JPH0248598B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to novel chemical methods and compositions;
In particular, certain substituted succinic acylating agents, methods for producing substituted acylated compositions, and acylated compositions obtained thereby, including the above-mentioned substituted succinic acylating agents and substituted acylated compositions. a method for producing certain carboxylic acid derivative compositions from the substituted succinic acylating agent and the substituted acylated composition; A lubricating composition comprising a small amount of one or more of the above-mentioned post-treated carboxylic acids; A lubricating composition comprising a small amount of at least one of the derivative compositions, further comprising a large amount of a generally liquid, substantially inert organic solvent/diluent, and one of the substituted succinic acylating agents and compositions described above. Concentrates comprising about 10 to about 80% by weight of the above. From one perspective, this invention can be considered an improvement in the field of lubricants involving high molecular weight carboxylic acid acylating agents and their acylated derivatives, which have been under development since the 1950's. For example, certain patent documents state that high molecular weight A method of making a carboxylic acylating agent is disclosed. Typical unsaturated carboxylic acids and their derivatives are acrylic acid, methyl acrylate, maleic acid, fumaric acid and maleic anhydride. An example of such patent documents is U.S. Patent No.
No. 3024237, No. 3087936, No. 3172892, No. 3215707, No. 3219666, No. 3231587,
Same No. 3245910, Same No. 3272746, Same No. 3288714,
Same No. 3312619, Same No. 3341542, Same No. 3367943,
Same No. 3381022, Same No. 3454607, Same No. 3407098,
Same No. 3630902, Same No. 3652616, Same No. 3755169,
3868330 and 3912764, British Patent No.
944136, 1085903, 1162436 and 1440219, as well as Canadian Patent No. 956397.
This is the number. These patent documents also describe various derivatives of these high molecular weight carboxylic acid acylating agents as additives in fuel and lubricating compositions.
It has been shown to be particularly useful as a dispersant/detergent that promotes engine cleaning and neutralizes acidic byproducts of combustion. Some of the compositions disclosed in the above documents are currently used in significant amounts as commercial lubricant additives. This invention provides certain novel high molecular weight carboxylic acylating agents that provide unique and useful properties to lubricating additives and lubricating compositions, while also providing novel high molecular weight carboxylic acylating agents that can be prepared from other conventional high molecular weight carboxylic acylating agents. It is based on the finding that desirable properties of lubricating additives and lubricating compositions can be preserved. In addition, the desirable properties mentioned above are not only retained as such, but are often increased or even improved. For example, given that certain lubricant additives made from conventional high molecular weight acylating agents are known to act as ashless dispersants in lubricating compositions, corresponding lubricant additives made from the new high molecular weight carboxylic acids described above are known to act as ashless dispersants in lubricating compositions. Additives that do so often exhibit improved ashless dispersant properties, etc. The novel high molecular weight carboxylic acid acylating agents and derivatives thereof of the present invention, especially the latter, e.g.
30 imparts sufficient fluidity modifying properties to a multigrade lubricating composition such as crankcase engine oil such that no or little viscosity index improver needs to be added to the lubricating composition. Fluidity modifiers, especially viscosity index improvers (hereinafter sometimes referred to as VI improvers), include polybutene with an average molecular weight of 60,000 to 80,000 or more, and hydrogenated butadiene-styrene copolymers with an average molecular weight of 20,000 to 200,000. As mentioned above, its properties are completely those of hydrocarbons, and it does not exhibit dispersibility or detergency. That is, they give the lubricant the desired
It is a monofunctional additive that only provides VI improving properties. Therefore, in order to obtain dispersant and detergent properties, for example, US Pat.
It is necessary to further add dispersants or detergents as described in No. 3761404. To produce multifunctional lubricant additives exhibiting both (a) flow-modifying properties, particularly VI-enhancing properties, and (b) dispersant and/or detergent properties.
Two methods have generally been used. One method is to suspend or incorporate some type of polar group (usually a carboxylic acid derivative such as a carboxylic acid amide or ester) into a high molecular weight polymer. The polymer material thus obtained continues to exhibit VI improving properties due to its high molecular weight hydrocarbon skeleton and dispersant or detergent properties due to its polar groups. This method is covered by US Patent No.
It is described in No. 3702300 and No. 3933761. For lack of a better term, the polymer obtained by this method is sometimes referred to in this specification as a "dispersibility VI improver." Another method is to modify the dispersant/detergent so that the dispersant/detergent has rheological properties, especially VI
It introduces improved properties. This method is described in US Pat. No. 3,219,666. This US patent is primarily concerned with acylated nitrogen derivatives of high molecular weight succinic acylating agents for use as dispersants in lubricating compositions. The acylating agent from which this dispersant is derived is a substituted succinic acylating agent preferably having a substituent derived from a polyolefin having a molecular weight of about 750 to 5,000. However, the US patent states that if VI-enhancing properties are desired in addition to dispersion properties, the above substituents may be
There is a statement that it must be derived from a high molecular weight olefin polymer of 100,000 or more. Again, for lack of a better term, multifunctional lubricant additives obtained by this method (i.e., the introduction of very high molecular weight substituents into the dispersant) are included in this specification. They will be referred to herein as "VI-enhancing dispersants,""VI-enhancingdetergents," and/or "VI-enhancing dispersants/detergents." A third method for making lubricant additives with both detergency and viscosity index improving properties is described in US Pat. No. 3,630,902. The method involves reacting a high molecular weight succinimide with a polymeric acid to produce a polymerizable acyl derivative of succinimide. This polymerizable derivative is
This is then polymerized to obtain the desired multifunctional lubricant additive. The carboxylic acylating agents and derivatives thereof of the present invention represent a more unique and hitherto unknown method of producing multifunctional lubricant additives. The main object of this invention is to provide novel substituted succinic acylating agents. Another object of the invention is a method for preparing novel substituted acylated compositions from polyalkenes, maleic acid and/or fumaric acid or derivatives thereof, and chlorine, as well as novel substituted acyl compositions obtained by this method. An object of the present invention is to provide a chemical composition. Yet another object of this invention is to provide lubricating compositions and concentrates containing the novel substituted succinic acylating agents and novel substituted acylating compositions. Still another object of the present invention is a method for producing a carboxylic acid derivative from the novel substituted succinic acylating agent and the novel substituted acylating composition, as well as lubricating compositions and concentrates containing the carboxylic acid derivative. The goal is to provide the following. Furthermore, the present invention provides a method for post-treating the carboxylic acid derivative, a post-treated carboxylic acid derivative composition obtained by this method, and a lubricant composition containing the post-treated carboxylic acid derivative composition. and concentrates. In some embodiments, one or more of the above objects is achieved when Mn is 1300 to about 5000 and Mw/Mn
is from about 1.5 to about 4, and a succinic acid group, and has an average of at least 1.3 succinic acid groups in its structure per equivalent weight of said substituent group. This is achieved by providing a substituted succinic acid-based acylating agent. In other embodiments, one or more objects of this invention provide that (A) the Mn value is from 1300 to about 5000;
Polyalkene with Mw/Mn value of about 1.5 to about 4, formula (B) A method for producing a substituted acylation composition comprising heating one or more of the acidic reactants represented by (X and This is achieved by providing a substituted acylated composition obtained by the method. However, the molar ratio of the above reactants (A) and (B) is at least 1.3 moles of (B) per 1 mole of (A) (the number of moles of (A) is the total weight of (A) and the amount of chlorine used is at least about 0.2 mole per mole of (B) to be reacted with (A).
The substituted acylation composition is characterized by having in its structure at least 1.3 groups derived from (B) per equivalent weight of substituents derived from (A). One or more objects of the present invention are to provide one or more of the above substituted succinic acylating agents or substituted acylating compositions with (a) at least one H-N group present in the structure; (b) an alcohol, (c) a reactive metal or reactive metal compound, and (d) a reactant (a) to (c) as described above.
By providing a method for producing a carboxylic acid derivative composition, which comprises reacting a carboxylic acid derivative composition with a reactant selected from the group consisting of a combination of two or more of the above, and a carboxylic acid derivative composition obtained by this method. It will be achieved. The components of reactant (d) above are reacted with the acylating agent simultaneously or in any order. One or more objects of this invention are to provide the above carboxylic acid derivative compositions in which the reactant is (a) boron oxide, hydrated boron oxide, boron halides, boron-containing acids, esters of boron-containing acids, Carbon sulfide, H ₂ S, sulfur, sulfur chloride, alkenyl cyanide, carboxylic acid acylating agent, aldehyde, ketone, urea, thiourea, guanidine, dicyandiamide, hydrocarbyl phosphate, hydrocarbyl phosphite, hydrocarbyl thiophosphate, thio 1 selected from the group consisting of hydrocarbyl phosphite, phosphorus sulfide, phosphorus oxide, phosphoric acid, hydrocarbyl thiocyanate, hydrocarbyl isocyanate, hydrocarbyl isothiocyanate, epoxide, episulfide, formaldehyde or formaldehyde-generating compound and phenol, and sulfur and phenol This is accomplished by providing a method for producing a post-treated carboxylic acid derivative composition, which comprises reacting with at least one post-treatment agent, and a post-treated carboxylic acid derivative composition obtained by this method. One or more objects of this invention are to provide the above carboxylic acid derivative compositions wherein the reactant is (b) boron oxide, hydrated boron oxide, boron halides, boron-containing acids, esters of boron-containing acids, sulfur, chloride. A method for producing a post-treated carboxylic acid derivative composition, which comprises reacting with one or more post-treatment agents selected from the group consisting of sulfur, phosphorus sulfide, phosphorus oxide, carboxylic acid acylating agents, epoxides and episulfides. and by providing a post-treated carboxylic acid derivative composition obtained by this method. One or more objects of this invention are to provide the above carboxylic acid derivative compositions in which the reactants are a combination of (a) and (b) with boron oxide, hydrated boron oxide, boron halides, boron-containing acids, boron. Containing acid esters, carbon disulfide, sulfur, sulfur chloride, alkenyl cyanide, carboxylic acid acylating agents, aldehydes, ketones, urea, thiourea, guanidine, dicyandiamide, hydrocarbyl phosphate, hydrocarbyl phosphite, hydrocarbyl thiophosphate , hydrocarbyl thiophosphite, phosphorus sulfide, phosphorus oxide, phosphoric acid, hydrocarbyl thiocyanate, hydrocarbyl isocyanate, hydrocarbyl isothiocyanate, epoxide, episulfide, formaldehyde or formaldehyde-generating compound and phenol, and sulfur and phenol. The present invention is achieved by providing a method for producing a post-treated carboxylic acid derivative composition, which comprises reacting the post-treated carboxylic acid derivative composition with one or more post-treatment agents, and a post-treated carboxylic acid derivative composition obtained by this method. One or more objects of this invention also provide a lubricating oil having a lubricating viscosity in bulk quantities and the substituted succinic acylating agents, substituted acylating compositions, carboxylic acid derivative compositions and post-treated carboxylic acids. This is achieved by providing a lubricating composition comprising a small amount of at least one derivative composition. Further, one or more objects of the present invention provide for the use of a generally liquid substantially inert organic solvent/diluent in a proportion of from about 20% to about 90% by weight and for said substituted succinic acylation agent. by providing a concentrated composition comprising from about 10% to about 80% by weight of at least one of the following: It will be achieved. This invention will be explained in detail below. Substituted Succinic Acylating Agent The novel substituted succinic acylating agent of the present invention is characterized by the presence of two groups in its structure. The first group, referred to herein as the "substituent group," is derived from a polyalkene. The polyalkenes from which this substituent group is derived are characterized by a Mn (number average molecular weight) of 1300 to about 5000 and a Mw/Mn of about 1.5 to about 4. The second group will be referred to as a "succinic acid group" in this specification. This succinic acid group has the structural formula It is a group characterized by. In the formula, X and X' are the same or different groups,
At least one of them enables the substituted succinic acid acylating agent to function as a carboxylic acid acylating agent. That is, at least one of X and or otherwise function as a conventional carboxylic acid acylating agent. For the purposes of this invention, transesterification reactions and transamidation reactions are considered to be conventional acylation reactions. That is, X and/or X' are usually -
OH, -O-hydrocarbyl, -O-M ⁺ (M ⁺ is a metal cation, ammonium cation or amine cation), _-NH2 , -Cl, -Br, or X and X' represent anhydride. It may be -O- which forms. X groups or X' groups other than those listed above are
There is no particular restriction as long as it does not interfere with the acylation reaction of the other group. However, preferably each of X and

[Formula] and Beauty

[Formula]) may participate in the acylation reaction. It is something. in the expression

[Formula] One of the dangling bonds in the group forms a carbon-carbon bond with a carbon atom in the substituent group. Other dangling bonds may form similar bonds with the same or different substituent groups, but normally, all dangling bonds other than those forming the above carbon-carbon bond are hydrogen. is combined with The substituted succinic acylating agent is characterized by having at least 1.3 succinic acid groups (ie, groups represented by the formula) per equivalent weight of substituent group in its structure. In this invention, the equivalent weight number of the substituent groups corresponds to the quotient of the total weight of the substituent groups present in the substituted succinic acylating agent divided by the Mn value of the polyalkene from which the substituent groups are derived. Thus, for example, if a substituted succinic acylating agent is characterized by the total weight of the substituent groups being 40,000 and the Mn value of the polyalkene from which the substituent groups are derived being 2000, then this substitution A total of 20 succinic acid-based acylating agents (40000/2000=
20) It has an equivalent weight of substituent groups. Therefore, in order to satisfy one of the requirements of the novel substituted succinic acylating agent of the present invention, this exemplified substituted succinic acylating agent must have at least 26 succinic acid groups in its structure. Characterized by existence. Another requirement of the substituted succinic acylating agents of this invention is that the substituent group be derived from a polyalkene having a Mw/Mn value of about 1.5 to about 4. Mw is the usual symbol indicating weight average molecular weight. In this invention, the Mn value and Mw value of the polyalkene are determined by gel permeation chromatography (GPC). This method is a column chromatography using a multiporous solvent-swollen polymeric structure of polystyrene gel, which differs in permeability to a large degree, as the stationary phase. As the liquid phase (tetrahydrofuran) containing the polymer sample passes through this gel, the polymer molecules diffuse into all parts of the gel that do not constitute a mechanical obstacle to them. Smaller molecules "penetrate" more completely and stay in the column longer, while larger molecules "penetrate" more easily and pass through the column faster. The Mn and Mw values of the polyalkenes used in this invention are readily obtained by comparison with distribution data obtained for a series of calibration standards of polymers with known molecular weight distributions. This invention uses a series of fractionated polymers of isobutene (preferably polyisobutene) as calibration standards. Polyalkenes having the above Mn and Mw values are known in the art and can be produced by conventional methods. Several such polyalkenes, especially polybutenes, are commercially available. Returning again to the properties of the substituted succinic acylating agents of this invention, the succinic acid group typically has the formula corresponds to Here, R and R' each independently form -OH, -Cl, -O-lower alkyl, or these R and R' form -O-. In this latter case, the succinic acid group becomes a succinic anhydride group. All succinic acid groups in each succinic acylating agent do not need to be the same, but may be the same. Preferably, the succinic acid group has the formula Or it corresponds to a mixture of formula (A) and formula (B). It will be easy for those skilled in the art to produce substituted succinic acylating agents with the same or different succinic groups, and the substituted succinic acylating agents themselves can be treated (for example, by hydrolyzing the anhydride to form free acids). or converting the free acid to the acid chloride by reacting with thionyl chloride), and/or
This can be accomplished by conventional methods such as selecting an appropriate maleic acid or fumaric acid reactant. As already mentioned, the minimum number of succinic acid groups per equivalent weight of substituent group is 1.3, preferably
It is 1.4. Usually 1.4 per equivalent weight of substituent group
From about 3.5 succinic acid groups are present. The minimum number of succinic acid groups per equivalent weight of substituent group is
1.5 is particularly preferred. Preferably, the number of succinic acid groups per equivalent weight of substituent group is from 1.5 to about 2.5. Based on the above, the substituted succinic acid acylating agent of the present invention can be represented by the following symbols. R ₁ (-R ₂ )y where R ₁ represents a substituent group with a weight of 1 equivalent,
R ₂ represents one succinic acid group corresponding to the above formula or y is 1.3 or more (i.e. 1.3)
Indicates the number of More preferred substituted succinic acylating agents include, for example, R ₁ and R ₂ are the preferred substituent groups and succinic groups described herein, respectively, and y is varied as described above (e.g., y is
1.4 or more (y1.4), y is 1.5 or more (y1.5), y
can be represented by 1.4 to about 3.5 (y=1.4-3.5) and y being 1.5 to about 3.5 (y=1.5-3.5). In addition to the cases in which preference depends on the number of succinic acid groups per equivalent weight of substituent groups, as discussed above, preference may also be based on the properties of the polyalkene from which the substituent groups are derived. . Regarding the Mn value, for example, a minimum value of about 1500 is preferred, and Mn values in the range of about 1500 to about 3200 are also preferred. A more preferred Mn value is approximately
It ranges from 1500 to about 2800. even more preferable
Mn values range from about 1500 to about 2400. For polybutene, a particularly preferred minimum Mn value is approximately
1700, and the particularly preferred range of Mn values is approximately
1700 to about 2400. There are also some preferred values for the Mw/Mn value. A preferred minimum Mw/Mn value is about 1.8, with values within the range of about 1.8 to about 3.6 also preferred.
A more preferable minimum Mw/Mn value is about 2.0, which is about
Values within the range of 2.0 to about 3.4 are also preferred. A particularly preferred minimum Mw/Mn value is about 2.5, with values in the range of about 2.5 to about 3.2 also particularly preferred. It should be noted that the preferred properties of substituted succinic acylating agents described above are both independent and dependent of each other. That is, for example, if the preferred minimum number of succinic acid groups per equivalent weight of substituent group is 1.4 or 1.5, the Mn value or Mw/
The above characteristics are independent in the sense that they are not related to the preferred Mn value. However, for example, the preferred minimum value of succinic acid groups is 1.4 or
Mn value and/or Mw/
The above properties are interdependent in the sense that when combined with the preferred value of the Mn value, this combination represents a more preferred embodiment of the invention. Therefore, while the various parameters have independent meaning when they are discussed individually, they can also be combined with other parameters to indicate a more preferred case. This concept refers to preferred values, ranges, ratios,
This applies to everything in this specification with respect to reactants, etc. The polyalkenes from which the substituent groups are derived are homopolymers and interpolymers of polymerizable olefin monomers having from 2 to about 16, usually from 2 to about 6 carbon atoms. The interpolymer is a polyalkene obtained by interpolymerizing two or more types of olefin monomers according to a conventional method and having units derived from each of the above two or more types of olefin monomers in its structure. It is. That is, interpolymers include binary copolymers, terpolymers, quaternary copolymers, and the like.
As will be appreciated by those skilled in the art, polyalkenes from which substituent groups are derived are often referred to as "polyolefins." The olefin monomer from which the polyalkene is derived is an ethylenically unsaturated group (i.e., C═C
) is a polymerizable olefin monomer characterized by having one or more of the following. That is, these are monoolefin monomers such as ethylene, propylene, butene-1, isobutene and octene-1, or polyolefin monomers (usually diolefin monomers) such as butadiene-1,3 and isoprene. . These olefin monomers are usually polymerizable terminal olefins, ie, olefins having C═CH ₂ groups in their structure. However, in the structure

Internal olefin monomers (sometimes referred to as medial olefins in some patent documents) having the group [formula] are also used in the preparation of polyalkenes. When internal olefins are used, they are usually used in conjunction with terminal olefins to produce interpolymerized polyalkenes. In this invention, if a certain polymerizable olefin monomer can be classified as both a terminal olefin and an internal olefin, it is considered to be a terminal olefin. Therefore, pentadiene-
1,3 (piperylene) is a terminal olefin. The polyalkenes of this invention are generally hydrocarbon polyalkenes, provided that they do not substantially inhibit the production of the substituted succinic acylating agents of this invention.
lower alkoxy group, lower alkylmercapto group,
Hydroxy, mercapto, oxo groups (i.e., as in keto and aldehyde groups)

[Formula] For example

[expression] and

[Formula]), nitro group, halo group, cyano group, Carbalkoxy group (i.e.

[Formula] alkyl, this alkyl is usually lower alkyl),
Alkanoyloxy group (i.e., alkyl

[Formula] This alkyl may contain a non-hydrocarbon group such as (usually lower alkyl). Such non-hydrocarbon groups, if present, usually do not exceed about 10% by weight of the total weight of the polyalkene. Since the polyalkene may contain a non-hydrocarbon group in this way, the olefin monomer from which the polyalkene is derived may also contain such a non-hydrocarbon group. However, from a practical and price point of view,
The olefin monomer and polyalkene contain no other non-hydrocarbon groups except for the chloro group that facilitates the formation of the substituted succinic acylating agents of this invention. (In this specification, when the word "lower" is used with respect to chemical groups, such as "lower alkyl" or "lower alkoxy," it refers to groups having up to seven carbon atoms.) Polyalkene is an aromatic group (particularly a phenyl group and a lower alkyl-substituted phenyl group and/or a lower alkoxy-substituted phenyl group such as para (tert-butyl) phenyl group) and a polymerizable cyclic olefin or a cycloaliphatic substituted polymerizable alicyclic group. Although it may contain cycloaliphatic groups such as those obtained from the formula olefin, it is usually free of such groups. An exception is polyalkenes derived from interpolymers of 1,3-diene and styrene, such as butadiene-1,3 and styrene or para(tert-butyl)styrene. Since aromatic groups and cycloaliphatic groups may be present in the polyalkene group, the olefin monomer from which the polyalkene is derived may contain aromatic groups and cycloaliphatic groups. From what I have said about polyalkenes,
It will be appreciated that aliphatic hydrocarbon polyalkenes free of aromatic and cycloaliphatic groups (other than diene-styrene interpolymers) are generally preferred. Within this general preference, polyolefins derived from homopolymers or interpolymers of hydrocarbon-terminated olefins having from 2 to about 16 carbon atoms are even more preferred. However, interpolymers of terminal olefins are generally preferred, with about 40% of the polymer units derived from internal olefins having up to about 16 carbon atoms.
Preference is likewise given to interpolymers which may contain up to More preferred polyalkenes are homo- or interpolymers of terminal olefins having from 2 to about 6 carbon atoms, more preferably from 2 to 4 carbon atoms. Other preferred olefins are the latter and include polymeric units derived from internal olefins having up to about 6 carbon atoms.
Contains up to 25%. Specific examples of terminal olefin monomers and internal olefin monomers that can produce polyalkenes by conventional polymerization methods include ethylene, propylene, butene-1, butene-2, isobutene, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1,
Pentene-2, propylene trimer, diisobutylene, isobutylene trimer, butadiene-1,2,
Butadiene-1,3, Pentadiene-1,2, Pentadiene-1,3, Pentadiene-1,4, Isoprene, Hexadiene-1,5,2-chloro-
Butadiene-1,3,2-methyl-heptene-
1,3-cyclohexylbutene-1,2-methyl-5-propyl-hexene-1, pentene-3,
octene-4,3,3-dimethyl-pentene-
1, styrene, 2,4-dichlorostyrene, divinylbenzene, vinyl acetate, allyl alcohol,
1-methyl-vinyl acetate, ethyl acrylate, methyl methacrylate, ethyl vinyl ether and methyl vinyl ketone. Among these, polymerizable hydrocarbon monomers are preferred, and among the polymerizable hydrocarbon monomers, terminal olefins are particularly preferred. Specific examples of polyalkylene include polypropylene, polybutene, ethylene-propylene copolymer, styrene-isobutene copolymer, isobutene-butadiene-1,3 copolymer, propene-isoprene copolymer, and isobutene-chloroprene copolymer. copolymer, isobutene-(paramethyl)styrene copolymer, copolymer of hexene-1 and hexadiene-1,3, copolymer of octene-1 and hexene-1, copolymer of heptene-1 and pentene-1 Polymers, copolymers of 3-methyl-butene-1 and octene-1, copolymers of 3,3-dimethyl-pentene-1 and hexene-1, terpolymers of isobutene, styrene and piperylene It is. More specific examples of the above interpolymers include a copolymer of 95% (by weight) isobutene and 5% (by weight) styrene, and a ternary copolymer of 98% isobutene, 1% piperylene, and 1% chlorprene. Combined, isobutene 95%
Terpolymer of 2% butene-1 and 3% hexene-1, 60% isobutene and pentene-1
Terpolymer with 20% and 20% octene-1, copolymer with 80% hexene-1 and 20% heptene-1, 90% isobutene and cyclohexene-2
% and 8% propylene, and further a copolymer of 80% ethylene and 20% propylene. A preferred source of polyalkenes is a _C4 refinery stream having a butene content of about 35 to about 75% by weight and an isobutene content of about 30 to about 60% by weight in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. It is poly(isobutene) obtained by polymerizing the following. This polyisobutene has the formula

It mainly contains isobutene repeating units (approximately 80% or more of the total repeating units) represented by the formula: Methods for producing the polyalkenes described above that satisfy various requirements regarding Mn and Mw/Mn will be apparent to those skilled in the art, and the present invention is not limited to such methods. Methods that readily occur to those skilled in the art include controlling the polymerization temperature, regulating the amount and type of polymerization inhibitor and/or catalyst, using chain termination groups in the polymerization process, etc. Other conventional methods such as stripping (including vacuum stripping) of very light components and/or oxidative or mechanical modification of high molecular weight polyalkenes to obtain lower molecular weight polyalkenes may also be used. It will be done. In producing the substituted succinic acylating agent of the present invention, one or more of the above polyalkenes are combined with the general formula One of the acidic reactants selected from the group consisting of maleic acid-based reactants or fumaric acid-based reactants represented by
React with more than one species. Preferably, the maleic and fumaric reactants have the formula (Here, R and R' are as described above). Usually, the maleic acid-based reactant or fumaric acid-based reactant is maleic acid, fumaric acid, maleic anhydride, or a mixture of two or more thereof. Generally, maleic acid-based reactants are preferred over fumaric-based reactants. The latter are more readily available and can generally be more easily reacted with polyalkenes (or derivatives thereof) to produce the substituted succinic acylating agents of this invention. Particularly preferred reactants are maleic acid, maleic anhydride and mixtures thereof. Maleic anhydride is usually used from the viewpoint of availability and ease of reaction. The above-mentioned one or more polyalkenes and one or more maleic acid-based or fumaric acid-based reactants can be reacted by applying several known methods to produce the substituted succinic acid-based acylating agent of the present invention. . The process for producing a substituted succinic acid acylating agent of the present invention involves replacing the conventional polyalkene (or polyolefin) with the specific polyalkene mentioned above, and adjusting the amount of the maleic acid or fumaric acid reactant used in the final substituted succinic acid acylating agent. Conventional high molecular weight succinic anhydrides and other similar succinic acid-based acylating agents, except that there are at least about 1.3 succinic acid groups per equivalent weight of substituent group in the acylating agent. The manufacturing method is basically similar to that of . For convenience, the term "maleic acid-based reactant" is often used hereinafter in this specification. Hereinafter, when this term is used, it is a general concept for acidic reactants selected from the group consisting of maleic acid-based reactants, fumaric acid-based reactants and mixtures thereof corresponding to the formula. One method for making the substituted succinic acylating agents of this invention is shown in US Pat. No. 3,219,666. This process is referred to as a "two-step" process and includes a first step in which the polyalkene is chlorinated until at least about one chlorine group per molecular weight of the polyalkene is introduced.
(In this invention, the molecular weight of the polyalkene corresponds to the Mn value.) Chlorination can be carried out simply by contacting the polyalkene with chlorine gas until the desired amount of chlorine is introduced into the polyalkene. Chlorination is generally carried out at a temperature of about 75 to about 125°C. When using a diluent in this chlorination step,
The diluent must not itself be easily chlorinated. Polychlorinated or perchlorinated and/or polyfluorinated or perfluorinated alkanes and benzene are examples of suitable diluents. The second stage of the two-stage chlorination process, according to the purpose of the present invention, usually comprises about 100% of the chlorinated polyalkene.
The reaction is carried out with a maleic acid-based reactant at a temperature of 100°C to about 200°C. The molar ratio of chlorinated polyalkene to maleic reactant is usually about 1:1.
It is. (In this invention, one mole of chlorinated polyalkene is the weight of chlorinated polyalkene that corresponds to the Mn value of the non-chlorinated polyalkene.) However, the maleic reactant can be used in stoichiometric excess. . For example, the molar ratio is 1:2. When an average of about one or more chlorine groups per polyalkene molecule is introduced during the chlorination step, one mole or more of the maleic acid-based reactant can react with each chlorinated polyalkene molecule. Because of this situation, it may be better to express the ratio of chlorinated polyalkene to maleic reactant in terms of equivalents. (In this invention, the equivalent weight of the chlorinated polyalkene is the weight corresponding to the Mn value divided by the average number of chloro groups per molecule of the chlorinated polyalkene, while the equivalent weight of the maleic acid-based reactant is In other words, the ratio of the chlorinated polyalkene to the maleic acid reactant is usually from about 1 equivalent of the maleic acid reactant per mole of the chlorinated polyalkene to about 1 equivalent of the maleic acid reactant per 1 mole of the chlorinated polyalkene. up to about 1 equivalent, usually with an excess of maleic reactant (e.g., about 5 to about 25
(wt% excess) is desirable. The unreacted excess maleic acid reactant can be usually distilled off from the reaction product under reduced pressure, or can be reacted at a later stage of the reaction process described below. The polyalkene-substituted succinic acylating agent thus obtained is chlorinated again if the desired number of succinic acid groups has not been introduced. If excess maleic reactant from the second stage step is present during this chlorination, this excess reacts with the chlorine further introduced during this chlorination step. Otherwise, additional maleic reactants are introduced during and/or after the chlorination step. This procedure can be repeated until the desired total number of succinic acid groups per equivalent weight of substituent group is reached. Other methods for making the substituted succinic acylating agents of this invention utilize the methods described in US Pat. No. 3,912,764 and British Patent No. 1,440,219. In this method, the polyalkene and maleic reactant are first reacted by "direct alkylation" by heating them together. Once this direct alkylation step is complete, chlorine is introduced into the reaction mixture to promote the reaction of unreacted maleic reactants. According to the above patent document, 0.3 to 2 or more moles of maleic anhydride are used in the reaction per mole of olefin polymer, ie polyalkene. This direct alkylation is carried out at temperatures between 180°C and 250°C. The temperature during chlorine introduction is between 160°C and 225°C. In utilizing this method to prepare the substituted succinic acylating agents of this invention, an amount of maleic acid is sufficient to introduce at least 1.3 succinic groups per equivalent weight of polyalkene into the final product. It is necessary to use acidic reactants and chlorine. Other methods that can be used to produce the substituted succinic acylating agents of this invention include (1) U.S. Patent Application No. 582,062 (Title of Invention: An Improved Process for Making Succinic Acid); (2) U.S. Patent Application No. 695234 (Title of invention: Two-Step Method for the Preparation of Substates)・Carboxylic Asc., filed on June 11, 1976). From the point of view of efficiency, overall economics, and performance of the resulting acylating agents and derivatives thereof, the currently most preferred method for producing the substituted succinic acylating agents of this invention is the so-called "one-step" method. . This method is described in US Pat. No. 3,215,707 and US Pat. No. 3,231,587. Essentially, this one-step process involves preparing a mixture of a polyalkene and a maleic reactant containing the necessary amounts of the polyalkene and maleic reactant to provide the desired substituted succinic acylating agent of this invention. It involves preparing. This means that there must be at least 1.3 moles of maleic reactant per mole of polyalkene in order for there to be at least 1.3 succinate groups per equivalent weight of substituent group. Chlorine is then introduced into the mixture while maintaining the temperature at at least about 140°C. This introduction of chlorine is usually carried out by passing chlorine gas through the mixture while stirring. As a variation of the above method, additional maleic reactants can be added during or after the chlorine introduction, but this method is
For reasons stated in 3215707 and 3231587, this is not currently preferred as mixing all the polyalkenes and all the maleic reactants before introducing chlorine. Generally, it is not necessary to use substantially inert, normally liquid solvents/diluents in the one-step process, provided that the polyalkene is sufficiently liquid at temperatures above 140°C. However, such solvents/
If a diluent is used, it is preferably one that is not chlorinated, as mentioned above. For this purpose, polychlorinated or perchlorinated and/or polyfluorinated or perfluorinated alkanes, cycloalkanes and benzenes are again used. Chlorine can be introduced continuously or intermittently during the one-step process. There is no particular limit to the rate of introduction of chlorine, but
In order to make maximum use of chlorination, the rate of introduction must be approximately the same as the rate of chlorine consumption during the reaction. When the rate of chlorine introduction exceeds the rate of consumption, chlorine is released from the reaction mixture. In order to prevent chlorine losses and maximize chlorine utilization, it is often advantageous to use a closed system that also includes superatmospheric pressure. The lowest temperature at which the reaction in the one-step process will occur at a reasonable rate is about 140°C. Therefore, the lowest temperature at which this method is normally performed is around 140°C. The preferred temperature range is usually about 160°C to about 220°C. Higher temperatures, such as 250°C or higher, may be used, but there is usually no significant advantage. In fact, temperatures above 220°C can crack polyalkenes (i.e. reduce their molecular weight through thermal degradation) and/or
Since it decomposes the maleic acid-based reactant, it is disadvantageous in producing the acylated succinic acid-based composition of the present invention. For this reason, maximum temperatures of about 200°C to about 210°C are usually not exceeded. The upper limit of useful temperatures in the one-step process is determined primarily by the decomposition temperatures of the components in the reaction mixture, including each reactant and the desired product. This decomposition temperature is
The temperature is such that the reactants or products decompose significantly and inhibit formation of the desired product. In this one-step process, the molar ratio of maleic reactant to chlorine is such that there is at least about 1 mole of chlorine per mole of maleic reactant to be incorporated into the product. For practical reasons, a slight excess of chlorine is used, usually from about 5 to about 30% by weight excess, to prevent loss of chlorine from the reaction mixture. An excess of chlorine may be used, but there is no significant advantage. As previously stated, the molar ratio of polyalkene to maleic reactant is such that there are at least about 1.3 moles of maleic reactant per mole of polyalkene. This is necessary so that there can be at least about 1.3 succinic acid groups per equivalent weight of substituent group in the product. however,
Preferably, the maleic reactant is used in excess. That is, typically about a 5% to about 25% excess of maleic reactant is used over the amount needed to provide the desired number of succinic acid groups in the product. A preferred method for making the substituted acylated compositions of this invention comprises: (A) a polyalkene having an Mn value of about 1300 to about 5000 and a Mw/Mn value of about 1.5 to about 4; (B) a polyalkene of the formula (Here, X and , the molar ratio of reactants (A):(B) is 1 mole of reactant (A)
(B) is at least about 1.3 moles (the number of moles of reactant (A) is the quotient of the total weight of reactants (A) divided by the Mn value), and the amount of chlorine used is
It is characterized in that it provides at least about 0.2 mole (preferably at least about 0.5 mole) of chlorine per mole of reactant (B) to be reacted with (A). The substituted acylated composition obtained by this method has a reactant (A) in its structure.
reactant per equivalent weight of substituent group derived from
Characterized by having on average at least 1.3 groups derived from (B). The substituted acylated compositions obtained by this method also form part of this invention. As already apparent, the preferred method just described is disclosed in US Pat. No. 3,912,764 and British Patent No.
1440219, and a method involving direct alkylation followed by chlorination, as described in U.S. Pat.
This method is a combination of the complete one-step method described in No. 3215707 and No. 3231587. Therefore, this method does not require that the initial mixture of polyalkene and acidic reactant contain all of the acidic reactant that is ultimately to be introduced into the substituted acylation composition. In other words, the entire amount of the oxygen reactant may be present from the beginning, or only a portion of it may be present initially and the remaining acidic reactant may be added during the reaction process. Similarly, an alkylation reaction may be carried out directly before introducing chlorine. However, the initial reaction mixture usually contains the total amount of polyalkene and acidic reactant to be used. Furthermore, the amount of chlorine to be used is usually such as to provide at least 1 mole of chlorine for every mole of unreacted reactant (B) present at the beginning of the chlorine introduction. Therefore, if the molar ratio of reactants (A):(B) is 1 mole of reactant (A) per mole of reactant (B)
If half the amount of reactant (B) is introduced into the product by direct alkylation, the amount of chlorine that must be introduced to complete the reaction is approximately 1.5 molar. The number of moles of (B) is 0.75. That is, at least about 0.75 moles (or more, as mentioned above) of chlorine are introduced. A more preferred method for making the substituted acylated compositions of this invention comprises (A) a polyalkene having an Mn value of about 1300 to about 5000 and a Mw/Mn value of about 1.5 to about 4; (B) a polyalkene of the formula (wherein R and R' are as defined above) and (C) chlorine, at a temperature of at least about 140°C; The molar ratio of A):(B) is at least about 1.3 moles of reactant (B) per mole of reactant (A) (the number of moles of reactant (A) is
is the quotient of the total weight divided by the Mn value),
The amount of chlorine used is characterized in that it provides at least about 1 mole of chlorine per mole of reactant (B) to be reacted with reactant (A). The substituted acylated composition obtained by this method contains in its structure an average of at least 1.3 groups derived from reactant (B) per equivalent weight of substituent groups derived from reactant (A). Characterized by having individuality. The substituted acylated compositions obtained by this method also form part of this invention. Here, the terms "substituted succinic acylating agent" and "substituted acylating composition" used in this specification will be explained. The former term is used to refer to substituted succinic acylating agents regardless of their method of preparation. As detailed above, several methods are available for making substituted succinic acylating agents. In contrast, the latter term is used to describe reaction mixtures prepared by certain preferred methods described herein. Therefore, the specificity of the particular substituted acylation composition depends on the particular manufacturing method. It is believed that the novel acylating agents of this invention can best be described by the terms listed above. In particular, although the product of this invention is clearly a substituted succinic acid-based acylating agent, as mentioned above, the structure cannot be expressed by a single chemical formula, so what I have just described is appropriate. . In fact, mixtures of products inherently exist. Regarding the above preferred production method, (a) substituted succinic acid acylating agent and (b) Mn value, Mw/Mn
value, polyalkene content and composition, acidic reactants (i.e. maleic reactants and/or
The preferences already mentioned for the fumaric acid reactants), the ratio of the reactants and the reaction temperature apply analogously. The same preferences also apply to substituted acylated compositions obtained by the preferred method of manufacture described above. For example, a method in which the reaction temperature is about 160 to about 220°C is preferred. Similarly, 2 to about 16
homopolymers or interpolymers of terminal olefins having up to about 16 carbon atoms (although in some cases the interpolymers may contain up to about 40% polymer units derived from internal olefins having up to about 16 carbon atoms) A method using a polyalkene which can be used is preferred, and a composition obtained by this method is preferred.
In a more preferred embodiment, the polyalkene is 2
A homopolymer or interpolymer of terminal olefins having from 1 to 6 carbon atoms containing up to about 25% of polymerized units derived from internal olefins having up to about 6 carbon atoms. It doesn't matter. Similarly, the succinic acid group content of the substituted acylating composition is preferably the same as described for the substituted succinic acylating agent. That is, substituted acylation compositions having an average of at least 1.4 succinic acid groups derived from reactant (B) in the structure per equivalent weight of substituent groups derived from reactant (A) are preferred; More preferred are substituted acylation compositions containing from at least 1.4 to about 3.5 succinic acid groups derived from reactant (B) per equivalent weight of substituent groups derived from (A). Furthermore, at least 1.5 succinic acid groups derived from reactant (B) per equivalent weight of substituent groups derived from reactant (A).
More preferred are substituted acylation compositions containing from at least 1.5 to about 2.5 succinic groups derived from reactant (B) per equivalent weight of substituent groups derived from reactant (A). Particularly preferred are substituted acylated compositions. Finally, similar to substituted succinic acylating agents,
The succinic acid group derived from reactant (B) has the formula

【formula】

Substituted acylated compositions obtained by methods corresponding to the formulas and mixtures thereof are preferred. A particularly preferred method for making substituted acylated compositions of this invention comprises (A) units derived from butenes having an Mn value of about 1700 to about 2400 and an Mw/Mn value of about 2.5 to 3.2; polybutenes, of which at least 50% of the total number of polybutenes are derived from isobutene, (B) of the formula (wherein R and R' are each -OH or combine to form -O-) and (C) chlorine, at about 160°C to about 220℃
Reactant (A): (B)
The molar ratio is at least about 1.5 moles of reactant (B) per mole of reactant (A) (the number of moles of reactant (A) is
the total weight of (A) divided by the Mn value) and the amount of chlorine used is at least about 1 mole of chlorine per mole of reactant (B) to be reacted with reactant (A). It is characterized by the fact that it provides The substituted acylated composition obtained by this method contains in its structure an average of at least 1.5 groups derived from reactant (B) per equivalent weight of substituent groups derived from reactant (A). Characterized by having individuality. Substituted acylated compositions obtained by this method also constitute a preferred species of this invention. For convenience, hereinafter, the substituted succinic acid-based acylating agent and the substituted acylating composition of the present invention will often be collectively referred to as the "acylating agent." The acylating agent of the present invention is useful as a lubricant and fuel additive in the same way as conventionally known high molecular weight carboxylic acid acylating agents. For example, the acylating agents of the present invention, which are certain succinic acids, succinic anhydrides, and lower alkyl esters of succinic acids, can be used in amounts of about 50 to about 1000 ppm in hydrocarbon fuels having boiling points of substantially 100 to 750. It can be used in concentrations as a fuel additive to reduce deposit formation. U.S. Patent No. 3,346,354 includes
Instructions are provided for the use of known high molecular weight carboxylic acid acylating agents that are applicable to the acylating agents of this invention. Similarly, U.S. Pat.
No. 3,288,714 discloses how to use a high molecular weight carboxylic acid acylating agent, known as succinic anhydride, as a dispersant/detergent in lubricating compositions; Applicable to softening agents. Similarly, US Pat. No. 3,714,042 is a reference for the use of the acylating agents of this invention in the treatment of overbased complexes. That is, the acylating agent of the present invention containing a succinic acid group, a succinic anhydride group, or a succinic ester group can be acylated using a high molecular weight carboxylic acid according to the method and process described in U.S. Pat. No. 3,714,042. It can be used to treat basic sulfonic acid metal complexes, sulfonate-carboxylate complexes and carboxylate complexes by replacing the agents with the acylating agents of this invention on an equivalent weight basis. Because the acylating agent of this invention has utility beyond its usefulness as an intermediate for preparing other novel compositions, the acylating agent is Lubricating compositions and concentrates containing agents also form part of this invention. Nevertheless, the primary use of the acylating agents of this invention is as an intermediate in the production of carboxylic acid derivative compositions, and this production method involves incorporating one or more acylating agents into (a) at least one Two H-N
(b) an alcohol, (c) a reactive metal or reactive metal compound, and (d) the above reactant (a)
It consists of reacting with a reactant selected from the group consisting of a combination of two or more of (c), wherein the component of reactant (d) is added to the acylating agent at the same time or in any order. can be reacted with. Amines characterized by the presence of at least one H--N group in their structure (ie, reactant (a) above) may be monoamine or polyamine compounds. For the purpose of this invention, hydrazine as well as substituted hydrazines containing up to 3 substituents are included as suitable amines for preparing the carboxylic acid derivative composition. One or more amines can be used in reacting with one or more of the acylating agents of this invention. Preferably, the amine contains at least one primary amino group (i.e. _-NH2 ), more preferably the amine contains a polyamine, especially at least two H-N groups, one or both of which primary or secondary amines). Polyamines not only produce carboxylic acid derivative compositions that are more effective as dispersants/detergents compared to monoamines, but also produce carboxylic acid derivative compositions that exhibit better VI enhancing properties. Reactant (a)
Monoamines and polyamines suitable as such will be described in more detail below. Alcohols that can be used as reactant (b) include monohydric alcohols and polyhydric alcohols. Polyhydric alcohols are preferred because they typically produce carboxylic acid derivative compositions that are more effective as dispersants/detergents than monohydric alcohols. Furthermore, polyhydric alcohols are particularly preferred reactants since carboxylic acid derivative compositions derived from polyhydric alcohols exhibit very good VI enhancing properties. Alcohols suitable as reactant (b) are discussed in more detail below. Reactive metals and reactive metal compounds useful as reactant (c) are those known to form salts and complexes when reacted with carboxylic acids and carboxylic acid-based acylating agents. These reactive metals and reactive metal compounds will be described further below. Mono- and polyamines useful as reactant (a) must have at least one H--N group present in their structure. Therefore, they contain at least one primary amino group (H ₂ N-)
or has a secondary amino group. These amines are aliphatic, cycloaliphatic, aromatic or heterocyclic; Also included are aromatic, alicyclic-substituted heterocyclic, heterocyclic-substituted aliphatic and heterocyclic-substituted aromatic amines, which may be saturated or unsaturated. If unsaturated, the amine is acetylenically unsaturated (-C≡
Does not contain C-). These amines may contain non-hydrocarbon substituents as long as they do not interfere with the reaction with the acylating agents of this invention.
Such non-hydrocarbon groups include lower alkoxy groups, lower alkylmercapto groups, nitro groups, intervening groups such as -O- and -S- (e.g. -CH ₂ CH ₂
In the -X-CH ₂ CH ₂ - group, X is -O- or -
S-), etc. Except for branched polyalkylene polyamines, polyoxyalkylene polyamines, and high molecular weight hydrocarbyl-substituted amines, which are discussed in more detail below, the amines used as reactant (a) will usually total no more than about 40, and usually no more than about 20. of carbon atoms. Aliphatic monoamines include aliphatic monosubstituted amines and aliphatic disubstituted amines, and the aliphatic group may be saturated or unsaturated, linear or branched. I don't mind. That is, these amines are primary or secondary aliphatic amines. Such amines include, for example,
Mention may be made of mono- or dialkyl-substituted amines, mono- or dialkenyl-substituted amines, and amines having one N-alkenyl group and one N-alkyl group. The total number of carbon atoms in the aliphatic amine, as stated above, usually does not exceed about 40 and usually does not exceed about 20.
Specific examples of such monoamines include ethylamine, diethylamine, n-butylamine,
These include di-n-butylamine, allylamine, isobutylamine, cocoaamine, stearylamine, laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine, octadecylamine, and the like. Examples of cycloaliphatic, aromatic and heterocyclic substituted aliphatic amines are 2-(cyclohexyl)-ethylamine, benzylamine, phenethylamine and 3-(furylpropyl)amine. Alicyclic monoamines are monoamines in which there is one alicyclic group directly bonded to the amino nitrogen via a carbon atom in the ring. To give a specific example,
cyclohexylamine, cyclopentylamine,
These include cyclohexenylamine, cyclopentenylamine, N-ethyl-cyclohexylamine, dicyclohexylamine, and the like. Examples of aliphatic-substituted alicyclic monoamines, aromatic-substituted alicyclic monoamines, and heterocyclic-substituted alicyclic monoamines include propyl-substituted cyclohexylamine, phenyl-substituted cyclopentylamine, and pyranyl-substituted cyclohexylamine. Aromatic monoamines suitable as reactant (a) are monoamines in which the carbon atom of the aromatic ring is directly bonded to the amino nitrogen. The aromatic ring is usually a mononuclear aromatic ring (ie, one derived from benzene), but may also include fused rings, especially rings derived from naphthalene. Examples of aromatic monoamines include aniline, di(paramethylphenyl)amine, naphthylamine, and N-(n-butyl).
Aniline etc. Examples of aliphatic-substituted aromatic monoamines, alicyclic-substituted aromatic monoamines and heterocyclic-substituted aromatic monoamines are paraethoxyaniline, paradodecylaniline, cyclohexyl-substituted naphthylamine and thienyl-substituted aniline. Polyamines suitable as reactant (a) are aliphatic, cycloaliphatic and aromatic polyamines similar to the monoamines described above except for the presence of additional amino nitrogens in the structure. The other amino nitrogen mentioned above may be a primary, secondary or tertiary amino nitrogen. Examples of such polyamines are:
N-aminopropyl-cyclohexylamine,
N,N'-di-n-butyl-paraphenylenediamine, bis-(paraaminophenyl)methane, 1,
4-diaminocyclohexane and the like. Heterocyclic monoamines and polyamines can also be used as the reactant (a) used in producing the carboxylic acid derivative composition of this invention. The term "heterocyclic monoamines and polyamines" refers to heterocyclic amines containing at least one primary or secondary amino group and at least one nitrogen as a heteroatom in the heterocycle. However, insofar as at least one primary or secondary amino group is present in this heterocyclic mono- or polyamine, the heteroatom N atom in the heterocycle has a tertiary amino nitrogen, i.e. a directly bonded hydrogen atom. It doesn't matter if it's nitrogen that we don't have. These heterocyclic amines may be saturated or unsaturated, and may include various groups such as nitro group, alkoxy group, alkylmercapto group, alkyl group, alkenyl group, aryl group, alkaryl group, and aralkyl group. It may contain a substituent. in general,
The total number of carbon atoms in this substituent does not exceed about 20. The heterocyclic amine may contain oxygen and sulfur as atoms other than nitrogen. Needless to say, these amines may contain one or more nitrogen atoms. Five-membered heterocycles and six-membered heterocycles are preferred. Examples of suitable heterocyclic amines include aziridines, azetidines, azolidines, tetra- or dihydropyridines, pyrroles, indoles, piperidines, imidazoles, di- or tetrahydroimidazoles, piperazines, isoindoles. , purines, morpholines, thiomorpholines, N-aminoalkylmorpholines, N-aminoalkylthiomorpholines, N-aminoalkylpiperazines, N,
N'-di-aminoalkylpiperazines, azepines, azocines, azonines, azecines, their tetra, di or perhydro derivatives, and mixtures of two or more thereof. Preferred heterocyclic amines are saturated five- and six-membered heterocyclic amines containing only nitrogen, oxygen and/or sulfur as heteroatoms in the heterocycle, especially piperidines, piperazines, thiomorpholines. , morpholines, pyrrolidines, etc. Particularly preferred are piperidine, aminoalkyl-substituted piperidine, piperazine, aminoalkyl-substituted piperazine, morpholine, aminoalkyl-substituted morpholine, pyrrolidine and aminoalkyl-substituted pyrrolidine. Typically, the aminoalkyl substituent described above is attached to a nitrogen that is part of the heterocycle. Specific examples of such heterocyclic amines include N-aminopropylmorpholine, N-
They are aminoethylpiperazine and N,N'-di-aminoethylpiperazine. Hydroxyamines similar to the amines listed above, whether mono- or polyamines, are useful as reactant (a) as long as they contain at least one primary or secondary amino group. Therefore, hydroxyamines having only a tertiary amino nitrogen, such as in trihydroxyethylamine, are excluded as reactant (a) (but may be used as reactant (b), as discussed below). The hydroxyamine referred to herein is an amine having a hydroxy substituent directly bonded to a carbon atom other than the carbonyl carbon atom. That is, this amine has a hydroxy group that can be used as an alcohol. Specific examples of such hydroxyamines include ethanolamine, di-(3-hydroxypropyl)amine, 3-hydroxybutylamine, 4-hydroxybutylamine, diethanolamine, di-(2-hydroxypropyl)amine, N-( hydroxypropyl) propylamine,
These include N-(2-hydroxyethyl)cyclohexylamine, 3-hydroxycyclopentylamine, para-hydroxyaniline, and N-hydroxyethylpiperazine. Similarly, suitable amines have the general formula (Here, R is -OH, _-NH2 , _ONH4 , etc., R _a
is a polyvalent organic group having a valence corresponding to x + y,
R _b and R _c are each independently hydrogen, a hydrocarbyl group, or a substituted hydrocarbyl group, and at least one of R _b and R _c is hydrogen per molecule of aminosulfonic acid; x and y are each 1 or more is an aminosulfonic acid or a derivative thereof represented by (an integer of ). From the above formula, each aminosulfonic acid reactant has at least one HN
or H ₂ H- group and at least one

[Formula] It will be understood that it has a group. These aminosulfonic acids are aliphatic, cycloaliphatic or aromatic aminosulfonic acids and functional derivatives of the sulfo group. Specifically, this aminosulfonic acid is an aromatic aminosulfonic acid, that is, R _a is a polyvalent aromatic group such as phenylene, and at least one

The [Formula] group may be an acid bonded directly to a ring carbon atom of the aromatic group. Also, aminosulfonic acid is a monoamino aliphatic sulfonic acid, i.e. x
is 1 and R _a is a polyvalent aliphatic group such as ethylene, propylene, trimethylene and 2-methylenepropylene. These aminosulfonic acids and methods of reacting them with the acylating agents of this invention (i.e., similar to reactions with other carboxylic acylating agents) are described in U.S. Patent Application No. 310,042 (November 28, 1972). This patent application is also helpful for methods of using carboxylic acid derivative compositions derived from the aminosulfonic acids mentioned above. Other suitable aminosulfonic acids and derivatives thereof useful as reactant (a) are described in US Pat. Nos. 3,926,820, 3,029,250 and 3,367,864. As reactant (a) also hydrazine and substituted hydrazines are used. At least one of the nitrogen atoms in hydrazine contains hydrogen directly bonded to it. Preferably, there are at least two hydrogens directly bonded to the hydrazine nitrogen;
More preferably, two hydrogens are bonded to the same nitrogen. Examples of substituents that may be present in hydrazine include alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkaryl groups, and the like. Usually, the substituents are alkyl groups, especially lower alkyl groups, phenyl groups, or substituted phenyl groups such as lower alkoxy-substituted phenyl groups and lower alkyl-substituted phenyl groups. Examples of substituted hydrazine are methylhydrazine, N,N-
Dimethylhydrazine, N,N'-dimethylhydrazine, phenylhydrazine, N-phenyl-
N'-ethylhydrazine, N-(para-tolyl)-
N'-(n-butyl)hydrazine, N-(para-nitrophenyl)hydrazine, N-(para-nitrophenyl)-N-methylhydrazine, N,N'-di-(para-chlorophenol)hydrazine, N-
phenyl-N'-cyclohexylhydrazine and the like. High molecular weight hydrocarbyl amines, whether mono- or polyamines, which can be used as reactant (a) are generally obtained by reacting chlorinated polyolefins having a molecular weight of at least about 400 with ammonia or amines. Such amines are known in the art and include, for example:
No. 3,275,554 and US Pat. No. 3,438,757. A requirement for these amines to be used as reactant (a) is that they have at least one primary or secondary amino group. Another group of amines suitable as reactant (a) are branched polyalkylene polyamines. The branched polyalkylene polyamine is characterized in that the branching groups contain an average of at least one, e.g.

It is a polyalkylene whose side chain contains [Formula]). Preferably, one branched side chain is present for every nine main chain units. These polyamines therefore contain at least three primary amino groups and at least one tertiary amino group. The above branched chain polyalkylene polyamine has the formula (wherein R is an alkylene group such as ethylene, propylene, butylene or other homologues (including both straight and branched chains), preferably ethylene, and x, y and z are integers and x can be for example 4 to 24 or more, preferably 6 to 18, y can be for example 1 to 6 or more, preferably 1 to 3, z can be for example 0 to 6, preferably 0 or 1) . The x and y units may be continuous or alternating, or regularly or randomly distributed. Preferred such polyamines have the formula (Here, n is an integer such as 1 to 20, preferably 1 to 3, and R is preferably ethylene, but may also be propylene, butylene, etc. (including straight chain or branched chain)) It is. A preferred example is the formula (Here, n is 1 to 3). The units in parentheses above are connected in a head-to-head structure or a head-to-tail structure. Compounds represented by the formula where n is 1 to 3 are manufactured and sold as polyamine N-400, polyamine N-800, polyamine N-1200, etc. Polyamine N-400 corresponds to the case where n is 1 in the above formula. U.S. Patent No. 3,200,106 and U.S. Pat. No. 3,259,578 describe a method for producing the above-mentioned polyamine and a method for reacting it with a carboxylic acid-based acylating agent, and a method similar to this is also used in this invention, so it can be used as a reference. . Suitable amines further include those having an average molecular weight of about 200 to 4000, preferably about 400 to about 2000.
polyoxyalkylene polyamines such as polyoxyalkylene diamines and polyoxyalkylene triamines. Examples of these polyoxyalkylene polyamines are represented by the following formulas. Formula NH ₂ -alkylene (-O-alkylene) - _n NH ₂ where m is about 3 to 70, preferably about 10
to 35) Formula R[alkylene(-O-alkylene) _-oNH2 ] _{3 to 6 ,} where n is from about 1 to 40 and the sum of all n's is from about 3 to about 70, generally from about 6 to about 70; about
35, and R is a polyvalent saturated hydrocarbon group having up to 6 carbon atoms and a valence of 3 to 6). Each of the above alkylene groups may be straight or branched and contain 1 to 7, usually 1 to 4 carbon atoms. The alkylene groups present in the above formulas and formulas may be the same or different. More specific examples of these polyamines are shown by the following formulas. formula (where x is about 3 to 70, preferably about 10
to 35) formula (where x+y+z is about 3 to 30, preferably about 5 to 10). For this invention, preferred polyoxyalkylene polyamines have an average molecular weight of about 200 to 2000.
polyoxyethylene diamine, polyoxypropylene diamine or polyoxypropylene triamine. These polyoxyalkylene polyamines include, for example, diamine (Jeffamine)
D-230, D-400, D-1000, D-2000, T-
It is commercially available from Jefferson Chemical Company under trade names such as 403. U.S. Pat. No. 3,804,763 and U.S. Pat. No. 3,948,800 describe such a polyoxyalkylene polyamine and a method for reacting it with a carboxylic acid acylating agent. Applicable to reactions with acylating agents. The most preferred amines as reactant (a) are alkylene polyamines, including the polyalkylene polyamines described in detail below. This alkylene polyamine has the formula (wherein n is from 1 to about 10, each R'' is independently a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group having up to about 30 carbon atoms, and an "alkylene" group is from about 1 to about having 10 carbon atoms, preferably ethylene or propylene. Particularly preferred are alkylene polyamines in which each R'' is hydrogen, most preferred are ethylene polyamines and mixtures of ethylene polyamines. Usually, On average, n is about 2 to about 7. Examples of such alkylene polyamines include methylene polyamine, ethylene polyamine, butylene polyamine,
propylene polyamine, pentylene polyamine,
Hexylene polyamine, heptylene polyamine, etc. Also included are higher homologs of such amines and related aminoalkyl-substituted piperazines. Examples of alkylene polyamines useful in producing the carboxylic acid derivative composition of the present invention include ethylene diamine, triethylene tetraamine, propylene diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, (heptamethylene)triamine, tripropylenetetraamine, tetraethylenepentamine, trimethylenediamine, pentaethylenehexamine, di(trimethylene)triamine, N-(2-aminoethyl)piperazine, 1,4-bis(2-amino) ethyl) piperazine, etc. Higher homologues obtained by condensing two or more of these alkylene polyamines and mixtures of two or more of the above polyamines are also useful as the reactant (a). From a cost and performance standpoint, ethylene polyamines such as those described above are particularly useful. Such polyamines are described in "Diamines" described in "The Encyclopedia of Chemical Technology" edited by Kirk and Ozmer, 2nd edition (Interscience Publishers, 1965), Volume 7, pp. 27-39. and Hire Amins. Such polyamines are
They are most conveniently prepared by reaction of alkylene chloride with ammonia or ethyleneimine with a ring opening agent such as ammonia. This reaction yields a somewhat complex mixture of alkylene polyamines including cyclic condensation products such as piperazine. This mixture is particularly useful in preparing the novel sulfur-containing compositions of this invention. on the other hand,
Equally satisfactory products are obtained using pure alkylene polyamines. Hydroxyalkylalkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atom are also useful in preparing the amide or ester functional derivatives of the olefinic carboxylic acids described above. Preferred hydroxyalkyl-substituted alkylene polyamines are those in which the hydroxyalkyl group is a lower (ie, having less than 8 carbon atoms) hydroxyalkyl group. Examples of such hydroxyalkyl-substituted polyamines include N-(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxyethyl)ethylenediamine, 1-(2-hydroxyethyl)piperazine, monohydroxypropyl-substituted These include diethylenetriamine, dihydroxypropyl-substituted tetraethylenepentamine, N-(3-hydroxybutyl)tetramethylenediamine, and the like. Higher homologues obtained by condensing these hydroxyalkylene polyamines via their amino or hydroxy groups are also useful as reactant (a). Condensation via the amino group gives higher amines with elimination of ammonia, while condensation via the hydroxy group yields products with ether linkages with elimination of water. A carboxylic acid derivative composition prepared from the acylating agent of this invention and the above-mentioned amine has an amine group,
Acylated amines such as amides, imides and imidazolines as well as mixtures thereof. To prepare a carboxylic acid derivative from an acylating agent and an amine, one or more acylating agents and one or more amines are combined, as the case may be, usually in liquid, substantially insoluble form. in the presence of an active organic solvent/diluent at a temperature from about 80°C to the decomposition temperature (decomposition temperature has already been mentioned), typically about 100°C.
Heat at a temperature between 300°C and 300°C (300°C must not exceed the decomposition temperature). Ordinary approx.
Temperatures of 125°C to about 250°C are used. The acylating agent and the amine are reacted in a proportion such that about 0.5 equivalent to about 2 moles of amine are present per equivalent of the acylating agent. In this invention, the equivalent weight of an amine is the total weight of the amine divided by the total number of nitrogen atoms present. Thus, for example, one equivalent weight of octylamine corresponds to the molecular weight, one equivalent weight of ethylenediamine corresponds to half the molecular weight, and one equivalent weight of aminoethylpiperazine corresponds to one third of the molecular weight. The number of equivalents of the acylating agent is determined by the number of equivalents of the carboxylic acid functional group present in the acylating agent (e.g.

【formula】

【formula】

[expression] and

[Formula] X, X', R and R' are already mentioned). That is, the number of equivalents of acylating agent varies depending on the number of succinic acid groups present. In determining the number of equivalents of the acylating agent, carboxylic acid functional groups that cannot react as a carboxylic acylating agent are excluded. However, generally there are two equivalents of acylating agent for each succinic acid group in the acylating agent. From another perspective, reactants
(B) That is, 2 equivalents are present for each group derived from the maleic reactant from which the acylating agent is derived. Generally known methods (eg, acid value, saponification number) can be used to determine the number of carboxylic acid functional groups, and therefore the number of equivalents of the acylating agent that reacts with the amine can also be determined. The acylating agent of this invention can be used in the production of acylated amines suitable as additives for lubricating oil compositions.
Since it can be used in the same way as conventional high molecular weight acylating agents, it can be used in the same way as conventional high molecular weight acylating agents.
No. 3272746 is a reference. These patent documents describe methods applicable to the reaction of the acylating agent of the present invention with the amine.
When the methods described in these patent documents are suitable for the present invention, the high molecular weight carboxylic acid acylating agents disclosed in these patent documents may be replaced with the acylating agent of the present invention on an equivalent basis. That is, when 1 equivalent of the high molecular weight carboxylic acid acylating agent is used in the above patent document, 1 equivalent of the acylating agent of the present invention is used. The above patent also discloses the use of the resulting acylated amines as additives in lubricating oil compositions. The dispersion/cleaning properties can be improved by replacing the acylated amine described in the above patent document on the same equivalent basis with the acylated amine obtained by the reaction of the acylating agent of the present invention with said amine. Can be added to lubricating oil. However, in practice, with the acylated amines of this invention, equivalent or superior dispersion/detergent properties can be obtained with the addition of lower amounts. Suitable alcohols as reactant (b) useful in preparing carboxylic acid derivative compositions from the acylating agents of this invention include compounds of the general formula R ₃ (-OH) _n formula XII. In this formula, R ₃ is carbon −
Oxygen bond {i.e.

[Formula] where the carbon is not part of the carbonyl group) a monovalent or polyvalent organic group bonded to the -OH group,
and m is an integer from 1 to about 10, usually from 2 to about 6. Like the amine reactant (a), this alcohol may also be aliphatic, alicyclic, aromatic or heterocyclic, including aliphatic-substituted alicyclic alcohols, aliphatic-substituted aromatic alcohols, aliphatic-substituted hetero Cyclic alcohol, alicyclic-substituted aliphatic alcohol, alicyclic-substituted aromatic alcohol, alicyclic-substituted heterocyclic alcohol, heterocyclic-substituted aliphatic alcohol, heterocyclic-substituted alicyclic alcohol, and heterocyclic-substituted Also includes aromatic alcohols. Except for polyoxyalkylene alcohols, monohydric or polyhydric alcohols corresponding to Formula XII usually contain no more than about 40 carbon atoms, and generally no more than about 20 carbon atoms. These alcohols may contain the same types of non-hydrocarbon substituents as mentioned for the amines, ie, non-hydrocarbon substituents that do not inhibit the reaction of the alcohol with the acylating agent of this invention. Generally, polyhydric alcohols are preferred.
Even if the amine and alcohol are considered, polyhydric alcohol is preferable. A carboxylic acid derivative composition derived from this polyhydric alcohol (i.e.
This is because esters) exhibit particularly excellent VI-improving properties. However, a combination of an amine and a polyhydric alcohol also yields a carboxylic acid derivative composition with excellent VI improving properties. Among the polyoxyalkylene alcohols suitable as reactant (b) in the preparation of the carboxylic acid derivative compositions of this invention are demulsifiers for aqueous emulsions. In this specification and claims, the term "demulsifier for aqueous emulsions" is capable of preventing or suppressing the formation of aqueous emulsions. Alternatively, the term "aqueous emulsion" referring to polyoxyalkylene alcohols that can destroy aqueous emulsions is a generic term for oil-in-water emulsions and water-in-oil emulsions. Many commercially available polyoxyalkylene alcohol demulsifiers can be used as reactant (b). Useful demulsifiers are the reaction products of various organic amines, carboxylic acid amides or quaternary ammonium salts with ethylene oxide. Such polyoxyethylated amines, amides and quaternary ammonium salts include ETHODUOMEN T (an ethylene oxide condensation product of N-alkyl alkylene diamines under the trade name DUOMEEN T), ETHOMEEN (an ethylene oxide condensation product of primary fatty amines); tertiary amine), ETHOMID (ethylene oxide condensation product of aliphatic amide), and
ETHOQUAD (polyoxyethylated quaternary ammonium salt such as quaternary ammonium chloride)
Armor Industrial Chemical Company (Armor Industrial Chemical Company)
Chemical Co.). Preferred demulsifiers are liquid polyoxyalkylene alcohols or derivatives thereof. The derivatives referred to herein are hydrocarbyl ethers and carboxylic acid esters obtained by reacting these alcohols with various carboxylic acids. Examples of such hydrocarbyl groups are alkyl, cycloalkyl, alkylaryl, aralkyl or alkylarylalkyl groups, each having up to about 40 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, a butyl group, a dodecyl group, a tolyl group, a phenyl group, a naphthyl group, a dodecylphenyl group, a para-octylphenylethyl group, a cyclohexyl group, and the like.
Carboxylic acids useful in the production of the above ester derivatives include acetic acid, valeric acid, lauric acid, stearic acid,
Mono- or polycarboxylic acids such as succinic acid and alkyl- or alkenyl-substituted succinic acids in which the alkyl or alkenyl group contains up to about 20 carbon atoms. This type of alcohol is PLURONIC (manufactured by Wyndham Chemical Corporation),
POLYGLYCOL112-2 (manufactured by Dow Chemical Company,
liquid triol derived from ethylene oxide and propylene oxide), TERGITOL (manufactured by Union Carbide, dodecylphenyl or nonylphenyl polyethylene glycol ether) and UCON (manufactured by Union Carbide,
It is commercially available under the trade name ``Polyalkylene glycol and its derivatives''. However, reactants
The demulsifier used as (b) must contain on average at least one free alcoholic hydroxy group per molecule of polyoxyalkylene alcohol. In these polyoxyalkylene alcohols that are demulsifiers, the alcoholic hydroxy group is bonded to a carbon atom that does not form part of the aromatic nucleus. Among the preferred polyoxyalkylene alcohols are polyols prepared as "block" copolymers. That is, a hydroxy-substituted compound R ₄ -(OH) _q (where q is 1 to 6, preferably 2 to 3, and R ₄ is a monohydric or polyhydric alcohol or a residue such as a monohydric or polyhydric phenol, naphthol, etc.). group) to alkylene oxide

[Formula] (where R ₅ is an alkyl group having up to 4 carbon atoms and R ₆ is H
or the same as R ₅ and the number of carbon atoms of this alkylene oxide does not exceed 10) to form a hydrophobic base. This hydrophobic base is then reacted with ethylene oxide to introduce a hydrophilic moiety to produce a molecule having both a hydrophobic moiety and a hydrophilic moiety. The relative sizes of the hydrophobic portion and the hydrophilic portion can be adjusted by regulating the ratio of reactants, reaction time, etc., as will be apparent to those skilled in the art. It will be clear to those skilled in the art how to prepare polyols having proportions of hydrophobic and hydrophilic parts suitable as demulsifiers for aqueous emulsions in various lubricant compositions and thus as reactant (b). Dew. That is, if higher oil solubility is required in a certain lubricant, the hydrophobic portion is increased and/or the hydrophilic portion is decreased. If higher aqueous emulsion breaking properties are required, the hydrophobic and/or hydrophilic parts are adjusted accordingly. To give an example of a compound represented by R ₄ −(OH) _q ,
Aliphatic polyols such as alkylene glycols and alkane polyols, such as ethylene glycol, propylene glycol, trimethylene glycol, glycerol, pentaerythritol,
Erythrite, sorbitol, mannite, etc., and aromatic hydroxy compounds such as alkylated mono- or polyhydric phenols and naphthols, such as cresol, heptylphenol, dodecylphenol, dioctylphenol, triheptylphenol, resorcinol, pyrogallol, etc. It has 2 or 3 hydroxyl groups and the molecule has

[Formula] consisting essentially of a hydrophobic part consisting of a group (wherein R ₅ is an alkyl group having up to 3 carbon atoms) and a hydrophilic part consisting of a -CH ₂ CH ₂ O- group Polyoxyalkylene polyol demulsifiers are particularly preferred as reactant (b). Such polyols are produced by first converting a compound represented by the formula R ₄ (-OH) _q (where q is 2 to 3) into the formula

It can be obtained by reacting with a terminal alkylene oxide represented by the formula and then reacting this reaction product with ethylene oxide. R ₄ (-OH) _q is TMP (trimethylolpropane), TME (trimethylolethane), ethylene glycol, trimethylene glycol, tetramethylene glycol, tri(β-hydroxypropyl)amine, 1,4-(2-hydroxy ethyl)
Cyclohexane, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine,
It can be N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, naphthol, alkylated naphthol, resorcinol, or the examples already mentioned. Polyoxyalkylene alcohol demulsifier is approx.
1000 to about 10000, preferably about 2000 to about
It has a molecular weight of 7000. Ethyleneoxy groups (i.e., _-CH2CH2O- ) usually constitute about 5% to about 40% of _the total average molecular weight. Polyoxyalkylene polyols in which the ethyleneoxy groups constitute from about 10% to about 30% of the total average molecular weight are particularly useful as reactant (b). The average molecular weight is about 2,500 to about 6,000, and about 10 to 100% of the molecules are
Polyoxyalkylene polyols in which up to 20% by weight are derived from ethyleneoxy groups produce esters with particularly good demulsifying properties. Ether or ester derivatives of these polyols are also useful as reactant (b). Representative examples of the above polyalkylene polyols include liquid polyols sold under the trade name PLURONIC polyols from Wyandot Chemical Company and other similar polyols. This PLURONIC polyol has the formula HO
(CH ₂ CH ₂ O) _x (CHCH ₂ O) _y (CH ₂ CH ₂ O) _z Corresponds to the −H formula. In this formula, x, y, and z are integers greater than 1, and the -CH ₂ CH ₂ O- group accounts for approximately the total molecular weight.
10 to about 15% by weight. The average molecular weight of this polyol is about 2,500 to about 4,500. Polyols of this type are obtained by reacting propylene glycol with propylene oxide and then with ethylene oxide. Another example of the preferred polyoxyalkylene alcohol demulsifier described above is liquid TETRONIC, commercially available from Wyndt Corporation.
It is a polyol. This polyol has the general formula It is indicated by. This polyol is covered by a U.S. patent
Described in No. 2979528. Polyols corresponding to this formula having an average molecular weight up to about 10,000 and containing ethyleneoxy groups in the percentage ranges described above are preferred. Specific examples include polyols with an average molecular weight of about 8000 and ethyleneoxy groups accounting for 7.5-12% by weight of the total molecular weight. Such polyols are prepared by reacting an alkylene diamine such as ethylene diamine, propylene diamine, or hexamethylene diamine with propylene oxide until the desired amount of hydrophobic moieties are obtained, and then reacting the reaction product with ethylene oxide to obtain the desired number of hydrophilic moieties. can be produced by introducing moieties into the molecule. Another commercially available polyoxyalkylene polyol demulsifier in this preferred class is Dow Chemical's POLYGLYCOL 112-2, which is a triol with an average molecular weight of about 4000-5000 made from propylene oxide and ethylene oxide;
Ethyleneoxy groups account for approximately 18% by weight. Such triols are firstly glycerol,
It can be produced by reacting TME, TMP, etc. with propylene oxide to produce a hydrophobic base, and then reacting this base with ethylene oxide to introduce a hydrophilic moiety. Alcohols useful as reactant (b) also include alkylene glycols, polyoxyethylene alcohol, polyoxypropylene alcohol,
There are polyoxyalkylene alcohols such as polybutylene alcohol. These polyoxyalkylene alcohols (also called polyglycols)
can contain up to about 150 oxyalkylene groups containing from 2 to about 8 carbon atoms. Such polyoxyalkylene alcohols are generally dihydric alcohols. That is, each end of the molecule is −
It ends with an OH group. For such polyoxyalkylene alcohols to be useful as reactant (b), they must contain at least one such -OH group. Therefore, the remaining -OH groups may be esterified with monobasic aliphatic or aromatic carboxylic acids having up to about 20 carbon atoms, such as acetic acid, propionic acid, oleic acid, stearic acid, benzoic acid, etc. . Monoethers of the above alkylene glycols and polyoxyalkylene glycols are also useful as reactant (b). Examples include monoaryl ethers, monoalkyl ethers, and monoal alkyl ethers of these alkylene glycols and polyoxyalkylene glycols.
This type of alcohol has the general formula HO(-R _A O)-pR _B -OR _C (where R _C is an aryl group such as phenyl, lower alkoxyphenyl or lower alkyl phenyl; ethyl , a lower alkyl group such as propyl group, tert-butyl group, pentyl group; or an aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group, p-ethylphenylethyl group, p is 0 to about 150, and R _A and R _B can represent a lower alkylene group having from 2 to about 8 carbon atoms, preferably from 2 to 4 carbon atoms. Polyoxyalkylene glycols in which the alkylene group is an ethylene or propylene group and p is at least 2 and their monoethers as described above are very useful. Monohydric and polyhydric alcohols useful as reactant (b) include monohydroxy and polyhydroxy aromatic compounds. Monohydric and polyhydric phenols and naphthols are preferred hydroxyaromatic compounds. In addition to the hydroxy group, the above-mentioned hydroxy aromatic compounds include a halo group, an alkyl group,
It may contain other substituents such as an alkenyl group, an alkoxy group, an alkylmercapto group, and a nitro group. Typically, the hydroxyaromatic compounds contain 1 to 4 hydroxy groups. Specific examples of these hydroxy aromatic compounds include phenol, p-chlorophenol, p-
- nitrophenol, beta-naphthol, alpha-naphthol, cresol, resorcinol, catechol, carvacrol, thymol, eugenol, p,p'-dihydroxybiphenyl,
Hydroquinone, pyrogallol, phloroglucin,
Hexylresorcinol, orcine, guaiacol, 2-chlorophenol, 2,4-dibutylphenol, propene tetramer substituted phenol, didodecylphenol, 4,4'-methylene-bis-methylene-bisphenol, alpha-decyl-beta- Naphthol, polyisobutenyl (molecular weight approx.
1000) Substituted phenols, condensation products of heptylphenol and 0.5 mol of formaldehyde, condensation products of octylphenol and acetone, di(hydroxyphenyl) oxide, di(hydroxyphenyl) sulfide, di(hydroxyphenyl)
disulfide, and 4-cyclohexylphenol. Particular preference is given to phenols and aliphatic hydrocarbon-substituted phenols having up to 3 aliphatic hydrocarbon substituents, such as alkylated phenols. The aliphatic substituents described above may contain 100 or more carbon atoms, but typically 1
Contains from 1 to 20 carbon atoms. Alkyl and alkenyl groups are preferred aliphatic hydrocarbon substituents. Further specific examples of monohydric alcohols that can be used as reactant (b) include methanol, ethanol, isooctanol, dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl alcohol, isobutyl alcohol. , benzyl alcohol, beta-phenethyl alcohol, 2-methylcyclohexanol, beta-chloroethanol, monomethyl ether of ethylene glycol, monobutyl ether of ethylene glycol, monopropyl ether of diethylene glycol, monododecyl ether of toluethylene glycol, ethylene glycol monooleate, monostearate of diethylene glycol,
Dioleates of sec-pentyl alcohol, tert-butyl alcohol, 5-bromdodecanol, nitro-octadodecanol and glycerol. The alcohol as reactant (b) can be an unsaturated alcohol such as allyl alcohol, cinnamyl alcohol, 1-cyclohexen-3-ol and oleyl alcohol. Other alcohols useful as reactant (b) are ether alcohols or amino alcohols, such as alcohols substituted with one or more oxyalkylene, aminoalkylene or amino-aryleneoxy-arylene groups. Specific examples of these alcohols include cellosolve, carbitol, phenoxyethanol,
heptyl phenyl-(oxypropylene) ₆ -OH,
Octyl-(oxyethylene) ₃₀ -OH, phenyl-(oxyoctylene) ₂ -OH, mono-(heptyl phenyl-oxypropylene) substituted glycerol, poly(styrene oxide), aminoethanol, 3-amino-ethylpentanol, di (hydroxyethyl)amine, p-aminophenol,
Tri(hydroxypropyl)amine, N-hydroxyethylethylenediamine, N,N,N',
N'-tetrahydroxy-trimethylenediamine and the like. The polyhydric alcohol preferably contains 2 to about
Contains 10 hydroxy groups. Specific examples of these alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol,
Alkylene glycols and polyoxyalkylene glycols already mentioned, such as dibutylene glycol, tributylene glycol, and also other alkylene glycols or polyoxyalkylene glycols in which the alkylene group has 2 to 8 carbon atoms. Other useful polyhydric alcohols include glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, methyl ester of 9,10-dihydroxystearic acid, 2,3-hexanediol, 2,4-
hexanediol, pinacol, erythritol,
Arabit, sorbit, mannit, 1,2-
Mention may be made of cyclohexane diol and xylene glycol. Carbohydrates such as sugars, starches, cellulose etc. can likewise be used as reactants (b). Specific examples of such carbohydrates are glucose, fructose, sucrose, rhamnose, mannose, glyceraldehyde and galactose. It has at least three hydroxyl groups, some of which are octanoic acid, oleic acid, stearic acid,
Polyhydric alcohols esterified with aliphatic monocarboxylic acids having about 8 to about 30 carbon atoms, such as linoleic acid, decanoic acid, and tall oil acid, can also be used as reactant (b). Further specific examples of such partially esterified polyhydric alcohols include sorbitol monooleate, sorbitol distearate, glycerol monooleate, glycerol monostearate, and erythrite didodecanoate. Preferred alcohols suitable as reactant (b) are polyhydric alcohols having up to about 12, especially 3 to 10 carbon atoms. Specific examples of this type of alcohol include glycerol,
Erythritol, pentaerythritol, dipentaerythritol, glucose, arabinose, 1,7
-peptanediol, 2,4-heptanediol, 1,2,3-hexanetriol, 1,2,
4-hexanetriol, 1,2,5-hexanetriol, 2,3,4-hexanetriol,
These include 1,2,3-butanetriol, 1,2,4-butanetriol, quinic acid, 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol, 1,10-decanediol, digitalose, and the like. Aliphatic alcohols containing at least 3 hydroxyl groups and up to 10 carbon atoms are particularly preferred. Particularly preferred polyhydric alcohols to be used as reactant (b) are polyhydric alkanols containing 3 to 10, especially 3 to 6 carbon atoms and having at least 3 hydroxyl groups. be. Examples of such alkanols include glycerol, erythritol, pentaerythritol, mannitol, sorbitol, 2-hydroxymethyl-2-methyl-1,3-propanediol (trimethylolethane), 2-(hydroxymethyl-2 -ethyl-1,3-propanediol (trimethylolpropane), 1,2,4-hexanetriol, etc. From what has been said so far, reactant (a) contains an alcoholic hydroxy substituent. It's okay,
It will be appreciated that reactant (b) may contain primary, secondary or tertiary amino substituents. Therefore, an amino alcohol falls within the category of both reactant (a) and reactant (b) if it contains at least one primary or secondary amino group. If only tertiary amino groups are present, the amino alcohol belongs only to reactant (b). Amino alcohols suitable as reactant (a) and/or reactant (b) are those having one or more amine groups and one or more hydroxy groups. Specific examples of suitable amino alcohols include 2-hydroxyethylamine, 3-
Hydroxybutylamine, di-(2-hydroxyethyl)amine, tri-(2-hydroxyethyl)
Amine, di-(2-hydroxypropyl)amine,
N,N,N'-tri-(2-hydroxyethyl)ethylenediamine, N,N,N',N'-tetra-(2
-hydroxyethyl)ethylenediamine, N-
(2-hydroxyethyl)piperazine, N,N'-
Di-(3-hydroxypropyl)-piperazine, N
-(2-hydroxyethyl)morpholine, N-(2
-hydroxyethyl)-2-morpholine, N-(2
-hydroxyethyl)-3-methyl-2-morpholine, N-(2-hydroxypropyl)-6-methyl-2-morpholine, N-(2-hydroxyethyl)-5-carbethoxy-2-piperidone, N-
(2-hydroxypropyl)-5-carbetoxy-
2-piperidone, N-(2-hydroxyethyl)-
5-(N-butylcarbamyl)-2-piperidone,
N-(2-hydroxyethyl)piperidine, N-
(2-hydroxybutyl)piperidine, N,N-
Di-(2-hydroxyethyl)glycine and its esters with aliphatic alcohols, especially lower alcohols, as well as N-(hydroxy-
(lower alkyl) amine or polyamine. Furthermore, the alkylene polyamine is a mono-N-hydroxyalkyl or poly-N-hydroxyalkyl-substituted alkylene polyamine as previously described, especially in which the alkylene group is
Examples include the reaction product of 2 moles of propylene oxide and diethylenetriamine, such that the alkylene polyamine contains up to 7 amino groups. Further examples of amino alcohols include the general formula R _a -NH ₂ described in U.S. Pat. No. 3,576,743, where R _a is a monovalent organic group containing at least one alcoholic hydroxyl group. and the total number of carbon atoms in R _a does not exceed about 20). Hydroxy-substituted aliphatic primary amines having up to about 10 total carbon atoms are particularly useful. Particularly preferred are polyhydroxy-substituted alkanol primary amines having one amino group (ie, primary amino group), one alkyl substituent having up to 10 carbon atoms, and up to six hydroxyl groups. These alkanol primary amines correspond to cases where R _a is a mono- or polyhydroxy-substituted alkyl group. It is desirable that at least one of the hydroxyl groups is a primary alcoholic hydroxyl group. Trismethylolaminomethane is the single most preferred hydroxy-substituted primary amine.
Specific examples of these hydroxy-substituted primary amines include 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, p-(beta-hydroxymethyl)aniline, 2-amino-1-butanol,
-Propanol, 3-amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, N-(beta-hydroxypropyl)- N'-(beta-aminoethyl)piperazine, tris(hydroxymethyl)aminomethane (also known as trismethylolaminomethane), 2-amino-1-butynol, ethanolamine, beta-(beta-hydroxyethoxy)- ethylamine, glucamine, glucosamine,
4-amino-3-hydroxy-3-methyl-1-
Butene (which is obtained by reacting isoprene oxide with ammonia according to conventional methods), N-(3-
aminopropyl)-4-(2-hydroxyethyl)
piperazine, 2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol, N-
(beta-hydroxyethyl)-1,3-diaminopropane, 1,3-diamino-2-hydroxypropane, N-(beta-hydroxyethoxyethyl)ethylenediamine, and the like. Other hydroxy-substituted primary amines useful as reactant (a) and/or reactant (b) are described in US Pat. No. 3,576,743. The carboxylic acid derivative composition obtained by reacting the acylating agent of this invention with alcohol is an ester. Both acidic and neutral esters are included. An acidic ester is one in which some of the carboxylic acid functional groups in the acylating agent are not esterified and exist as free carboxyl groups. Of course, acidic esters are readily prepared by using an insufficient amount of alcohol to esterify all the carboxyl groups in the acylating agent. The acylating agent of this invention is reacted with an alcohol according to conventional esterification techniques. That is, the acylating agent of this invention and the alcohol are typically heated, optionally in the presence of a generally liquid, substantially inert organic solvent/diluent and/or in the presence of an esterification catalyst. It is something. Reaction temperatures of at least about 100°C up to the decomposition temperature (which decomposition temperature has already been mentioned) are used. This temperature is usually about 100°C to about 300°C, with temperatures of about 140°C to about 250°C often being used. Usually, at least about 0.5 equivalents of alcohol are used per equivalent of acylating agent. The equivalent weight of acylating agent is the same as described above in connection with the reaction with the amine. The equivalent weight of an alcohol is its molecular weight divided by the total number of hydroxyl groups present in the molecule. Thus, for example, one equivalent weight of ethanol corresponds to its molecular weight, and one equivalent weight of ethylene glycol corresponds to half its molecular weight. Techniques for obtaining acidic esters and neutral esters by reacting a high molecular weight carboxylic acid acylating agent with alcohol are described in many patent documents, and these techniques are based on the reaction between the acylating agent of the present invention and alcohol. It can also be applied to the production of esters. What is necessary is to use the high molecular weight carboxylic acid acylating agent described in such patent documents,
Typically, it will be substituted with the acylating agent of this invention on an equivalent basis. Patent documents that can be referred to for the reaction of the acylating agent and alcohol of this invention are U.S. Patent Nos. 3331776, 3381022, 3522179,
No. 3542680, No. 3697428 and No. 3697428
It is number 3755169. Reactive metals and reactive metal compounds useful as reactant (c) include those which produce carboxylic acid metal salts upon reaction with the acylating agents of this invention, and those which form carboxylic acid metal salts by reaction with the acylating agents of this invention, as well as those which react with the acylating agents of this invention and the amines described above. and/or a metal-containing complex is produced by reaction with a carboxylic acid derivative composition obtained by reacting with alcohol. No. 3,306,908 discloses reactive metal compounds useful as reactant (c) to form complexes with the reaction products of acylating agents and amines of this invention. Complex-forming metal reactants useful as reactant (c) include cadmium and atomic number 24.
Nitrates, nitrites, halides, carboxylates, phosphates, phosphites, sulfates, sulfites, carbonates, boron of up to 30 metals (chromium, manganese, iron, cobalt, nickel, copper and zinc) Includes acid salts and oxides. These metals are so-called transition metals or coordination metals, ie metals that can form complexes due to their secondary or coordination valences. Specific examples of these complex-forming metal compounds include cobaltous nitrate, cobaltous oxide, cobaltous oxide, cobaltous nitrite, cobaltous phosphate, cobaltous chloride, cobaltous chloride, and cobaltous carbonate. Cobalt, chromium acetate, chromium acetate, chromium bromide, chromium chloride, chromium fluoride, chromium oxide, chromium dioxide, chromium oxide, chromium sulfite, chromium sulfate Chromium heptahydrate, dichromic sulfate, dichromic formate, dichromic hexanoate, chromium oxychloride, dichromic phosphite, manganese acetate,
Manganous benzoate, manganous carbonate, manganous dichloride, manganous trichloride, manganous citrate, manganous formate, manganous nitrate, manganous oxalate, manganese monoxide, manganese dioxide, trioxide Manganese, manganese heptoxide, manganous phosphate, manganese pyrophosphate, manganous metaphosphate, manganous hypophosphite, manganese valerate, ferrous acetate, ferric benzoate, odor Ferrous chloride, ferrous carbonate, ferric formate, ferrous lactate, ferrous nitrate, ferrous oxide, ferric oxide, ferric hypophosphite, ferric sulfate, ferrous sulfite Monoiron, ferric hydrosulfite, nickel dibromide, nickel dichloride, nickel nitrate, nickel dioleate, nickel stearate, nickel sulfite, cupric propionate, cupric acetate, cupric metaborate, benzoic Cupric acids, cupric formate, cupric laurate, cupric nitrite, cupric oxychloride, cupric palminate, cupric salicylate, zinc benzoate, zinc borate, odor Zinc chloride, zinc chromate, zinc dichromate, zinc diiodide, zinc lactate,
These are zinc nitrate, zinc oxide, zinc stearate, zinc sulfite, cadmium benzoate, cadmium carbonate, cadmium butyrate, cadmium chromacetate, cadmium fumarate, cadmium nitrate, cadmium dihydrogen phosphate, cadmium sulfite and cadmium oxide. Hydrates of these compounds are particularly advantageous for the process of the invention. US Pat. No. 3,306,908 describes reactive metal compounds suitable for complex formation and methods of complex formation. This method can be applied to this invention by replacing the high molecular weight carboxylic acid acylating agent shown herein with the acylating agent of this invention on an equivalent basis. The equivalent ratio of acylated amine to reactive metal compound is the same as in US Pat. No. 3,306,908. US Reissue Patent No. 26,443 discloses metals useful in preparing salts from the carboxylic acid derivatives of acylating agents and amines of this invention. According to this patent document, the metal salts include alkali metals,
Manufactured from alkaline earth metals, zinc, cadmium, lead, cobalt and nickel. Examples of reactive metal compounds suitable as reactant (c) include sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodium propylate, sodium pentylate, sodium phenoxide, potassium oxide, hydroxide. Potassium, potassium carbonate, potassium methylate, potassium pentylate, potassium phenoxide, lithium oxide,
Lithium hydroxide, lithium carbonate, lithium pentylate, calcium oxide, calcium hydroxide, calcium carbonate, calcium methylate, calcium ethylate, calcium propylate, calcium chloride, calcium fluoride, calcium pentylate, calcium phenoxide, nitric acid Calcium, barium oxide, barium hydroxide, barium carbonate, barium chloride, barium fluoride, barium methylate, barium propylate, barium pentylate, barium nitrate, manganese oxide, manganese hydroxide, manganese carbonate, manganese ethylate,
Manganese propylate, manganese chloride, manganese bromide, barium iodide, manganese phenoxy, zinc oxide, zinc hydroxide, zinc carbonate, zinc methylate, zinc propylate, zinc pentylate, zinc chloride, zinc fluoride, zinc nitrate Hydrate, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium methylate, cadmium propylate,
Cadmium chloride, cadmium bromide, cadmium fluoride, lead oxide, lead hydroxide, lead carbonate, lead ethylate, lead pentylate, lead chloride, lead fluoride, lead iodide, lead nitrate, nickel oxide, nickel hydroxide, carbonic acid Nickel, nickel chloride, nickel bromide, nickel fluoride, nickel methylate, nickel pentylate, nickel nitrate hexahydrate, cobalt oxide, cobalt hydroxide, cobaltous bromide, cobaltous chloride, cobalt butyrate, Cobaltous nitrate hexahydrate, etc. These metal compounds are merely examples, and the invention is not limited thereto. US Patent Reissue No. 26,433 describes reactive metal compounds useful as reactant (c) and methods for utilizing these compounds in forming salts. In order to apply this method to the present invention, it is only necessary to replace the high molecular weight carboxylic acid acylating agent described in this patent document with the acylating agent of the present invention on an equivalent basis. US Pat. No. 3,271,310 describes a method for preparing metal salts of high molecular weight carboxylic acylating agents, particularly alkenylsuccinic acids. The metal salts shown here are acid salts, neutral salts and basic salts. Examples of reactive metal compounds used to produce acidic, neutral and basic salts of high molecular weight carboxylic acids described in this patent document include lithium oxide, lithium hydroxide, carbonate, etc. Lithium, lithium pentylate, sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodium propylate, sodium phenoxide, potassium oxide, potassium hydroxide, potassium carbonate, potassium methylate, silver oxide, silver carbonate, oxidized Magnesium, magnesium hydroxide, magnesium carbonate, magnesium ethylate, magnesium propylate, magnesium phenoxide, calcium oxide, calcium hydroxide, calcium carbonate, calcium methylate, calcium propylate, calcium pentylate, zinc oxide, zinc hydroxide , zinc carbonate, zinc propylate, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium ethylate, barium oxide, barium hydroxide, barium hydrate, barium carbonate, barium ethylate, barium pentylate, These are aluminum oxide, aluminum propylate, lead oxide, lead hydroxide, lead carbonate, tin oxide, tin butyrate, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt pentylate, nickel oxide, nickel hydroxide, and nickel carbonate.
The invention is not limited to the use of these metal compounds. These metal compounds are merely examples of those that can be used in this invention. US Pat. No. 3,271,310 is described here because it discloses a reactive metal compound suitable for producing the salt of the acylating agent of the present invention and a method for producing the salt applicable to the present invention. The method described in this patent document can be applied to this invention by simply replacing the high molecular weight carboxylic acid with the acylating agent of this invention on an equivalent basis. From what has been said so far, the acylating agent of the present invention can be reacted with individual amines, alcohols, reactive metals, or reactive metal compounds, or can be reacted with any two or more of these reactants. It will be obvious that it is also possible to react with combinations. That is, the acylating agent of this invention can be reacted with one or more amines, one or more alcohols, one or more reactive metals, or one or more reactive metal compounds, or any mixture thereof. . This mixture consists of two or more kinds of amine mixture, two or more kinds of alcohol mixture, and two or more kinds of alcohol mixture.
Mixtures of two or more reactive metals, mixtures of two or more reactive metal compounds, mixtures of two or more amines and alcohols, mixtures of two or more amines and reactive metals or reactive metal compounds, reacting with alcohols. It may be a mixture of two or more kinds of reactive metals or reactive metal compounds, or a mixture of one or more kinds of each of amines, alcohols, and reactive metals or reactive metal compounds. Furthermore, the acylating agent of this invention can be reacted with an amine, an alcohol, a reactive metal, a reactive metal compound, or a mixture thereof as described above, simultaneously or in any order. Canadian Patent No. 956397 describes a method for reacting the acylating agent of the present invention with an amine, an alcohol, a reactive metal, a reactive metal compound, or a mixture thereof, either sequentially or simultaneously. There is. In order to apply the method described therein to the present invention, it is only necessary to replace the described high molecular weight carboxylic acid acylating agents with the acylating agents of the present invention on an equivalent basis. The carboxylic acid derivative compositions of the present invention prepared using the process described in this Canadian patent document constitute a preferred class of carboxylic acids and carboxylic acid derivatives. For the same reason as above, U.S. Patent No. 3836469, U.S. Patent No. 3836470, which corresponds to the above Canadian patent,
Same No. 3836471, Same No. 3838050, Same No. 3838052,
Same No. 3879308, Same No. 3957854, Same No. 3957855,
Furthermore, U.S. Patent Application No. 644677 (December 29, 1975)
Please write down here. Additionally, these documents explain that the amount of polyoxyalkylene alcohol demulsifier used to prepare the dispersant/detergent from the acylating agents of this invention is typically very small on an equivalent basis. There is. More specifically, a more preferred carboxylic acid derivative composition of the present invention is one prepared according to the method of the above-mentioned Canadian patent and its corresponding US patent, but without the use of a polyalkylene alcohol demulsifier. In other words, preferred carboxylic acid derivative compositions of the present invention replace the high molecular weight carboxylic acid of the Canadian patent with the acylating agent of the present invention on an equivalent basis, and do not use a polyalkylene alcohol demulsifier. Various reaction products obtained by reacting the acylating agents of the invention with one or more amines, alcohols, or reactive metal compounds. Additionally, U.S. Pat. No. 3,806,456 describes methods useful in making products from the acylating agents of this invention and the polyoxyalkylene polyamines described above. By replacing the high molecular weight carboxylic acylating agents described in this patent with the acylating agents of this invention on an equivalent basis, compounds with similar utility and the desired VI improving properties can be obtained. It will be done. US Patent No. 3,576,743 discloses a method for preparing carboxylic acid derivative compositions from polyhydric alcohols and amines, particularly hydroxy-substituted primary amines. A composition having desired dispersion/detergent properties and VI improving properties by replacing the high molecular weight carboxylic acylating agent shown in this U.S. patent with the acylating agent of this invention on an equivalent basis. You can get things. US Pat. No. 3,632,510 describes a method for making mixed ester-metal salts. To prepare a mixed ester-metal salt from the acylating agent of this invention, an alcohol, and a reactive metal compound, the high molecular weight carboxylic acylating agent shown in this U.S. patent is used on an equivalent basis. The reaction may be carried out according to the method of this US patent by replacing the acylating agent. The carboxylic acid derivative composition thus obtained is a preferred embodiment of this invention. Finally, U.S. Patent No. 3755169, U.S. Patent No. 3804763
No. 3,868,330 and No. 3,948,800 disclose a method for producing a carboxylic acid derivative composition. A wide variety of carboxylic acid derivative compositions of the present invention can be obtained by following the methods of these patents and replacing the high molecular weight carboxylic acid acylating agents shown in these patents with the acylating agent of the present invention. . Numerous patent documents have been cited for convenience and for the preparation of carboxylic acid derivatives from the acylating agent of this invention and amines, alcohols, reactive metals, reactive metal compounds, or mixtures thereof. This is because the methods for doing so are obvious to those skilled in the art and a detailed description thereof is not considered necessary. Among the carboxylic acid derivative compositions mentioned so far, those prepared from the acylating agents of the invention and alkylene polyamines, especially polyethylene polyamines and/or polyhydric alcohols, especially polyhydric alkanols, are particularly preferred. . As already mentioned, mixtures of polyamines and/or polyhydric alcohols have also been used. In this preferred carboxylic acid derivative composition, all carboxyl groups of the acylating agent are usually esterified or involved in the formation of an amic acid, amide, imide or imidazoline. As mentioned above, in order to impart the desired viscosity index improving properties to the carboxylic acid derivative composition of the present invention, it is necessary to react the acylating agent of the present invention with a polyfunctional reactant. For example, polyamines with two or more primary and/or secondary amino groups, polyhydric alcohols, aminoalcohols with one or more primary and/or secondary amino groups and one or more hydroxy groups, polyols with one or more primary and/or secondary amino groups and one or more hydroxy groups, These include valent metals and polyvalent metal compounds. It is believed that such polyfunctional reactants provide a bridge or cross-linked structure to the carboxylic acid derivative composition and thus contribute to the viscosity index improving properties. However, the mechanism by which the viscosity index improving property is obtained is not clear, and the present invention is not bound by such a theory. Reactants (a), (b), as carboxylic acid derivative compositions derived in part or in whole from polyhydric alcohols are particularly effective in reducing the use of viscosity index improvers in lubricating compositions. The polyfunctionality of ) and (c) does not fully explain the viscosity index improving properties of the carboxylic acid derivative composition. However, it is not necessary that all of the amines, alcohols, reactive metals, or reactive metal compounds that react with the acylating agent be polyfunctional. Therefore, combinations of monofunctional and polyfunctional amines, alcohols, reactive metals or reactive metal compounds can be used. Examples include a combination of a monoamine and a polyhydric alcohol, a combination of a monohydric alcohol and a polyamine, a combination of an amino alcohol and a monovalent metal compound, and the like. Although the individual factors have not been definitively determined,
The acylating agent of this invention can be reacted with an amine, an alcohol, a reactive metal, a reactive metal compound, or a mixture thereof containing a sufficient number of polyfunctional reactants (e.g., polyamines, polyhydric alcohols). It is therefore believed that at least about 25% of the total number of its carboxyl groups (succinic acid groups, i.e., groups derived from maleic acid-based reactants) must be allowed to react with the polyfunctional reactant. . As far as the viscosity index improving properties of the resulting carboxylic acid derivative compositions are concerned, better results appear to be obtained when at least about 5.0% of the carboxyl groups participate in the reaction with the polyfunctional reactant. In most cases, best results are obtained when the acylating agent of this invention is reacted with a sufficient amount of polyamine and/or polyhydric alcohol (or amino alcohol) to react at least about 75% of its carboxyl groups. is obtained. The percentage values stated herein are "theoretical" in the sense that that percentage of carboxyl groups need not actually react with the polyfunctional reactant. Rather, these percentage values are used to characterize the amount of polyfunctional reactant desirably available for reaction with the acylating agent to obtain the desired viscosity index enhancing properties. From what has been described so far, it can be seen that the carboxylic acid derivative composition of the present invention is somewhat similar to the derivatives of high molecular weight carboxylic acid acylating agents described in the patent literature described above. Will. However, the carboxylic acid derivative compositions of this invention are distinct in important respects because of their unique multifunctionality. Another aspect of this invention is the post-treatment of carboxylic acid derivatives. The method for post-treating carboxylic acid derivatives is similar to that for post-treating derivatives of conventional high molecular weight carboxylic acid acylating agents. Therefore, the same reaction conditions, reactant ratios, etc. as in the prior art can be used. The acylated nitrogen composition obtained by reacting the acylating agent of this invention with the above-mentioned amine can contain boron oxide, boron oxide hydrate, boron halide, boron-containing acid, boron-containing acid, etc. Esters of carbon disulfide, H ₂ S, sulfur, sulfur chloride, alkenyl cyanide, carboxylic acid acylating agents, aldehydes, ketones, urea, thiourea, guanidine,
Dicyandiamide, hydrocarbyl phosphate, hydrocarbyl phosphite, hydrocarbyl thiophosphate, hydrocarbyl thiophosphite, phosphorus sulfide, phosphorus oxide, phosphoric acid, hydrocarbyl thiocyanate, hydrocarbyl isocyanate, hydrocarbyl isothiocyanate, epoxide, episulfide, formaldehyde or formaldehyde-generating compounds. Post-treatment is carried out by contacting with phenols and one or more post-treatment agents selected from the group consisting of sulfur and phenols. The same post-treatment agents can be used for carboxylic acid derivative compositions prepared from the acylating agents of this invention, amines, and alcohols. However, when the carboxylic acid derivative composition of the present invention is derived from an alcohol and an acylating agent, that is, when it is an acidic or neutral ester, the post-treatment agent is usually boron oxide, boron oxide hydrate, selected from the group consisting of boron halides, boron-containing acids, esters of boron-containing acids, sulfur, sulfur chloride, phosphorus sulfide, phosphorus oxide, carboxylic acid acylating agents, epoxides and episulfides. Post-processing methods involving the use of the above-mentioned post-processing agents include:
Since it is known as far as its application to the reaction products of conventional high molecular weight carboxylic acid acylating agents and amines and/or alcohols is concerned,
There is no need to explain it in detail here.
In order to apply conventional methods to the carboxylic acid derivative composition of the present invention, it is sufficient to simply apply conventional reaction conditions, ratios of reactants, etc. to the carboxylic acid derivative composition of the present invention. Post-treatment methods and post-treatment agents applicable to the carboxylic acid derivative compositions of this invention are shown in the following US and British patents: U.S. Patent No. 3087936, U.S. Patent No. 3200107,
Same No. 3254025, Same No. 3256185, Same No. 3278550,
Same No. 3281428, Same No. 3282955, Same No. 3284410,
Same No. 3338832, Same No. 3344069, Same No. 3366569,
Same No. 3373111, Same No. 3367943, Same No. 3403102,
Same No. 3428561, Same No. 3502667, Same No. 3513093,
No. 3533945, No. 3541012 (Use of acidified clay in post-treatment of carboxylic acid derivative compositions derived from acylating agents and amines of the present invention), No. 3639242, No. 3708522, Same number
No. 3859318, No. 3865813, No. 3470098, No. 3369021, No. 3184411, No. 3185645,
Same No. 3245908, Same No. 3245909, Same No. 3245910,
Same No. 3573205, Same No. 3269681, Same No. 3749695,
Same No. 3865740, Same No. 3954639, Same No. 3459530,
Same No. 3390086, Same No. 3367943, Same No. 3185704,
Same No. 3551466, Same No. 3415750, Same No. 3312619,
Same No. 3280034, Same No. 3718663, Same No. 3652616,
UK Patent No. 1085903, UK Patent No. 1162436 and US Patent No. 3558743. The methods shown in these patents belong to this invention when applied to the carboxylic acid derivative compositions of this invention, and the post-treated carboxylic acid derivative compositions obtained according to the methods also belong to this invention. belong to As previously mentioned, the acylating agents, carboxylic acid derivative compositions and post-treated carboxylic acid derivative compositions of the present invention are useful as additives in lubricating oils.
From what has been said so far, it is clear that the acylating agents, carboxylic acid derivative compositions and post-treated carboxylic acid derivative compositions of the present invention, especially the latter two, function primarily as dispersants/detergents and viscosity index improvers. You will find that it does. The lubricating compositions of this invention include lubricating oils and greases, but in most cases are lubricating oils. The lubricating oil compositions of this invention are based on natural oils, synthetic oils or mixtures thereof. The lubricating compositions of this invention include crankcase lubricants for spark ignition and compression ignition internal combustion engines, such as automobile and truck engines, marine and railroad diesel engines. The acylating agent and carboxylic acid derivative composition of the present invention may be used in automatic transmission fluids, transmission shaft lubricants, gear lubricants, metal processing lubricants, pressure fluids, and other lubricating oils and grease compositions. Useful. Natural fuel oils include animal and vegetable oils (e.g. castor oil and lard oil), as well as liquid petroleum oils and paraffinic, naphthenic or mixed paraffinic-naphthenic solvent-treated or acid-treated mineral lubricating oils. . Oils of lubricating viscosity derived from coal or shale are also useful base oils. Synthetic lubricating oils include homopolymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes,
Propylene-isobutylene copolymer, chlorinated polybutylene, etc., poly(1-hexene), poly(1-hexene),
-octene), poly(1-decene), etc. or mixtures thereof), alkylbenzenes (e.g.
dodecylbenzenes, tetradecylbenzenes,
Dinonylbenzenes, di-(2-ethylhexyl)
- hydrocarbon oils and halo-substituted hydrocarbon oils such as benzenes, etc.) and polyphenyls (e.g. biphenyls, terphenyls, alkylated polyphenyls, etc.), as well as alkylated diphenyl ethers and alkylated diphenyl sulfates. and their derivatives, analogs, and homologs. Homopolymers and interpolymers of alkylene oxides, as well as derivatives thereof whose terminal hydroxyl groups have been modified by esterification, etherification, etc., also constitute another group of known synthetic lubricating oils. Examples of this include oils obtained by polymerizing ethylene oxide and propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (e.g. methyl polyisopropylene glycol ether with an average molecular weight of 1000, diphenyl ether of polyethylene glycol, diethyl ether of polypropylene glycol with a molecular weight of 1000-1500) or their mono- and polycarboxylic acid esters, such as acetic acid esters, mixed _C3 - _C8 fatty acid esters or _C13 of tetraethylene glycol It is an oxoacid diester. Other suitable groups of synthetic lubricating oils include dicarboxylic acids (e.g. phthalic acid, succinic acid, alkylsuccinic acid, alkenylsuccinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid) dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid, etc.) and various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). They are esters. Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, dinormalhexyl fumarate, dioctyl sebacate, diisooctyl azelaate, diisodecyl azelate, dioctyl phthalate, and didecyl phthalate. , dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, complex ester of 1 mole of sebacic acid, 2 moles of tetraethylene glycol, and 2 moles of 2-ethylcaproic acid, and the like. Esters useful as synthetic oils also include:
There are those produced from C ₅ -C ₁₂ monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythrite, dipentaerythrite, and tripentaerythrite. Silicone-based oils such as polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils also constitute another useful group of synthetic lubricants (e.g., tetraethyl silicate, tetraethyl silicate, Impropyl, tetra(2-ethylhexyl) silicate, tetra(4-methylhexyl) silicate, tetra(para-tert-butylphenyl) silicate, hexa-(4-methyl-2
- pentoxy)disiloxanes, poly(methyl)siloxanes, poly(methylphenyl)siloxanes, etc.); other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, decylphosphonate). acid diethyl ester, etc.), polymerized tetrahydrofuran, etc. Any of the above-mentioned natural and synthetic types (including mixtures of any two or more of these) of unrefined oil, refined oil, and rerefined oil can be used in the lubricating composition of the present invention. Unrefined oils are those obtained directly from natural or synthetic sources without additional refining treatment. For example, sierre oil obtained directly by retorting, petroleum oil obtained directly by primary distillation, or ester oil obtained directly by esterification and used without further treatment are unrefined oils. It is. Refined oils are similar to unrefined oils except that they have been treated with one or more refining steps to improve one or more properties. The above purification methods are well known to those skilled in the art. For example, solvent extraction, secondary distillation,
These include acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by applying the processes used to obtain refined oils to already used refined oils. Such rerefined oils are also known as reclaimed oils and are often further processed by methods to remove spent additives and oil breakdown products. Generally, to obtain a satisfactory lubricating composition, about 0.05 to 30 parts by weight of at least one of the acylating agent, carboxylic acid derivative or post-treated carboxylic acid derivative composition of this invention per 100 parts of oil is usually used. Dissolve or stably disperse in a proportion of about 0.1 to 15 parts by weight. The lubricant composition may contain, in addition to the composition of the invention, other additives commonly used in lubricants. Such additives include, for example, flow modifiers, ash-forming or ashless auxiliary detergents and dispersants, antioxidants, pour point depressants, defoamers, extreme pressure agents and color stabilizers. be. The acylating agent, carboxylic acid derivative composition, and post-treated carboxylic acid derivative composition of this invention may be added directly to a lubricant such as a lubricating oil to prepare a lubricating composition of this invention. The lubricating compositions of this invention are diluted with at least one substantially inert, normally liquid, organic solvent/diluent, such as a low viscosity oil, to form a concentrate, and this concentrate is added to the lubricating oil in the required amount. You may also prepare the following. The concentrate typically contains from about 20 to about 90% by weight of a substantially inert, normally liquid organic solvent/diluent and the acylating agent, carboxylic acid derivative composition, post-treated carboxylic acid derivative of the present invention. The composition or a mixture of two or more thereof is contained in a proportion of about 10 to about 80% by weight. One or more other additives to be added to the final lubricating composition may be added to the concentrate of this invention, as is commonly practiced in the art. Another advantage of the carboxylic acid derivative compositions of this invention, in particular of the compositions obtained by reaction of the acylating agents of this invention with polyamines and/or polyhydric alcohols, is that they do not pose certain problems. It is said to be effective as a dispersant/detergent in mineral oils. Many mineral oils contain aromatic hydrocarbon components, most of which are fused ring aromatic hydrocarbons. Although the reason is not well understood, oils containing more than 3% by weight of such aromatic hydrocarbons are treated with known dispersants/
It is not improved even by the addition of normal amounts of detergent. However, the carboxylic acid derivative compositions of the present invention, especially those obtained by reaction of the acylating agent of the present invention with one or more polyethylene polyamines and/or one or more polyhydric alkanols, are as described above. It is far superior to known dispersants/detergents in treating heavy oils. Hereinafter, preferred embodiments of the present invention and methods for producing the acylating agent, the carboxylic acid derivative composition, and the post-treated carboxylic acid derivative composition will be explained using Examples. This example illustrates the presently preferred embodiment of the invention. In the following examples, all "%" and "parts" as in this specification and patent claims are by weight unless indicated otherwise. Next, the present invention will be specifically explained by showing examples and comparative examples. Example 1 Polyisobutene (Mn=1845, Mw=5325) 510
(0.28 mol) and 59 parts (0.59 mol) of maleic anhydride was heated to 110°C. The mixture was then heated to 190° C. for 7 hours, during which time 43 parts (0.6 moles) of chlorine gas were introduced from below the surface. 190～
At 192°C, an additional 11 parts (0.16 moles) of chlorine were added over 3.5 hours. The reaction mixture was stripped by heating at 190-193° C. for 10 hours with nitrogen bubbling. The residue has a saponification equivalent number of 87
It was a polyisobutene-substituted succinic acid-based acylating agent in which 1.74 succinic acid groups were bound per equivalent weight of substituent group (measured according to ASTM D-94). So that this acylating agent is 0.3% by weight,
A lubricant composition was prepared by adding an oil having a lubricating viscosity. Example 2 Polyisobutene (Mn=2020, Mw=6049)
A mixture of 1000 parts (0.495 mol) and 115 parts (1.17 mol) of maleic anhydride was heated to 110°C. The mixture was then heated to 184° C. for 6 hours, during which time 85 parts (1.2 moles) of chlorine gas were added subsurface.
At 184-189℃, add 4 parts of chlorine (59 parts (0.83 moles))
I added it over time. The reaction mixture was stripped by heating at 186-190°C for 26 hours with nitrogen bubbling. The residue is the saponification equivalent number
87 (as measured by ASTM D-94), the polyisobutene-substituted succinic acid acylating agent had 1.90 succinic acid groups bound per equivalent weight of substituent group.
Then, in the same manner as in Example 1, the acylating agent was
A lubricant composition containing 0.5% by weight was prepared. Example 3 Polyisobutene (Mn=1696, Mw=6594)
A mixture of 3251 parts of polyisobutene chloride produced by introducing 251 parts of chlorine gas into 3000 parts at 80°C and 345 parts of maleic anhydride was heated to 200 parts in 0.5 hours.
It was heated to ℃. 6.33 This reaction mixture was heated to 200-224℃.
The mixture was held for an hour, then stripped and filtered at 210°C under reduced pressure. The filtrate has a saponification equivalent number of 94 (ASTM D-94
It was a polyisobutene-substituted succinic acid-based acylating agent in which 1.74 succinic acid groups were bonded per equivalent weight of the substituent group (measured by 1). Then, in the same manner as in Example 1, a lubricant composition containing 0.7% by weight of the acylating agent was prepared. Example 4 Polyisobutene (Mn=1845, Mw=5325)
A mixture of 3000 parts (1.63 moles) and 344 parts (3.51 moles) of maleic anhydride was heated to 140°C. The mixture was then heated to 201° C. for 5.5 hours, during which time 312 parts (4.39 moles) of chlorine gas were added subsurface. While bubbling nitrogen through the reaction mixture,
Heat at 201-236°C for 2 hours and strip at 203°C under reduced pressure. By filtering this, the desired saponification equivalent number of 92 (measured by ASTM D-94) is obtained.
A polyisobutene-substituted succinic acid-based acylating agent in which 1.85 succinic acid groups were bonded per equivalent weight of the substituent group was obtained. Then, in the same manner as in Example 1, a lubricant composition containing 0.9% by weight of the acylating agent was prepared. Example 5 Polyisobutene (Mn=2020, Mw=6049)
A mixture of 3000 parts (1.49 moles) and 364 parts (3.71 moles) of maleic anhydride was heated at 220°C for 8 hours.
This mixture was cooled to 170°C. At 170-190℃,
105 parts (1.48 moles) of chlorine gas was added from below the surface over a period of 8 hours. The reaction mixture was heated at 190°C for 2 hours with nitrogen bubbling and then stripped at 190°C under reduced pressure. By filtering this, a desired polyisobutene-substituted succinic acid acylating agent having 2.04 succinic acid groups bound per equivalent weight of the substituent group was obtained. Then, in the same manner as in Example 1, a lubricant composition containing 1.1% by weight of the acylating agent was prepared. Example 6 Within the scope of the claims of this invention, approximately
800 parts polyisobutene with Mn 2000, mineral oil
A mixture of 646 parts and 87 parts of maleic anhydride was heated to 179°C for 2.3 hours. 100 parts of chlorine gas was added subsurface over a period of 19 hours at 176-180°C. This reaction mixture was stripped with nitrogen at 180°C for 0.5 hours, and the resulting residue was a polyisobutene-substituted succinic acylating agent having 1.82 succinic acid groups bound per equivalent weight of substituent group. It was an oil solution. Then, in the same manner as in Example 1,
A lubricant composition containing 1.3% by weight of the acylating agent was prepared. Example 7 Polyisobutene (Mn=1845, Mw=5325)
The process of Example 1 was carried out by replacing polyisobutene with Mn of 1457 and Mw of 5808 on an equimolar basis to obtain the desired polyisobutene-substituted succinic acid system in which 1.71 succinic acid groups were bonded per equivalent weight of substituent group. An acylating agent was obtained. Then, in the same manner as in Example 1, a lubricant composition containing 1.5% by weight of the acylating agent was prepared. Example 8 Polyisobutene (Mn=1845, Mw=5325)
The process of Example 1 was carried out by replacing polyisobutene with Mn of 2510 and Mw of 5793 on an equimolar basis to obtain the desired polyisobutene-substituted succinic acid system in which 1.73 succinic acid groups were bonded per equivalent weight of substituent group. An acylating agent was obtained. Then, in the same manner as in Example 1, a lubricant composition containing 1.7% by weight of the acylating agent was prepared. Example 9 Polyisobutene (Mn=1845, Mw=5325)
The process of Example 1 was carried out by replacing polyisobutene with Mn of 3220 and Mw of 5660 on an equimolar basis to obtain the desired polyisobutene-substituted succinic acid system in which 1.74 succinic acid groups were bonded per equivalent weight of substituent group. An acylating agent was obtained. Then, in the same manner as in Example 1, a lubricant composition containing 1.9% by weight of the acylating agent was prepared. Comparative Example 1 In Example 1, polyisobutene was Mn=
940, Mw/Mn = 2.6 on an equimolar basis, and carried out the process of Example 1 to obtain polyisobutene-substituted succinic acylation in which 1.70 succinic acid groups were bonded per equivalent weight of substituent group. obtained the drug. Then, a lubricant composition was prepared in the same manner as in Example 1. Comparative Example 2 In Example 1, polyisobutene (Mn=
The desired succinic acid group A polyisobutene-substituted succinic acid-based acylating agent having 1.12 bonds per equivalent weight of substituent group was obtained. Then, a lubricant composition was prepared in the same manner as in Example 1. [Evaluation] Table 1 shows the results of evaluating the performance of the lubricant compositions obtained in Examples and Comparative Examples using the following evaluation method. Evaluation Methods The usefulness of the lubricant compositions of the present invention and the advantages of the present invention when compared to the prior art are demonstrated by evaluating the performance of the compounds in the following standard laboratory tests. This test is used to determine the dispersion properties of the oil and its properties in gasoline engine oils (particularly the food sequence V-
It is designed to predict the properties in either the B test or the V-D test. The relative engine burnish and sludge performance of the test lubricants is evaluated by observing the loss of spot shape in formulations containing dispersants. The lubricant formulation is prepared using a fully formulated lubricant designed for V-B and V-D testing. The lubricating oils had the same concentration of acylating agent in each Example and Comparative Example for accurate comparison. Thus, equal chemical concentrations contain the dispersant compounds to be evaluated. An oxidation catalyst is added to the lubricant being tested. The oil is then further contaminated with a sample of the engine drain of the Ford V-C or V-D precipitate. The lubricating oil sample thus impure is maintained at high temperature (approximately 145° C. in an oil bath). During this time, air is passed through the oil sample over an extended period of time, and samples of the test oil are removed and evaluated intermittently. Oil performance is evaluated by spotting samples on Owatman No. 1 chromatographic paper. The samples are evaluated and evaluated based on the time to loss of spot shape. Disappearance of spots is generally noted by a dark external ring with an irregularly shaped internal spot or by the appearance of small dark spots. Such spots indicate that the dispersibility of the sample has deteriorated. This is because in dispersed oil, impurities do not reach the ends of the oil spots. Lubricating oil compositions that have been subjected to this test and which ultimately have increased time to spot disappearance, and therefore have a high rating, are those with Sequence V
-B test or sequence V-D test is expected to show good performance. Evaluation results of lubricating compositions of the invention and comparative compositions (which are summarized in Table 1 (Test A))
was obtained from the dispersibility test method described above. Here, this oil was adulterated by V-C synthetic engine drain testing. The fully formulated lubricant used in this test was Food Sequence V-
The oil was designed for use in the B test. The ratings stated for each oil tested were determined by the following formula: Evaluation = Time to Disappearance of Test Sample / Time to Disappearance of Baseline x Baseline Rating In Test A, the standard baseline dispersant is produced by reacting a substituted succinic acylating agent with a polyamine. It was a dispersant for carboxylic acid derivative compositions. The rating for the baseline dispersant used in Test A was 100.

【table】

[Table] In this way, the effect of the present invention is 30% higher than that of the comparative example.
It is understood that ~67% is also better.

Claims (1)

[Claims] 1. A large amount of oil having lubricating viscosity, and a substituent group derived from a polyalkene having an Mn value of 1300 to about 5000 and an Mw/Mn value of about 1.5 to about 4, and a succinic acid group. A lubricating composition comprising a small amount of one or more substituted succinic acylating agents comprising at least about 1.3 succinic groups per equivalent weight of substituent groups. 2 Succinic acid group is the formula (Here, R and R' are each independently -
OH, -Cl or -O-lower alkyl, or combined to form -O-), and all succinic acid groups need not be identical. The lubricating composition described in . 3 Homopolymers of terminal olefins in which the substituent groups have from 2 to about 16 carbon atoms and interpolymers which may have up to about 40% units derived from internal olefins having up to about 16 carbon atoms. One of the polyalkenes selected from the group consisting of
A lubricating composition according to claim 2, characterized in that it is derived from one or more species. 4 Homopolymers of terminal olefins in which the polyalkene has 2 to about 16 carbon atoms and about 16
Claim 3: one or more polyalkenes selected from the group consisting of interpolymers which may have up to about 40% units derived from internal olefins having up to 40% carbon atoms. The lubricating composition described in .