US20070049504A1

US20070049504A1 - Fluid additive composition

Info

Publication number: US20070049504A1
Application number: US11/217,181
Authority: US
Inventors: Scott Culley; Chente Huang
Original assignee: Afton Chemical Corp
Current assignee: Afton Chemical Corp
Priority date: 2005-09-01
Filing date: 2005-09-01
Publication date: 2007-03-01
Also published as: KR100827972B1; CN1940041A; JP2007063558A; FR2890078A1; DE102006040495A1; KR20070026207A

Abstract

A fluid additive composition comprising a stabilizing-effective amount of at least one dispersant comprising greater than or equal to 50% of terminal vinylidene, wherein said at least one dispersant is a reaction product of at least one hydrocarbyl substituted acylating agent and at least one amine.

Description

FIELD OF THE DISCLOSURE

The present disclosure relates to a fluid additive composition comprising a stabilizing-effective amount of at least one dispersant comprising greater than or equal to 50% of terminal vinylidene, wherein said at least one dispersant is a reaction product of at least one hydrocarbyl substituted acylating agent and at least one amine. The fluid additive composition may be added to lubricant and fuel compositions to improve, for example, stability.

BACKGROUND

Additive packages may be used for making finished fuels and lubricants, including automatic transmission fluids. If the components in the package are not compatible, the package may separate into layers or show signs of inhomogeneity. For example, the packages are manufactured and then shipped to remote locations where they are usually stored until use. The combined transit and storage times may be months or years. In order to properly blend the fuel or lubricant, the additive package must be stable upon storage and remain homogeneous, or at least substantially homogenous, with all of the components in solution. Some dispersants and viscosity index improvers exhibit stability problems, such as separating when both are incorporated into the additive package. Accordingly, there is a need for fluid additive compositions having satisfactory stability.

SUMMARY

According to various embodiments, there is provided a fluid additive composition comprising a stabilizing-effective amount of at least one dispersant comprising greater than or equal to 50% of terminal vinylidene, wherein said dispersant is a reaction product of at least one hydrocarbyl substituted acylating agent and at least one amine.
Additional objects and advantages of the disclosure will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the disclosure. The objects and advantages of the disclosure will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present disclosure, as claimed.

DESCRIPTION OF THE INVENTION

In accordance with the present disclosure, there is provided a fluid additive composition comprising a stabilizing-effective amount of at least one dispersant comprising greater than or equal to 50% of terminal vinylidene, wherein said dispersant is a reaction product of at least one hydrocarbyl substituted acylating agent and at least one amine.
The dispersant disclosed herein may include acylated amines, that is, a reaction product of at least one hydrocarbyl substituted acylating agent, for example hydrocarbyl-substituted carboxylic acylating agents, and at least one amine characterized by the presence within its structure of at least one amino nitrogen. The acylated amine may be prepared in a well-known manner by reacting a stoichiometric excess of the at least one amine with at least one hydrocarbyl-substituted acylating agent. That is, greater than about 1 equivalent of the at least one amine may be reacted with each equivalent of carboxylic acid of the at least one hydrocarbyl substituted acylating agent. In certain embodiments, from about 1.0 to about 8, for example, from about 1.2 to about 7, and as a further example from about 1.4 to about 6 equivalents of the at least one amine may be reacted with each equivalent of carboxylic group of the at least one acylating agent.
The at least one hydrocarbyl substituted acylating agent used to prepare the at least one dispersant may be substantially a polyolefin, with polydispersity and other features as described below; generally it has a number average molecular weight ranging from about 600 to about 5000, for example from about 700 to about 3000, and as a further example from about 800 to about 2500. The hydrocarbyl group may be derived from a polyalkene, including homopolymers and interpolymers of olefin monomers having from about 2 to about 16, for example from about 4 to about 6 carbon atoms, and mixtures thereof. In an embodiment, the polyalkene may be polyisobutene.
The polymers useful in preparing the present dispersants may be polyisobutylenes having a M_ngreater than about 300. For the C₄isobutylene, this would correspond to an average degree of polymerization (dp) of about 5.3. The M_nof polyisobutylene may be at least about 500, for example from about 1000 to 5000, and as a further example from about 2000 to about 5000. The polymers (whether polyisobutylenes or other polyolefins) may not have an extensive low molecular weight fraction. That is, they may comprise less than about 10%, for example less than about 5%, and as a further example less than about 3% by weight of a fraction having a number average molecular weight of less than about 350, for example less than about 500, and as a further example less than about 800 units.
Such materials may be useful when used in reactions to alkylate maleic anhydride and for subsequent derivatization to form the dispersants disclosed herein. In addition to isobutylenes, other C₂-C₃₀olefins and derivatives thereof may be used herein as well as styrene and derivatives thereof, conjugated dienes such as butadiene and isoprene and non-conjugated polyenes.
Useful polymers may be derived from C₂-C₃₀olefin monomers, mixtures thereof, and derivatives thereof. Under this terminology, styrene and derivatives would be a C₂-olefin substituted by a phenyl group. In an embodiment, the polymers can be terminal vinylidenes, for example an α-vinylidene as represented by the following general formula:

wherein R can be H or a hydrocarbon group. In an embodiment, a polyisobutylene with a high concentration of terminal vinylidene, such as, for example greater than or equal to 50% terminal vinylidene, can be used. It is believed, without being limited to any particular theory, that polymers comprising a high concentration of terminal vinylidene can be more reactive than polymers comprising a low concentration of terminal vinylidene, such as, for example, less than 50%.
Useful olefin monomers from which the polyolefins disclosed herein can be derived include, but are not limited to, polymerizable olefin monomers characterized by the presence of at least one unsaturated double bond; that is, they may be monoolefinic monomers such as ethylene, propylene, butene-1, isobutylene, and octene-1 or polyolefinic monomers (usually diolefinic monomers) such as butadiene-1,3 and isoprene. In an embodiment, the monomer can be isobutylene.
These olefin monomers may be polymerizable terminal olefins; that is, olefins characterized by the presence in their structure of the group —R′—CH═CH₂, wherein R′ may be H or a hydrocarbyl group. However, polymerizable internal olefin monomers (sometimes referred to in the patent literature as medial olefins) characterized by the presence within their structure of the group:

can also be used to form the polyalkenes. When internal olefin monomers are employed, they normally will be employed with terminal olefins to produce polyalkenes which are interpolymers. For purposes of this disclosure, when a particular polymerized olefin monomer can be classified as both a terminal olefin and an internal olefin, it will be deemed to be a terminal olefin. Thus, for example, pentadiene-1,3 (i.e., piperylene) is deemed to be a terminal olefin for purposes of this disclosure.
While the polyalkenes used herein may be hydrocarbon polyalkenes, they can comprise substituted hydrocarbon groups such as lower alkoxy and carbonyl, provided the non-hydrocarbon moieties do not substantially interfere with the functionalization reactions disclosed herein. In an embodiment, such substituted hydrocarbon groups normally may not contribute more than 10% by weight of the total weight of the polyalkenes. Because the polyalkene can comprise such non-hydrocarbon substituents, it is apparent that the olefin monomers from which the polyalkenes may be made can also contain such substituents. Normally, however, as a matter of practicality and expense, the olefin monomers and the polyalkenes may be free from non-hydrocarbon groups (as used herein, the term “lower” when used with a chemical group such as in “lower alkyl” or “lower alkoxy” is intended to describe groups having up to seven carbon atoms.)
Although the polyolefins useful herein may include aromatic groups (such as phenyl groups and lower alkyl- and/or lower alkoxy-substituted phenyl groups such as para-(tert-butyl)phenyl) and cycloaliphatic groups such as would be obtained from polymerizable cyclic olefins or cycloaliphatic substituted-polymerizable acrylic olefins, the polyalkenes may usually be free from such groups. Again, because aromatic and cycloaliphatic groups can be present, the olefin monomers from which the polyalkenes are prepared can contain aromatic and cycloaliphatic groups.
Specific examples of terminal and internal olefin monomers which can be used to prepare the polyalkenes disclosed herein include propylene; butene-1; butene-2; isobutylene; pentene-1; hexene-1; heptene-1; octene-1; nonene-1; decene-1; pentene-2; propylene-tetramer; diisobutylene; isobutylene trimer; butadiene-1,2; butadiene-1,3; pentadiene-1,2; pentadiene-1,3; isoprene; hexadiene-1,5; 2-chloro-butadiene-1,2; 2-methyl-heptene-1; 3-cyclohexyl-butene-1; 2-methyl-5-propyl-hexene-1; pentene-3; octene-4; 3,3-dimethyl-pentene-1; styrene; 2,4-dichlorostyrene; divinylbenzene; vinyl acetate; allyl alcohol; 1-methyl-vinyl acetate; ethyl vinyl ether; and methyl vinyl ketone. Of these, the hydrocarbon polymerizable monomers may be used in an embodiment. For example, of these hydrocarbon monomers, the terminal olefin monomers may be used in another embodiment.
Useful polymers formed herein may include, but are not limited to, alpha-olefin homopolymers and interpolymers, and ethylene/alpha-olefin copolymers and terpolymers. Specific examples of polyalkenes include, but are not limited to, polypropylene, polybutene, ethylene-propylene copolymer, ethylene-butene copolymer, propylene-butene copolymer, styrene-isobutylene copolymer, isobutylene-butadiene-1,3 copolymer, propene-isoprene copolymer, isobutylenechloroprene copolymer, isobutylene-(para-methyl)styrene copolymer, copolymer of hexene-1 with hexadiene-1,3, copolymer of octene-1, copolymer of 3,3-dimethyl-pentene-1 with hexene-1, and terpolymer of isobutylene, styrene and piperylene. More specific examples of such interpolymers include, but are not limited to, copolymer of 95% (by weight) of isobutylene with 5% (by weight) of styrene; terpolymer of 98% of isobutylene with 1% of piperylene and 1% of chloroprene; terpolymer of 95% of isobutylene with 2% of butene-1 and 3% of hexene-1; terpolymer of 60% of isobutylene with 20% of pentene-1; and 20% of octene-1; terpolymer of 90% of isobutylene with 2% of cyclohexene and 8% of propylene; and copolymer of 80% of ethylene and 20% of propylene. U.S. Pat. No. 5,334,775 describes polyolefin based polymers of many types and their monomer precursors and is herein incorporated by reference for such disclosure.
Relative amounts of end units in conventional and high vinylidene polyisobutylenes can be determined from ¹H NMR spectra made using a Bruker AMX 500 MHz instrument and UXNMRP software to work up the spectra. The molecular weight of the polymers may be determined by GPC on a WATERS™ 2000 instrument run with tetrahydrofuran solvent (mobil phase). Known polyisobutylene can be used as a standard. M_n(number average molecular weight) and M_w(weight average molecular weight) may be determined from comparative elution volume data. Molecular weight values of the polymers may vary according to their degree of polymerization (dp). The dp range may range from about 6 to about 350 or even higher.
The hydrocarbyl-substituted carboxylic acylating agents disclosed herein may be prepared by the reaction of at least one of the above-described polyalkenes with at least one unsaturated carboxylic reagents. The unsaturated carboxylic reagents may include unsaturated carboxylic acids per se and functional derivatives thereof, such as anhydrides, esters, amides, imides, salts, acyl halides, and nitriles. The unsaturated carboxylic reagents include mono-, di-, tri, or tetracarboxylic acids. Examples of useful unsaturated monobasic acids include, but are not limited to, acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, and 2-phenylpropenoic acid. Polybasic unsaturated carboxylic acids include, but are not limited to, maleic acid, fumaric acid, mesaconic acid, itaconic acid, and citraconic acid; their anhydrides may be used. For example, in an embodiment maleic anhydride may be used. Reactive equivalents of such anhydrides include, but are not limited to, the above-mentioned derivative, e.g., acids, esters, half esters, amides, imides, salts, acyl halides, and nitriles, which can also serve as acylating agents. Another suitable acid may be glyoxylic acid, which can be reacted with the polymer as described in U.S. Pat. No. 5,912,213, the disclosure of which is hereby incorporated by reference. Reactive equivalents of glyoxylic acid, including esters and lactones, as well as other materials described in the foregoing U.S. patent, can also be used.
The at least one hydrocarbyl substituted acylating agent can be prepared by reacting at least one of the polyalkenes with, for example, a stoichiometric excess of a carboxylic acylating reagent such as maleic anhydride. Such reaction may provide a substituted carboxylic acylating agent wherein the number of succinic groups, for each equivalent weight of the hydrocarbyl group, may range from about 1.3 to about 5, for example from about 1.4 to about 4.5, and as a further example from about 1.5 to 3.5. That is, such acylating agents may be characterized by the presence of at least 1.3 succinic groups for each equivalent weight of substituent group. For purposes of this calculation, the number of equivalent weight of substituent groups may be deemed to be the number corresponding to the quotient obtained by dividing the M_n, (number average molecular weight) value of the polyalkene from which the substituent is derived into the total weight of the substituent groups present in the substituted succinic acylating agent.
It is also possible that the acylating agent can be prepared in such a way that the number of succinic groups for each equivalent of the hydrocarbyl group may be less than 1.3.
In the formation of the hydrocarbyl-substituted acylating agent, the conditions for the reaction of the olefin polymer with the acylating reagent such as maleic anhydride, and the relative concentrations of such components, should, for example, be sufficient that a majority of the olefin polymer has reacted with at least one molecule of the acylating reagent. For example, for optimum performance of the dispersant, no more than 30 percent by weight, for example no more than 25 percent by weight, and as a further example no more than 20 percent by weight polyisobutene or other olefin polymer should remain unreacted in the resulting acylating agent and, subsequently, in the resulting dispersant. Determination of conditions to assure a sufficient degree of reaction may be within the abilities of the person skilled in the art.
Dispersants may be prepared by reacting the hydrocarbyl-substituted acylating agent with an amine, an alcohol, or mixtures thereof. The amines used to prepare the dispersants can be primary, secondary, or tertiary amines. In an embodiment, a polyamine as disclosed in U.S. Pat. No. 4,234,435 at column 21, line 4 to column 27, line 50, may be used. The amines may also be heterocyclic polyamines or alkylenepolyamines. Alkylenepolyamines may be represented by the formula H(R¹)N-(Alkylene-N(R¹))_nR¹, wherein each R¹may be independently hydrogen or an aliphatic group or a hydroxy-substituted aliphatic group; n may be an integer from about 1 to about 10, and the “Alkylene” group comprises from about 1 to about 10 carbon atoms. Non-limiting examples of such polyamines include the ethyleneamines and polyethyleneamines, such as ethylenediamine, triethylenetetramine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and mixtures thereof, including complex commercial mixtures which include cyclic condensation products. Such materials may be described in detail under the heading “Ethylene Amines” in Kirk Othmer's Encyclopedia of Chemical Technology, 2d Edition, Vol. 7, pages 22-37, Interscience Publishers, New York, 1965. Other amine mixtures include “polyamine bottoms” which is the residue resulting from stripping of the above-described polyamine mixture. In another embodiment, the polyamine can be a condensed polyamine resulting form the condensation reaction of at least one hydroxy compound with at least one polyamine reactant containing at least one primary or secondary amino group. Such condensates are described in U.S. Pat. No. 5,230,714, the disclosure of which is hereby incorporated by reference. Similarly, amines can be amino alcohols of any of a variety of well-known types.
Alcohols can be used in preparation of the dispersants disclosed herein. Such dispersants may comprise ester groups. Suitable alcohols can be aliphatic, cycloaliphatic, aromatic, or heterocyclic, alcohols and can contain non-hydrocarbon substituents of a type which do not interfere with the reaction of the alcohols with the acylating agent to form the ester. The alcohols can be monohydric alcohols such as methanol, ethanol, isooctanol, dodecanol, and cyclohexanol, although they may be polyhydric alcohols, such as alkylene polyols. In an embodiment, such polyhydric alcohols may comprise from about 2 to about 40, for example from about 2 to about 20 carbon atoms; and from about 2 to about 10 hydroxyl groups, for example from about 2 to about 6. Polyhydric alcohols may include ethylene glycols such as di-, tri- and tetraethylene glycols; propylene glycols; glycerol; sorbitol; cyclohexane diol; erythritol; and pentaerythritols, including di- and tripentaerythritol.
Commercially available polyoxyalkylene alcohol demulsifiers can also be employed as the alcohol component. Such materials include the reaction products of various organic amines, carboxylic acid amides, and quaternary ammonium salts with ethylene oxide. Some such materials are available under the names ETHODUOMEEN T™, an ethylene oxide condensation product of an N-alkyl alkylenediamine; ETHOMEEN™, ethylene oxide condensation products of primary fatty amines; ETHOMIDS™, ethyene oxide condensates of fatty acid amides, and ETHOQUADS™, and polyoxyethylated quaternary ammonium salts such as quaternary ammonium chlorides.
The dispersants disclosed herein can be further borated or treated with metallizing agents. Boration of the dispersant can be effected by well-known techniques, in particular, by reaction of the dispersant with at least one boron compound. Suitable boron compounds include boric acid, borate esters, and alkali or mixed alkali metal and alkaline earth metal borates. These metal borates may be generally a hydrated particulate metal borate and they, as well as the other borating agents, are known in the art and are available commercially. Typically the dispersant may be heated with boric acid at 50-100° C. or 100-150° C. In a similar way, the dispersants can be metallized or treated with reactive metal containing compounds, such as zinc compounds.
The fluid additive composition may comprise a stabilizing-effective amount of the at least one dispersant. For example, the at least one dispersant may be present in the composition in an amount ranging from about 1% to about 80%, for example, from about 20% to about 70%, and as a further example from about 30% to about 60%, by weight relative to the total weight of the composition.
In embodiments, a lubricating composition may comprise the fluid additive composition disclosed herein. For example, the lubricating composition may include fluids suitable for any power transmitting application, such as a step automatic transmission or a manual transmission. Further, the transmission fluid may be suitable for use in at least one transmission with a slipping torque converter, a lock-up torque converter, a starting clutch, and at least one shifting clutch. Such transmissions may include four-, five-, six-, and seven-speed transmissions, and continuously variable transmissions (chain, belt, or disk type). They may also be used in manual transmissions, including automated manual and dual-clutch transmissions.
In embodiments, the lubricating composition may also comprise a base oil. The base oil may be selected from, for example, natural oils such as mineral oils, vegetable oils, paraffinic oils, naphthenic oils, aromatic oils, synthetic oils, derivatives thereof, and mixtures thereof. The synthetic oils may comprise at least one of an oligomer of an alpha-olefin, an ester, an oil derived from a Fischer-Tropsch process, and a gas-to-liquid stock. The base oil may be present in the composition in a major amount. A “major amount” may be understood to mean greater than or equal to about 50%.
The fluid additive composition may also comprise at least one additive in the appropriate proportions thereby providing a multifunctional additive package. Examples of at least one additive which may be used include, but are not limited to, dispersants, detergents, antioxidants, carrier fluids, metal deactivators, dyes, markers, corrosion inhibitors, biocides, antistatic additives, drag-reducing agents, demulsifiers, dehazers, anti-icing additives, anti-knock additives, anti-valve-seat recession additives, lubricity additives, combustion improvers, cold flow improvers, friction modifiers, antiwear agents, antifoam agents, viscosity index improvers, antirust additives, seal swell agents, metal deactivators, and air expulsion additives.
In various embodiments, a lubricating composition may comprise the disclosed fluid additive composition and at least one additive as disclosed above. In other embodiments, a fuel composition may comprise the disclosed fluid additive composition and at least one additive as disclosed above.
In selecting at least one additive, it is important to ensure that the selected additive is/are soluble or stably dispersible in an additive package and finished composition, are compatible with the other components of the composition, and do not interfere significantly with the performance properties of the composition, such as improved storage stability, friction durability, rust inhibition, corrosion inhibition, improved lubricity, friction modification, oxidation resistance, wear inhibition, and improved lead compatibility, needed or desired, as applicable, in the overall finished composition.
For the sake of convenience, the at least one additive may be provided as a concentrate for dilution. Such a concentrate forms part of the present disclosure and typically comprises from about 99 to about 1% by weight additive and from about 1 to about 99% by weight of solvent or diluent for the additive, which solvent or diluent may be miscible and/or capable of dissolving in a fluid composition, such as an automatic transmission fluid, in which the concentrate may be used. The solvent or diluent may, of course, be mineral oil, (either paraffinic or naphthenic oils), aromatic oils, synthetic oils, or derivatives thereof. However, examples of other solvents or diluents include white spirit, kerosene, alcohols (e.g., 2-ethyl hexanol, isopropanol, and isodecanol), high boiling point aromatic solvents (e.g., toluene and xylene) and cetane improvers (e.g., 2-ethyl hexylnitrate). Of course, these may be used alone or as mixtures.
In general, the at least one additive may be employed in minor amounts sufficient to improve the performance characteristics and properties of the base fluid. The amounts will thus vary in accordance with such factors as the viscosity characteristics of the base fluid employed, the viscosity characteristics desired in the finished fluid, the service conditions for which the finished fluid is intended, and the performance characteristics desired in the finished fluid.
It will be appreciated that the individual components employed can be separately blended into the base fluid or can be blended therein in various subcombinations, if desired. Ordinarily, the particular sequence of such blending steps may not be crucial. Moreover, such components can be blended in the form of separate solutions in a diluent. According to various embodiments, however, the additive components may be blended in the form of a concentrate, as this simplifies the blending operations, reduces the likelihood of blending errors, and takes advantage of the compatibility and solubility characteristics afforded by the overall concentrate.
In embodiments, a fuel composition may comprise the disclosed fluid additive composition. For example, a fuel composition may comprise a major amount of a base fuel and a minor amount of a fluid additive composition. A “minor amount” may be understood to mean less than about 50%.
The base fuels used in formulating the fuel compositions according to the present disclosure include any base fuels suitable for use in the operation of spark-ignition internal combustion engines, such as leaded or unleaded motor and aviation gasolines, diesel, and so-called reformulated gasolines which typically contain both hydrocarbons of the gasoline boiling range and fuel-soluble oxygenated blending agents, such as alcohols, ethers and other suitable oxygen-containing organic compounds. Suitable oxygenates include, for example, methanol, ethanol, isopropanol, t-butanol, mixed C₁to C₅alcohols, methyl tertiary butyl ether, tertiary amyl methyl ether, ethyl tertiary butyl ether, and mixed ethers. Oxygenates, when used, will normally be present in the base fuel in an amount below about 25% by volume, for example in an amount that provides an oxygen content in the overall fuel in the range of about 0.5 to about 5% by volume.
The fluid additive, lubricating, and fuel compositions disclosed herein can contact an actuated injector. Non-limiting examples of an actuated injector include direct-injection gasoline, port-fuel, sequential central port-fuel, and director plate injectors.
In various embodiments, there is disclosed a vehicle comprising a transmission comprising the disclosed fluid additive composition, lubricating composition, and fuel composition. In other embodiments, there are disclosed methods for improving storage stability of compositions, such as lubricating and fuel compositions, comprising adding to a lubricating composition and a fuel composition a fluid additive composition as disclosed herein.

EXAMPLES

A 2100 MW dispersant was made from polyisobutylene having a terminal vinylidine content of greater than 80% (high reactivity) by first reacting maleic anhydride with polyisobutylene having a terminal vinylidine content of greater than 80% at elevated temperatures. The polyisobutylene succinic anhydride (PIBSA) intermediate was further reacted with tetraethylenepentamine in approximately 2:1 ratio to produce a bis-succinimide dispersant. The dispersant made from the high reactivity polyisobutylene was formulated into two automatic transmission fluid additive packages as was the corresponding dispersant made from a conventional polyisobutylene. The additive packages contained typical components to control friction, foam, wear, oxidation, rust, and corrosion. Moreover, the additive packages contained polymethacrylate type polymers that function as viscosity modifiers. The compositions for the additive packages and the fully formulated automatic transmission fluids that would be made from said additive packages are outlined below.

TABLE 1


Composition of ATFs and Additive Packages with PIB
based Dispersants. All values in weight percent

Additive	Additive	Additive	Additive
Package	Package	Package	Package
1a	1b	2a	2b

High Reactive		38.04		55.6
Dispersant
Conventional	38.04		55.6
Dispersant
Viscosity Modifier A	19.0	19.0
Viscosity Modifier B			10.4	10.4
Other Dispersants	3.17	3.17	3.5	3.5
Detergents	.70	.70	1.4	1.4
Friction Modifiers	2.0	2.0	4.1	4.1
Dibutyl hydrogen	0.5	0.5	.56	.56
phosphite
Thiadizole	1.3	1.3	1.4	1.4
Sulfurized oil			3.5	3.5
Antioxidant	3.2	3.2	1.7	1.7
Minor components	.33	.33	.55	.55
Diluent oil	31.7	31.7	17.4	17.4
Base oil	NA	NA	NA	NA

All of the products were stored at room temperature. After 8 weeks the samples were examined. Additive package 1b with the high reactivity polyisobutylene based dispersant was clear and homogeneous. However, additive package 1a made with a conventional dispersant had separated into two distinct layers. Additive package 1b with the high reactivity polyisobutylene was placed in a 55° C. oven and stored for four weeks. Examination of this package at the end of four weeks showed that it was clear and homogenous.
After 8 weeks, additive package 2b made with the high reactivity polyisobutylene based dispersant was clear and homogenous. However, additive package 2a made with the conventional dispersant showed haze and signs of phase separation. Both the samples were placed in a 55° C. oven and stored for four weeks. Examination of the samples after four weeks at 55° C. showed that the sample that used the dispersant made from high reactivity polyisobutylene was clear and homogenous. The sample made from conventional polyisobutylene was hazy and showed partial separation. The samples were stored an additional five months at room temperature. Examination of the samples at that time showed that the sample made with the conventional dispersant had separated into two distinct layers. However, the sample made with the high reactivity polyisobutylene remained clear and homogeneous.
A 2100 MW dispersant was made from polyisobutylene having a terminal vinylidine content of greater than 80%. The dispersant was further reacted with boric acid and phosphorus acid to incorporate boron and phosphorous into the dispersant. The dispersant made from the high reactivity polyisobutylene was formulated into two preblends with viscosity modifier and diluent oil as was the corresponding dispersant made from conventional polyisobutylene. The preblends can be used to toptreat fully formulated ATFs or blended with other additive components to generate the complete additive package. The compositions for the preblends are as outlined below.

TABLE 2

Viscosity Modifier - Dispersant Mixtures

Dispersant (Conventional or HR) 26

Viscosity Modifier B 26

Diluent Oil A 26

Diluent Oil B 22
The preblends were stored at room temperature. After one week the samples were examined. The sample made from the dispersant that employed high reactivity polyisobutylene was clear and homogenous with no signs of separation. The sample made from the conventional dispersant had separated. The sample made from high reactivity polyisobutylene was stored at 55° C. for four weeks after which time it was examined. The sample was clear and homogenous with no signs of separation.
The test results show that the dispersants made from the polyisobutylene having, for example, greater than 80% terminal vinylinde content have better compatibility in additive packages than dispersants made from conventional polyisobutylene. The packages that employed dispersants made from high reactivity polyisobutylene based dispersants were stored for extended periods at either room temperature or elevated temperatures and remained homogenous with no signs of separation. These packages can be used to make fully formulated transmission fluids that meet the desired composition, chemical, and physical properties whereas these same additive packages made from conventional based polyisobutylene dispersants cannot. The results also show that mixtures of high reactivity polyisobutylene based dispersants with polymethacrylate polymers are stable whereas mixtures of conventional based dispersants with the same polymethacrylate polymers are not stable.
For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Moreover, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a range of “less than 10” includes any and all subranges between (and including) the minimum value of zero and the maximum value of 10, that is, any and all subranges having a minimum value of equal to or greater than zero and a maximum value of equal to or less than 10, e.g., 1 to 5.
It is noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the,” include plural referents unless expressly and unequivocally limited to one referent. Thus, for example, reference to “a succinimide” includes two or more different succinimides. As used herein, the term “include” and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items.
It will be apparent to those skilled in the art that various modifications and variations can be made to various embodiments described herein without departing from the spirit or scope of the present teachings. Thus, it is intended that the various embodiments described herein cover other modifications and variations within the scope of the appended claims and their equivalents.

Claims

1. A fluid additive composition comprising a stabilizing-effective amount of at least one dispersant comprising greater than or equal to 50% of terminal vinylidene, wherein said at least one dispersant is a reaction product of at least one hydrocarbyl substituted acylating agent and at least one amine.

2. The additive composition of claim 1, wherein the at least one dispersant is present in the composition in an amount of from about 1% to about 80% by weight relative to the total weight of the composition.

3. The additive composition of claim 2, wherein the at least one dispersant is present in the composition in an amount of from about 20% to about 70% by weight relative to the total weight of the composition.

4. The additive composition of claim 1, wherein the at least one hydrocarbyl substituted acylating agent is derived from a polyalkene.

5. The additive composition of claim 4, wherein the polyalkene is selected from the group consisting of homopolymers and interpolymers of olefin monomers comprising from 2 to 16 carbon atoms.

6. The additive composition of claim 4, wherein the polyalkene is polyisobutene.

7. The additive composition of claim 4, wherein the polyalkene is reacted with at least one carboxylic acylating reagent.

8. The additive composition of claim 7, wherein the at least one carboxylic acylating reagent is maleic anhydride.

9. The additive composition of claim 1, wherein the at least one amine is selected from the group consisting of primary, secondary and tertiary amines.

10. The additive composition of claim 1, further comprising at least one additive selected from the group consisting of dispersants, detergents, antioxidants, metal deactivators, dyes, markers, copper corrosion inhibitors, biocides, antistatic additives, demulsifiers, dehazers, anti-icing additives, lubricity additives, extreme pressure additives, cold flow improvers, friction modifiers, antiwear agents, antifoam agents, viscosity index improvers, antirust additives, seal swell agents, metal deactivators, and air expulsion additives.

11. A lubricating composition comprising the fluid additive composition of claim 1.

12. The lubricating composition of claim 11, further comprising a base oil.

13. The lubricating composition of claim 12, wherein the base oil comprises at least one of natural oil and synthetic oil.

14. The lubricating composition of claim 13, wherein the natural oil comprises at least one of a mineral oil and a vegetable oil.

15. The lubricating composition of claim 13, wherein the synthetic oil comprises at least one of an oligomer of an alpha-olefin, an ester, an oil derived from a Fischer-Tropsch process, and a gas-to-liquid stock.

16. The lubricating composition of claim 12, wherein the base oil is present in the composition in a major amount.

17. The lubricating composition of claim 11, further comprising at least one additive selected from the group consisting of dispersants, detergents, antioxidants, metal deactivators, dyes, markers, copper corrosion inhibitors, biocides, antistatic additives, demulsifiers, dehazers, anti-icing additives, lubricity additives, extreme pressure additives, cold flow improvers, friction modifiers, antiwear agents, antifoam agents, viscosity index improvers, antirust additives, seal swell agents, metal deactivators, and air expulsion additives.

18. The lubricating composition of claim 11, wherein the composition is suitable for use in a transmission employing at least one of a slipping torque converter, a lock-up torque converter, a starting clutch, and at least one shifting clutch.

19. The lubricating composition of claim 11, wherein the fluid is suitable for use in a belt, chain, or disk-type continuously variable transmission.

20. The lubricating composition of claim 11, wherein the lubricating composition is a power transmission fluid.

21. The lubricating composition of claim 20, wherein the power transmission fluid is an automatic transmission fluid.

22. The lubricating composition of claim 20, wherein the power transmission fluid is a manual transmission fluid.

23. A vehicle comprising a transmission, the transmission including the lubricating composition of claim 11.

24. A vehicle comprising a transmission, the transmission including the fluid additive composition of claim 1.

25. A method for improving storage stability of a lubricating composition comprising adding to a lubricating composition a fluid additive composition of claim 1.

26. A method for improving storage stability of a fuel composition comprising adding to a fuel composition a fluid additive composition of claim 1.

27. A fuel composition comprising:

a) a base fuel in a major amount, and

b) a fluid additive composition of claim 1 in a minor amount.

28. The fuel composition of claim 27, further comprising at least one additive selected from the group consisting of dispersants, detergents, antioxidants, metal deactivators, dyes, markers, copper corrosion inhibitors, biocides, antistatic additives, demulsifiers, dehazers, anti-icing additives, lubricity additives, extreme pressure additives, cold flow improvers, friction modifiers, antiwear agents, antifoam agents, viscosity index improvers, antirust additives, seal swell agents, metal deactivators, and air expulsion additives.

29. A vehicle comprising an engine, the engine comprising the fuel composition of claim 27.

30. An engine combusting the fluid additive composition of claim 1.

31. An engine combusting the fuel composition of claim 27.

32. An actuated injector contacting the fluid additive composition of claim 1.

33. An actuated injector contacting the fuel composition of claim 27.

34. The injector of claim 32, wherein the actuated injector is selected from the group consisting of direct-injection gasoline, port-fuel, sequential central port-fuel, and director plate injectors.