JPS5917757B2 - Additives for lubricants and fuels - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to lubricants and normally liquid fuel additives, and more particularly to N-substituted morpholines containing at least one hydrocarbyl group having at least 15 carbon atoms.

Also within the scope of this invention are methods of making this N-substituted morpholine and lubricant and fuel compositions containing it in small but effective amounts.

U.S. Patent No. 3275554, U.S. Patent No. 3438757, U.S. Patent No. 3454555, U.S. Patent No. 348
No. 4859, No. 3575804, No. 37536
No. 70 and No. 3,775,433 disclose lubricants and fuels containing reaction products made from rhodanized polyolefins and mono- or polyamines, including certain heterocyclic amines.

French Patent No. 2,143,128 describes high molecular weight polyamines in which at least one amine group is substituted with one or more hydroxyalkyl groups.

This invention provides novel N-substituted morpholines useful as lubricants and additives for normally liquid fuels.

This N-substituted morpholine has the formula 0(CH2CH2)2NR
'YR'', in which R' is a divalent organic group having at least 1 to about 30 carbon atoms, Y is 101, -S-, or at least one carbon atom; and R" is at least 15
is a monovalent hydrocarbyl group containing 5 carbon atoms.

Lubricant compositions and normally liquid fuel compositions containing these N-substituted morpholines and methods for producing the morpholines, which will be described in detail below, also belong to the scope of the present invention.

In the above N-substituted morpholines, at least one R' group is present.
Divalent organic radicals having from 1 to about 30 carbon atoms, preferably from 11 to about 6 carbon atoms, and more preferably aliphatic radicals having from 1 to about 3 carbon atoms.

In its broadest sense, this R' group can be a hydrocarbyl group or a hydrocarbyl group interrupted by a Y group.

Please note that when the term "hydrocarbyl" is used in this specification and claims to describe a group, it also includes substantive hydrocarbyl groups, unless otherwise specified. used in a meaning.

A substantial hydrocarbyl group within the meaning of this invention is a hydrocarbyl group substituted with a non-hydrocarbyl group (such groups are listed below) that does not substantially inhibit the hydrocarbyl properties and properties. .

Such groups would be considered by those skilled in the art to be included within the term hydrocarbyl.

For example, a C20 alkylene group and a C29 alkylene group substituted with a methylmercapto group or a methoxy group are substantially similar in nature for use in this invention, and in fact are equivalent. Those skilled in the art will recognize this.

Examples of substituents that do not significantly change the hydrocarbyl nature of the hydrocarbyl group within the meaning of this invention are listed below.

However, this example is not limited.

Ether groups (and hydrocarbyloxy groups with up to 10 carbon atoms, especially alkoxy groups with up to 10 carbon atoms), nitro groups, cyanogen groups, hydroxyl groups, fluorine groups (e.g., monochloro groups, trifluoromethyl groups, etc.), aromatic groups,・Rogen group (for example, a halogen atom directly connected to a carbon atom of an aromatic ring), a thioether group (particularly 01-CIO alkylthioethers), a sulfonyl group (-8O2-), a sulfinyl group (-SO-), etc. of such non-hydrocarbyl groups. Other examples will be apparent to those skilled in the art.

When non-hydrocarbyl substituents as described above are present in the hydrocarbyl group, their number is at most 2, preferably at most 1, for every 10 carbon atoms in the hydrocarbyl group.

However, it is generally preferred that no such non-hydrocarbyl substituents are present and the hydrocarbyl group is purely hydrocarbyl.

Typically, hydrocarbyl groups are free of ethylenically or acetylenically unsaturated bonds.

Examples of pure hydrocarpyl w groups have 1 to 3 carbon atoms.
0 saturated or unsaturated divalent aliphatic group, such as methylene, ethylene, 1,2-propylene, 1,3
-Propylene (i.e. trimethylene), l, 2-normal butylene, ■, 3-isobutylene, 1,4-pentylene, 1,3-hexylene, 1,2-dodecylene, l,
8-octadecylene, ■・2-butadienyl, ■・4-
Examples include groups such as butadienyl and 1,2-decane-5,6-enyl.

Examples of saturated and unsaturated alicyclic groups include 1,2-cyclohexylene, 1,4-cyclopentylene, 1,8-cyclohexylene, 1,3-cyclohexagenyl, 1,
Examples include 2-cyclopentadienyl.

Examples of aromatic divalent R groups include 1,2-phenylene, 1,4
-phenylene, 2,5-toluylene, 1,8-naphsarylene, etc.

Examples where the R' group is substantially hydrocarbyl are given above.

For example, the k group is 1 CF3(CH2)8CHCH2 group, It's a chair like the base. It's okay.

As mentioned above, the R' group may be a hydrocarbyl group interrupted by the Y group.

Usually such R' groups contain from 1 to about 6 Y groups.

Examples include alkylene groups having from 1 to about 6 carbon atoms and the corresponding sulfur, and amine analog groups (-
It is a polyalkylene group containing NR3).

To take a further example of an R' group interrupted by a Y group, if the R' group is a hydrocarbyl group interrupted by a Y group, the Y groups in different parts of the group need not be the same. .

For example, the following are also included within the scope of the above-mentioned definition of the group.

That is, the -CH2CH20CH2CH2NH- group and the Y group in the aforementioned N-substituted morpholine formula can each be a group containing oxygen, sulfur, or nitrogen.

Such groups include oxygen, divalent sulfur, tetravalent sulfur in the form of a sulfinyl group, hexavalent sulfur in the form of a sulfonyl group, or divalent sulfur in the form of a saturated or unsaturated amine group.
There is a valence of nitrogen.

When Y is an amino group -NR3, R3 is at least 1
a hydrocarbyl group or a hydrogen atom having 5 carbon atoms, or R''.

In some cases R3 may be R'' and in other cases it may be a C1-C14 hydrocarbyl group.

If R3 is R", everything that follows regarding R" also applies in this case.

R3 preferably contains no olefinic or acetylenic unsaturated bonds and contains up to 10 carbon atoms.

More preferably R3 is hydrogen, a C1-C8 alkyl group, or a phenyl group.

Examples of R3 groups include methyl group, ethyl group, furoyl group, phenyl group, benzyl group, tolyl group, cyclopentyl group, octyl group, isooctyl group, heptyl group, cyclohexyl group, dodecyl group, dodecenyl group, and the like.

The N-substituted morpholines of this invention contain at least one R" group, which R" group has at least 15 carbon atoms.
It has a hydrocarbyl group.

Preferably R" is small (containing 40 carbon atoms, more preferably at least 70 carbon atoms).

In a preferred embodiment, R has up to 1000 carbon atoms, and in a more preferred embodiment it has up to 250 carbon atoms.
That's it.

The hydrocarbyl group R'' can be derived from pure chemical compounds or from animal or vegetable oils such as tallow or coconut oil.

It may also be derived from mineral sources such as cracked wax olefins, various petroleum distillates, and the like.

However, more preferably it is ethylene, propylene, 1-butene, 2-butene, isobutyne, styrene,
It is derived from the polymerization (or copolymerization) of low molecular weight C2-C81 monoolefins such as hexene and the like.

Medial olefins having 2 to 8 carbon atoms can also be used.

Examples are 2-butene, 3-pentene and 4-octene.

In certain preferred embodiments, the R" group is derived from a . . . rogenated hydrocarbon having at least 15 carbon atoms, such that one or more . . . rogen atoms are bonded directly to an aliphatic carbon atom.

In this case, chlorinated or brominated hydrocarbons are preferred, with chlorinated hydrocarbons being particularly preferred.

Many such compounds are known.

As a specific example, para-tertiary octylbenzyl chloride, 1
-Iodopentadecane, 3-7' lomotricontane, 6
-chloro-tetracontane and the like.

Mixtures of these compounds can also be used.

However, as noted above, it is often preferred that R'' be derived from an olefinic polymer of low molecular weight 1-olefins.

Sometimes an intermediate step is included to halogenate the polymer.

Useful...rhodanized olefinic polymers have a number average molecular weight (Mn) of about 210 to about 100,000 (higher molecular weights are also useful and, in fact, N
It is preferred when it is desired that substituted morpholines have viscosity improving properties in lubricating oils).

Particularly useful are halogenated polymers with a minimum Mn of about 600.

The preferred maximum Mn is about 6000.

Examples of such polymers each have an Mn of 600.80
0.1900.2500.3000, etc.

Interpolymers of the C2-C8 olefins described above may also be used as a source of material for the rhodanized polymers of this invention.

Such interpolymers include, for example, isobutyne and ethylene, ethylene and propylene, propylene and 1-butene, 1-octene and 1-hexene, 1-heptene and 1-pentene, 3-methyl-1-butene and 1 - There are those obtained by polymerization of each such as octene.

The polymer used as a source of R" should preferably contain at least 80%, more preferably at least 95%, of saturated units derived from aliphatic monoolefins, and must contain at least 80%, more preferably at least 95%, of saturated units derived from aliphatic monoolefins and The olefinic bonds are up to 5% of the total number of bonds.

Specific examples of such polymers include a homopolymer of inbutylene, a binary copolymer of ethylene (65%) and propylene, a binary copolymer of 95% isobutyne and 5% allene, and isobutylene. Terpolymer of 98% and 1% of piperylene and 1% of 1-pentene, terpolymer of 95% of isobutene, 4% of propene and 1% of butadiene, 80% of 1-hexene and 20% of 1-heptene. and a terpolymer of 90% isobutene, 2% cyclohexene, and 8% propene.

(In this specification and claims, all "%"
'' and ``parts'' are by weight unless otherwise indicated.) Chlorinated and brominated polymers of butane, especially isobutane, are particularly preferred sources of R'' groups.

Such polymers are conveniently obtained by polymerizing butanes, such as isobutane, using Friedel-Crauff catalysts such as aluminum chloride, bromine trifluoride, titanium tetrachloride, and the like.

If commercially available isobutane is used for this polymerization, the polymer may contain small amounts of polymerized units of 1-butene or 2-butene, which are often present as impurities in commercially available isobutane.

For the purposes of this invention, the polyisobutyne may contain small amounts of polymerized or interpolymerized 1-butene or 2-butene.

A logenated hydrocarbon from which R" is derived can be obtained by treating a suitable hydrocarbon, such as the polymers described above, with a logenating agent such as chlorine, bromine, N-promosuccinimide, N-iodo-phthalimine, etc. It is conveniently manufactured by

Such methods are well known to those skilled in the art.

For example, by simply contacting the hydrocarbon with the halogenating agent at a temperature from about 50°C (preferably about 80°C) to below the decomposition point of the reaction mixture.

Typically, such halogenations are carried out at 80°C to 250°C, the exact temperature being determined by the halogenating agent used and the nature of the hydrocarbon to be halogenated.

The relative amounts of the hydrocarbon and the rogenating agent used in this reaction include, on average, at least about 1 atomic ratio of rogen per hydrocarbon molecule, and the aliphatic There is an atomic ratio of up to about 1 halogen for every 25 carbon atoms.

Such amounts will most often be about 1 mole of hydrocarbon and at least about 1 mole of halogenating agent.

The halogenated polymers useful for incorporating R" into the N-substituted morpholines of this invention contain at least about 1, and often 2, It contains halogen in an atomic ratio of 10 or more (for example, 10).

In most cases, the halogen content of such halogenated hydrocarbons is approximately O11% of the total weight of the halogenated hydrocarbons.
to 15%, preferably a minimum of about 2% and a maximum of about 9%.
It is.

In order to further produce a polymer with a high halogenation rate,
Needless to say, two or more moles of halogenating agent are used.

Halogenation can be carried out in the presence of a substantially inert solvent or diluent such as carbon tetrachloride, chloroform, chlorobenzene, benzene and the like.

This reaction often produces hydrogen halide, which is dissipated from the reaction mixture as the process progresses.

Although the exact chemical composition of the halogenated** polymers described above is not always known, such compounds contain on average about one or more .

For example, isobutane, chloroprene, vinyl bromide, etc.
It is preferable to use an interpolymerization reaction with a halogenated monomer and appropriately select the ratio of polymerizable olefin and polymerizable haloolefin so that the resulting interpolymer has a halogen content within the above range. It is also possible to produce halogenated polymers.

For this invention, there is no limit to the method by which the halogen is introduced into the olefin polymer.

Accordingly, any method known in the art may be used and the products obtained therefrom may be used as reactants in this invention.

Mixtures of halogenated hydrocarbons can also be used.

The methods for producing the N-substituted morpholines of this invention will be obvious to those skilled in the art.

A particularly preferred method is 0(CH2CH2)2NR'YH
The N-substituted morpholine intermediate having the structure is reacted with the above-mentioned halogenated polymer at a ratio of about 1 to 2 moles.

The more N-substituted morpholine intermediates described above can also be prepared by multiple methods well known to those skilled in the art.

For example, there is a method of producing 3-aminopropylmorpholine by reacting morpholine itself with acrylonitrile, which is available in many commercially available products, by microcondensation and hydrogenating the resulting product.

Similarly, epoxides such as ethylene oxide and propylene oxide, or mixtures thereof, can be reacted with morpholine to produce poly'N-hydroxyalkylenemorpholines of the formula:

(n is 1 to about 6) Similar reactions using episulfides and azelidines will be apparent to those skilled in the art.

Furthermore, there is a method in which a desired N-substituted morpholine intermediate is produced by reacting morpholine with an appropriately substituted low molecular weight organic halide, for example, by the following steps.

(X is halogen, R' and Y are as described above).

The reaction between the above-mentioned N-substituted morpholine intermediate and the above-mentioned rogenated hydrocarbon can be carried out by a known method using about 1 to about 2 moles of the latter for every 1 mole of the former.

It is often preferred or advantageous to have a hydrogen halide scavenger present during this reaction.

Examples of such scavengers include metal and ammonium carbonates, bicarbonates, oxides, hydroxides, amines (in particular,
tertiary amines such as pyridine) and also salts of organic acids such as carboxylic acids (especially alkali metal salts or alkaline earth metal salts of lower carboxylic acids).

Among the above-mentioned scavengers, preferred are carbonates, bicarbonates, oxides or hydroxides.

This is because, in addition to the metal halide and water, only carbon dioxide is produced by the reaction with the hydrogen halide produced during the above reaction.

In general, carbonates, bicarbonates, oxides and hydroxides of any metal are useful hydrogen halogen scavengers, but those of alkali metals and alkali metals are preferred, especially sodium, potassium , lithium, calcium and magnesium salts are preferred.

The hydrogen halide scavenger is preferably used in the reaction mixture in an amount of about 1 to 2 gram equivalents per gram equivalent of halogen present in the halogenated hydrocarbon.

Generally, about 0 per gram atom of halide present
．． From 5 to about 2 moles of hydrogen halide scavenger are used.

In general, the reaction of the aforementioned N-substituted morpholine intermediates with halogenated hydrocarbons will not pose much of a problem to those skilled in the art.

This reaction is carried out in an inert solvent in the presence of the hydrogen halogenide scavenger described above at about 20 to about 250°C with a temperature of about 0.0°C.
Preferably, this is carried out for 5 to about 24 hours.

Of course, the reaction temperature and reaction time can be changed depending on the type of reactants actually used.

Suitable inert solvents and diluents for the above reactions include readily available low-boiling hydrocarbon solvents such as pentane, heptane, benzene, toluene and xylene, oxygenated substances such as lower alkanols and ketones, and There are also high boiling hydrocarbons such as processed oils, natural oils, bright stocks, and various types of lubricant paste stocks.

If desired, the product can be recovered from such solvents or diluents by standard methods such as distillation, evaporation, precipitation, etc.

Alternatively, if the solvent or diluent is, for example, a lubricating oil base or a low molecular weight hydrocarbon, the product may be retained in the solvent or diluent to form a concentrate as described below.

Preferred embodiments of this invention are described below.

The products of Examples 1-5 consisted essentially of the formula: 17.75 parts of isopropyl alcohol, 17.7 parts of xylene.
A mixture of 75 parts of aminopropylmorpholine, 7.2 parts of aminopropylmorpholine, and 4.19 parts of a saturated aqueous solution of IJium hydroxide was heated to 75°C.

35.5 parts of polyisobutenyl chloride (Mn: 1000, chlorine content 5%) was gradually added to this mixture over 15 hours.

The reaction mixture was heated to 95-98°C for 5 hours,
This was then distilled off over 9.5 hours until the pot temperature was 175.
℃.

The organic layer was carefully decanted from the solids and the solids were washed with xylene.

The combined organic layers were vacuum stripped to 205° C./111 LwHg.

15.79 parts of xylene were added to the residue to obtain a 70% concentration of the desired product.

This was filtered through diatomaceous earth to make it transparent.

The nitrogen content of this concentrate was between 1.28% (Kjeldahl method) and 1.51% (Dumas method).

The product obtained in this example corresponds to formula (A) in which R' is propylene, R3 is hydrogen and R'' is polyisobutenyl with Mn 1000.

Example 2 Almost the same operation as in Example 1 was performed except that twice the amount of chlorinated polyisobutyne was used.

The desired dihydrocarbyl substituted aminopropylmorpholine was obtained.

This product has the formula (A), R' is propylene, R
3 and R'' each correspond to polyisobutenyl of Mn1OOO.

Example 3 Aminated N-ethoxylated morpholins containing on average 4 carbon atoms and 2 oxygen atoms in the ethoxyl substituents (
Amine C-6) 139.4 manufactured by Jefferson Chemical Company
A mixture of 100 parts of isopropyl alcohol and 100 parts of xylene was heated at 70°C in a nitrogen atmosphere.
heated to.

415 parts of polyisobutenyl chloride containing 4.3% chlorine and Mn 1300 were slowly added to the above mixture and then heated to 160° C. for 7 hours.

This mixture was filtered to remove solids and heated to 155°C/11r.
It was distilled down to LrlL.

190 parts of diluent oil were then added to this solution and filtered through diatomaceous earth to yield the desired product as a filtrate containing 30% diluent oil.

This concentrate contained 1.43% nitrogen.

This product mainly consists of formula (A) in which R' is ethyleneoxyethylene, R3 and R" are each Mn
It corresponded to 1300 polyisobutylene.

Incidentally, a product in which R' was ethylene was also produced as a by-product.

Example 4 The same operation as in Example 3 was carried out except that polyisobutenyl chloride having an Mn of 300 and having an average of one chlorine atom per molecule was used.

This product is the same as Example 3 except that the Mn of the polyisobutenyl is 300.

Example 5 Chlorine gas was passed through 500 parts of polyethylene having an Mn of 2500 and a Mw (weight average molecular weight) measured by gel permeation of 5000 at a rate of 1.25 parts per minute.

The polyethylene was maintained at 115-124° C. under a nitrogen atmosphere and irradiated with light from a commercially available solar lamp.

The chlorination was continued for 1 hour, and the polyethylene was then purified with a stream of nitrogen for 1 hour, yielding 531 parts of chlorinated product.

A mixture of 100 parts of the above chlorinated product and 24 parts of N-aminopropylmorpholine was heated at 190 to 200°C for 9 hours.
heated for an hour.

A mixture of 125 parts of xylene and 42 parts of saturated aqueous sodium hydroxide solution was then added and the reaction mixture thus obtained was maintained at 100-110° C. for 1 hour.

Separate the organic layer, dry it by azeotropic distillation,
The temperature was distilled down to 180°C/15mmHg.

To this was added 66 parts of diluent oil, and the mixture was filtered through diatomaceous earth at 110°C to obtain the desired N-substituted morpholine as a filtrate with an effective concentration of 60%.

This product has the formula (A), R' is propylene, R
3 is a mixture of polyethylene with Mn 2500 and R'' corresponding to hydrogen or polyethylene with Mn 2500.

Here we return to the main topic.

The morpholines of this invention are useful as additives in lubricant compositions that primarily act as dispersants (ie, keep sludge and dirt that accumulates in the compositions dispersed).

The morpholine of this invention can be used in various oils (
They can be used in a variety of lubricant compositions based, for example, on natural or synthetic lubricating oils or mixtures thereof.

Examples of such lubricant compositions include crankcases for spark-ignited and compression-ignited internal combustion engines (e.g., automotive and tractor engines, two-stroke engines, aircraft piston engines, marine and railway diesel engines, etc.). The lubricant is al.

It is also effective for use in lubricants, automatic transmission fluids, transmission shaft lubricants, gear lubricants, metalworking lubricants, pressure fluids, and other lubricating oil and grease compositions.

The natural oils include animal oil, vegetable oil (eg, castor oil, lard oil), and petroleum, solvent- or acid-refined paraffinic, naphthenic or mixed paraffin-naphthenic mineral lubricating oils.

Oils with lubricating viscosities derived from coal or shale are also useful base oils.

Synthetic lubricating oils include hydrocarbon oils such as polymerized and interpolymerized olefins and halogen-substituted hydrocarbon oils (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene, etc.), alkylbenzenes (e.g., dodecyl Benzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes, etc.), polyphenyls (e.g., eva, hypohenyls, terphenyls, etc.).

Polymers and interpolymers of alkylene oxides, as well as derivatives thereof, in which the terminal hydroxyl groups have been modified by esterification, etherification, etc., also constitute another category of known synthetic lubricating oils.

Examples of these include oils obtained by polymerization of ethylene oxide and propylene oxide, alkyl ethers and aryl ethers of these polyoxyalkylene polymers (for example, methyl-polyisopropylene glycol ether with an average molecular weight of 1000, molecular weight 500 to 1000) diphenyl ether of polyethylene glycol, molecular weight 10
00 to 1500 polypropylene glycol diethyl ether, etc.), or their mono- or polycarboxylic acid esters (e.g. acetate ester, mixed C3
~C8 fatty acid ester, C of tetraethylene glycol
13 oxo acid diester).

Other suitable synthetic lubricating oils include dicarboxylic acids (e.g., phthalic acid, succinic acid, maleic acid, azelaic acid, superric acid, sebacic acid, fumaric acid, adipic acid, lyluic acid dimer, etc.) and various alcohols. (Example: Eva, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-
There are esters of ethyl alcohol, ethylene glycol, etc.

Specific examples of these esters include dibutyl adipate, di(2-4-F-ruhexyl) sebacate, dinormalhexyl fumarate, dioctyl sebacate, diisooctyl azelaate, diisododecyl azelate, dioctyl phthalate, Examples include didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl diester of lyluic acid dimer, and complex esters obtained by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol.

Esters useful as synthetic oils further include C5-C1
□ Those obtained from monocarboxylic acids and polyols and polyol ethers such as trimethylolpropane, pentaerythritol, dipentaerythritol, etc.

Silicone oils such as polyalkylsiloxane oils, polyarylsiloxane oils, polyalkoxysiloxane oils or polyaryloxysiloxane oils as well as silicate oils are other suitable examples of synthetic lubricating oils.

Specific examples include tetraethyl silicate, tetraisopropyl silicate, tetra(2-ethylhexyl) silicate, tetra(4-methyl-2-tetraethyl) silicate,
Tetra silicate (tert-butylphenyl), hexyl-
Examples include (4-methyl-2-pentoxy)-disiloxane, poly(methyl)siloxanes, and poly(methylphenyl)siloxanes.

Still other synthetic lubricants include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate,
(diethyl ester of decanephosphinic acid, etc.), polymerized tetrahydrofurans, etc.

Generally, the lubricant compositions of this invention contain a sufficient amount of N-substituted morpholine to impart detergent properties to the composition.

Typically, this amount will be from about 0.05 to about 20% of the total weight of the lubricating composition.

Preferably, the minimum is about 0.50% and the maximum is about 10%.

For example, when the lubricant is used under extremely severe conditions, such as in a lubricant for marine diesel engines, up to about 30% by weight of the N-substituted morpholine of the present invention may be added.

In addition to the N-substituted morpholine, the lubricant composition of the present invention may contain other additives commonly used in lubricants.

Such additives include, for example, auxiliary detergents of the molded and ashless type, viscosity index improvers, pour point depressants, defoamers, extreme pressure agents, rust inhibitors, antioxidants and corrosion inhibitors. There is.

In a preferred embodiment of this invention, the N-substituted morpholine is used with an ashless dispersant.

Such ashless dispersants are preferably esters of monools or polyols and esters of high molecular weight mono- or polycarboxylic acylating agents containing at least 30 carbon atoms in the acyl moiety.

Such esters are well known in the art.

For example, French Patent No. 1396645, British Patent No. 981850 and British Patent No. 1055337, as well as US Patent No. 3255108, British Patent No. 3311558,
Same No. 3331776, Same No. 3346354, Same No. 3
No. 522179, No. 3579450, No. 3542
No. 680, No. 3381022, No. 3639242
No. 3697428 and No. 3708522
See also British Patent No. 1,306,529.

These patent documents describe suitable esters and their production methods.

Generally, the weight ratio of the N-substituted morpholine of this invention to the ashless dispersant is from about 0.1 to about 10.0 parts, preferably from about 1 to about 10 parts, of N-substituted morpholine per part of ashless dispersant. be.

In yet another embodiment of this invention, the N-substituted morpholines of this invention are used with Mannich condensation products made from substituted phenols, aldehydes, polyamines, and substituted pyridines.

Such condensation products are described in U.S. Pat. No. 3,649,659;
Same No. 3558743, Same No. 3539633, Same No. 3
No. 704308 and No. 3725277.

The N-substituted morpholines of this invention may be added directly to a lubricant or diluted with an inert solvent/diluent such as mineral oil to form an additive concentrate.

Such concentrates generally contain from about 20 to about 90% of the N-substituted morpholines of this invention and, in addition, include the conventional additives described above, as well as an ashless dispersant in the proportions described above. I don't mind.

Examples of lubricant compositions and concentrates of this invention are provided below.

Example 6 Solvent refined neutral 5AEIO mineral oil containing 1.5% of the product of Example 3.

Example 7 A synthetic lubricant consisting primarily of a 05-C9 normal alcohol ester of a 50:50 molar mixture of adipic acid and glutaric acid, containing 2.5% of the product of Example 2.

Example 8 A lubricating oil blending concentrate consisting of 50% of the mineral oil of Example 3 and 50% of the product of Example 2.

The fuel compositions of this invention may be used, for example, in accordance with ASTM Specification D-
Usually liquid fuels, such as gasoline as specified in ASTM Specification D-439-73 and diesel fuel as specified in ASTM Specification D-439-73, usually contain large amounts of hydrocarbonaceous petroleum distillate fuels.

Fuel compositions containing non-hydrocarbons such as alcohols, ethers, and organic nitrogen compounds also fall within the scope of this invention.

Particularly preferred is gasoline, a mixture of hydrocarbons having an ASTM boiling point of about 60° C. at 10% distillation point and about 205° C. at 90% distillation point.

Generally, these fuel compositions contain a sufficient amount of the N-substituted morpholines of this invention to impart detergency to the fuel.

Usually this amount is 1 to 50,000, preferably 4 to 5,000 parts by weight of the N-substituted morpholine per million parts by weight of fuel.

Preferred gasoline-based fuel compositions generally exhibit excellent carburetor cleanliness and anti-icing properties.

Furthermore, it exhibits excellent demulsifying properties and forms clean water-free fuel compositions.

The fuel composition of the present invention may contain other known additives in addition to the N-substituted morpholine that is the additive of the present invention.

Such additives include anti-knock agents such as tetraalkyl chains, lead scavengers such as haloalkanes, anti-sedimentation agents and modifiers such as triaryl phosphates, dyes, cetane improvers, 2.6 - Antioxidants such as di-tert-butyl-4-methylphenol, rust inhibitors such as alkylated co-phosphoric acids and their anhydrides, bacterial growth inhibitors, gum inhibitors, metal deactivators, upper cylinders. There are lubricants, etc.

In a preferred embodiment of this invention, the N-substituted morpholines described above are used in gasoline with an ashless dispersant.

This ashless dispersant has already been mentioned.

Generally, the weight ratio of the N-substituted morpholine of this invention and the ashless dispersant is about 0.1 to about 1 part of the former to 1 part of the latter.
0.0, preferably from about 1 to about 10 parts.

In still other embodiments, the N-substituted morpholines of this invention are used with Mannich condensation products, as in the lubricant compositions described above.

This condensation product has also been mentioned above.

The N-substituted morpholines of this invention can be added directly to a fuel or diluted with an inert solvent/diluent such as mineral oil and added to the fuel to form an additive concentrate. good.

Such concentrates generally contain from about 20 to about 90% of the N-substituted morpholines of this invention and, in addition, include the conventional additives described above, as well as an ashless dispersant in the proportions described above. I don't mind.

Examples of fuel compositions and concentrates of this invention are described below.

Example 9 Has a Reid vapor pressure of 10,5 psi and 2 per gallon
．． Gasoline containing 5 grams of lead and 100 parts of the product of Example 1 per million parts.

Example 10 Diesel fuel oil containing 200 parts of the product of Example 4 per million parts.

Example 11 Gasoline having a Reid vapor pressure of 15 psi and containing 2.1 grams of tetraethyl lead per gallon and 15 parts of the product of Example 2 per million parts.

TEST EXAMPLE A vaporizer freeze test was conducted on the product of Example 1.

In this test, a temperature of 7 to 9°C and a relative humidity of 10
0 air is fed to a Venturi Opel carburetor connected to a 6 cylinder Chevrolet engine running at 1750 rpm (no load).

The engine is run until enough ice forms on the throttle plate that it stalls when returned to idle speed.

1 750 required to stop in idle state
The time in the rpm state is measured in 15 second increments, and the time between one 15 second and the next 15 seconds is counted as the closest of the two.

The fuel oil used in this test was a hydrocarbon type that is particularly sensitive to freezing conditions.

When this fuel oil was subjected to the above test without adding any additives, the average time it took for the engine to stop was 2.75 minutes.

In contrast, the product of Example 1 was added to the same fuel oil containing 0.2% commercially available upper cylinder lubricant (no antifreeze) at 20% per 1000 barrels of fuel oil.
Add this at a rate of 4 pounds! When tested, the times ranged from 3.90 to 4.06 minutes for the two tests.

When the addition of the product of Example 1 was increased to 44.8 pounds per 1000 barrels of fuel oil, it was 3.95 to 4.13 minutes.

This result shows that the additive of the present invention has an extremely excellent anti-freezing effect.

Note that instead of the product of Example 1, Examples 2 to 5 were used.
A similar effect was obtained using the product.

Claims (1)

[Scope of Claims] 1 General formula (where R' is an alkylene group having up to 3 carbon atoms or an ethyleneoxyethylene group, R' is a hydrocarbyl derived from polybutene or polyethylene with a number average molecular weight of 300 to 2500) group, and R3
An additive for lubricants and fuels whose main component is an N-substituted morpholine compound represented by hydrogen or R''.