NO171790B - OIL-SOLUBLE PREPARATION COMPREHENSING THE REACTION PRODUCT OF AN ACYLATION REACTION PRODUCT, A POLYAMINE AND A MONOFUNCTIONAL CARBOXYLIC ACID, A PROCEDURE FOR PREPARING THEREOF USING USE - Google Patents

Description

The present invention relates to an oil-soluble preparation comprising the reaction product of an acylation reaction product, a polyamine and a monofunctional carboxylic acid, a method for its preparation and use of the preparation.

Until now, various dissolution reactions have been carried out between a polymer containing unsaturation and an anhydride.

For example, US Patent No. 2,524,424 relates to the treatment of the rubber-like polymers from butadiene hydrocarbons with carboxylic anhydrides.

US patent no. 2,845,403 relates to the production of rubbery adducts by chemical reaction between maleic anhydride and butyl rubber.

US Patent No. 2,993,057 relates to copolymers prepared from multiolefins and vinyl aromatic compounds having a hydrocarbon group attached to the a-position of the vinyl group.

US Patent No. 3,240,762 relates to a polycyclopentadiene reaction product which is hydrogenated with maleic anhydride.

US Patent No. 3,365,411 relates to a mixture of (1) a polymeric half-ester of a hydroxylated polymer and a saturated or unsaturated polycarboxylic acid or an anhydride or its amination product with (2) a polymeric adduct of a polymer or copolymer of a conjugated diolefin and a unsaturated polycarboxylic anhydride or its amination product.

US Patent No. 3,527,736 relates to the improvement of raw strength of synthetic diene polymers (lithium-polyisoprene) by the reaction with an olefinically unsaturated 1,2-dicarboxylic acid (maleic anhydride) in a solvent.

US patent no. 3,567,691 relates to a method for producing reaction products of synthetic diene rubber with maleic anhydride.

US patent no. 3,766,215 relates to a method for producing adducts from maleic anhydride and liquid polybutadienes of low molecular weight.

US patent no. 3,887,527 relates to the modification of cis-1,4-polyisoprene rubber with maleic anhydride with essentially no increase in gel formation.

US Patent No. 3,935,140 relates to an aqueous coating composition containing a water-soluble or dispersible material prepared by the addition reaction of at least one a,p-unsaturated dicarboxylic compound with a mixture of a natural drying oil and a specific liquid copolymer containing 1,3-pentadiene- and 1,3-butadiene units.

US patent no. 3,952,023 relates to the preparation of an adduct of

(A) a butadiene lower polymer or butadiene lower copolymer and (B) an α,<p->ethylenically unsaturated dicarboxylic acid compound

by a method which is characterized in that said (A) and (B) are caused to react in the presence of one or more compounds selected from (C) p-phenylenediamine derivatives.

US patent no. 3,953,541 relates to a method for the production of polyolefin graft copolymers.

US patent no. 3,998,912 relates to the grafting of carboxylic acids onto copolymers of ethylene and carboxylates.

US Patent No. 4,033,888 relates to lubricating oil additives claimed to have both dispersant and viscosity index improving properties, which are prepared by reacting a block copolymer with maleic anhydride and an alkane polyol. British Patent No. 1,548,464 relates to the reaction of a hydrogenated block copolymer with maleic anhydride and subsequent reaction with an amine-containing compound.

TJS Patent No. 4,073,737 relates to hydrogenated copolymers of conjugated dienes and, if desired, a vinyl aromatic monomers, which are useful as oil additives.

US patent no. 4,410,656 relates to a process for splitting diene gum in the presence of maleic acid or maleic anhydride together with sulfur or an organic sulfur compound capable of generating a thiyl residue.

US patent no. 4,010,223 relates to an adduct containing succinic acid groups linked to an elastomeric copolymer of an EPDM-type copolymer. The reaction is carried out without any free radical initiators.

US patent no. 4,080,493 relates to a method for producing the maleic anhydride adduct of a. liquid polymer.

US patent no. 4,082,817 relates to a process for producing a maleic anhydride adduct of high molecular weight 1,2-poly-butadiene.

US Patent No. 4,089,794 relates to polymeric dispersant additives for lubricating oils comprising ethylene and one or more C3-C28-0(-Olefins which are solution grafted in the presence of a free radical initiator with an ethylenically unsaturated carboxylic acid material at elevated temperatures, and then reacted with a polyfunctional material reactive with the carboxyl groups, such as a polyamine or a polyol.

US patent no. 4,117,036 relates to functional high polymer substances containing a,<p->unsaturated carboxylate and preparations thereof.

US Patent Nos. 4,160,739 and 4,161,452 relate to polyolefinic copolymer additives for lubricants and fuels in which the backbone may be styrene-butadiene copolymers and the grafted units are the residues of a monomer system comprising maleic acid or anhydride with one or more other copolymerizable monomers with this one. Further reaction with amine compounds is described.

US patent no. 4,161,571 relates to a method for producing the maleic anhydride adduct of a liquid polymer.

US Patent No. 4,284,414 relates to mixed alkyl esters of interpolymers for use in crude oils.

US patent no. 4,292,414 relates to a method for producing modified block copolymers by grafting at least one maleic acid compound with an aromatic vinyl compound/conjugated diene compound block copolymer.

US Patent No. 4,505,834 relates to lubricating oil formulations containing graft copolymers as a viscosity index improving agent-dispersant.

US Patent Nos. 4,077,893 and 4,141,847 relate to lubricating oil additives claimed to have both dispersant and viscosity index improving properties which are prepared by hydrogenation of star-shaped polymers with at least four arms of polymers or copolymers of diene and monoalkenyl arenes with an a, <p->unsaturated carboxylic acid, and then reacting the resulting intermediate with either a polyol or an amine.

US Patent No. 4,145,298 relates to nitrogen-containing copolymers which are prepared by the reaction of lithium-treated hydrogenated, conjugated diene-vinylarene copolymers with nitrogen-containing organic compounds.

US patent no. 4,320,019 relates to reaction products produced by reacting EPDM-type copolymers with olefinic carboxylic acid acylating agents to form an acylation reaction intermediate which is further reacted with an amine.

US Patent No. 4,486,573 relates to hydrocarbyl-substituted carboxylic acid reagents containing from 2 to 20 carbon atoms, excluding the carboxyl-based groups, with one or more high molecular weight olefin polymers containing 1-20 carbon atoms.

US Patent No. 4,137,185 relates to a stabilized imide grafting of ethylene copolymer additives for lubricants.

British Patent No. 2,097,800 relates to oil-soluble viscosity index improving ethylene copolymers, such as copolymers of ethylene and propylene, which are reacted or grafted with ethylenically unsaturated carboxylic acid units and further reacted with polyamines containing two or more primary amine groups and a carboxylic acid component.

Accordingly, it is a feature of the present invention to provide an oil-soluble preparation containing polyamines reacted with an acylating, hydrogenated block copolymer in the presence of monofunctional acid.

It is a further feature of the present invention to provide an oil-soluble composition, as indicated above, which is useful as a dispersant as well as a viscosity-improving agent, and which can be prepared in the presence of a solvent or in a solvent-free environment. These and other features of the invention will be apparent from the following description, which describes in detail the preparation of the preparation.

The present invention provides an oil-soluble preparation comprising the reaction product of (D) an acylation reaction product, (F) a polyamine and (G) a monofunctional carboxylic acid, characterized in that (G) consists of a monocarboxylic acid acylating agent or a hydrocarbon-based monocarboxylic acid with from 8 to 20 carbon atoms , while (D) the acylation reaction product is the reaction product of : (A) a hydrogenated block copolymer containing not more than 0.5% of olefinically unsaturated residues which is prepared from a monovinyl substituted aromatic and an aliphatic conjugated diene, which copolymer is a normal block copolymer or a randomized block copolymer with 2 to 5 polymer blocks with at least one block of monovinyl-substituted aromatic and at least one block of aliphatic conjugated diene, and with 20 to 70 wt # monovinyl substituted aromatic blocks and 30 to 60 wt # aliphatic conjugated diene blocks reacted with from 0.2 to 20 wt-# of (B) an α,β-olefinic unsaturated carboxyl reagent contained containing 2 to 20 carbon atoms, other than the carboxyl groups based on the total amount of said (A) block copolymer and said (B) unsaturated carboxylic reagent, and 0.2 to 5 wt # of (C) a free radical initiator based on the weight of said (A) block copolymer and said (B) unsaturated carboxylic reagent.

The invention further provides a method for the production of an oil-soluble preparation, characterized in that it includes reaction of (D) an acylation reaction product, (F) a polyamine and (G) a monofunctional carboxylic acid, wherein said (G) is characterized in that it is a monocarboxylic acid acylating agent or a carbon-based monocarboxylic acid having from 8 to 20 carbon atoms, and wherein said (D) acylation reaction product is the reaction product of: (A) a hydrogenated block copolymer containing not more than 0.5$ of olefinically unsaturated residues which is prepared from a monovinyl substituted aromatic and an aliphatic conjugated diene, which copolymer is a normal block copolymer or a randomized block copolymer with 2 to 5 polymer blocks with at least one block of monovinyl-substituted aromatic and at least one block of aliphatic conjugated diene and with 20 to 70 wt. # monovinyl substituted aromatic blocks and 30 to 80 wt-# aliphatic conjugated diene blocks, 0.2 to 20 wt-# of (B) of a cx-p olefinic unsaturated carboxylic reagent containing 2 to 20 carbon atoms, excluding the carboxyl groups, based on the total weight of said (A) copolymer and said (B) unsaturated carboxylic acid reagent, and 0.1 to 5 wt-56 of a (C ) free radical initiator based on the weight of said (A) copolymer and said (B) unsaturated carboxylic reagent.

Finally, the invention includes the use of a preparation as mentioned above in an amount of from 1 to 40% by weight together with a liquid diluent, as an additive concentrate.

As for the (A) hydrogenated block copolymer, it includes either a normal block copolymer, i.e. a true block copolymer or a randomized block copolymer. As for the true or normal block copolymer, it is generally prepared from conjugated dienes containing 4-10 from vinyl-substituted aromatic units containing 8-12 carbon atoms, and preferably 8 or 9 carbon atoms.

Examples of vinyl-substituted aromatic units include styrene, α-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, para-tertiary-butylstyrene, styrene being preferred. Examples of such conjugated dienes include piperylene, 2,3-dimethyl-1,3-butadiene, chloroprene, isoprene and 1,3-butadiene, isoprene and 1,3-butadiene being particularly preferred. Mixtures of such conjugated dienes are useful.

The normal block copolymers contain a total of from 2 to 5, and preferably 2 or 3, polymer blocks of the vinyl-substituted aromatic unit and the conjugated diene with at least one polymer block of said vinyl-substituted aromatic unit and at least one polymer block of said conjugated diene present . The conjugated diene block is hydrogenated as indicated more fully below. The normal block copolymers may be linear block copolymers in which a significantly long sequence of one monomer unit (block I) is linked to another long sequence of a second (block II), third (block III), fourth (block IV) or fifth (block V) monomer unit. If e.g. a is a styrene monomer unit and d is a conjugated diene monomer unit, a tri-block copolymer of these monomer units can be represented by the formula:

These copolymers can also be radial block copolymers in which the polymer blocks are connected radially as indicated by the formula:

In practice, the number of repeating units included in each polymer block is usually greater than 500, but may be less than 500. The sequence length in a block should be long enough for the block copolymer to exhibit the inherent homopolymer physical properties, such as glass transition temperature and polymer melting temperature.

The content of the vinyl-substituted aromatic unit in these copolymers, i.e. the total amount of vinyl-substituted aromatic blocks in the normal block copolymer, ranges from 20 to 70 wt-56, and preferably from 40 to 60 wt-#. Accordingly, the content of aliphatic conjugated diene, i.e. the total diene block content, in these copolymers ranges from 30 to 80 wt-56, and preferably from 40 to 60 wt-#.

These normal block copolymers can be prepared by conventional methods well known in the art. Such copolymers are usually prepared by anionic polymerization using, for example, an alkali metal hydrocarbon (eg, sec-butyllithium) as a polymerization catalyst.

Examples of suitable normal block copolymers, as indicated above, include "Shellvis-40" and "Shellvis-50", both hydrogenated styrene-isoprene block copolymers, manufactured by Shell Chemicals.

As for the randomized block copolymer which may be used separately, in combination with the normal block copolymers indicated above, or not at all, it is generally defined as a block copolymer containing one or more block polymer moieties. More specifically, the randomized block copolymers can be defined as an indefinite number of a- and d-blocks of indefinite lengths. These randomized copolymers are generally prepared from conjugated dienes of the type indicated above with butadiene and isoprene being particularly preferred. The remaining monomer used to prepare the randomized block copolymer comprises vinyl-substituted aromatic units of the type indicated above. A suitable type of aromatic monomer is styrene. The randomized block copolymer can be prepared by simultaneously feeding a mixture of monomers to a polymerization system rather than feeding the monomers in a stepwise manner. The amount by weight of the various blocks is as indicated above, ie from 20 to 70 wt-56 vinyl-substituted aromatic blocks, 40-60 wt-# such blocks being preferred. Consequently, the amount of the diene blocks is the difference. The number average molecular weight and the weight average molecular weight. for the randomized block copolymers are as indicated above. The randomized block copolymers contain substantial blocks of a vinyl-substituted aromatic repeating unit and/or substantial blocks of a conjugated diene repeating unit and/or random or randomly decreasing conjugated diene/vinyl-substituted aromatic blocks. These copolymers can also be represented as A'-B'-A'-B'-, where A<*>is a block of a vinyl-substituted aromatic compound, B' is a block of conjugated diene, and the length of A'- and B' blocks vary greatly and are significantly shorter than the A and B blocks of a normal block copolymer. The range of aromatic block content in the randomized block copolymer should preferably range from 15 to 45, more preferably 25 to 40 wt.

Examples of such commercially available randomized block copolymers include the various "Glissoviscal" block copolymers manufactured by BASF. A previously available randomized block copolymer was "Phil-Ad" viscosity improver, manufactured by Phillips Petroleum.

Regardless of whether a true or normal block copolymer or a randomized block copolymer is used, or combinations thereof, they are hydrogenated prior to use in the present invention to remove substantially all of the olefinic double bonds. Techniques for achieving this hydrogenation are well known to those skilled in the art and will not be described in detail at this point. Briefly, hydrogenation is achieved by contacting the copolymers with hydrogen at above atmospheric pressure in the presence of a metal catalyst, such as colloidal nickel, palladium supported on charcoal, etc.

In general, it is preferred that these block copolymers, for reasons of oxidative stability, contain no more than 5%, and preferably no more than 0.5%, of residual olefinic unsaturation based on the total number of carbon-to-carbon covalent bonds in the average molecule. Such unsaturation can be measured by a variety of methods well known to those skilled in the art, such as infrared spectroscopy, NMR, etc. Most preferably, these copolymers contain no detectable unsaturation, as determined by the aforementioned analytical techniques.

The (A) block copolymers typically have number average molecular weights in the range from 10,000 to 500,000, preferably

30,000 to 200,000. The weight average molecular weight of these copolymers is generally in the range of 50,000 to 500,000, preferably 30,000 to 300,000.

The unsaturated carboxyl reagent (B) generally contains an α,<p->olefinic unsaturation. By the term oe, p-olefinically unsaturated carboxylic acid reagent is meant including a,<p->olefinically unsaturated carboxylic acids (B) per se and functional derivatives thereof, such as anhydrides, esters, amides, imides, salts, acyl halides and nitriles. These carboxylic acid reagents can be either monovalent or polyvalent in nature. When polyvalent, they are preferably dicarboxylic acids, although tri- and tetracarboxylic acids may be used. Examples of the monovalent α,β-olefinically unsaturated carboxylic acid reagents are the carboxylic acids corresponding to the formula:

wherein R is hydrogen or a saturated aliphatic or alicyclic, aryl, alkylaryl or heterocyclic group, preferably hydrogen or a lower alkyl group, and R 2 is hydrogen or a lower alkyl group. By lower alkyl is meant containing from 1 to 10 carbon atoms. The total number of carbon atoms in R and Rj should not exceed 18 carbon atoms. Specific examples of useful monovalent α,β-olefinically unsaturated carboxylic acids are acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, 2-phenylpropenoic acid, etc. Examples of polyvalent acids include maleic acid, fumaric acid, mesaconic acid, itaconic acid and citraconic acid.

The α,β-olefinically unsaturated reagents (B) also include functional derivatives of the preceding acids, as indicated. These functional derivatives include the anhydrides, esters, amides, imides, salts, acid halides and nitriles and other nitrogen-containing compounds of the aforementioned acids. A preferred α,<β->olefinically unsaturated carboxylic acid reagent (B) is maleic anhydride.

Methods for the preparation of such functional derivatives are well known to those skilled in the art and they can be satisfactorily described by noting the reactants used to prepare them. Consequently, e.g. derivative esters for use in the present invention are produced by esterification of monohydric or polyhydric alcohols or epoxides with any of the previously mentioned acids. Amines and alcohols, described below, can be used to prepare these functional derivatives. The nitrile-functional derivatives of the above-mentioned carboxylic acid which are useful in the production of the products according to the present invention can be prepared by converting a carboxylic acid into the corresponding nitrile by dehydrating the corresponding amide. The preparation of the latter is well known to those skilled in the art and is described in detail in "The Chemistry of the Cyano Group" edited by Zvi Rappoport, Chapter 2. Specific examples of such nitrogen-containing functional derivatives include maleimide and maleamic acid. More specifically, such amine-functional derivatives of the α,β-olefinically unsaturated reagent (B) may have the formula:

wherein R<**> and R<3>, independently of each other, may be hydrogen, an alkyl containing from 1 to 12 carbon atoms, and preferably from 1 to 6 carbon atoms, an alkyl-substituted aromatic group containing from 7 to 12 carbon atoms, and preferably from 7 to 9 carbon atoms, or a unit containing N, O or S as heteroatoms. Examples of highly preferred compounds include N-(3,6-dioxaheptyl)maleimide, N-(3-

dimethylaminopropyl)maleimide and N-(2-methoxyethoxyethyl)maleimide.

Ammonium salt derivatives may also be prepared from any of the amines described below, as well as from tertiary amino analogs thereof, ammonia or its derivatives, (e.g., NE4Cl, NH4OH, (NH4)2CO3, etc.) by conventional techniques which are well known to the person skilled in the art.

The acid halide-functional derivative of the previously mentioned olefinic carboxylic acids (B) can be prepared by the reaction of the acids and their anhydrides with a halogenating agent, such as phosphorus tribromide, phosphorus pentachloride or thionyl chloride. Esters can be prepared by reacting the acid halide with the previously mentioned alcohols or phenolic compounds such as phenol, naphthol, octylphenol, etc. Furthermore, amides and imides and other acylated nitrogen derivatives can be prepared by reacting the acid halide with the above-mentioned amino compounds. These esters and acylated nitrogen derivatives can be prepared from the acid halides by conventional techniques well known to those skilled in the art.

It is important that an effective amount of the (B) reagent is used so that sufficient dispersibility is provided to (D) the acylated reaction product. Often an amount of (B) reagent of from 0.20 to 20 wt-#, and suitably from 0.5 to 5 wt-#, based on the combined weight of the (A) block copolymer and (B) reagent, is used. In general, such amounts are sufficient to ensure that from 0.1 to 3% by weight of the (D) reaction product is said (B) reagent.

With respect to the solvent-free reaction, the reaction temperature between (A) the hydrogenated block copolymer and (B) reagent will depend to some extent on the type of block copolymer as well as the type of initiator system used. Generally, the reaction temperature is from 100°C to 300°C, suitably from 160°C to 260°C, preferably from 220°C to 260°C. Although not necessary, the reaction may be carried out in an inert atmosphere, such as nitrogen .

The solvent-free reaction between the hydrogenated block copolymers and the unsaturated carboxylic acids or derivatives thereof can generally take place in any suitable container, device or apparatus without the presence of any solvent. Conveniently, the reaction takes place in a mixing device such as an extruder, a Banbury mixer, a two-roll mill or the like.

As an optional and important feature of the present invention, the mixing device provides high mechanical energy to such an extent that a sufficient force is applied to the (A) block polymer chains to cause their cutting or breakdown. The application of such high mechanical energy to cause chain cutting is generally not desirable. However, it may be desirable in situations where the molecular weight of the block copolymer is higher than desired and consequently breaks down to a suitable range, or when the viscous nature of the block copolymer requires a mixing system with high mechanical energy for processing. Such devices with high mechanical energy can be the same type of mixing device as indicated above and generally provide high torque or breakdown of the constituents contained therein. As a side reaction, it is assumed that the block copolymer chains which are thereby broken down give terminal chain ends which serve as reaction sites for the (B) reagent. Accordingly, it is believed that in addition to causing the actual chain degradation, the high mechanical energy devices create reaction sites in addition to those formed by the (C) free radical initiators. However, it must be emphasized that such chain decomposition creates very few reaction sites compared to the free radical reaction.

To promote reaction and to create reaction sites, free radical initiators are generally used. Two types of such initiators include the various organic peroxides as well as the various organic azo compounds. The amount of initiators, based on the amount of the (A) block copolymers and (B) reagent, used is generally from 0.01 to 5.0 wt-#, and suitably from 0.05 to 2.0 wt-56 is used . Typical organic peroxides include benzoyl peroxide; t-butyl peroxy pivalate; 2,4-dichlorobenzoyl peroxide; decanoyl peroxide; propionyl peroxide; hydroxyheptyl peroxide; cyclohexanone peroxide; t-butyl perbenzoate; dicumyl peroxide; 2,5-dimethyl-2,5-di(t-butylperoxyl)-3-hexane; 2,5-dimethyl-2,5-di(t-butylperoxyl)hexane; 2,5-dimethyl-2,5-dibenzoyl-peroxyhexane; t-butyl peroxide; cumene hydroperoxide; 2,5-dimethyl-2,5-di(hydroperoxy)hexane;

t-butyl hydroperoxide; lauroyl peroxide; t-amyl perbenzoate and mixtures thereof. Preferred organic peroxides are benzoyl peroxide, t-butyl peroxide and t-butyl perbenzoate. Mixtures of two or more of the above peroxides can also be used.

Naturally, handling of the peroxides must be done with the greatest care because of their tendency to decompose or react violently. Accordingly, the user should be thoroughly familiar with their properties as well as appropriate handling procedures prior to any contact with the compounds.

Examples of suitable organic azo initiators include 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylvaleronitrile) and 4,4'-azobis(4-cyanovaleric acid).

The extent of reaction between the (B) reagent, such as maleic anhydride, as incorporated on the block copolymers is generally measured by a total acid number or TAN. The TAN number is suitably from 0.1 to 60, from 0.5 to 20 is preferred. The definition of the TAN number is the number of mg of K0E required to neutralize the acid functional groups in 1 g of the reaction product of (A) the block copolymer and (B) the α,β-olefinically unsaturated carboxyl reagent. (D) the reaction products of the present invention are useful as intermediates as well as viscosity improvers for all-season oils.

In the following, the invention will be described in more detail by means of examples.

EXAMPLES I - III

Three commercial viscosity index improvers (VI improvers) were functionalized with maleic anhydride in a laboratory scale extruder. The extruder used in these experiments was of the single screw type driven by a "C.W. Brabender Plasti-Corder" torque rheometer. No form was used.

To ensure homogeneous extruder feedstocks, the crushed VI-enhancing polymer was coated with maleic anhydride and tert-butyl peroxide prior to extrusion. This was accomplished by dissolving both maleic anhydride and tert-butyl peroxide in acetone, spraying the acetone solution evenly over the separated polymer, and allowing the acetone solvent to evaporate. This process leaves only the maleic anhydride and peroxide coated crushed polymer as a residue. Specifically, a homogeneous extruder feedstock consisting of 96.5 wt-# ground polymer, 3.2 wt-# maleic anhydride and 0.3 wt-# di-tert-butyl peroxide was fed to the feed zone of the extruder.

The reaction mixture was passed through the three heating zones of the extruder vessel by means of a single screw. The container length of the laboratory scale extruder used was 47.63 cm. The residence time in each of the three zones of the extruder vessel is given by the following relation: In each of the following three examples, the first zone was used only to preheat the extruder feedstock to an initiation temperature of 160°C. Although the reaction between the components started, it took place at a low rate and most of the reaction took place in the last two zones. The approximate reaction times are indicated in the examples.

Example I

Maleinized "Shellvis 40"

Extruder raw material: 760 g "Shellvis 40"

26 g of maleic anhydride

3 g di-tert-butyl peroxide Extruder screw speed = 75 rpm

Residence time at temperatures:

7 seconds at 160°C (zone 1)

7 seconds at 240°C (zone 2)

7 seconds at 260°C (zone 3)

Approximate reaction time = 21 seconds

TUE 10-15

Example II

Maleinized BASF "Glissoviscal CE 5260"

Extruder raw material: 626 g "Glissoviscal CE"

21 g of maleic anhydride

2 g di-tert-butyl peroxide Extruder screw speed = 50 rpm

Residence time at temperatures:

10 seconds at 160°C (zone 1)

10 seconds at 240°C (zone 2)

10 seconds at 260°C (zone 3)

Approximate reaction time = 30 seconds

TAN 10-15

Example III

Maleinized "Shellvis 50"

Extruder raw material: 626 g "Shellvis 50"

21 g of maleic anhydride

2 g di-tert-butyl peroxide Extruder screw speed = 50 rpm

Residence time at temperatures:

10 seconds at 160°C (zone 1)

10 seconds at 240°C (zone 2)

10 seconds at 260"C (zone 3)

Approximate reaction time = 30 seconds

TAN 10-15

In a similar way, the same mixing experiments were carried out at other temperatures, such as at approx. 160, 180, 200 and 220°C.

The reaction mixture is dissolved as a 10% solution in toluene. It is then slowly poured into methyl alcohol with rapid stirring to precipitate the polymer. The polymer is isolated by decantation and dried in an open bowl at approx. 60°C. Conveniently, any unreacted (B) carboxyl reagent, such as maleic anhydride, is removed by any conventional means, e.g. by cleavage in vacuum.

An alternative method is to carry out the above reaction in the presence of one or more solvents to form

(D) the acylation reaction product. The solvent used may be any common or conventional solvent, such as those known in the art and literature. Appropriate and suitable solvents include the various oils which are lubricant feedstocks such as the natural and/or synthetic lubricating oils listed below. Briefly, natural oils include mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Animal and vegetable oils

can also be used. Synthetic lubricating oils used are alkylated aromatic compounds, poly-a-olefins, alkyl phosphates and the esters derived from polyhydric acids, polyols and fatty acids. Examples of solvents include solvent-refined 100-200 neutral mineral paraffinic and/or naphthenic oils, diphenyldodecanes, didodecylbenzenes, hydrogenated decene oligomers and mixtures of the above. The amount of oil should be regulated so that the viscosity of the reaction mixture is suitable for mixing. Typically, from 70 to 99% by weight of the overall reaction mixture can be used in the form of oil.

Although the reactions in this embodiment of the invention are carried out in the presence of a solvent, the various reactants are the same as stated above. For example, the various (A) hydrogenated block copolymers can be either the normal block copolymers indicated above, containing from 2 to 5 total block moieties or the randomized block copolymers. The randomized block copolymers may also have the same number average molecular weight range as indicated above. The unsaturated carboxyl reagent (B) is the same as stated above. The reagent can therefore contain cx,p-olefinically unsaturated carboxylic acids including various functional derivatives thereof containing from 2 to 20 carbon atoms, apart from the carboxyl-based groups. (C) the initiators are also the same as stated above with respect to the solvent-free reaction and include the organic peroxides and the various organic azo compounds. The various reaction parameters, conditions, methods and the like are also the same as stated above, unless otherwise stated below.

The preparation of the (D) acylation reaction product is generally equivalent to the procedure indicated above, except that a solvent, e.g. a neutral mineral oil is used. Any conventional or suitable reaction vessel or container is used, such as a reaction flask. The mineral oil is initially added to the reaction vessel in a desired amount and heated. If the reaction is to be carried out in an inert atmosphere, the container can initially be flushed with an inert gas such as nitrogen. Longer residence times are generally required to react the generally larger amounts of reactants contained in the reaction vessel. Although the temperature may therefore be from 100°C to 300°C, they are suitably somewhat lower, such as from 130°C to 180°C, from 140°C to 175°C is preferred. The process is generally carried out by heating the solvent to a suitable reaction temperature. (A) the block copolymer is then added and allowed to dissolve over a period of time on the order of hours, e.g. a few hours. The (B) α,β-olefinically unsaturated carboxyl reagent is then added. The (C) free radical initiator is then added, and the reaction is carried out at a suitable temperature, such as from 140°C to 170°C. Appropriately, the initiator is added slowly, e.g. drop by drop, over a period of several minutes and even hours. When the addition of the (C) initiator is complete, the solvent is held at the reaction temperature for a period of time until a desired yield is obtained, typically for Vt to 2 hours. Naturally, much shorter and longer time periods can be used. (D) the acylation reaction product thereby formed can be used as a viscosity improving agent or as an intermediate for further reaction with a (E) primarily amine-containing compound.

The invention will be better understood with the help of the following examples.

EXAMPLE IV

A 1750 g sample of a hydrogenated styrene/butadiene copolymer (BASF "Glissoviscal CE 5260") is placed in a 12 L bottle containing 5250 g of Sun "HPO 100N" oil heated to 150°C. During this step and throughout the reaction sequence, a blanket of N2 and mechanical stirring is maintained. Within 3 hours, a homogeneous solution is achieved. 35 g of maleic anhydride are filled into the flask and dissolved completely, while the reaction temperature is increased to 160°C. A dropwise addition of 14.1 g of the t-butyl peroxide initiator is added to the reaction mixture over the course of one hour. The solution is stirred at 160°C for an additional 1.5 hours, the ^-blanket is then replaced with a subsurface flush (0.06 m<5>/hour). The reaction mixture is heated to 170°C and held there for 2.0 hours to remove unreacted maleic anhydride and peroxide decomposition products. Infrared analysis of the polymer solution confirms the presence of succinic anhydride groups in the product. Treatment of a 50 g sample of the product with 0.1 g DETA (diethylenetriamine) at 110°C causes immediate gelation. This confirms that on average each polymer molecule contains more than one succinic anhydride group. Titration of a toluene solution of the product with 0.1N NaOCH3 indicates a TAN = 5.4 (95% maleic anhydride converted). Dialysis of the polymer solution shows that 20-3056 of the TAN is succinic anhydride bound to the polymer substrate, while 70-8056 of the TAN is succinic anhydride associated with the "100N" oil.

EXAMPLE V

Similarly, a reaction product is prepared using "Shellvis 40", a hydrogenated styrene-isoprene block copolymer manufactured by Shell Chemicals. The amount of "Shellvis 40" is 10.0 wt-56, the amount of maleic anhydride is 0.50 wt-56 and the amount of neutral oil is 89.5 wt-56. These components are filled into a flask as indicated in Example IV, and heated while 0.5 wt-56 t-butyl peroxide is added dropwise over a period of one hour. The solution is stirred at 160°C for a further 1.5 hours. The nitrogen blanket is then replaced with a subsurface flush. The reaction mixture is heated to 170°C and held there for 2 hours to remove unreacted maleic anhydride and peroxide decomposition products. Infrared analysis of the polymer solution confirms the presence of succinic anhydride groups in the product. Treatment of a 50 g portion of the product with 0.1 g of diethylenetriamine at 110°C causes a dramatic viscosity increase confirming that a significant amount of succinic anhydride groups are attached to the polymer substrate. TAN was 5.4 (theoretical 5.5 ).The number average molecular weight is about 160,000, and the weight average molecular weight is about 200,000.

EXAMPLE VI

In a method similar to example IV, a reaction product is prepared using "Shellvis 50", a hydrogenated styrene-isoprene block copolymer manufactured by Shell Chemicals, with a lower molecular weight than "Shellvis 40". The amount of "Shellvis 50" is 14.9 wt-#, the amount of maleic anhydride is 0.3%, and the amount of 100 neutral oil is 84.8 wt-#. The reactants are heated as indicated in Example IV, and then 0.2 wt # of t-butyl peroxide initiator is added to the reaction mixture over a period of one hour, and the solution is stirred at 160°C for a further 1.5 hours. As before, the nitrogen blanket is replaced by a flush under the surface. The reaction mixture is heated to 170°C and held at this temperature for 2 hours to remove unreacted maleic anhydride and peroxide decomposition products. Infrared analysis of the polymer solution confirms the presence of succinic anhydride groups in the product. Treatment of a portion of 50 g of product with 0.1 g of diethylenetriamine at 110°C causes a significant increase in viscosity. This confirms that a significant amount of succinic anhydride groups are attached to the polymer. TAN was 3.5 (theoretical 3.4), and the polymer solution was clear.

Regardless of whether a solvent-free process is used, carried out in an extruder or other apparatus, or whether a dissolution process is used, (D) reacts the reaction product with (E) a primarily amine-containing compound. The term "primary amine-containing compound" means ammonia or a compound containing only one primary amino group. That is that although the compound may contain a large number of nitrogen atoms, only one such nitrogen atom forms a primary amine group. Otherwise, an undesirable gel is often obtained.

The (E) primarily amine-containing compounds in connection with the present invention can roughly be represented by the formula R-NH2, where R is hydrogen, an alkyl, a cycloalkyl, an aromatic group or combinations thereof, e.g. an alkyl-substituted cycloalkyl. Furthermore, R can be an alkyl, an aromatic group, a cycloalkyl group, or combinations thereof containing one or more secondary or tertiary amine groups. R can also be an alkyl, a cycloalkyl, an aromatic group, or combinations thereof containing one or more heteroatoms (eg oxygen, nitrogen, sulfur, etc.). R can also be an alkyl, a cycloalkyl, an aromatic group or combinations thereof containing sulphide or oxy bonds. In general, R is hydrogen, or said various R groups containing from 1 to 25 carbon atoms, from 1 to 6 or 7 carbon atoms being desirable. Examples of such (E) primarily amine-containing compounds are the following, in which R is as indicated above: ammonia, N,N-dimethylhydrazine, methylamine, ethylamine, butylamine, 2-methoxyethylamine, N,N-dimethyl-1,3-propanediamine, N -ethyl-N-methyl-1,3-propanediamine, N-methyl-1,3-propanediamine, N-(3-aminopropyl)morpholine, 3-Alkoxypropylamines in which the alkoxy group contains 1-18 carbon atoms, usually an alkoxy group containing 1-8 carbon atoms and have the formula R<1->0-CH2CH2CH2-NH2such as 3-methoxypropylamine, 3-isobutoxy-propylamine and 3-(Alkoxypolyethoxy)propylamines with the formula R<1>0(CH2CH20)XCH2CH2CH2NH2in which the alkoxy group is as stated above and where x is 1-50, 4,7-dioxaoctylamine, N-(3-amino-propyl)-N^-methylpiperazine, N-(2-aminoethyl)piperazine, (2-aminoethyl)-pyridines, aminopyridines, 2-aminomethylpyridines, 2 -aminomethylfuran, 3-amino-2-oxotetrahydrofuran, N-(2-aminoethyl)pyrrolidine, 2-aminomethylpyrrolidine, l-methyl-2-aminomethylpyrrolidine, 1-aminopyrrolidine, l-(3-aminopropyl)-2-methylpiperidine, 4- amino methylpiperidine, N-(2-aminoethyl)-morpholine, 1-ethyl-3-aminopiperidine, 1-aminopiperidine, N-aminomorpholine and the like.

Of these compounds, N-(3-aminopropyl)morpholine and N-ethyl-N-methyl-1,3-propanediamine are preferred, N,N-dimethyl-1,3-propanediamine is strongly preferred.

Another group of (E) primarily amine-containing compounds are the various amine-terminated polyethers. A specific example of such a polyether is given by the formula:

wherein n is from 0 to 50, from 5 to 25 is preferred, m is from 0 to 35, from 2 to 15 is preferred, and R<2> is an alkyl containing from 1 to 18 carbon atoms.

The reaction between (E) the primarily amine-containing compound and

(D) the acylation reaction product can be carried out without a solvent or in a solvent system, such as in a

lubricating oil.

In the formation of the (D) reaction product, any suitable container or device can be used, such as an extruder, a Banbury mixer or the like. The mixing device suitably provides a suitable high mechanical energy to the compounds, i.e. (D) the acylation reaction product and (E) the primarily amine-containing compound, so that a solvent-free reaction can be carried out with good mixing of the components. The reaction between (D) the acylation reaction product and (E) the primarily amine-containing compound generally takes place by heating to from 50° C. to 250° C., from 140° C. to 180° C. is preferred. Conveniently, the reaction takes place in the presence of an inert gas, such as nitrogen or argon. The time for carrying out the reaction generally depends on the reaction temperature, the desired yield and the like. When a mixing device such as an extruder is used, which contains a relatively small amount of reactants, the reaction time is generally relatively short.

The reaction with (E) the primarily amine-containing compound can also be carried out in the presence of one or more solvents. The solvent used in the solvent or solvent-type reaction may be any common or conventional solvent known in the art or literature. More specifically, the solvent may be as indicated above in connection with the solvated formation of the (D) acylation reaction product. That is that conventional oils of general lubricating viscosity, such as natural and/or synthetic lubricating oils indicated above, can be used. A more detailed description of such oils is also provided below. In general, a neutral lubricating oil is used.

The solvent, e.g. lubricating oil, may be added to the reaction vessel, heated and (D) the acylation reaction product may be added thereto. (E) the primarily amine-containing compound may then be added. Although this addition order is appropriate, it can be varied. Another source of oil is to use the solution of the (D) acylation reaction product which is carried out in a significant amount of oil.

The reaction conditions for (D) the acylation reaction product with (E) the primarily amine-containing compound in a solution are essentially the same as stated above in connection with the solvent-free reaction conditions. However, the temperature of the reaction is from 50°C to 250°C, and preferably from 150°C to 190°C. The reaction is conveniently carried out in an inert gas. The amount of the various reactants is also as indicated above.

In any case, it is an important feature of the present invention that essentially only (E) primarily amine-containing compounds are used, i.e. compounds which only contain a primary amine group as described above.

An effective amount of (E) the primarily amine-containing compound is used so that an oil-soluble dispersant-VI improver is formed. In general, an amount of (E) the primarily amine-containing compound is used so that there are from 0.1 to 3.0 primary amine groups for every two carbonyl groups or for every anhydride group of said (D) acylation reaction product. Suitably there are from 0.5 to 1.5 primary amine-containing groups for every two carbonyl groups or each anhydride group, and preferably from 0.9 to 1.1 primary amine groups for every two carbonyl groups or each anhydride group. Naturally, larger or smaller amounts can be used, but tend to be ineffective and/or expensive.

The invention will be easier to understand with the help of the following examples.

EXAMPLE VII

A 3000 g sample of the 24.956 polymer solution prepared in Example IV is charged to a 12 L flask equipped with a mechanical stirrer, thermometer, Ng inlet, addition funnel, Dean-Stark water trap, cooler and heating jacket. "Wibarco Heavy Alkylate"

(Wibarco GmbH; 3212.9 g) is added and the mixture is stirred and heated to 150°C under a Ng blanket to obtain a homogeneous solution (about 2.0 hours). When this solution is obtained, 14.9 g of N,N-dimethyl-1,3-propanediamine (Eastman Kodak Co.) is added dropwise to the mixture from the dropping funnel over the course of 0.5 hours. When all the amine has been added, the reaction mixture is heated to 170°C and held there for 3.0 hours. The Ng blanket is switched to subsurface flushing (0.03 m<5>/hr) during the last hour of the reaction period to remove byproduct water. This 12 wt-56 polymer solution is the final product. Analysis of the final product gives an ANA nitrogen content of 0.06556. Infrared analysis of the product confirms imide formation without any residual anhydride absorption. The kinematic viscosity at 100°C for this dispersant VI concentrate is 240 cSt.

An API SF/CC, SAE 15W40 oil was prepared by blending 12.5 wt-# of the final product of Example VII, 10.6 wt-56 of performance additive A<a>), 0.4 wt-# "Acryloid 156 " in a lubricating oil feedstock. This oil thus contains 1.5% by weight of the product copolymer. When examined in the "Caterpillar 1G-2" engine trial, a characteristic of TGF = 73 was observed; WTD = 217.6 after an experimental period of 480 hours.

An API SF/CC SAE 10W30 oil was prepared by mixing 11 wt-56 of Product Dispersant-VI, 8.45 wt-56 of Performance Additive B<*>), 0.2 wt-56 "Acryloid 156" in a lubricating oil -raw material. This oil therefore contains 1.32 wt-56 of the product copolymer. When examined in the "Ford Sequence VD" engine test, a performance characteristic of 9.5 sludge, 7.2 coating and 6.8 piston skirt coating was achieved after 192 test hours.

a) Performance Additive A; % SA - 13.44, #Zn = 1.12, SéP = 1.02,

%Ca = 2.04, #Mg = 0.99, 5ÉN = 0.25, %S = 3.47, TBN =96.9

b) Performance additive B: #SA - 12.29, #Zn = 1.56, 5éP = 1.41,

#Ca = 1.23, #Mg - 1.16, #N = 0.52, $>S = 4.27, TBN = 85.8

EXAMPLE VIII

In a method corresponding to example VII, 5500 g of the 10 wt-56 polymer solution prepared in example V is filled into a reactor. Diphenylalkane (Vista Chemical Co.; 2332.1 g) is added and the mixture is stirred and heated to 150°C under a Ng blanket. When a homogeneous solution is obtained, 27.3 g of N,N-dimethyl-1,3-propanediamine (Eastman Kodak Co.) is added dropwise to the mixture over 0.5 hour. After all the amine has been added, the reaction mixture is heated to 170°C and held there for 3.0 hours. The nitrogen blanket is changed to a subsurface flush during the last hour of the reaction period to remove byproduct water and provide a final product. Analysis of the final product gives an ANA nitrogen content of 0.09456 (theoretical 0.09456). Infrared analysis of the product confirms imide formation without any residual anhydride absorption. The kinematic viscosity at 100°C for this dispersant VI concentrate is 4353 cSt. The product is ready.

An API SF/CC, SAE 10W30 oil is made by mixing 9.556W of Product Dispersant-VI, 4.2 wt-56 of Performance Additive C<c>), into a lubricating oil feedstock. This oil therefore contains 0.67 wt-56 of the product copolymer. When evaluated in the "Ford Sequence VD" engine test, a performance characteristic of 9.55 sludge, 7.1 coating, 6.7 piston skirt coating is achieved after 192 test hours.

c) Performance additive C: 56SA - 17.4, 56Zn - 2.45, 56P = 2.21,

56Ca = 1.36, 56Mg = 0.87, 56N = 0.62, 56S = 6.22, 56Na = 1.56,

TBN = 115.9

EXAMPLE IX

7000 g of the 14.9 wt-56 polymer solution prepared in Example VI was charged to a flask equipped as indicated in Example VII. 6067 g of "Wibarco Heavy Alkylate" (Wibarco GmbH) is added and the mixture is heated to 150°C. When a homogeneous solution has been obtained, 22.5 g of N,N-dimethyl-1,3-propanediamine are added dropwise over a period of twenty hours. After all the amine was added, the reaction vessel was heated to 170°C and held there for 3.0 hours. The nitrogen blanket was replaced with a subsurface purge during the last hour of the reaction period to remove byproduct water. The polymer solution of 8.0 wt-56 gives the final product. Analysis of this final product gives an ANA nitrogen content of 0.0556 (theoretical 0.0556). Infrared analysis of the product confirms imide formation without any residual anhydride absorption. Appearance of the concentrate was clear.

EXAMPLE X

A maleic anhydride-functionalized, solvent-free polymer obtained from Example II is reacted with a primary amine compound as follows: The solvent-free polymer, in an amount of two carbonyl equivalents (based on the TAN number), is reacted with one equivalent of a primary amine group in the same type of extruder , i.e., a single screw type extruder driven by means of a "C.W. Brabender Plastic-Corder" torque rheometer. The temperature for the extruder is approx. 160°C. The primarily amine-containing compound, N,N-dimethyl-1,3-propanediamine in the amount indicated above was premixed with the solvent-free polymer and both were added to the feed portion of the extruder. Residence time for the extruder was approx. 20 seconds. The imidized neat polymer in an amount of 12 wt-# was dissolved in "Wibarco Heavy Alkylate". The kinematic viscosity at 100°C for the dispersant VI concentrate was 760 cSt.

If relatively small amounts of polyamines containing two or more primary amino groups are used for reaction with (D) the acylation reaction product containing an acid group or anhydride group, the viscosity of the product will increase dramatically and often a gel is formed which thereby gives an insoluble material. However, it is possible that polyamines containing two or more primary amino groups can be used to produce an oil-soluble effective VI improver/dispersant product. This depends on the functionality of the polyamine and the (D) acylation reaction product.

The gel formation point is theoretically predicted using mathematical formulas as stated in Prof. George Odian's book, "Principles of Polymerization", 2nd edition, pp. 96-107, 1970, McGraw Hill Book Co., New York.

Accordingly, assume that diethylenetriamine (DETA) is used as a polyamine for reaction with the (D) acylation reaction product. DETA has a functionality of two, because it contains two primary amino groups per molecule. If the number average functionality of the (D) acylation reaction products is two or lower, theory predicts that no gel, a cross-linked product, will be formed. However, if the functionality is greater than two, a gel is predicted to form. The theory is that the higher the functionality, the more extensive the gelation will be. Even if the functionality is two or less, the oil-soluble product may be undesirable, because the viscosity will be increased too much in many cases.

The number of anhydride groups attached to each molecule of (D) depends on the average molecular weight of the (A) block copolymer and the TAN of the (D) copolymer. The following table illustrates this feature. On the other hand, a compound (E) containing only a primary amine group as indicated above will form an oil-soluble product regardless of the functionality of (D).

According to the present invention, it is required that the VI improvers/dispersants are oil-soluble so that they can be used for various lubrication applications indicated below. To illustrate this, examples are given which show how critical it is to use essentially only compounds containing a primary amine group.

As stated above, the products according to the present invention are suitable as VI improvers/dispersants. Consequently, the preparation according to the present invention can be effectively used in a number of lubricant preparations composed for a number of applications. These lubricant preparations are based on various oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. These lubricating preparations containing the relevant additive concentrates are effective as crankcase lubricating oils for spark ignition and compression ignition engines with internal combustion, including car and trailer engines, two-stroke engines, free piston engines, marine and low-load diesel engines and the like. Furthermore, fluids for automatic transmissions, cardan shaft lubricants, gear lubricants, metal-working lubricants, hydraulic fluids and other lubricating oils and grease preparations can benefit from the inclusion of the relevant additive concentrates.

Another feature of the present invention concerns the use of a (F) polyamine in connection with a (G) monofunctional acid to further delay the (D) acylation reaction product. As stated above, the reaction product (D) can either be prepared by a solvent process, a desired method, or in a solvent-free environment. It is an important feature of the present invention to use an effective amount of the monofunctional acid in connection with the polyamines for the production of the desired gel-free oil-soluble products. The reaction with polyamines is desirable in that it gives the compound dispersing agent properties, and when such a compound is added to a hydrocarbon oil it controls the thickening of the oil. In addition to (F) the polyamine and (G) the monofunctional acid, (E) primarily amine-containing compounds can also be used. However, it is essential in the present invention that (F) a polyamine and (G) a monofunctional acid are used in a suitable ratio and in a suitable quantity to allow chain extension and give a gel-free product.

The term "polyamine" means an amine compound containing at least two amino groups where each group contains at least one active hydrogen. Accordingly, the polyamine may contain two or more primary amino or one or more secondary amino groups.

A suitable (F) polyamine compound which can be used is the alkylene polyamines including the polyalkylene polyamines. The alkylene polyamines include those corresponding to the formula:

wherein n is from 1 to 10, each R" is independently a hydrogen atom or a hydrocarbyl group containing up to 30 atoms, and the "alkylene" group contains from 1 to 10 carbon atoms, but the preferred alkylene is ethylene or propylene. Particularly desirable are the alkylene polyamines where each R" is hydrogen, with the ethylene polyamines and mixtures of the ethylene polyamines being the most desirable. Usually, n will have an average value from 2 to 7.

Such alkylene polyamines include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines, heptylene polyamines, etc. The high homologues of such amines and related aminoalkyl-substituted piperazines are also included.

Alkylene polyamines useful in the preparation of the dispersant/viscosity modifier compositions of the present invention include ethylenediamine, triethylenetetramine, propylenediamine, trimethylenediamine, hexamethylenediamine, decamethylenediamine, octamethylenediamine, di(hepta-methylene)triamine, tripropylenetetramine, tetraethylenepentamine, trimethylenediamine, pentaethylenehexamine, di(trimethylene) triamine, N-(2-aminoethyl)piperazine, 1,4-bis(2-aminoethyl)piperazine and the like. Higher homologues obtained by condensation of two or more of the above alkylene amines are useful, as are mixtures of two or more of any of the polyamines discussed.

Ethylene polyamines, such as those listed above, are particularly useful in terms of cost and efficiency. Such polyamines are described in detail under the heading "Diamines and Higher Amines" in "The Encyclopedia of Chemical Technology", 2nd ed. , Kirk and Othmer, vol. 7, pp. 27-39, Interscience Publishers, Division of John Wiley and Sons, 1965. Such compounds are most conveniently prepared by reacting an alkylene chloride with ammonia or by reacting an ethyleneimine with a ring-opening reagent, so such as ammonia, etc. These reactions result in the production of somewhat complex mixtures of alkylene polyamines, including cyclic condensation products such as piperazines. Very satisfactory products can also be obtained by the use of pure alkylene polyamines.

Other useful types of polyamine mixtures are those produced by cleavage of the above-mentioned polyamine mixtures. In this case, lower molecular weight polyamines and volatile contaminants are removed from an alkylene polyamine mixture, leaving a residue often referred to as the "polyamine bottom fraction". In general, alkylene polyamine bottom fractions can be characterized as containing less than two, usually less than one percent (wt-56) of material boiling below 200°C. In the case of ethylene polyamine bottom fractions, which are readily available and have been found to be very useful, the bottom fractions contain less than 256 (wt-56) total diethylenetriamine (DETA) or triethylenetetramine (TETA). A typical sample of such ethylene polyamine bottom fractions obtained from Dow Chemical Company, Freeport, Texas, designated "E-100" showed a specific gravity at 15.6°C of 1.0168, a wt-56 nitrogen of 33.15 and a viscosity at 40°C of 121 centi-stokes. Gas chromatographic analysis of such a sample showed that it contained approx. 0.93% "Light Ends" (DETA), 0.7256 TETA, 21.7456 Tetraethylenepentamine and 76 .6156 Pentaethylenehexamine and higher (wt-56). These alkyl enpolyamine base fractions include cyclic condensation products such as piperazine and higher analogs of diethylenetriamine, triethylenetetramine and the like.

When reacted with the previously mentioned (D) acylation reaction products, these polyamine bottom fractions often provide carbocyclic derivative preparations which provide improved viscosity modifying properties to the lubricants containing them. While not wishing to be bound by any particular theory or idea, it is believed that these improved viscosity properties are due to coupling of the (D) acylation reaction products via the polyamine bottom fractions which contain both longer molecules and an excess of reactive amino groups compared to their lower molecular weight counterparts , such as triethylenetetramine.

These alkylene polyamine bottom fractions can be reacted exclusively with the (D) acylation reaction products in the presence of said (G) monofunctional acid, in which case the amino reactant consists essentially of alkylene polyamine bottom fractions, or they can be used with other amines and polyamines. In these latter cases, at least one amino reactant includes alkylene polyamine bottom moieties.

Another group of (F) polyamine compounds which can be used for reaction with (G) the monofunctional acids and (D) the acylation reaction product are the branched polyalkylene polyamines. The branched polyalkylene polyamines are polyalkylene polyamines in which the branching group is a side chain containing on average at least one nitrogen-bonded amino alkylene

group per 9 amino units present on the main chain, e.g. 1-4 such branched chains per 9 units on the main chain, but preferably one side chain unit per 9 main chain units. Accordingly, these polyamines contain at least three primary amino groups and at least one tertiary amino group.

These reagents can be expressed by the formula:

wherein R is an alkylene group containing 2-20 carbon atoms, such as ethylene, propylene, butylene and other homologues (both straight chain and branched), etc., but preferably ethylene; and x, y, and z are integers; x is e.g. from 4 to 24, but more

preferably from 6 to 18; y is e.g. 1 to 6, or more preferably 1 to 3, and z is e.g. 0-6, preferably 0-1. These x and y units can be sequential, alternatively ordered or randomly distributed.

The preferred class of such polyamines include those of the formula:

wherein n is an integer, 1-20, or more preferably 1-3, wherein R is preferably ethylene, but may also be propylene, butylene, etc. (straight chain or branched).

The preferred embodiments are represented by the following formula:

where n = 1-3.

The residues in the parentheses can be joined head-to-head or head-to-tail. Compounds described in this formula where n = 1-3 are manufactured and sold as "Polyamines N-400", "N-800", "N-1200", etc. "Polyamine N-400" has the above formula with an average number of n = 1.

US patents 3,200,106 and 3,259,578 describe how such polyamines are produced and indicate methods for reacting them with carboxylic acid acylating agents. Analogous processes can be used with the acylation reagents according to the present invention.

Another class of suitable (F) polyamine compounds includes the polyoxyalkylene polyamines, e.g. polyoxyalkylene diamines and polyoxyalkylene triamines, with average molecular weights varying from 200 to 4000, preferably from 400 to 2000. Illustrative examples of these polyoxyalkylene polyamines can be indicated by the formula: where m has a value of 3 to 70, and preferably from 10 to 35.

wherein n is such that the aggregate value is from 1 to 40, provided that the sum of all n's is from 3 to 70, and generally from 6 to 35, and R is a polyvalent saturated hydrocarbon residue of up to 10 carbon atoms which has a valency of from 3 to 6. The alkylene groups can be straight-chain or branched and contain from 1 to 7 carbon atoms, and usually from 1 to 4 carbon atoms. The different alkylene groups present in the two formulas closest to the above may be the same or different.

More specific examples of these polyamines include: wherein x has a value from 3 to 70, and preferably from 10 to 35; and where x + y + z has a total value varying from 3 to 30, and preferably from 5 to 10.

When used, the desired polyoxyalkylene polyamines for the purposes of the present invention include the polyoxyethylene and polyoxypropylene diamines and the polyoxytriamines having average molecular weights varying from approx. 200 to 2000. The polyoxyalkylene polyamines are commercially available and can be obtained, e.g. from Jefferson Chemical Company, Inc. under the trademark "JEFFAMINES D-230, D-400, D-1000, D-2000, T-403, etc.". Furthermore, US patent nos. 3,804,763 and 3,948,800 describe such polyoxyalkylene polyamines and methods for acylating them with carboxylic acid acylating agents, these processes can be applied to their reaction with the acylating agents according to the present invention.

Although the above-mentioned polyamines are generally preferred, various other polyamine compounds can be used in the present invention. Such compounds are disclosed in US Patent No. 4,234,435.

The following description with regard to both the natural and the synthetic lubricating oils in which the VI improver/dispersant can be used are also useful solvents for either (D) the acylation reaction product formation or the subsequent reaction between the reaction product and (E) the primarily amine-containing compound. Consequently, it should be emphasized that the following list of compounds can be used as a solvent in the above mentioned reactions. Examples of natural oils include animal oils and vegetable oils (eg, castor oil, lard oil) as well as mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful. Synthetic lubricating oils include hydrocarbon oils and halogen-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (eg, oligobutylenes, oligopropylenes and propylene-ethylene oligomers, chlorinated polybutylenes, etc.); oligo(1-hexenes), oligo(1-octenes), oligo(1-decenes), etc. and mixtures thereof; alkylbenzenes (eg, dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)benzenes, etc.); polyphenyls (eg, biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl sulphides and their derivatives, analogues and homologues and the like.

The (G) monofunctional acids that can be used in the present invention can generally be any carboxylic acid acylating agent or any hydrocarbon-based monocarboxylic acid in which the definition of "hydrocarbon-based" is as indicated below. Such monocarboxylic acids are saturated or unsaturated acids containing from 1 to 50 carbon atoms, from 8 to 20 carbon atoms being preferred. Conveniently, these acids are usually saturated. Examples of such specific acids include octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid and the like. In addition, polycarboxylic acids can only be used when they form a cyclic imide compound. Consequently, succinic acids, glutaric acids, maleic acids, itaconic acids, phthalic acids and the like can also be used.

As the terms are used here, "hydrocarbon-based", "hydrocarbon-based substituent" and the like means a substituent which has a carbon atom directly linked to the rest of the molecule and which has mainly hydrocarbyl character within the scope of the present invention. Such substituents include the following: (1) hydrocarbon substituents, i.e., aliphatic (eg, alkyl or alkenyl), alicyclic (eg, cycloalkyl, cycloalkenyl) substituents, aromatic-, aliphatic-, and alicyclic-substituted aromatic nuclei and the like, as well as cyclic substituents in which the ring is completed by another part of the molecule (ie any two of the indicated substituents may together form an alicyclic residue); (2) substituted hydrocarbon substituents, i.e. those substituents containing non-hydrocarbon residues which, within the scope of the present invention, do not alter the predominant hydrocarbyl substituent; those skilled in the art will readily recognize such residues (e.g., halogen, especially chlorine and fluorine), alkoxy, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.; (3) hetero-substituents, i.e. substituents which, although mainly of hydrocarbyl character within the scope of the present invention, contain atoms other than carbon present in a ring or chain which otherwise consists of carbon atoms. Suitable heteroatoms will be known to those skilled in the art and include, for example, sulphur, oxygen, nitrogen and examples of these heterosubstituents are such substituents as e.g. pyridyl, furanyl, thio-phenyl, imidazolyl, etc.

Carboxylic acid acylating agents are more suitably used. Such carboxylic acid acylating agents are known in the art 3,272,746, 3,381,022, 3,254,025, 3,278,550, 3,288,714, 3,271,310, 3,373,111, 3,346,354. 3,272,743, 3,374,174. 3,307,928. 3,394,179. Such carboxylic acid acylating agents are generally prepared by reacting an olefin, an olefin polymer or chlorinated analogue thereof with an unsaturated carboxylic acid or derivative thereof, such as acrylic acid, fumaric acid, maleic anhydride and the like. Often they are polycarboxylic acid acylating agents such as hydrocarbyl-substituted succinic acids and anhydrides. These acylating agents have at least one hydrocarbyl-based substituent of from 3 to 1000 carbon atoms, generally from 8 to 500, and preferably from 12 to 500 carbon atoms. As the term is used here, the terms "hydrocarbon-based", "hydrocarbon-based substituent" and the like refer to a substituent which has carbon atoms directly attached to the remaining part of the molecule and which has mainly hydrocarbyl character as defined above, which includes hydrocarbon substituents, substituted hydrocarbon substituents and hetero-substituents. In general, no more than approx. 3 heteroatoms, and preferably no more than one, be present for every ten carbon atoms in the hydrocarbon-based substituents. Typically, there will be no such heteroatoms in the hydrocarbon-based substituent and it will therefore be pure hydrocarbyl.

In general, the hydrocarbon-based substituents present in the acylating agents used in the present invention are free of acetylenic unsaturation. Ethylenic unsaturation, when present, will generally be such that no more than one ethylenic bond is present for every 10 carbon-to-carbon bonds in the substituent. The substituents may be fully saturated and therefore contain no ethylenic unsaturation.

As stated above, the hydrocarbon-based substituents present in the acylating agents of the present invention may be derived from olefin polymers or chlorinated analogues thereof. Olefin monomers from which the olefin polymers are derived are polymerizable olefins and monomers characterized by the fact that they contain one or more ethylenically unsaturated groups. They can be monoolefinic monomers such as ethylene, propylene, 1-butene, isobutene and 1-octene or polyolefinic monomers (usually di-olefinic monomers such as 1,3-butadiene and isoprene). Usually these monomers are terminal olefins, i.e. olefins characterized by the presence of the group =C=CH 2 . However, certain internal olefins can also serve as monomers (these are sometimes referred to as medial olefins). When such medial olefin monomers are used, they are normally used in combination with terminal olefins for the production of olefin polymers which are interpolymers. Although the hydrocarbyl-based substituents may also include aromatic groups (especially phenyl groups and lower alkyl and/or lower alkoxy-substituted phenyl groups such as para-tertiary butylphenyl groups) and alicyclic groups obtained from polymerizable cyclic olefins or alicyclic-substituted polymerizable cyclic olefins. The olefin polymers are usually free of such groups. Nevertheless, olefin polymers derived from such interpolymers of both 1,3-dienes and styrenes such as 1,3-butadiene and styrene or para-tertiary-butylstyrene are exceptions to this general rule.

In general, the olefin polymers are homo- or interpolymers of terminal hydrocarbyl olefins having 2 to 16 carbon atoms. A more typical class of olefin polymers is selected from the group consisting of homo- and interpolymers of terminal olefins having 2 to 6 carbon atoms, especially those having 2 to 4 carbon atoms.

Specific examples of terminal and medial olefin monomers that can be used to prepare the olefin polymers from which the hydrocarbon-based substituents are derived include ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1 -octene, 1-nonene, 1-decene, 2-pentene, propylene tetramer, diisobutylene, triisobutylene, 1,2-butadiene, 1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, isoprene, 1,5 -hexadiene, 2-chloro-1,3-butadiene, 2-methyl-1-heptene, 3-cyclohexyl-1-butene, 3,3-dimethyl-1-pentene, styrene, vinyl acetate, allyl alcohol, 1-methyl vinyl acetate , acrylonitrile, ethyl acrylate, ethyl vinyl ether and methyl vinyl ketone. Among these, the pure hydrocarbyl monomers are more typical and the terminal olefin monomers are particularly typical.

Often the olefin polymers are poly(isobutene)s obtained by polymerization of a C4 refinery stream having a butene content of 35 to 75 wt% and an isobutene content of 30 to 60 wt% in the presence of a Lewis acid catalyst such as aluminum chloride or boron trifluoride. These polyisobutenes contain mainly (ie more than 80% of the total repeating units) isobutene repeating units of the configuration:

Typically, the hydrocarbyl-based substituent in the carboxylic acid acylating agent used in the present invention is a hydrocarbyl, alkyl or alkenyl group of 3 to 1000 carbon atoms which can be represented by the character "hyd". Useful acylating agents include substituted succinic acid agents containing hydrocarbyl-based substituents containing a number average of from 12 to 500 carbon atoms.

Often (G) the monofunctional acids used in the production of the solubilizing agents are substituted succinic acids or derivatives thereof which can be represented by the formulas:

Succinic acid is a monofunctional acid due to the stoichiometry indicated below.

Such succinic acid acylating agents can be prepared by the reaction of maleic anhydride, maleic acid, or fumaric acid with the previously mentioned olefin, olefin polymer or chlorinated analogues thereof as indicated in the above mentioned patents. Generally, the reaction involves exclusively heating the two reactants to a temperature of 150°C to 300°C. Mixtures of the previously mentioned polymeric olefins, as well as mixtures of the unsaturated mono- and dicarboxylic acids can also be used.

The reaction between (F) the polyamine and (G) the monofunctional acid and (D) the acylation reaction product generally takes place by heating, e.g. from 50°C to 250°C, and suitably from 140°C to 180°C. Optionally, the reaction can take place in an inert atmosphere such as nitrogen. The reaction time will naturally vary with the reaction temperature, the desired yield and the like. Since water is generated during the reaction, it can be removed by any conventional means. The total amount of carbonyl groups including those in the (D) acylation reaction product and (G) the monofunctional carboxylic acid for each primary amine group in the (F) polyamine is such that no excessive viscosity increase is produced. When generally compounds of the succinic acid group are used, the ratio of the total number of carbonyl groups for each primary amine group is from 0.5. to 8, conveniently from 1 to 4, preferably from 1.8 to 2.2, a very preferred amount is 2. When (G) the monofunctional acid is a monocarboxylic acid, the above ratios are reduced by a factor of 10; ie, the preferred amount of monocarboxylic acids for each amine group is 1.0, each amine group being able to react with each monofunctional acid. Furthermore, the monocarboxylic acid, unlike succinic acid, can react with both primary and secondary amines. Although larger or smaller amounts of acid can be used, they tend to be ineffective and/or expensive. The amount of (G) the monofunctional carboxylic acid to the amount of carbonyl groups derived from (D) cx, p-olefinically unsaturated carboxyl reagents on the polymer backbone is such that, upon reaction with (F) polyamine, gel-free or substantially gel-free products are formed, ie products that do not have an excessively high viscosity. That is that although some gel or some increase in viscosity is produced, the reaction product is essentially free of gel. A desirable ratio of (D) to (G) depends on such factors as the number of acylating chemical functions attached to (D), the number of primary amino groups attached to (F), and the amount of (G) added to the reaction mixture, as discussed below.

When (D) the acylation reaction product reacts with (F)

the polyamine in the absence of (G) the monofunctional acid, hereinafter designated (D), (F) and (G) respectively, the reaction proceeds with the formation of branches and in many cases a three-dimensional network or structure arises due to the multifunctional nature of the reactants. This results in an excessive increase in the oil thickening property of the product and, in the latter case, formation

of an oil-insoluble gel. When (D) reacts with (F) in the presence of (G), unwanted gelation is avoided which creates a desirable additional dispersant in the product. The gel formation can be theoretically predicted using mathematical formulas stated in Prof. George Odian's book, "Principles of Polymerization", 2nd edition, pp. 96-107, McGraw Hill Book Co., New York.

As an example, a theoretical feature of a gelation reaction will be discussed. Assume that the number average molecular weights of (D) and (G) substrate polymers are 200,000 and 1,000, respectively; the acylating chemical function is the succinic acid group for both (D) and (G); (F) is a polyamine containing two primary amino groups such as diethylenetriamine (DETA), triethylenetetramine or tetraethylenepentamine; the ratio of succinic acid group to primary amine is one to one or two carbonyl groups to a primary amino group; and the number of succinic anhydride groups attached to (D) is variable. The critical extent of reaction (Pc) at the gel point is calculated using

where faVg is the number average functionality for a reaction mixture of (D), (G) and (F). The value of faVg can be calculated using where n^, ng and nf are the number of molecules of (D), (G) and (F) respectively; f,} is the number-averaged functional of (D) which is variable; fg is a, the functionality of (F) a monofunctional acid; and ff are two, the functionality of (F) a polyamine containing two primary amino groups. The table below is the result of H Pc calculation against two variables, the weight ratio between (D) and (G), and the number average functionality, f^, of (D) acylation product.

It appears from the table that

(i) No gelation takes place when the functionality of (D), f(j, is two or less, regardless of whether (G) is present or not. (ii) Gelation takes place when f^ is greater than two, and the larger the f^ value, the more frequently gelation occurs.(iii) The addition of (G) either delays gelation or eliminates it depending on the relative amount of (G) added to (D).

From this example, it is easy to understand the function of (G) of the present invention, such as: 1. Elimination of unwanted formation of oil-insoluble gel; 2. Increase in the oil thickening properties of the product to any defined degree; 3. Allows an increased amount of (F) in the reaction. This results in an improved dispersibility in the product; and 4. Allows the use of a wide variety of more cost/performance effective amines.

Accordingly, various factors affect the ability to avoid too high a viscosity or gel, but these can be easily determined with respect to any given system, as indicated above.

An alternative reaction method for the present invention is, although not desired, to initially react (F) the polyamine with (G) the monofunctional carboxylic acid. The reaction conditions are generally the same as stated above, except that the reaction temperature may be much lower, e.g. room temperature. That is the reaction temperature can be from room temperature, i.e. from 20° C to 250° C, and the reaction can optionally be carried out in the presence of an inert atmosphere. In general, water must not be removed at lower temperatures, but at higher temperatures it is generally removed, e.g. by cleavage in vacuum. The reaction is generally carried out in the presence of a solvent such as mineral oil, neutral oil or the like. Once the pre-reacted amino acid component is formed, the amount thereof can be easily calculated based on the above stated overall ratio of the number of carbonyl groups for each primary amine group or for each primary and secondary amine group.

The reaction between (F) the polyamines and (G) the monofunctional acids with the acylation reaction product (D) can take place in a solvent medium or in a solvent-free environment, as indicated above. Typical solvents are known in the art and in the literature and include various oils which are lubricant raw materials such as natural and/or synthetic lubricating oils such as the following: natural oils, e.g. mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of paraffinic, naphthenic or mixed paraffinic-naphthenic types. Alternatively, animal or vegetable oils can also be used. Synthetic lubricating oils include alkylated aromatic compounds, poly-cx-olefins, alkyl phosphates and esters derived from polyhydric acids, polyols and fatty acids. Specific examples of such solvents include refined 100 to 200 neutral mineral oils, paraffinic oils and/or naphthenic oils, diphenyldodecanes, didodecylbenzenes, hydrogenated dodecene, oligomers and mixtures of the above. The amount of oil is generally regulated so that the viscosity of the reaction mixture is suitable for mixing. Typically, the amount of oil is from 50 to 99 wt-56, and more suitably from 70 to 95 wt-56, based on the weight of the total reaction mixture. When the reaction is carried out in a solvent-free process, the various reactants can be added to any suitable container, device or apparatus in the absence of a solvent. Conveniently, the various steps in the reaction sequence take place in a mixing apparatus such as an extruder, a Banbury mixer, a two-roll mill or the like. As the reaction mixture is often very viscous, mixing devices with a high torque are preferred. The temperature for the solvent-free process corresponds to that indicated above with respect to the solvent process, except that a higher preferred temperature, ie from 140°C to 200°C is desirable. Preferred types of high torque mixing devices include a twin screw extruder and the like.

Regardless of whether the reaction is carried out in a solvent medium or in a solvent-free environment, emphasis should be placed on removing any unreacted (B) α,β-carboxylic acid, e.g. by cleavage. Otherwise, the unreacted acid will react with the polyamine.

In the above conditions, with regard to the different amounts of carbonyl compounds based on the number of available primary amine groups from the (F) polyamines, it should also be noted that different amounts of (E) primary amine compounds can also be used. The amount of such (E) primary amine compounds is such that the conditions stated above are met. That is the amount of (E) primary amine compounds can be substantially substituted for up to 99% by weight of the total amount of (F) polyamine compounds.

The final or oil-soluble composition which is the reaction product of (D) the acylation reaction product, (F) the polyamine and (G) the monofunctional acid can be used in various types of lubricating oils derived not only from petroleum, but also including synthetic lubricating oils and the like, as indicated below. The amount of said reaction product (D) + (F) + (G) in such lubricating oils is generally from 0.1 to 30 wt-#, and preferably from 0.5 to 6 wt-56 based on the total weight of said lubricating oil composition which may contain various additives. Furthermore, the reaction product (D) + (F) + (G) according to the present invention can be used in concentrated form, such as from 1 to 40 wt-56, and preferably from 5 to 25 wt-56, based on the total weight of the lubricating oil including the concentrate and various additives. The lubricating oil compositions or concentrates may contain additives such as anti-wear agents, antioxidants, viscosity index improvers, dispersants, agents for suppressing the solidification point, dyes and the like.

The invention will be better understood by reference to the following examples.

EXAMPLE XI

A 3505 g sample of the 24.956 polymer solution prepared in Example IV is charged into a 12 L flask equipped with a mechanical stirrer, thermometer, N 2 inlet, addition funnel, Dean-Stark trap, cooler and heating jacket. "Wibarco Heavy Alkylate" (Wibarco GmbH; 3561.7 g) is added together with 195.0 g of polyisobutynyl succinic anhydride (TAN = 98) and the mixture is stirred and heated to 150° C under a blanket of N2 to obtain a homogeneous solution (approx. . 2 hours). When this solution is obtained, 23.6 g of DETA (diethylenetriamine) are added dropwise to the mixture from the dropping funnel over the course of one hour. When all the amine is added, the reaction mixture is heated to 170°C and held there for 4.0 hours, while N 2 is flushed subsurface (0.03 m<5>/hour) to remove byproduct water. This 1256 polymer solution is the final product. Analysis of the final product gives an ANA nitrogen content of 0.1356. Infrared analysis of the product confirms imide formation without any residual anhydride absorption. The kinematic viscosity at 100°C for this dispersant-viscosity modifier is 460.0 cSt.

An API SF/CC, SAE 10W30 oil was prepared by blending 9.056 of the final product from Example XI, 8.1356 W performance additive D<d>), 0.256 W "Acr 156", into a lubricant feed stock. This oil thus contains 1.0856 W of the product copolymer. When examined by the "Ford Sequence VD" engine test, a performance characteristic of 9.51 sludge, 6.64 coating and 6.88 piston-skirt coating is obtained after 192 test hours.

d) Performance additive D: 56SA - 12.9, 56Zn = 1 , 56 , 56P = 1.41,

56Ca = 1.23, 56Mg = 1.16, 56N = 0.52, 56S = 4.27, TBN = 85.8

EXAMPLE XII

700 g of the polymer solution of 14.9 wt-56 prepared in Example VI is filled into a flask equipped in the same way as in Example XI. 321.2 g of "Wibarco Heavy Alkylate" (Wibarco GmbH) are added together with 24.8 g of polyisobutenylsuccinic anhydride (TAN = 98) and heated to 150°C under a Ng blanket. When a homogeneous solution is obtained, 3.0 g of DETA is added dropwise over the course of one hour. After all the amine is added, the reaction mixture is heated to 175°C and held at this temperature for 4.0 hours with Ng subsurface flushing (3.11 m<5>/hr) to remove byproduct water. Analysis of the final product gives an ANA nitrogen content of 0.1256 (0.1256 theoretical). Infrared analysis of the product confirms imide formation without any residual anhydride absorption. The concentrate has a clear appearance.

The following description with respect to natural and synthetic lubricating oils in which the VI improver/dispersant according to the present invention is applicable applies with respect to (D) the acylation reaction product formation, the subsequent reaction between (D) the acylation reaction product and (E) the primarily amine-containing compound, or the reaction between (D) the acylation reaction product and (F) the polyamine and (G) the monofunctional acid. Accordingly, the following list serves not only as lubricating oils to which the compositions according to the present invention can be added, but also as preparations that can serve as suitable solvents. Suitable lubricating oils include natural oils, animal oils and vegetable oils as well as mineral lubricating oils such as liquid petroleum oils, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful. Synthetic lubricating oils include hydrocarbon oils and halogen-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (eg, oligobutylenes, oligopropylenes and propylene-ethylene oligomers, chlorinated polybutylenes, etc.); oligo(1-hexenes), oligo(1-octenes), oligo(1-decenes), etc. and mixtures thereof; alkylbenzenes (eg, dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)benzenes, etc.); polyphenyls (eg, biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl sulphides and their derivatives, analogues and homologues and the like.

Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic lubricating oils which can be used. These are exemplified by the oils produced by polymerization of ethylene oxide or propylene oxide, alkyl and aryl ethers of these polyoxy-alkylene polymers (e.g. methyl polyisopropylene glycol ether which has an average molecular weight of about 1000, diphenyl ether of polyethylene glycol which has a molecular weight of 500 1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500, etc.) or mono- and polycarboxylic acid esters thereof, e.g. the acetic acid esters, mixed C3-C8 fatty acid esters or the C3-oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils which may be used include the esters of dicarboxylic acids (eg, 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 acids, alkenylmalonic acids, etc. .) with a variety of alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include butyl adipate, (2-ethylhexyl)sebacate, n-hexyl fumarate, octyl sebacate, isooctyl azelate, isodecyl azelate, octyl phthalate, decyl phthalate, eicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting 1 mole of sebacic acid with 2 mol tetraethylene glycol and 2 mol 2-ethylhexanoic acid and the like.

Esters useful as synthetic oils also include those prepared from C 5 to C 8 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.

Silicon-based oils such as polyalkyl-, polyaryl-, poly-alkoxy or polyaryloxysiloxane oils and silicate oils constitute another useful class of synthetic lubricants (e.g. tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4 -methyl-2-hexyl)silicate, tetra-(p-tert-butylphenyl)silicate, hexyl-(4-methyl-2-pentoxy)di-siloxane, poly(methylsiloxanes), poly(methylphenylsiloxanes), etc. ).

Unrefined, refined and re-refined oils, either natural or synthetic (as well as mixtures of two or more of any of these) of the types described above may be used in the concentrates of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retort operations, a petroleum oil obtained directly from primary distillation or an ester oil obtained directly from an esterification process, and used without further purification, would be an unrefined oil. Refined oils are equivalent to the unrefined oils, except that they have been further treated with one or more purification steps to improve one or more properties. Many such purification techniques are known to those skilled in the art, such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Re-refined oils are obtained by processes similar to those used to obtain refined oils, applied to refined oils that have already been used in operation. Such rerefined oils are also known as recycled or reprocessed oils and are often additionally processed by techniques aimed at removing used additives and oil degradation products.

Other additives can also be used in combination with the viscosity-improving preparations according to the present invention. Such additives include, for example, cleaning agents and dispersants of the ash-producing or ashless type, corrosion and oxidation inhibiting agents, pour point depressants, extreme pressure agents, antiwear agents, color stabilizers and antifoam agents.

The ash-producing cleaning agents can be exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids or organophosphoric acids characterized by at least one direct carbon-to-phosphorus bond, such as those produced by the processing of an olefin polymer (e.g. polyisobutene with a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorus thioic acid chloride. The most used salts of such acids are the salts of sodium, potassium, lithium, calcium, magnesium, strontium and barium.

The term "basic salt" is used to indicate metal salts in which the metal is present in stoichiometrically greater amounts than the organic acid residue. The commonly used methods for preparing the basic salts include heating a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate or sulfide at a temperature of about 50°C, and filtering the resulting mass. The use of a "promoter" in the neutralization step to facilitate the incorporation of a large excess metal is also known. Examples of compounds useful as promoters include phenolic substances such as phenol, naphthols , alkylphenols, thiophenol, desulfurized alkylphenols, and condensation products of formaldehyde with phenolic substances; alcohols such as methanol, 1-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine . such as 60-200°C.

Ashless cleaners and dispersants are designated as such despite the fact that, depending on the composition, they can produce a non-volatile material such as boron oxide or phosphorus pentoxide when burned; however, they normally do not contain metal and therefore do not produce a metal-containing ash when burned. Many types are known in the art, and any of these are suitable for use in the lubricant preparations according to the present invention. The following are illustrative: (1) Reaction products of carboxylic acids (or derivatives thereof) containing at least 34, and preferably at least 54 carbon atoms, with nitrogen-containing compounds such as amine, organic hydroxy compounds such as phenols and alcohols, and/or basic inorganic materials. Examples of these "carboxylic dispersants" are described in British Patent No. 1,306,529 and in many US patents including the following: (2) Reaction products of relatively high molecular weight aliphatic or alicyclic halides with amines, preferably oxyalkylene polyamines. These can be characterized as "amine dispersants" and examples of such are described, e.g. in the following US patents: 3,275,554 3,454,555 3,438,757 3,565,804 (3) Reaction products of alkylphenols in which the alkyl group contains at least 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines), which can be characterized as "Mannich dispersants ". The materials described in the following US patents are illustrative: (4) Products obtained by post-treatment of the carboxyl, amine or Mannich dispersants with such reagents as urea, thiourea, carbon disulphide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles , epoxides, boron compounds, phosphorus compounds or the like. Examples of materials of this type are described in the following US patents: (5) Interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g. aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates. These can be characterized as "polymeric dispersants" and examples of such are described in the following US patents: 3,329,658 3,519,565 3,687,849

3,449,250 3,666,730 3,702,300

Agents for extreme pressures and corrosion and oxidation inhibiting agents which can be included in the lubricants according to the invention can be exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wax; organic sulfides and polysulfides such as benzyl disulfide, (chlorobenzyl)disulfide, butyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentene and sulfurized terpenes; phosphorus-sulphurised hydrocarbons such as the reaction product of a phosphorus sulphide with turpentine or methyl oleate; phosphorous esters including mainly dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite, dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethylnaphthyl phosphite, oleyl-4-pentyl phenyl phosphite, polypropylene (molecular weight 500) substituted phenyl phosphite, diisobutyl substituted phenyl phosphite ; metal thiocarbamates, such as zinc dioctyldithiocarbamate and barium heptylphenyldithiocarbamate; Group II metal phosphorodithioates such as zinc dicyclohexyl phosphordithioate, zinc dioctyl phosphordithioate, barium di(heptylphenyl) phosphordithioate, cadmium dinonyl phosphordithioate and the zinc salt of a phosphorodithioate prepared by the reaction of phosphorus pentasulfide and an equimolar amount of isopropyl alcohol and n-hexyl alcohol.

Many of the above-mentioned extreme pressure aids and corrosion-oxidation inhibitors also serve as anti-wear agents. Zinc dialkyl phosphorodithioates are well known examples.

Pour point depressants are particularly useful types of additives that are often included in the lubricating oils described here. The use of such agents which suppress the pour point of oil-based compositions to improve low-temperature properties of oil-based compositions is well known in the art. See e.g. page 8 of "Lubricant Additives" of CV. Smalheer and R. Kennedy Smith, Lezius-Hiles Co., Publishers, Cleveland, Ohio, 1967.

Examples of useful agents that suppress the pour point are polymethacrylates; polyacrylates; polyacrylamides; condensation products of halogenated paraffin waxes and aromatic compounds; vinyl carboxylate polymers; and terpolymers of dialkyl fumarates, vinyl esters of fatty acids and alkyl vinyl ethers. Pour point depressants useful for the purposes of the present invention, techniques for their preparation and their use are described in US patents 2,387,501, 2,015,748, 2,655,479, 1,815,022, 2,191,498, 2,666,746, 2,721,877, 2,721,878 and 3,250,715.

Ant in the foam in d1e r is used to reduce or prevent the formation of stable foam. Typical foams include silicones or organic polymers. Additional antifoam compositions are described in "Foam Control Agents", by Henry T. Kerner, Noyes Data Corporation, 1976, pp. 125-162.

Claims (21)

1. Oil-soluble preparation comprising the reaction product of (D) an acylation reaction product, (F) a polyamine and (G) a monofunctional carboxylic acid, characterized in that (G) consists of a monocarboxylic acid acylating agent or a hydrocarbon-based monocarboxylic acid with from 8 to 20 carbon atoms, while (D) the acylation reaction product is the reaction product of : (A) a hydrogenated block copolymer containing not more than 0.5$ of olefinically unsaturated residues which is prepared from a monovinyl substituted aromatic and an aliphatic conjugated diene, which copolymer is a normal block copolymer or a randomized block copolymer with 2 to 5 polymer blocks with at least one block of monovinyl-substituted aromatic and at least one block of aliphatic conjugated diene, and with 20 to 70 wt-56 monovinyl-substituted aromatic blocks and 30 to 60 wt-56 aliphatic conjugated diene blocks, which are reacted with from 0.2 to 20 wt-56 of (B) an α,β-olefinically unsaturated carboxyl reagent containing 2 to 20 carbon atoms, except for a the carboxyl groups, based on the total amount of said (A) block copolymer and said (B) unsaturated carboxylic reagent, and 0.2 to 5 wt-56 of (C) a free radical initiator, based on the weight of said (A) block copolymer and said • (B) unsaturated carboxylic reagent. 2. Oil-soluble preparation according to claim 1, characterized in that said (F) polyamine is an amine compound containing at least two amino groups where each amino group contains at least one active hydrogen, and in which said (G) monofunctional carboxylic acid is a carboxylic acid acylating agent or a hydrocarbon-based monocarboxylic acid containing from 1 to 50 carbon atoms. 3. Oil-soluble preparation according to claim 2, characterized in that said (F) polyamine is an alkylene polyamine, a polyamine bottom product, a branched polyalkylene polyamine, or a polyoxyalkylene polyamine and wherein said (G) carboxylic acid acylating agent contains a hydrocarbon-based substituent where the hydrocarbon-based substituent contain from 3 to 1000 carbon atoms. 4. Oil-soluble preparation according to claim 1, characterized in that the amount of said (G) monofunctional carboxylic acid is an effective amount which essentially gives a mainly gel-free product. 5. Oil-soluble preparation according to claim 1, characterized in that the (A) normal block copolymer contains a total of two or three polymer blocks, wherein the number average molecular weight of said block and said randomized copolymer is from 30,000 to 200,000, wherein the total amount of said conjugated diene in block -copolymer is from 40 to 60 wt-56 and, the total amount of said vinyl-substituted aromatic unit is from 40 to 60 wt-56, wherein the (B) unsaturated carboxyl reagent is selected from maleic anhydride, citraconic anhydride, itaconic anhydride, glutaconic anhydride , chloromaleic anhydride, methylmaleic anhydride, acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleimide, maleamic acid, lower alkyl esters of such acids, and combinations thereof, and wherein the amount of said (B) unsaturated carboxyl reagent is from 0.5 to 5.0 wt-56. 6. Oil-soluble preparation according to claim 2, characterized in that (G) the monofunctional acid is said carboxylic acid acylating agent, where the carboxylic acid acylating agent has the formula: wherein hyd is said hydrocarbon substituent. 7. Oil-soluble preparation according to claim 1, characterized in that said reaction product has a total acid number of from 0.1 to 60, wherein said polyamine is an alkylene polyamine, where the alkylene polyamine has the formula: wherein n is from 1 to 10, wherein each R" is independently hydrogen or a hydrocarbyl group containing from 1 to 30 carbon atoms, and wherein said alkylene group contains from 1 to 10 carbon atoms. 8. Oil-soluble preparation according to claim 1, characterized in that said (C) free radical initiator is an organic peroxide or an organic azo initiator. 9. Oil-soluble preparation according to claim 1, characterized in that said reaction product has a total acid number of from 0.5 to 20 and in which said (B) unsaturated carboxyl reagent is selected from fumaric acid, maleic acid and maleic anhydride. 10. Oil-soluble preparation according to claim 8, characterized in that said alkylene polyamine is from 2 to 7, in which each R" is hydrogen, and said hydrocarbon substituent on the hydrocarbon-based monofunctional acid contains from 12 to 500 carbon atoms. 11. Oil-soluble preparation according to any one of claims 1-12, characterized in that said (D) acylation reaction product is present in a mixture with a solvent. 12. Process for the production of an oil-soluble preparation, characterized in that it includes the reaction of (D) an acylation reaction product, (F) a polyamine and (G) a monofunctional carboxylic acid, wherein said (G) is characterized by the fact that it is a monocarboxylic acid acylating agent or a carbon-based monocarboxylic acid having from 8 to 20 carbon atoms, and wherein said (D) acylation reaction product is the reaction product of: (A) a hydrogenated block copolymer containing not more than 0.5$ of olefinically unsaturated residues which is prepared from a monovinyl substituted aromatic and an aliphatic conjugated diene , which copolymer is a normal block copolymer or a randomized block copolymer with 2 to 5 polymer blocks with at least one block of monovinyl-substituted aromatic and at least one block of aliphatic conjugated diene and with 20 to 70 wt-56 mono-vinyl substituted aromatic blocks and 30 to 80 wt-56 aliphatic conjugated diene blocks, 0.2 to 20 wt-56 of (B) of a cx-p olefinic unsaturated carboxylic reagent containing 2 to 20 carbon atoms , except for the carboxy groups, based on the total weight of said (A) copolymer and said (B) unsaturated carboxylic reagent, and 0.1 to 5 wt-56 of a (C) free radical initiator based on the weight of said ( A) copolymer and said (B) unsaturated carboxylic reagent. 13. Process according to claim 12, characterized in that as said (F) polyamine an amine compound is used which contains at least two amino groups where each amino group contains at least one active hydrogen, and in which said (G) monofunctional acid is a monocarboxylic acid acylating agent or a hydrocarbon-based monocarboxylic acid containing from 1 to 50 carbon atoms. 14. Process according to claim 13, characterized in that an alkylene polyamine, a polyamine bottom product, a branched polyalkylene polyamine, or a polyoxyalkylene polyamine is used as said polyamine, and wherein said carboxylic acid acylating agent contains a hydrocarbon-based substituent where the hydrocarbon-based substituent contains from 3 to 1000 carbon atoms. 15. Method according to claim 13, characterized in that the hydrocarbon-based monocarboxylic acid used has the formula: wherein said hyd is the hydrocarbon-based substituent. 16. Process according to claim 12, characterized in that the reaction product obtained has a total acid number of from 0.5 to 20 and in which said (B) unsaturated carboxyl reagent is selected from fumaric acid, maleic acid and maleic anhydride, and in which said (D) acylation reaction product is a reaction product of: (A) a hydrogenated block copolymer including a normal block copolymer or a randomized block copolymer, wherein the normal block copolymer is prepared from a vinyl substituted aromatic unit and an aliphatic conjugated diene, wherein the normal block copolymer contains from 2 to 5 polymer blocks with at least one polymer block of said vinyl-substituted aromatic unit and at least one polymer block of said hydrogenated aliphatic conjugated diene, the randomized block copolymer is prepared from vinyl-substituted aromatic and aliphatic conjugated diene monomers, and the total amount of said vinyl-substituted aromatic blocks in the block copolymer range from 20 to 70 wt -%, and the total amount of said diene blocks in said block copolymer is in the range from 30 to 80% by weight; and the number average molecular weight of said block copolymer and said random block copolymer ranges from 10,000 to 500,000; (B) an α,β-olefinically unsaturated carboxyl reagent including functional derivatives thereof containing 2 to 20 carbon atoms excluding the carboxyl-based groups, in an amount of from 0.25% to 20% by weight, based on the total weight of said ( A) block copolymer and said (B) unsaturated carboxyl reagent; and (C) from 0.01 to 5 wt-# of a free radical initiator based on the weight of said (A) block copolymer and said (B) unsaturated carboxyl reagent. 17. Method according to claim 16, grade i-, characterized in that the conjugated diene used is isoprene or butadiene, the vinyl-substituted aromatic unit is styrene, the (A) hydrogenated normal block copolymer or randomized block copolymer contains not more than 0.5% residual olefinic unsaturation and wherein said reaction product has a total acid number of from 0.1 to 60, wherein said polyamine is alkylene polyamine, where said alkylene polyamine has the formula: wherein n is from 1 to 10, wherein each R" is independently hydrogen or a hydrocarbyl group containing from 1 to 30 carbon atoms, and wherein said alkylene group contains from 1 to 10 carbon atoms. 18. Method according to any one of claims 12-17, characterized in that the reaction is carried out at a temperature of from 50°C to 250°C. 19, Method according to any one of claims 12-18, characterized in that the reaction is carried out in a solvent. 20. Method according to any one of claims 12-18, characterized in that the reaction is carried out in a solvent-free environment. 21. Use of a preparation according to any one of claims 1-11 in an amount of from 1 to 40 wt-# together with a liquid diluent, as an additive concentrate.