RU2139921C1 - Detergent-dispersing additive to lubricating oils for internal combustion engine and method of preparation thereof - Google Patents

Abstract

FIELD: lubricants. SUBSTANCE: additive consists of imide and/or ester and/or ester-amide derivative of product of interaction of polyisobutylene with malonic acid and/or its anhydride. Above- mentioned polyisobutylene with molecular weight 800 to 30000 is brought into graft copolymerization or interaction with copolymer including polyisobutylene succinic anhydride residues and prepared from reactive low-molecular comonomer with molecular weight below 500 and having one double bond or from mixture of such comonomers and maleic acid and/or its anhydride observing molar ratio maleic anhydride/comonomer/polyisobutylene 1.25: 3.5: 1. Interaction product contains on average 1.6-6.0 succinic derivative units per one polyisobutylene chain, concentration of molecules including more than one succinic anhydride residues exceeding 25 wt %. Expansion of molecular weight distribution constitutes less than 70% with regard to initial polyisobutylene. Succinic anhydride residues of copolymer bound to polyisobutylene are brought into contact with compound including at least bifunctional amino and/or hydroxyl groups at ratio from 0.7:1 to 5.5:1. EFFECT: improved working characteristics and compatibility with sealing materials. 9 cl, 5 tbl

Description

 The present invention relates to an ashless detergent-dispersant (MD) additive based on a grafted polyolefin-polysuccinic anhydride, which increases both viscosity and viscosity index and which can be advantageously used to improve the properties of lubricating oils, and to a method for producing it.

 Ashless imide and ester type synthesized from alkenyl succinic acid derivatives have been used for more than thirty years to improve the washing and dispersing properties of motor oils. Due to their polar and basic nature, these additives reduce the formation and deposition on the surfaces of insoluble acid contaminants generated during engine operation. Thus, due to this, the service life of the engine and the service life of oils are markedly increased.

> 2000), придают улучшенные вязкостные свойства и повышающие индекс вязкости.In addition to their MD effect, various so-called modified derivatives, including atoms of sulfur, boron, halogens, molybdenum, copper, etc., exhibit good anti-corrosion and anti-wear properties, while products that include large molecular weight polymer side chains (

> 2000), give improved viscosity properties and increase the viscosity index.

 Alkenyl succinic acid derivatives are usually added to lubricating oils together with other metal-containing MD additives, viscosity index improvers, antioxidants, anti-corrosion and anti-wear components, friction modifiers and antifoam agents, ensuring their positive interaction.

 Over the past decade, oil additive manufacturers have conducted studies to increase MD potency and achieve beneficial side effects. In accordance with the results of tests in engines, this can be achieved either by increasing the molecular weight of the intermediate products and the final product, or by producing polysuccinimides, polyesters, polyethers, etc., linked by their polar groups (see, for example, US Pat. No. 4,234,435).

 The synthesis of such additives is based on the fact that in the first stage of succinimide synthesis, when, under the interaction of polyolefins with maleic anhydride (MAG), under special conditions, more than one MAG molecule combines with the polyolefin molecule, or alternatively, the so-called olefin-MAG copolymers are formed. When intermediates thus obtained containing more than two carboxyl groups are reacted with amines, polyamines, alcohols, polyhydric alcohols, alkanolamines or mixtures thereof of various compositions, higher molecular weight end products of the polyimide, polyamide, polyester or polyether amide type are obtained (see for example, U.S. Patent 4,234,435.

 Despite their strong MD action, such ashless additives have a low alkaline number due to blocking of their main amino and imino groups, and in comparison with traditional succinimides they cause less damage to fluorine-containing elastomeric seals in engines.

 Due to the stronger MD action and the noticeable effect of increasing the viscosity and viscosity index of such ashless additives, the latter increase the performance level of motor oils and also confirm their suitability for replacing some of the traditional additives used to improve the rheological properties (flow characteristics), thereby reducing the cost motor oil production. In various literary sources, various methods for the synthesis of intermediates such as alkenyl succinic anhydride are recommended.

= 1300-5000) можно увеличивать до более 1,05 путем одно- или многостадийного добавления хлорного катализатора и повышения температуры до 160-220^oC. Существенный недостаток такой методики заключается в том, что в полиолефиновой молекуле во время реакции присоединения накапливается опасный хлор, а в присадке он остается в количестве 0,001-0,5 вес.%.In accordance with US patent 4234435 and European patent 0208560, the molar ratio between succinic anhydride (AA) polyisobutylene (PIB,

= 1300-5000) can be increased to more than 1.05 by adding one or several stages of adding a chlorine catalyst and raising the temperature to 160-220 ^o C. A significant drawback of this technique is that hazardous chlorine accumulates in the polyolefin molecule during the addition reaction, and in the additive it remains in an amount of 0.001-0.5 wt.%.

Methods are also described in which the polyisobutylene-MAG addition is carried out at a high temperature (above 190 ^° C.) without using a catalyst. The molar ratio of the combined YA / PIB exceeds that achieved using a highly reactive (with an alpha-olefin content of more than 70%) polyisobutylene starting material and a large excess of MAG. The disadvantages of this method are the need to use more expensive source material, a high reaction temperature and a longer duration of interaction (see, for example, European patent 0271937).

= 10000-150000).WO 90/03359 describes a low temperature technique in which a polyisobutylene-maleic anhydride copolymer is prepared using a radical polymerization initiator and an aromatic or chlorinated hydrocarbon solvent. In such a PIB-MAG copolymer of intermittent structure, the average number of PIB-MAG units varies between 1.1-20. When intermediates of this type are used for the acylation reaction, the molecular weight of the final products can be in a wide range (

= 10000-150000).

 In accordance with European Patents 0400866 and 0002286, maleic anhydride and other unsaturated comonomer or comonomers are grafted onto traditional viscosity index-improving ethylene-propylene copolymers of a number average molecular weight higher than 10,000, preferably 100,000-200,000, determined by average viscosity molecular weight using chlorinated hydrocarbons or other solvents in the presence of a radical polymerization initiator. Then, the copolymer thus obtained was reacted with amines, polyamines, and the like, thereby obtaining a viscosity index improver with dispersant properties. According to the aforementioned patents, for this purpose, the use of polymers with a number average molecular weight below 30,000, as well as a medium viscosity molecular weight below 100,000, is considered impractical. As indicated in these patents, work with hydrocarbon polymers of number average molecular weight below 30,000 was difficult due to their unfavorable low temperature rheological properties.

 Described to date in the literature, methods for the preferred synthesis of high molecular weight multifunctional succinimides are characterized by both technological and structural limitations.

= 1300-2500. Хорошо известно, что увеличение средней молекулярной массы исходных полиизобутиленов сверх предельного значения

= 2500 в традиционных методах ведет к значительным затруднениям технологического порядка из-за высокой вязкости сырья. В дополнение к этому, как показывает опыт, от применения этих исходных материалов можно ожидать значительного нежелательного возрастания вязкости на холоду и уменьшения концентрации полярных азотсодержащих групп на единицу массы присадки и одновременного ослабления МД-действия.In accordance with the patented preferred variants of the synthesis of succinimides based on polyisobutylene, the use of medium molecular weight polyisobutylenes can be considered typical and appropriate.

= 1300-2500. It is well known that an increase in the average molecular weight of the starting polyisobutylene beyond the limit value

= 2500 in traditional methods leads to significant difficulties of the technological order due to the high viscosity of the raw material. In addition to this, experience shows that the use of these starting materials can expect a significant undesirable increase in viscosity in the cold and a decrease in the concentration of polar nitrogen-containing groups per unit mass of the additive and at the same time weaken the MD action.

= 15000-200000. Об успешном применении олефиновых сополимеров среднечисленной молекулярной массы менее 15000 в литературе не сообщалось, по- видимому, вследствие утраты ими эффекта улучшения реологических свойств.Succinimide derivatives formed by grafting onto ethylene-propylene copolymers are obtained and used, in addition to their main functions of increasing viscosity and viscosity index, to achieve an additional MD effect (European patents 400866 and 002286). For additives of this type, the optimal effect of increasing the viscosity and viscosity index is achieved in the range of molecular weights

= 15000-200000. Successful use of number average molecular weight olefin copolymers of less than 15,000 has not been reported in the literature, apparently due to the loss of the effect of improving rheological properties.

The closest analogue is patent EP 208560, which describes an additive that is an imide and / or ester derivative of the reaction product of a C ₂ -C ₁₀ olefin polymer, for example, polyisobutylene of molecular weight 1300-5000, with maleic anhydride in an amount of 1.05-1 , 25 moles per polyolefin molecule.

 An object of the present invention is to provide an additive of a new molecular structure with high washing and dispersing properties, exhibiting the effect of a higher viscosity and an improved viscosity index, while improving compatibility with sealing materials.

 The problem is solved in that in a detergent-dispersant additive for lubricating oils for internal combustion engines based on an imide and / or ester and / or ester derivative of the product of the interaction of polyisobutylene and maleic acid and / or its anhydride, according to the invention, polyisobutylene of number average molecular weight mass 800-30000, preferably 800-15000, which is introduced into the grafted copolymerization or in the interaction with the copolymer, including units of succinic anhydride and obtained from the reaction optionally low molecular weight comonomer of molecular weight less than 500, including a double bond, or from a mixture of such comonomers and maleic acid and / or its anhydride, using the molar ratio maleic anhydride: comonomer: polyisobutylene 1.2-5.5: 0.1-3 , 5: 1, and the interaction product contains an average of 1.6-6.0 units of succinic anhydride derivative per polyisobutylene chain, and the concentration of molecules comprising more than one unit of succinic anhydride derivative exceeds 25 wt.%, Molecular weight expansion distribution of less than about 70 percent relative to the starting polyisobutylene, wherein the ratio between compounds containing succinic anhydride groups, and compounds containing at least bifunctional amine and / or hydroxyl groups is 0,7-5,5.

 Preferably, the component of the copolymer grafted onto the polyisobutylene chain is a derivative of succinic anhydride.

 It is preferable that the component of the copolymer grafted onto the polyisobutylene chain comprise an average of 1.8-4.0 units of succinic anhydride derivative.

 The copolymer grafted onto the polyisobutylene chain may include identical or different units of succinic anhydride derivatives, preferably imide, amide, ester, ester, and / or mixtures thereof.

 In a copolymer grafted onto a polyisobutylene chain, the concentration of molecules comprising more than one succinic anhydride derivative may exceed 25%.

 The average number of molecules of the components of different average molecular weights, linked due to the reaction of carboxyl groups, can be 2-100.

The problem is also solved by a method of obtaining a detergent-dispersant additive for lubricating oils for internal combustion engines, in which maleic anhydride and double bond comonomer or their copolymers are grafted onto polyisobutylene of average molecular weight 800-30000 using the molar ratio maleic anhydride: comonomer: polyisobutylene 1.2-5.5: 0.1-3.5: 1 in the presence of a solvent, where the concentration of the solvent, ensuring the formation of a homogeneous phase, is 10-75 wt.%, preferred But 30-60 wt.% in terms of the reaction mixture carried out in the presence of a radical polymerization initiator in an amount of 5-25 wt.% and a component that regulates the ratio of the introduced monomers in an amount of 0.01-5 wt.% in terms of maleic anhydride , under a pressure of 1-15 • 10 ² kPa and preferably in a nitrogen and / or hydrocarbon atmosphere at 80-180 ^o C for 1-16 hours while maintaining the concentration of maleic anhydride and comonomer below 5 wt.%, while the intermediate product is separated from the solvent, if necessary they are diluted with refined base oil and, if necessary, clarified and filtered in the presence of an auxiliary filter medium, and reacted with compounds comprising one or more at least bifunctional amino and / or hydroxyl groups, the ratio between the compounds bearing the residues of succinic anhydride, and compounds with amino and / or hydroxyl groups is 0.7-5.5, which is carried out in the presence of a catalyst in an amount of 0.1-2 wt.% in terms of the reaction mixture od pressure 0,015-6 • February ¹⁰ kPa at a temperature of 120-235 ^o C for 2-15 hours and, if necessary, the product is modified in a usual way, diluted and filtered.

Preferably, the interaction between the polyisobutylene, maleic anhydride and the comonomer is carried out in a solvent or mixture of solvents comprising hydrocarbon components with a boiling point of less than 250 ^° C. in an amount of at least 3% by weight.

 The additive can be modified with compounds including boron, sulfur, copper and / or molybdenum, and / or polyalkenyl succinic anhydride or ether.

 Currently, polyisobutylenes of number average molecular weight in the range of 1300-8000, especially average molecular weight of more than 5000, find rather limited use as additives to improve viscosity and viscosity index. Despite their good resistance to thermal oxidation and shear stability, their widespread use is hindered by the fact that they increase the viscosity of oils at low temperatures to a greater extent than other types of viscosity index improving polymers. For this reason, upon receipt of modern universal motor oils, they cannot be used individually. The method proposed by the present invention, can dramatically reduce, and in preferred cases, eliminate these disadvantages of index additives on a PIB basis. The grafting of the polar side chain onto the main PIB molecular chain leads to the formation of a combined polymer structure having good thermal and chemical stability, as well as the viscosity increase effect characteristic of polyisobutylene, and at the same time a noticeably weaker effect of increasing the viscosity in the cold due to a decrease the solubility of the polymer.

As comonomers, reactive polar and nonpolar low molecular weight monomers are used, such as ethylene, propylene, butene-1, 1,3-butadiene, isobutylene, C ₅ -C ₂₀ alpha-olefins, styrene, acrylic acid, methacrylic acid, acrylates and methacrylates derived from C ₁ -C ₂₀ alcohols, acrylonitrile and mixtures thereof.

где R обозначает полиизобутилен

= 800-30000, предпочтительно 800- 15000),
n обозначает целое число 1-4, предпочтительно 1,
m обозначает целое число 0-5, предпочтительно 1,
p обозначает целое число 1-15, предпочтительно 2-6,
Y обозначает группу

и/или группу, содержащую менее 30 углеродных атомов, образованную другим олефином или диолефином либо их смесью,
X обозначает водород или насыщенную либо ненасыщенную группу, образованную Y-группой, и
R₁ и R₂ обозначают водород или C₁-C₂₀алкильную группу.The copolymers of polyisobutylene and derivatives of polysuccinic acid obtained from polyisobutylene, maleic acid and / or its anhydride and from a comonomer or mixture of comonomers correspond to the General formula 1:

where R is polyisobutylene

= 800-30000, preferably 800-15000),
n is an integer of 1-4, preferably 1,
m is an integer of 0-5, preferably 1,
p is an integer of 1-15, preferably 2-6,
Y represents a group

and / or a group containing less than 30 carbon atoms formed by another olefin or diolefin, or a mixture thereof,
X is hydrogen or a saturated or unsaturated group formed by a Y group, and
R ₁ and R ₂ are hydrogen or a C ₁ -C ₂₀ alkyl group.

 Most preferred are those derivatives in which the number of succinic anhydride (YA) residues associated with one polyolefin molecule is on average 1.6-6, preferably on average 1.8-4, and the number of molecules comprising more than one YA group is at least 25 weight. %, the content of free maleic acid is less than 0.3 wt.%, and the increase in number average molecular weight of the components, determined by GPC, is less than 2.5 times the molecular weight of the starting polyolefin. An intermediate product comprising the aforementioned long chain of a non-polar polyolefin and a shorter chain of a highly polar statistical or alternating copolymer is particularly suitable for the preparation of imide and / or ester and / or amide and / or ester derivatives with a strong dispersing effect, the derivatives being contained in one polyolefin chains may be the same or different.

 The presence of multifunctional, usually polar groups, at the ends of the chains also ensures that when appropriate at least bifunctional basic reagents are used during the acylation reaction under favorable conditions, addition products of chain-like polymers are formed in addition to conventional crosslinked polymers.

 The additive obtained in accordance with the present invention may include components of different average molecular weight, in which the average number of molecules linked by carbonyl groups is 2-100.

 The additive obtained in accordance with the present invention, it is advisable to apply in an oil solution. In this oil solution, the oil content is at least 10 wt.%, Preferably 30-80 wt.%. Refined oil, lubricating oil or any type of base oil can be used for this purpose.

 In the practice of practical preparation, maleic anhydride and comonomer or comonomers containing a double bond or their copolymers are grafted onto the starting polyolefins. During this reaction, double bonds of maleic anhydride and comonomer or comonomers are activated by a radical polymerization initiator. Due to the stepwise combination with polyolefins and / or due to the combination of statistical or alternating copolymers derived from maleic anhydride and comonomer, a polymer chain is formed comprising several JA groups (general formula 1).

 The first stage of the synthesis of the additive, i.e. the interaction of polyisobutylene with maleic acid and / or its anhydride and comonomer or comonomers is carried out in a homogeneous solution at an energetically favorable low temperature and with the appropriate choice of the weight ratio corresponding to the molar ratio between reactants of different reactivity, under conditions that are unfavorable for the multiple combination of the polyolefin, sometimes in the presence of compounds that regulate the structure of the side chain, including polar groups.

The interaction of polyisobutylene with maleic acid and / or its anhydride and comonomer or comonomers is carried out in a solvent containing components with a boiling range of 110-250 ^o C, where the reactants and intermediates are readily dissolved in a concentration of 20-75 wt.%, Preferably 35- 60 wt.% In terms of the reaction mixture. The interaction is carried out in a temperature range of 80-180 ^o C, preferably in the range of 120-160 ^o C, for 1-16 hours, using the molar ratio maleic anhydride: comonomer: polyisobutylene 1.2-5.5: 0.1-3, 5: 1 and using peroxide in an amount of 5-25 wt.% In terms of maleic anhydride or another type of initiator, such as azobisisobutyronitrile or cumene hydroperoxide, or, if necessary, compounds or mixtures thereof, regulating the amount of attached monomers, in the range of 0.01 -5 weight. % of the amount of maleic anhydride under a pressure of 1-15 • 10 ² kPa, preferably 1-5 • x10 ² kPa in an inert atmosphere, such as nitrogen and / or hydrocarbon gas.

It was found that an average high molar ratio of YA / polyisobutylene can be achieved while maintaining the minimum amount of oil-insoluble by-product formed if a solvent or mixture of solvents is used, where the fraction of components whose boiling point is less than 250 ^° C is at least 3 wt.%. To reduce the concentration of by-products that are not insoluble in oil, the concentration of comonomer or comonomers in the reaction mixture should be kept at a level of less than 5 wt.% During addition. These conditions are fulfilled if the corresponding rates of addition of MAG, comonomer or comonomers and a radical polymerization initiator decomposing in the temperature range of 80-180 ^° C are maintained. To do this, the radical polymerization initiator, MAG, as well as the comonomer or comonomers are introduced in two or more portions or in a continuous way.

 As the initiator, organic peroxides, hydroperoxides or azo compounds, such as dibenzoyl peroxide, di-tert-butyl peroxide, azobisisobutyrodinitrile, azodicarboxylic acid amide, or a mixture thereof can be used.

 To suppress undesirable side reactions, such as decarboxylation and gum formation, or to control the ratio of the attached MAG and comonomer, compounds such as carboxylic acids with 1-20 carbon atoms, dicarboxylic acids or anhydrides, hydroxycarboxylic acids, ketones, simple and complex can be used esters, alcohols, water or mixtures of these substances and their derivatives. It is advisable to use isobutyl alcohol, isopropyl alcohol, succinic acid monobutyl ether. If necessary, such additives are used in a concentration of 0.01-5 wt.% Of the amount of maleic anhydride. During the decomposition of such compounds or radical polymerization initiators, products of high reactivity can be formed, which can take part in the addition and polymerization reactions taking place in the reaction mixture.

The reaction products are identified by their ¹³ C and ¹ H-NMR spectrum using deuterium-containing chloroform as solvent. It should be noted that under the experimental conditions created by the present invention, the monomers introduced into the reaction mixture are combined mainly by the α-double bond of polyisobutylene. This is confirmed by the disappearance of ¹³ C-peaks at 114.5 and 143.6 ppm, characteristic of the terminal double bonds of polyisobutylene, as well as peaks of the ¹ H-spectrogram at 4.3 ppm and ¹³ C-peaks at 136, 6 frequent ppm for maleic anhydride and peaks characteristic of double bonds of comonomers. Experiments with maleic anhydride enriched in ¹³ C-isotope confirmed the existence of bonds characteristic of the appearance in the comonomer of groups forming chains of the grafted copolymer.

From the colorless to light brown intermediate obtained in accordance with the present invention, the solvent can be removed by distillation of the components with a boiling point below 250 ^° C., and the remaining higher boiling portion can be diluted, if necessary, to 20-60 wt.% Refined oil, preferably refined oil, the viscosity of which at 100 ^o C is 2-15 mm ² / s

 This solution of the intermediate product can be filtered without or with the addition of an auxiliary filter substance or accelerating the filtration of the material in a concentration of 0.5-5 wt.%.

где R обозначает полиизобутиленовую группу (молекулярная масса 800- 30000, предпочтительно 800-15000),
U обозначает по меньшей мере бифункциональную группу, полученную из полиалкиленполиаминов и/или многоатомных спиртов и/или полиалканоламинов или других обычных соединений, включающих основной азотный атом и/или гидроксильную группу,
Y' обозначает группу

или другую бифункциональную группу, полученную из олефина или диолефина или из их смеси, или монофункциональную группу, полученную трансформацией групп, указанных выше,
Z обозначает водород или группу -NH-(CH₂CH₂NH)-H или - OR₁,
R₁ и R₂ каждый обозначает С₁-С₂₀алкильную группу,
а, b, с, d, e и f обозначают целые числа 0-5, предпочтительно 1,
q, m и n обозначают 0, 1 или целое число, превышающее 1, при условии, что сумма m и n представляет собой целое число более 1, доля молекул в продукте, включающих группы (II.b) и/или (II.с), превышает 25 вес.% и соединения структурных формул (II.a), (II.b) и (II.с) могут быть связаны между собой в необязательной последовательности.In the second, so-called acylation step, the intermediate product obtained in accordance with the present invention is reacted with polyamines, polyhydric alcohols, alkanolamines containing at least two reactive groups, and / or mixtures thereof, and / or with their derivatives in the presence of hydrocarbon and / or refined oil as a solvent at 120-235 ^o C in an inert atmosphere, for example, in an atmosphere of gaseous nitrogen, at a pressure of 0.05-6 • 10 ² kPa, in the presence of a catalyst in a concentration of 0.01-2 weight .%. In this case, a mixture of an additive based on polysuccinimide and / or polyamide and / or polyester and / or polyether amide (such as polysuccinimide of general formula II) is obtained, where, depending on the reagents used and the molar ratios, one or more components can be obtained with markedly different molecular weights:

where R is a polyisobutylene group (molecular weight 800-30000, preferably 800-15000),
U denotes at least a bifunctional group derived from polyalkylene polyamines and / or polyols and / or polyalkanolamines or other conventional compounds comprising a basic nitrogen atom and / or a hydroxyl group,
Y 'represents a group

or another bifunctional group derived from an olefin or diolefin or a mixture thereof, or a monofunctional group obtained by transformation of the groups indicated above,
Z is hydrogen or a group —NH— (CH ₂ CH ₂ NH) —H or —OR ₁ ,
R ₁ and R ₂ each represents a C ₁ -C ₂₀ alkyl group,
a, b, c, d, e and f are integers 0-5, preferably 1,
q, m and n denote 0, 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 in the product, including groups (II.b) and / or (II.c ), exceeds 25 wt.% and compounds of structural formulas (II.a), (II.b) and (II.c) can be interconnected in an optional sequence.

 An important feature of the additive obtained in accordance with the present invention, due to the new structure of the intermediate product. It is assumed that in this intermediate product, reactive AA and other groups are located near the end of a long polyolefin chain. Thus, the growth of a macromolecule due to multiple or chain-type combination is not sterically difficult, as in the case of other intermediate products in which JA residues are randomly placed either at the end or between polyolefin chains.

 As the polyfunctional polyamine component, for example, ethylene diamine, diethylene triamine, triethylenetetramine, tetraethylene pentamine, pentaethylene hexamine, cyclic polyamine, in particular piperazine, diethyleneaminopiperazine or mixtures thereof, can be used; as the polyhydric alcohol, for example, ethylene glycol, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane or pentaerythritol can be used; as the amino alcohol, for example, ethanolamine, diethanolamine, triethanolamine or mixtures and derivatives thereof can be used.

 Since in the additive the molar fraction of various polymers of different molecular weights can be varied over a wide range, the need for various engine oils can easily be satisfied by a slight modification of the preparation procedure. In accordance with the experience of the inventors, those additive compositions were particularly successful in which the weight percentage ratio between components with higher and lower molecular weights was 0.01-5.

 The average molecular weight of the lower molecular weight polymer is on average less than six times the number average molecular weight of the polyolefin used as starting material. The experimental acylation conditions should be chosen in such a way as to accelerate the formation of multiple bonds during the conduct of condensation reactions with the formation of amide, imide, and ester, i.e. so that the final compounds are characterized by a polyamide, polyimide and polyester structure, or a combination thereof. This can be achieved by maintaining a molar ratio between succinic anhydride residues in the intermediate and the acylated component in the range of 0.7-5.5: 1, preferably in the range of 1.7-4.5: 1.

 To ensure the desired level of conversion, the acylation process is carried out for 2-15 hours and, if necessary, conventional acidic or basic catalysts are used at a concentration in the range of 0.1-2 wt.%.

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

< 3500) алкениловых эфиров янтарной кислоты (патент Венгрии 205778).When producing a polyester, which is one of the possible variants of acylation products, it is especially advisable to use petroleum sulfonic acid, which until now was supposed to be used only as a catalyst in the production of low molecular weight (

<3500) alkenyl esters of succinic acid (Hungarian patent 205778).

If necessary, after the acylation reaction, unreacted acid can be removed. In order to enhance other preferred side effects, such as anti-corrosive or anti-wear effect, antioxidant effect, as the final step, the 5th step of structural modification can be carried out. For this purpose, the modifying compound is added in a concentration of 0.1-8 weight. % in terms of the reaction mixture, which is then stirred for 0.5-10 hours at a temperature of 80-230 ^o C in an inert atmosphere.

 Conventional modifying reagents, such as sulfur, active sulfur-containing compounds, phosphorus pentasulfide, boric acid and its derivatives, zinc-containing compounds such as zinc dialkyldithiophosphate, copper compounds, including organic copper salts or complexes, molybdenum dioxide, organic acids, for example, can be used for the modification. , fatty acids, glycolic acids, malic acid, fumaric acid, amides, alkenyl succinimide, mixtures thereof or their derivatives.

After completion of the acylation reactions and optionally modifications, volatile components can be distilled off from the reaction mixture in vacuo at 160-210 ^° C, after which the reaction product is diluted with refined oil and, if necessary, can be filtered without or using filter aid.

 Different components of the final product of different average molecular weights show characteristic differences, with additives containing lower molecular weight components at a higher concentration, have a higher ability to neutralize acids and sediment flushing effect, while products containing higher concentration of higher molecular weight components, have a noticeable ability stabilize dispersions, increase viscosity and viscosity index, as well as a more pronounced antiwear effect.

где

обозначает среднечисленную молекулярную массу,
n₁ обозначает мольное число i-той полимерной молекулы,
M_i обозначает молекулярную массу i-той полимерной молекулы,
i обозначает целое положительное число 1, 2,...The components of the products presented in this description are characterized by their number average molecular weight, which is calculated as follows:

Where

denotes number average molecular weight,
n ₁ denotes the molar number of the i-th polymer molecule,
M _i denotes the molecular weight of the i-th polymer molecule,
i denotes a positive integer 1, 2, ...

где

обозначает средневесовую молекулярную массу, а другие символы имеют значения, указанные выше.The degree of polydispersity, which characterizes the molecular weight distribution, is the ratio between the weight average and number average molecular weights. The weight average molecular weight is calculated by the following equation:

Where

denotes weight average molecular weight, and other symbols have the meanings indicated above.

Расширение молекулярно-массового распределения (Δα) определяют по уравнению:

где α_ПИБ обозначает полидисперсность исходного полиизобутилена и
α обозначает полидисперсность реакционного продукта.Polydispersity is calculated by the following equation:

The expansion of the molecular weight distribution (Δα) is determined by the equation:

where α _PIB denotes the polydispersity of the starting polyisobutylene and
α denotes the polydispersity of the reaction product.

 The invention is illustrated below in non-limiting examples.

2250) и 1450 г ксилола, смесь нагревают до 76±4^oC в инертной атмосфере и при перемешивании добавляют 98,6 г (1 моль) малеинового ангидрида и со скоростью 0,7 г/ч добавляют 2,8 г дибензоилпероксида и в общей сложности 28 г изобутилена в виде четырех порций по 7 г в каждой. После завершения добавления реакционную смесь перемешивают в вышеуказанных условиях в течение часа. Ксилол и другие непрореагировавшие легколетучие компоненты можно удалять перегонкой, проводимой при 140^oC и давлении 15 кПа в течение 1,5 ч. К промежуточному продукту добавляют 1200 г рафинированного смазочного масла (вязкостью 3,5 мм²/с при 100^oC, с индексом вязкости 95, температурой застывания -22^oC). После гомогенизации при 135-150^oC и осветления смесь фильтруют в присутствии 3,5 вес.% вспомогательного фильтровального вещества. Кислотное число желто-коричневого вязкого маслянистого промежуточного продукта составляет 43,0 мг КОН/г, содержание в нем малеинового ангидрида равно 1,5 мг/г, а среднее число остатков янтарного 40 ангидрида на одну ПИБ-молекулу равно 1,7. Соотношение ЯА/ПИБ при сукцинировании рассчитывают по следующему уравнению:

где CC обозначает соотношение сукцинирования ЯА/ПИБ,
E обозначает кислотное число промежуточного продукта (мг КОН/г),

обозначает среднечисленную молекулярную массу ПИБ.Example "A"
1125 g (0.5 moles) of polyisobutylene are charged into a 3-liter, pressurized stirred reactor equipped with a thermometer, an inert gas supply device and a refrigerator at the top that communicates with the condensate collection vessel.

2250) and 1450 g of xylene, the mixture is heated to 76 ± 4 ^o C in an inert atmosphere and 98.6 g (1 mol) of maleic anhydride are added with stirring and 2.8 g of dibenzoyl peroxide are added at a rate of 0.7 g / h and in total complexity 28 g of isobutylene in four portions of 7 g each. After complete addition, the reaction mixture is stirred under the above conditions for one hour. Xylene and other unreacted volatile components can be removed by distillation carried out at 140 ^° C and a pressure of 15 kPa for 1.5 hours. 1200 g of refined lubricating oil (viscosity 3.5 mm ² / s at 100 ^° C, s) are added to the intermediate product. viscosity index 95, pour point -22 ^o C). After homogenization at 135-150 ^o C and clarification, the mixture is filtered in the presence of 3.5 wt.% Filter aid. The acid value of the tan viscous oily intermediate is 43.0 mg KOH / g, the content of maleic anhydride is 1.5 mg / g and the average number of residues of succinic 40 anhydride per PIB molecule is 1.7. The ratio of YA / PIB during succination is calculated by the following equation:

where CC denotes the ratio of succination of AA / PIB,
E is the acid number of the intermediate (mg KOH / g),

denotes the number average molecular weight of PIB.

= 2250, 950 г базового масла SAE-30 (вязкостью 9,5 мм²/с при 100^oC) и 110 г растворителя фирмы MOL с высоким содержанием ароматических продуктов (поставляется на рынок под товарным знаком AROMATOL) и смешивают. Эту смесь перемешивают под атмосферным давлением в инертной атмосфере при 135±6^oC и в нее в течение 4 ч в виде 8 равных порций добавляют 118,3 г МАГ, 76 г октилметакрилата и 9,6 г ди-трет-бутилпероксида. Затем реакционную смесь дополнительно перемешивают в течение 6 ч и кипячением при 155^oC и давлении 12 кПа удаляют AROMATOL и другие легкокипящие компоненты. К промежуточному продукту при 120^oC добавляют 250 г рафинированного масла SN-150/A (фирма MOL). Полученный таким образом промежуточный продукт вначале осветляют фильтрованием с 2 вес.% вспомогательного фильтровального вещества и затем в присутствии 1 вес.% ускоряющего фильтрацию материала его фильтруют при 110^oC. Кислотное число разбавленного и отфильтрованного промежуточного продукта составляет 5 39,7 мг КОН/г, содержание в нем малеинового ангидрида равно 2,8 мг/г, и он включает в среднем по 1,6 остатка янтарного ангидрида на каждую ПИБ - молекулу. Увеличение средней молекулярной массы составляет менее 60 процентов, а доля соединений, включающих более одного остатка янтарного ангидрида на молекулу, превышает 55 процентов.Example "B"
1125 g (0.5 mol) of a number average molecular weight polyisobutylene are loaded into the reaction vessel described in Example A;

= 2250, 950 g of base oil SAE-30 (viscosity 9.5 mm ² / s at 100 ^° C) and 110 g of MOL solvent with a high content of aromatic products (marketed under the trademark AROMATOL) and mixed. This mixture is stirred under atmospheric pressure in an inert atmosphere at 135 ± 6 ^° C and 118.3 g of MAG, 76 g of octyl methacrylate and 9.6 g of di-tert-butyl peroxide are added in 8 equal portions over 4 hours. Then the reaction mixture was further stirred for 6 hours and AROMATOL and other low boiling components were removed by boiling at 155 ^° C and a pressure of 12 kPa. To the intermediate product at 120 ^o C add 250 g of refined oil SN-150 / A (company MOL). The intermediate product thus obtained is first clarified by filtration with 2% by weight of filter aid and then, in the presence of 1% by weight of a filter aid, it is filtered at 110 ^° C. The acid number of the diluted and filtered intermediate is 5 39.7 mg KOH / g , the content of maleic anhydride in it is equal to 2.8 mg / g, and it includes on average 1.6 residues of succinic anhydride for each PIB molecule. The increase in the average molecular weight is less than 60 percent, and the proportion of compounds comprising more than one residue of succinic anhydride per molecule exceeds 55 percent.

= 8000) и 500 г ксилола. Затем эту смесь нагревают до 115^oC и в течение 3 ч в виде шести равных порций добавляют 59,2 г (0,6 моля) малеинового ангидрида, 12,0 г азобисизобутиронитрила и 24,0 г стирола. После этих стадий добавления реакционную смесь нагревают до 180^oC и дополнительно перемешивают в течение 6 ч. Непрореагировавший малеиновый ангидрид удаляют при 195^oC и давлении 10 кПа, после чего продукт смешивают с 1150 г рафинированного смазочного масла, упомянутого в примере "А", и образовавшуюся смесь фильтруют в присутствии 3 вес.% вспомогательного фильтровального вещества. Кислотное число отфильтрованного и разбавленного промежуточного продукта составляет 23,9 мг КОН/г, содержание в нем малеинового ангидрида равно 1,3 мг/г, и он включает в среднем по 3,3 остатка янтарного ангидрида на каждую ПИБ-молекулу. Увеличение среднечисленной молекулярной массы и расширение молекулярно-массового распределения составляют менее 20 процентов, а доля соединений, включающих более одного ЯА-остатка на молекулу, равна 42 вес.%.Example "B"
In a reaction vessel described in Example A, 1200 g (0.15 mol) of polyisobutylene (

= 8000) and 500 g of xylene. This mixture is then heated to 115 ^° C. and 59.2 g (0.6 mol) of maleic anhydride, 12.0 g of azobisisobutyronitrile and 24.0 g of styrene are added in six equal portions over 3 hours. After these addition steps, the reaction mixture is heated to 180 ^° C. and further stirred for 6 hours. Unreacted maleic anhydride is removed at 195 ^° C. and a pressure of 10 kPa, after which the product is mixed with 1150 g of the refined lubricating oil mentioned in Example “A”, and the resulting mixture is filtered in the presence of 3 wt.% filter aid. The acid number of the filtered and diluted intermediate is 23.9 mg KOH / g, the content of maleic anhydride is 1.3 mg / g, and it includes an average of 3.3 residues of succinic anhydride per PIB molecule. The increase in number average molecular weight and the expansion of the molecular weight distribution are less than 20 percent, and the proportion of compounds comprising more than one JA residue per molecule is 42 wt.%.

Example "G"
1200 g (0.5 mol) of polypropylene and a mixture of base oil SN-150 / A (a commercial product of MOL) and kerosene in a weight ratio of 9: 1 are loaded into the reaction vessel described in Example “A”. 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 hours, the temperature is raised to 160 ^° C. and the following components are added to the mixture: 33 g of isobutylene, as an initiator, 11.4 g of di-tert.-butylper oxide, for 2 hours, 2 equal parts per hour of 43.3 g of maleic anhydride, 6.5 g of succinic acid monobutyl ester, 33 g of styrene and for 6 hours in the form of 5 equal portions of 88.7 g of maleic anhydride.

Unreacted low boiling components are removed at 200 ^o C and a pressure of 10 kPa for one and a half hours. Then the product is diluted with 1060 g of the base oil mentioned in Example B, and the resulting mixture is filtered in the presence of 4 wt.% Filter aid; the acid number of the filtered and diluted intermediate is 60.1 mg KOH / g, the content of maleic anhydride in it is 2.1 mg / g, the average succination ratio of YA: PIB is 2.4, the proportion of components comprising more than one YA-residue per molecule, is 64 percent, the increase in average molecular weight is less than 60 percent, and the expansion of the molecular weight distribution according to measurements is 68 percent.

= 15000), 600 г ксилола, 0,4 г гидропероксида кумола и смесь фумаровой кислоты и малеинового ангидрида в весовом соотношении 1:1. Смесь перемешивают и нагревают до 180±5^oC в инертной атмосфере под давлением 6 бар в течение 2,5 ч. Затем реакционную смесь охлаждают до 150±4^oC и при перемешивании в виде 6 равных порций в течение 6 ч добавляют 9 г акриловой кислоты и 1,8 г ди- трет.-бутилпероксида, а также 12,8 г вышеуказанной кислотной смеси таким образом, что перед каждой стадией добавления акриловой кислоты в смесь добавляют также 0,5 г изобутилового спирта. После перегонки, проводимой в течение двух часов при 165^oC под давлением 15 кПа, добавляют 1000 г масла, указанного в примере "А", 2% вспомогательного фильтровального вещества и 2% ускоряющего фильтрацию материала и фильтруют. Кислотное число отфильтрованного и разбавленного промежуточного продукта составляет 9,3 мг КОН/г, содержание в нем малеинового ангидрида равно 1,7 процента, средняя величина соотношения дикарбоновая кислота/полиизобутилен равна 2,3, доля компонентов, включающих более одного остатка, полученного из дикарбоновой кислоты, составляет 47 процентов, увеличение средней молекулярной массы и расширение молекулярно-массового распределения составляет менее 10 процентов.Example "D"
In the reaction vessel described in example "A", load 0.08 mol of polyisobutylene (

= 15000), 600 g of xylene, 0.4 g of cumene hydroperoxide and a mixture of fumaric acid and maleic anhydride in a weight ratio of 1: 1. The mixture is stirred and heated to 180 ± 5 ^° C in an inert atmosphere under a pressure of 6 bar for 2.5 hours. Then the reaction mixture is cooled to 150 ± 4 ^° C and 9 g of acrylic are added in 6 equal portions over 6 hours. acid and 1.8 g of di-tert-butyl peroxide, as well as 12.8 g of the above acid mixture, such that 0.5 g of isobutyl alcohol is also added to the mixture before each step of adding acrylic acid. After distillation, which was carried out for two hours at 165 ^° C. under a pressure of 15 kPa, 1000 g of the oil specified in Example “A”, 2% of filter aid and 2% of filtering accelerating material were added and filtered. The acid number of the filtered and diluted intermediate is 9.3 mg KOH / g, the content of maleic anhydride is 1.7 percent, the average dicarboxylic acid / polyisobutylene ratio is 2.3, and the proportion of components comprising more than one residue obtained from dicarboxylic acid, is 47 percent, the increase in average molecular weight and the expansion of molecular weight distribution is less than 10 percent.

= 2250) и 43,3 г (0,5 моля) малеинового ангидрида, после чего реакционную смесь нагревают до 140±5^oC и перемешивают в течение 1 ч. Непрореагировавшие легкокипящие компоненты смеси удаляют кипячением при 175^oC и давлении 15 кПа в течение 1,5 ч. Затем полученный таким образом продукт разбавляют 1200 г базового масла, указанного в примере "Б", и отфильтровывают в присутствии 2 вес.% ускоряющего фильтрацию материала. Число омыления отфильтрованного и разбавленного промежуточного продукта составляет 78,8 мг КОН/г, содержание в нем малеинового ангидрида равно 1,9 мг КОН/г, средняя величина соотношения сукцинирования ЯА/ПИБ равна 3,1, увеличение средней молекулярной массы составляет менее 30 процентов, расширение молекулярно-массового распределения составляет 40 процентов, доля компонентов, включающих более одного остатка янтарного ангидрида на молекулу равна 65 процентам.Example "E"
In a reaction vessel described in Example A, 500 g of xylene saturated with water and 28.5 g of isobutylene are charged and the mixture is heated at 130 ± 5 ^° C for 2 hours with stirring, 73.95 g (0.75 g) are added. mole) of maleic anhydride and under continuous supply of 14 g of di-tert.-butyl peroxide as an initiator at 130 ^° C, then 3 g of succinic acid monobutyl ester are added dropwise to this reaction mixture over half an hour, and after approximately 0.25 h, 98.6 g of maleic anhydride, 60 g of styrene and 27 g of di-tert.-butyl peroxide are added as an initiate ora, and this last - in the form of 6 equal portions. Before adding the last two servings of initiator, 0.5 mol of polyisobutylene (

= 2250) and 43.3 g (0.5 mol) of maleic anhydride, after which the reaction mixture is heated to 140 ± 5 ^o C and stirred for 1 h. Unreacted low-boiling components of the mixture are removed by boiling at 175 ^o C and a pressure of 15 kPa in within 1.5 hours. Then, the product thus obtained is diluted with 1200 g of the base oil indicated in Example B and filtered off in the presence of 2 wt.% filtering accelerating material. The saponification number of the filtered and diluted intermediate is 78.8 mg KOH / g, the content of maleic anhydride in it is 1.9 mg KOH / g, the average succination ratio YA / PIB is 3.1, and the average molecular weight is less than 30 percent , the expansion of the molecular weight distribution is 40 percent, the proportion of components comprising more than one residue of succinic anhydride per molecule is 65 percent.

Example "F"
In the reaction vessel described in Example A, 800 g of SN 150 / A base oil and 200 g of xylene saturated with water were charged. 10 g of “C ₄ fractions” (product of naphtha pyrolysis, a commercial product of TVK) are bubbled through this mixture and with stirring the mixture is heated for 2 hours to 90 ± 3 ^° C at a rate of 50 ^° C / h, 3 are added in equal portions 49 3 g (0.5 mol) of maleic anhydride and 12 g of dibenzoyl peroxide, then the temperature of the reaction mixture is raised to 140 ± 5 ^° C. and 70 g of styrene, 147.9 g (15 mol) of maleic anhydride and 14 are continuously added. g di-tert.-butyl peroxide. 1125 g (0.5 mol) of polyisobutylene are added to the oily xylene solution of the low molecular weight copolymer, then the reaction mixture is heated to 140 ± 5 ^° C and 10 g of diethyl-butyl peroxide are added with continuous stirring over 1 hour, after which the mixture is further stirred within 1.5 hours. Unreacted lighter components of the mixture are removed by boiling in the same manner as in Example “A”, and the obtained intermediate product, diluted further with 300 g of SN-150 / A oil, is suitable for subsequent use without filtering and further processing. Its acid number is 72.4 mg KOH / g, the content of maleic anhydride is 1.8%, the average succination ratio of YA / PIB is 3.3, the average molecular weight is less than 35 percent, the molecular weight distribution is 45 percent , and the proportion of components comprising more than one succinic anhydride residue per molecule is 73 percent.

Example "3" (comparative)
1125 g (0.5 mol) of polyisobutylene and 500 g of xylene are charged into the reaction vessel described in Example “A”. The mixture is heated to 135 ± 5 ^° C. and in an inert atmosphere, 111.0 g (1.1 mol) of maleic anhydride are added in equal portions with 5 equal portions and 9 g of di-tert are added in 7 equal portions. β-butyl peroxide as an initiator. Lighter boiling components of the mixture are removed analogously to example “A”, and the resulting intermediate product is diluted with 1300 g of the oil specified in example “B”, its acid number after clarification and filtration is 31.6 mg KOH / g, the content of free maleic anhydride in it is 3.2 mg / g, an increase in the average molecular weight is less than 15 percent, the expansion of the molecular weight distribution is 45 percent, the depletion of the molar ratio of YA / PIB is 1.3, the proportion of components comprising more than one amber residue per one molecule per molecule, equal to 35 percent.

Example "And"
950 g (1 mol) of polyisobutylene are charged into the reaction vessel described in make-up room "A" and 270 g of a mixture of isobutylene with styrene (in a weight ratio of 4: 5) are added over an inert atmosphere at 180 ± 10 ^° C over 5 5 parts in equal portions of 246.5 g (2.5 mol) of maleic anhydride and for 7 hours 28 g of di-tert.-butyl peroxide. After the first hour of the reaction, but before the total amount of maleic anhydride has been added, 1 g of isopropyl alcohol is added dropwise to the reaction mixture. Lighter boiling unreacted components of the mixture are removed as described in example "B", and the resulting intermediate product is diluted with 1300 g of the base oil specified in example "B". Its acid number after clarification and filtration, also in accordance with Example B, is 87.6 mg KOH / g, the content of free maleic anhydride in it is 3.0 mg / g, the average succination ratio of YA / PIB is 1.5, the increase in its average molecular weight is 60 percent, the expansion of the molecular weight distribution is less than 68 percent, the proportion of components including more than one succinic anhydride residue per molecule is 47 percent.

Example "K" (comparative)
1300 g (1 mol) of polyisobutylene and 350 g of xylene are charged into the reaction vessel described in Example “A”. While stirring the mixture in an inert atmosphere under atmospheric pressure, it is heated to 145 ^° C. and 197.2 g (2 moles) of maleic anhydride are added over 6 hours, as well as 11.9 g of cumene hydroperoxide and 6.8 g, respectively, in 4 and 7 portions. di-tert.-butyl peroxide. Unreacted lighter boiling components of the mixture are removed by boiling for 1 h at 150 ^o C under a pressure of 15 kPa. The mixture of the intermediate product thus obtained was further diluted with 1150 g of the oil indicated in Example “A” and filtered in the presence of 3% by weight of a filter aid. The saponification number of the filtered and diluted intermediate is 70.3 mg KOH / g, the content of maleic anhydride is 2.5 mg / g, and the average number of succinic anhydride residues associated with one PIB molecule is 1.6. The proportion of components comprising more than 3 residues of succinic anhydride per molecule is 34 percent, the increase in average molecular weight is 550 percent, the expansion of the molecular weight distribution relative to the polyisobutylene used as starting material is 85 percent.

Example "1"
In a stirred reactor equipped with a reagent loading device, a condenser, a sampling device, a nitrogen removal tube, a thermometer and a manometer, 783.3 g of the acylating agent described in Example A are charged at 65 ^° C, and 14 , 2 g of tetraethylene pentamine, as well as 0.1 weight. % triethanolamine as a catalyst. Then, the reaction mixture is heated to 175-180 ^° C with stirring in an inert atmosphere, after which an acylation reaction is carried out under these conditions for 5 hours. After that, 3.1 g of diethylenetriamine was added to the reaction mixture, and at 190 ^° C and a pressure of 50, 30 and 10 kPa, the mixture was stirred for 1 hour. The nitrogen content in the final product was 0.8 percent, the ratio between high and low molecular weight polymers equal to 0.6.

Example "2"
84.7 g of the acylating agent specified in Example B, 5 g of triethylenetetramine and 22.4 g of triethanolamine are charged to a stirred reactor described in Example 1 at 60 ^° C. Then, with stirring in an inert atmosphere, the reaction mixture is heated to 175-180 ^o C and for 6 hours under such conditions, an acylation reaction is carried out. Over the past four hours, the acylation reaction for 3 hours creates a pressure of 300 kPa, after which over the next hour - 10 kPa. After filtration in the presence of 1 wt.% Filter aid, the nitrogen content in the resulting product is 0.40 wt. %, and the ratio between high and low molecular weight polymers is 0.5.

Example "3"
In the stirred reactor described in Example 1, 938.9 g of the intermediate from Example B were charged at room temperature, and then 10.3 g of diethylene triamine were added thereto at 140 ^° C. The acylation reaction is carried out with stirring in an inert atmosphere under a pressure of 50 kPa for 4 hours, while increasing the temperature to 190 ^o C at a rate of 20 ^o C / h After filtering at 120 ^o C in the presence of 1 wt.% Filter aid, the nitrogen content in the resulting product is 0.4 wt.%, And the ratio between high and low molecular weight polymers is 2.3.

Example "4"
In a stirred reactor described in Example 1, two portions at room temperature and 130 ^° C. were charged with 746.8 g of the intermediate from Example G, 0.2 wt.% Malic acid as a catalyst, and 12.3 g glycerol, after which in an inert atmosphere at 210 ^o C and a pressure of 400 kPa for 4 hours and at 10 kPa for 3.5 hours, acylation is carried out. Then the reaction mixture was cooled to 120 ^° C and 3.1 g of diethylene triamine was added thereto, followed by stirring at 155 ^° C and a pressure of 65 kPa for 1 h, and then at 185 ^° C and a pressure of 10 kPa for 2 h. After filtration in the presence of 1 weight. % of the auxiliary filter substance, the nitrogen content in the resulting product is 0.11 wt.%, and the ratio between the high and low molecular weight components is 0.2.

Example "D"
844.5 g of the intermediate from Example D are charged into the stirred reactor described in Example 1. While stirring in an inert atmosphere at room temperature, 1.24 g of diethylene triamine are added, then 2.27 g of tetraethylene pentamine are added at 70 ^° C. and the reaction is carried out for 2 hours at 130 ^° C. An additional 0.6 is added dropwise to the reaction mixture. g of diethylene triamine and 1.1 g of tetraethylene pentamine. The reaction is carried out at atmospheric pressure for 4 hours at 190 ^° C. and then at 120 ^° C. the mixture is filtered in the presence of 1 weight. % filter aid. The nitrogen content in the resulting product is 0.2 wt.%, And the ratio between the high and low molecular weight components is 0.1.

Example "6"
In the stirred reactor described in Example 1, 711.9 of the intermediate from Example E were charged and, in the presence of 0.2 wt.% Petroleum sulfonic acid, 6.0 were added as a catalyst to this mixture at room temperature and atmospheric pressure. g of ethylenediamine. Then the temperature is increased to 190 ^° C. and the pressure is increased to 15 · 10 ² kPa and the acylation reaction is carried out for 6 hours. 11.3 g of tetraethylene pentamine are added to the reaction mixture and at 215 ^° C. and a pressure of 10 ³ kPa, the reagents are stirred including after filtering at 120 ^o C in the presence of 1 wt.% filter aid, the nitrogen content in the resulting product is 0.9 wt. %, and the ratio between the high and low molecular weight components is 1.25.

Example "7"
In the stirred reactor described in Example 1, 774.9 g of the acylating agent used in Example G were charged. In an inert atmosphere at atmospheric pressure, 8.76 g of triethylenetetramine is charged and 9.49 g of diethanolamine are added with continuous stirring. After completion of the acylation reaction carried out at 175 ^° C. and under a pressure of 50 kPa for 4 hours, 25 g of a monosuccinimide derivative (KOMAD-303, MOL) are added dropwise at 120 ^° C. over 10 minutes. The reaction is carried out for 3 hours at 170 ^o C and 2 • 10 ² kPa, and over the next 1.5 hours at a pressure of 15 kPa. The nitrogen content in the resulting product is 0.54 wt.%, And the ratio between the high and low molecular weight polymers is 0.7.

Example "8" (comparative)
To the stirred reactor described in Example 1, 711.3 g of the intermediate obtained in accordance with Example 3 are charged, and then 10.3 g of diethylene triamine are added at room temperature under nitrogen and 37 are added at 120 ^° C. , 8 g of tetraethylene pentamine and an acylation reaction is carried out for 2 hours at 250 ^° C., after which 13.6 g of pentaerythritol and 2.4 g of petroleum sulfonic acid are added as a catalyst. After the last 3 hours of the reaction under a pressure of 15 kPa, the product is filtered off in the presence of 3 weight. % filter aid. Hard-to-filter product is only partially soluble in base oil due to its 2.2% nitrogen content.

Example "9"
In a stirred reactor described in Example 1, in an inert atmosphere at atmospheric pressure, 768.5 g of the acylating agent used in Example I were charged. With continuous stirring at 80 ^° C., first, during the course of 0.5 hours, at a heating rate of 80 ^° C./h, 21.2 g of diethylene glycol are added, and then 18.9 g of tetraethylene pentamine are added dropwise to the reaction mixture and at 180 ^° for 6 hours C at atmospheric pressure, an acylation reaction is carried out. The nitrogen content in the filtered final product is 0.82 wt.%, And the ratio between the high and low molecular weight components is 0.4.

 To simplify the work with all final products and compare them before subsequent use, the oil content in them was brought up to 50%. If the oil content in the final products obtained in the various examples turned out to be less than 50 percent, it was brought to this value by dilution with the oil component used in the synthesis. For dilution, refined lubricating oils as indicated in Examples A and B were used.

 A comparison of the characteristics of the intermediate products obtained in Examples A, G, and I made it possible to establish that under the conditions created by the practice of the present invention, the interaction between comonomer (s), polyolefin and MAG leads to the binding of copolymer chains, including an average of 1.6-6, preferably 1.8-4, of succinic anhydride per polyolefin molecule.

 The effectiveness of the detergent-dispersant action of the additives indicated in the above examples was evaluated in accordance with the method described by L. Bartha et al.: Method of detemunation of optimum composition of detergent-dispersant engine oil additives, Hung. J. Ind. Chem., 1979, 7, 359-366. The potential parameters of the washing-dispersing action (PMDD) are presented in percent as the 225th part of the sum of the dispersion-stabilizing action of the additive (detergent index DI,%) and its washing action (M, mm). The effect of reducing the amount of deposits was evaluated by identical methods described in the above publication, based on the results obtained by the so-called bench coking method. In addition to the above characteristics, the dispersing effect of the additive was also evaluated by the so-called dispersion test method of the applied sample. In accordance with this method, the oil mixture, including the test additive or additives, is mixed in a high-speed mixer with 2 percent specialty carbon black and the resulting suspension is treated using six different methods (keeping it at different temperatures in the presence or absence of water). Samples of these six suspensions are applied dropwise to filter paper, and after 48 hours the ratio between the diameters of the soot from gas soot and oil is determined. The theoretical sum of the six results is 600 percent, and the stronger the dispersing effect, the higher this value.

 The washing-dispersing effect of the products prepared in examples 1-9 was evaluated on lubricating oils; the results are presented in table. 1 (see the end of the description).

During such studies, products prepared in accordance with the above examples were mixed in a 3 percent concentration with a base oil, which was characterized by the following parameters:
Kinematic viscosity (100 ^o C): - 5.2 mm ² / s;
Viscosity Index, IV _E : - 101.

 The results of the study of the washing-dispersing effect of oil compositions prepared using the products obtained in examples 1, 2, 3, 7 and 8, as well as the products of comparative experiments are shown in tables 2 and 3, while the results of evaluating the improvement of viscosity and VI are presented in table .4 (see end of description).

 Compatibility with sealing materials was investigated in accordance with the Volkswagen test VW-3344, the results of which are presented in table. 5 (see the end of the description).

 Dispersants were investigated in the oil compositions shown in table 3.

 The structure and properties of the intermediate products prepared in accordance with examples "A" - "G" and "I", and the final products synthesized from them in accordance with examples 1-7 and 9, turned out to be similar to other products prepared in accordance with the present invention, which were also obtained in the preferred experimental conditions and in compliance with combinations of parameters of the present invention. The structure and properties of the intermediate products and final products in accordance with examples "Z" and "K", as well as 8 and the processes for their preparation in a certain way are different from the preferred structures and methods of the present invention.

 The results related to the study of detergent-dispersant properties, the ability to modify the viscosity and compatibility with the seals of the final products prepared in accordance with the invention under preferred acylation conditions and modifications from intermediate products of the preferred structure and composition obtained in accordance with the recommended conditions of the invention are presented in tables 1-5; they show that, in terms of effectiveness, these products are either identical or superior to reference additives, i.e. their detergent-dispersant effect both in the base oil itself and in the oil compositions is indeed more effective. In their ability to improve the viscosity index and in their compatibility with sealing materials, they significantly exceed commercially available reference additives. The use of additives prepared in accordance with the present invention, can further improve the properties of lubricants or fuels.

 Due to the less noticeable effect of increasing viscosity in the cold, their acceptable concentration can be further increased, especially in the case of motor oils. Their ability to preferably improve viscosity and viscosity index makes it possible to more widely replace them with traditional high molecular weight polymers. The possibility of using in a higher concentration of additives prepared in accordance with the present invention on the basis of low molecular weight polyolefins, especially polyisobutylene, so far used in the production of ashless dispersants, opens up the possibility for more economical preparation of lubricants.

Claims (9)

 1. Detergent-dispersant additive for lubricating oils for internal combustion engines based on an imide, and / or ester, and / or ester derivative product of the interaction of polyisobutylene and maleic acid and / or its anhydride, characterized in that they use a number-average molecular weight polyisobutylene. 800-30000, preferably 800-15000, which is introduced into grafted copolymerization or into a reaction with a copolymer comprising succinic anhydride units and obtained from a reactive low molecular weight comonomer of mol.m less than 500, including a double bond, or from a mixture of such comonomers and from maleic acid and / or its anhydride, using a molar ratio of maleic anhydride: comonomer: polyisobutylene 1,2-5, 5: 0, 1-3, 5: 1, and the interaction product contains an average of 1.6-6.0 units of succinic anhydride derivative per polyisobutylene chain, and the concentration of molecules comprising more than one unit of succinic anhydride derivative exceeds 25 wt.%, the molecular weight distribution is less than 70% relative to the original polyis butylene, and the ratio between compounds containing succinic anhydride groups and compounds comprising at least bifunctional amino and / or hydroxyl groups is 0.7-5.5.  2. The additive according to claim 1, characterized in that the component of the copolymer grafted onto the polyisobutylene chain is a derivative of succinic anhydride.  3. The additive according to claim 1, characterized in that the component of the copolymer grafted onto the polyisobutylene chain includes an average of 1.8-4.0 units of succinic anhydride derivative.  4. The additive according to claim 1, characterized in that the copolymer grafted onto the polyisobutylene chain includes identical or different units of succinic anhydride derivatives, preferably imide, amide, ester, ester, and / or mixtures thereof.  5. The additive according to claim 1, characterized in that in the copolymer grafted onto the polyisobutylene chain, the concentration of molecules comprising more than one derivative of succinic anhydride exceeds 25%.  6. The additive according to claim 1, characterized in that the average number of molecules of the components of different average molecular weight associated due to the reaction of carboxyl groups is 2-100. 7. A method of obtaining a detergent-dispersant additive for lubricating oils for internal combustion engines, characterized in that the polyisobutylene medium mol.m. 800-30000, maleic anhydride and a double bond comonomer or their copolymers are inoculated with the addition reaction using the molar ratio maleic anhydride: comonomer: polyisobutylene 1.2-5, 5: 0, 1-3, 5: 1 in the presence of a solvent, where the concentration of solvent , ensuring the formation of a homogeneous phase, is 10-75 wt.%, preferably 30-60 wt.% in terms of the reaction mixture carried out in the presence of a radical polymerization initiator in an amount of 5-25 wt.% and a component that regulates the ratio of the introduced monomers, in quantity 0.01-5 wt.% in terms of maleic anhydride, under a pressure of 1-15 • 10 ² kPa and preferably in a nitrogen and / or hydrocarbon atmosphere at 80-180 ^o C for 1-16 hours while maintaining the concentration of maleic anhydride and comonomer at a level below 5 wt.%, while the resulting intermediate product is separated from the solvent, if necessary, diluted with refined base oil and, if necessary, clarified and filtered in the presence of an auxiliary filter substance and subjected to interaction with compounds including and one or more at least bifunctional amino and / or hydroxyl groups, the ratio between the compounds bearing the residues of succinic anhydride and the compounds with amino and / or hydroxyl groups being 0.7-5.5, which is carried out in the presence of catalyst in an amount of 0.1-2 weight. % in terms of the reaction mixture under a pressure of 0.015-6 • 10 ² kPa at a temperature of 120-235 ^o C for 2-15 hours and, if necessary, the product is modified in the usual way, diluted and filtered. 8. The method according to claim 7, characterized in that the interaction between polyisobutylene, maleic anhydride and comonomer is carried out in a solvent or solvent mixture comprising hydrocarbon components with a boiling point of less than 250 ^o C in an amount of at least 3 wt.%.  9. The method according to claim 7, characterized in that the additive is modified with compounds including boron, sulfur, copper, and / or molybdenum, and / or polyalkenyl succinic anhydride, or ether.

Images