JPH0362891A - Improved, branched amide-amine dispersion additive - Google Patents

Abstract

PURPOSE: To obtain an improved amide-amine dispersant additive composition capable of preventing the fouling of carburetor, etc., and excellent in viscosity properties by further adding a NH group-containing compound to an adduct of a reactive nitrogen component-containing compound and a multifunctional reaction product and then contacting the resultant with a specific component.

CONSTITUTION: First, (A) a nitrogen compound containing a plurality of reactive nitrogen components is brought into contact with (B) a multifunctional reactant having a plurality of functional groups reactive with an NH group in a liquid reaction mixture to react the reactive nitrogen components of component (A) with at least part of the functional groups of component (B). Then, the first adduct thus obtained is brought into contact with (C) a nitrogen-containing compound having a plurality of NH groups to obtain a second adduct having two or more of each of the nitrogen-containing component and the primary or secondary amine group from component (C) based on the nitrogen-containing component from component(A). Finally, this second adduct is brought into contact with (D) a component selected from a halogenated long chain hydrocarbon and a mixture of an aldehyde and a phenol substituted with a long chain hydrocarbon, etc.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to improved oil-soluble dispersing additives useful in fuel and lubricating compositions and concentrates containing the additives.

Prior Art US Pat. No. 2,921,085 relates to reacting an alkyl amine with an acrylate to form an alkyl acronobrobionate and reacting the compound with an amine to produce beta-aminopropionamide. The resulting compounds can be used as surfactants, especially emulsifiers, wetting agents,
It is disclosed that it has practical utility as a blowing agent and a cleaning agent.

US Pat. No. 3,337,609 relates to adducts of hydroxyalkylalkylene polyamines and acrylates. The resulting adduct is added to polyepoxide to form a composition. The composition is suitable for use as a barrier coating for polyethylene surfaces and for additional end uses such as molding. Additionally, the adducts are disclosed to be useful as catalysts in resin production and as corrosion inhibitors for ferrous metals in aqueous systems.

U.S. Pat. No. 3,417,140 discloses polyalkyleneboria bases and fatty acid bases (including diamines or diamines having as one of the substituents on the nitrogen atom a hydrocarbyl radical having 8 to 24 carbon atoms). 9 and alpha-beta unsaturated luponylic compounds to produce amido-amine compositions useful as epoxy curing agents. This reaction is disclosed to occur by microaddition of amine groups with unsaturated groups of carbonylic compounds and by condensation of amine groups with carbonylic groups.

U.S. Pat. No. 3,247,163 also relates to curing agents for polyepoxide compositions made by reacting organic amines with acrylates.

U.S. Pat. No. 3,445,441 discloses that at least Boria a.
The present invention relates to amino-amide polymers which are characterized in that they are reaction products of compounds of the acrylate type, such as methyl or ethyl acrylate, methyl or ethyl methacrylate. The patent states that the polymers are useful in a wide variety of applications, such as flocculants, water clarifiers, corrosion inhibitors in oil and gas wells, and as lubricant additives. The patent further describes monocarboxylic acids, polycarboxylic acids, aliphatic dicarboxylic acids, aromatic dicarboxylic acids such as diglycolic acid, phthalic acid,
It is disclosed that the polymer can be synthesized inductively with acylation with succinic acid, etc.

U.S. Patent No. 3,903,003 has an average molecular weight of 20.0
00 to 250,000 is reacted with a nitrogen compound of the group consisting of polyethylene amines and hydroxyl polyalkylene amines. The invention relates to a lubricating composition containing an amide-amine reaction product of a formulated inprene polymer.

U.S. Pat. No. 4,493,771 relates to scale inhibition with compounds containing quaternary ammonium and methylene phosphonic acid groups. These compounds are derivatives of polyamines in which the amine hydrogen is substituted with both a methylene phosphonic acid group or a salt thereof and a hydroxypropyl quaternary ammonium halide group. The patent discloses that any amine containing reactive amino hydrogens may be used, such as polyglycolamines, amidoamines, oxyacylated amines, and the like.

U.S. Pat. No. 4,459,241 includes U.S. Pat.
It contains the same disclosure content as No. 3,771.

Arrangements of the Invention (a) A first nitrogen-containing compound having at least two reactive nitrogen components, a first functional group reactive with an -NH- group and at least one additional functional group reactive with an -NH- group. in a first liquid reaction mixture, reacting at least a portion of the first functional groups in the multifunctional reactant with the reactive nitrogen component to form a first adduct. (b) bringing the first adduct and a second nitrogen-containing compound having at least two -NH- groups into contact with the additional functional group in the first adduct and the second nitrogen-containing compound; one NH- group in the nitrogen-containing compound is contacted with the nitrogen-containing compound in an amount and under conditions sufficient to react with (i) a second nitrogen-containing compound per nitrogen-containing moiety derived from the first nitrogen-containing compound; and (ji) at least two unreacted primary or primary amine groups per molecule; (c) (8) contacting the second adduct in the second liquid reaction mixture with at least one long chain hydrocarbon-substituted reactant comprising at least one member selected from the group consisting of: long chain hydrocarbons substituted with mono- or dicarboxylic acid, anhydride or ester groups; (B) halogenated long chain hydrocarbons; (C) mixtures of formaldehyde and long chain hydrocarbyl substituted phenols; (D) Formaldehyde and mono- or dicarboxylic acid,
Nitrogen-containing lubricating oil containing a mixture of a reaction product formed by reacting a long-chain hydrocarbon substituted with an anhydride or ester group and an aryno-substituted and optionally hydrocarbyl-substituted phenol. A method for producing a dispersion additive.

The present invention, in one preferred embodiment, is directed to a branched amide-amine dispersion additive, preferably a star-branched amide-amine dispersion useful in an oil-based composition produced by (a) a first nitrogen-containing compound (e.g. ammonia or an organic amine) and an alpha, beta unsaturated compound of the formula: (wherein W+ is sulfur or oxygen; Y is -OR'
, -SR' or -NR'(R'), and RI, R2
, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl) to contain an unreacted -c(w')-y group. (b) the first adduct and boria (
(C) a second adduct containing an unreacted -NH- group (preferably a primary amine group) and a branched amide-amine oligomer; 2 adduct and at least 0.3 (e.g., about 1 to 4) mono- or dicarboxylic acid-forming components (preferably acid or anhydride components) per polyolefin molecule.
Substituted with number average molecular weight 300 to, oo.

long-chain hydrocarbyl-substituted mono- or dicarboxylic acid materials containing polyolefins.

The materials of the invention differ from the prior art in their effectiveness and ability to impart high dispersibility. The additives serve to minimize the degree of fouling of the carburetor and fuel injectors from deposits in the fuel. In addition, the additives of the present invention possess excellent viscosity properties.

Accordingly, the present invention is also directed to a novel method of manufacturing the dispersant fuel adduct of the present invention.

As mentioned above, the first adduct used in the present invention contains at least 2 (e.g. 2 to 2), preferably at least 3, per molecule of polyfunctional reactant and first nitrogen-containing compound.
(eg, from 3 to 15), most preferably from 3 to 8 reactive nitrogen components (i.e., total nitrogen-bonded H atoms). The first nitrogen-containing compound is ammonia, an organic primary monoamine and at least one primary amine group per molecule or at least two
at least lf! a member selected from the group consisting of organic polyamines containing three secondary amino groups; It is normal to include J. The organic amine has a total carbon atom population in the molecule of about 2 to 60, preferably 2 to 40 (e.g., 3 to 20) and a total nitrogen atom of about 2 to 12, preferably 3 to 12, most preferably 3 to
8 (for example, 5 to 9). These amines can be hydrocarbyl amines or can be hydrocarbyl amines containing other groups, such as hydroxy groups, alkoxy groups, amide groups, nitriles, imidacillin groups, and the like.

Hydroxyamines having 1 to 6, preferably 1 to 3 hydroxy groups are particularly useful. Preferred amines are aliphatic saturated amines, including those of the general formula: (T) (n
) where R, R', R'' and Rlo are independently selected from the group consisting of: hydrogen, C3-C25 straight or branched chain alkyl radical, CI-C12 alkoxy C2-C
6 alkylene radical; C2-CI2 hydroxyaminoalkylene radical, and CI'''''CI2 alkylamino02-C6 alkylene radical, R''' can further include components of the formula, where R' is as previously defined. S and S' can be the same or different and are in number from 2 to 6, preferably 2 to 4; and t' can be the same or different. , 0 to 10, preferably 2 to 7, most preferably about 3 to 7, with the sum of t and t' being less than or equal to 15. To ensure facile reaction, RR'R #, R”°, s,
s', and t' to typically impart at least one primary or secondary amino group, preferably at least two primary or secondary amino groups to the compounds of formulas 1 and 11. It is preferable to choose in a sufficient manner. This is R, R', R
'' or by choosing at least one of the R' groups to be hydrogen, or if Rlo is H, or by choosing II+
When the component has a secondary amino group, t in formula 11
Distant relatives can be established by making the number at least 1.

Examples of suitable organic axon compounds include, but are not limited to: l,2-cyanoethane 1,3-diaminopropane: 1,4-diaminobutane: 1,6-diamithexane: polyethyleneamine , e.g. diethylenetriamine, triethylenetetramine; tetraethylenepenta-based polypropyleneamine, e.g. 1,2-propylenediamine: di(l,2-propylene)triamine, di(1,3-propylene)triamine, N N -dimethyl-1,3-diaminopropane, N,N-di(2-aminoethyl)ethylenediamine, N,N-di(2-hydroxyethyl)-1,3-propylenediamine; 3-F
Decyloxypropylamine; N-dodecyl-IJ-propanethyl trishydroxymethylaminomethane (THA M) diisopropylamine: jetanolamine: triethanolamine; mono-, di- and tritallowamine; amino Morpholine, e.g. N-(
3-Acnoprovir) morpholine; and mixtures thereof.

Other useful amine compounds include cycloaliphatic diamines such as 1,4-di(azitumethyl)cyclohexane, heterocyclic nitrogen compounds such as imitasoson, N-aminoalkylbiverazine of general formula (IV) below: Here, l) I and p are the same or different and are each an integer of 1 to 4, and nl, n2 and n3 are the same or different and are each an integer of 1 to 3; Examples of such aminos include, but are not limited to: 2-
Pentadecyl-Dublin-(2-aminoethyl)
Piperazine et al.

Commercial mixtures of amine compounds can be advantageously used. For example, one method for producing alkylene amines is to react an alkylene civalide (e.g., ethylene dichloride or propylene dichloride) with ammonia, and the pair of nitrogens are linked by an alkylene group to form diethylene triamine,
triethylenetetramain, tetraethylenepentamine,
It involves producing complex mixtures of alkylene amines forming compounds such as isomeric piperazines.

An inexpensive poly(ethyleneamine) compound with an average of about 5 to 7 nitrogen atoms per molecule is available under the trade name PolyamineH.
”, r Polyamine 400 J, r Dow
Polyamine E-100J, etc. are commercially available.

Useful amines also include polyoxyalkylene polyamines, such as those of the formula: NH2-alkylene+
O-alkylene → -NH2 (v) where m is about 3-7
and R+alkylene→○-alkylene□□□-NH2) p
(Vl) where "n" has a value of about 1 to 40, provided that the sum of all n's is about 3 to about 70, preferably about 6 to about 35, and R is up to 10 carbon atoms. is a polyvalent saturated hydrocarbon radical, and the number of substituents on the R group is "p
” and is a number from 3 to 6. The alkylene group in either formula (V) or formula (Vl) is
It can be a straight or branched button containing 2 to 7, preferably about 2 to 4, carbon atoms.

A polyoxyalkylene polyamine of the above formula (V) or (Vl), preferably a polyoxyalkylene diamine,
Polyoxyalkylene triamine has an average molecular weight of approximately 200
to about 4000, preferably 1 to about 400 to about 2000. Preferred polyoxyalkylene polyamines include polyoxyethylene and polyoxypropylene diamines and polyoxypropylene triamines having an average molecular weight of 200 to 2000. Polyoxyalkylene polyamines are commercially available, for example from the Jefferson Chemical Company, Inc. under the trade name Jeffamine.
D-230, D-400, D-1000, D2000,
It can be obtained from T-403J etc.

Additional amines useful in the present invention are U.S. Pat.
No. 5,441, the entire disclosure of which is incorporated herein by reference.

Most preferred as the first nitrogen-containing compound are ammonia and 2 to 12 carbon atoms and 2 to 8 nitrogen atoms per molecule.
is a member selected from the group consisting of organic dibrymylamines having the following: Examples of such preferred organic diprimary amines are: ethylenediamine,
Propylene, diethylenetriamine, dipropylene, triethylenetetramine, tripropylenetetramine, tetraethylenepentaamine, tetrapropylenepentaamine, polyhexamethylenediamine, phenyldiamine.

Multifunctional Reactants Multifunctional reactants useful in the present invention include compounds having the following formula (■): where Wl and W2 are the same or different and are 0 or S; , X and Y are the same or different, preferably each -NH- group (i.e. NH3 or -
or a secondary amine group), T is a substituted or unsubstituted hydrocarbon moiety, and "aJ is O or 1
, "b" is O or 1, and "c" is an integer of at least 1, provided that when a=0, c=1, and a
= 1, then b = 1, and X, Y
and T are reactive with the NH- group.

The X and Y functional groups may be the same or different and include groups selected from the group consisting of: halai-OR', -SR'
, -N (R')(R5)Z'C(0)OR'
, -C(0)R'(R3)C=C(R')(R2),
-Z'-, =-tolyl, -Zl-cyano, -Zl-
Thiocyano.

zl -isothiocyano and -21-isocyano, where RI, R2, R3, R4 and R5 are the same or different and are H or substituted or unsubstituted hydrocarbyl, and zl is c1-C2Q (preferably is C1~
C1゜) When containing at least one divalent hydrocarbylene (preferably alkylene or arylene), X and Y together further contain 10- or -S- to form a group of ethylenic non-hydrocarbylenes. Saturated and aromatic anhydrides and sulfo-anhydrides can be provided as reactants. The X and Y groups in the selected polyfunctional reactants are different, and the reactivity of the X component with the -NH- group under the selected reaction conditions is greater than the reactivity of the Preferably, it is large enough to allow a substantially selective reaction of the X group with the first M-free compound. This will be explained below. The relative reactivity of these groups with polyfunctional reactants can be readily determined by conventional methods.

When R1, R2, R3, R4 or R5 are hydrocarbyl, these groups can include alkyl, cycloalkyl, aryl, alkaryl, aralkyl or polycyclic groups, which are suitable for producing amidoamines. Substitution can be made with groups that are substantially inert to any component of the reaction mixture under the conditions selected. Such substituents include hydroxy, halide (e.g. CfL, F, I, Br)
, -SH, and alkylthio. When one or more of R1-R5 is alkyl, such alkyl group can be straight-chain or branched and usually contains 1 to 20 carbon atoms, usually 1 to 20 carbon atoms. -10, preferably 1-4. Examples of such alkyl groups are: methyl, ethyl, propyl, butyl, pentyl, hexyl, he5-butyl, octyl, nonyl, decyl, dodecyl, tridecyl, hexadecyl, octadecyl, and the like.

When one or more of R1-R5 is aryl, the aryl group usually contains 6 to 10 carbon atoms (eg phenyl, naphthyl).

When one or more of R1-R5 is alkaryl, alkaryl usually contains 7 to 20, preferably 7 to 12 carbon atoms. Examples of such alkaryl groups are tolyl, m-ethylphenyl, 0-ethyltolyl,
m-hexyltolyl. When one or more of R' to R11 is aralkyl, the aryl component usually consists of phenyl or (C+ to C6) alkyl-substituted phenol, with the alkyl component and 1 to 12 carbon atoms, preferably Usually it contains 1 to 6. Examples of such aralkyls are benzyl, 〇-ethylbenzyl, 4-
It is isobutylbenzyl. When one or more of RI and R5 is cycloalkyl, the cycloalkyl group usually contains 3 to 12 carbon 6 atoms, preferably 3 to 6 carbon atoms. Examples of such cycloalkyl groups are cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl,
It is cyclododecyl.

When one or more of RI-R5 is heterocyclic, the heterocyclic group is a 6- to 12-membered ring in which one or more ring carbon atoms are replaced with oxygen or nitrogen. It usually consists of a compound having at least one. Examples of such heterocyclic groups are furyl, pyranyl, pyridyl, piperidyl, dioxanyl, tetrahydrofuryl, pyrazinyl,
, 4-oxazinyl.

T is a polyvalent organic radical whose valence is equal to c+1, where rcJ is at least 1, preferably from 1 to
It is an integer of 3. Typically T will contain no more than 20 carbon atoms, preferably no more than 10 carbon atoms. Thus, T includes divalent groups such as saturated and unsaturated hydrocarbylenes (eg, alkylene, alkenylene, arylene, etc.). If T is replaced, ding is halo,
It can contain one or more substituents selected from the group consisting of lower alkoxy, lower alkyl mercapto, nitro, lower alkyl, carboxy and oxo. T can also be an interlabeling group, e.g. -o-, -s-, -
It may contain s(o)S(0)2-, -NH-, -C(0), and the like.

Examples of the 21 groups are as follows. C1-CIO branched and straight-chain alkylenes, such as -(CH2) t-('
f' is an integer from 1 to 10) (e.g., CH2-, -
C2Ha-, C3Ht-, C4HaC5HIO, etc.),
C6-C2Q arylene and alkyl-substituted arylene, such as -Ar-, -Ar ((CH2) r
((CR2)t-A r-, -A r ((CR2)
r) Ar, etc., where Ar is phenylene, methylphenylene, naphthylene, methylnaphthylene, etc., and f is as defined above.

■Formula (where X is (R') (R2)C= C(R3)
and a = b = o, c = 1).
a functional reactant comprising a beta-ethylenically unsaturated compound, where Wl is sulfur or oxygen and Y is as defined above, preferably -0R4-3R' or -N
R'(R5), Rl, R2R3, R4 and R
5 is as defined above.

The alpha, beta ethylenically unsaturated carboxylate compounds used in the present invention have the following formula: where R1, R2, R3 and R4 are the same or different and are hydrogen or substituted as defined above. or unsubstituted hydrocarbyl.

Examples of such alpha, beta ethylenically unsaturated carboxylate compounds of the formula are as follows: Niacrylic acid, methacrylic acid, methyl, ethyl, isopropyl, n-butyl and isobutyl esters of acrylic acid and methacrylic acid; -butenoic acid, 2-hexenoic acid, 2-decenoic acid, 3-methyl-2-heptenoic acid, 3-methyl-2
-butenoic acid, 3-phenyl-2-propenoic acid, 3-cyclohexyl-2-butenoic acid, 2-methyl-2-butenoic acid, 2-propyl-2-propenoic acid, 2-isopropyl-
2-hexenoic acid, 2,3-dimethyl-2-butenoic acid, 3-
Cyclohexyl-2-methyl-2-pentenoic acid, 2-propenoic acid, methyl 2-propenoate, methyl 2-methyl 2-propenoate, methyl 2-butenoate, ethyl 2-hexenoate, isopropyl 2-decenoate, phenyl 2-pentenoate, t -Butyl 2-propenoate, octadecyl 2-propenoate, dodecyl 2-decenoate, cyclopropyl 23-dimethyl-2
-butenoate, methyl 3-phenyl-2-propenoate, etc.

■ The alpha, beta ethylenically unsaturated reactants of the formula (-OR' is replaced by -R4) are aldehydes and ketones of the formula: where R1, R2, R3 and R4 are the same. or alternatively, hydrogen or substituted or unsubstituted hydrocarbyl as defined above.

Examples of such alpha, beta ethylenically unsaturated aldehydes and ketones of formula IXa are: 112cmC11-C(0)-C)I382C-CH
-C(0) -(:2H5)12cmCH-G (0)
-C3H782C-CIl-C(0) -C(CH3
) 31(2C-OH-G (0)-C3H782C-
C(CH3) -C(0) -CI((CIL+) 2
the-C(CH3)-C(0)-CJSH(CI
l3) C-CH-C, (0)-CH2O(C1h) C
-CH-C(0)-11:H(CI-13) 2II
(C1b) C-CH-C(0) -C2Hs+I
(CI+3) C-CH-C(0) -C3)17II
(C2H5) C-Cl1-C(0) -C(CI+
3) 511(Cl13)C-CH-C(0)-CsH
++(CL) (C2H5) C-C(CH3) -C
(0) -CH2O(Ctl+)C-C(CH3)-C
(0) -C2H5 The alpha, beta ethylenically unsaturated carboxylate thioester compound used in the present invention has the following formula: where RI, R2, R3 and R4 are the same or different and as defined above. is hydrogen or substituted or unsubstituted hydrocarbyl.

Examples of such alpha, beta ethylenically unsaturated carboxylate thioesters of formula
t-Butyl mercapto 2-propenoate, octadecyl mercapto 2-propenoate, dodecyl mercapto 2 decenoate, cyclopropyl mercapto 2.3 dimethyl-2-butenoate, methyl mercapto 3-phenyl-2-propenoate, methyl mercapto 2-propenoate, methyl mercapto 2 -methyl-2-propenoate, etc.

The alpha, heter ethylenically unsaturated carboxamide compound used in the present invention has the following formula.

wherein R1, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, heterethylenically unsaturated carboxamides of the formula are as follows = 2-butenamide, 2-hexenamide, 2-deceneate, 3-methyl-2-hebutenamide, 3-methyl- 2-butenamide, 3-phenyl 2
-propenamide, 3-cyclohexyl-2-butenamide, 2-methyl-2-butenamide, 2-propyl-2
-Propenamide, 2-isopropyl-2-hexenamide, 2,3-dimethyl-2-butenamide, 3-cyclohexyl-2-methyl-2-pentenamide, N-methyl 2-butenamide, N,N-diethyl 2-hexene Amide, N-isopropyl 2-decenamide, N-phenyl 2-hentenamide, N-t-butyl 2-propenamide, N-octadecyl 2-propenamide, N,N-
Didodecyl 2-decenamide, N-cyclopropyl2.
3-dimethyl-2-butene acid, N-methyl 3-phenyl-2-propenamide, 2-propenamide, 2-
Methyl-2-propenamide, 2-ethyl-2-propenamide, etc.

The alpha, beta ethylenically unsaturated thiocarboxylate compounds used in the present invention have the formula: where R1, R2, R3 and R4 are the same or different and are hydrogen or substituted as defined above. or unsubstituted hydrocarbyl.

Examples of alpha, beta ethylenically unsaturated thiocarboxylate compounds of formula (2) are as follows. 2-butenethioic acid, 2-hexentioic acid, 2-decentioic acid, 3-
Methyl-2-heptenethioic acid, 3-methyl-2-butenethioic acid, 3-phenyl-2-propenthioic acid, 3-cyclohexyl-2-butenethioic acid, 2-methyl-2-butenethioic acid, 2-propyl-2-propenthioic acid , 2-ituproyl-2-hexentioic acid, 2,3-dimethyl-2
-butenethioic acid, 3-cyclohexyl-2-methyl-2
-Pentenethioic acid, 2-propenthioic acid, methyl 2-propenthioate, methyl 2-methyl 2-propenthioate, methyl 2-butenethioate, ethyl 2-hexethioate, isopropyl 2-decentioate, phenyl 2-pententhioate ate, t-butyl 2-propenthioate, octadecyl 2-propenthioate, dodecyl 2-decentioate, cyclopropyl 2
．． 3-dimethyl-2-butenethioate, methyl 3-phenyl-2-propenthioate, etc.

The alpha, beta ethylenically unsaturated dithioic acid and acid ester compounds used in the present invention have the formula: where RI, R2, R3 and R4 are the same or different and are hydrogen or substituted as previously defined. unsubstituted or unsubstituted hydrocarbyl.

Examples of alpha, beta ethylenically unsaturated dithioic acids and acid esters of the formula are as follows = 2-butenedithioic acid, 2-hexenedithioic acid, 2-decenedithioic acid, 3
-Methyl-2-hebutenedithioic acid, 3-methyl-2-butenedithioic acid, 3-phenyl-2-propenedithioic acid,
3-Schiff0hexyl-2-butenedithioic acid, 2-methyl 2-butenedithioic acid, 2-propyl-2-propenedithioic acid, 2-isopropyl-2-hexenedithioic acid, 2.
3-dimethyl-2-butenedithioic acid, 3-cyclohexyl-2-methyl-2-pentenedithioic acid, 2-propenedithioic acid, methyl 2-propennedithioate, methyl 2
-Methyl 2-propenedithioate, methyl 2-butenedithioate, ethyl 2-hexenedithioate, isopropyl 2-decenedithioate, phenyl 2-pentenedithioate, t-butyl 2-propenedithioate, octadecyl 2-propenedithioate Eight, Dodecyl 2
-decenedithionyi 1., cyclopropyl 2,3-dimethyl-2-butenedithioate, methyl 3-phenyl-
2-propenedithioate, etc.

The alpha, beta ethylenically unsaturated thiocarboxamide compounds used in the present invention have the formula: 8 where RI, R2, R3, R4, and R5 are the same or different and are hydrogen or hydrogen as previously defined. W-substituted or unsubstituted hydrocarbyl. Examples of stratified alpha, beta ethylenically unsaturated thiocarboxamides are: 2-butenethioamide,
2-Hexentioamide, 2-Decentioamide, 3-
Methyl-2-butenethioamide, 3-methyl-2-butenethioamide, 3-phenyl-2-propenthioamide, 3-cyclohexyl-2-butenethioamide, 2-methyl-2-butenethioamide, 2-propyl-2-propene Thioamide, 2-isopropyl-2-hexentioamide, 2,3-dimethyl-2-butenethioamide, 3
-Cyclohexyl-2-methyl-2-pentenethioamide, N-methyl 2-butenethioamide, N,N-diethyl 2-hexenedioic acid, N-isopropyl 2-decentioamide, N-phenyl 2-pentenethioamide,
N-t-butyl 2-propenthioamide, N-octadecyl 2-propenthioamide, N,N-didodecyl 2-
Decentioamide, N-cyclopropyl 2,3-dimethyl-2-butenedioactine, N-methyl 3-phenyl-2
-propenthioamide, 2-propenthioamide, 2-
Methyl-2-propenthioamide, 2-ethyl-2propenthioamide, etc.

An example of a polyfunctional reactant in which a = b = c = 1 in the formula (2) is a compound of the following formula (XV): where w',
w2. x, y and T are as defined above, and X and Y are different. Preferred members of this class of reactants are compounds of formula (X Vl ) below.

where X and Y are as defined above, and X and Y
is different, and T' is: substituted or unsubstituted divalent C1-C2° (preferably 01-C+o)
Alkylene or alkenylene, such as -C2Hs-, -
(CH2)3-, -(CH2)4-CH=CH, C(C
H2)-CH2, etc., or C6-C2G (preferably 0
6-C14) divalent substituted or unsubstituted arylene, such as phenylene, naphthylene, bisphenylene, -
Phenyl-〇-phenyl-1 etc.

Examples of difunctional reactants of the formula XV+ are as follows.

H2C-Cl1-C(0) -CH-C(0)-0CH
31(2C-f;HC([1)-L;2H4-C(
0) -00H382G-[:H-C(0)-C2H4
-G (0) -0C2Hs1-1. C-CH-C(0
) -c3ha-c (o) -CILC-[;H-C
(0) -C2H4-C(0) -5H1(,C-C1
1-1: (0)-Cdl,. -G (0) -5CH3
H2C-C(G)+3) -C(0) -Cd4-C(
0) -0CH3HzC-C([:H3) -C(0)
-(:2H4-C(0) -〇C2H3H2C-(:
II-C(0)-C)I-C(0)-CH2+1.
C-CH-C(0)-C2H,l-C(0)-CHI
H2C-C8-C(0)-C2H4-C(01-G2H
5H((:H3) C-CI(-C(0) -CH2-
C(0) −0CI+.

1+ (CH3) C-ell-C(0) -C2)+
4-C(0) -0ClbH(CH3)C-CH-C(
0)-C2+14-C(0)-0C2H5H(CH3)
C-CH-C(0)-C31a-c(0)-C
IH(C21(s) C-(:)I-C(0) -C2
H4-C(0)-51(H(083)C-elf-
C(0) -C5H+ o-C(0) -5CH3(f
:H3) (C2Hs) C-C(CH3) -C(0
) -C2L-C(0) -0clhH(CIl3)
C-C(CH3) -C(0) -C2H4-C(0)
-0(:2H5H(CH3)C-CH-C((1)-
CI(2-C(0)-CH2O(CH3) C-C)
l-C(0)-C2H4-C(0)-CH311(C
H3) C-CH-C(0)-C2L-C(0)-CJs
Cl-C(0)-CIl2-C(0)-0CH3CI-
C(0)-Cd4-G (0)-QC)+3CI-C
(0)-C2H4-C(0)-00J5CI-C(0)
-CJa-C(0) -0ilC1-C(0)-C2
H4-C(0)-511CI-C(0)-C5H,. −
G (0) -5GH31 CI-C(0) -C2H4-C(0)-QC:H+C
I-C(0) -02114-C(0) -0C2HB
C1-C(0)-C)12-C(0)-CH2Cl
-C(0) -C2H4-C(0) -C)I! ICI
-C(0)-C2H4-C(0) -CJsCH30-
C(0) -CH2-C(0) -011CI+30-
C(0) -C2H4-C(0) -0HC)+30-
C(0) -C2L-C(0) -5HCJO-C(0
)-C3Ha-(:(0)-CIC2H=,0-C(0
)-C2H4-C(0-5t(CH30-C: (0
)-CsH+o-(: (0) -5CH3CH3S-
C(0) -CH2-C(0) -QC)13CH3-
C(0) -C112-C(0) -0HCH3-C(
0)-C2Ha-G (0)-01(CH3-C(Q
)-C2H4-C (Q-511) In the formula, a=b
Examples of reactants where =c=1 and X and Y together contain 10- or -S- are as follows: ■In the formula, a=b=1 and c> An example of a polyfunctional reactant that is 1 is a compound of formula (X) below: where W', W2. Y, T and "c" are as defined above, and X and Y are different. Examples of compounds of formula X are as follows: 82G-[:)l-[: (0) -C1h-[C(0
)-0CH3]2112cmCH-C(0)-0211
3~[C(0)-0C1+3] 282C-CIl-
G (0)-8RYL-[C(Q)-0fd13] 2
1(2cll:)I-C(0)-8RYL~[C(0)
-0GH+]2H2C-CH-C(0) -C2H3-
[C(0) -0Czlls] 2C2fkneeC)I-
C(0)-NAPTHYL-[C(0)-0CHa]2
C2C"CH-C(0)-NAPHTHYL-[C(0
)-0CH3]2LC”C)I-C(0)-C2+1
3- [C(0) -0C2)+51282C-CH-
C(0)-G, H5-[C(0)-C1]2+12cm
Cl1-C(0)-C2H3-[c(0)-5H
] 2) 12C-CH-C(0)-C5H9-[0(0
)-5CH3h112C-C(CH3)-C(0)-C
2H3-[C(0)-〇CH3121bc”f: (
CH3) -C(0) -C2+(3-[C(0) -
0CJsl 2ToC-CII-C(0) -CH2-
[C(0)-CH2F2o,c-co-c(0)-
C2H3-[C(0)-CH3]282C-CI-C(
0)-ARYL-[C(0)-CH3]2H(CHd
c-co-c (Q) -C)I-[C(0)~0CH
31211(C)h) C-CH-C(0) -CaH
13-[C(0)-0CH3]2+I (f:l+3)
C-Cl-1-C(0) -C2113-[C(0)
-002)Is] 2H(CH3)C-CH-C(0
)-C3H5-[C(0)-C1]2+1 ((:21
15) C-CH-C(0)-C2)13-[C(0
) -5)l] 2II (CH3) C1:H-C(
0)-CsHe-EC(0)-5C)Is12(CHs
) (II:2Hs) C-G (CH3) -C(0
)-C2H3-[0(01-0CH3] 2H(el+
3) CC(CI'+3) -C(0) -C2H3
-[C(0)-0C2H8]2H(CH3)C-CH-
C(0) H(CH3)C-CO-C(0) H(CHs) C-Cl-1-C(0)CI-1-[C
(0) -C1hl 2G2H3-[C(0)-CH3
]2 CJ3-[C(0)-C2)1s]2 CI-C(0)-CH-[C(0)-0CH3hC1-
C(0)-C2H3-[C(0)-0CH3]2Cue
(0) -C+3- [C(0) -0C2115]
2Cl-C(Q)-CaH5-[C(0)-0t+
] xCI-C(0)-C+3-[C(0)-5H]2
C1-C(0) -Csl19- [0(0)-5C1
+312CI-C(0)(:J3-[C(0)-0Cf
hhC1-C(0)-C2Hs-[C(0)-0C2t
15]2Cl-C(0)-CH-[C(0)-CHa
ltCI-C(0)-f:J3-[0(0)-C)Is
]2cl-11:(0)-C+3-[C(0)-CJs
]2C)130-C(0)-C)I-(C(0)-
011] 2CH30-C(0) -02H3-[C(
0) -OH] 2CH30-C(0) -C2H3-
[C(0)-5H] 2CH30-C(0)-[5H
s-[C(0)-CI]2CI50-C(0)-C2
H3-[C(0)-5R] 2C:H2O-C(0)
-CaH2-1G (0)-5CH+12CH+5-
C(0)-[:H-[C(0)-0CHshC113-
C(0)-0H-[C(0)-0H]2CTo-C(0
)-C2H3-[C(0)-01412C)13-C
(0) -C2H3-[C(0) -5)+12■ In the formula, an example of a polyfunctional reactant in which a=O and b=c=1 is a difunctional compound of the following formula (X+X). There is: where w', w2. x and Y are as defined above, and X and Y are different. XD [Examples of compounds of formula are: CxC-CH-C(0) -C(0) -0CI
2C-C) I-C(0) -C(0) -0CH3H2
C-C1l-C(0)-C(0)-0C21(51(2
CJ:)I-C(0)-C(0)-CI)12C-
C) I-C(0)-C((1)-5)182C-C
H-C(0) C(0)-5C)13H,C-C(C
H,) -G (0) -[: (0) -0CII.

H2C-C(C)13) -C(0) -C(0)-0
CzH5CzC-C41-C(0) -C(0) -C
H5C2C-CH-C(0)-C(0)-CHll(2
C-CH-C(0)-C(0)-C2H5H([:H3
) C-CI(-C(0) -C(0) -0C)13
H(CHs) C-CH-C(0) -C(0) -0
C1bH(C)+3) c-cH-c (0) -C(
0) -0C2)15H(CI-13) C-Cl1-
C(0) -C(0) -CIH(C21(5) C-
G)l-C(0)-G(0)-511H(CH3
) C-CH-C(0) -C(0)-5CH3(CI
(a) (C2)IS) C-C(CHs) -C(0
) -C(0) -0CHsH(CH3) c-c (
cH,)-c (0) -C(0) -oc2o5H(
CH3) C-CH-C(0) -C(0) -CH2
O(CIh) C-C3-C(0) -C(0) -C
H5II (CH3) C-C11-C(0) -C(
0) -C2+15cl-c(o)-c(o)-oco
.

CI-C (0) -G (0) -QC)+3CI-C
(0)-C(0)-0C2H5CI-C(0)-C(
0) -0H CI-C(0) -C(0) -5H CI-G (0) -C(0) -5C)+3CI-C
(0) -C(0) -0CI-13C1-C(0)-
f: (0) -0C2H5C1-C(0) -C(0)
-(:H3CI-C(0)-C:(0)-GH3 CI-C(0) -C(0) -02115CH30-
C(0) -[: (0) -01(C2H50-C(
0)-C(0)-OHGtl+OC(0)-C(0
) -5llCH30-C(0) -C(0) -CI
021150-C(0) -C(0) -5HC1+3
0-C(0)-C(0)-5GlhCH30-C(
0) -G (0) -00113GH3-C(0)
-C(0) -011Ctl+-C(0) -C(0)
-0ilH3 C(0) C(0) Sl+ Also useful as polyfunctional reactants in the present invention are compounds of formula (XX) below: where R1 and W+ are as defined above. and “dl” and “d2” are each an integer of 1 to 10; a compound of the following formula (XXI): where RI, R2 and R3 are the same or different, and hydrogen or substituted or unsubstituted hydrocarbyl as defined in , and Y'' contains a reactive functional group selected from the group consisting of:

9 Halide, -OR', SR', N (R')
(R5)z'c(o) ○R4 and -(R3) C=
C(R') (R2) (R4 is eH or substituted or unsubstituted hydrocarbyl as defined above)
: Compound of formula (XXIa) below 2 R3 R' -C=C-CN where Rl, R2 and R3 are the same or different and are hydrogen or substituted or unsubstituted as defined above. Substituted hydrocarbyl.

Examples of such compounds of formula XX are: C1hOC(0) CJ4Sfl:I2-ANHYCt
l+OC(0)CH2SCH2-8NHYCHsOC(
0) CI2SCH2-ANHYCH30C(0) [
: (CH3) 2sGH2-^NIIYCI+30C
(0)C1l (CH3)5CH2-8NHYC2)1
50G (0)C7lI45c)I2-8NHYC21
150G (0) CH25C) 12-ANIIYC2
11sOC(0)C3H65CH2-8N)IYC2H
BOC(0)C(CH3)25C1+2-ANIIYC
211sOC(0) (:lI (CH3) SCI+
2-8 NIIY Here, ANHY is the following component. Examples of compounds of formula XX1 are as follows: H2C-CI-5(0) 2-OCH3)12C-el
l-5(0) 2-OC1++82C-CH-5(0)
2-OCJsthe-OH-5(0) 2-CH 82C-OH-5(0) 2-Sl+ 82G-CH-5(0) 2-5CH3) 12C-C(
C)13)-5(0) 2-OC8382CI-C(C
I(3)-S (0) 2-00205112cmC1
l-5(0) 2-OCH(CH3) 2H(CI+3
) C-C11-3(0) 2-QC)I3H(OH3
) C-f:H-5(0) 2-OCRlH(C113
) C-CH-5(0) 2-LC)ls+I(CHI
)C-CI-5(0)2-CIH(CJs) C-C1
4-5(0) 2-51(H(Clla) c-cH-
s (0) 2-5CH3(elf3) (G211s
) C-C(CH3) -5(0) 2-OGH3H(
CI+3) CC(el+3) -S (0) 2-
o2co5 Examples of such compounds of formula XXIa are 82C-CH-CN H2fneyC(el+3)-ON H(C)131 C-CH-CN H(C2)15) C-CH-CN H(CI+,) CC(C)I,) -CN(CH3
) (CJs) C-C(CH3)-CN Preferred compounds to be reacted with the first nitrogen-containing compound according to the present invention are acrylic acid and lower alkyl alpha-substituted lower alkyl esters of acrylic acid. Specific examples of such preferred compounds are compounds of the formula: where R3 is hydrogen or a C1-C4 alkyl group, such as methyl, and R4 is hydrogen or a C3-C4 alkyl group, and is removed. Ado groups can be formed, such as methyl, ethyl, propyl, isopropyl, butyl,
5ec-butyl, tart-butyl, aryl, hexyl, etc., propyl acrylate and propyl methacrylate. In the most preferred embodiments, these compounds are acrylic and methacrylic esters, such as methyl or ethyl acrylate, methyl or ethyl methacrylate.

The polyfunctional reactants useful in the present invention are known materials and can be prepared by conventional methods known to those skilled in the art, and there is no need to describe such conventional methods herein. do not have.

Preparation of the First Adduct A selected first nitrogen-containing compound and a polyfunctional reactant are combined in a first adduct.
In the reaction mixture, the latter X functional group is contacted with at least a portion, preferably substantially all, of the reactive nitrogen moiety in the first nitrogen-containing compound in an amount and under conditions sufficient to cause the reaction.

When preparing the first adduct, the moles of polyfunctional reactant used are divided into equivalents of the reactive nitrogen moiety in the first nitrogen-containing compound (
That is, nitrogen-bonded H in the first nitrogen-containing compound
preferably at least equal to the sum of the atoms). Preferably, the polyfunctional reactant is used in a molar excess of about at least 10%, such as from 10 to 300% or more, such as from 25 to 2'00%. A -layer excess can be used if desired. For example, in the present invention, NH3 is considered to have three reactive nitrogen components per molecule, and preferably at least 3 (e.g., 33 to 10) moles of polyfunctional reactant are used per mole of NH3 in the first reaction mixture. A first adduct having an average of three N-bonded moieties derived from the functional reactants, each containing the following (xxm) groups: 4 where W', W2 . Y, T, ra'', rl)'' and ``c'' are as previously defined.

The first adduct preferably contains on average at least 3 groups of the formula xXlI1, more preferably 3 to 20 Tsumego, and most preferably 3 to 8 Tsumego.

The polyfunctional reactant and the first nitrogen compound undergo a pentafunctional reaction during the introduction of the first nitrogen compound with mixing into the liquid reaction mixture containing the polyfunctional reactant and charging the first nitrogen compound. It is preferable to mix by overfeeding the body.

The temperature and pressure conditions used to contact the first nitrogen-containing compound and the multifunctional reactant can vary widely, but are preferably about -10' to 40'C (preferably about 10
6 to 20°C). IR of reaction progress
The disappearance of the -N-H- bond can be observed by following the equation. - Although lower temperatures can be used -
may require long reaction times. Elevated temperatures can also be used, but tend to increase the amount of less reactive Y functional groups. The Y functional group reacts with the reactive nitrogen moiety of the first nitrogen-containing compound, thereby reducing the desired selectivity for reacting with the -layer-reactive X functional group.

The reaction times involved can vary widely depending on a wide variety of factors. For example, there is a relationship between time and temperature. Generally, the lower the temperature, the longer the time required. The reaction time is usually about 2 to 30 hours, for example 5 to 25 hours, preferably 3 to 10 hours.

Although a solvent can be used, the reaction can be carried out without any solvent. It is preferable to avoid using aqueous solvents such as water, but considering the effect of the solvent on the reaction, solvents, whether organic or inorganic, polar or non-polar, can be used if desired. Any suitable solvent can be used. Suitable solvents include: alkanols (e.g. C1-C6 alkanols such as methanol, isopropanol, ethanol, etc.), ethers, xylene, benzene, toluene, tetrahydrofuran, methylene chloride, chloroform, chloroheamine,
etc.

The resulting first adduct product mixture is then optionally treated to remove volatile reaction by-products, such as by stripping or sparking (e.g., with nitrogen gas) (e.g., from about 20' to about 100°C) under reduced pressure. It is preferred to remove the product and unreacted polyfunctional reactants to minimize reaction with the first nitrogen-containing compound in the second step of the process of the invention. Therefore, the second adduct is generated. r! i. The reaction mixture is preferably substantially free of unreacted polyfunctional reactants, e.g., contains less than about 1% by weight of unreacted polyfunctional reactants, and contains about 0.1% by weight of unreacted polyfunctional reactants. More preferably, it is less than % by weight.

The reaction between the polyfunctional reactant of the formula ■ and the first nitrogen-containing compound can be exemplified as follows. Selective reaction with the mono-tertylenically unsaturated compounds leads to the addition of reactive nitrogen equivalents via the double bonds of these polyfunctional reactants.

The average degree of branching in the first adduct increases as the number of reactive nitrogen moieties in the first nitrogen-containing compound increases.

The average degree of branching of the first adduct ('DBIJ) can be calculated by the following formula: DBI = [3(n,)+2 (np)+
(ni) Ko × Nicode, "nl" is 1 when ammonia is used as the first nitrogen-containing compound, and O when ammonia is not used, 'np J and "
"n6" is the number of primary and secondary amine groups, respectively, in the organic amine group when an organic amine is used as the first nitrogen-containing compound; "C" is an integer of at least 1 (and (r- 1), where “r” is the above ■
is the number of functional groups in each molecule of the polyfunctional reactant reactive with the -NH- group as defined in the formula). The DBI in the first attachment body is at least 2 (e.g. 2-3
0), preferably at least 3 (e.g. 3 to 20), -
The number of layers is preferably 3 to 15. If the first nitrogen-containing compound comprises a mixture of ammonia and an organic amine, the average degree of branching is the weighted average of each of the factors in the above formula for each of the nitrogen-containing compounds participating in the first adduct. You can ask by giving.

For example, ammonia gives a 3-branched first adduct (DB=3) and diethylenetriamine gives a 5-branched first adduct (DB.

=5) where...Y represents a difunctional reactant bonded to a reactive nitrogen moiety. If trifunctional reactants are used, the degree of branching is increased even further.

for example, Ammonia preferably has the following structure (DB).

6) yields the first adduct of: \ Diethylenetriamine has the following structure (DB.

10) yields the first adduct of Represents a functional reactant.

Second Nitrogen-Containing Compound The second nitrogen-containing compound has a reactive nitrogen component, i.e. a total of H atoms bonded to nitrogen, of at least 2 (e.g. from 2 to 20, preferably at least 3) per molecule of the second nitrogen-containing compound. For example, it contains at least one polyamine containing 3 to 15), most preferably 3 to 10.

The second nitrogen-containing compound contains at least one primary amine group (preferably at least 2 (e.g. 2-6, preferably 2-4) primary amine groups) or at least 2 primary amine groups per molecule. at least one member selected from the group consisting of organic secondary and secondary polyamines containing secondary amine groups;
It is normal to include fffl. The organic polyamine has a total carbon atom concentration in the molecule of 2 to 60, preferably 2 to 40 (e.g., 3 to 20) and a total nitrogen atom concentration of 2 to 12, preferably 3 to 12, most preferably 3 to 8 (e.g. 5 to 9). These amines can be hydrocarbyl amines or can be hydrocarbyl amines containing other groups, such as hydroxy groups, alkoxy groups, ado groups, nitriles, imidacillin groups, and the like. Hydroxyamines having 1 to 6, preferably 1 to 3 hydroxy groups are particularly useful. Preferred amines are aliphatic saturated amines, including those of the following general formula: (XXIV) where R, R', R# and R'' are independently selected from the group consisting of: hydrogen; C26 straight chain or branched button alkyl radical, C8~CI2 alkoxyC2~C
6 alkylene radical; C2-C1° hydroxyamino alkylene radical; and C1-CI2 alkylamino C2-C6 alkylene radical. ; S and S' can be the same or different and are a number from 2 to 6, preferably 2 to 4; and t' can be the same or different, and 0 10, preferably 2 to 7, most preferably about 3 to 7, with the proviso that the sum of t and t' is 15 or less. To ensure easy reaction, R,
R'R'', R''', s, s', and t')lf
It is preferred that the compound of formula fV be selected in a manner sufficient to provide typically at least two primary or secondary amino groups, preferably a total of 2 to 8 primary and secondary amino groups. This can be done by choosing at least one of the R, R', R'' or R- groups to be hydrogen, or if R°°'' is H, or if the XXV component has a secondary amino group. If it has, it can be distantly related by making t in x'M at least 1.

Examples of suitable organic amine compounds include, but are not limited to, 1,2-cyanoethane; 13-diaminopropane; 1,4-diaminobutane; 1,6-diamithexane; polyethylene amines such as diethylenetriamine. , triethylenetetramine; tetraethylenepentamine; boline pyreneamine, such as 1,2-propylenediamine; di(1,2-propylene)triamine; di(1,3-propylene)triamine, N,N-dimethyl-1, 3-cyanopropane, N, N-di(2-
achnoethyl)ethylenediamine; N,N-di(2-
hydroxyethyl)-1,3-propylenediamine 3
-dodecyloxyprobylamine/N-dodecyl-1,
3-propanediamine; trishydroxymethylaminomethane (THAM); diisopropanolamine, jetanolamine, triethanolamine, mono-, di- and tritaloamine; acinomorpholine, e.g.
-(3-aminopropyl)morpholine; and mixtures thereof.

Other useful akun compounds include those discussed above with respect to the first nitrogen-containing adducts in Formulas IV to IV.

Commercial mixtures of amine compounds can be advantageously used. For example, one method for producing alkylene amines is to react an alkylene civalide (e.g., ethylene dichloride or propylene dichloride) with ammonia, and the pair of nitrogens are linked by an alkylene group to form diethylene trichloride,
triethylenetetramine, tetraethylenepentamine,
It involves producing complex mixtures of alkylene amines forming compounds such as isomeric piperazines.

An inexpensive poly(ethyleneamine) compound with an average of about 5 to 7 nitrogen atoms per molecule is available under the trade name PolyamineH.
”, r Polyamine 400 J, r Dow
Polyamine E-1004, etc. are commercially available.

The second nitrogen-containing compound is produced by reacting a polyamine with an alpha, heterethylenically unsaturated compound (e.g. ), polyoxyethylene and polyoxypropylene amines, such as polyoxyethylene diyone, trismethylolactumethane, pentaerythritol and combinations thereof, and the acrylate type compound of formula (X) above, most preferably lower reacting with an acrylate-type reactant selected from the group consisting of alkyl alkyl acrylates (e.g., methyl, ethyl, isopropyl, propyl, isobutyl, n-butyl, t-butyl, etc. esters of methacrylic acid, acrylic acid, etc.). The resulting amide-amine may be included.

An example of such an amido-amine is a compound of the formula: NH2[(CH2)-NH]xC(0)C2H4
[NH(CH2) 1xNH2 where X is an integer from 1 to 10, and Z is an integer from 2 to 6.

Most preferred as the second nitrogen-containing compound are organic diprimary compounds having 2 to 30 carbon atoms, 2 to 12 total nitrogen atoms, and 0 to 10 secondary nitrogen atoms per molecule.
ary) is a member selected from the group consisting of amines. Examples of such preferred organic dibrary amines are: ethylenediamine, propylene diamine, diethylene triamine, dipropylene triamine, triethylenetetraamine, tripropylenetetraamine, tetraethylenepentamine, tetrapropylenepentamine, polyaminocyclohexyl. methane, etc.

Preparation of the second adduct An average of at least 2 (e.g. 2-10), preferably at least 3 (e.g. 3-8) unreacted functional Y groups per molecule
The first adduct and the second nitrogen-containing compound are brought into contact with each other in an amount and under conditions that cause the residual functional group to react with the reactive nitrogen component of the second nitrogen-containing compound, so that on average (
+) at least 2 nitrogen-containing components derived from a second nitrogen-containing compound per nitrogen-containing component derived from a first compound;
(e.g. 2-30), preferably at least 3 (e.g. 3-20) and (i+) at least 2 (e.g. 2-6, preferably 2-4) unreacted primary or secondary amine groups. A second adduct characterized by:

The reaction between Boriakun and the third adduct can be exemplified as follows. CJJH)<CJ
4NH21g+C) 1.011 The reaction between the selected polyyone and the secondary adduct is carried out at any suitable temperature. Temperatures up to the point of decomposition of the reactants and products can be used. In reality, the reactants were heated to 100°C.
The reaction is usually carried out by heating at a lower temperature, e.g. 80 DEG -90 DEG C., for a suitable period of time, e.g. several hours. When using an acrylic type ester to form the first adduct, the progress of the reaction can be judged by the removal of alcohol in producing the amide. During the initial part of the reaction, the alcohol is very easily removed at temperatures below 100° C. in the case of low boiling alcohols such as methanol or ethanol.

As the reaction slows, the temperature may be increased to complete the polymerization, and the temperature may be raised to iso 0 C towards the end of the reaction. Removal of alcohol is a convenient way to determine the progress and completion of a reaction, and the reaction is usually continued until no more alcohol is produced. Yields are usually stoichiometric based on alcohol removal. - In difficult reactions, yields of at least 95% are usually obtained.

Similarly, when forming a second adduct, the reaction of a polyamine with a second adduct made using an ethylenically unsaturated carboxylate thioester of formula The reaction of the polyamine with the first adduct made using the ethylenically unsaturated carboxamide of formula
It will be understood that when each is hydrogen, ammonia) is liberated as a by-product.

The reaction times involved can vary widely depending on a wide variety of factors. For example, there is a relationship between time and temperature. Lower temperatures (eg, at about 25° C.) typically require longer times.

The reaction time is usually about 2 to 30 hours, for example 5 to 25 hours, preferably 3 to 10 hours.

Although a solvent can be used, the reaction can be carried out without any solvent. Preferably, polar solvents such as water are avoided. However, any suitable solvent, whether organic or inorganic, polar or non-polar, may be used if desired, taking into account the effect of the solvent on the reaction. can. Suitable solvents include: alkanols (e.g. C,-C6 alkanols such as methanol, isopropanol, ethanol,
etc.), ether, xylene, benzene, toluene, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, etc.

If the selected polyfunctional reactant comprises an alpha, beta unsaturated compound of the formula (wherein Wl is oxygen), then the first adduct reaction product formed and such material is referred to herein as an "amide-amine." Similarly, ■
When the selected alpha, beta unsaturated compounds of the formula include compounds where W is sulfur, they contain compounds formed with polyamines and these materials are referred to herein as "thioa-do-a-yo-yo". For convenience, the following discussion is directed to the preparation and use of acyl-do-amines, but it will be understood that such discussion may also apply to thio-amido-amines.

These amidoamine adducts so produced are characterized by both amide and amino groups. Such adducts can, in the simplest embodiment, be represented by units of the following idealized formula: where R may be the same or different and represent hydrogen or a substituted group, e.g. groups, such as alkyl, alkenyl, alkynyl, aryl, etc., where A is a component of the polyamine and can be, for example, aryl, cycloalkyl, alkyl, etc., and n is from 1 to 10 or more, etc. is an integer. It is preferable that each molecule of the amide-amine adduct and the amide-amine adduct contains 1 to 3 amide groups on average.

However, it is preferred that the amide-amines of the present invention are not crosslinked to any substantial degree, and more preferably substantially branched.

If desired, steps (a) and (b) in the method of the invention
) can be repeated to produce more highly branched adducts. For example, the "first nitrogen-containing compound" can be passed through repeated steps (a) and therein preferably Second
The more highly branched "first" adduct is contacted in molar excess relative to the reactive nitrogen component in the adduct (i.e., the total number of N--H- bonds remaining unreacted in the second adduct). the body, which is then processed to remove excess unreacted polyfunctional reactant and contacted in a separate step with an additional second nitrogen-containing compound, such as a polyalkyleneboryank, as described above. be able to. Such highly branched nitrogen-containing adducts exhibit properties as described above for secondary adducts, i.e., on average, there are at least two unreacted or Diamine group and step (a
), and in the following reaction: It can be used with selected reactants A-D to form the dispersants of the present invention.

(8) The dispersible material of the present invention containing a long hydrocarbyl compound can be prepared by reacting the second adduct with a hydrocarbyl-substituted acid, anhydride, or ester material, as described above. The long chain hydrocarbyl polymer substituted mono- or dicarboxylic acid material, i.e., acid, anhydride or ester, used in the present invention is a long chain hydrocarbon polymer, usually a polyolefin, and at least one member selected from the group consisting of: (i)
Monounsaturated 04-CIO dicarboxylic acids (preferably,
(a) the carboxyl group is vicinyl (i.e., located on adjacent carbon atoms); and (b) at least one, preferably both, of the adjacent carbon atoms are the monounsaturated moieties. There is); (if) (+)
derivatives such as (i) anhydrides or C,-C, alcohol-derived mono- or di-esters; (iii) carbon-
A carbon double bond is attached to a carboxy group, i.e. the following structure: -C=C-C- monounsaturated 03-C1 monocarboxylic acid; and (i
v) Derivatives of (iN), such as (iii) 01-
The monounsaturation of the C5 alcohol-derived monoester, the monounsaturated carboxylic reactant, reacts with the polymer and becomes saturated. Thus, for example, maleic anhydride becomes polymer-substituted succinic anhydride, and acrylic acid becomes polymer-substituted propionic acid.

Typically from about 0.7 to about 4.0 (e.g., from 0.8 to 2.6 moles), preferably from about 1.0 to about 2.0
, most preferably from about 1.1 to about 1.7 molar to the reactor.

All of the polymers do not react with the monounsaturated carboxylic reactant, and the reaction mixture typically contains non-acid substituted polymers. Polymer-substituted mono- or dicarboxylic acid materials (herein referred to as "functionalized")
cationalized) J polymers or polyolefins), non-acid substituted polyolefins and all other polymer by-products, such as chlorinated polyolefins (herein referred to as "unfunctionalized"
yzed) J polymers) are referred to herein - collectively as the "product residue" or "product mixture." Typically, the non-acid substituted polymer is not removed from the reaction mixture (such removal is difficult and commercially impractical) and the monounsaturated carboxylic reactant is stripped of the product mixture. The dispersant is then further reacted with an alcohol or an alcohol as described hereinafter to form a dispersant.

Functionality is defined herein as a characterization of the average number of moles of monounsaturated carboxylic reactant reacted per mole of polymer (reacted or unreacted) charged to the reaction. . The functionality was determined using techniques well known in the art: (i) measuring the saponification number of the product mixture produced using potassium hydroxide; and (ii) determining the number average molecular weight of the charged polymer. based on. Functionality is simply defined for the product isotherm formed. The amount of the reacted polymer contained in the resulting product mixture can subsequently be modified, i.e., the build-up can be reduced, by techniques well known at the time, but such modifications are not limited to the methods specified above. It does not change the functionality as it is. As used herein, the terms "polymer-substituted monocarboxylic acid material" and "polymer-substituted dicarboxylic acid material" are intended to refer to product mixtures, whether or not they have undergone such modifications. It is.

Accordingly, the functionality of the polymer-substituted mono- and dicarboxylic acid materials will typically be at least about 0.5, preferably at least about 0.8, most preferably at least about 0.9, and typically It will range from about 0.5 to about 2.8 (e.g. 0.6 to 2), preferably from about 0.8 to about 1.4, most preferably from about 0.9 to about 1.3.

Examples of such monounsaturated carboxylic reactants are fumaric acid, itaconic acid, maleic acid,
Maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, lower alkyl as mentioned above (e.g. 01-C4 alkyl)
Acid esters such as methyl maleate, ethyl fumarate, methyl fumarate, etc.

Preferred olefin polymers for reacting with monounsaturated carboxylic reactants to form reactant A are C2
-C3°, e.g. C2-C5 monoolefins, in major molar amounts. Such olefins include ethylene, propylene, butylene, isobutylene, pentene,
Contains octene-1, styrene, etc. The polymers can be homopolymers such as polyisobutylene, as well as copolymers of two or more of such olefins, such as ethylene and propylene; butylene and isobutylene; propylene and imbutylene; and the like. An example and preferred olefin polymer is a mixture of polymers made by polymerizing a mixture of isobutylene, butene-1 and butene-2, e.g.
Up to 1% is polyisobutylene derived from 1-butene and 2-butene. Other copolymers include those in which small molar amounts of copolymer monomers, e.g. 1-10 mole %, are 04-CI8 non-conjugated diolefins, e.g. copolymers of isobutylene and butadiene; or copolymers of ethylene, propylene and
．． 4-hexadiene copolymers, etc.

There are some cases in which it is advantageous to fully saturate the olefin polymer, such as an ethylene-propylene copolymer made by Ziegler-Natsuta synthesis using hydrogen as a modifier to control the molecular weight.

The olefin polymer used to form Reactant A has a number average molecular weight of about 300 to about to, ooo.

Usually about 700 to about 5,000, preferably about i,ooo
to about 4,000, -layer preferably about 1.300 to about 3,
It has a range of 000. Particularly useful olefin polymers have number average molecular weights ranging from 1500 to about 3,000 and have approximately one terminal double bond per polymer chain.

A particularly useful starting material for the high potency dispersing additives useful in accordance with the present invention is polyisobutylene in which up to about 40% of the monomer units are derived from butene-1 and/or butene-2. Number average molecular weight for such polymers can be determined by several known techniques. A convenient method for such measurements is by gel permeation chromatography (GPC), which also provides molecular weight distribution information. W, W, Yau
), J. Kirkland and D. Bly, Modern Size Exclusion Liquid Chromatography, Schon Willey and Sons, New York, 1979.

Olefin polymers have a molecular weight distribution (ratio of weight average molecular weight to number average molecular weight, i.e. M w / M n
) about 1.0 to 4.5, typically about 1.5 to 3.
It is normal to have 0.

The polymer and monounsaturated carboxylic reactant can be reacted by various methods. For example, chlorine or bromine may be added to a polymer at a temperature of 60' to 250°C, preferably 110 to 160°C, e.g.
Over a period of 5 to 10 hours, preferably 1 to 7 hours, the polymer is first halogenated, chlorinated or brominated to about 1 to 8% by weight of chlorine or bromine, preferably 3 to 8% by weight, based on the weight of the polymer. 7% by weight. The halogenated polymer is then heated with sufficient monounsaturated carboxylic reactant at 100-250°C, usually about 180''-235°C.
and react for about 0.5 to 10 hours, for example 3 to 8 hours,
The resulting product contains the desired number of moles of monounsaturated carboxylic reactant per mole of halogenated polymer. This general type of process is described in U.S. Pat.
No. 087.436: No. 3,172,892, No. 3.2
No. 72.746, et al. Alternatively, the polymer and monounsaturated carboxylic reactant are mixed and heated while chlorine is added to the heated material. This type of process is described in U.S. Pat. No. 3,215,707:
No. 231,587; No. 3,912,764: No. 4.1
No. 10,349; No. 4,234.435 and British Patent No. 1,440.219.

Alternatively, the polymer and monounsaturated carboxylic reactant are contacted at elevated temperatures to cause a thermal "ene" reaction. Thermal "ene" reaction was previously described in U.S. Patent No. 3,361,67.
No. 3 and No. 3,401,118, the entire disclosures of these US patents are incorporated herein by reference.

Preferably, the polymers used in the present invention contain less than 5% by weight of the polymer fraction containing polymer molecules having a molecular weight of less than about 300, as determined by high temperature gel permeation chromatography using a corresponding polymer calibration curve. , -layer preferably contains less than 2% by weight, most preferably less than 1% by weight. It has been found that such preferred polymers allow reaction products to be prepared with reduced sedimentation, especially when maleic anhydride is used as the unsaturated acid reactant. If the polymer prepared as described above contains more than about 5% by weight of such low molecular weight polymer fraction, the polymer is preferably combined with the selected unsaturated carboxylic reactant before initiating the ene reaction. Prior to contacting, the polymer may first be treated by conventional means to remove low molecular weight fractions to the desired level. For example, the polymer can be heated at elevated temperature under reduced pressure, preferably with an inert gas (eg, nitrogen) strip, to volatilize the low molecular weight polymer components, which can then be removed from the heat treatment vessel. The exact temperature, pressure and time for this heat treatment depends on the polymer number average molecular weight,
It can vary widely depending on factors such as the amount of low molecular weight fraction removed, the particular monomers used, and other factors. Temperature about 60'~100℃, pressure 0.1~
0.9 atm, time approximately 0.5 to 20 hours (for example, 2 to 8
time) is usually sufficient.

In this method, a selected polymer, a monounsaturated carboxylic reactant, and, if used, a halogen (e.g., chlorine gas) are combined under conditions effective to produce the desired polymer-substituted mono- or dicarboxylic acid material. and contact it for an appropriate amount of time. Typically, the polymer and monounsaturated carboxylic reactant are combined in a molar ratio of unsaturated carboxylic reactant to polymer, usually about 0.7:1 to 41, preferably about 1.
・1-2:1, high temperature, usually about 120"-260℃
, preferably at about 160' to 240°C. The molar ratio of halogen to monounsaturated carboxylic reactant charged also varies, typically about 0.5:1 to 4.1;
- layer typically about 0.7:1 to 2:1 (e.g. about 0,
9 to 1.4:1). The reaction is usually carried out with stirring for about 1 to 20 hours, preferably about 2 to 6 hours.

By using a halogen, it is common for about 65 to 95 weight percent of the polyolefin, such as polyisobutylene, to be reacted with the monounsaturated carboxylic acid reactant. When carrying out thermal reactions without the use of halogens or catalysts, it is common for only about 50 to 75 weight percent of the polyisobutylene to react. Chlorination helps increase reactivity.

For convenience, the functionality ratio of mono- or dicarphonic acid-forming units to the polyolefins described above, e.g. 1.1 to 1.8.
, etc. are based on the total amount of polyolefins used to make the product, ie, the sum of both reacted and unreacted polyolefins.

The reaction is preferably carried out in the substantial absence of 02 and water (to avoid competing side reactions) and is therefore carried out in an atmosphere of dry N2 gas or other gas that is inert under the reaction conditions. can be done. The reactants can be charged to the reaction zone separately or together as a mixture, and the reaction can be carried out continuously, semi-continuously or batchwise. Although not usually necessary, the reaction may be carried out using a liquid diluent or solvent.
For example, it can be carried out in the presence of a hydrocarbon diluent such as mineral lubricating oil, toluene, xylene, dichlorobenzene, and the like. The polymer-substituted mono- or dicarphonic acid material thus formed is removed from the liquid reaction mixture, for example by stripping the reaction mixture with an inert gas such as N2 to remove unreacted unsaturated carboxylic acid. After the reactants have been removed, they can be recovered.

If desired, a catalyst or promoter for reacting the olefin polymer and the monounsaturated carboxylic reactant (whether the olefin polymer and the monounsaturated carboxylic reactant are contacted in the presence of a halogen (e.g., chlorine) or (contacting in the absence of halogen) can be used in the reaction zone. Such catalyst zones include promoters containing Ti, Zr, V, and An alkoxides and nickel salts (e.g., Ni acetoacetonate, Ni iodide), and such catalysts or promoters have a weight relative to the weight of the reaction medium. Approximately 1~
5. It is usually used in an amount of OOOppm.

(B) Also useful as long chain hydrocarbyl reactants in forming the improved dispersants of this invention are halogenated long chain aliphatic hydrocarbons (U.S. Pat. Nos. 3,275,554 and 3,565,804). (the entire disclosures of these US patents are incorporated herein by reference), and the halogen group attached to the halogenated hydrocarbon is replaced by a second adduct in a subsequent reaction.

(C) Another class of long chain hydrocarbyl reactants for producing the improved dispersants of this invention are long chain hydrocarbyl substituted hydroxyl reactants known at the time to be useful in producing Mannich condensation products. Any aromatic compound.

Such Mannich condensation products include about 1 mole of a high molecular weight hydrocarbyl-substituted hydroxyaromatic compound (e.g., having a number average molecular weight of 700 or greater) and about 1 to 2 moles of an aldehyde, such as formaldehyde or paraformaldehyde. 5 mol and about 0.5 to 2 mol of the second adduct, for example, in U.S. Pat.
No. 49,229 and No. 3,798,165, the entire disclosures of which are hereby incorporated by reference. .

Such Mannich condensation products can include long chain high molecular weight hydrocarbons attached to the phenolic group, or hydrocarbons such as those shown in the above-mentioned U.S. Pat. No. 3,442,808, e.g. It may also be reacted with a compound containing alkenylsuccinic anhydride.

Optionally substituted hydroxyaromatic compounds used to prepare Mannich base products include those compounds having the formula: R21AI--(OH)z where Ar represents: where q is 1 or 2, and R'' is 1 to about 3 carbon atoms.
or a substituted hydrocarbon radical or a halogen radical, such as a bromide or chloride radical, X is an integer from O to 2; R21 is a long-chain hydrocarbon; y is from 1 to 2. is an integer: Z is 1 to 2
is an integer.

Examples of such Ar groups are phenylene, biphenylene, naphthylene, and the like.

The long chain hydrocarbon R'' substituents are olefin polymers as described above for those olefin polymers useful in forming the reactants.

Representative hydrocarbyl-substituted hydroxyaromatic compounds contemplated for use in the present invention include, but are not limited to: 2-polypropylenephenol, 3-
Polypropylene phenol, 4-polypropylene phenol, 2-polybutylene phenol, 3-polyisobutylene phenol, 4-polyisobutylene phenol, 4
-Polyisobutylene-2-chlorophenol, 4-polyisobutylene-2-methylphenol, etc.

Suitable hydrocarbyl-substituted polyhydroxyaromatic compounds include: polyolefin catechols, polyolefin resorcinols, polyolefin hydroquinones, such as 4-polyisobutylene-1,2-dihydroxybenzene, 3-polypropylene-1,2-dihydroxybenzene, 5-polyisobutylene-13-dihydroxybenzene, 4-boriadine-13-dihydroxybenzene, etc.

Suitable hydrocarbyl-substituted naphthols include 1-polyisobutylene-5-hydroxynaphthalene, 1-polypropylene-3-hydroxynaphthalene, and the like.

(D) Yet another class of long chain hydrocarbyl reactants for producing the improved dispersants of this invention are Mannich base aminophenol type condensation products as known in the art. Such Mannich condensation products contain about 1 mole of long-chain hydrocarbon-substituted mono- and dicarboxylic acids or their anhydrides (e.g., polyisobutylene-substituted succinic anhydride) and an amine-substituted hydroxy aromatic acid. long-chain hydrocarbon-substituted amide- or dihydro-containing compounds by reacting with about 1 mole of a long-chain hydrocarbon-substituted amide- or dihydrocarbyl-based compound (e.g., an amine phenol) (the aromatic compound can also be halogen- or hydrocarbyl-substituted). About 1 molar proportion of a phenol intermediate (usually having a number average molecular weight of 700 or more) containing an ado- or imide substituted with a long chain hydrocarbon and about 1 to 2 formaldehyde; .5 mol and about 0.5 mol of the second adduct of the invention.
It is usually made by condensing 5 to 2 moles.

Suitable aminophenols are 2-ayonophenol, 3-
Contains aminophenol, 4-acunophenol, 4-amino-3-methylphenol, 4-amino-3-chlorophenol, 4-amino-2-bromophenol, and 4-amino-3-ethylphenol.

Methods of making and uses of hydroxyaromatic compounds and acuno-substituted hydroxyaromatic compounds, and methods useful for reacting them with aldehydes and selected second adducts of the invention, are described in U.S. Pat. No. 432 and No. 4
, 828.742, the entire disclosures of these US patents are incorporated herein by reference.

Preparation of the dispersant (A) An oil solution containing 5 to 95% by weight of the polymer-substituted dicarboxylic acid material is heated to about 100° to 250°C, preferably 125° to 175°C, for usually 1 to 10 hours, e.g.
By heating for ~6 hours to remove the desired amount of water, the second adduct (e.g., a branched amide-amine oligomer) is converted to a selected polymer-substituted mono- or dicarboxylic acid material, e.g., an alkenyl succinate. Easily reacts with acid anhydrides. Preferably, heating is applied to favor the formation of imides and/or amides rather than salts. Per reactive nitrogen equivalent of the second adduct (preferably per equivalent of first nitrogen), the mono- or dicarboxylic acid component content (e.g. grafted maleic anhydride or grafted acrylic acid content) is from 1 to
It is common to use 5 moles, preferably about 15 to 3 moles.

An example of a reaction between a second adduct and a polymer-substituted dicarboxylic acid producing reactant is a reaction between polyisobutylene (PIB) substituted succinic anhydride (PIBSA) and a second adduct having three terminal -NH2 groups. It is a reaction with
4NH) XC (0nC2)+4 (NIIGJ4)
x (x is an integer from 0 to 10, preferably from 2 to 6).

An example of the reaction of the second adduct with a polymer-substituted monocarboxylic acid producing reactant is polyisobutylene propionic acid (
PIBA) with a second adduct having three terminal -NH2 groups, which can be exemplified as follows: where rLink'' and X are as previously defined.

It will be appreciated that the second adduct may be used alone or in admixture with any of the above-mentioned amines useful in preparing the second adduct, such as polyalkylene polyamines.

Preferably, the polymer-substituted mono- or dicarboxylic acid generating material and the amidoan are contacted for a period of time under conditions such that substantially all of the first nitrogen in the second adduct reactant is reacted. The progress of this reaction can be followed by infrared analysis.

The dispersant generation reaction can be carried out in a polar or non-polar solvent (e.g. xylene, toluene, Hensen, etc.),
Preferably, it is carried out in the presence of mineral oil or synthetic lubricating oil.

The nitrogen-containing dispersant material of the present invention as described above can be post-treated by contacting the nitrogen-containing dispersant material with one or more post-treatment agents selected from the group consisting of: Carbon sulfide, sulfur, sulfur chloride, alkenyl cyanide, aldehyde, ketone, urea, thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphate, hydrocarbyl phosphite, hydrocarbyl thiophosphate, hydrocarbyl thiophosphite, phosphorus sulfide,
Phosphorus oxide, phosphoric acid, hydrocarbyl thiocyanate, hydrocarbyl isocyanate, hydrocarbyl isothiocyanate, epoxide, episulfide, formaldehyde or formaldehyde-generating compound + phenol,
Sulfur + phenol, 01-C30 hydrocarbyl substituted succinic acid and anhydride (e.g. succinic anhydride, dodecylsuccinic anhydride, etc.), fumaric acid, itaconic acid,
Maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, lower alkyls of the above (e.g. C1-
C4 alkyl) acid esters, such as methyl maleate,
Ethyl fumarate, methyl fumarate, etc.

Since post-treatment processes involving the use of these post-treatment reagents are known as applied to high molecular weight nitrogen-containing dispersants of the prior art, these processes will not be further described herein. There is no need to do so. In order to apply the prior art process to the compositions of the present invention, all that is required is to apply the reaction conditions, ratios of reactants, etc. as described in the prior art to the novel compositions of the present invention. It is to be. The following U.S. patents are incorporated herein by reference for their disclosure of post-treatment processes and post-treatment reagents that may be applied to the compositions of the present invention: U.S. Pat. No. 3,087,936;
No. 3,200,107: No. 3,254,025; No. 3,25 [i, No. 185, No. 3,278,550; No. 3,281,428, No. 3,282,955: Same 3
, No. 284,410; No. 3,338,832; No. 3,
No. 344,069: No. 3.366.569; No. 3,3
No. 73,111: No. 3,367.943; No. 3,40
No. 3,102: No. 3,428,561; No. 3.502
, No. 677; 3,513,093. Number: 3,533
, No. 945; No. 3,541,012; No. 3,639,
No. 242; No. 3,708,522: No. 3,859,3
No. 18; No. 3,865,813, No. 3,470,09
No. 8; No. 3.369.021; No. 3.184,411
No. 3,185,645; No. 3,245,908; No. 3,245,909; No. 3,245,910;
No. 3,573,205; No. 3,1i92,681;
No. 3,749,695; No. 3,865,740; No. 3.954.639; No. 3.458.530, No. 3
, No. 390,086: No. 3.367.943, No. 3.
No. 185,704; No. 3,551.466; No. 3.4
No. 15,750: No. 3,312,619; No. 3,28
No. 0,034; No. 3,718.61 + No. 3; No. 3,65
No. 2,61fi; British Patent No. 1,085,903, No. 1
, 162,438, U.S. Pat. No. 3,558,743.

The nitrogen-containing dispersant materials of the present invention can also be embedded with polymerizable lactones (e.g., epsilon-caprolactone) to form dispersant adducts having the following components: ko ffl
H where Z is a number from 4 to 8 (e.g., 5 to 7) and m has an average value of about O to 100 (e.g., 0.2 to 20). The dispersants of the present invention are prepared with a C5-C9 lactone (e.g., a C6-C9 lactone such as epsilon-caprolactone) by introducing a mixture of the dispersant material and lactone into a reaction vessel at a temperature of about 50° to about 200° C. in the absence of a solvent.
°C, - layer can be post-treated by heating, preferably from about 75" to about 180°C, most preferably from about 90° to about 160°C, for a period sufficient to effect the reaction. Optionally, the lactone, Dispersant materials and/or solvents for the resulting adduct may be used to adjust viscosity and/or reaction rate.

In one preferred embodiment, a C5-C9 lactone, such as epsilon-caprolactone, is reacted with a dispersant material in a 1:1 molar ratio of lactone to dispersant material. In practice, the ratio of lactone to dispersant material can be varied considerably as a means of controlling the length of the sequence of lactone units in the adduct. For example, the molar ratio of lactone to dispersant material ranges from about 10:1 to about 0.1+1. -layers preferably about 5=
1 to about 0.2+1. Most preferably about 2.1 to about 0.4
: Can be in the range of 1. The average degree of polymerization of the lactone monomer is preferably kept lower than about 100, preferably about 0.2 to about 50, and more preferably about 0.2 to about 20. A sequence of about 1 to about 5 lactone units in a row is preferred to optimize dispersant performance.

Catalysts useful for promoting the lactone-dispersant material reaction are selected from the group consisting of: stannous octoate, stannous hexanoate, tetrabutyl titanate, Marcel Detzker, 1969, Frisch and Regan, eds. R, D, Land Barb (L
un+]berg) and E, F Cox (Cox
) various organic hese acid catalysts and akin catalysts as described in the chapter by Stannous octoate is a particularly preferred catalyst. catalyst to the reaction mixture, total reaction mixture 10
Add at a concentration level of about 50 to about 10,000 parts by weight catalyst per 10,000 parts.

The reaction of such lactones with dispersant materials containing nitrogen or ester groups is more fully described below:
Co-pending U.S. Patent Application No. 916.108, 91B, 217916.218, filed October 7, 1986
; 91fi, 287: 916,303,
916,113 and 916.114; 198
Co-pending U.S. Patent Application No. 178 filed on April 6, 2008
, No. 099. The entire disclosure of each of these applications is incorporated herein by reference.

The nitrogen-containing dispersant material of the present invention is also an alkyl acetoacetate or alkylthioacetate of the formula:

(wherein x'' is 0 or S, Rb is H or R8, and R'' is independently substituted and unsubstituted alkyl or aryl (preferably ,
alkyl having 1 to 6 carbon atoms, e.g. can be formed: where R' is as defined above.

Preferably, the reaction is conducted at a sufficiently high temperature so as to substantially minimize the formation of enaminone and instead produce the ketoenol-positive variant. Temperatures of at least about 150°C are preferred to meet this goal, but the proper selection of temperature depends on many factors, including the reactants, concentrations, choice of reaction solvent, etc. The temperature is about 120゛～
It is common to use 220<0>C, preferably about 150' to 180<0>C. The nitrogen-containing dispersant material reacts with the alkyl acetonate and alkylthioacetate to liberate the corresponding HOR" and H3Rb by-products, respectively. Prior to use of the dispersant adduct thus prepared, such by-products are It is preferable to substantially remove it by distillation or stripping with an inert gas (eg, N2).

Such distillation and stripping processes involve high temperatures;
For example, it may be convenient to carry out the reaction at a selected reaction temperature (eg, 150° C. or higher). Neutral diluents such as mineral oil may be used in the reaction.

The amounts of alkyl aceto-acetate and/or alkylthioacetate reactants used can vary widely and are preferably selected to avoid significant excesses of these reactants. These reactants are present in a molar ratio of reactant to amine nitrogen equivalent of 01 to 1:1, preferably about 0.5 to 1.
It is common to use 1 and 15. where the moles of amine nitrogen equivalents are the moles of secondary nitrogen in the nitrogen-containing dispersant material (e.g., polyisobutenyl succinimide) thus contacted with the alkyl acetonate or alkylthioacetate + the moles of primary nitrogen. It is twice the mole of The reaction is also
Strong acids (e.g. mineral acids, e.g. HCJl, HB2, N
2S04.

H3PO3, etc., should be carried out in the substantial absence of sulfonic acids, such as vara-toluenesulfonic acid) to avoid undesirable side reactions and reduced yields to the adducts of the invention.

The reaction of such alkyl acetoacetates and thioacetoacetates with nitrogen-containing dispersant materials was published in May 1987.
Co-pending U.S. Patent Application No. 51.27 filed on May 18th
No. 6, the entire disclosure of which is incorporated herein by reference.

A further aspect of the invention consists in forming a novel dispersant additive metal composite made in accordance with the invention. Suitable metal complexes can be formed during or after forming the present dispersant materials according to known techniques using reactive metal ion species. Complexing metal reactants include transition metals such as iron, cobalt, nickel, copper, chromium, manganese, molybdenum, tungsten, ruthenium, palladium, platinum, cadmium, lead,
Metal nitrates, thiocyanates, halides, carboxylates, phosphates of silver, mercury, antimony, etc.
Includes thio-phosphates, sulfates, borates.

Prior art disclosures of these complex-forming reactions are also found in U.S. Patent No. 3,306,908 and U.S. Reissue Patent No. 26,4
No. 33, the entire disclosures of which are incorporated herein by reference.

The processes of these incorporated patents as applied to the compositions of the invention and the post-treated compositions thus produced constitute a further aspect of the invention.

The dispersant production reaction can be carried out in a polar or non-polar solvent (e.g. xylene, toluene, benzene, etc.),
Preferably, it is carried out in the presence of mineral oil or synthetic lubricating oil.

Nitrogen-containing dispersants may be subjected to boration as generally taught in U.S. Pat. No. 3,087,936 and U.S. Pat. ) can be further processed. This is accomplished by using a selected acyl nitrogen dispersant with a boron compound selected from the class consisting of boron oxide, boron halides, boric acid, and esters of boric acid to provide about 0.1 atomic proportion per mole of the acylated nitrogen composition. Boron to about 20 per atomic percent nitrogen of the acylated nitrogen composition
This is easily achieved by treating with an atomic proportion of boron. The dispersant of the inventive combination is characterized by the borat
ed) approximately 0.0 based on the total weight of the acyl nitrogen compound.
It is useful to contain 5 to 2.0% by weight boron, such as 0.05 to 0.7% by weight. The boron that is believed to be present in the product as dehydrated boric acid polymer (primarily (HBO2)3) is believed to be bound to the dispersant imide and diimide as an amine salt, such as the metaborate salt of the diimide.

The treatment involves a boron compound, preferably about 0.05-4% by weight of boric acid, most commonly added as a slurry;
For example, 1 to 3% by weight (based on the weight of the acyl nitrogen compound) is added to the acyl nitrogen compound and the
℃, e.g. 140° to 170°C with stirring.
This is facilitated by heating for ~5 hours followed by nitrogen stripping in the temperature range. Alternatively, boron treatment involves adding boric acid to a thermal reaction mixture of a monocarboxylic acid material and an amine;
The amount of water can be removed.

The ashless dispersants of the present invention can be used alone or in combination, for example, from the long chain hydrocarbon substituted dicarboxylic acid materials mentioned above and from hydroxy compounds such as -hydric and polyhydric alcohols or from aromatic compounds such as phenol, naphthol, etc. It can be used in admixture with other dispersants such as derived esters. Polyhydric alcohols are the most preferred hydroxy compounds and preferably contain from 2 to about 10 hydroxy radicals, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and alkylene radicals containing from 2 to about 10 carbon atoms. Other alkylene glycols containing 8. Other useful polyhydric alcohols include glycerol, monooleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, dipentaerythritol, and mixtures thereof.

Ester dispersants can also be derived from unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexan-3-ol, oleic alcohol. Still other classes of alcohols which can give rise to the esters of the invention include ether alcohols, a-arylene alcohols containing one or more oxy-alkylene, amino-alkylene or a-arylene oxy-arylene radicals. Oxy-alkylene, oxy-arylene-, amino-alkylene- and amino-arylene- having the above
Contains substituted alcohols. Such alcohol is C
e1losolveCarbitol, N, N,
Illustrated by N', N'-tetrahydroxytrimethylene diamine, an ether-alcohol having up to about 150 oxy-alkylene radicals in which the alkylene radical contains from 1 to about 8 carbon atoms.

Ester dispersants are diesters or acid esters of succinic acid, i.e. partially esterified succinic acid; and partially esterified polyhydric alcohols or phenols;
That is! 1111 alcohol or an ester having a phenolic hydroxyl radical.

Mixtures of the esters exemplified above are likewise intended to be within the scope of this invention.

Ester dispersants are described, for example, in U.S. Pat. No. 3,381,022.
can be manufactured by one of several known methods, such as those exemplified in No. Ester dispersants, like nitrogen-containing dispersants, can also be borated as described above.

Hydroxia compounds that can be reacted with the long chain hydrocarbon-substituted dicarboxylic acid materials mentioned above to form dispersants include 2-amino-1-butanol, 2-amino-2-methyl-1-propanol. tool, p-(betahydroxyethyl)aniline, 2-amino-1-propatur, 3-amino-1-propatur, 2-amino 2-
Methyl-1,3-propane-diol, 2-amino-2
-ethyl-1,3-propanediol, N-(betahydroxy-propyl)-N"(heteraminoethyl)-piperazine, tris(hydroxymethyl)aminomethane (also known as trismethylonylaminomethane) ), 2-aryono-1-butanol, ethanolamine, beta(beta-hydroxyethoxy)ethylamine, etc. Mixtures of these or similar amines may also be used.Hydrocarbyl-substituted dicarboxylic acids or anhydrides The above description of nucleophilic reactants suitable for reacting with compounds includes amines, alcohols, mixed amines containing reactive functional groups, and hydroxy compounds, ie, amino-alcohols.

Tris(hydroxymethyl)aminomethane (THAM)
British patent 984,409
or as taught in U.S. Pat.
No. 402.798; No. 4,116,876 and No. 4,
Oxazoline compounds and borated oxazoline compounds can be formed as described in No. 113,639.

Other dispersants that can be used in admixture with the novel dispersants of the present invention are those derived from the long chain hydrocarbyl-substituted dicarboxylic acid materials mentioned above and the amines mentioned above, such as polyalkylene polyamines, e.g. It is a hydrocarbyl-substituted succinilide. Examples of such other dispersants are those assigned to co-pending US Application No. 95,056, filed September 9, 1987.

A preferred group of ashless dispersants are those substituted with succinic anhydride groups and polyethylene amines such as tetraethylenepentamine, pentaethylenehexamine, polyoxyethylene and polyoxypropylene amines such as polyoxypropylene diamine, trismethylolaminomethane,
Pentaerythritol and combinations thereof with ammonia or 2 to 12 total nitrogen atoms and 2 to 3 carbon atoms per molecule
0 and an acrylate-type compound of formula (IX) above, most preferably a lower alkyl alkyl-acrylate (e.g. methyl, ethyl, isopropyl, propyl, isobutyl, n-butyl of methacrylic acid, acrylic acid, etc.). on average at least 6 ( For example 6~
It is derived from polyisobutyne which is reacted with the reactive nitrogen component of 30) and a second adduct containing 2 to 4 primary nitrogen groups.

The dispersants of the present invention can be incorporated into the lubricating oil (or fuel) in any convenient manner. That is, these mixtures can be dispersed or dissolved in the lubricating oil (or fuel) at the desired concentration level of the dispersant and added directly to the lubricating oil (or fuel). Such blending into additional lubricating oil (or fuel) can be done at room temperature or elevated temperature. Alternatively, the dispersant can be mixed with a suitable oil-soluble solvent/diluent (
For example, benzene, xylene, toluene, lubricating base oil,
a petroleum distillate (including various commonly liquid fuels described in detail below) to form a concentrate, and then the concentrate is blended with a lubricating oil (or fuel) to form the final formulation. can be obtained. Such a dispersant concentrate contains (active ingredient (A, 1.)
typically from about 3 to about 45%, preferably from about 10 to about 35% by weight of the dispersing additive (based on the weight of the concentrate) and typically from about 30 to 90% by weight, based on the weight of the concentrate; Preferably it contains about 40-60% by weight base oil.

Oil-Based Compositions The additive mixtures of the present invention have very good dispersion properties as determined in the present invention in a wide range of environments. Therefore, the additive mixture is used by adding and dissolving it into an oily substance such as fuel or lubricating oil. The additive mixture of the present invention is boiling at 65°C.
When used in normally liquid petroleum fuels such as middle distillates (including kerosene, diesel fuel, home heating fuel oil, jet fuel, etc.) of ~430t, the additives in the fuel add up to the total weight of the composition. Typically about 0.001 as a standard
~0.5% by weight, preferably 0.005~0.15% by weight
It is usually used in a concentration of % by weight. Such fuel properties can be found, for example, at Ameri, 1916 Race Street, Philadelphia, Pennsylvania 19103.
can 5ociety forTesting Ma
ASTM 5specification obtained from terials (r ASTM J)
It is well known as described by D #396-73 (Fuel 0ils) and D #439-73 (Gasolines).

The fuel compositions of the invention may contain, in addition to the products of the invention, other additives well known to those skilled in the art. These may include: anti-knock agents such as tetraalkyl lead compounds, lead scavengers.
1, e.g. haloalkanes, antifouling agents or modifiers such as triaryl phosphates, cetane improvers, antioxidants such as 2,6-ditarjaso-butyl-4
- Methylphenol, rust inhibitor, bacteriostatic agent, gum inhibitor, metal deactivator, upper cylinder lubricant, etc.

The additive mixture of the present invention finds its primary use in lubricating oil compositions that utilize a base oil in which the additive is dissolved or dispersed. Such base oils may be natural or synthetic. Base oils suitable for use in making the lubricating oil compositions of the present invention are commonly used as crankcase lubricants for spark-ignited and compression-ignited internal combustion engines, such as automobile and truck engines, marine and railroad diesel engines, etc. including those commonly used. The advantageous results also indicate that the additive mixture of the invention can be used in power transmitter fluids, universal tractor fluids, hydraulic fluids,
This is achieved by use in base oils conventionally used in and/or adapted for use in heavy duty hydraulic fluids, power steering fluids, etc. Gear lubricants, industrial oils, pump oils and other lubricating oil compositions may also benefit from incorporating the additives of this invention.

These lubricating oil formulations commonly contain several different types of additives that provide the required properties of the formulation. Among these types of additives are viscosity index improvers, antioxidants, corrosion inhibitors, detergents, dispersants, pour point depressants, antiwear additives, friction modifiers, etc.
These are described in US Pat. No. 4,797,219, the entire disclosure of which is incorporated herein by reference. Some of these numerous additives can provide multiple effects, such as dispersant-antioxidant. This approach is well known and need not be elaborated further herein.

In the preparation of lubricating oil formulations, the additives are added in a hydrocarbon oil, such as a general lubricant extract or other suitable solvent.
It is usual practice to introduce the active ingredient in the form of a concentrate of 0% by weight, for example 20-80% by weight. In forming the final lubricant, e.g. crankcase motor oil, it is common to dilute these concentrates with 3 to 100 parts by weight of lubricant, e.g. 5 to 40 parts by weight of lubricant per part by weight of additive package. be. Of course, the purpose of the concentrate is to reduce the difficulty and inconvenience of handling the various materials and to facilitate their dissolution or dispersion in the final blend. It is therefore common to use dispersants in the form of concentrates, for example 40-50% by weight in the lubricating oil fraction.

The ashless dispersants of the present invention are typically used in admixture with lubricating oil base oils consisting of oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.

Natural oils include animal and vegetable oils (eg, castor oil, lard oil), liquid petroleum, hydrogenated, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Also useful base oils are oils of lubricating viscosity derived from coal or sierre.

Alkylene oxide polymers, interpolymers, and derivatives thereof modified by esterification, etherification, etc. of the terminal hydroxyl groups constitute another known class of synthetic lubricating oils. These 1+ are polyoxyalkylene polymers made by polymerizing ethylene oxide or propylene oxide,
Alkyl and aryl ethers of these polyoxyalkylene polymers (e.g. methyl-polyisopropylene glycol ether with average molecular weight 1000, diphenyl ether of polyethylene glycol with molecules Jixsoo to tooo, molecules fi 11000 to 1
500), and their mono- and poly-carboxylic esters, such as acetate esters of tetraethylene glycol, mixed 03-C8 fatty acid esters and C+s oxo acid diesters.

Another suitable class of synthetic lubricating oils is dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acid, alkenylsuccinic acid, maleic acid, azelaic acid, speriic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dicarboxylic acid). mass,
malonic acid, alkylmalonic acid, alkenylmalonic acid) and various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adibate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate-1. , dioctyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, a complex ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethyl xanoic acid.

Esters useful as synthetic oils also include those made from c5-CI2 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol.

Silicon-based oils such as polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy-siloxane oils and silicate oils constitute another useful class of synthetic lubricants and include: tetraethyl silicate, Tetraisopropyl silicate, tetra-(2-
ethylhexyl) silicate, tetra-(4-methyl-
2-ethylhexyl) silicate, tetra-(pt-butylphenyl) silicate, hexa-(4-methyl-2
-pentoxy)disiloxane, poly(methyl)siloxane and poly(methylphenyl)siloxane. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids 32 (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofuran.

Unrefined, refined and rerefined oils can be used in the lubricants of the present invention. , unrefined oils are those obtained directly from natural or synthetic sources and have not undergone further refining IA processing. For example, shale oils obtained directly from retorting operations, petroleum oils obtained directly from distillation, or ester oils obtained directly from esterification processes become unrefined oils when used without further treatment. Refined oils are similar to unrefined oils, except that they have been further processed in one or more refining steps to improve one or more properties. Many such purification techniques are known to those skilled in the art, such as distillation, solvent extraction, acid or base extraction, filtration and percolation. Rerefined oil is obtained by a process similar to that used to obtain refined oil by applying it to refined oil that has already been used in service. Such rerefined oils, also known as reprocessed oils, are often further processed by techniques to remove spent additives and oil breakdown products.

When the composition contains these conventional additives, they are typically blended into the base oil in amounts effective to provide their normal attendant functions. Typical effective amounts of such additives (as each active ingredient (A, 1.)) in a fully formulated oil are illustrated below: Viscosity modifier Detergent Corrosion inhibitor Antioxidant portion Powder Pour point depressant Antifoam agent Anti-wear additive Friction modifier Mineral oil base (1,01-40,01-12 0,01-30,01-20 0,01-1,50,01-5 0,01-1,50,01-5 0,1-80,1-20 0,01-1,50,01-5 0,001-0,150,001-3 0,001-1,50, 001-5 0,01-1,50,01-5 Balance Balance If other additives are used, a concentrated solution or dispersion of the novel dispersant of the present invention (herein, in the concentration amount described above) ) together with 12ffi or more of the other additives (the concentrate when forming an additive mixture is referred to herein as an additive package). Although desirable, several additives can be added to the base oil at the same time to form a lubricating oil composition.Dissolution of the additive concentrate into the lubricating oil is accomplished by means of a solvent and by gentle heating. This may be facilitated by concomitant mixing, but this is not required. Concentrates or additives -
The package is typically formulated to contain the additive in an appropriate amount to provide the desired concentration in the final formulation when combining the additive package with a predetermined amount of base lubricant. That is, the dispersants of the present invention, together with other desirable additives, are added to a small amount of base oil or other comparable solvent, typically from about 2.5% to about 90% by weight of the active ingredient.
, preferably from about 15 to about 75% by weight, most preferably from about 25 to about 60% by weight, with the remainder being base oil. can.

The final formulation should typically use 10% by weight of additive-package, with the remainder being base oil.

All weight percentages expressed herein (unless otherwise indicated) refer to the active ingredient (A,i) content of the additive and/or the A, 1. Based on the total weight of the package or formulation - any additives that add up to the weight of the whole oil or dilution.

The invention will be further understood by the following examples, which include preferred embodiments of the invention. In the examples below, all parts are parts by weight unless otherwise noted.

Preparation of LL, NH3-methyl acrylate adduct.

82g of ammonia - 100ml of anhydrous methanol at 10℃
Bubble into j2. The ammonia methanol mt& that was removed was converted into methyl acrylate (MeAe29).
6 g is added dropwise under a nitrogen atmosphere while keeping the liquid reaction mixture at a temperature of 20 DEG to 25 DEG C. with external cooling. After the addition is complete, the reaction mixture is allowed to stir at room temperature overnight.

The reaction mixture is then stripped with N2 gas to remove excess methyl acrylate and methanol to constant weight. Analysis of the product showed C52.3% by weight, N7.89
wt% and N4.5 wt% (theoretically, 0524 wt%,
N7.6% by weight, N5.1% by weight).

(+lI 2 , N H3M e A c + T
Preparation of ET A second adduct.

55 g (0.2 mol) of the product of Example 1 are charged to a reaction flask and diluted with 100 mJ2 of anhydrous isopropanol. Add triethylenetetramine (TETA) 87 6H (0.6 mol) with stirring and under N2 atmosphere,
Heat to 100° C. with nitrogen sparge for about 10 hours.

Infrared analysis shows complete disappearance of Esralhant and the reaction mixture is stripped at 100° C. for 30 minutes to collect the product. The product was analyzed and N27.2% by weight;
4.21 molar equivalents of primary nitrogen per gram of sample.

Example 3. Preparation of NH,-MeAc+PAM second adduct.

Following the second procedure, 27.5 g (0.1 mol) of ammonia-methyl acrylate first adduct and the molecule (PA
70.6 g of poly(ethyleneamine) (PAM) having an average of 5 to 7 nitrogen atoms per M) (0.6 meq of primary nitrogen) are used. The product was analyzed to be 27.6% by weight N and 3.38 t primary nitrogen equivalents per gram of sample.

Preparation of 4H4,NH3-MeAc+TETA+PIBSA dispersant.

Polyisobutylene with Mn 2225 (M w / M n
= 2.5), saponification value 37.4 (active ingredient 6
300 g (0.1 mol) of polyisobutenylconophosphoric anhydride having 7.7%) are charged to a reaction flask together with 127 g of 315ON and heated to 150 DEG C. with stirring under a blanket of nitrogen gas.

Then, 232 g of the second adduct prepared in Example 2 (0.1 equivalents of primary nitrogen) are slowly added over about 30 minutes. The reaction mixture is stirred and heat leaked for 3 hours with a nitrogen strip. The oil solution containing the dispersant is filtered and evaluated while hot. It is found to have a kinematic viscosity of 341 cst at 100°C and contain 1.52% by weight N.

4N5. Preparation of NH3-MeAc-PAM+PI BSA dispersant.

The procedure of Example 4 is repeated, but using 296 g of the adduct of Example 3 (0.1 equivalents of primary nitrogen) and 300 g of PIBSA. The filtered oil solution is found to have a kinematic viscosity of 490 cSt at 100°C and 1.81% by weight N.

Preparation of pseudotongue DEA-methyl acrylate tertiary adduct.

Using the procedure of Example 1, diethylenetriamine (DETA
) 51.5 g (0.5 mol) are charged to the reaction flask and diluted with 10040 ml of anhydrous isopropanol. Then methyl acrylate 258
g (3 mol) are added at a rate that keeps the reaction temperature below 30°C. When the addition is complete, the reaction mixture is stirred at room temperature overnight. The reaction mixture was stripped to constant weight with a stream of N2 gas, and the products were analyzed to contain 17 wt.% C54, 67 wt.% H8, and 74 wt.% H (theoretically, C5.
4.0% by weight, H8.1% by weight, H7.8% by weight).

Example 7. Preparation of MeAc-DETA+TETA\S2 adduct.

The procedure of Example 2 is repeated, but using 3 g (0.1 mol) of the methyl-acrylate-DETA adduct 5 from Example 6 and 73 g (0.5 mol) of triethylenetetramine (TETA). The product was analyzed to be 28% by weight N and 3.88 milliequivalents of primary nitrogen per gram of sample.

Example 8. Preparation of MeAc-DETA+PAM second adduct.

Following the procedure of Example 7, but with 53.3 g of adduct of Example 6 and PA
Use 17 g of MI. The product was analyzed to be 28.2% by weight N and 3.33 main equivalents of primary nitrogen per gram of sample.

Example 9, Preparation of MeAc-DETA-TETA+PIBSA dispersant.

The procedure of Example 4 is carried out, but 12.9 g of the product of Example 7 (
0.05 equivalents of primary nitrogen), PI B5Al sog and 64.5 g of 515ON are used. The filtered oil solution is 10
Kinematic viscosity at 0°C 300 cSt and N 1.59% by weight
has.

Example 10, MeAc-DETA-PA
Preparation of M+PI BSA dispersant.

Repeat the procedure of Example 4, but with 15 g of the product of Example 8 (0.05 equivalents of primary nitrogen), 150 g of PIBSA and S15ON.
Use 67g. Analyze the filtered oil solution for 7 nights at 100℃
The kinematic viscosity is 592 cSt and N is 1.83% by weight.

Comparative Example A, Preparation of PIBSA-TETA dispersant.

Repeat the procedure of Example 4, but with 150 g of PIBSA (005
mole), triethylenetetramine 3.65g (0,0
25 mol) and 56 g of 315ON are used. The filtered oil solution was analyzed to have 167% by weight N0 and a kinematic viscosity of 381 cSt at 100°C.

Comparative Example B, Preparation of PIBSA-PAM dispersant.

Repeat the procedure of Example 4, but with 150 g of PIBSA (O, O
S mol), PAM5. asg (0.05 equivalents of primary nitrogen) and 58 g of Sl 5ON are used.

The filtered oil solution was analyzed for N0191% by weight and 100% by weight.
The kinematic viscosity at ℃ is 450 cSt.

The resulting product dispersants are summarized as described in Table I below.

Table I 4 2225 5 〃 9 〃 10 〃 Comparison A 〃 Comparison B 〃 (1) Kinematic viscosity Example 2 product 1.52 Example 3 product 1,81 Example 4 product 1.59 Example 8 raw material 1.83 T E T A O,67P A
M O,9143 The following lubricating oil compositions are Examples 4, 5, 9.10 and Comparative Example A.
-Made using dispersant B. The resulting compositions are then tested for sludge prevention (by S I B test) and varnish prevention (by VIB test) as follows.

The SIB test has been found to be an excellent test for evaluating the dispersing power of lubricant dispersant additives after numerous evaluations.

The medium chosen for the SIB test was a used crankshaft with a viscosity of 3253 US compared to that at 38°C used in taxis, which were usually driven only short distances, thus causing the accumulation of high concentrations of sludge precursors. Case mineral lubricating oil composition. The oil used contained only refined base mineral lubricating oil, viscosity index improver, pour point depressant, and zinc dialkyldithiophosphate antiwear additive. The oil contained no sludge dispersant. Such a large amount of used oil can cover 1,000 to 2,000 liters of taxi crankcase.
It was obtained by draining and refilling at intervals of 1,000 miles (16,000-3,200 km).

The SIB test is carried out as follows: The milky brown used crankcase oil described above is weighed at approximately 39,000 g.
Centrifuge for 1 hour at ) to eliminate sludge. The resulting clear bright red skim oil is then decanted from the insoluble sludge particles and separated therefrom. However, the skimmed oil still contains oil-soluble sludge precursors that tend to form additional oil-insoluble sludge deposits when heated under the conditions used in this test. The anti-sludge properties of the additives to be tested are determined by adding a small amount, for example 0.5.1 or 2% by weight, of the particular additive to be tested to a portion of the skimmed used oil. 10 g of each blend to be tested is placed in a stainless steel centrifuge tube and heated at 135° C. for 16 hours in the presence of air. After heating, the tube containing the oil to be tested is cooled and then about 30 g of about 39,000 g 5 at room temperature are heated. Centrifuge for minutes. The supernatant oil is decanted and the sludge deposits are then carefully washed with 25 mu of heptane to remove any residual oil from the sludge and further centrifuged to separate the new sludge deposits formed in this step from the oil. The residue is dried and weighed to determine the weight (in milligrams) of the new solid sludge produced in the test. Results are reported as amount of settled sludge compared to a blank settled sludge containing no additional additives. Rating blank 10
Standardize to. The less new sludge settles in the presence of the additive, the lower the SIB value and the more effective the additive is as a sludge dispersant. In other words, the blank is standardized to 10, so if the additive produces about half the amount of settled sludge as the blank, it will be rated 50.

Determine varnish protection using the VIB test. Here, each test sample consisted of 10 g of lubricating oil containing a small amount of the additive being tested.

The test oil in which the additives are mixed is of the same type used in the SIB test described above. Each 10 g sample is further heat leaked at approximately 140° C. and then centrifuged to remove sludge. The supernatant of each sample is subjected to thermal cycling from about 150° C. to room temperature over a period of 35 hours at a frequency of about 2 cycles/min. During the heating step, a gas mixture of 0.7% by volume 5O2, 4% by volume NOI, and the balance air is bubbled through the test sample.

During the cooling phase, water vapor is bubbled through the test sample. The test cycle can be repeated as necessary to determine the inhibitory effect of any additive, and at the end of the test period, the walls of the test flask containing the sample are visually evaluated for varnish prevention. The amount of varnish pressed onto the wall soil is rated from 1 to 11 compared to a blank without additives rated at 11. The larger the number, the greater the amount of varnish.

SIB test oil 10. OOg was mixed with 0.05g of the example product as described in Table II and added to SIB and VI as described above.
Tested in test B.

The data obtained through these methods is shown in Table 1 below! summarized in.

4 NH3-MeAc+TET8
1.52 1.3 35 NH
3-MeAc+PAIJ 1.81
1.58 39 DETA-MeAc
+TETA 1.59 0.22
310 DETA-Me8+PAM
],,83 1.63 3 comparison A T
ET 80, 67 3.59 7 Comparison B
PAM O,911,797 The above data obtained by them shows that the inventive dispersant has excellent S
Demonstrates I B/V I B performance and sludge and varnish prevention properties.

A series of lubricating formulations were prepared containing 6% by volume of the novel branched dispersant produced in Examples 4, 5.9 and 10, each lubricating composition also containing: Oil, overbased M
g Mixture of sulfophor 1 dispersant inhibitor and overbased Ca sulfonate dispersant inhibitor, zinc dialkyldithiophosphate antiwear agent, antioxidant, ethylene propylene viscosity index improver.

The table below illustrates methods for making additional first and second adducts using the present invention.

48 (1) Examples 11, 12, 14, 16, 18 and 19 - Example 1
Repeat the procedure (80% molar excess of polyfunctional reactant)
.

Examples 13, 15, 17 and 20 - Repeat the procedure of Example 6 (
80% excess of polyfunctional reactants>.

(2) Degree of branching of the first adduct.

(3) A second product mixture stripped of excess polyfunctional reactants.

Examples 11-20 - Repeat the procedure of Example 2.

(4) TEPA=tetraethylenepentamine; DETA
-diethylenetriamine/TETA=triethylenetetrayone, HPHA-hexapropyleneheptaamine, E
DA = ethylenediamine.

The principles, preferred embodiments, and operating modes of the present invention have been described above. The specific embodiments disclosed herein are to be regarded as illustrative rather than limiting, and the invention intended to be protected should not be considered limited to such specific embodiments. Modifications and changes may be made by those skilled in the art without departing from the spirit of the invention.

Continuation of page 1 @) Int, C1,5 Identification symbol Internal office reference number 40:25

Claims (1)

[Claims] 1. (a) a first compound having at least two reactive nitrogen components;
A nitrogen-containing compound and a multifunctional reactant having in its structure a first functional group reactive with the -NH- group and at least one additional functional group reactive with the -NH- group are subjected to a first liquid reaction. (b) contacting at least a portion of the first functional groups of the multifunctional reactant with the reactive nitrogen component in a mixture in an amount and under conditions such that the reactive nitrogen component reacts to form a first adduct; 1 adduct and a second nitrogen-containing compound having at least two -NH- groups in an amount and under conditions sufficient to cause the additional functional group in the first adduct to react with the -NH- group in the second nitrogen-containing compound. contacting the structure with an average of (i) at least two nitrogen-containing components derived from the second nitrogen-containing compound per nitrogen-containing component derived from the first nitrogen-containing compound and (ii) no nitrogen-containing components per molecule. producing a second adduct characterized by having at least two reactive primary or secondary amine groups; (c) combining the second adduct and at least one member selected from the group consisting of: Contact in a two-liquid reaction mixture: (A) a long chain hydrocarbon substituted with a mono- or dicarboxylic acid, anhydride or ester group; (B) a halogenated long chain hydrocarbon; (C) an aldehyde and a long chain. Mixtures with hydrocarbyl-substituted phenols; (D) amino-substituted and optionally hydrocarbyl-substituted phenols with aldehydes and long-chain hydrocarbons substituted with mono- or dicarboxylic acid, anhydride or ester groups; A method for producing a lubricating oil nitrogen-containing dispersion additive, comprising: a mixture with a reaction product produced by reacting with a nitrogen-containing dispersion additive; 2. The long chain hydrocarbyl reactant has a number average molecular weight of 3.
00 to 10,000, and at least one of the C_4 to C_1_0 monounsaturated dicarboxylic acid materials and the C_3 to C_1_0 monounsaturated monocarboxylic acid materials. one long-chain hydrocarbyl-substituted mono- or dicarboxylic acid generator, the acid generator containing an average of at least The dispersing additive of claim 1 having a dicarboxylic acid forming component of 0.5. 3. The polyfunctional reactant contains at least one of the following: (i) A compound having the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, W^1 and W^2 are the same or different;
O or S, X and Y are the same or different,
Including members selected from the group consisting of: halide, -
OR^4, -SR^4, -N(R^4)(R^5S),
-Z^1C(O)OR^4, -C(O)R^4, -(R
^3) C=C(R^1)(R^2), -Z^1-nitrile, -Z^1-cyano, -Z^1-thiocyano, -Z^
1-isothiocyano and -Z^1-isocyano (where R^1, R^2, R^3, R^4 and R^5 are the same or different, H or substituted or unsubstituted (Z^1 is C_1-C_2_0 divalent hydrocarbylene), T is a substituted or unsubstituted hydrocarbon moiety, "a" is 0 or 1, "b
” is 0 or 1, “c” is an integer of at least 1, and X and Y are together when “a” is 1, −
O- or -S-, T can contain a ▲mathematical formula, chemical formula, table, etc. group, and at least two of X, Y and T are reactive with the -NH- group. group, provided that when a=0, c=1, and when a=1, b=1; (ii) Compound of the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, W ^1 is as defined before and R^1 is H
or a substituted or unsubstituted hydrocarbyl, and "d1" and "d2" are each an integer of 1 to 10; (iii) A compound of the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here , R^1, R^2 and R^3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above, and Y'' is selected from the group consisting of: Contains reactive functional group: halide, -OR^4
, -SR^4, -N(R^4)(R^5), -Z^1C
(O)OR^4, -(R^3)C=C(R^1)(R^
2) where R^4 is as defined above; (iv) a compound of the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ where R^1, R^2 and R^3 are Oil additives according to claim 1, which are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. 4. The polyfunctional reactant contains at least one alpha, beta unsaturated compound of the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein X is sulfur or oxygen, Y is -OR^4, -SR^4 or -NR^4 (R^5), and R^1, R^2, R^3, R^4 and R^5 are the same or different , hydrogen or substituted or unsubstituted hydrocarbyl). 5. The second nitrogen-containing compound has 2 to 6 carbon atoms per molecule.
2. The dispersing additive according to claim 1, comprising at least one polyamine containing 0 and 2 to 12 nitrogen atoms. 6. The polyamine has alkylene groups each having 2 to 6 carbon atoms.
The dispersing additive of claim 5, wherein the polyalkylene polyamine contains from 5 to 9 nitrogen atoms per molecule. 7. The hydrocarbyl-substituted monounsaturated acid generating substance is substituted with a succinic anhydride component and has a number average molecular weight of 700.
a hydrocarbyl-substituted C_4-C_1_0 monounsaturated dicarboxylic acid generator comprising ~5,000 polyisobutylene, wherein the first nitrogen-containing compound comprises ammonia and the second nitrogen-containing compound comprises The polyalkylene polyamine contains 2 to 6 carbon atoms and the polyalkylene polyamine contains 5 to 9 nitrogen atoms per molecule, and the alpha, beta unsaturated compound is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate. The dispersing additive according to claim 2, comprising at least one member selected from the group consisting of , ethyl methacrylate, propyl methacrylate, and butyl methacrylate. 8. The dispersion additive according to claim 1, wherein the second nitrogen-containing compound comprises polyethylene polyamine or polypropylene amine. 9. The dispersion additive according to claim 5, wherein each of the dispersion additives is borated so that the boron content in the borated dispersion additive is 0.05 to 2.0% by weight. 10. The dispersion additive according to claim 1, wherein the olefin polymer comprises polyisobutylene. 11. The dispersion additive according to claim 2, wherein the ratio of the acid-forming component per olefin polymer molecule in the dispersion additive is 0.9 to 1.3. 12. The number average molecular weight of the olefin polymer is 1.3.
12. The dispersing additive according to claim 11, which has a molecular weight of 0.00 to 3,000. 13. The dispersion additive according to claim 2, wherein the monounsaturated acid substance comprises maleic anhydride. 14. The dispersion additive of claim 2, wherein in the liquid reaction mixture of step (c), 1 to 5 moles of the acid generating material are present per equivalent of the first nitrogen of the second adduct. 15. The second nitrogen-containing compound comprises a polyamine containing an average of at least two first nitrogen atoms per molecule, the polyfunctional reactant comprises at least one alpha, beta unsaturated compound, and the first nitrogen-containing compound A dispersion according to claim 5, wherein the compound and the alpha, beta unsaturated compound are contacted in an amount of 1.1 to 3 moles of alpha, beta unsaturated compound per equivalent of reactive nitrogen component in the first nitrogen-containing compound; Additive. 16. The dispersion additive according to claim 15, wherein the first adduct has an average degree of branching of 3 to 18. 17. The second nitrogen-containing reactant comprises a polyamine containing an average of at least 2 primary nitrogen atoms per molecule, and the second adduct comprises an average of 2 to 4 unreacted primary amines and 0 to 8 primary nitrogen atoms per molecule. 17. The dispersing additive of claim 16 containing unreacted secondary amine groups. 18. Claim 17, wherein the amide-amine contains an average of 1 to 3 amide groups per molecule of amide-amine.
Dispersing additives as described in section. 19. (a) provide a nitrogen-containing branched adduct characterized by having at least two unreacted primary or secondary amine groups per molecule in its structure, the branched adduct having: (i) a first nitrogen-containing compound having at least two reactive nitrogen components and a first functional group reactive with an -NH- group and at least one additional reactive with an -NH- group; in a first liquid reaction mixture, reacting the first functional group in the multifunctional reactant with the reactive nitrogen component to form a first adduct. (ii) the first adduct and a second nitrogen-containing compound having at least two -NH- groups in a second liquid mixture;
contacting an adduct functional group in the first adduct with an -NH- group in a second nitrogen-containing compound in an amount and under conditions sufficient to cause a reaction, to produce a second adduct comprising a branched adduct;
The branched adduct is further characterized in that it has on average in its structure at least two nitrogen-containing components derived from a second nitrogen-containing compound for each nitrogen-containing component derived from a first nitrogen-containing compound; b) C_ having a number average molecular weight of 300 to 10,000
2 to C_1_0 monoolefin olefin polymer and C_4 to C_1_0 monounsaturated dicarboxylic acid substance and C
_3 to C_1_0 A long chain hydrocarbyl-substituted mono- or dicarboxylic acid-generating substance produced by reacting with at least one of the monounsaturated monocarboxylic acid substances, the acid-generating substance on average at least 0.5 dicarboxylic acid-generating moieties per olefin polymer molecule present in the reaction mixture used to produce; (c) the acid-generating material and the branched nitrogen-containing adduct; contacting the branched nitrogen-containing adduct in an amount and under conditions sufficient to cause a reaction between at least some of the primary amino groups attached to the branched nitrogen-containing adduct and at least some of the acid-generating groups in the acid-generating substance; A method of making a dispersant additive useful in oil additives, the method comprising producing a dispersant additive. 20. The olefin polymer has a number average molecular weight of 700 to
5,000 per molecule of said olefin polymer present in the reaction mixture used to produce said acid generating material. Claim 1 having an average succinic anhydride content of at least 0.8
The method described in Section 9. 21. The polyfunctional reactant contains at least one of the following: (i) A compound having the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, W^1 and W^2 are the same or different;
O or S, X and Y are the same or different,
Including members selected from the group consisting of: halide, −
OR^4, -SR^4, -N(R^4)(R^5), -
Z^1C(O)OR^4, -C(O)R^4, -(R^
3) C=C(R^1)(R^2), -Z^1-nitrile, -Z^1-cyano, -Z^1-thiocyano, -Z^1
-isothiocyano and -Z^1-isocyano (where R
^1, R^2, R^3, R^4 and R^5 are the same or different and are H or substituted or unsubstituted hydrocarbyl, and Z^1 is C_1-C_2_0 divalent hydrocarbylene), T is a substituted or unsubstituted hydrocarbon moiety, "a" is 0 or 1, and "b"
is 0 or 1, "c" is an integer of at least 1, and X and Y together form -O when "a" is 1.
- or -S-, T is ▲mathematical formula, chemical formula,
There are tables etc. ▼ Contains a group, and at least two of X, Y and T are groups reactive with -NH- group, provided that when a=0, c=1, and a=1 When b=1; (ii) Compound of the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, W^1 is as defined before, and R^1 is H
or a substituted or unsubstituted hydrocarbyl, and "d1" and "d2" are each an integer of 1 to 10: (iii) A compound of the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here , R^1, R^2 and R^3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above, and Y'' is from the group consisting of Contains reactive functional groups of choice: halide, -OR^4, -
SR^4, -N(R^4)(R^5), -Z^1C(O
)OR^4, -(R^3)C=C(R^1) (R^2) where R^4 is as defined above; (iv) a compound of the following formula: ▲ Formula, There are chemical formulas, tables, etc. ▼ where R^1, R^2 and R^3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above; Claim No. 19
The method described in section. 22. The polyfunctional reactant contains at least one alpha, beta unsaturated compound of the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (wherein, X is sulfur or oxygen, and Y is -OR^4, -SR^4 or -NR^4 (R^5), and R^1, R^2, R^3, R^4 and R^5 are the same or different , hydrogen or substituted or unsubstituted hydrocarbyl). 21. The method of claim 20. 23. The second nitrogen-containing compound has 2 to 2 carbon atoms per molecule.
23. The method of claim 22, comprising at least one polyamine containing 60 and 2 to 12 nitrogen atoms. 24. The polyamine has alkylene groups each having 2 to 2 carbon atoms.
24. The method of claim 23, wherein the polyalkylene polyamine contains from 5 to 9 nitrogen atoms per molecule. 25. The first nitrogen-containing compound contains ammonia, and the alpha, beta unsaturated compound is at least selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. 25. The method of claim 24, comprising one member. 26. Claim 2, wherein the second nitrogen-containing compound comprises polyethylene polyamine or polypropylene amine.
The method described in Section 5. 27. The method of claim 26, wherein the olefin polymer comprises polyisobutylene. 28. The method of claim 27, wherein each of the dispersion additives is borated to provide 0.05 to 2.0% by weight of boron in the borated dispersion additive. 29. The method according to claim 27, wherein the ratio of acid-forming component per molecule of olefin polymer in the dispersing additive is from 0.8 to 1.3. 30, the number average molecular weight of the olefin polymer is 1,3
00 to 3,000, and substantially no polyfunctional reactants are present in the second liquid reaction mixture.
The method described in Section 9. 31. The method of claim 19, wherein the first adduct and the polyamine are contacted after the first liquid reaction mixture is treated to remove unreacted polyfunctional reactants. 32. The process of claim 19, wherein in step (c) there are from 1 to 5 moles of said acid generator per equivalent of first nitrogen of said second adduct in the liquid reaction mixture. 33. The second nitrogen-containing compound comprises a polyamine containing an average of at least two first nitrogen atoms per molecule, the polyfunctional reactant comprises at least one alpha, beta unsaturated compound, and the first nitrogen-containing compound 21. The method of claim 20, wherein the compound and the alpha, beta unsaturated compound are contacted in an amount of from 1.1 to 3 moles of alpha, beta unsaturated compound per equivalent of reactive nitrogen component in the first nitrogen-containing compound. 34. The method according to claim 33, wherein the first adduct has an average degree of branching of 3 to 18. 35. The second nitrogen-containing reactant comprises a polyamine containing an average of at least 2 primary nitrogen atoms per molecule, and the second adduct comprises an average of 2 to 4 unreacted primary amines and 0 to 8 primary nitrogen atoms per molecule. 35. The method of claim 34 containing unreacted secondary amine groups. 36. Claim 35, wherein the amide-amine contains an average of 1 to 3 amide groups per molecule of amide-amine.
The method described in section. 37. Repeating steps (a) and (b) at least once to provide a nitrogen-containing adduct with increased branching followed by contacting with an acid-generating material to produce the dispersible material. Method described. 38, dispersion additive according to claim 1 0.00
A fuel oil composition containing 1 to 0.5% by weight. 39, dispersion additive according to claim 1 from 0.1 to
A lubricating oil composition containing 20% by weight. 40, dispersion additive according to claim 6 from 0.1 to
A lubricating oil composition containing 8% by weight. 41. The dispersion additive of claim 1, wherein the polyolefin comprises an ethylene-propylene copolymer. 42. The method of claim 19, wherein said polyolefin comprises an ethylene-propylene copolymer.