reference)

To the stirred tank reactor described in Example 1 was weighed 711.3 g of the intermediate prepared according to Example H, then 10.3 g of diethylenetriamine was added under nitrogen at room temperature and 120 ° C at 37.8 g of tetraethylenepentamine and after 2 h acylation reaction. at 250 ° C, 13.6 g of pentacrytritol and 2.4 g of petroleum sulfonic acid catalyst were added. After a final reaction time of 3 h at 15 kPa, the product was filtered in the presence of 3% by weight of filter aid. The poorly filterable product was only partially soluble in the base oil due to a nitrogen content of 2.2%.

Example 9

To the stirred tank reactor described in Example 1, 768.5 g of the acylating agent used in Example 1 was weighed under an inert atmosphere at atmospheric pressure. While stirring at 80 ° C, at first 21.2 g of the ethylene glycol diet was added at a rate of 0.5 h. heating at 80 ° C / h, then 18.9 g of tetraethylenepentamine was added dropwise to the reaction mixture and the acylation reaction was carried out for 6 h at atmospheric pressure at 180 ° C. The nitrogen content of the filtered end product was 0.82% by weight, and the ratio of the higher and lower molecular components was 0.4.

For ease of handling and comparison, the oil content of all end products was adjusted to 50% before use. If the oil content of the end product prepared in the individual examples was less than 50%, it was adjusted to this value by diluting the oil component used for the synthesis. The refined lubricating oils described in Examples A and B were used for dilution.

By comparing the characteristics of the intermediates prepared in Examples A to G and I, it was found that under the conditions used according to the invention, the reaction between the comonomer (s), the polyolefin and ΜΑΗ leads to the coupling of copolymer chains containing on average 1.6 to 6, preferably 1.8 to 6 4 succinic anhydride groups per mole. polyolefin sphere.

The detergency-dispersing effect of the additives described in the examples was evaluated by the method described in Bartha et al., Method of Determination, Optimum Composition of Detergent Dispersant Oil Additives, Hung. J. Ind. Chem., 1979, 7, 359-366. Potential Detergent-Dispersing Effect (PDDE) values are given in percent as 225 times the sum of the dispersion-stabilizing additive effect ("detergent index", D1,%) and its washing effect (M, mm). The sediment-reducing effect was evaluated by the same methods as those cited in the cited publication, based on the results obtained by the so-called panel coking method.

In addition to the above characteristics, the dispersing effect of the additive was further evaluated by the so-called spot dispersancy test method. According to this method, the oil mixture containing the additive or additives of interest is mixed in a high-speed mixer with 2% carbon black of specific quality and the suspension obtained is treated in six different ways (maintaining at different temperatures in the presence or absence of water). filter paper and after 48 h the ratio of soot-to-oil spot diameters is evaluated. The theoretical maximum of these six results is 600%; the higher the dispersing effect, the higher this value.

The detergent dispersant effect of the products prepared in Examples 1 to 9 was evaluated in lubricating oils and the results are shown in Table Liax. - 'L ..-.

Table DD potency of additive Compositions (3 ‘, thiostasis pot in o» SN-150 i

P, au.) PDDIr,% · (100 mex.) 1 96 76 69 74 ^ä! mu) K multiplication point 86

♦ PDDE - potential derergent-dispersing effect

Dispersants have been studied in the following motor oil compositions:

base petroleum oil variable% pour point depressant 1.0%

PAO-6 (poly-.alpha.-olefin synth. Oil) 15.0% polyisoprene enhancer VI variables% partial SG / CD performance block without dispersant 6.4% dispersant 7.6% total 100 * commercially available MOL Rt. : traditional monobissuccinimide type dispersant synthesized from polyisobutylene (M = 1000) * * * carrier Maximol 99 10W-40 *** carrier MSF 15W-40

For these studies, the products prepared according to the examples were blended at a concentration of 3% by weight in the base oil, characterized by the following parameters: kinematic viscosity (100 ° C): 5.2 mm ² / s viscosity index, VIE: 101

The results of the detergency-dispersing effect studies of the oil compositions obtained using the products prepared according to Examples 1, 2, 3, 7 and 8 and the reference additive are shown in Tables 2 and 3, while the results of viscosity improvement and viscosity index studies are shown in Table 4.

Table 2. DD properties of oil compositions

Table 4 VI-improving effect in oily compositions

oil composition Base oil * Viscosity at 100 ‘C. pl /.-'s need amount of amplifier VI,% by _P ,.: 5 3 6.5 _P T.Ž WITH.·'. 6.9 3 5.8 5.0 KGMAD-302 5.4 8.0

Oil paints * PDDE,% ** ^*** tisadet-iny on the board. mg additive according to pr. 1 94 3.2 pr. 2 92 5.7 pr 3 85 ID.4 _P r. 7 9 i) 14.0 reference acii (KOMAD-301 * · *) 81

* composition ingredients: SAE-30 base oil 91.0% additive according to example 1, 2, 3 or 7 4.0% commercially available additives hyperbasic Ca sulfonate 3.8

Zn dialkyldithiophosphate 2.2 ** PDDE - potential detergent-dispersant effect *** commercially available additive KOMAD-301 (Mn 1 / _L = 950, MOL Rt.) 4% wt.

rsl '3 of DD efficacy studies using' dispetsancy teii '

oils * composition d'speraíeia f.kvroy,% according to j-i 1 42 » under pt 7 41S according to pr. 2 112 noéfi! pr> 4C2 KOMAD-SC2 · 428 typical tcierend. * see Al SG1CD hl typical refining. E.Lee; 4P) SF-CC '17 <1

The dispersants were studied in the SAE 10W-40 oil compositions listed in Table 3. The viscosity of the compositions was adjusted with the Improver VII within the following limits: kinematic viscosity at 100 ° C 14.0 -15.0 mm ² / s CCS at -20 ° C 3400 mPas * Base Petroleum Oil and PAO-6 Synthetic Oil

Compatibility with sealants was studied using the Volkswagen VW-3344 test and the results are shown in Table 5.

Table 5. Data for oil compositions obtained by the VW 3344 method

oil composition limit load, MPa elongation,% storage at 100% predlienl additive according to pr 1 9.8 225 without cracks pr. 7 9.9 215 without cracks pi. 2 11.1 V í without cracks pr 3 11.4 269 without cracks Commando-302 7.3 136 rupture iniirtual level 8.0 í 60 without irhlin

Dispersants were studied in the oil compositions listed in Table 3.

The structure and properties of the intermediates prepared according to Examples A to Gala of the end products synthesized therefrom according to Examples 1 to 7 and 9 are similar to the other compounds prepared according to the invention and were also obtained under preferred experimental conditions and combinations of parameters according to the invention.

The structure and properties of the intermediates and end products of Examples H and J and Example 8, as well as their preparation, are somewhat different from the preferred structures and processes of the invention.

The results concerning studies of detergency dispersant properties, viscosity modification, compatibility with sealants in end products obtained under preferred acylation conditions, and modifications of the invention from intermediates of preferred structure and composition prepared under preferred conditions of the invention are shown in Tables 1 to 5 and show that the efficacy of these products is either equal or higher compared to the reference additives, i. j. their detergency-dispersing effect in the base oil either alone or in oil compositions is indeed advantageous. Their effect on improving the viscosity index and their compatibility with sealing materials is significantly higher compared to commercially available reference additives. The use of additives prepared according to the invention further improves the properties of lubricants or fuels.

Due to their less significant cold viscosity increasing effect, the usable concentration can be further increased especially in the case of motor oils. Their advantageous viscosity-improving effect and viscosity index allow for a more extensive substitution of traditional high molecular weight polymers. The applicability of higher dosing of the additives prepared according to the invention from low molecular weight polyolefins, in particular polyisobutylenes, hitherto used for the preparation of ashless dispersants offers a more economical formulation of lubricants.

Claims (9)

An additive used in an oily solution for internal combustion engine lubricating oils, containing imide and / or ester and / or esteramide derivatives of a reaction product of an unsaturated polyisobutylene and an unsaturated reactive dicarboxylic acid and / or an anhydride thereof, characterized in that it comprises a reaction product of polyisobutylene having a number average molecular weight of 800 to 15,000 and an unsaturated reactive dicarboxylic acid and / or anhydride thereof, preferably maleic anhydride, containing on average 1.6 to 6.0 succinic anhydride derivative per polyisobutylene chain in which the concentration of molecules containing more than one succinic anhydride derivative is more than 25% by weight and the polyisobutylene is inoculated or reacted with a succinic anhydride-containing copolymer obtained from a more reactive, low molecular weight comonomer of less than 500, containing an olefinic double bond, or from a mixture of such comonomers and from an unsaturated reactive dicarboxylic acid and / or an anhydride thereof, preferably maleic anhydride, using a maleic anhydride: comonomer: polyisobutylene molar ratio of 1.2 to 5.5: 0.1 to 3.5: 1 and widening the distribution the molecular weight is less than 70% based on the starting polyisobutylene, wherein the succinic anhydride groups of the copolymer bound to the polyisobutylene are reacted in a ratio of 0.7 to 5.5 with compounds containing at least bifunctional amine and / or hydroxyl groups. An additive according to claim 1, wherein the dicarboxylic acid component of the copolymer grafted onto the polyisobutylene chain is a succinic anhydride derivative. The additive according to claim 1, characterized in that the dicarboxylic component of the copolymer grafted onto the polyisobutylene chain contains on average 1.8 to 4.0 succinic anhydride derivatives. An additive according to claim 1, characterized in that the copolymer grafted onto the polyisobutylene chain contains the same or different succinic anhydride derivatives, preferably imide, amide, ester, esteramide and / or mixtures thereof. 5. The additive of claim 1 wherein the concentration of molecules comprising more than one succinic anhydride derivative in the copolymer grafted onto the polyisobutylene chain is greater than 25%. An additive according to claim 1, characterized in that the average number of molecules bound by the reaction of the carboxyl groups in the components with different average molecular weights is 2 to 100. A process for the preparation of an additive according to claim 1, characterized in that maleic anhydride and an olefinic double bond comonomer or copolymers thereof are grafted to a polyisobutylene having an average molecular weight of 800 to 15000 using a maleic anhydride: comonomer: polyisobutylene molar ratio of 1.2 to 5.5: 0.1 to 3.5: 1, wherein the concentration of the solvent providing the homogeneous phase is 10 to 75, preferably 30 to 60% by weight, based on the reaction mixture, and the reaction is carried out in the presence of a radical initiator in an amount of 5 to 25 % and a component controlling the monomer incorporation ratio in an amount of 0.01 to 5% by weight, based on maleic anhydride, at a pressure of 1 to 15.10 ² kPa and preferably under a nitrogen and / or hydrocarbon atmosphere, at a temperature of 80 to 180 ° C for 1 to 16 h, while the concentration of maleic anhydride and comonomer is kept below 5% by weight, the intermediate obtained is separated from the solvent by stripping and optionally diluted with a refined base oil, and if necessary clarified and filtered in the presence of a filter aid, whereupon the intermediate is reacted with compounds containing one or more at least bifunctional amine and / or hydroxyl groups, the ratio of compounds containing succinic anhydride groups and amine and / or hydroxyl groups is 0.7 to 5.5 and the reaction is carried out in the presence of a catalyst in an amount of 0.1 to 2% by weight, based on the reaction mixture, at a pressure of 0.015 to 6.10 ² kPa at 120 up to 235 ° C for 2 to 15 h and the product, if desired, is modified in the usual manner, diluted and filtered. The process according to claim 7, wherein the reaction between the polyolefin, maleic anhydride and the comonomer is carried out in a solvent or a mixture of solvents containing hydrocarbon components with a boiling point lower than 250 ° C at a concentration of at least 3% by weight. Process according to claim 7, characterized in that the modification is carried out with compounds containing boron, sulfur, copper and / or molybdenum, and / or polyalkenyl succinic anhydride or ester amide.