JPS58167692A - Nitrogen-containing organic composition, additive concentrate, lubricating composition, fuel composition and internal combustion engine operating method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to nitrogen-containing compositions. The composition is useful as a lubricant and fuel additive. The invention also relates to concentrates of this composition as well as lubricating and fuel compositions containing this composition. Furthermore, the invention now also relates to a method of operating an internal combustion engine by lubricating the engine with said lubricating composition during its operation.

An object of this invention is to provide a new nitrogen-containing composition.

Another object of this invention is to impart to lubricants and fuels one or more of the following properties: detergency, dispersibility, oxidation resistance, corrosion resistance, abrasion resistance, friction reduction and flow modification properties. An object of the present invention is to provide a novel nitrogen-containing composition.

Another object of the present invention is to provide a concentrate containing these organic compositions.

It is a further object of the present invention to provide lubricating compositions and fuel compositions containing these nitrogen-accumulated organic sound engine compositions.

21- Furthermore, it is an object of the present invention not to lubricate an internal combustion engine with the above-mentioned lubricating composition during its operation.
General formula (wherein R is a substantially saturated hydrocarbon substituent having at least 8 aliphatic carbon atoms, a, b and C are each from 1 to 3 times the number of aromatic nuclei present in Ar) , and the sum of a, l) and C does not exceed the effective valence number of Ar, and Ar is an arbitrary group consisting of a lower alkyl group, a lower alkoxyl group, a nitro group, a hal group, or a combination of two or more of these. (B) at least one amine phenol represented by an aromatic moiety having 0 to 3 substituents; and (B) an Mn value of dj 1200 to about 5000"
22-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-1-2-1-2-1-2-1-2-1-2-1-2-1-2-1-2-2-2-2-2-2 substituents are derived from a polyalkene and a succinic acid group having a Mw/Mn value of about 1.5 to about 6, and at least 1.3 of substituents per equivalent weight. (1k) at least one substituted cono-phosphate acylating agent having a succinic acid group;
amine having two H-N groups, (b) alcohol, (
C) a reactive spectrum or reactive metal compound and (d)
These compounds are obtained by reacting with a reactant selected from the group consisting of a combination of two or more of these (,) or c). A nitrogen-containing organic composition is provided.

One or more objects of the present invention are to provide a nitrogen-containing organic composition comprising components (4) and (B), wherein component (B) contains one or more of the at least one carboxylic acid visiting conductor. This can also be achieved by providing a post-treated carboxylic acid derivative obtained by reacting with a post-treatment agent.

It is also an object of the present invention to apply the above-mentioned nitrogen-containing composition to Hata et al.
This can also be achieved by providing a composition in combination with at least one chlorine-containing compound selected from the group consisting of chloroJl polyhydrocarbon compounds and mixtures thereof.

Furthermore, one or more objects of this invention provide that: (4) the general formula %, where R is a substantially saturated hydrocarbon substituent having at least 8 aliphatic carbon atoms, a, b and C are numbers up to three times the number of aromatic nuclei present in Ar or Ar, and the sum of a, b and C does not exceed the effective valence number of Ar, and Ar is a lower alkyl group, a lower at least one aminophenol represented by an aromatic moiety having 0 to 3 alkoxyl groups, nitro groups, hexagonal groups, or a combination of two or more thereof; and (C) a chloroaliphatic hydrocarbon compound and a cycloaliphatic hydrocarbon group. This can also be achieved by providing a nitrogen-containing organic composition comprising a combination with at least one chlorine-containing compound selected from the group of hydrocarbon thread compounds.

Furthermore, the object of the present invention can also be achieved by providing a nitrogen-containing organic composition in which the above-mentioned combination of components (4) and (Q) is further combined with at least one sulfurized olefinically unsaturated compound. .

(4) Amine Phenol The aminophenol useful in this invention has the general formula %. The aromatic moiety Ar is a single aromatic group such as a benzene nucleus, a pyridine nucleus, a thiophene nucleus, a 1,2,3,4-tetrahydronaphthalene nucleus, etc. It may be a nucleus or a polynuclear aromatic moiety. Such a polynuclear moiety may be of a condensation type in which an aromatic nucleus is condensed with another nucleus 25- at two points, as seen in 7talene, anthracene, azonaphthalene, and the like. In addition, polynuclear aromatic moieties have at least two nuclei (
It may also be of a bonding type in which mononuclear or polynuclear types are bonded to each other by bridges. Such crosslinking bonds include carbon-carbon single bonds, ether bonds, keto bonds, sulfide bonds, polysulfide bonds having 2 to 6 sulfur atoms, sulfinyl llae, sulfonyl bonds, methylene bonds, alkylene bonds, di(lower alkyl) bonds, A methylene bond, a lower alkylene ether bond, an alkylene keto bond, a lower alkylene sulfur bond, a lower alkylene polysulfide bond having 2 to 6 sulfur atoms, an amino bond, a polyamino bond, and a combination of these divalent cross-linked bonds. You can choose.

In some cases, two or more crosslinks may exist between two aromatic nuclei in Ar. For example, in the fluorene nucleus, two benzene nuclei are bonded by a methylene bond and a covalent bond. Such a nucleus is thought to have three nuclei26-, of which only two are aromatic. However, usually Ar contains only carbon atoms in the aromatic nucleus itself (and any lower alkyl or alkoxy substituents).

The number of aromatic nuclei (condensed type, crosslinked type, or both) in Ar determines the maximum values of a s b and C in the formula (I). For example, when Ar contains a mononuclear aromatic nucleus, Q.

Each of b and C is independently 1 to 3. Ar
When contains two aromatic nuclei, each of a, b and C can be an integer from 1 to 6, ie up to three times the number of aromatic nuclei present (2 in naphthalene). For trinuclear Ar moieties, each of a, b and C is an integer from 1 to 9. For example, when Ar is a biphenyl or naphthyl moiety, each of a, b and C is an integer from 1 to 6. It goes without saying that the values of a, b and C are limited by the fact that their sum cannot exceed the total effective valence of Ar. The sum cannot exceed the number of carbon atoms in the aromatic moieties (Ar) that would otherwise be bonded to hydrogen.

The monoaromatic aromatic nucleus that can be substituted with the Ar moiety has the general formula % (where ar is a monoaromatic aromatic nucleus having 4 to 10 carbon atoms (e.g., benzene), and Q is lower alkyl. group, lower alkoxy group, nitro group or halodane atom,
And m can be expressed as 0 to 3). As used herein, the term "lower" refers to groups having 7 or fewer carbon atoms. Halodan atoms include fluorine,
Typically halodane atoms are fluorine and chlorine atoms, although @ atoms of chlorine, bromine and iodine are included.

If we were to discuss a specific example of a monomer Ar tfB, it would be 1'12, etc. Here, Me is methyl, Et is ethyl, Pr
is n-propyl, and Nit is nitro. When OAr is a polynuclear fused ring aromatic moiety, it can be expressed as (showing a pair of condensed bonds producing two carbon atom moieties in each monkey). Specific examples of the fused ring type aromatic moiety Ar are listed below.

30- When the aromatic moiety Ar is a crosslinked type polynuclear aromatic moiety, it is expressed by the general formula ar-(-Lng -ar→-(Q) w mW (in the above formula, W is an integer from 1 to about 20, ar is as above, except that at least three free valences are present, Q and m are as above, and each Lng is a carbon compound (i.e. -5-), sulfur Polysulfide bonds with 2 to 6 atoms (e.g. 8
2-6), sulfinyl bond (-8(0)
-), sulfonyl bond (e.g. 5(0)2), lower alkylene bond (e.g. -'CH-1-CH2-C
H2-1-CH-CH-0 etc.), -(lower alkyl)methylene bond (e.g. -CR
2), lower alkylene ether bond (e.g. -CH2
0-1-Cf(20-CH2-1-CH2-Cf(20
-, id bond (for example, one or more of the 10- atoms in the above alkylene ether bond are replaced with 18 atoms), lower alkylene polysulfide bonds (for example, 10- in the above alkylene ether bond) one or more of - is replaced with a -82 to 6- group), an amine bond (for example, (atk is alkylene, etc.), a polyamino bond (for example, a mixture thereof, etc.) Specific examples of the polynuclear aromatic moiety Ar of the crosslinking type are listed below.

33- etc.O Normally, all these Ar moieties are R groups, -OH groups and -
It is unsubstituted except for the NH2 group (and the bridging group).

For reasons of cost, availability, performance, etc., the k site is usually a benzene nucleus, a lower alkylene bridged benzene nucleus, or a naphthalene nucleus. That is, a typical Ar moiety is a benzene or naphthalene nucleus with 3 to 5 free valences, where 1 or 2 of the valences are satisfied by a hydroxyl group and the remaining free valences are as free as possible. , which is located at the ortho position or the ortho position with respect to the hydroxyl group. Preferably, Ar is a benzene nucleus with at least 3 free valencies, one of which is satisfied by a hydroxyl group, and two or three of the remaining valencies are in the ortho or para position of the human 34-roxyl group. It is highly regarded.

The aminophenol used in this invention contains a substantially saturated monovalent hydrocarbon group R having at least 8 aliphatic carbon atoms directly connected to the aromatic moiety Ar. The R group can have up to about 750 aliphatic carbon atoms. Usually the number of R groups present on each aromatic nucleus in the aromatic moiety Ar is at most 2 or 3, although more than one R group may be present. The total number of R groups is indicated by a in formula (1). Ordinarily, the hydrocarbon group will have at least about 30 aliphatic carbon atoms, typically at least about 50, and up to about 750, typically about 400 aliphatic carbon atoms.
It has up to 5 carbon atoms.

Generally, the hydrocarbon group R is ethylene, nolopyrene, butene-1, isobutyne, butatsuene, isoprene, 1-
They are made from homo- or interpolymers (e.g., dipolymers, terpolymers) of mono- and diolefins having 2 to 10 carbon atoms, such as hexene, 1-octene, etc.

Typically these olefins are 1-monoolefins such as homopolymers of ethylene. The R group can be derived from such homo- or interpolymeric halogenated (eg chlorinated or brominated) products. However, the R group can be derived from other sources such as low molecular weight alkenes (e.g., 1-tetracontine) and their chlorinated and hydrochlorinated products,
Aliphatic petroleum fractions, especially paraffin waxes and their decomposed and chlorinated products, white oils, synthetic alkenes, such as those obtained by the Ziegler-Natsuta process (eg, poly(ethylene) grease), as well as other sources, can be made. Unsaturation in the R group can be reduced or removed by accumulating water by known techniques prior to the nitration step described below.

As used in this specification, the term ``hydrocarbon thread'' refers to carbon atoms directly connected to the remainder of the molecule! i--curing and having predominantly hydrocarbon character'! i-point.

Thus, a hydrocarbon group may contain up to one non-hydrocarbon group for every ten carbon atoms, provided this does not significantly alter the predominant hydrocarbon character of the group. Such non-hydrocarbon groups include hydroxyl groups, halo groups (chloro and fluoro in percent), alkoxyl groups, alkylmercapto groups, alkylsulfoxy groups, and the like. However, usually the hydrocarbon group R is purely a hydrocarbyl group sb, and therefore does not contain any non-hydrocarbon groups.

Further, R is substantially saturated. What is practical intellectual saturation?
The group has at most 1 carbon-carbon bond for every 10 carbon-carbon bonds present.
This means that it contains only one carbon-charcoal unsaturated bond. Typically, R will contain at most one non-aromatic unsaturated bond for every 50 carbon-carbon bonds.

Hydrocarbon group R [substantially aliphatic. That is, R
contains at most one non-aliphatic moiety (cycloalkyl, cycloalkenyl or aromatic) having up to 6 carbon atoms for every 10 carbon atoms in it. Typically, R contains at most one non-aliphatic group per 5037 carbon atoms, and often contains no non-aliphatic groups (i.e., a typical R
groups are purely aliphatic). Typically, these purely aliphatic R groups are alkyl or alkenyl groups.

Specific examples of the substantially saturated hydrocarbon group R are listed below.

tetra(propylene) group tri(isobutyne) group tetracontanyl group hempentacontanyl group mixture of poly(ethylene/propylene) groups having about 35 to about 70 carbon atoms, having about 35 to about 70 carbon atoms; Mixtures of oxidatively or mechanically degraded poly(ethylene/propylene) groups having from about 80 to about 150 carbon atoms Mixtures of poly(nolopylene/1-hexene) groups having from about 20 to 32 carbon atoms Mixture of poly(isobutyne) groups 38 - Mixture of poly(isobutyne) groups having an average of 50 to 75 carbon atoms A preferred source of R groups is a mixture of poly(isobutyne) groups with a butene content of 35 to 75
Poly(isobutyne) obtained by polymerizing a C4 refinery stream containing 15 to 60% by weight of isobutyne in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. This poly(butene) is mainly composed of 9 isobutyne repeating units (i.e.,
50% or more of the total repeating units).

Aromatic moiety A of aminone enol used in this invention
Attachment of the hydrocarbon group R to r can be accomplished by a number of methods well known to those skilled in the art. A particularly suitable method is the Friedel-Krach reaction, in which an olefin (eg, a polymer with olefinic bonds) or a halodanated or hydrohalodanated derivative thereof is reacted with phenol. This reaction is carried out in the presence of a Lewis acid catalyst (for example, boron trifluoride and its complexes with ethers, phenols or hydrogen fluoride, aluminum chloride, aluminum bromide, zinc dichloride, etc.). Techniques and conditions for carrying out this reaction are well known. For example, Kirkoo and Marr's Encyclopedia of Chemical Technology, 2nd edition (Interscience Publishers, 1963).
“Alkylation” on pages 894-895 of Volume 1
of phenols”. Other suitable methods for attaching an aliphatic R substituent to an aromatic moiety Ar will be apparent to those skilled in the art.

The amine phenol used in this invention contains at least one of each of the following substituents. namely, the hydroxyl group, the R group (already mentioned), and the primary amino group (-NH2). Each of these groups is Ar
It is bonded to the carbon atoms that make up the aromatic nucleus in the site. However, when two or more aromatic nuclei are present in Ar, these groups do not need to be bonded to the same aromatic ring.

In a preferred embodiment, the amino enol has one of each of the above substituents (a = b = c = 1) and only monoaromatic benzene. The preferred amine phenol is a substantially saturated hydrocarbon group of the formula (wherein R' is 4-position relative to the hydroxyl group) having from about 30 to about 400 aliphatic carbon atoms; can be represented by a lower alkyl group, a lower alkyl group, a xyl group, a nitro group, or a halogen atom, 2 can be represented by It is a pure hydrocarbyl aliphatic group. Often R' is an alkyl or alkenyl group in the opposite position to the 10H group. Also, often only one amino group is present, but two amino groups are present. It's okay.

In a further preferred embodiment, the amine phenol has the formula (where R' is a homopolymerized or interpolymerized C2-
Those derived from C4°1-olefins and having an average of about 30 to about 400 aliphatic carbon atoms! and 2 are indicated by the above-mentioned standard). Typically R' is derived from ethylene, propylene, butylene or mixtures thereof. Typically W is derived from polymerized inbutene.

Preferably, R' is at least about 50 aliphatic carbons. has an elementary atom, and 2 is O.

The amine phenols used in this invention can be made by many known synthetic routes. These routes can vary in the type of method used and the order in which they are used. For example, an aromatic hydrocarbon such as benzene can be alkylated with an alkylating agent such as an olefin polymer to produce an alkylated aromatic intermediate. In step b, this intermediate is nitrated to produce, for example, a polynitro intermediate. This polynitro intermediate is then reduced to a diamine, which is diazotized,
One of the amino groups can be converted to a hydroxyl group by reaction with water to yield the desired amine phenol.

Alternatively, one of the nitro groups in the polynitro intermediate described above is converted to a hydroxyl group by bath melting with total sodium hydroxide or the like to form a hydroxy-nitroalkylated aromatic, which is then reduced to form the desired hydroxyl group. Amine phenol can be obtained.

Other useful routes to obtain the amine phenols used in this invention include alkylating phenols with olefinic alkylating agents to produce alkylated phenols. The alkylated phenol can then be nitrated and the resulting nitrophenol intermediate converted to the desired amino enol by reducing at least some of its nitro groups to amine groups.

Alkylation of phenols is carried out by the above-mentioned Kirkoo Osmer's "
It is well known as shown in the Encyclopedia of Chemical Chemistry. Nitration of phenols is also well known. For example, the section on "Nitrophenols" in Kirku Ozmar's "Encyclopedia of Chemical Chemistry", 2nd edition, vol. 13, pages 888 et seq., P, B, D, type and J, H, Lid. ``Aromatic Φ Suspension System, N;
(Academic Press, 1959), Nitration and Aromatic Reactivity (Cambridge University Press, 1961) by J.G. The Nitro & Nitron Groups” (Interscience) J?
See Frillacher, 1969).

Aromatic hydroxy compounds can be nitrated with nitric acid, mixtures of nitric acid and acids such as sulfuric acid or boron trifluoride, nitrogen pentoxide, nitronium tetrafluoroborate, and acyl nitrates. Generally, nitric acid at a concentration of, for example, about 30 to 9 liters is a convenient nitrating agent.Substantially inert liquid diluents and solvents, such as acetic acid or butyric acid, may be used by improving contact of the reactants. Assist in carrying out reactions.

Conditions and concentrations for nitrating hydroxyaromatic compounds are also well known. For example, start the reaction at about -15°C.
It can be carried out at a temperature of from about 150°C to about 150°C. It is usually convenient to carry out the nitration at a temperature of about 2545-75°C.

Generally, depending on the nitrating agent used, about 0.5 to 4 moles of nitrating agent are used per mole of aromatic nuclei present in the hydroxyaromatic intermediate to be nitrated. Ar
When more than one aromatic nucleus is present in the site, the amount of nitrating agent can be increased proportionally to the number of aromatic nuclei. Generally, from about 1 to 4 moles of nitrating agent are used, since one mole of naphthalene-based aromatic intermediate is equivalent to two "monocyclic" aromatic nuclei in this invention.

When nitric acid is used as a dioxidizing agent, usually aromatic nuclei 1
The rapid nitration of hydroxyaromatic intermediates in which about 1.0 to about 3 moles per mole is used generally
．． This occurs in 25 to 24 hours, but it may be advantageous to allow the nitration mixture to react for a longer period of time, for example 96 hours.

Methods for reducing aromatic nitro compounds to the corresponding amines are also well known. See, for example, Kirku Ozmer's Encyclopedia of Chemical Chemistry, 2nd Edition, Volume 2, Volume 2, 76-99, Negative [Amination φ Pyreduction. Generally, this reduction can be carried out using hydrogen, -carbon oxide or hydrazine (or mixtures thereof) in the presence of metal catalysts such as palladium, platinum and its oxides, nickel, copper chromite and the like. In this catalytic reduction reaction, a promoter such as an alkali metal or alkaline earth metal hydroxide or an amine (including amine phenol) may be used. Reduction of hydroxide can be carried out with hydrazine, with or without a catalyst, as described in Canadian Patent No. 1,096,887.

Reduction can also be performed by reducing gold Ig in the presence of an acid such as hydrochloric acid.
This can be done using Typical reducing metals are zinc, iron and tin, and their salts are also used.

Nitro groups are also known as organic reactions.
It can be reduced by the zinin reaction discussed in Vol. 20, p. 455 et seq. (John Wiley and Φ Sons, 1973). Generally, the Tzinin reaction involves the reduction of a nitro group with divalent, negative yellow compounds such as alkali metal sulfides, polysulfides, and hydrosulfides.

Furthermore, the nitro group! It can also be reduced by decomposition reaction. For example, see ``Amination Pyrillidaxis'' mentioned above.

Typically, the aminophenols of this invention are obtained by reduction of nitrophenol with hydrazine as described above. This reduction is generally carried out in the absence of a catalyst for about 5
Temperatures from 0 to 250°C typically about 1oo to 200 tl:
It is carried out in The reaction time is approximately 2 to 24 hours. The reaction can be facilitated using substantially inert liquid diluents and solvents such as ethanol, hexane, cyclohexane, naphtha, mineral oil, etc. The aminophenol product can be prepared using a number of methods such as distillation, filtration, extraction, etc. Obtained by known methods.

The reduction is carried out until at least about 50, and usually about 80%, of the di-o groups present in the nitro intermediate have been converted to amine groups.

A typical route for obtaining the aminophenol used in this invention can be summarized as follows.

(1) Formula (where R is a substantially saturated hydrocarbon group having at least 10 aliphatic carbon atoms, a and C are each an integer up to three times the number of aromatic nuclei in Atte A
r is part of a streak aromatic nucleus and has at least one carbon atom directly bonded to hydrogen, and the sum of a and C does not exceed the effective valence of the remaining Ar, and Ar is a lower An aromatic 49-group moiety having 0 to 3 substituents selected from alkyl groups, lower alkoxyl groups, nitro groups, hal groups, and combinations of two or more thereof, in which Ar represents a hydroxyl group. At least one compound of benzene having only one and one R group, the R group being in the ortho position of the hydroxyl group or in the 1,000-2 position, is treated with at least one nitrating agent. nitration to form a first reaction mixture containing a nitro intermediate, and then (■) converting at least about 50% of the nitro groups in the first reaction mixture to amine groups.

This means that the formula (where R is a substantially saturated hydrocarbon group having at least 10 aliphatic carbon atoms, ab and cld,
The number of each is from 1 to 3 times the number of aromatic nuclei in Ar, and the sum of asb and C does not exceed the effective valence of Ar, and Ar is a lower alkyl group, a lower alkoxyl group,
An aromatic moiety having 0 to 3 substituents selected from the group consisting of a Hal group and a combination of two or more thereof.
- in the case of benzene in which Ar has only one hydroxyl group and only one R group, at least one
It is meant to reduce at least about 50% of the nitro groups in a species of compound to amino groups.

Amine phenols useful in this invention and methods for making them are described in US Pat. No. 4,100,082.

(B) Carboxylic acid derivatives and post-treated carboxylic acid derivatives Substituted succinic acid-based acylating agents (hereinafter referred to as acylating agents) useful for producing component (B) used in the present invention are present in the structure of 2 It can be characterized by two groups. The first group, referred to for convenience as the "substituent", is derived from a polyalkene. The polyalkene from which this substituent is derived has an Mn (number average molecular weight) of 1
200 to about 5000 and characterized by a Mw/Mn value of about 1.5 to about 6.

The second group is called a "cono-phosphate group." This succinic acid group has the formula (where X and are the same or different groups,
At least one of the acylating agents is Cal? acylating agents). In other words, at least one of X and It must be capable of forming other common acids and functioning as an acid-based acylating agent. Transesterification and transamidation reactions are also considered common acylation reactions.

The pick, X and/or X' are usually OH%
O-hydrocarbyl, -0-M+ (M+ is the whole range of 1, ammonium or amine cation), -Nf (2
, -C4, -Br, and X and X' may be combined to form an anhydride. Among X and r, those other than those mentioned above are not particularly limited as long as their presence does not interfere with the acylation reaction of the -10,000 group. However, it is preferably such that it can undergo an acylation reaction.

Free valence in -C-C- of the above succinic acid group (
One of the bonds) forms a carbon-carbon bond with a carbon atom in the substituent. All free valences except the one above are usually hydrogen (-) although other free valences may form similar bonds with the same or different substituents
H) is satisfied.

Substituted cono-phosphate acylating agents are characterized by the presence in their structure of at least 1.3 succinic groups per equivalent of substituent. In this invention, the equivalent weight of the succinic group corresponds to the quotient of the total number of substituents present in the acylating agent divided by the Mn value of the polyalkene from which the substituents are derived. Thus, for example, an acylating agent may have a total capacity of 140,000 substituents.
If the acylating agent is characterized by a Mn value of 2000 for the polyalkene from which the substituents are derived, then the acylating agent has a total of 20 equivalent weights of substituents.

Therefore, this exemplary acylating agent contains at least 26 succinic acid groups.

Another requirement for the acylating agent is that the substituent is M
That is, it must be derived from a polyalkene having a w/Mn value of about 1.5 to about 6. Here, MwrIiM! Represents average molecular weight.

In this invention, the Mn value and MNY value are determined by Glue Permeation Chromatography (GPC). This separation method uses column chromatography in which the stationary phase is a heteroporous, water-swollen polymer network polystyrene whose permeability varies greatly. As the liquid phase (tetrahydrofuran) containing the polymer sample passes through the coll, the polymer molecules diffuse into all parts of the coll that are not mechanically impeded. Smaller molecules tend to "penetrate" more completely and remain in the column for longer periods of time, while larger molecules "penetrate" to a lesser extent and pass through the column more quickly. The Mn value and yiw vi of a polyalkene are obtained by comparing the distribution data obtained to a series of calibration standards for polymers with known molecular weight distributions. In this invention, a series of fractionated isobutyne polymers (polyisobutyne is preferred) are used as calibration standards.

For example, the Mw value is 2.5 ml siphon, 2 ml BA
, four diameter injection loops and a diameter of 7.8 inches and a length of 120 cm.
Obtained using a Waters Associates model 200 Dull permeation chromatograph equipped with two stainless steel columns. Each column is packed with μ Styrodal, which is a commercially available solid porous dull (granular) made of crosslinked styrene/divinylbenzene copolymer. This dal also has water.
Available from Associates. The first column is fully filled with μ Styrodal with a holding capacity of 10 A, the second and third columns are filled with μ Styrodal with a holding capacity of 1500 A, and the 40th column is filled with Styrodal with a holding capacity of 60 A. The first column is connected to the sample injection loop using a length of 83.8 mm stainless steel tubing. The first column is also connected to the second column by a 2.3 cm long stainless steel tube. The second and 30th columns each have a length of 10.2
Connect with tM tube. The 40th column is connected to the detector by a tube of length 25.40.

The diameter of all connecting tubes is 6 cm.

Specific gravity at 60°C (15.5°C) is 0.89 and 210
'F (99℃)' viscosity is 12.5 OSU
Calibration standards are prepared by dialyzing a polyisobutyne sample of S. The sample is fractionated by dialysis using a rubber membrane and a Soxhlet extractor using refluxing petroleum ether as the solvent. Collect 11 fractions. That is, one sample was taken every hour for the first 7 hours, then 3 samples were taken every 4 hours, and finally the residue that did not pass through rubber M was taken during the 4 hours. , each Mn is measured using gas phase osmotic pressure method and benzene as a solvent.

Each calibration sample is then chromatographed.

After weighing approximately 7 In9 of the sample into a small bottle, 41 of reagent grade tetrahydrofuran is added. After sealing 1. The bottle is left overnight before analysis.

The above liquid phase chromatograph was degassed at 59°C and
d Maintain the flow rate of tetrahydrofuran.

Sample pressure was 180 psi, reference pressure was 175 pal.
It is. Measure the retention time of each sample. M of each calibration sample
w is calculated from Mn assuming 2 Mn = Mw. Retention time and Mw of famous samples shown in the table below
A standard curve is obtained by zolotting. Next, this curve and Jack Cages' ``Topics of Chemical Instrumentation, mXX'r!, Vol., Dal?--Miesi, N. Chromatography'' (The Journal of Chemical Obtain the Mn and Mw of the Taniwake blood combination using the method described in J.D. Education, Volume 43, Numbers 7 and 8 (1966) Table Rt*Mw Rt Mw Rt*Mw
* 30 42240 40 638 50
22931 26400 41 539
51 21632.16985 42 453
52 20233 10780 43
400 53 18934 6710 44
361 54 17835 4180
45 330 55 16736 2640
46 304 56 15637
1756 47 282 38 1200 48 26439 865
49 246 Note: Rt is the retention time per unit number of times the siphon (2.5m) empties. The siphon is emptied every 2.5 minutes.

Polyalkynes having the above-mentioned Mn and MW values are still known in the art and can be prepared by conventional methods. Some such polyalkenes, particularly polybutenes, are commercially available.

Returning again to the properties of the succinic acylating agent, the succinic group is usually selected from the group p such as -Ct, and 10-lower alkyl groups, or R1 and R2 form 10-.

In the latter case, the cono-phosphate group corresponds to a succinic anhydride group. All succinic acid groups in an individual acylating agent do not have to be the same, but they can be and preferably correspond to succinic acid groups or a mixture thereof. It is easy for those skilled in the art to provide acylating agents in which the cono-monolytic acid groups are the same or different, and to process the acylating agent itself (e.g., by hydrolyzing the anhydride to the free acid). or, alternatively, by converting the free acid to the acid chloride with thionyl chloride) and/or by selecting the appropriate maleic or fumaric acid reactant.

As mentioned above, the minimum number of cono-phosphate groups per equivalent N of substituents is 1.3. Preferably, this minimum number is 1
．． 4, and there are usually 1.4 to about 3.5 succinic groups per equivalent weight of substituent. Particularly preferably at least 1.5 succinic groups are present per equivalent weight of substituent. The preferred range based on this minimum value is
At least 1.5 to about 2.5 to about 2.5 to 1 equivalent weight of substituent
This corresponds to succinic acid group.

As can be seen from the above, the substituted co/·phosphate acylating agent is synyl (y is a number of 1.3 or more). In a more preferred embodiment of this invention, X and X2 represent a more preferred substituent and a cono-phosphate group, respectively, and the value of y is varied as described above (for example, y is 1.4 or more. , 1.5 or more,
1.4 to about 3.5, or 1.5 to about 3.5
) can be displayed similarly.

So far, we have described the number and type of Conori-1 group per equivalent weight of the substituent regarding preferable substituted Cono-phosphate groups, but what is preferable is the type and characteristics of the polyalkene from which the substituent is derived. It is also described based on

61-For example, for Mn values, a minimum value of about 1200 is preferred, and Mn values in the range of about 1200 to about 3200 are also preferred. A highly preferred Mn is in the range of about 1500 to about 2800. The most preferred range of Mn values is about 1500 to about 2400. For polybutenes, a particularly preferred minimum Mn value is about 1700, with a particularly preferred Mn value range of about 1700 to about 2400.

There are also some preferred values for the Mw7Mn ratio. A minimum My/Mn value of about 1.8 is favorable;
．． hhr/Mn values ranging from 8 to about 3.6 are also preferred. A more preferred minimum Mw/Mn value is about 2.0, with a preferred range of about 2.0 to about 3.4. A particularly preferred minimum Mw/Mn value is approximately 2.5;
A particularly preferred range is about 2.5 to about 3.2.

Before discussing further the polyalkenes from which substituents are derived, it should be pointed out that the preferred properties of these acylating agents can be independent or dependent. In other words, it is preferable that the minimum number of succinic acid groups per equivalent weight of substituent is 1.4 or 1.5. It is independent in the sense that it is not associated with a more favorable value. However, these preferences are subordinate in the sense that, for example, a minimum number of succinic groups of 1.4 or 1.5 represents a more preferred embodiment when combined with a more preferred Mn value and/or Mw/Mn value. It is true. That is, each characteristic is independent in itself with respect to the individual characteristics discussed therein, but can be combined with other characteristics to determine what is more desirable. This concept applies to all descriptions in this specification of preferred values, ranges, ratios, reactants, etc., unless expressly stated to the contrary.

The polyalkenes from which the substituents in component (B) are derived are derived from polymerizable olefin monomers having from 2 to about 16, usually from 2 to about 6 carbon atoms, singly and in combination. Interpolymers are produced by intermerging two or more olefin monomers to produce a polyalkene having in its structure units derived from each of the two or more olefin monomers. @That is, the term "interpolymer" includes comonomers, ternary copolymers, quaternary copolymers, and the like. As will be readily understood by those skilled in the art, polyalkenes from which substituents are derived are often referred to as polyolefins.

The olefin monomer from which the polyalkene is derived is a polymerizable olefin monomer characterized by the presence of one or more ethylenically unsaturated groups (i.e. ';c=(), i.e. it is ethylene, propylene , butene-1
, isobutene and octene-1 or polyolefin monomers (usually diolefins) such as butadiene-1,3 and isoprene.

These olefin monomers are usually polymerizable terminal olefins, ie, olefins with c=CH2 groups. However, to produce polyalkenes)
-aJ-c polymerizable internal olefin monomer having a group (
Sometimes medial olefins can also be used. When an internal olefin is used, it is typically used to make interpolymer polyalkenes. For the purposes of this invention, an individual polymerized olefin monomer is considered a terminal olefin if it can be classified both as a terminal olefin and as an internal olefin. That is, pentazene-1,3 (i.e., biperyl) is considered a terminal olefin in this invention.

Polyalkenes are generally hydrocarbon polyalkenes, but as long as the formation of the acylating agent is not substantially hindered, non-hydrocarbon groups such as lower alkoxy groups, lower alkylmercapto groups, hydroxyl groups, mercapto groups, oxo groups, etc. (i.e. backs, such as in keto and aldehyde groups, e.g. 65-OO miC-C-Cmi and miC-C-H), nitro groups, no\
cyano group, carboalkoxy group (i.e., -C-O-alkyl, where "alkyl" is usually a lower alkyl group), alkanoyloxy group, (i.e., 1 alkyl-C- - group, however, "alkyl" usually includes a lower alkyl group), etc.

Such non-hydrocarbon groups, if present, amount to about 10- or less by weight of the total weight of the polyalkene. Since the polyalkene may contain such non-hydrocarbon groups, the olefin monomer from which it is derived may also contain such non-hydrocarbon groups.

Usually, however, for practical and cost reasons, polyalkenes do not contain non-hydrocarbon groups except for chloro groups, which usually facilitate the formation of substituted succinic acylating agents. (When the term "lower" is used in this specification with chemical groups such as "lower alkyl" or "lower alkoxy," it refers to groups having up to 7 carbon atoms).

Polyalkenes may contain aromatic groups (in particular phenyl groups and lower alkyl- and/or lower alkoxy-substituted phenyl groups, such as para-(M-tributyl)-phenyl) and alicyclic groups (polymerizable rings). (such as those obtained from formula olefins or alicyclic-substituted polymerizable acyclic olefins), but polyalkenes usually do not contain such groups. However, 1,3-dienes and styrenes (for example, butadiene-1,3 and styrene or para=(
Polyalkenes derived from interpolymers with (tert-butyl)styrene) are an exception. Again, the olefin monomers from which the polyalkenes are derived may contain aromatic and alicyclic groups, as aromatic and ring ring groups may be present.

As can be seen from what has been said above regarding polyalkenes, aliphatic hydrocarbon bed polyalkenes that are free of aromatic and alicyclic groups are generally preferred (with the exception of the tsene-styrene copolymers mentioned above).

Of this general preference, polyalkenes derived from homo- or interpolymers of terminal olefins having from 2 to about 16 carbon atoms are more preferred. More preferably, the interpolymer of terminal olefins contains up to about 40'% polymer units derived from internal olefins containing up to about 16 carbon atoms, which is usually preferred. Certain interpolymers are also preferred. More preferred polyalkenes are selected from homo- and interpolymers of terminal olefins having from 2 to about 6 and preferably from 2 to 4 carbon atoms. However, another preferred group of polyalkenes is about 6
The latter, more preferred polyalkenes contain up to about 25% of polymer units derived from up to 2 internal olefins.

Specific examples of terminal olefins and internal 71-L/fins from which polyalkenes can be prepared according to conventional and well-known 1-combination procedures include ethylene, zolopyrene, butene-1
, butene-2, isobutyne, pentene-11hexene-
1, heptene-1, octene-1, nonene-1, decene-1, pentene-2, nolopyrene tetramer, soisobutylene, isobutylene trimer, butadiene-1,2, butadiene-1,3, pentagene-1, 2. Pendadiene-
1,3, pentadiene-1,4, isogrene, hexadiene-1,5,2-chlorobutatsuene-1,3,2-methylhegetene-1,3-cyclohexylbutene-1,2
-Methyl-5-propylhexene-1, octene-4,
3,3-dimethylpentene-1, styrene, 2,4-dichlorostyrene, divinylbenzene, vinyl acetate, allyl alcohol, 1-methylvinyl acetate, acrylonitrile, ethyl acrylate, methyl methacrylate, ethyl vinyl ether, and methyl vinyl ketone It is. Among these, hydrocarbon polymerizable monomers are preferred, and wood end olefin monomers are particularly preferred.

69- Specific examples of polyalkynes include polynolopyrene, polybutene, ethylene-nolopyrene copolymer, styrene-
Isobutyne copolymer, imbutene-butadiene-1,3
Copolymer, propene-isoprene copolymer, inbutene-chloroprene copolymer, inbutene-(paramethyl)
Styrene copolymer, hexene-1 and hexadiene-1,
copolymer with 3, copolymer with octene-1 and hexene-1, copolymer with heptene-1 and pentene-1, 3-
Copolymer of methylbutene-1 and octene-1, 3.3
- copolymer of trimethylpentene-1 and hexene-1,
and a terpolymer of isobutyne, styrene, and piperylene. Specific examples of the above-mentioned interpolymers include a copolymer of 95ts (1% by weight, the same hereinafter) isobutene and 5% styrene, a ternary copolymer of 98ts imbutene, 1% piperylene, and 1ts chloroprene. Combined, 95ts
Ternary copolymer of isobutyne, 2-thibutene-1 and 3% hexene-1, terpolymer of 60% isobutyne, 20% pentene-1 and 2070-thioctene-1, 80% hexene-1
and 20% heptene-1, a copolymer of 90% isobutyne, 2% cyclohexene, and 8% nolopyrene,
and a copolymer of 80q6 ethylene and 20 thipropylene. A preferred source of polyalkenes is a C4 sheath oil stream having a butene content of 35 to 75 weight percent and an isobutyne content of 30 to 60 weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. It is poly(isobutyne) obtained by polymerizing the

This poly(butene) consists primarily of inbutene repeating units of the formula % (i.e.,
50% or more of the total repeating units).

It goes without saying that it is obvious to one skilled in the art to produce said polyalkenes satisfying various requirements regarding Mn and Mw/Mn values, but does not constitute this invention. Techniques include controlling the polymerization temperature, regulating the amount of polymerization initiators and/or catalysts and citrus, using chain terminators in the polymerization process, etc. Stripping very light ends (vacuum Other conventional techniques may also be used, including stripping) and/or oxidative or mechanical degradation of high molecular weight polyalkenes to obtain lower molecular weight polyalkenes.Acylation of the Invention In order to produce the agent, one or more of the polyalkenes mentioned above are selected from the group consisting of maleic acid-based or fumaric acid-based reactants represented by the formula (where X and X' are the same as above). The maleic acid and fumaric acid reactants are preferably reacted with one or more acidic reactants having the formula % (where R1 and R2 are the same numbers as previously described). . Normally maleic and fumaric reactants such as hamaric acid, fumaric acid, maleic anhydride, or 2 m
It is a mixture of the above. Generally, maleic acid based reactants are preferred over fumaric acid based reactants. This is because it is easily available and generally reacts easily with polyalkenes (i or derivatives thereof). Particularly preferred reactants are maleic acid, maleic anhydride or mixtures thereof. Maleic anhydride is commonly used because of its availability and ease of reaction.

The polyalkenes and maleic or fumaric reactants can be reacted according to several known techniques. Basically, this approach replaces the conventional polyalkene (polyolefin) with the polyalkene described above and replaces f[ of the maleic or fumaric reactant with the final substituted succinic 73- substituent 1 in the acylating agent. The procedure is similar to that used to produce high molecular weight succinic anhydrides and equivalent acylating agents, except that the number of equivalent weight succinic groups is at least 1.3.

In terms of efficiency, overall economy and performance of the resulting acylating agents and derivatives thereof, the best method for producing the acylating agents of this invention is the so-called "one-step" method.

This method is described in U.S. Pat. Nos. 3,215,707 and 323
It is described in No. 1587.

Basically, the "one-step" method described above consists of a polyalkene and an acidic reactant (i.e., the formula (where XtX', R1 and R2 are as previously described))
It involves making a mixture containing the necessary ingredients. That is, in order to have at least 1.3 succinic groups present per equivalent weight of substituent, at least 1.3 moles of acid 74-based reactant are required per mole of polyalkene. Chlorine is then introduced to the mixture (usually by passing chlorine gas through the mixture) while maintaining the temperature at at least about 140°C.

Variations on this process include adding an additional acid-based reaction during or after the introduction of chlorine, but the US Pat.
For reasons described in Nos. 15707 and 3231587, this variant is not considered preferable if all polyalkenes and all acidic reactants are mixed before introducing chlorine. do not have.

Generally, if the polyalkene exhibits sufficient fluidity at temperatures above 140°C, there is no need to add any additional substantially inert, normally liquid solvent/diluent. However, if a solvent/diluent is used, it is preferred that it be resistant to chlorination. Poly- and per-chlorinated and fluorinated alkanes, cycloalkanes, and benzenes are used for this purpose.

Chlorine is introduced continuously or intermittently.

There is no limit to the rate of chlorine introduction, but for maximum utilization of chlorine it is necessary that the rate of introduction be the same as the rate of chlorine consumption in the reaction.

When the rate of chlorine introduction exceeds the rate of consumption, chlorine is released from the reaction mixture. In order to prevent chlorine loss and maximize chlorine utilization, it is often advantageous to use a closed system with overpressure.

The lower limit of the temperature at which the reaction in the one-step 1 process occurs at a reasonable rate is about 140°C. That is, the lowest temperature at which this process is normally conducted is around 140°C. The preferred temperature range is usually about 160°C. ℃ to about 220℃.Higher temperatures (e.g., 250℃ or higher)
may be used, but there is little advantage. Actually, 220
Temperatures in excess of 0.degree. C. are undesirable because they tend to crack the polyalkene (ie, reduce dimolecular weight through thermal degradation) and/or decompose the acidic reactant. Therefore, the maximum temperature does not exceed about 200 to about 210°C.

The upper limit of useful temperatures is determined primarily by the decomposition temperatures of the components of the reaction mixture. The decomposition temperature is the temperature at which the reactants or products decompose to a degree that does not impair the production of the desired product.

In the above one-step method, the molar ratio of acidic reactant to chlorine is 1:1 of maleic reactant to be introduced into the reaction product.
The proportion is such that there is at least about 1 mole of chlorine per mole. Additionally, for practical reasons, a slight excess of chlorine, usually about 5 to about 3 ON, is used to offset the loss of chlorine from the reaction mixture. Although excess chlorine may be used, there are no particular advantages.

As previously stated, the molar ratio of polyalkene to maleic reactant is at least about 1.3 moles of maleic reactant per mole of polyalkene. This is necessary because at least 1.3 cono-phosphate groups are present. However, preferably an excess of maleic reactant is used. That is, typically from about 577% to about 25% excess of acidic reactant is used relative to the required bar to provide the desired number of cono-phosphate groups in the final product.

The carboxylic acid derivative used in this invention contains one or more substituted succinic acylating agents, (a) at least one H-
An amine having an Nte group, (b) an alcohol, (C) a reactive gold ingot or a reactive gold compound, and (d) component (
, ) to c) by reacting with a reactant selected from the group consisting of a mixture of two or more of the above. Component (d) may be reacted simultaneously or sequentially with the acylating agent.

The above amine (,) has at least one H--N group, and may be a monoamine or a polyamine. In this invention, hydrazine and substituted hydrazine amines containing up to three substituents are included.

A mixture of two or more amines may also be used. Preferably, the amine has at least one primary amino group (i.e.
-NH2), more preferably the amine is a polyamine, especially a polyamine having at least two H-N: groups, one or both of which is a primary or secondary amine.

Polyamines produce carboxylic acid derivatives that are more conventional as dispersants/detergents than those derived from monoamines. Suitable monoamines and polyamines will be described in detail below.

Alcohol (b) contains full-cold poly(illi 7 /recole). A carboxylic M-conductor that is more effective as a dispersant/detergent than carboxylic acid derivatives derived from -hydric alcohols. Reactive metals and reactive metal compounds useful as O component (c), which are also described in detail below, react with carbanoic acid or cardic acid-based acylating agents. These synthetic fibers and gold-brown compounds are also known to produce salts or complexes.

Amines (,) ''The monoamines and preamines used in this invention are those having at least one E(-N group. They therefore have at least one primary amino group (F12N -) or secondary amino group ( H-N-). These amines may be aliphatic, cycloaliphatic, aromatic or dicyclic, including aliphatic-substituted aromatic, aliphatic-substituted cycloaliphatic, aliphatic Substituted aromatic, aliphatic substituted aromatic, aromatic substituted aliphatic, aromatic substituted alicyclic, aromatic substituted heterocyclic, heterocyclic substituted aliphatic, heterocyclic substituted aromatic amines are also included,
It may be saturated or unsaturated. Unsaturated amines do not contain acetylenic unsaturation (-CyoC-). The amine may also contain non-hydrocarbon substituents as long as the reaction between the amine and the acylating agent is not significantly impaired. Examples of such non-hydrocarbon substituents include lower alkoxyl groups, lower alkylmercapto groups, nitro groups, and intervening groups such as -〇-
, -5- (e.g. -CH2CH2-X-CH2CH2
- groups (as in where X is 10- or -5-).

Except for the case of branched polyalkylene polyamines, polyoxyalkylene polyamines, and hydrocarbyl-substituted amines described in detail below, the number of amines used in the inventions (i) and (i) is usually about 40 or less in total, usually about 20 or less. contains carbon atoms.

Aliphatic monoamines include mono-aliphatic substituted amines and non-aliphatic substituted amines, and the aliphatic group may be saturated or unsaturated, and may be linear or branched. That is, these amines are primary or secondary aliphatic amines. Such amines include, for example, mono- and di-alkyl substituted amines, mono- and di-alkenyl substituted amines, and single N-alkenyl substituted amines. and one N-alkyl substituent. The total number of carbon atoms in these aliphatic monoamines generally does not exceed about 40, and usually does not exceed about 20, as mentioned above. Specifically, ethyleneamine, diethyleneamine 1
n-butylamine, di-n-butylamine, oriruamino, isobutylamine, cocoamine, 81-stearylamine, laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine,
Dodecylamine, octadecylamine, etc. Examples of alicyclic-substituted aliphatic amines, aromatic-substituted aliphatic amines, and alicyclic-substituted aliphatic amines'f! r, for example, 2-(
cyclohexyl)ethylamine, benzylamine, phenylethylamine and 3-(furylpropyl)amine.

An alicyclic monoamine is a monoamine having one alicyclic group directly connected to the amine nitrogen via a carbon atom in the ring structure. Examples include cyclohexylamine, cyclopentylamine, cyclohexenylamine, cyclopentenylamine, N-ethyl-cyclohexylamine, dicyclohexylamine, and the like. Examples of aliphatic-substituted, aromatic-substituted and heteroaromatic-substituted fatty monoamines include:
These are propyl-substituted cyclohexylamine, phenyl-substituted cyclopentylamine and pyranyl-substituted cyclohexylamine.

82- Suitable aromatic amines include those in which the carbon atom of the aromatic ring is directly attached to the amino nitrogen. The aromatic ring is usually a mononuclear aromatic ring (derived from benzene), but may also include fused aromatic rings, especially those derived from naphthylene. Examples of aromatic monoamines include aniline, so()f-dimethylphenyl)amine, naphthylamine,
N-(n-butyl)aniline and the like.

Examples of aliphatic-substituted, alicyclic-substituted, and heterocyclic-substituted aromatic monoamines include: 9-ethyl alcohol.

Dianiline, 9-raddecylaniline, cyclohexyl-substituted naphthylamine, and chenyl-substituted aniline.

Suitable polyamines are similar to the monoamines described above except for the presence of another amine nitrogen in the structure. Another amino nitrogen may necessarily be a primary, secondary or tertiary amino nitrogen. Examples include N-aminoglobyl-cyclohexylamine, N,N'-no-f-halarphenylenesoamine, bis(noclaraminophenyl)methane, and 1,4-diaminocyclohexane.

Heterocyclic mono- and polyamines are also used. ``Heterocyclic mono- and polyamines'' are heterocyclic amines containing at least one primary or secondary amino group and at least one nitrogen as a heteroatom in the heterocycle. It is. However, as long as at least one primary or secondary amino group is present in the heterocyclic mono- and polyamines,
The N atom of the base may be a tertiary amino group. Heterocyclic amines may be saturated or unsaturated and may contain various substituents such as nitro, alkoxy, alkylmercapto, alkyl, alkenyl, allyl, alkaryl, aralkyl, and the like. Generally, the total number of carbon atoms in the substituent is about 20
Heterocyclic amines containing nitrogen as a heteroatom do not exceed 2
Is it a problem even if it contains more than one element, and is it a different atom other than nitrogen, such as V element or sulfur? : You can say it. Vertical and six-membered heterocycles are preferred.

Suitable heterocyclic amines include aziridines, azetidines, azolidines, tetra- and nohydropyridines,
Virolles, indoles, piperidines, imidazoles, di- and tetra-hydroimidazoles, piperazines, isoindoles, purines, morpholines,
thiomorpholines, N-aminoalkylmorpholines,
N-aminoalkylthiomorpholines, N-aminoalkylpiperazines, N,N'-diaminoalkylpiperazines, azepines, azocines, azoenes, azecines, and their di-, tetra- and perhydro derivatives, as well as their two It is a mixture of more than one species. Preferred heterocyclic amines are saturated five- and six-membered heterocyclic amines containing only one nitrogen, oxygen and (
or) containing sulfur, especially piperidines, piperazines, thiomorpholines, morpholines, pyrrolidine M! It is. Particularly preferred are piperidine, aminoalkyl-substituted piperidone, piperazine, amino-85-alkyl-substituted piperazine, morpholine, aminoalkyl-substituted morpholine, pyrrolidine, and aminoalkyl-substituted pyrrolidine. Usually, the substituent aminoalkyl 1 is attached to a nitrogen atom that forms part of the heterocycle. Specific examples of such heterocyclic amines are N-aminopropylmorpholine, N-aminoethylpiperazine, and N,N'-diaminoethelpiperazine.

Hydroxyamines similar to the amines described above are also useful, provided they have at least one primary or secondary amino group. Therefore, hydroxyamines having only a tertiary amino group, such as trihydroxyethylamine, are excluded as amines. However, such hydroxyamines can be used as the alcohols described below. The hydroxyamines intended here are:
Those in which Cal has a hydroxyl group directly bonded to a carbon other than the nyl carbon, i.e., thia /l/ = 1f as r-r
It has a hydroxyl group that can function as I4. Examples of such hydroxyamines include ethanolamine, di(3-hydroxypropyl)amine, 3-hydroxybutylamine, 4-hydroxybutylamine, jetanolamine,
No(2-hydroxypropyl)amine, N-(hydroxypropyl)globylamine, N-(2-hydroxyethyl)cyclohexylamine, 3-hydroxycyclopentylamine, Noya-dihydroxyaniline, N-
Hydroxyethylpiperazine and the like.

Hydroxyamine and aminoalcohol refer to the same class of compounds and are used interchangeably. In this specification, hydroxyamine includes amino alcohol and hydroxyamine.

Similarly suitable as amines are those of the general formula % (where R3 is -OH, -NH2, 0NH4, etc., R is a polyvalent organic group having a valency equal to x y, R5 and R8 are hydrogen, a hydrogelbyl group, or a substituted hydrocarbyl group, and at least one of R5 and Rc is hydrogen per aminosulfone molecule,
is an integer of 1 or more)
There are 84 bodies of M't fc B'c. From the above formula,
It can be seen that each aminosulfonic acid-based reactant has at least one hanging ζ or H2N- group and at least one 1-S-R3 group. These aminosulfonic acids may be aliphatic, cycloaliphatic or aromatic aminosulfonic acids, and may also be 1'-functional derivatives of the sulfo group. Specifically, aminosulfonic acids are aromatic sulfonic acids, that is, R is a polyvalent aromatic group such as phenylene, and at least one -8-R3 group is directly bonded to the core carbon of the aromatic ring group. Get help with things. The aminosulfonic acids may also be monoamino aliphatic sulfonic acids where X is 1 and IRa is a polyvalent aliphatic group such as ethylene, propylene, trimethylene and 2-methylenepropylene.

Other suitable aminosulfonic acid and acid conductors are disclosed in US Pat. Nos. 3,926,820, 3,029,250, and 3,367,864.

Hydrazine and substituted hydrazines can also be used as amines. At least one of the nitrogens in the hydrazine must have an aqueous system directly connected to it. Preferably, there are at least two hydrogens directly bonded to the hydrazine atom, and more preferably both hydrogens are bonded to the same nitrogen. Substituent groups that may be included in hydrazine include groups such as alkyl, alkenyl, aryl, aralkyl, and alkaryl. Typically, 1f candidate groups are alkyl groups, especially lower alkyl groups, phenyl groups, and substituted phenyl groups such as lower alkoxy-substituted phenyl groups and lower alkyl-substituted phenyl groups. Specific examples of substituted hydrazine are 89
- Methylhydrazine, N,N-dimethylhydrazine, N,N'-dimethylhydrazine, phenylhydrazine, N-phenyl-N'-ethylhydrazine, N-(
para-tolyl)-N'-(n-butyl)hydrazine, N
-(para-nitrophenyl)hydrazine, N-(para-
nitrophenyl)-N-methylhydrazine, N,N'-
These include no(para-fluorophenol)hydrazine, N-phenyl-■-cyclohexylhydrazine, and the like.

The high molecular weight hydrocarbyl amines (monoamines and polyamines) used as amines in this invention are:
Generally, they are prepared by reacting a chlorinated polyolefin having a molecular weight of at least about 400 with ammonia or an amine. Such amine values are well known,
Examples are U.S. Pat. No. 3,275,554 and U.S. Pat.
It is described in No. 757. All that is required for these amines to be used is that they have at least one primary or Fi, secondary amino group.

90- Another group of amines suitable for use in this invention are branched polyalkylene polyamines. The amine is an aminoalkylene bonded to nitrogen for every 9 amine units present on the main chain (i.e., 1 to 4 branches per 9 units on the main chain). However, there is preferably one chain for every nine primary amino groups and at least one tertiary amino group of the main chain.

Thisra polyalkylene polyamine has the formula (R1 an alkylene group such as ethylene, propylene, butylene and other congeners (straight or branched), preferably an ethylene group, X, y and 2 are integers, e.g. X is 4 ~2
y is preferably 4 or more, preferably 6 to 18, y is 1 to 6 or more, preferably 1 to 3.2 is 0 to 6, preferably 0-1). The X units and the yj1 position may be continuous, alternating, ordered, or random.

Preferred polyalkylene polyamines have the formula (ζ where,
n is an integer, for example, 1 to 20 or more, preferably 1 to 3, and R is preferably ethylene, but may also be propylene, butylene, etc. (straight or branched chain).

Preferred ones are shown by the formula (where n=1 to 3). The groups within the parentheses above are connected head-to-head or head-to-tail. The compound represented by this formula is polyamine N-400゜N-800, N-120
It is commercially available as 0 etc. Polyamine N-400 has n=1 in the above formula.

US Pat. No. 3,200,106 and US Pat. No. 3,259,578 describe a method for producing the above-mentioned polyamine and a method for reacting it with a carboxylic acid-based acylating agent, and similar methods can be used in the present invention.

Suitable amines include polyoxyalkylene polyamines such as polyoxyalkylene diamines and polyoxyalkylene triamines having an average molecular weight of about 200 to 4000, preferably about 400 to 2000. Examples of these polyamines include the formula % (where m is about 3 to 70, preferably about 10 to 35); R6 alkylene + 0-alkylene → 7NH2] 3-6
(Here, n is a value such that the total value is about 1 to 40,
However, the sum of all n is about 3 to about 70, generally about 6 to about 35, and R is a polyvalent saturated carbyl group having up to 10 carbons.

Alkylene may be straight or branched and has carbon atoms of from 7 to 7 and usually from 1 to 4 carbons. Each alkylene in each of the above formulas may be the same or different.

Specific examples of the above polyoxyalkylene diamines include CH, CH3 94- (wherein, X is about 3 to 70, preferably about 10 to 35), and H5 (where x + y + z is about 3 to 30, preferably about 5 to 10).

Preferred polyoxyalkylene polyamines include polyoxyethylene and polyoxypropylene diamines and polyoxynolopylene triamines having an average molecular weight of about 200 to 2000. These polyoxyalkylene polyamines are manufactured by, for example, Soefason Chemical Co., Ltd.
Kanno arm knee collar [Chefamine D-230, D-40
0, D-1000, D-, 2000, T-403, etc.

U.S. Pat. No. 3,804,763 and U.S. Pat. No. 3,948,800 describe such polyoxyalkylene polyamines and a method for acylating the same with a carboxylic acid acylating agent. The most preferred amines are alkylene polyamines including polyalkylene polyamines, which will be described in detail hereinafter. The alkylene polyamine has the formula (where n is 1 to about 10,
Each t is a hydrogen atom, a hydrocarbyl group having up to about 30 carbon atoms is also a hydroxy-substituted hydrocarbyl group, and "alkylene" has from about 1 to about 10 carbon atoms, preferably ethylene or propylene. ). Particularly preferred are alkylene polyamines in which each t is hydrogen; most preferred are ethylene polyamines and mixtures thereof. usually,
On average, n is about 2 to about 7. Examples of such alkylene polyamines include methylene polyamines,
Ethylene polyamine, butylene polyamine, propylene polyamine, benchlene polyamine, hexylene polyamine, hexylene polyamine, etc. Also included are higher homologs as well as related aminoalkyl-substituted piperazines.

Examples of useful alkylene polyamines include ethylene diamine, triethylene tetraamine, propylene diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene) triamine, tripropylene tetraamine, tetra These include ethylenepentamine, trimethylenediamine, pentaethylenehexamine, di(trimethylene)triamine, N-(2-aminoethyl)piperazine, 1,4-bis(2-aminoethyl)piperazine, and the like. Both higher homologues obtained by condensing two or more of the above alkylene amines and mixtures of two or more of the above polyamines are useful.

The above ethylene polyamines are particularly useful due to their cost and effectiveness. Such polyamines are described in Kirkhu Ozmer's Encyclopedia of Chemical Technology, 2nd edition, Volume 7, pages 22-39.
and ψ Hyeramines'.

The compounds are most advantageously prepared by reaction of alkylene chloride with ammonia'' or by reaction of ethyleneimine with a ring-opening reagent such as ammonia.The result of this reaction is an alkylene polyamine containing cyclic condensation products such as piperazine. A somewhat complex mixture of is produced.

Also useful are hydroxyalkylalkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atom. Preferred hydroxy-substituted alkylene polyamines are those in which the hydroxyalkyl groups are lower hydroxyalkyl groups, ie, have fewer than 8 carbons.

Examples of hydroxyalkyl-substituted polyamines such as 98- Norovir-substituted diethylenetriamine, dihydroxynorovir-substituted tetraethylenepentamine, N-
(3-hydroxybutyl)tetramethylenediamine and the like. Higher homologues obtained by condensing the above hydroxyalkylene amines via the amino or hydroxy group are also useful. Combination through the amine group gives higher amines with elimination of ammonia, while condensation through the hydroxyl groups gives products forming ether bonds with elimination of water.

Substituted carboxylic acid derivatives obtained by reaction of acylating agents with amines give acylated amines of amine salts, amides, imides and imidacillins and mixtures thereof. In order to produce a carboxylic acid salt conductor from an acylating agent and an amine, one or more acylating agents and one or more amines are optionally mixed in a normally liquid substantially inert organic liquid solvent/ In the presence of a diluent, from about 80°C to the decomposition temperature (
(i.e., at a temperature at which the reactants and products decompose to the extent that they interfere with the production of the desired chemical), typically from 100°C to about 300°C (provided that 300°C does not exceed the decomposition temperature). . Typically, temperatures of about 125°C to about 250°C are used. What are acylating agents and amines? Acylating agent 1
The reaction is carried out at a ratio of about 0.5 equivalents to 2 moles of amine per equivalent. One equivalent of amine corresponds to the quotient of the amine molecular weight divided by the total number of nitrogens present. That is, octylamine has an equivalent weight corresponding to its molecular weight, ethylenediamine has an equivalent weight corresponding to its molecular weight A, and t7'c
7minoethylbiperazine has an equivalent weight corresponding to 1/3 of its molecular weight. Also, for example, the equivalent weight of a commercially available polyalkylene polyamine mixture corresponds to the quotient of the atomic weight of nitrogen (14) divided by the %N in the polyamine. Therefore, 3
A polyamine mixture with 4% nitrogen has an equivalent weight of 41.2. The number of equivalents of the acylating agent depends on the number of carboxylic acid functional groups (eg, carboxylic acid groups or functional derivatives thereof) present in the acylating agent.

That is, the number of equivalents of the acylating agent varies depending on the number of caloxy groups present. In determining the number of equivalents of the acylating agent, carboxylic acid functional groups that cannot react as an acylating agent are excluded. However, in general, one equivalent of the acylating agent will be present for each cal-oxy group in the acylating agent. For example, the acylating agent obtained by reacting 1 mole of olefin polymer with 1 mole of maleic anhydride is 2 equivalents. Techniques for determining the number of carboxylic acid functional groups (e.g., acid number, saponification number) are obvious and therefore methods for determining the number of equivalents of the acylating agent used in the reaction with the amine. is also clear.

U.S. Pat.
A method for preparing the acylated amines of No. 1- et al. is described), which method is also applicable to the reaction of the acylating agents of this invention with the amines mentioned above. To apply the methods of these patents to the present invention, the high molecular weight acylating agents disclosed in these patents may be replaced with the acylating agents of the present invention on a similar basis.

That is, if one equivalent of high molecular weight acylating agent is used in the above patent, one equivalent of the acylating agent of this invention can be used.

Alcohol (b) Alcohol (b) useful in preparing carboxylic acid fatty conductors from the previously described acylating agents has the formula % (where R3 is bonded to the 10H group by a carbon-oxygen bond). (i.e., -COH, where the carbon is not a carbunyl carbon), where m is an integer from 1 to about 10, usually from 2 to about 6. Like the reactants, alcohols are also aliphatic,
Can be alicyclic, aromatic or heterocyclic, including aliphatic substituted aliphatic alcohols, aliphatic substituted aromatic alcohols, aliphatic substituted heterocyclic alcohols, alicyclic substituted aliphatic alcohols, alicyclic Also included are substituted aromatic alcohols, alicyclic substituted heterocyclic alcohols, heteroaromatic substituted aliphatic alcohols, heteroaromatic substituted aliphatic alcohols, and heteroaromatic substituted aromatic alcohols. Monohydric and polyhydric alcohols corresponding to the formula Rs+OH) usually contain no more than about 40 carbon atoms, and generally no more than about 20 carbon atoms. These alcohols may contain the same types of non-hydrocarbon groups as mentioned for the amines, ie non-hydrocarbon groups that do not interfere with the reaction of the alcohol with the acylating agent. Generally, polyhydric alcohols are preferred.

Polyoxyalkylene alcohols suitable for producing the caldic acid derivatives of this invention include polyoxyalkylene alcohol demulsifiers for aqueous emulsions. [Aqueous emulsion demulsifier] is one molecule of polyoxyalkylene alcohol that can prevent or inhibit the formation of an aqueous emulsion or that can destroy an aqueous emulsion. "
Aqueous emulsion is a generic term for oil-in-water emulsions and water-in-oil emulsions.

Many commercially available polyoxyalkylene alcohol demulsifiers are used. Useful demulsifiers include various organic amines,
Cal? It is a reaction product of acid amide or quaternary ammonium salt and ethylene oxide. Such polyoxyethylated amines, amides and quaternary ammonium salts are commercially available from Armour Industrial Chemical Co. as Ethoduomeen.
)T (an ethylene oxide condensation product of N-alkylalkylene diamines sold under the trade name Niomine T), Ethomido (an ethylene oxide condensation product of fatty acid amides), and Ethoquad (an ethylene oxide condensation product of fatty acid amides) Preferred demulsifiers are liquid polyoxyalkylene alcohols and their derivatives. Derivatives include carboxylic acid esters obtained by reacting alcohols with various carboxylic acids to carry hydrocarbyl ethers. Hydrocarpyl radicals are illustrative of alkyl, cycloalkyl, alkylaryl, aralkyl, argylarylalkyl, and the like groups having up to about 40 carbon atoms. Specific examples of the hydrocarbyl group include methyl, butyl, dodecyl, tolyl, phenyl, naphthyl, dodecylphenyl, p-octylphenylethyl, cyclohexyl, and the like. Carganic acids useful in preparing ester derivatives include acetic acid, valeric acid, lauric acid, stearic acid, succinic acid, alkyl- or alkenyl-substituted succinic acids in which the alkyl A/or alkenyl group has up to about 20 carbons. Etc. mono or political? acid. The alcohols mentioned here are commercially available. For example, sol-mouth 105-nick available from Wyanne Dot Chemical Co., polyglycol 112-2 (liquid triol available from ethylene oxide and propylene oxide) available from Tau Chemical Co., and terditol (dodecylphenyl available from Union Carbide Co., respectively). (polyalkylene glycols and derivatives thereof), but the demulsifier used has on average at least one free alcohol hydroxyl group per molecule of polyoxyalkylene alcohol. In polyalkylene alcoholnide, which is a demulsifier, the alcohol hydroxyl group is bonded to a carbon atom that does not constitute an aromatic nucleus.

This preferred class of polyoxyalkylene alcohols includes polyols obtained as block copolymers. That is, a hydroxy compound R4(-OH)9 (where q is 1 to 6, preferably 2 to 3, R4 is a residue of a monohydric or polyhydric alcohol or a mono or polyhydroxyphenol, naphthol, etc.) alkylene υ lower alkyl group, R6 is the same as H or R5. However, the alkylene oxide does not contain more than 10 carbon atoms) to form a hydrophobic base. Next, this base is reacted with ethylene oxide to create residual water,
In this way, a molecule having a hydrophobic part and a hydrophilic part is obtained. It will be apparent to those skilled in the art that the relative sizes of these fractions can be controlled by controlling the proportions of reactants, reaction times, etc. It will be apparent to those skilled in the art to formulate polyols having hydrophobic and hydrophilic portions in such proportions as to be suitable as demulsifiers for aqueous emulsions. That is, if higher oil solubility is required in a certain lubricating composition, the hydrophobic portion may be increased or the hydrophilic portion may be decreased.

If greater aqueous emulsion breaking ability is required, the hydrophobic and/or hydrophilic portions can be hooked as such.

Examples of R4(-OH) include alkylene glycols and alkane polyols, such as ethylene glycol, nolopylene glycol, trimethylene glycol,
glycerol, pentaerythritol, erythritol, sorbitol, mannitol, etc., as well as aromatic hydroxy compounds such as alkylated and polyhydric phenols and naphthols (e.g. cresols, henotylphenol, dodecylphenol, dioctylphenol, triphenol). hebutylphenol, resorcinol, pyrogallol, etc.).

having 2 or 3 hydroxyl groups, -CHCH2
A polyoxyalkylene polyol demulsifier mainly consisting of a hydrophobic part consisting of -0 (R5 is a lower alkyl group having up to 3 carbon atoms) and a hydrophilic part consisting of a -CH2CH20- group is particularly preferred. This polyol can be produced by first reacting with 2R4-foH)9(q=2) oxide and then reacting the resulting product with ethylene oxide.R4('-0H)9 is
For example, TMP()limeterolpropane L TME
()! J methylolethane), ethylene glycol, trimethylene glycol, tetramethylene glycol, tri(β-hydroxyglobil)amine, 1.4-
(2-hydroxyethyl)cyclohexane, N, N, N
',N'-tetrakis(2-hydroxyzorovir)
Ethylenediamine, N, N, N', N'-tetrakis (
2-hydroxyethyl)ethylenecyamine, naphthol, alkylated naphthol, resorcinol, or others mentioned above.

The polyoxyalkylene alcohol demulsifier should have an average molecular weight of 1,000 to about 10,000, preferably about 2,000 to about 7,000.

Ethyleneoxy groups (-CH2CH2O-) usually constitute about 5 to about 40% of the total average molecular weight. Particularly useful are polyoxyalkylene polyols in which the ethyleneoxy groups make up from about 10 to about 109-30 molecules of the total average molecular weight. Polyoxyalkylene polyols having an average molecular weight of about 2,500 to about 6,000, of which about 10 to 20% by weight are ethyleneoxy groups, produce esters with particularly good demulsifying properties. Ester and ether derivatives of these polyols are also useful.

Representative of such polyoxyalkylene polyols are liquid polyols available from Wyandotte Φ Chemical Company under the name Pluronic and other similar polyols.

Pluronic is a formula (where x, y and 2 are integers greater than 1, -C
f (2CH20- group is about 10 to about 1 of Dalicol molecular weight
5. Average molecular weight from about 2500 to about 4500
). This type of polyol is obtained by reacting noropylene glycol with noropylene oxy-11F-site and then with ethylene oxide.

A preferred class of polyoxyalkylene alcohol demulsifiers mentioned above is Tetronic, available from Winetod Chemical Company.

This polyol is represented by the formula: This polyol is disclosed in U.S. Patent No. 297952.
It is stated in No. 8. Corresponds to the above formula, approximately 10,000
Polyols having an average molecular weight of 1 and whose ethyleneoxy groups fall within the above-mentioned range are preferred. A specific example is a polyol having an average molecular weight of about 8000, of which 7.5 to 12% by weight are ethyleneoxy groups. Such polyols are prepared by reacting alkylene diamines such as ethylene diamine, propylene diamine, hexamethylene diamine, etc. with propylene oxide to create a hydrophobic moiety, and then reacting the resulting product with ethylene oxide to add hydrophilic units. can get.

Another commercially available polyoxyalkylene polyol demulsifier belonging to this preferred group is Polyglycol 112 from Dow.
-2, a triol having an average molecular weight of about 4000-5000, made from nolopyrene oxide and ethylene oxide, with the ethylene oxy groups making up about 18% of the triol molecular weight. This triol is obtained by first reacting glyceryl, TMEXTMp, etc. with propylene oxide to form a hydrophobic base, and then reacting this base with ethylene oxide to add a hydrophilic moiety.

Alcohols useful in this invention include alkylene glycols and polyoxyalkylene alcohols, e.g.
(d' Polyoxyethylene alcohol, polyoxypropylene alcohol, polyoxybutylene alcohol, etc. are also included. These polyoxyalkylene alcohols (also called polyglycols) are oxyalkylene groups in which the alkylene group has 2 to about 8 carbon atoms 'rls.

It may contain up to 100%. The polyoxyalkylene alcohol is generally a dihydric alcohol, ie, one having 10H groups at each end of the molecule.

In order for such a polyoxyalkylene alcohol to be useful, it must have at least one such -0H group. However, the remaining 10H groups may be esterified with a monovalent aliphatic or aromatic carboxylic acid having up to 20 carbon atoms, such as acetic acid, propionic acid, oleic acid, stearic acid, benzoic acid. Monoethers of the above alkylene glycols and polyoxyalkylene glycols are also useful. These include monoaryl ether,
Includes monoalkyl ethers and monoaralkyl ethers. This group of alcohols has the general formula % (where Rc is aryl, e.g. phenyl, lower 113
- Alkoxyphenyl 1 fc Id low R7 rukylphenyl; lower alkyl such as ethyl, propyl, t-butyl, pentyl, etc.; or aralkyl such as benzyl, phenylethyl, phenylpropyl, p-ethylphenylethyl, pif, preferably from 0 to about 8 is 2 to 4
) can be shown. Polyoxyalkylene glycols in which the alkylene group is ethylene or nolopyrene and p is at least 2 and their monoethers as described above are very useful.

Monohydric and polyhydric alcohols useful in this invention also include monohydroxy and polyhydroxy aromatic compounds. -hydric and polyhydric phenols and naphthols are preferred hydroxyaromatic compounds. These hydroxyaromatic compounds may contain other substituents in addition to the hydroxy group, such as hahalo, alkyl, alkenyl, alkoxy, alkylmercapto, nitro, and the like. Usually hydroxyaromatic compounds contain 1 to 4 hydroxy groups and b
Ru. Specific examples include phenol, p-chlorophenol, p-nitrophenol, β-naphthol, α-naphthol, cresols, resorcinol, catechol, carvacrol,
thymol, eike9nol, p,p'-nohydroxybiphenyl, hydroquinone, pyrogallol, chlorodarcinol, hexylresorcinol, orcine, guaiacol, 2-chlorophenol, 2.4-)butylphenol, noropene tetramer f&phenol, Nododecylphenol, 4,4'-methylene-bis-methylene-bis-phenol, α-decyl-β-naphthol, polyimbutenyl (molecular weight (Mw) approximately 1000) substituted phenol, as well as henotylphenol and formal
These are the condensation product with 0.5 mole of human, the condensation product of octylphenol with acetone, di(hydroxyphenyl)oxide, no(hydroxyphenyl)sulfide, no(hydroxyphenyl)nosulfide, and 4-cyclohexylphenol.

Particular preference is given to phenol itself and to phenols directly substituted with aliphatic hydrocarbons, such as alkylated phenols with up to 3 aliphatic hydrocarbon substituents. Common aliphatic hydrocarbon substituents can contain 100 or more carbon atoms, but carry from 1 to 20 carbon atoms. Alkyl and alkenyl groups are preferred aliphatic hydrocarbon substituents.

Further examples of alcohol include methanol,
Ethanol, isooctatool, dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol, II
-Phenylethyl alcohol, 2-methylcyclohexanol, β-chloroethanol, monopropyl ether of ethylene glycol, monododecyl ether of triethylene glycol, monostearate of ethylene glycol, monostearate of diethylene glycol, 8e
c-pentyl alcohol, t-butyl alcohol, 5-
Dioleates of bromododecanol, nitrooctadecanol, and glycerol. Alcohols useful in this invention may be unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, 1-cyclohexen-3-ol and oleyl alcohol.

Other useful alcohols include ether alcohols and amino alcohols, such as oxyalkylene, oxyarylene, aminoalkylene and aminoarylene substituted alcohols containing one or more nooxyalkylene, aminoalkylene or 7-minoaryleneoxyarylene groups. It is. Examples include cellosolve, carbit, phenoxyethanol, heptyl phenyl (oxypropylene → jO1 () octyl (oxyethylene) OH% phenyl (oxyarylene + "OH1 mono (heptylphenyl-oxypropylene) oxide), amine ethanol,
3-amino-ethylpentanol, di(hydroxy=11
7-ethyl)amine p-aminophenol, tri(hydroxypropyl)amine, N-(hydroxyethyl)
These include amine, p-aminephenol, tri(hydroxypropyl)amine, N-hydroxyethylethylenediamine, N,N,N',N'-tetrahydroxytrimethylenediamine, and the like.

The polyhydric alcohol preferably contains from about 2 to about 10 hydroxy groups. An example of this is ethylene glycol, diethylene glycol-A, ,')! J ethylene glycol, tetraethylene glycol, diethylene glycol, tripropylene glycol, diethylene glycol, tributylene glycol, and other alkylene glycols and polyoxyalkylene glycols in which the alkylene group contains from 2 to about 8 carbon atoms. alkylene glycols and polyoxyalkylene glycols.

Examples of other useful polyhydric alcohols include 118-glycerol, monooleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, n-butyl ester of 9.10-dihydroxystearic acid, 9. -10-dihydroxystearic acid trimethyl ester, l,2-butanediol, 2,3-hexanediol, 2,4-hexanediol, pinacol, erythritol, arabit, sorbitol, mannitol, 1,2-cyclohexanediol, and xylene glycol. sucrose,
Carbohydrates such as starch, ramose, mantool, glyceraldehyde and galactose are also used.

It has at least 3 hydroxyl groups, some but not all of which are about 8
Also useful are aliphatic monocals having up to about 30 carbon atoms esterified with phosphoric acid. Further examples of these partially esterified polyhydric alcohols include:
These include sorbitol monooleate, sorbitol distearate, glycerol monooleate, glycerol monostearate, and erythrite didodecanoate.

A preferred class of alcohols suitable for use in this invention are polyhydric alcohols having up to 12 carbon atoms;
In particular, polyhydric alcohols having 3 to 10 carbon atoms. The In alcohols include glycerol, erythritol, pentaerythritol, dipentaerythritol, gluconic acid, glyceraldehyde, glucose, arabinose, 1,7-hebutanediol, 2,4-hebutanediol, 1, 2.3-hexanetriol, 1,2.4
-Hexanetriol, 1.2.5-hexanetriol, 2,3.4-hexanetriol, 1.2.3-butanetriol, 1,2.4-butanetriol, quinic acid, 2,2,6.6 -tetrakis-(hydroxymethyl)cyclohexanol, 1,10-decanediol, nogitalose, and the like. The number of hydroxyl groups is at least 3
and aliphatic alcohols having up to 10 carbon atoms are particularly preferred.

A particularly preferred class of polyhydric alcohols for use in this invention are polyhydric alkanols having 3 to 1 carbon atoms, especially polyhydric alcohols having 3 to 6 carbon atoms and at least 3 hydroxyl groups. be. Examples of such alcohols include glycerol, erythritol, pentaerythritol, mannitol, sorbitol, 2-hydroxymethyl-
2-methyl-1,3-propanediol (trimethylolethane), 2-hydroxymethyl-2-ethyl-1,
3-Glononzool (trimethylolethane)
, 1,2,4-hexanetriol, and the like.

From the above it can be seen that amines may contain alcoholic hydroxy substituents and alcohols may contain primary, secondary or tertiary amino substituents. That is, amino alcohols can be classified as both amino and alcohols if they contain at least one primary or secondary amino group.

If only tertiary amino groups are present, aminoalcohols belong only to alcohols.

Amino alcohols contemplated for use in this invention have one or more amine groups and one or more hydroxyl groups. Examples of suitable amino alcohols include 2-hydroxyethylamine, 3-
Hydroxybutylamine, no(2-hydroxyethyl)-amine, tri(2-hydroxyethyl)amine,
No(2-hydroxynorobyl)amine, N, N, N'
-) Lee(2-hydroxyethyl)ethylene cyamine, N,N,N',N'-tetra-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piperazine, N,N'-no( 3-hydroxynorovir)piperazine, N-(2-hydroxyethyl)morpholine, N-(2-hydroxyethyl)L2-morpholine, N-(2-hydroxyethyl)-3-methyl-2-
Morpholine, N-(2-hydroxypropyl-122-l)-6-methyl-2-morpholine, N-(2-hydroxyethyl)-5-cal? Ethoxy-2-piperitone, N-(2-hydroxypropyl)-5-carboethoxy-2-piperidone, N-(2-hydroxyethyl)
-5-(N-butylcarbamyl)-2-piperitone, N
-(2-hydroxyethyl)piperidine, N-(4-hydroxyethyl)piperazine, N-(hydroxy-lower alkyl)amines and polyamines of N,N-di(2-hydroxyethyl)glycinenato, and these and fatty acids. group alcohols, especially lower alkanols, N,
There are ethers such as N-si(3-hydroxypropyl)glycine. Also contemplated are other mono- and poly-N-hydroxyalkyl-substituted alkylene polyamines such as those mentioned above, particularly those in which the alkylene group has 2 to 3 carbon atoms, and 7, where the polyamine is the reaction product of about 2 moles of nolopyrene oxide and 1 mole of soethylenetriamine.
Some contain up to 3 amine groups.

Furthermore, as amino alcohols, US%F! l-
3,576,743, where Rd is a monovalent organic group containing at least one alcohol hydroxyl group, and the total number of carbon atoms in C1Rd is approximately There are hydroxy-substituted primary amines represented by the formula (not exceeding 20).

Hydroxy-substituted aliphatic primary amines having up to 10 total carbon atoms are particularly useful. Particularly preferred are
Polyhydroxy-substituted alkanol primary amines having one alkyl substituent with up to 10 carbon atoms and only one amino group having up to 6 hydroxyl groups. These alkanol primary amines correspond to R, -NH2, where R4 is a mono- or poly-hydroxy substituted alkyl group. It is desirable that at least one of the hydroxyl groups is a primary alcoholic hydroxyl group. Trismethylaminomethane is the single most preferred hydroxy-substituted primary amine. Specific examples of hydroxy-substituted primary amines include 2-amino-1-butanol, 2-amino-1-butanol,
Amino-2-methyl-1-propatool, p-(β-hydroxyethyl)aniline, 2-amino-1-propatool, 3-amino-1-propatool, 2-amino-2
-Methyl-1,3-pronononsol, 2-amino-
2-Ethyl-1,3-fronomandiol, N-(β-
hydroxypropyl)-N'-(β-aminoethyl)piperazine, tris(hydroxymethyl)aminomethane (
(also known as trismethylolaminomethane), 2-amino-1
-butanol, ethanolamine, β-(β-hydroxyethoxy)ethylamine, glucamine, glucamine, 4-amino-3-hydroxy-3-methyl-1-butene (known in the art by reacting isoprene oxide with ammonia). N-3-(aminonorovir)-4-(2-hydroxyethyl)piperazine, 2-a,mino-6-methyl-6
-heptanol, 125- 5-amino-1-pentanol, N-(β-hydroxyethyl) -1,3-diaminoprono(n), 1,3-diamino-2-hydroxyethylyann, N-(/y- Hydroxyethoxyethyl) ethylenenoamine, etc.

Hydroxy-substituted primary amines intended to be useful as amines and/or alcohols are described in US Pat. No. 3,576,743.

The carboxylic acid functional groups produced by reacting the acylating agents of this invention with alcohols are esters. Both acidic esters and neutral esters are within the scope of this invention. Acidic esters are those in which some of the carboxylic acid functionalities in the acylating agent are not esterified and the free cal is present as a xyl group. Clearly, acidic esters are readily prepared by using an amount of alcohol insufficient to esterify all of the carboxy groups in the acylating agents of this invention.

The acylating agent is reacted with the sia-126-alcohol by conventional esterification techniques. This typically involves heating the acylating agent of the invention with an alcohol, optionally in the presence of a typically liquid, substantially inert organic liquid solvent/diluent and/or in the presence of an esterification catalyst. . Temperatures from at least about 100° C. to decomposition point 1 are used (decomposition points have already been described). This temperature is usually about 100
Within the range from ℃ to about 300℃, about 140℃ to 2
A temperature of 50° C. is used. Typically, at least v2 im of alcohol is used per equivalent of acylating agent. One equivalent of acylating agent is the same as described above for the reaction with the amine. One equivalent of alcohol is the molecular weight divided by the total number of hydroxyl groups present in the molecule. Therefore, one equivalent of ethanol is its molecular weight, and an equivalent of ethylene glycol is one-half its molecular weight. The equivalent weight of an amino alcohol is equal to the molecular weight divided by the total number of hydroxyl groups and nitrogen atoms present in the molecule.

A number of issued patents describe processes in which high molecular weight carboxylic acylating agents are reacted with alcohols to form acidic and neutral esters. These contacts are applicable to the production of esters from the acylating agents of this invention and the alcohols above.

All that is required is that the acylating agents of this invention or the high molecular weight carboxylic acylating agents discussed in these patents are typically used on an equivalent basis. The following U.S. patent discloses a preferred method of reacting the acylating agents of this invention with the alcohols described above and is hereby incorporated by reference: No. 3,331,776.
No. 3.381. ．． No. 022; No. 3,522,179
No. 3,542,680; No. 3,697,428; No. 3,755,169.

a reactive range or group useful as reactant (c);
Compounds of the genus include those that form carboxylic acid gold peach salts with the acylating agent of the present invention, and carboxylic acid visiting conductors produced by reacting acylated horn 1 with the above-mentioned amines and/or alcohols. It forms a metal-containing complex. Reactive gold bullion compounds useful as (c) to form complexes with the reaction products of acylating agents and amines include those disclosed in US Pat. No. 3,306,908. Complex-forming metal compounds useful as (c) include cadmium and 4[(
chromium, manganese, iron, cobalt, nickel, copper and zinc) nitrates, nitrites, halodides, carnates, phosphates, phosphites, sulfates, sulfites, carbonates, borates Examples include salts and oxides.

These metals are so-called transition metals or coordinating metals. However, these metals are capable of forming complexes due to their sub-valencies or coordination valences. Specific examples of complex-forming metal compounds useful as the reactant (c) in this invention include cobaltous nitrate, cobaltous oxide, cobaltous oxide, cobalt nitrite,
Cobaltous phosphate, cobaltous chloride, 129-cobaltous chloride, cobaltous carbonate, chromous acetate, dichromic acetate, dichromic bromide, chromic chloride, dichromic fluoride, dichromic oxide Chromium, chromium dioxide, dichromium oxide, average dichromium, chromium monosulfate heptahydrate, (dichromium IC acid, dichromium formate, dichromium hexanoate, chromium oxychloride, tinnitus MM dichrome,
Manganese acetate, manganous benzoate & manganese, manganous carbonate, manganese dichloride, manganous trichloride, manganous citrate, manganous formate, manganous nitrate, manganous oxalate, manganous oxide, Manganese dioxide, manganese trioxide, manganese soil oxide, manganese phosphate, manganese birophosphate, manganese metaphosphate, manganese hypophosphite, valerian & m-manganese,
Ferrous acetate, ferric benzoate, ferrous bromide, ferrous carbonate, ferric formate, ferrous lactate, ferrous nitrate, ferrous oxide,
Ferric oxide, ferric hypophosphite, Wc acid ferric acid #L
Ferric acid, ferric hydrosulfite, northern nickel diodoro, 13F nickel dichloride, nickel nitrate, nickel dioleate, nickel suderate, nickel sulfite, cupric noropionate,
Cupric acetate, cupric metaborate, cupric benzoate, cupric formate, cupric turine, cupric nitrite, cupric oxychloride, cupric thioluminate, cupric salicylate Dicopper, zinc benzoate, zinc borate, zinc bromide, zinc chromate, zinc dichromate, zinc iodide, zinc lactate, zinc nitrate, zinc oxide, zinc stearate, zinc sulfite, cadmium benzoate, cadmium carbonate , cadmium butyrate, cadmium chloroacetate, cadmium fumarate, cadmium nitrate, cadmium dihydrophosphate, cadmium sulfite, and cadmium oxide. Hydrates of the above compounds are particularly advantageous for use in this invention.

U.S. Pat. No. 3,306,908 describes reactive metal compounds suitable for forming such complexes,
and describes a method for preparing the complex. Fundamentally,
These methods are performed by substituting the acylating agent of the present invention on an equivalent basis with the high molecular weight carboxylic acid acylating agent disclosed in U.S. Patent No. 3,306,908. It is applicable to carboxylic acid conductors with amines and as mentioned above. The cancer ratio between the acylated amine thus produced and the metal reaction m* forming a lead body is shown in the above-mentioned patent No. 3.
, 306,908.

US Reissue Patent No. 26,443 discloses metals useful in preparing salts from the reaction of acylating agents with amines such as those described above. Metal salts include alkali metals, alkaline earth metals, zinc, cadmium, lead,
Prepared from cobalt and nickel. Reactant (c)
Examples of reactive metal compounds suitable for use as sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodium pentylade, sodium pentylade, sodium phenoxide,
Potassium oxide, potassium hydroxide, potassium carbonate, potassium methylate, potassium pentylate, potassium phenoxide, lithium oxide, lithium hydroxide, lithium carbonate, lithium pentylate, calcium oxide, calcium hydroxide, calcium carbonate, calcium methylate, Potassium methylate, cadmium methylate, calcium chloride, calcium fluoride, calcium pentylate, calcium phenoxide, calcium nitrate, barium oxide,
Barium hydroxide, barium carbonate, barium chloride, barium fluoride, barium methylate, barium bentelate, barium benteler, barium nitrate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium ethylate, magnesium ethylate, chloride Magnesium, magnesium bromide, magnesium iodide,
Magnesium phenoxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc methylate, zinc zolobyrate, zinc pentylade, zinc chloride, zinc fluoride, zinc nitrate trihydrate,
Cadmium oxide, cadmium hydroxide, cadmium carbonate,
Cadmium methylate, cadmium 7'r-+ bi-133
− Lard, cadmium chloride, cadmium bromide, cadmium fluoride, lead oxide, lead hydroxide, lead carbonate, lead ethylate, lead ventilate, lead chloride, lead fluoride, lead iodide, lead nitrate, nickel oxide, hydroxide Nickel, nickel carbonate, nickel chloride, nickel bromide, nickel fluoride, nickel methylate, nickel pentylate, nickel nitrate hydrate,
Examples include cobalt oxide, cobalt hydroxide, cobaltous bromide, cobaltous chloride, cobalt butylade, and cobaltous nitrate hexahydrate.

The above metal compounds are merely illustrative of those useful in this invention, and this invention should not be considered limited to such compounds.

US Reissue Patent No. 26,443 is incorporated herein by reference as it discloses reactive gold bullion compounds useful as (c) and methods of utilizing these compounds in the formation of salts. Furthermore, when applying the technology of this patent to the present invention, the acylating agent of this invention may be used on an equivalent basis in place of the high molecular weight carboxylic acid-based acylating agent of this patent. It only requires

U.S. Pat. No. 3,271,310 discloses a method for preparing molecular weight carboxylic acylating agents, particularly gold salts of alkenylconophosphates. The metal salts Fi disclosed in Part 1' are acidic salts, neutral salts and basic salts.

Examples of reactive metal compounds used to prepare acidic, neutral, and basic salts of island molecular weight caldic acids as disclosed in U.S. Pat. No. 3,271,310 include lithium oxide, hydroxide, Lithium, lithium carbonate, lithium pentylate, sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodium propylade, sodium phenoxide, potassium oxide, potassium hydroxide, potassium carbonate, potassium methylate, silver oxide,
Silver carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium ethylate, magnesium propizite, magnesi 6-mufenoxide, calcium oxide, calcium hydroxide, -lucium carbonate, calcium methylate, calcium propylade, calcium ethylate , zinc oxide, zinc hydroxide, zinc carbonate, zinc propylade, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium ethylate, nogium oxide, barium hydroxide, barium hydrate, carbonate・Marilum, barium ethylate, lead oxide, lead hydroxide, lead carbonate, tin oxide, tin butirad, cobalt oxide, cobalt hydroxide, cobalt carbonate, conortobenzite, nickel oxide, nickel hydroxide, and carbonic acid. Nickel etc. This invention should not be considered limited to the use of the following metal compounds; these metals are mentioned merely to illustrate the metal compounds included in this invention.

U.S. Pat. No. 3,271,310 discloses that the disclosure in this patent provides exemplary reactive metal compounds suitable for forming the salts of the acylating agents of this invention as well as exemplary methods for preparing salts of these acylating agents. This method is described here for reference. As can be seen, the process of U.S. Pat. No. 3,271,310 is capable of producing the acyl of this invention simply by substituting the acylating agent of this invention in place of the high molecular weight carboxylic acid of this patent. Applicable to oxidizing agents.

From the foregoing description, it can be seen that the acylating agent of the present invention can be used with any individual amine, alcohol, reactive metal, reactive metal compound, or a mixture of two or more of these; It is clear that it is possible to react with more than one amine, one or more alcohols, one or more reactive metals or reactive metal compounds, or mixtures of any of these. As a mixture, a mixture of two yuzu or three or more types of amines, a mixture of two yuzu or three or more types of alcohol, 2
Glaze or three or more metals or reactive metal compounds selected from amines and alcohols, amines and reactive metals or reactive metal compounds, alcohols and reactive metal compounds 137- These include two or more components, or mixtures of two or more components each from amines, alcohols, and reactive metals or reactive metal compounds.

Furthermore, the acylating agents of this invention include amines, alcohols,
Reaction b=b, reactive metal compounds or mixtures thereof can be reacted simultaneously (together) or sequentially in any reaction order, as described above.

Canadian Percentage No. 956,397 discloses methods for sequentially and simultaneously reacting the acylating agents of this invention with amines, alcohols, reactive metals, and reactive metal compounds, or mixtures thereof. Since it is about the process, I will describe it here in Reference 1. All the points necessary to apply the method of this patent to this invention are as follows. It is to be used in. These six carboxylic acid derivatives prepared using the method disclosed in the Canadian patent constitute a preferred class of carboxylic acids or carboxylic acid fatty conductors. The following U.S. patents are similar to the above Canadian patent for the same reasons given in describing the Canadian patent above and are included here for reference: No. 3,836,469; ,47
No. 0; No. 3,836,471; No. 3,838,050
No. 3,838,052; No. 3,879,308; No. 3,957,854; No. 3,957,855;
No. 4.031,118. The Canadian patent and these U.S. patents also illustrate that the amount of polyoxyalkylene alcohol demulsifier used in preparing the dispersant/detergent from the acylating agent of this invention is usually quite small on an equivalent basis. I am posting it here for your reference.

It is also noted that the more preferred carboxylic acid visiting conductors of this invention are those prepared according to the above-referenced Canadian patents and corresponding US patents, omitting the polyoxyalkylene alcohol demulsifier. That is, a preferred class of carboxylic acid preventers of the present invention has the acylating agent of this invention substituted on an equivalent basis, and furthermore, in addition to being different from the polyoxylic acid, the high molecular weight carboxylic acid acylating agent of the above Canadian patent is used. Various reaction products with one or more amines, alcohols, and reactive metal compounds as disclosed herein.

U.S. Pat. No. 3,806,456 also discloses that the disclosure in this patent is a method useful for preparing products from the acylated KM of this invention and polyoxyalkylene polyamines as described above. It is included here for reference. The use of the acylated reagents of this invention on an equivalent basis in place of the high molecular weight carboxylic acid acylating agents disclosed in U.S. Pat. No. 3,806,456 has viscosity index improving properties. This produces a compound that is further characterized.

U.S. Pat. No. 3,576,743 is described herein by reference as this patent discloses a method for preparing carboxylic acid conductors from both polyhydric alcohols and amines, particularly hydroxy-substituted amines. It is something. Also, by using the acylating agents of this invention on an equivalent basis in place of the cylindrical molecular weight carboxylic acylating agents disclosed in U.S. Pat. A composition that provides index enhancement is produced.

U.S. Pat. No. 3,632,510 is hereby incorporated by reference because it discloses a method for preparing mixed ester/metal salts. The mixed ester/metal salts obtained from the acylating agents, alcohols, and reactive metal compounds of this invention can be used in place of the molecular weight carboxylic acid acylating agents of U.S. Pat. No. 3,632,510. can be prepared by following the methods disclosed in this patent except using the agents on an equivalent basis. The carboxylic acid conductors thus produced also represent a preferred aspect of the invention.

U.S. Patent Application No. 160,751 (June 18, 1980)
This application discloses a method for producing a polyamine ester/cal-141-zenic acid derivative useful as (B) in the present invention, and is therefore not described here for reference. be.

Generally, this method consists of the following steps (1) and (II) to form a polyester intermediate:
4) at least one polyhydric alcohol having (B) a number average molecular weight (Mn) of at least about 1200 and a weight average log average molecular weight ratio (Mw/Mn) of about 1.5 to 6;
, a substituted cono-phosphate, which has a substituent derived from at least one alkene and a combination of 0 and which has at least about 1.3 sysuccinic acid groups per substituent in its molecular structure on average. react with an acylating agent; and (II) then, the above polyester for cattle is reacted with (Q
The amine-modified polyester composition is formed by reacting with at least one acylatable polyamine.

This method includes steps (1) above, (necessary to carry out ID 9: 35% by weight of the above amine-modified polyvarnish 142-thiol in a first mineral oil having a kinematic viscosity of 36 to 4.3 centistokes at 100°C). the first solution has a nitrogen content of at least 0.0175% by weight, and the first solution has a kinematic viscosity of 100% by weight;
at 100°C; The second bath solution prepared by dissolving an amount to obtain a second bath having a kinematic viscosity of at least about 9 centistokes;

US Time WFM 3,75 S, R69; No. 3. go4
, No. 763; M3. s6s, 3ao; and 3,9
No. 48,800 is included here for reference since these patents disclose a method for preparing carboxylic acid conductors.

By following the techniques of these patents and by using the acylating agent of the present invention in place of the molecular weight carboxylic acid-based acylating agents of these patents, it is possible to produce a wide variety of carbon fibers within the scope of the present invention. Fatty conductors can be prepared.

The reason for the listing of so many patents is that it is necessary to prepare carboxylic acid-based conductor visit compositions from acylating agents, amines, alcohols, and reactive metals and reactive metal compounds, and mixtures thereof. The steps are believed to be sufficiently within the skill of those skilled in the art that detailed description is not necessary here.

Among the carnic acid derivatives described above, those prepared from an acylating agent and alkylene I amines, especially polyethylene polyamines, and/or polyhydric alcohols, especially polyhydric alkanols, are particularly preferred. As mentioned above, mixtures of polyamines and/or polyhydric alcohols are also contemplated. Typically, all carboxy functional groups of the acylating agents of this invention are either esterified or this preferred group of the carboxylic acid derivative participates in the formation of an amine salt, amide, imide or imidacilline. .

In addition to detergent/dispersant properties, the carboxylic acid derivatives and post-processes discussed herein act as viscosity index improvers, and their viscosity index improving ability is due to the combination of acylating agents and polyfunctional reactants. It is enhanced when prepared by reaction with For example, polyamines having two or more primary and/or secondary amino groups, polyhydric alcohols, one or more primary and secondary amino groups, and one or more hydroxyl groups. and polyvalent metal compounds. It is believed that the polyfunctional reactant acts to "bridge" or crosslink in the carboxylic acid derivative composition, which is responsible to some extent for the viscosity index improvement. However, the mechanism by which the viscosity index improvement of 7 is obtained is not known, and there is no intention to be bound by this theory. Carboxylic acid derivatives derived in whole or in part from polyhydric alcohols can be used to improve the viscosity index in lubricating compositions.
Since it seems to be particularly effective in reducing agent F,
5. The polyfunctionality of substances (a), (b), and (e) may not fully explain the viscosity index improvement properties of carboxylic acid derivatives.

Clearly, however, the amine, alcohol, reactive metal compound reacted with the acylating agent need not all be polyfunctional. Therefore, combinations of monofunctional and polyfunctional amines, alcohols, reactive compounds and reactive metal compounds; for example, monoamines and polyhydric alcohols, -hydric alcohols and polyamines, amino alcohols and reactive metal compounds ( The metal is monovalent), etc. can be used.

・The acylating agent of this invention has not been fully determined so far, but the acylating agent of this invention can be synthesized from an amine, an alcohol, a reactive metal, a reactive metal compound, or a carboxy group (from a succinic acid group or from a maleic acid group). 146- should be reacted with a mixture thereof containing sufficient polyfunctional reactants (e.g., polyamines, polyhydric alcohols) so that at least about 25% of the total number of groups derived from the system reactants are reacted. It seems to be. As far as the viscosity index improving properties of carboxylic acid derivatives are concerned, better results are believed to be obtained if at least 50% of the carboxyl groups participate in reaction with such polyfunctional reactants. In most cases, the best viscosity index improvement is achieved by using a sufficient amount of the acylating agent of this invention to react with at least about 75% of the carboxy groups. This is believed to be achieved when reacting with amines and/or polyhydric alcohols (or amino alcohols). It should be appreciated that the .P-cents described above are theoretical in the sense that it is not necessary that the .o-cents of the carboxyl group actually react with the polyfunctional reactant. Rather, these...
Cent is used to characterize the amount of polyfunctional reactant that desirably reacts with the acylating agent to achieve the desired viscosity index improvement.

Post-treated carboxylic acid derivatives Another aspect of the invention CB) is post-treated carboxylic acid derivatives prepared by reacting one or more post-treatment reagents with one or more carboxylic acid derivatives. can be. In addition, (B) includes a mixture of one or more carboxylic acid derivatives and one or more post-treated carboxylic acid derivatives. Methods for post-treatment of carboxylic acid derivatives include similar induction of prior art high molecular weight carboxylic acid acylating agents. Similar to post-treatment methods used for bodies. Therefore, the same reaction conditions, reactant ratios, etc. can be used.

Acylated nitrogen compounds prepared by reacting the acylating agent of this invention with amines (a) as described above are:
The acylated nitrogen compound composition (eg, carboxylic acid derivative) thus formed is post-treated by contacting it with one or more post-treatment agents. These post-treatment agents include boron oxide, boron oxide hydrate, boron rhodanides, boron-containing acids, boron-containing acid esters,
Carbon disulfide, hydrogen sulfide, sulfur, sulfur chlorides, alkenyl cyanamides, carboxylic acid acylating agents such as terephthalic acid, aldahytes, ketones, urea, thiourea, guanidino, noaanoamide, hydrocarbyl phosphates, hydrocarbyl Phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites, phosphoric oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocarbyl inthiocyanates, epoxides, episulfides, formaldehyde is selected from the group consisting of formaldehyde-generating compounds and phenols, and sulfur and phenols. Acylating agents of this invention and amines as described above (
) and alcohol (b), the same post-treatment agents are used. However, the carboxylic acid derivative of this invention is alcohol (b)
and acylating agents, i.e., when these derivatives are acidic or neutral esters, the post-treatment agents are usually boron oxide, phospho(quadrate hydrate, boron) rhodanide. , boron-containing acids, boron-containing acid esters, sulfur, sulfur chlorides, phosphorus sulfides, phosphorus oxides, carboxylic acid acylating agents such as terephthalic acid, epoxides, and episulfides. be.

Since post-treatment methods involving the use of these post-treatment agents are limitedly known in the prior art for application to reaction products of high molecular weight carboxylic acid acylating agents with amines and/or alcohols, these methods will be described herein. A detailed explanation of is unnecessary.

To apply conventional methods to the carboxylic acid derivatives of this invention, all that is necessary is to apply the reaction conditions, reactant ratios, etc. as described in the prior art to the novel carboxylic acid derivatives of this invention. That's true. The following U.S. patents are listed for reference as they disclose post-treatment methods and post-treatment agents applicable to the carboxylic acid derivatives of this invention: No. 3,087,936
No. 3.200.108; 150- No. 3,254,025; No. 3.256.185; No. 3,278,550; No. 3,2!81,428; No. 3.282 No. .955; No. 3.284,410; No. 3
．． No. 338,832: No. 3,344,069; No. 3.
No. 366.596; No. 3,373,111: No. 3.3
No. 67.943: @3,4 (No. 13,102; No. 3,
No. 428,561; p4'g3.502.677; No. 3,513. Q93; No. 3,533,945; H3
, s 41,012 (Use of acidified clays in post-treatment carboxylic acid derivatives derived from acylating agents and amines of this invention); No. 3.639,242; No. 3.70
No. 8.522; No. 3,859,318; No. 3,865
, No. 813; No. 3,470,098; No. 3. ．． 369
, No. 021; No. 3,184.411; No. 3.185.
No. 645; No. 3.245.908; No. 3,245.9
No. 09; No. 3,245,910; No. 3,573,20
No. 5; No. 3.269.681; No. 3.749.695
No. 3.86/5.740; No. 3,954,639
No. 3,459,530; No. 3.390.086; No. 3.367.943; No. 3.185.704;
No. 3.551. , No. 466; No. 3,415,750;
No. 3,312.619; No. 3,280,034; No. 3,718,663; No. 3,652,616; British Patent No. 1,085,903; British Patent No. 1.162.
No. 4.36; U.S. Patent No. 3,558.743. The methods of these patents as applied to the carboxylic acid derivatives of this invention, and the post-treated carboxylic acid derivative compositions thus produced, form a further aspect of this invention.

The above-described carboxylic acid derivatives, post-treated carboxylic acid derivatives, acylating agents, and methods for their preparation are described in US Pat. No. 4,234,435.

(C) Chlorine-Containing Compounds The chlorine-containing compounds useful in this invention are selected from the group consisting of chloroaliphatic hydrocarbons, chloroalicyclic hydrocarbons, or mixtures thereof.

Furoaliphatic hydrocarbon compounds useful for the purposes of this invention are compounds consisting of a chlorine atom and an aliphatic hydrocarbon group. The term "aliphatic hydrocarbon group" as used in this specification means a group in which an aliphatic carbon atom is directly bonded to a chlorine atom and which has primarily aliphatic hydrocarbon properties. Such bases include:

(1) Aliphatic hydrocarbon groups; for example, alkyl, alkenyl, and aromatic and aliphatic group-substituted alkyl and alkenyl groups. Such groups are known to those skilled in the art.

Examples include ethyl, globyl, butyl, quantyl, octyl, decyl, stearyl, dodecenyl, and oleyl (all isomers included).

(2) Substituted aliphatic hydrocarbon groups; ie, groups containing non-hydrocarbon substituents that do not alter the predominant aliphatic hydrocarbon nature of the group within the context of this invention.

Those skilled in the art will be aware of suitable substituents (eg, alkoxy, hydroxy, alkylthio, carnoalkoxy, nitro).

(3) Heteroaliphatic hydrocarbon group; that is, within the context of this invention, a group which is primarily aliphatic hydrocarbon in nature, but in which atoms other than carbon are present in a chain or ring otherwise composed of carbon atoms. Groups present in Examples of suitable heteroatoms that will be apparent to those skilled in the art include oxygen and nitrogen.

Generally, there will be no more than about 3, and preferably no more than 1, substituent-spanning heteroatoms for every ten carbon atoms in the aliphatic hydrocarbon group.

Preferably, the aliphatic hydrocarbon groups present in the chlorinated compounds of this invention are also free of acetylenic and usually ethylenic unsaturation and contain at least 5 carbon atoms.
Contains.

This aliphatic hydrocarbon group is most often an alkyl group,
Usually an alkyl group.

As used in this specification, the term "alkyl group" means an alkyl group within the scope of the explanation of the term "aliphatic hydrocarbon group", and includes the above-mentioned "aliphatic hydrocarbon group". Similar groups include alkyl hydrocarbon groups, substituted alkyl hydrocarbon groups, and heteroalkyl hydrocarbon groups.

Roloalicyclic hydrocarbon compounds useful for the purposes of this invention are compounds consisting of a chlorine atom and an alicyclic hydrocarbon group. As used in this specification, the term "alicyclic hydrocarbon group" refers to a group in which an alicyclic carbon atom is directly bonded to a chlorine atom and, within the context of the present invention, is primarily alicyclic hydrocarbon in nature. means. Such groups include: (1) Cycloaliphatic hydrocarbon groups; such as cycloalkyl or cycloalkenyl, and aromatic- and aliphatic-substituted cycloaliphatic groups. Such groups are known to those skilled in the art,
Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclooctyl, methylcyclohexyl, cycloenthel, cyclopentagenyl and cyclohexyl.

(2) Substituted cycloaliphatic hydrocarbon group: ie, in the context of this invention, a group containing non-hydrocarbon substituents that do not alter the primarily cycloaliphatic nature of the group. Those skilled in the art will be aware of suitable substituents (eg, alkoxy, hydroxy, alkylthio, carbalkoxy, nitro).

(3) Heteroalicyclic hydrocarbon group; i.e., which is primarily alicyclic hydrocarbon in nature within the meaning of this invention, but in which atoms other than carbon are present in a chain or ring otherwise composed of carbon atoms. Groups that exist. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, oxygen, nitrogen.

Generally no more than 3, preferably no more than 1
A substituent or heteroatom is present for every tenth carbon atom in the alicyclic hydrocarbon group.

Preferably, the cycloaliphatic hydrocarbon groups present in the chlorine-containing compounds of this invention are free of acetylenic and usually also ethylenic unsaturation and contain at least 5 carbon atoms.
Contains.

As mentioned above, the chlorine-containing compound may also be one or a mixture of 2a or more of chloroaliphatic hydrocarbon compounds and/or chloroalicyclic hydrocarbon compounds. In addition, chlorine-containing compounds usually contain chlorine at a concentration of about 30 to about 7
Contains 0 weight coefficient. The preparation of chlorine-containing compounds (C) is well known to those skilled in the art and a detailed explanation of this method is unnecessary. Briefly, such compounds are prepared by reacting chlorine gas with a suitable hydrocarbon compound in a trench that provides the desired capacitance of chlorine.

A preferred chlorine-containing compound is a chlorinated paraffin wax composition. The molecular weight of these chlorinated rough-in wax compositions is usually in the range of about 300 to about 1100, preferably about 350 to about 700, and preferably contains about 35 to 50% by weight of chlorine. These preferred chlorine-containing compounds are commercially available from Diamond Chemicals under the tradename chlorowax.

Sulfurized Olefinically Unsaturated Compounds The compositions of this invention may further be combined with at least one sulfurized olefinically unsaturated compound.

157- The olefinically unsaturated compounds that are sulfurized to obtain the sulfurized olefinically unsaturated compounds useful for the purposes of this invention vary in nature.

They contain at least one olefinic double bond, which is defined as a non-aromatic double bond: ie, one double bond connects two aliphatic carbon atoms. In the broadest sense, an olefin has the formula R7R8C-CR2R1o (
where each of R, , R8, R, and Rlo is hydrogen or an organic group). Generally, the R group that is not hydrogen in the above formula may be a group such as:
Each R is independently hydrogen, alkyl, alkenyl, aryl, substituted alkyl, substituted alkenyl, or substituted aryl, and any two R groups are alkenyl or substituted to form a ring of up to 12 carbon atoms. M may be alkenyl; M is an equivalent of a metal cation (preferably Group 1 or Group II, such as sodium, potassium,
58- Mu, barium, calcium) 'jl';
f Ha.

Y is oxygen or divalent sulfur; Ar is an aryl group or a substituted aryl group having up to 12 carbon atoms in the substituent.

Any two of R7, R8, R9 and R+0 may both be alkylene groups or substituted alkylene groups, or the olefinic compound forming the group may be a cyclic type.

The nature of the substituents on the above-described substituted moieties is generally not an essential aspect of the invention, and any such substituents are compatible or compatible with the lubricating environment and are not hindered under the intended reaction conditions. It is useful to keep the key in place. As such, substituted compounds are not intended to be unstable enough to deleteriously decompose under the reaction conditions employed. However, certain substitutions such as keto or aldehyde can desirably undergo sulfidation. Selection of suitable substituents is within the skill of the art, and may be accomplished by routine experimentation. Such substituents typically include any of the moieties listed above, as well as hydroxy, amidine, amine, sulfonyl, sulfinyl, sulfo-4-
Examples include nitro, phosphate, phosphite, and alkali metal merka.

Olefinically unsaturated compounds are usually those in which each R group that is not hydrogen is independently an alkyl, an alkenyl aryl, or (rarely) a corresponding substituent. Monoolefinic and noolefinic compounds, especially the former, are preferred, especially terminal monoolefinic (α-olefinic) hydrocarbons; that is, R and R are hydrogen and R9 and R are alkyl or aryl. , especially those compounds that are alkyl (ie the olefin is aliphatic). From about 8 to about 36 carbon atoms, especially from about 8 to about 2 carbon atoms
0 olefinic compounds are particularly desirable.

C8-36 aliphatic α-□ olefins (ie, terminal olefins) are usually those with olefinic carbon atoms that are unbranched; ie, those that contain the moiety CH,=CH-. Also.

It is usually substantially free of branching at the allylic carbon atom; ie, preferably contains the moiety CH2-CHCH2-. Preferred olefins are in the C8-2o range. Mixtures of these olefins are commercially available and such mixtures are suitable for use in this invention.

Furthermore, fatty acid esters derived from one or more unsaturated carboxylic acids are particularly useful as olefinically unsaturated compounds.

As used herein, the term fatty acid refers to acids that can be obtained by hydrolysis of naturally occurring vegetable or animal fats or oils. These are usually in the C46-2o range and include oleic acid, lyluic acid, and others.

Useful fatty acid esters include aliphatic alcohols, including -hydric alcohols such as methanol, ethanol, n-7' lovanol, isonorononol, butanols, and ethylene glycol, noropylene glycol, trime-161-tylene. There are esters of polyhydric alcohols including glycol, neopentyl glycol, glycerol, and the like. Particularly preferred are fatty oils derived primarily from unsaturated acids, ie naturally occurring long-chain unsaturated carboxylic acid triglycerides, especially lyluic acid and oleic acid. These fatty oils include such naturally occurring animal and vegetable oils, such as lard oil, peanut oil, cotton purlin oil, soybean oil, corn oil, and the like.

The composition and properties of fats and oils are well known to those skilled in the art;
M, P, Dozen's Nolopties Op the〉Linshinori, Fatty, Fatty Oils, Wax, Fatty Assid, And Zede Salt'' (Tesasus C
o”, 1952) (This document describes fatty oils and unsaturated carboxylic acids useful in this invention, so it is included here for reference). □ Olefinic Sulfidation of unsaturated compounds can be carried out, for example, by combining elemental sulfur with one or two of the above-mentioned olefinically unsaturated compounds at a temperature of about 00°C to about 250°C to about 250°C, -16'
2- Preferably, the reaction can be carried out at a temperature of about 25°C to about 200°C. The amount of sulfur per mole of olefinically unsaturated compound is usually about 0.3 to about 20
gram atom, about 05 to about 15 gram atom.

The following U.S. patents exemplify sulfurized olefinically unsaturated compounds and methods for their preparation useful in this invention, and are hereby incorporated by reference as they are discussed in Section 1. 3.796.661, No. 3,91
No. 9,187; No. 3, 850.825; Silk 3,9'8
No. 6,966; No. 4.053,427; No. 4,119
, No. 550.

In the following illustrative examples, amine phenols (A)
and a method for producing a carboxylic acid visiting conductor/post-treated carboxylic acid derivative composition (B) comprising the combination composition of the present invention.

In these examples, as well as in this specification, all percentage parts and ratios are by weight unless otherwise indicated. Temperatures are in °C unless otherwise stated.

Example 1A Polyimbutene-substituted phenol prepared by catalytic alkylation of phenol with boron trifluoride-phenol with polyisobutyne having a number average molecular weight of about 1000 (gas phase osmometry), 4578 parts of polyimbutene-substituted phenol, 3052 parts of diluent mineral oil and textile grade A mixture consisting of 725 parts of pennon was heated to 60° until homogeneous. After cooling it to 30° C., 3195 parts of 1 Gmol nitric acid in 600 parts of water were added to the mixture. Cooling is necessary to keep the temperature of the mixture below 40°. After stirring the reaction mixture for an additional 2 hours, 37
A 10 part aliquot was transferred to a second reaction vessel. This second portion was treated with 127.8 parts of 1 Gmol nitric acid in 130 parts of water at 25-30°. The reaction mixture was stirred for 15 hours and then slipped to 220°/30 tor. Filtration gave an oil solution of the desired intermediate (IA).

Example IB 810 parts of an oil solution of intermediate (IA) as described in Example IA,
405 parts of isonorobyl alcohol and 405 parts of toluene
The mixture consisting of 1.5 parts was charged into an appropriately sized autoclave. Platinum oxide catalyst (0.81 parts) was added and the autoclave was evacuated four times with nitrogen to remove any residual air. Autoclave hydrogen to 29-55 psig
The contents were stirred and heated at 27-92°1 for a total of 13 hours. Excess residual hydrogen was removed from the reaction mixture by evacuating and purging with nitrogen four times. The reaction mixture was then filtered through diatomaceous earth and the filtrate was stripped to obtain the desired aminophenol solution in oil. This solution contained 0.578% nitrogen.

Example 2 Phenol with a number average molecular weight of about 1000 (gas phase osmotic pressure method)
The alkylated phenols were prepared by reacting the polybutenes with 100% of polybutene in the presence of a boron trisulfide/phenol catalyst. The catalyst was 165-neutralized and removed by filtration. Product filtrate 1 part 230
760 tor (steam temperature), then 205 tor 50
Stripping to tor (steam temperature) yielded purified alkylated phenol as a residue.

To a mixture consisting of 265 parts of alkylphenol, 176 parts of mixed mineral oil and 42 parts of petroleum naphtha having a boiling point of approximately 20° was slowly added a mixture of 184 parts of concentrated nitric acid (69-70°) and 35 parts of water. The reaction mixture was stirred at about 30-45° for 3 hours, stripped to 120 liters (steam temperature) and filtered to give an oil solution of the desired nitrophenol intermediate.

Example 3 1900 parts of a mineral oil solution (mineral oil 43%) of the alkylated nitrophenol described in Example 2 was heated at 145° under a nitrogen atmosphere.
heated to. Then, 70 parts of hydrazine hydrate were slowly added to the mixture over a period of 5 hours while maintaining the temperature at about 145°C. The mixture was then heated to 160° C. for 1 hour, during which time 56 parts of the aqueous fraction were collected.

166- Add another 7 parts of hydrazine hydrate and bring the mixture to 140
° for an additional hour. Filter at 130° to eliminate nitrogen
An oil solution of the desired aminophenol product containing 5% was obtained.

Example 4 To a mixture of 800 parts of polybutene-substituted phenol prepared essentially as described in Example 2 and 944 parts of diluent mineral oil was added 72 parts of concentrated nitric acid at 59°. Set the reaction temperature to 59~
The reaction was controlled to maintain the temperature at 68°. 69% of the reaction mixture
Stirred for 2 hours at ~73° and then heated at 140°-1 while passing nitrogen through the mixture and distilling off the water. Then, hydrazine hydrate (90 parts) was added to the mixture at 130-13
Addition was made slowly over 3 hours at 7°.

The mixture was stirred at this temperature for 0.5 hours, then nitrogen was slowly passed through the mixture and the aqueous fraction was collected for 16 hours.
It was heated in a 0°C trench.

Example 5 A mixture of 609 parts of polybutene-substituted phenol prepared essentially as described in Example 2 and 454 parts of diluent mineral oil was mixed at 57°. Add concentrated nitric acid (66.3%) to this mixture.
46.5 parts of nitric acid were added over 8 hours. The mixture was stirred at 58-63° for 15 hours and then heated to 142°C for 17 hours while slowly passing nitrogen through the mixture. The mixture was kept at 143-145°C for 05 hours and then cooled to 114°C. During the reaction, 23 parts of a fraction were collected. The mixture was filtered at 113-126° to ensure a nitrogen content of 0.
．． A 64% oil solution of the desired nitro intermediate was obtained.

Example 6 To 320 parts of an oil solution of the polybutene-substituted nitrated phenol described in Example 5, 12 parts of aqueous hydranone (64 thihydrazine) were added at a temperature of 160° over a period of 625 hours. Filtration was performed to obtain an oil solution of the desired amino enol product with a nitrogen content of 0.59%.

Example 7 To a mixture of 3,000 parts of an alkylated phenol having a polybutene substituent of 70 carbon atoms, prepared essentially as described in Example 2, and 3,000 parts of glacial acetic acid, 5 parts of concentrated nitric acid was added.
40 parts were added over 3 hours at 51°. During addition,
The mixture was kept at 51-63°. The mixture was left at room temperature for 18 hours and then heated to 120° for 6 hours while passing nitrogen through the mixture. The aqueous fraction was collected.

The reaction mixture was then stripped to 140'/28 tor (steam temperature) and the residue was filtered at 120° to obtain the desired final product with a nitrogen content of 255%.

Based on this, it was calculated that the product contained two nitro groups per alkylated phenol.

Example 8 Alkylated dinitrophenol 5 as described in Example ψ147
100 parts of hydrazone hydrate were added at 1256 parts to a mixture of 45 parts of diluent mineral oil and 340 parts of diluent mineral oil. This addition was carried out at 2.5°C under a nitrogen atmosphere while maintaining the temperature between 122 and 125°.
Time went. The reaction mixture was then refluxed at 123° for 2.5 hours and heated to 155° for an additional 2 hours while collecting the aqueous fraction. Nitrogen was passed slowly through the reaction mixture for a further 2 hours at 150-155° and the residue was filtered to a nitrogen content of 1.
A 16% oil solution of the desired aminophenol product was obtained.

Example 9 361 parts of tetrapropenyl-substituted phenol and 27 parts of glacial acetic acid
A mixture of 90 parts of concentrated nitric acid (70% HNO6) and 90 parts of glacial acetic acid was added at 7-17°. The addition was carried out at 1° C. while cooling the reaction mixture externally to 7-17°.
．． It lasted 5 hours. The cooling bath was removed and the reaction mixture was stirred at room temperature for 2 hours. 134735 tor
(steam temperature) and filtered to give the desired nitrated intermediate as a residue with a nitrogen content of 4.65%.

Example 10 To 303 parts of the nitration intermediate described in Example 9, 100 parts of hydrazone hydrate were added over a period of 2.4 hours at 125° under nitrogen atmosphere. The mixture was refluxed for 2.5 hours and then 170° distilled to a steam temperature of 155°. A slow stream of nitrogen into the reaction mixture
The temperature was maintained at 190°. Filter the residue and
The desired aminophenol product with a nitrogen content of 4.89% was obtained.

Example 11 110 parts of a mixture of 510 parts and 59 parts of maleic anhydride
heated to °. The mixture was heated to 190° over a period of 7 hours, during which time 43 parts (0.6 mol) of gaseous chlorine were added subsurface. At 1900 DEG -192 DEG, a further 11 parts (0.16 mol) of chlorine were added over a period of 3.5 hours. This was done by heating the strip of reaction mixture for 10 hours at 190°-193° with nitrogen bubbling. The residue was the desired polyisobutyne-substituted succinic acylating agent with a saponification equivalent number of 87 (as measured by ASTM D-94).

Example 12 Polyisobutyne (Mn=2020:Mw=6049) 1
000 parts (0,495 mol) and maleic anhydride 115
(117 mol) was heated at 110°.

The mixture was heated to 184° over 6 hours, during which time 85 parts (1.2 moles) of gaseous chlorine were added subsurface.

At 184°-189°, a further 59 parts (0.83 mol) of chlorine were added over a period of 4 hours. The reaction mixture was stopped by heating at 186°-190° for 26 hours with nitrogen bubbling. The residue has a saponification equivalent number of 87 (
The desired 7J seriisobutyne-substituted succinic acylating agent (as measured by ASTM D-94)

Example 13 251 parts of gaseous chlorine was added to polyisobutyne (Mn=1696
:Mw=6594) A mixture of 3251 parts of chlorinated polyisobutyne and 345 parts of maleic anhydride prepared by adding to 3000 parts at 80°C over 4.66 hours was heated to 200° over 0.5 hours. did. The reaction mixture was held at 200°-224° for 6.33 hours, stripped at 210° under vacuum, and filtered. The filtrate was the desired polyisobutyne-substituted succinic acylating agent with a saponification equivalent number of 94 (ASTMD-94-c7+++1).

Example 14 10.2 parts (0.25 parts i:) of a commercially available mixture of ethylene polyamine having about 3 to about 10 nitrogen atoms per molecule was mixed with 1 part of mineral oil.
A mixture was prepared by adding 13 parts of the substituted succinic acylating agent prepared in Example 11 to 161 parts (0.25 equivalents) at 138°. The reaction mixture was heated to 150
Heating was continued for 2 hours to a temperature of 50°C and stopped by bubbling with nitrogen. The reaction mixture was filtered to obtain the filtrate as an oil solution of the desired product.

Example 15 57 parts (138 equivalents) of a commercially available mixture of ethylene polyamines having about 3 to 10 nitrogen atoms per molecule were added to 1067 parts of mineral oil and 893 parts of the substituted succinic acylating agent prepared in Example 12 at 140-145°. A mixture was prepared by adding at. The reaction mixture was heated to 155° over 3 hours and stopped by bubbling with nitrogen.

The reaction mixture was filtered to extract the desired product -173= It was obtained as an oil solution.

Example 16 18.2 parts (0,433 equivalents) of a commercially available mixture of ethylene polyamines having about 3 to 10 nitrogen atoms per molecule were mixed with 39 parts of mineral oil.
A mixture was prepared by adding 2 parts and 348 parts (per 0.52) of the substituted succinic acylating agent prepared in Example 12 at 140°C. 1 of the reaction mixture
It was heated to 50° for 1.8 hours and stripped by blowing with nitrogen. The reaction mixture was filtered to obtain the filtrate as an oil solution of the desired product.

Example 17 334 parts (052 equivalents) of the polyisobutyne-substituted succinic acylating agent prepared in Example 11, 548 parts of mineral oil,
A mixture of 30 parts (0,0057 equivalents) of pentaerythritol was heated at 150° for 2.5 hours. The reaction mixture was heated to 210° over 5 hours and heated to 210° for 3 hours.
．． I kept it for 2 hours. The reaction mixture was cooled to 1900 ℃ and 85 parts (0.2 equivalents) of a commercially available mixture of ethylene polyamines having an average number of nitrogen atoms per molecule of about 3 to about 10 were added.

The reaction mixture was stripped by heating at 205° with nitrogen bubbling for 3 hours and then filtered to give the filtrate as an oil solution of the desired product.

Example 18 A mixture consisting of 3225 parts (5,0 equivalents) of the polyisobutyne-substituted co-phosphate acylating agent prepared in Example 12, 289 parts (85 equivalents) of pentaerythritol, and 5204 parts of mineral oil was heated at 225° to 235°. The mixture was heated for 5.5 hours. The reaction mixture was filtered at 130° to obtain an oil solution of the desired product.

Example 19 A mixture of 631 parts of the product oil solution prepared in Example 18 and 50 parts of anthranilic acid was heated at 195-212° for 4 hours. The reaction mixture was then filtered at 130° to obtain an oil solution of the desired product.

Example 20 14 parts of aminoprobylsoethanolamine was added to Example 1
190-20 to 867 parts of the oil solution of the product prepared in step 8.
Mixtures were prepared by addition at 0°. The reaction mixture was held at 195° for 2.25 hours, then 120°
It was cooled and filtered. The filtrate was washed with an oil solution of the desired product.

Example 21 A mixture of 62 parts of boric acid and 2720 parts of an oil solution of the product prepared in Example 14 was heated at 150° C. for 6 hours under nitrogen. The reaction mixture was filtered to obtain the filtrate as an oil solution of the desired boron-containing product.

Example 22 Oleyl borate ester was prepared by heating an equimolar mixture of oleyl alcohol and boric acid in toluene at reflux temperature with azeotropic removal of water. The reaction mixture was then heated to 1500 °C under vacuum, and the residue was an ester containing 3.2% boron and a saponification number of 62. A mixture of 344 parts of this ester and 2720 parts of an oil solution of the product prepared in Example 14 was heated at 150° for 6 hours and then filtered. The filtrate was an oil solution of the desired boron-containing product.

Example 23 Boron trifluoride (34 parts) was bubbled into 2190 parts of an oil solution of the product prepared in Example 15 at 80° C. for up to 3 hours. The resulting mixture was bubbled with nitrogen at 70-80° for 2 hours to obtain a residue as an oil solution of the desired product.

Example 24 A mixture of 3420 parts of the oil-containing solution of the product prepared in Example 16 and 53 parts of acrylonitrile was heated at 125° to 14°C.
Heated at 5° reflux for 1.25 hours, 145° for 3 hours, then stripped under vacuum at 125°. The residue was an oil solution of the desired product.

Example 25 A mixture was prepared by adding 44 parts of ethylene oxide to 1460 parts of an oil solution of the product prepared in Example 15 at 150° over 177 hours. The reaction mixture was kept at 150° for 1 hour and then filtered to obtain the filtrate as an oil solution of the desired product.

Example 26 A mixture of 3880 parts of an oil solution of the product of Example 14 and 120 parts of terephthalic acid is heated at 1150° to 160°,
It was then filtered. The filtrate was an oil solution of the desired product.

Example 27 1 mole of phosphorus pentoxide to 3 moles of decyl alcohol at 32°~
Add at a temperature within the range of 55° and then bring the mixture to 60°
The acid decyl ester was prepared by heating at 63° until reaction completion. The product was a mixture of phosphoric acid decyl esters with a phosphorus content of 9.9% and an acid value of 250 (20%/-lufthalein indicator). A mixture of 1750 parts of the oil solution of the product prepared in Example 14 and 112 parts of the above decyl ester was heated at 145-150° for 1 hour. The reaction mixture was filtered to obtain a filtrate as a solution of the desired 178-product in oil.

Example 28 A mixture of 2920 parts of an oil solution of the product prepared in Example 15 and 69 parts of thiourea was heated to 80° and kept at 80° for 2 hours. The reaction mixture was then heated to 150-155°
The mixture was heated for 4 hours at the end of which nitrogen was bubbled through the mixture.

The reaction mixture was filtered E7 to obtain a filtrate as an oil solution of the desired product.

Example 29 A mixture of 1460 parts of an oil solution of the product prepared in Example 15 and 81 parts of a 37% aqueous formaldehyde solution was heated at reflux for 3 hours and the reaction mixture was stripped under vacuum at 150°. The residue was an oil solution of the desired product.

Example 30 A mixture of 1160 parts of an oil solution of the product prepared in Example 14 and 67 parts of sulfur monochloride was heated at 150° C. for 1 hour under nitrogen. The mixture was filtered to obtain an oil solution of the desired sulfur-containing product.

Example 31 A mixture was prepared by adding 115 parts of formic acid to 1000 parts of an oil solution of the product prepared in Example 15 at 60°. The reaction mixture was heated at 60-100° for 2 hours, 92-
Heated at 100° for 175 hours and then filtered to obtain an oil solution of the desired product.

Example 32 58 parts of propylene oxide are added to 1170 parts of the oil solution of the product prepared in Example 18 and 10 parts of birinone from 80 to 58 parts of propylene oxide.
Solutions were prepared by addition at 90°. The reaction mixture was then heated at 100-120° for 2.5 hours,
Then, the IJ was heated at 170° under vacuum. The residue was an oil solution of the desired product.

Example 33 A mixture of 1170 parts of an oil solution of the product prepared in Example 18 and 36 parts of maleic anhydride is heated to 200° by 1.5
Heat for 5,5 hours and then 200-21 hours
It was kept at 0°. During the last 15 hours of heating, the reaction mixture was
Infused with ingredients.

The reaction mixture was spun in a 190° trench under vacuum and then filtered to obtain the filtrate as an oil solution of the desired product.

As shown above, the nitrogen-containing organic composition of the present invention has (
Consisting of a blend of A) and (B) or (C).

Blends of (A), (B) and at least one sulfurized olefinically unsaturated compound are also preferred embodiments of this invention. A nitrogen-containing organic composition comprising a blend of (A), (B) and (C) is another preferred embodiment of this invention. A further preferred embodiment of this invention is (A)
, (B), (c) and at least one sulfurized olefinically unsaturated compound.

The nitrogen-containing organic composition preferably facilitates the use and/or handling of conventional mixing techniques, such as mixing the component compositions at a temperature sufficient to ensure uniform mixing, and the component compositions 181 - is prepared by blending the above component compositions using a solvent/diluent such as mineral oil, xylene, naphtha-based liquid fuel, etc. to ensure uniform mixing of the components. Such techniques are well known to those skilled in the art and therefore need not be discussed further.

Generally, the weight ratio of the component compositions (B), (C) and the sulfurized olefinically unsaturated compound to the aminophenol compound (A) is about 0.1 part to 1 part of aminephenol.
~about 10.0 parts.

The examples in the following table represent nitrogen-containing compositions of the present invention.

Table 1 16.5 ... 70 1
0 3.5II 16.5 70
... 10 3.5III -
65... 35...
IV 20 80
・・・ ・・・V 20 80
... ... * Chlorinated paraffin wax (containing about 40% chlorine by weight) commercially available from Diamond Chemicals As mentioned above, the composition of the present invention can be used as a lubricant. It is useful as an additive for lubricants, acting as an antioxidant, corrosion inhibitor, detergent, dispersant, flow modifier, and particularly improving one or more of the following properties: corrosion protection, wear resistance, and friction-reducing properties. Add to the agent. These properties are unexpected and especially effective in protecting silver, copper and lead components in engines.

The compositions of this invention are used in a variety of lubricants based on extreme oils of lubricating viscosity, such as natural oils, synthetic oils, and mixtures thereof. These lubricants include crankcase lubricants for spark ignition and compression ignition internal combustion engines such as automotive and truck engine engines, two-stroke engines, aircraft piston engines, marine and railroad diesel engines, and the like. These lubricants are also used in gas engines, stationary power systems and turbines. Automotive transmission fluids, transmission shaft fluids, gear lubricants, as well as metalworking lubricant oils, pressure fluids, and other oil and grease compositions also benefit from the addition of the nitrogen-containing compositions of this invention.

Natural oils include animal and vegetable oils (e.g. castor oil, lard oil) as well as mineral lubricants such as liquid petroleum,
and solvent-treated or acid-treated mineral lubricating oils of rough-hewn, naphthenic, or mixed porcelain-nanthenic oils.

Coal or oils of lubricating viscosity derived from coal may also be used.
It is a base oil for use in cooking. Synthetic lubricating oils include hand-polymerized olefins and interpolymerized olefins (e.g., polybutylene, polyglobylene, propylene-isobutylene copolymer, chlorinated polybutylene, etc.), poly(11-hexene), poly(1-octene), poly(1-octene), -decene) and mixtures thereof, alkylbenzenes (e.g. dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2
-ethylhexyl)benzene, etc.), polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls, etc.), alkylated diphenyl ethers and alkylated diphenyl sulfides, and their derivatives, analogs and congeners. There are mouth displacement hydrocarbon oils.

Homopolymers and interpolymers of alkylene oxide and derivatives thereof whose terminal hydroxyl groups have been modified by esterification, etherification, etc. are also known lubricating oils. Examples include oils obtained by polymerization of ethylene oxide or zolopyrene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (e.g.
Methyl polyisopropylene glycol ether with average molecular weight -11ooo, diphenyl ether of polyethylene glycol with molecular weight 500-1000, molecular weight 1000-1000
1500 polypropylene glycol diethyl ether etc.) or their mono and polycarenic acid esters, e.g. acetate esters, mixed C3-C8 fatty acid varnishes 18
It is a C3 oxo acid diester of 5-methyl or tetraethylene glycol.

Other suitable synthetic lubricating oils include dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acid, alkenylsuccinic acid, maleic acid, azelaic acid, superric acid, hexaphosphoric acid, fumaric acid, adipic acid, lyluic acid) dimer, malonic acid, alkylmalon F'flukenylmalon M, etc.) and various alcohols (e.g., EVA, methyl alcohol, hexyl alcohol, dotecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether hepropylene glycol, etc.) It is an ester of

Specific examples include dibutyl adipate, sepacy:
y acid) (2-ethylhexyl), di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, noisodecyl azelate, nodecyl phthalate dioctinopephthalate, soeicosyl sepacate, 2- of riluic acid dimer These include ethylhexyl diester and a complex ester obtained by reacting 1 mole of sepacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

Esters useful as synthetic oils also include those derived from C5-C12 monocardic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol norocene, pentaerythritol, noventaerythritol, and tripentaerythritol.

Polyalkylsiloxane oils, polyarylsiloxane oils, polyalkoxysiloxane oils or polyaryloxysiloxane oils, and silicate oils are also useful as synthetic lubricating oils (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra(2-ethylhexyl) silicate, tetra(4-methylhexyl)silicate, tetra(p-tert-butylphenyl)silicate, hexyl-(4-methyl-2=pentoxy)nosiloxane, poly(methyl)siloxane, poly(methylphenyl)siloxane, etc.). Other synthetic lubricants include
Examples include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid, etc.), polymerized tetrahydrofuran, and the like.

Unrefined, refined and rerefined oils of the types described above, whether natural or synthetic (including mixtures thereof), may be used in the lubricating compositions of this invention.

Unrefined oils are those obtained directly from natural or synthetic sources without additional refining treatment. For example, sierre oil obtained directly by retorting, petroleum oil obtained directly by distillation, or ester oil obtained directly by esterification and used without further treatment are unrefined oils. Refined oils are similar to unrefined oils except that they have been treated with one or more refining steps to improve one or more properties. The above purification methods are well known to those skilled in the art. For example, solvent extraction, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by applying the processes used to obtain refined oils to already used refined oils. Such rerefined oils are also known as reclaimed oils and are often further processed by methods to remove spent additives and oil breakdown products.

In general, the lubricating compositions of this invention contain a nitrogen-containing organic compound of this invention in an amount sufficient to impart antioxidant, wear, corrosion, detergent, dispersant, friction-reducing, or flow-modifying properties. Contains a composition. Typically, this amount will be from about 0.05% to about 20%, preferably from about 0.1% to about 10%, of the total weight of the lubricating composition.

In lubricating oils that operate under extremely harsh conditions, such as marine nosel engine lubricating oils, the nitrogen-containing organic compositions of this invention may be present up to about 30% by weight.

As used in this specification, a "small amount" refers to a total amount of less than 50 kg.

As used herein, a "major amount" is an amount greater than 50% of the total amount.

189- This invention also contemplates the use of other additives with the nitrogen-containing compositions of this invention. °Such additives include, for example, free-form and ashless auxiliary detergents and dispersants, auxiliary oxidation and corrosion inhibitors, pour point depressants, extreme pressure additives, tone activators, color stabilizers and There is an antifoaming agent.

The ash-forming detergent is an olefin polymer (e.g., molecular weight 10
1IiII is made by treating phosphorus trichloride, phosphorus chloride, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and sulfur halide, or phosphorus additives such as phosphorothioyl chloride. Organic phosphorus-containing acids characterized by at least one carbon-phosphorous direct bond, such as nulphonic acids, carbanoic acids or alkali metals with phenols! or oil-soluble neutral and basic salts of alkaline earth metals.

The most commonly used salts of such acids are sodium, potassium, lithium, calcium, magnesium,
Salts such as strontium and barium.

-(9()-) The term "basic base" is used to refer to all bases in which a metal is present in a stoichiometrically greater amount than the organic acid group. It is commonly used to prepare basic salts. As a method,
A stoichiometric excess of a metal neutralizing agent, such as a metal oxide, hydroxide, carbonate, bicarbonate or sulfide, and an acid solution in mineral oil are heated at a temperature of 50° C. or higher to form this product. There is a method of filtering the mixture. It is also known to use "accelerators" in the neutralization process to eliminate the incorporation of large excess metals. Examples of compounds useful as accelerators include phenols, naphthols, argylphenols, thiophenols, sulfurized alkylphenols, and tonophenols, which are combination products of formaldehyde and phenolics; methanol, 2-propanol, Tools, octyl alcohol, cellosolve, carbide, ethylene glycol, stearyl alcohol and cyclohexyl alcohol (D alcohols; and amines such as aniline, phenylenecyamine, phenothiazine, phenyl-β-naphthylamine and dodecylamine) A particularly effective method for preparing basic salts is to mix an acid with an excess of a basic alkaline earth metal neutralizer and at least one alcoholic promoter, and to mix this mixture with a
It consists of carbonation at a high temperature such as 0 to 200°C.

Basic alkali metal and alkaline earth metal carbonates, nulfonates and phenoxytes useful with the metal-containing compositions of this invention are well known and examples are limited. It is well described in US Pat. No. 3,779,920.

Supplemental ashless detergents and dispersants are so called even though the dispersant, depending on its structure, burns to produce non-volatile substances η such as boron oxide or phosphorus pentoxide.

However, kneaded dispersants usually contain metals and therefore do not produce metal-containing ash upon combustion. (1) At least about 34, preferably at least about 54.
Reaction products of carganic acid (or its derivatives) having 2 carbon atoms with organic hydroxy compounds such as amines, phenols and alcohols, and (also) ``basic inorganic compounds''. These products are referred to herein as "carboxylic dispersants" and are covered in a number of US patents, including British Patent No. 1,306,529 and those numbered below.

3.163,6,03 3.3'51,552 3
．． 541.0123.184,474 3,381,
022 3,542.6783.215,707
3,399,141 3,542.6803.219
,666 3,415,750 3,567.63
73.271,310.3,433,744 3,5
74,1013.272.746 3.444.170
3,576.7433.281,357 3,4
48,048. ．． 3.6'30,9043.306,9
08 3.448.04'1 3,632.510
3.311,558 3,451,933 3,6
32.5113.316.1?7 3,454,60
7 3,697,4283.340,281 3,
467.668 3,725,441193- 3.341,542 3,501,405 Re
26,4333.346,493 3,522.1
79(2) Reaction products of relatively high molecular weight aliphatic or alicyclic halides and amines, preferably polyalkylene polyamines. These can be referred to as "amine dispersants" and examples thereof include, for example, U.S. Pat. No. 3,275.
No. 554, No. 3,438,757, No. 3,454,555
No. 3,565.804.

(3) Reaction products of alkylphenols in which the argyl group contains at least about 30 carbon atoms with aldehydes (particularly formaldehyde) and amines (% polyalkylene polyamines).

This can be called a "Mannich dispersant". The following U.S. patent provides a representative example of how to arrange ships.

2.459,112 3,442.808 3,
591,5982.962.442 3,448.
047 3.600,3722.984,550
3,454,497 3,634,5153.03
6,003 3.459,661 3,649,
229194- 3.166.516 3,461,172 3.6
97,5743,236,770 3,493,5
20 3.725, 2773.355, 270
3.539.633 3.725,4803.3
68,972 3,558,743 3,726,
8823.413,347 3,586,629
3,980,569(4) Carboxylic acid dispersant, amine dispersant or Mannich dispersant Total sulfur, urea, thiourea, guar; non, carbon disulfide, aldehyde,
Ketones, carboxylic acid, hydrogen ash-displaced succinic anhydride,
Products obtained by post-treatment with reagents such as nitriles, epoxides, boron compounds, 11 compounds. These products are described in the following US patents:

3.036,003 3,282.955'3,49
3.5203.639,242 3,087,936
3.312.6193.502,677 3,6
49,229 3,200,1073.366.56
9 3,513.093 3,649,6593.2
]6,936 3,367.943 3.533,
9453.658,836 3,254,025
3,373,1113539.633 3,697,5
74 3,256185 3.403.1023.57
3,010 3,702.757 3,278
,5503.442,808 3.579,450
3,703,5363.280,234 3
,455,831 3,591,5983.704
,308 3.281,428 3.455,
8323.600,372 3,708,522(
5) Oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and relatively high molecular weight olefins, and aminoalkylacrylates, aminoalkylacrylamides and poly-(oxyalkylene)-
Interpolymer with polar group-containing monocapsules such as substituted alkyl acrylates. These can be referred to as "polymeric dispersants", examples of which are given in the following US patents:

3.329,658 3,666.730 3,4
49,2503.687,849 3,519,56
5 3,702,300 Extreme pressure agents and supplementary corrosion inhibitors and antioxidants, such as sulfurized alkylphenols, phosphorus sulfide carbonates, such as the reaction products of phosphorus chloride and turpentine or methyl oleate. Hydrogen; dibutylhonupite, dihezoterhonupite, dicyclohexylhonupite, hentyl phenylhonupite, dibentylphenylhonupite, tridecyl phosphite,
distearylhonupite, dimethylnaphtherhonupite, oleyl 4-bentylphenylhonupite, polyzolopyrene (molecular weight 500)-substituted phenylhonupite, diisobutyl-substituted phenylhonuphiite) & which carbonized frozen phosphite and tricarbonized frozen phosphite Phosphorus enethers, which mainly contain phyto; metal thiocarbates such as zinc dioctyl dithiocarbamate and barium hebutylphenyl dithiocarbamate; zinc dicyclohexyl phosphorodithioate, zinc dioctyl phonuprodithioate, barium di(heptylphenyl)
Zinc 197-salt of phosphorodithioic acid obtained by reacting bosphorodithioate, cadmium dinonyl phosphorodithioate, and surface-imaged phosphorus with a mixture of equimolar amounts of isopropyl alcohol and n-hexyl alcohol.

Still other additives that can be used with the nitrogen-containing compositions of this invention are 2,5-bis-C5-C2o alkyl dithiothiodiazoles, such as 2,5-bis(octylditheo)thiadiazole, which is Antioxidant,
Functions as a sulfur deactivator and antiwear agent. The diazole is used in a proportion of 0.01 to 1% by weight of the final composition, preferably 0.02 to 0.1% by weight.

The nitrogen-containing compositions of this invention can be added directly to all lubricating oils. However, it is preferred to dilute it with at least one substantially inert, normally liquid organic solvent/diluent such as mineral oil, naphtha, benzene, toluene or xylene to form a concentrate. The concentrates generally contain from about 20 to about 80 weight parts of the nitrogen-containing composition of this invention. The concentrate may also contain the usual additives mentioned above.

The fuel compositions of the present invention are suitable for use in hydrocarbonaceous petroleum distillate fuels (e.g., motor gasoline as shown in ASTM Specification D-439-73 and ASTM Specification D-3).
It usually contains a large amount of liquid fuel, such as diesel fuel or fuel oil (as shown in No. 96). Normally liquid fuel compositions containing non-hydrocarbons such as alcohols, ethers, and organic nitro compounds (e.g., methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) may also be prepared from corn, purple corn, or However, they are within the scope of this invention, as are fuel oils derived from vegetable and mineral sources such as charcoal and lime. Fuel oils consisting of mixtures of any of the above may also be used. Examples of such mixtures include gasoline and ethanol, diesel fuel and ether, and gasoline and nitromethane.

Particularly preferred is gasoline, which has an ASTM 10% distillation point of 60°C and a 90% boiling point of about 20°C.
It is a mixture of hydrocarbons at 5°C.

Generally, the fuel composition will contain the nitrogen of the present invention in an amount sufficient to provide the fuel with antioxidant, anti-corrosion, anti-corrosion, low temperature, dispersibility, or cleanliness properties. Contains a composition. Generally, this amount will be from about 0,001 to about 5 parts by weight, preferably from 0,001 to 1 parts by weight of the final composition.

The fuel compositions of this invention may contain B%A and other additives known in the art in addition to the compositions of this invention. Additives include anti-knock agents such as tetraalkyl lead compounds, lead scavengers such as noroalkanes (e.g. ethylene dichloride, ethylene tribromide), anti-deposition agents such as triaryl phosphates, modified agent, dye, hydranium number improver, 2,6-di-tert-butyl-4
- auxiliary antioxidants such as methylphenol, rust inhibitors such as alkylated succinic acids and their anhydrides, bacterial growth inhibitors, gum inhibitors, metal deactivators, demulsifiers, upper cylinder lubricants, anti-icing agents. There are drugs etc.

In certain preferred fuel compositions of this invention, the nitrogen-containing compositions of this invention are used in conjunction with other ashless dispersants in gasoline. Such ashless dispersants are preferably esters of mono- or polyols and polymeric capped mono- or I-ricarponic acylating agents having at least 30 dust atoms in the acyl moiety.

Such esters are well known in the art. For example, French Patent No. M139664, British Patent No. 9
No. 81850 and No. 1055337, and U.S. Pat.
No. 331776, No. 3346354, No. 35°221
No. 79, No. 3579450, No. 3542680, No. 3381022, No. 3639242, No. 36974
Nos. 28 and 3708522 and British Patent No. 1
See No. 306529. Generally, from about 0.01 to about 10.0% of the nitrogen-containing composition of this invention per part of the ashless dispersant.
It is used in a ratio of about 1 to about 10 parts, preferably 0 parts to 1 part. In yet another embodiment of this invention, the nitrogen-containing compositions of this invention are used in combination with Mannich condensation products formed from substituted phenols, aldehydes, polyamines, and monosubstituted birinnones. Such condensation products are described in U.S. Pat.
No. 9633, No. 3704308 and No. 372527
It is stated in No. 7.

The nitrogen-containing composition of this invention may be added directly to the above fuel to form a fuel composition, or it may be added to mineral oil,
A concentrate is produced by diluting with xylene or at least one of the substantially inert normally liquid organic solvents/diluents such as the above-mentioned normally liquid fuels, and the concentrate is then used as a fuel for optical dispersion. The fuel compositions described above may be made in addition to the above amounts. The concentrates generally contain about 2% of the nitrogen-containing composition of this invention.
0 to about 80% by weight. 1, this concentrate may contain the conventional additives mentioned above, preferably the ashless dispersants mentioned above, in the proportions mentioned above. The remainder of this concentrate is the solvent/filler.

Below V, the lubricating composition and fuel composition of the present invention 202- and examples of additive concentrates.

Example A Re1d 8.4 psi gasoline containing 24 parts per million parts of the nitrogen-containing product of Example 1.

Example B A diesel fuel oil containing 40 parts per million parts of the nitrogen-containing product of Example 2.

Example C Solvent Purification - Toral SAE 10 mineral oil containing 7% i of the nitrogen-containing product of Example 2.

EXAMPLE A solvent refined SAE 40 mineral oil containing all 6 of the nitrogen-containing product of Example 2.

Example E A synthetic lubricant consisting primarily of a C5-C9 normal alcohol ether in a 50150 molar mixture of adipic acid and daltaric acid, containing 5 parts of the nitrogen-containing product of Example H.

Example F Concentrate consisting of 50% mineral oil and 50% of the product of Example I.

Although this invention has been fully described above with examples, this invention is not limited to these examples, and there are many modifications and variations.
It also includes examples of changes.

Claims (1)

[Scope of Claims] (1) (A) General formula (where t and R are substantially saturated hydrocarbon substituents having at least 8 aliphatic carbon atoms, alb and C are each from 1 to Ar) The total number of a, b and C does not exceed the effective valence number of Ar, and Ar is a lower alkyl group, a lower alkoxyl group, a nitro group, a halo group, etc. an aromatic moiety having 0 to 3 optional substituents consisting of groups or combinations of two or more of these); (B) at least one aminophenol as shown; (B) an Mn value of 1200 to about 5000; It is characterized by comprising a substituent derived from a polyalkene having a value of about 1.5 to about 6 and a succinic acid group, and having at least 1.3 succinic acid groups per equivalent weight of the substituent. (a) at least one H-N
(b) an alcohol, (C) a reactive metal or a reactive metal compound, and (d) these (,
A nitrogen-containing organic composition comprising a combination of reactants selected from the group consisting of two or more combinations of a) to c). (2) Claim 1 in which R contains up to about 750 carbon atoms and there are no optional substituents bonded to Ar.
Compositions as described in Section. (3) R is an alkyl group or an alkenyl group '1:! A composition according to claim 2. (4) The composition of claim 1, wherein R contains about 30 to about 750 aliphatic carbon atoms and is derived from a C2-C4 olefin polymer or interpolymer. . (5) The composition according to claim 4, wherein the olefin is selected from ethylene, zolopyrene, butylene, or a mixture thereof. (6) There are 1 each of aX b and C, there is no arbitrary substituent bonded to Ar, and Ar is
A composition according to claim 1. (Claim 6) wherein R is an alkyl or alkenyl group containing at least about 30 and up to about 750 carbon atoms and derived from homo- or interpolymers of 02-C1o1-monoolefins. (8) The amine phenol has the formula (where R' is a substantially saturated hydrocarbon substituent having an average of about 30 to about 400 aliphatic carbon atoms;
The composition according to claim 1, wherein R' is a lower alkyl group, a lower alkoxyl group, a nitro group, or a ).p group, and 2 is O or 1)'t%. (91R' is a pure hydrocarpyl group having at least about 50 carbon atoms, and at least one C
Those derived from homopolymers or interpolymers of 2-C4゜1-monoolefins.Claim No. 8
Compositions as described in Section. 00) The composition according to claim 9, wherein z is Of. 1. The composition according to claim 1, wherein the 1υ succinic acid group constitutes a lower alkyl group or two of them constitute a lower alkyl group. 02 The substituents in component (B) are derived from one or more polyalkenes selected from the group consisting of homo- and interpolymers of 2 to about 16 terminal olefins, said interpolymers having about 16 12. A composition according to claim 11, which may contain up to about 40% olefins derived from internal olefins having 1 carbon atom. α3) The composition of claim 12, wherein the Mn value is at least about 1500. Q4) The composition according to claim 13, having a Mw/Mn value of at least about 18. The substituents in component (B) are derived from one or more polyalkenes selected from the group consisting of homopolymers and interpolymers of 2 to about 6 terminal olefins, and the interpolymers are 15. The composition of claim 14, which may contain up to about 25 molecules derived from internal olefins having up to about 6 carbon atoms. Q6) The composition according to claim 15, wherein the substituent in component (B) is derived from polybutene, ethylene-propylene copolymer, polypropylene, or a mixture of two or more thereof. . 17. The composition of claim 16, wherein component (B) has an average of at least 1.4 succinic acid groups per equivalent weight of substituent. The composition of claim 17 having an aFjMn value of about 1500 to 2800ffi. (The composition according to claim 18, wherein the t1Mw/Mn value is about 2.0 to about 3.4.) Component (B) contains 15 to about 2.5 substituents per equivalent weight. The composition of claim 19, wherein at least about 50% of the total phosphorus positions in component (B) in which the substituents in component (B) are derived from polybutene are derived from isobutene. The composition according to claim 20, which has a 221 Mn value of about 1500 & 2400. (c!3) My/Mn value is about 1500 & 2400. The composition of claim M22, wherein the succinic acid group is from about 2.5 to about 3.2.6-(2i) The composition of claim M23, wherein the succinic acid group is of the formula The composition of claim 11, 16, 22 or 24, wherein CI!51 R contains up to about 750 carbon atoms and there are no optional substituents attached to Ar. (The composition of claim 25, wherein 20R is an alkyl or alkenyl group. (27) R contains about 30 to about 7'50 aliphatic carbon atoms and is a C2-C4 olefin. Compositions according to certain claims 11, 16, 22, or 24, derived from polymers or interpolymers of ethylene, propylene, butylene, or mixtures thereof. The composition according to claim 27, which is selected from: (29) a, b and C are each 1, there is no optional substituent bonded to Ar, and Ar is a benzene nucleus 11, 16, 22, or 24. (30) R contains at least about 30 and up to about 750 carbon atoms, and C2-C1o1-monoolefin An alkyl or alkenyl group derived from a mono or interpolymer of the compositions of claim 29. C31) An amine phenol of the formula a substantially saturated hydrocarbon substituent having aliphatic carbon atoms;
12. The composition according to claim 11, wherein R11 is a lower alkyl group, lower alkoxyl group, nitro group, or halo group, and 2 is O or 1). Claims 1, 3, and 5, wherein the C32 component (B) is a post-treated carboxylic acid derivative obtained by reacting one or more post-treatment agents with one or more of the carboxylic acid derivatives. , 7, 8, 11, 22 or 24. (To)) The carboxylic acid derivative is produced from reactant (a), and the post-treatment agent is boron oxide, boron oxide hydrate, boron halide, boron-containing acid, ester of boron-containing acid, carbon disulfide, Hydrogen sulfide, sulfur, sulfur chloride, alkenyl cyanide, cardic acid acylating agent, aldehyde, ketone, urea, thiourea, guanidine, dicyandiamide, hydrocarbyl phosphate, hydrocarbyl phosphite, hydrocarbyl thiophosphate, hydrocarbyl thiophosphite , phosphorus sulfide, phosphorus oxide, phosphoric acid, hydrocarbyl thiocyanate, hydrocarbyl isocyanate, hydrocarbyl isothiocyanate, epoxide, shrimp sulfide 1-formaldehyde or formaldehyde raw 9-acid compound and phenol, and sulfur and phenol. 33. The composition according to claim 32, which is at least one selected one. 04) Carboxylic acid derivatives prepared from reactant (b), where the post-treatment agent is boron oxide, boron oxide hydrate, boron halide, boron-containing acids, esters of boron-containing acids, sulfur, chloride (ilfi: at least one selected from the group consisting of yellow, phosphorus sulfide, phosphorus oxide, caldic acid-based acylating agent, epoxide, and episulfide)
33. The composition of claim 32, which is a species. 051 There are carboxylic acid derivatives prepared from a combination of reactants (,) and (b), and the post-treatment agent is boron oxide, boron oxide hydrate, boron halide, boron-containing acid, boron-containing acid. Ester, carbon disulfide, hydrogen sulfide, sulfur, sulfur chloride, alkenyl cyanide, cardic acid acylating agent, aldehyde, ketone, urea, thiourea, guanidine, dicyandiamide, hydrocarbyl phosphate,
Hydrocarbyl phosphite, hydrocarbyl thiophosphate, hydrocarbyl thiophosphite, phosphorus sulfide, phosphorus oxide, phosphoric acid, hydrocarbyl thiocyanate, hydrocarbyl isocyanate, hydrocarbyl isothiocyanate, epoxy 1:', episulfide, formaldehyde or 33. The composition of claim 32, wherein the composition is at least one member selected from the group consisting of a formaldehyde-generating compound and phenol, and sulfur and phenol. (36'l Component (B) is a floor-treated calcinic acid derivative obtained by reacting one or more post-treatment agents with one or more of the calinic acid derivatives↑Claim 31) The composition described above, wherein the chlorine acid salt conductor is prepared from reactant (a), and the post-treatment agent is boron oxide, boron oxide hydrate, boron chloride, or boron-containing acid. , esters of boron-containing acids, carbon disulfide, hydrogen sulfide, sulfur, sulfur chloride, alkenyl cyanides, carboxylic acylating agents, aldehydes, ketones, urea, thiourea, guanidine, dicyanide, diamide, hydrocarbyl phosphates, Hydrocarbyl sulfate, hydrocarbyl thiophosphate, hydrocarbyl thiophosphite, phosphorus sulfide, phosphorus oxide, phosphoric acid, hydrocarbyl thiocyanate, hydrocarbyl isocyanate, hydrocarbyl inthiocyanate, epoxide,
37. The composition according to claim 36, wherein shrimp sulfide 1 is at least one member selected from the group consisting of formaldehyde or a formaldehyde-generating compound and phenol, and sulfur and phenol. C38) There are 11% of cardinic acid derivatives produced from reactant (b), and the post-treatment agent is boron oxide, boron oxide hydrate, boron halides, boron-containing acids, esters of boron-containing acids, sulfur. 37. The composition according to claim 36, comprising at least one selected from the group consisting of: (39) Carzenic acid derivative is reactant (a) and b)
The after-treatment agent is boron oxide, boron oxide hydrate, boron halide, boron-containing acid, ester of boron-containing acid, carbon disulfide, hydrogen sulfide, sulfur, sulfur chloride, Alkenyl cyanide, carboxylic acid acylating agent, aldehyde, ketone, urea, thiourea,
Guanidine, dicyandiamide, hydrocarbyl phosphate, hydrocarbyl phosphite, 1:'locarbyl thiophosphate, hyphocarbyl thiosulfite, phosphorus sulfide, phosphorus oxide, phosphoric acid, hydrocarbyl thiocyanate, hydrocarbyl incyanate, hydrocarbyl 37. The composition according to claim 36, comprising at least one selected from the group consisting of isothiocyanates, epoxides, episulfides, formaldehyde or formaldehyde-generating compounds, and phenol, and sulfur and phenol. (40) at least one chlorine-containing compound selected from the group consisting of chloroaliphatic hydrocarbon compounds and chloroalicyclic hydrocarbon compounds each containing about 30 to about 70 heavy components of chlorine; Claims M1, 3, 5, 7, 8, 11, 16, 2 further comprising:
The composition according to item 2, item 24, item 31 or item 36. (41) About 30 to about 70 weights each! % chlorine-containing chlorine-containing compound selected from the group consisting of chloroaliphatic hydrocarbon compounds and chloroalicyclic hydrocarbon compounds containing The composition according to item 32. (4th function (A) General formula (where R is a substantially saturated hydrocarbon substituent having at least 8 aliphatic carbon atoms, aXb and C are each 1 to 1 to the aromatic nucleus present in Ar) The total number of aX b and C does not exceed the effective valence number of Ar, and Ar is a lower alkyl group, a lower alkoxyl group, a nitro group, a halo group, or a combination of two or more of these. 14- aromatic moiety having 0 to 3 and 1 optional substituents consisting of
A combination of at least one aminophenol represented by (C) at least one chlorine-containing compound selected from the group consisting of chloroaliphatic hydrocarbon compounds and cycloalicyclic hydrocarbon compounds. a nitrogen-containing organic composition comprising (4) the composition of claim 42, wherein R contains about 750 carbon atoms and there are no optional substituents bonded to Ar; 44. The composition of claim 43, wherein 441R is an alkyl or alkenyl group. (45) R contains from about 30 to about 750 aliphatic carbon atoms and has a concentration of C2 to C4. Claim 4, which is derived from a German interpolymer
Composition according to item 2. f4G) Olefin is ethylene, propylene,
46. The composition of claim 45, wherein the composition is selected from 1.1 tyrene or a mixture thereof. (47) The composition according to claim 42, wherein each of a, b and C is 1↑, there is no arbitrary substituent bonded to Ar, and Ar is a benzene nucleus. (48) R is at least about 30 pieces and about 750 pieces
Composition 1 of Claim 47, (49) Aminephenol is a substantially saturated hydrocarbon substituent having an average of about 30 to about 400 aliphatic carbon atoms, R'' is a lower alkyl group, a lower alkoxyl group, a nitro group, or The composition of claim 1, wherein the halo group, 2 is O or 1). (50) Claim 42, wherein the chlorine-containing compound contains up to about 70% by weight of chlorine. Section, Section 44, Section 46
49. The composition according to item 48 or item 49. 61) Chlorine-containing compounds are chlorinated. 51. The composition according to claim 50, which is a sugar. 6. Chlorinated paraffin wax is about 35 to about 50
52. A composition according to claim 51 containing % by weight of chlorine. (to) Claims 42, 44, and 4 further comprising at least one sulfurized olefinically unsaturated compound.
The composition according to item 6, item 48 or item 49. (f) Claims in which the sulfurized olefinically unsaturated compound is derived from an olefin represented by the formula % (wherein R, R8, R, and Rlo are each hydrogen or an organic group) Composition according to paragraph 53. 55. The composition of claim 54, wherein the olefin has about 8 to about 36 carbon atoms. [Phase] Claim 5, wherein the olefin is an α-olefin having about 8 to about 20 carbon-17 atoms.
Composition according to item 5. (2) The composition of claim 50, further comprising at least one sulfurized olefinically unsaturated compound. (ii) the sulfurized olefinically unsaturated compound is derived from orenzine represented by the formula % (wherein R7, R8, R7 and R4° are each hydrogen or an organic group); Composition according to paragraph 57. 59. The composition of claim 58, wherein the olefin has about 8 to about 36 carbon atoms. - an alpha-olefin in which the olefin has from about 8 to about 20 carbon atoms. 53. The composition of claim 52 further comprising at least one sulfurized olefinically unsaturated compound. 18- Information The sulfurized olefinically unsaturated compound has the formula R7R8C-C
62. The composition of claim 61, wherein R2R1° (wherein R7, R8, R2 and Rlo are each hydrogen or an organic group)1 is derived from the olefin shown. 63. The composition of claim 62, wherein the ring olefin has about 8 to about 36 carbon atoms. 64. The composition of claim 63, wherein the branched olefin is an alpha-olefin having about 8 to about 20 carbon atoms. Claims 1, 3, 5, 7,
Section 8, Section 11, Section 16, Section 22, Section 24, Section 31, Section 32, Section 36, Section 40, Section 41, Section 42, Section 44, Section 46. Section 48, Section 49, Section 50, Section 52 1, Section 53, Section 56, Section 57,
An additive concentrate, such as from about 20 to 90 parts of the composition described in paragraph 60, paragraph 61, or paragraph 64, and a substantially inert, normally liquid, organic diluent. A large amount of oil having lubricating viscosity, and claims 1, 3, 5, 7, 8, 11, 16, 22, and 24. , Section 31, Section 32, Section 36, Section 40, Section 41, Section 42, Section 44, Section 46, Section 48, Section 49, Section 50, Section 52, Section A lubricating composition comprising a small amount of a composition as described in item 53, item 56, item 57, item 60, item 61 or item 64. ■ A large amount of normally liquid fuel, and claims 1, 3, 5, 7, 8, 11, 16, 22, 24, Items described in Section 31, Section 32, Section 36, Section 40, Section 41, Section 42, Section 44, Section 46, Section 48, Section 49, Section 50 or Section 52. Fuel composition 19 comprising a small amount of the composition
A method for operating an internal combustion engine, comprising lubricating a wheel with the lubricating composition according to claim 66.