JPH0360876B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to novel compositions useful as lubricant additives, as well as additive concentrates and lubricants containing the same. In its broadest aspects, the invention provides for the presence of (A) at least one sulfurized alkyl phenol and (B) an aliphatic hydrocarbon group having a number average molecular weight of at least 1300 in its molecular structure attached to a polar group. This is a composition containing an oil-soluble carboxylic acid dispersant characterized by the following. In recent years, the demands on internal combustion engines have increased, leading to the development of multi-purpose additives that improve some of the stability and other desired properties of lubricants used in these engines under increasingly severe conditions. It is requested. In particular, today's internal combustion engines are often operated at much higher temperatures than has been the case in the past. It is necessary to add additives to this engine lubricant that improve its viscosity properties and disperse insoluble impurities in order to prevent them from depositing on engine parts. Under higher operating temperatures both the lubricating oil and the additives it contains degrade faster (through oxidation and other decomposition);
This results in more impurities to be dispersed and less additives capable of dispersing them and maintaining the desired viscosity. One solution to this is to add more additives into the lubricant, but
This solution is only effective over a long period of time if the additive in question is resistant to oxidative or similar degradation under the high temperatures at which the engine is operated. Accordingly, it is a primary object of this invention to provide a composition that imparts improved dispersion and viscosity modifying properties to lubricants under severe engine operating conditions. Furthermore, it is an object of the invention to provide compositions that have a high degree of resistance to oxidative degradation at elevated temperatures. It is also an object of this invention to provide additive compositions that are effective over a wide range of concentrations in lubricants. Another object is to provide lubricants for internal combustion engines that are useful under a variety of operating conditions, including at elevated temperatures, and additive concentrates that can be used in the manufacture of such lubricants. Component A of the compositions of this invention is at least one sulfurized alkylphenol. Sulfurized alkylphenols and methods for making them are known in the art and are described in the following US patents: US Pat. No. 2139766 No. 3285854 No. 2198828 No.
No. 3538166 No. 2230542 No. 3844956 No.
No. 2836565 No. 3951830 In general, sulfurized alkylphenols contain alkylphenols containing elemental sulfur, halogenated sulfur (e.g.
sulfur monochloride or sulfur dichloride), a mixture of hydrogen sulfide and sulfur dioxide, and the like. Preferred sulfiding agents are sulfur and sulfur halides, especially sulfur chloride, especially sulfur dichloride (SCl ₂ ). The alkylphenols that are sulfurized to form component A are generally compounds containing at least one hydroxy group and at least one alkyl group attached to the same aromatic ring. The alkyl group usually contains about 3 to 100 carbon atoms, preferably about 6 to 20 carbon atoms. Alkylphenols may contain more than one hydroxy group, as exemplified by alkylresorcinol, hydroquinone, and catechol, or may contain more than one alkyl group. However, usually it contains only one hydroxy group and one alkyl group each. Those in which the alkyl and hydroxy groups are ortho, meta and para to each other and mixtures thereof belong to the scope of this invention. Specific examples of alkylphenols include n-propylphenol, isopropylphenol, n-butylphenol, t-butylphenol, hexylphenol, heptylphenol, octylphenol, n-dodecylphenol, (propene tetramer) substituted phenol, Octadecylphenol, eicosylphenol,
Polybutene (molecular weight approximately 1000) substituted phenol, n
-dodecylresorcinol and 2,4-di-t
-Butylphenol. Also included are methylene-bridged alkylphenols of the type that can be made by reacting an alkylphenol with formaldehyde or a formaldehyde-generating reagent such as trioxane or paraformaldehyde. Sulfurized alkylphenols are typically produced by reacting an alkylphenol with a sulfiding agent at temperatures of about 100-250°C. This reaction may be carried out in a substantially inert diluent such as toluene, xylene, petroleum naphtha, mineral oil, cellosolve, and the like. When the sulfurizing agent is a sulfur halide, and especially when no diluent is used, acidic substances such as hydrogen sulfide can be removed by vacuum stripping the reaction mixture or by bubbling the reaction mixture with an inert gas such as nitrogen. It is often preferable to remove. When the sulfiding agent is sulfur, it is often advantageous to bubble the sulfided product with an inert gas such as nitrogen or air to remove oxidized sulfur and the like. A typical production example of a sulfurized alkylphenol is described below. In the following manufacturing examples, all "parts"
is based on weight. Production Example 1 A reactor was charged with 1000 parts of tetrapropene-substituted phenol, heated to 38°C, and nitrogen was blown into the reactor. 290 parts of sulfur dichloride were added over 4 hours, during which time the temperature rose to 54°C. The mixture was sparged with nitrogen for 2 hours at 147°C, cooled to 136°C, diluted with 400 parts of mineral oil, and stirred at 95°C for 2 hours. The mixture was then filtered through a filter aid to obtain an oil solution of the desired sulfurized alkylphenol containing 4.88% sulfur. Component B is an oil-soluble carboxylic acid dispersant, which is characterized by the presence in its molecular structure of a hydrocarbon group having a number average molecular weight of at least 1300 and bonded to a polar group. As will be seen from the following description, under certain conditions, dispersant molecules can
It may contain more than one hydrocarbon group or polar group. This type of dispersant is also an example of viscosity modification due to the presence of relatively high molecular weight hydrocarbon groups. As used in this specification, the term "aliphatic hydrocarbon group" refers to an aliphatic group having a carbon atom directly bonded to the remainder of the molecule and having primarily hydrocarbon character in the context of this invention. means base. Examples of such groups are shown below. (1) Hydrocarbon groups, i.e. alkyl or alkenyl groups. (2) Substituted hydrocarbon groups, ie, alkyl or alkenyl groups containing non-hydrocarbon substituents that do not alter the predominant hydrocarbon character of the group in the context of this invention. Suitable substituents will be apparent to those skilled in the art (eg, halo, nitro, hydroxy, alkoxy, alkylthio, carbalkoxy). (3) Heterogroups, that is, although they are primarily hydrocarbon in character, they contain atoms other than carbon in the chain or ring that would otherwise constitute the chain or ring. Base. Suitable heteroatoms will be apparent to those skilled in the art. For example, oxygen, nitrogen and sulfur. Generally, there will be no more than about 3, and preferably no more than 1 substituent or heteroatom for every 10 carbon atoms in the aliphatic hydrocarbon group. Dispersants intended to be used as component B are carboxylic dispersants, which consist of carboxylic acids or derivatives thereof and nitrogen-containing compounds having at least one NH group, such as amines, urea and hydrazine, and phenols or organic hydroxy compounds such as alcohols, and/or
It is a reaction product with a reactive metal or a reactive metal compound. US Pat. No. 3,271,310 describes the molecular structures and manufacturing methods of various types of carboxylic acid dispersants. A favorable example is the West German patent publication.
Described in No. 2808105. Various post-processed products of carboxylic dispersants are also useful as component B. Examples of post-treatment agents are sulfur and sulfur compounds, ureas, thioureas, guanidines, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds and phosphorus compounds. Suitable post-treatment agents and methods of manufacture are described in the following US patents: No. 3036003 No. 3254025 No. 3087936 No.
No. 3256185 No. 3200107 No. 3278550 No.
No. 3216936 No. 3280234 No. 3281428 No.
No. 3573010 No. 3282955 No. 3579450 No.
No. 3312619 No. 3591598 No. 3366569 No.
No. 3600372 No. 3367943 No. 3639242 No.
No. 3373111 No. 3649229 No. 3403102 No.
No. 3649659 No. 3442808 No. 3658836 No.
No. 3455831 No. 3697574 No. 3455832 No.
No. 3702757 No. 3493520 No. 3703536 No.
No. 3502677 No. 3704308 No. 3513093 No.
No. 3708522 No. 3533945 No. 4161475 No.
No. 3539633 Preferred carboxylic acid dispersants used as component B are those in which the acid moiety is substituted succinic acid. Dispersants of this type are most often prepared by reaction of an amine, alcohol, reactive metal or reactive metal compound with a suitable substituted succinic acylating agent. Suitable acylating agents include the aforementioned acids, acid anhydrides, esters and acid halides, with acids and acid anhydrides being preferred. The acylating agent comprises maleic acid, fumaric acid, maleic anhydride, etc. as a source of the desired hydrocarbon group, e.g. a polymer containing at least one olefin linkage (optionally in the presence of chlorine); Alternatively, it can be produced by alkylation with a polymer containing at least one halogen (preferably chlorine). As mentioned above, the number average molecular weight of the polymer is at least
It is 1300. This number average molecular weight is usually about 1500~
5000, but could be 1000000 or more in some cases. The ratio of weight average molecular weight to number average molecular weight (w/n) is approximately
1.5 to 6.0, usually about 1.5 to 4.0. The molecular weight of these polymers can be conveniently determined by gel permeation chromatography. The polymers that are the source of the hydrocarbon substituents are generally homo- or interpolymers of polymerizable olefin monomers containing from about 2 to 16 carbon atoms, usually from about 2 to 6 carbon atoms. Examples of monomers of this type are ethylene, propylene, 1-butene, 2-butene, isobutene, 1-octene and 1-decene. The polymers include conjugated dienes such as 1,3-butadiene and isoprene, non-conjugated dienes such as 1,4-hexadiene, 1,4-cyclohexadiene, 5-ethylidene-2-norbornene and 1,6-octadiene, and 1-isopropylidene-3a,4,7,7a-tetrahydroindene, 1-isopropylidenedicyclopentadiene and 2-(2-methylene-4-methyl-3
-pentenyl) [2.2.1] may contain units derived from triene-containing polyenes such as bicyclo-5-heptene. A first preferred class of such polymers are polymers of terminal olefins such as propylene, 1-butene, isobutene and 1-hexene. Particularly preferred within this class are polybutenes consisting primarily of isobutene units. A second preferred class are terpolymers of polyenes selected from the group consisting of ethylene, _C3 - _C8 alpha-monoolefins, and non-conjugated dienes (especially preferred) and trienes. An example of this terpolymer is Orthollium 2052, manufactured by DuPont, which contains 48 mol% ethylene units, 48 mol% propylene units, and 4 mol% 1,4-hexadiene. It is a terpolymer containing an intrinsic viscosity of 1.35 (carbon tetrachloride 100ml
8.2 g of medium polymer (30°C). Processes for making substituted succinic acids and their anhydrides are well known and need not be discussed in detail here. The ratio of polymer to maleic acid or its anhydride is 1, greater than 1, or less than 1, depending on the type of dispersant product desired. However, if the dispersant is on average at least
It is often preferred to use a ratio that will contain 1.3 succinic acid moieties. Such a dispersant can be referred to as a "polysuccinated dispersant." Particularly preferred are about
Polysuccinated dispersants containing 1.4 to 3.5 and most preferably about 1.5 to 2.5 succinic acid groups. The carboxylic acid dispersants are prepared by reacting a substituted succinic acid, its anhydride, or other acylating agent with at least one nitrogen compound, hydroxy compound, reactive metal or reactive metal compound, or a mixture of any of these. You can get it. Particularly preferred dispersants are those obtained by reacting a succinic acylating agent with at least one amine or a combination of at least one amine and at least one alcohol in any order.
Suitable amines and alcohols are discussed below. Preferred nitrogen compounds are groups having the structure NH, where the remaining two valencies are satisfied by hydrogen, amino groups or organic groups bonded to the nitrogen atom by direct carbon-nitrogen bonds. It is characterized by: These compounds include aliphatic amines, aromatic amines, alicyclic amines, and carbocyclic amines, as well as substituted ureas, thioureas, hydrazines, guanidines, amidines, amides, thioamides, cyanamides, and the like. Amines useful in making dispersants include monoamines. The monoamine may be secondary, ie, having only one hydrogen atom directly bonded to the amino nitrogen atom. however,
Preferably, the monoamine contains at least one primary amino group, ie a group in which an amino nitrogen atom is bonded directly to two hydrogen atoms. These monoamines are generally substituted with _C1 - _C30 hydrocarbon groups. Preferably, these hydrocarbon groups are aliphatic in character, free of acetylenic unsaturation, and contain 1 to 10 carbon atoms. 1
Particularly preferred are saturated aliphatic hydrocarbon radicals containing up to 10 carbon atoms. Preferred monoamines for making dispersants have the general formula HNR ¹ R ² , where R ¹ is an alkyl group having up to 10 carbon atoms, and R ² is hydrogen or 10
(alkyl groups having up to 5 carbon atoms). Other preferred monoamines have the general formula
HNR ³ R ⁴ (wherein R ³ is a phenyl group, an alkylated phenyl group, a naphthyl group or an alkylated naphthyl group each having up to 10 carbon atoms,
and R ⁴ is an aromatic monoamine represented by hydrogen, an alkyl group having up to 10 carbons or the same group as R ³ ). Examples of suitable monoamino acids include ethylamine, diethylamine, n-butylamine, di-n-butylamine, allylamine,
Isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine, oleylamine, aniline, methylaniline, N-
Methylaniline, diphenylamine, benzylamine, tolylamine and methyl-2-cyclohexylamine. Hydroxyamines are also included in the class of useful monoamines. This compound is a hydroxyhydrocarbyl substituted analog of the monoamine. Preferred hydroxyamines are HNR ⁵ R ⁶ and HNR ⁷ R ⁸
(where R ⁵ is an alkyl group or a hydroxy-substituted alkyl group each having up to 10 carbon atoms, R ⁶ is hydrogen or a group similar to R ⁵ , and R ⁷ is a hydroxy-substituted alkyl group each having up to 10 carbon atoms. Phenyl group, alkylated phenyl group, naphthyl group or alkylated naphthyl group, R ⁸ is hydrogen or R ⁷
and at least one of R ⁵ and R ⁶ and at least one of R ⁷ and R ⁸ are substituted with hydroxy. Suitable hydroxy-substituted monoamines include ethanolamine, di-3-propanolamine, 4-hydroxybutylamine, diethanolamine, N
-methyl-2-propylamine, 3-hydroxyaniline, N-hydroxyethylethylenediamine, N,N-di(hydroxypropyl)propylenediamine and tris(hydroxymethyl)methylamine. Generally, hydroxyamines containing only one hydroxy group are used as reactants, although those containing more hydroxy groups can also be used. Heterocyclic amines are also useful in preparing the dispersants used in this invention if they contain primary or secondary amino groups. The heterocycle may contain unsaturation and may be substituted with hydrocarbon groups such as alkyl, alkenyl, aryl, alkaryl or aralkyl groups. Additionally, the heterocycle may contain other heteroatoms such as oxygen, sulfur, or other nitrogen atoms such as nitrogen atoms to which no hydrogen atom is attached. Generally, these heterocycles have 3 to 10 members, preferably 5 or 6 members. Such heterocycles include aziridine, azetidine, azolidine, pyridine, pyrrole, piperidine, imidazole,
These include indole, piperazine, isoindole, purine, morpholine, thiamorpholine, N-aminoalkylmorpholine, N-aminoalkylthiamorpholine, azepine, azocine, azonine, azecine and their respective tetrahydro, dihydro and perhydro derivatives. Preferred heterocyclic amines are saturated with a 5- or 6-membered ring, in particular the abovementioned piperidine, piperazine and morpholine. Polyamines are preferred for making dispersants.
This polyamine contains the formula (where n is an integer from about 1 to 10, preferably from 2 to 8, each A is independently hydrogen or a hydrocarbon group having up to about 30 carbon atoms or a hydroxy-substituted hydrocarbon group, and R ⁹ is Alkylene polyamines (and mixtures thereof) include those having divalent hydrocarbon radicals having about 1 to 18 carbon atoms. Preferably, A is an aliphatic group having up to about 10 carbon atoms, which may be substituted with 1 or 2 hydroxy groups;
And ^R9 is a lower alkylene group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms. Particularly preferred are alkylene polyamines in which each A is hydrogen. Such alkylene polyamines include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines, and heptylene polyamines. Higher homologs of such amines and related aminoalkyl-substituted piperazines are also included. Specific examples of such polyamines include ethylenediamine, triethylenediamine, tris(2-aminoethyl)amine, propylenediamine, trimethylenediamine, hexamethylenediamine, decamethylenediamine, octamethylenediamine, and di(heptamethylene)triamine. , tripropylenetetraamine, tetraethylenepentamine, trimethylenediamine, pentaethylenehexamine, di(trimethylene)triamine, 2-heptyl-3-
(2-aminopropyl)imidazoline, 1,3-
Bis(2-aminoethyl)imidazoline, 1-
(2-aminopropyl)piperazine, 1,4-bis(2-aminoethyl)piperazine and 2-methyl-1-(2-aminobutyl)piperazine. Higher homologs obtained by condensing two or more of these alkylene aminos are also useful. The ethylene polyamines exemplified above are particularly useful in terms of price and performance. Such polyamines are described in Kirk-Osmer's Encyclopedia of Chemical Technology, 2nd edition, No. 7.
It is described in detail in the section entitled ``Diamins and Higher Amins'' on pages 22 to 39 of Volume 22. These are most conveniently prepared by reaction of alkylene chloride with ammonia or by reaction of ethyleneimine with a ring opening agent such as ammonia. These reactions produce somewhat complex mixtures of alkylene polyamines including cyclic condensation products such as piperazine. Such mixtures are particularly useful in the preparation of dispersants because of their ready availability. Satisfactory products are also obtained by using pure alkylene polyamines. Also useful are hydroxypolyamines, such as alkylenepolyamines having one or more hydroxyalkyl groups on the nitrogen atom. Preferred hydroxyalkyl-substituted alkylene polyamines are those in which the hydroxyalkyl group has about 10 or fewer carbon atoms.
Examples of such hydroxyalkyl-substituted polyamines include N-(2-hydroxyethyl)ethylenediamine, N,N'-bis(2-hydroxyethyl)ethylenediamine, 1-(2-hydroxyethyl)piperazine, monohydroxypropyl Substituted diethylenetriamine, dihydroxypropyltetraethylenepentaamine and N-(3
-hydroxybutyl)tetramethylenediamine. Higher homologues obtained by condensation of the above hydroxyalkyl-substituted alkylene aminos via amino or hydroxy groups are also useful. Other amino compounds useful for making dispersants include aliphatic and aromatic amino sulfonic acids, such as 2-amino-2-methylpropanesulfonic acid and anthranilic acid, as well as aliphatic and aromatic aminosulfonic acids such as There are polyoxyalkylene polyamines such as "diefamine". Dispersant is hydrazine or general formula (where each R <sup>10</sup> is independently hydrogen or C <sub>1</sub> ~
It can also be prepared from an organic substituted hydrazine in which the <sub>C30</sub> hydrocarbon group is represented by at least one <sup>R10</sup> being hydrogen, preferably the other <sup>R10</sup> being a <sub>C1</sub> - <sub>C10</sub> aliphatic group. Preferably at least two R <sup>10</sup> 's are hydrogen, more preferably at least two <sup>10</sup> 's bonded to the same nitrogen atom are hydrogen and the remainder are alkyl groups containing up to 10 carbon atoms. Examples of suitable substituted hydrazines include methylhydrazine,
N,N-dimethylhydrazine, N,N'-dimethylhydrazine, phenylhydrazine, N-phenyl-N'-ethylhydrazine, N-(p-tolyl)
-N'-(n-butyl)hydrazine, N-(p-nitrophenyl)-N-methylhydrazine, N,
N'-di(p-chlorophenyl)hydrazine and N-phenyl-N'-cyclohexylhydrazine. Suitable organic hydroxy compounds include methynol,
Ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, dodecanol, hexadecanol, etc.
"Chemical Technology" 2nd edition, Volume 1, 542~
“Higher Foothold Alcohols” on page 557
There are monohydric and polyhydric hydrocarbon alcohols, such as fatty alcohols and mixtures thereof, which are described in detail in the section . This type of alcohol includes lauryl alcohol, myristyl alcohol,
There are cetyl alcohol, stearyl alcohol and behenyl alcohol. Fatty alcohols containing small amounts of unsaturation (e.g., up to two carbon-carbon unsaturations per molecule) are useful as well, such as palmitole alcohol (C <sub>16</sub> H <sub>30</sub> O),
Illustrated by oleyl alcohol (C <sub>18</sub> H <sub>36</sub> O) and eicosenyl alcohol (C <sub>20</sub> H <sub>40</sub> O). Higher grades of the type obtained by the oxo process (e.g. 2-ethylhexyl alcohol), by aldol condensation or by organoaluminium-catalyzed oligomerization of α-olefins (especially ethylene) followed by oxidation. Monohydric synthetic alcohols are also useful. These higher synthetic alcohols are described in detail in "Encyclopedia of Chemical Technology", Volume 1, pages 560-569. Also useful as organic hydroxy compounds are the cyclic analogs of the alcohols mentioned above. Examples are cyclopentanol, cyclohexanol and cyclododecanol. Polyhydroxy compounds are also useful. This includes ethylene, propylene, butylene, in which the hydroxy group is separated by two carbon atoms,
Pentylene, hexylene and heptylene glycols, as well as tri, tetra, penta, hexa and heptamethylene glycols and their hydrocarbon substituted analogues, as well as diethylene glycol and higher polyethylene glycols, tripropylene glycol, dibutylene glycol, dipentylene Included are glycols, dihexylene glycol and diheptylene glycol and their monoethers. Phenols, naphthols, substituted phenols (e.g. cresol) and dihydroxy aromatic compounds (e.g. resorcinol, hydroquinone) as well as benzyl alcohol and similar dihydroxy compounds in which a second hydroxy group is attached directly to the aromatic ring (e.g. HOC <sub>6</sub> H <sub>4</sub> CH <sub>2</sub> OH) also has the general formula
HOCH <sub>2</sub> (CHOH) <sub>1-5</sub> CH <sub>2</sub> OH sucrose alcohols such as glycerol, sorbitol, mannitol, etc. (see Encyclopedia of Chemical Technology, Vol. 2, pp. 569-588) and partially esterified derivatives thereof Also useful are pentaerythrite and its oligomers (such as di- and tripentaerythrite), methylol polyols such as trimethylolethane and trimethylolpropane. Additionally, useful hydroxy compounds are polyoxyalkylene compounds of the type commonly commercially available as demulsifiers. These include “etmene”;
These include ``Etduomene,''``Pluronik,''``Tergitol,''``Tetronik,'' and ``Dow Polyglycol.'' Preferred hydroxy compounds are alcohols containing up to about 40 aliphatic carbon atoms, especially about 2 to 10
polyhydric alcohols containing about 3 to 6 carbon atoms and usually about 3 to 6 hydroxy groups (e.g.
glycerol, pentaerythritol, sorbitol, mannitrate, trimethylolethane and trimethylolpropane). Pentaerythritol is particularly preferred. Examples of reactive metal compounds include lithium oxide, lithium hydroxide, lithium carbonate, lithium pentyl oxide, sodium oxide, sodium hydroxide, sodium carbonate, sodium methoxide,
Sodium propoxide, potassium oxide, potassium hydroxide, potassium carbonate, potassium methoxide,
Magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium methoxide, magnesium propoxide, magnesium salt of ethylene glycol monomethyl ether, calcium oxide,
Calcium hydroxide, calcium carbonate, calcium methoxide, calcium propoxide, calcium pentyl oxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc propoxide, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmium carbonate, Cadmium ethoxide, barium oxide, barium hydroxide, barium carbonate, barium ethoxide, barium pentyl oxide, aluminum oxide, aluminum isopropoxide, cupric acetate, lead oxide, lead hydroxide, lead carbonate, tin oxide, tin butoxide , cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt pentyl oxide, nickel oxide, nickel hydroxide, nickel chloride, nickel carbonate and chromium acetate (). A production example of a carboxylic acid dispersant useful as component B is shown below. Production Example 2 A mixture of 510 parts (0.28 mol) of polybutene (n = 1845, w = 5325) mainly consisting of isobutene units and 59 parts (0.59 mol) of maleic anhydride was heated to 190°C over 7 hours, during which time chlorine gas was added. 43
(0.6 mol) was added subsurface. An additional 11 parts (0.16 moles) of chlorine were added over 3.5 hours at 190-192°C. The reaction mixture was stripped by bubbling nitrogen at 190-193°C for 10 hours. The residue was polybutene-substituted succinic anhydride having a hydrogen number of 87. 10.2 parts (0.25 equivalents) of a commercially available mixture of ethylene polyamines having an average of 3 to 10 nitrogen atoms per molecule were mixed with 113 parts of mineral oil and the above substituted succinic anhydride.
A mixture was prepared by adding 161 parts (0.25 equivalents). The mixture was heated to 150°C for 2 hours and stripped by nitrogen blowing,
An oil solution of the desired dispersant was obtained by filtration. Manufacturing example 3 Manufacturing example 2 except that n is 2020 and w is 6049
1000 parts (0.495 mol) of polybutene similar to that of
A mixture of 115 parts (1.17 moles) of maleic anhydride and maleic anhydride was heated to 184°C over 6 hours while 85 parts (1.2 moles) of chlorine gas was added subsurface. 184～189
An additional 59 parts (0.83 moles) of chlorine was added over a period of 4 hours. The reaction mixture was stripped by bubbling nitrogen at 186-190°C for 26 hours. The residue was polybutene-substituted succinic anhydride having a hydrogen valence of 87. A mixture was prepared by adding 57 parts (1.38 equivalents) of the ethylene polyamine mixture from Preparation Example 2 to 1067 parts mineral oil and 893 parts (1.38 equivalents) of the above substituted succinic anhydride. Cook this mixture for 3 hours
It was heated to 155° C., stripped with nitrogen blowing, and filtered to obtain an oil solution of the desired dispersant. Production Example 4 18.2 parts (0.433 equivalents) of the ethylene polyamine mixture from Production Example 2 were added to 392 parts of mineral oil and 348 parts (0.52 equivalents) of the substituted succinic anhydride from Production Example 3 to prepare a mixture. This mixture was heated to 150℃ for 1.8 hours.
The mixture was heated to , stripped with a nitrogen purge, and filtered to give an oil solution of the desired dispersant. Production Example 5 334 parts (0.52 equivalents) of the substituted succinic anhydride of Production Example 3, 548 parts of mineral oil, 30 parts (0.88 equivalents) of pentaerythrite, and Dow Polyglycol 112-2
A mixture of 8.6 parts (0.0057 equivalents) of demulsifier was heated to 210°C over 8.2 hours. Then, this was cooled to 190°C, and 8.5% of the ethylene polyamine mixture of Production Example 2 was added.
part (0.2 equivalents) was added. Add 3 to this mixture at 205℃
Stripped by bubbling nitrogen for an hour and filtered to obtain an oil solution of the desired dispersant. Manufacturing example 6 Following the process of manufacturing example 2, n is 1457 and w is 5808
Substituted succinic anhydride was prepared using a similar polybutene. A mixture of 5,500 parts of this anhydride, 3,000 parts of mineral oil, and 236 parts of the ethylene polyamine mixture of Preparation Example 2 was heated at 155-165°C for 2 hours and filtered to obtain an oil solution of the desired dispersant. Preparation Example 7 Preparation Example using 1 equivalent of the substituted succinic anhydride of Preparation Example 3, 1 to 8 equivalents of pentaerythritide, 0.2 equivalents of the ethylene polyamine mixture of Preparation Example 2, and an amount of mineral oil to provide a 30% solution of the product. The desired product was obtained according to step 5. Production example 8 98 parts of maleic anhydride was used as "Orthollium 2052"
The desired product was obtained by the process of Preparation Example 3 using the substituted succinic anhydride obtained by reacting with a 10% solution of C. in mineral oil. Preparation Examples 9-26 The desired products were prepared according to the steps in Preparation Example 2 using the ingredients shown in the table.

In Preparation Example 9, ZnO was added to a polybutene-substituted succinic anhydride-mineral oil mixture at 78° C. with water, the mixture was heated to 95° C. for 4 hours, and then the steps of Preparation Example 2 were followed. Generally, the compositions of this invention will contain from about 0.3 to 3.0 parts by weight of Component A per 1 part by weight of Component B. This proportion refers to the active compound. That is, this percentage ignores diluents such as mineral oil. The preferred ratio is Component A to 1 part of Component B.
is about 0.3 to 1.0 parts. As previously stated, the compositions of this invention are useful as lubricant additives, where they act primarily as dispersants and viscosity modifiers. The compositions of this invention are particularly useful for lubricating machinery operating at relatively high temperatures and are effective over a wide range of concentrations. Additionally, this composition contains antioxidants that must be included in the lubricant (examples of which are given below).
decrease the amount of The compositions of this invention can be used in a variety of lubricants based on a variety of oils of lubricating viscosity, including natural and synthetic lubricating oils, as well as mixtures thereof. These lubricants include crankcase lubricants for spark ignition and compression ignition internal combustion engines such as automotive and truck engines, two-stroke engines, piston aircraft engines, marine and railroad diesel engines, and the like. The compositions of this invention may also be used in gas engines, stationary power engines, turbines, and the like. Automotive transmission fluids, transmission shaft lubricants, gear lubricants, metal working lubricants, pressure fluids, and other lubricating oil and grease compositions may also benefit from the compositions of this invention. Natural oils include animal and vegetable oils (e.g. castor oil, lard oil), as well as petroleum and paraffinic oils.
Included are mineral lubricating oils, such as naphthenic or paraffin-naphthenic mixed solvent-treated or acid-treated 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 halo-substituted hydrocarbon oils [e.g., polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene, poly(1-hexene), poly( 1-octene), poly(1-decene), etc., and mixtures thereof], alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene, etc.), polyphenyl (e.g., biphenyl, terphenyl) , alkylated polyphenyls, etc.), alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives, analogs and congeners, and halo-substituted hydrocarbon oils. Polymers and interpolymers of alkylene oxide, as well as derivatives thereof whose terminal hydroxyl groups have been modified by esterification, etherification, etc., are also known synthetic lubricating oils. Examples of these are:
Oils obtained by polymerization of ethylene oxide or propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (for example, methylpolyisopropylene glycol ether with an average molecular weight of 1000, diphenyl ether of polyethylene glycol with a molecular weight of 500 to 1000, molecular weight
1000~1500 polypropylene glycol diethyl ether etc.) or acetate ester, mixed C3 _~
These include mono- and polycarboxylic acid esters such as C ₈ fatty acid esters, or C ₁₃ oxoacid diesters of tetraethylene glycol. Other suitable synthetic lubricating oils include dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acid, alkenylsuccinic acid, maleic acid, azelaic acid,
suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid, etc.) and various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol) , ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, and sebacin. These include dieicosyl acid, 2-ethylhexyl diester of linoleic acid dimer, and composite ester obtained by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid. Esters useful as synthetic oils include those made from C ₅ -C ₁₂ monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythrite, dipentaerythrite, tripentaerythrite, etc. Also included. Silicone-based oils such as polyalkyl, polyaryl, polyalkoxy or polyaryloxysiloxane oils and silicate oils are also useful synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra(2)
-ethylhexyl) silicate, tetra(4-methyl-2-ethylhexyl) silicate, tetra(p-tert-butylphenyl) silicate, hexyl(methyl-2-pentoxy)disiloxane,
poly(methyl)siloxane, poly(methylphenyl)siloxane, etc.). Other synthetic lubricating oils include liquid esters of phosphorous acids (tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid, etc.), polymerized tetrahydrofurans, and the like. Unrefined, refined and rerefined oils of the above types, natural or synthetic (and even mixtures of two or more of these), may be used in the lubricant compositions of this invention. Unrefined oils are those obtained directly from natural or synthetic sources and have not undergone any refining treatment. For example, sierre oil obtained directly from a retorting operation, petroleum oil obtained directly from a primary distillation, or ester oil obtained directly from an esterification process 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. Many such purification methods are known to those skilled in the art. For example, solvent extraction, acid or base extraction, filtration, percolation, etc. Rerefined oil is obtained by applying a method similar to that used to obtain refined oil to already used refined oil. Such rerefined oils, also known as reclaimed oils, are often further processed by methods to remove spent additives and oil breakdown products. Generally, the lubricant compositions of this invention contain a sufficient amount of the compositions of this invention to impart dispersibility and improve viscosity properties. Usually this amount is
About 0.05 to 10.0% by weight, preferably about 0.1 to 5.0% by weight per 100 parts of lubricant. In lubricating oils that operate under extremely harsh conditions, such as lubricating oils for marine diesel engines, the magnesium complexes of this invention may be present up to about 20%. This invention also contemplates the use of other additives in addition to the compositions of this invention. Other additives useful in lubricants include, for example, ash-forming or ashless auxiliary detergent dispersants, corrosion inhibitors, antioxidants, pour point depressants, extreme pressure agents, color stabilizers and quenchers. It is a foaming agent. Particularly preferred in this invention is that together with component A and component B, (C) at least one
Component C
and component A is usually about 0.05 to 1.0:1, preferably about 0.1 to 0.5:1. Examples of ash-forming detergents useful as component C include sulfonic acids (preferred), carboxylic acids or olefin polymers (e.g.
polyisobutene), phosphorus trichloride, phosphorus heptasulfide,
Characterized by having at least one direct carbon-phosphorus bond, such as those obtained by treatment with phosphorous agents such as phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and sulfur halides, or phosphorodithioyl chloride. oil-soluble neutral and basic alkali metal or alkaline earth metal salts of organic phosphorus-containing acids. The most commonly used salt is
sodium, potassium, lithium, calcium,
those of magnesium, strontium and barium. Calcium and magnesium salts are preferred. The properties of suitable ash-forming detergents are well described in the literature and will be apparent to those skilled in the art. "Basic salt" means a metal salt in which the metal is present in a stoichiometrically larger amount than the organic acid radical.
A commonly used method for preparing this basic salt is to prepare a solution of the acid in mineral oil with a stoichiometric excess of a metal neutralizing agent such as a metal oxide, hydroxide, carbonate, bicarbonate or sulfide. This method involves heating the product at a temperature of 50°C or higher and filtering the resulting product.
It is known to use "accelerators" in the neutralization step to assist in introducing large excesses of metal.
Examples of compounds useful as accelerators include phenols, naphthols, alkylphenols, thiophenols, sulfurized alkylphenols and phenolic substances such as condensation products of formaldehyde and phenolic compounds, methanol, 2-
Alcohols such as propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol and cyclohexyl alcohol, and aniline, phenylene diamine, phenothiazine, phenyl-β-
Amines such as naphthylamine and dodecylamine. An effective method for producing basic salts is to mix the acid with an excess of an alkaline earth metal neutralizer and at least one alcoholic accelerator, and to raise the temperature of the mixture to between 60 and 200°C. This method involves carbonation at the bottom. Particularly preferred as component C for certain purposes are basic magnesium sulfonates and basic magnesium sulfonates in a ratio of about 0.2 to 2.0:1, especially about
It is a mixture in a ratio of 0.5 to 1.5:1. Compositions containing such mixtures have been found to exhibit excellent cleanliness and dispersibility under high temperature engine operating conditions, such as in diesel engines. These properties are evidenced by the very low levels of carbon and lacquer deposits. Supplemental ashless detergents and dispersants are so called despite the fact that, depending on their structure, they burn to produce non-volatile substances such as boron oxide and phosphorus pentoxide. However, since it usually does not contain metals, it does not produce metal-containing ash upon combustion. Many types are known and are described in patents and the like that refer to component B. The interpolymerization of oil-soluble monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers having polar groups such as aminoalkyl acrylates, acrylamide and poly(oxyethylene) substituted acrylates. Coalescing agents are also useful as supplemental dispersants. This is characterized as a "polymeric dispersant" and is described in the following US patents: No. 3329658 No. 3666730 No. 3449250 No.
No. 3687849 No. 3519565 No. 3702300 Examples of extreme pressure agents, corrosion inhibitors and antioxidants include chlorinated aliphatic hydrocarbons such as chlorinated waxes, benzyl disulfide, bis(chlorbenzyl) disulfide, Organic sulfides and polysulfides such as dibutyl tetrasulfide, sulfurized methyl esters of oleic acid, sulfurized alkylphenols, sulfurized dipentene and sulfurized terpenes, phosphosulfurized carbons such as the reaction products of phosphorus sulfide and turpentine or methyl oleate. Hydrogen, dibutyl phosphinate, diheptyl phosphinate, dicyclohexyl phosphinate, pentylphenyl phosphinate, dipentylphenyl phosphinate, tridecyl phosphinate, distearyl phosphinate, dimethylnaphthyl phosphinate, oleyl 4-pentylphenyl phosphinate, phosphine Acid polypropylene (molecular weight 500)
Substituted phenyl, diisobutyl phosphinate Phosphorus esters mainly based on dihydrocarbons or trihydrocarbons such as substituted phenyl, thiocarbamate metal salts such as zinc dioctyl dithiocarbamate and barium heptyl phenyl dithiocarbamate, dicyclohexyl phosphorodithio Zinc acid, zinc dioctylphosphorodithioate, barium di(heptylphenyl)phosphorodithioate,
Group metal salts of phosphorodithioic acids, such as cadmium dinonylphosphorodithioic acid, and zinc salts of phosphorodithioic acids obtained by reaction of phosphorus pentasulfide with an equimolar mixture of isopropyl alcohol and n-hexanol. The compositions of this invention can be added directly to lubricants or fuels. Preferably, however, it is diluted to a concentrate with a substantially inert conventional liquid organic diluent such as mineral oil, naphtha, benzene, toluene or xylene. The additive concentrate generally contains about 20 to 90% by weight of the composition of the invention and may additionally contain one or more of the other additives mentioned above. The table below lists examples of lubricants of this invention. All amounts except for the products of Preparations 1, 3, 4 and 7 exclude diluents such as mineral oil.
The ratio of component A to component B in the bottom column of the table excludes mineral oil.

[Table] The composition listed as lubricant A in the table was subjected to a Ford Sequence V-C test (Ford Sequence V-C test).
Evaluation was made using the V-C Test). Although high temperature performance is a desirable feature of the lubricants of the present invention, such lubricants must also exhibit satisfactory performance over a wide range of operating conditions. Therefore, performance at low temperatures is also important. The Food Sequence V-C test shows performance at low temperatures, particularly with respect to sludge and varnish formation. This test used a 302 cubic inch (5) displacement Ford V-8 engine that was operated for a total of 192 hours. This engine was run at 175〓 (79℃) for 2 hours, then 200〓
One set consists of operating for 1.25 hours at (93℃) and 0.75 hours at 120〓 (49℃), and this set is repeated for a total of 16 hours, followed by a 16-hour period in which the engine is not running.
The 16 hour run and 8 hour soak period continued until 192 hours had elapsed. Used leaded fuel. The performance parameters measured are average engine sludge and average engine varnish. The test results for Lubricant A are shown in the table. Table test item Lubricant A details Average engine sludge 9.34 Minimum 8.5 Average engine varnish 7.76 Minimum 8.3 The composition listed as Lubricant B in the table was tested in the Caterpillar 1-H-2 test (Caterpillar 1-H-2 test).
2 Test). In this exam,
A single-cylinder supercharged diesel test engine with a displacement of 2188 ^cm3 was used. The test was conducted for a total of 480 hours at 1800 rpm while maintaining the oil temperature at 82°C.
The factor evaluated is piston deposits. Two parameters determine the rating. The first
is the top group filling (top
groove filling (TGF). As is known in the art, pistons have lands and grooves, and the piston rings are located in the grooves.
Deposits that build up in the grooves interfere with the function of the piston rings. The second parameter is weighted total demerits (WTD).
To evaluate WTD, evaluate the entire piston surface. Deposits at the bottom of the piston are believed to exhibit lower performance than deposits near the top of the piston. Deposits in the lower part of the piston are therefore given a higher numerical weight in the total disadvantage determined. As shown in the table below, Lubricant B passed the Caterpillar 1-H-2 test.

[Table] Evaluation: Pass The composition listed as Lubricant C in the table was evaluated using the Oldsmobile Sequence-D test. In this test, the Oldsmobile 5.7
Using a Ritter V-8 engine, total at 3000 rpm
It operated for 64 hours. Used leaded fuel. Oil temperature is 149℃. The factors to be evaluated are high temperature oxidation,
Sludge, varnish and cam/lifter wear. This test measures lubricant performance at high temperatures. The results are shown in the table. Test requirements may be found to be met or exceeded.

[Table] Evaluation: Pass

Claims (1)

[Scope of Claims] 1 (A) at least one sulfurized alkylphenol; and (B) a hydrocarbon group having a number average molecular weight of at least 1300 bonded to a polar group in the molecular structure. A lubricant additive composition comprising at least one oil-soluble carboxylic acid dispersant, characterized in that component (A) contains sulfur or halogenated sulfur, and the alkyl group has 3 to 100 alkyl groups. Component (B) has at least 1300 alkylphenols bonded to a succinic acid group.
At least one substituted succinic acid-based acylating agent having a polyalkylene group having a number average molecular weight of A product obtained by reacting with at least one compound selected from the group in any order, wherein the compound having at least one H-N= group has at least one of 1 to 30
Amines selected from the group consisting of secondary or primary monoamines substituted with hydrocarbon or hydroxyhydrocarbon groups having 5 carbon atoms; heterocyclic amines selected from piperidine, piperazine, and morpholine; alkylene a polyamine; a hydroxyalkylene polyamine; a polyoxyalkylene polyamine; and hydrazine, wherein the organic hydroxy compound is a compound selected from alcohols and hydroxyalkylene compounds having up to 40 carbon atoms, and the reactive metal is sodium, potassium, lithium, barium,
An additive composition for a lubricant comprising calcium, magnesium, strontium, cadmium, nickel, chromium, zinc and aluminum, and containing component (A) in a ratio of 0.3 to 3.0 parts by weight per 1 part by weight of component (B). 2. The composition according to claim 1, wherein the reactant for producing component (A) is sulfur chloride. 3. The composition according to claim 2, wherein the sulfur chloride is sulfur dichloride. 4. A composition according to claim 3, wherein the alkyl group in component (A) contains 6 to 20 carbon atoms. 5. The composition of claim 1, wherein component (B) has an average of at least 1.3 succinic acid groups per each polyalkylene group. 6 The acylating agent of component (B) is substituted succinic acid or its anhydride, and is reacted with at least one amine or a mixture of at least one amine and at least one alcohol. Composition according to item 5. 7. The composition according to claim 6, wherein the polyalkylene group has a number average molecular weight of 1500 to 5000 and its Mw/Mn is 1.5 to 6.0. 8 The polyalkylene group is derived from polybutene mainly consisting of isobutene units,
8. The composition of claim 7, wherein the amine is an alkylene polyamine and the alcohol is pentaerythritol. 9. The composition according to claim 8, wherein the alkylene polyamine is ethylene polyamine. 10. The composition according to claim 9, wherein substituted succinic acid or its anhydride is reacted with a mixture of ethylene polyamines. 11. The composition of claim 9, wherein a substituted succinic anhydride is reacted with a mixture of ethylene polyamines and pentaerythritol. 12 (A) At least one compound obtained by reacting sulfur dichloride with tetrapropene-substituted phenol
(B) polybutene-substituted succinic acid or its anhydride in which the polybutene substituent group has a number average molecular weight of 1500 to 5000 and is mainly composed of isobutene units, and (B) polybutene-substituted succinic acid or its anhydride, in which the polybutene substituent has a number average molecular weight of 1500 to 5000, and has an average of 3 to 10 nitrogen atoms per molecule. 2. A composition according to claim 1, comprising an oil-soluble dispersant obtained by reacting a mixture of ethylene polyamines having ethylene polyamines, or in any order with this mixture and pentaerythritol. 13 Characterized by the presence in the molecular structure of (A) at least one sulfurized alkylphenol and (B) a hydrocarbon group having a number average molecular weight of at least 1300 and bonded to a polar group. and (C) at least one ash-forming detergent, wherein component (A) contains sulfur or halogenated sulfur. The alkyl group is obtained by reacting with at least one alkylphenol having 3 to 100 carbon atoms, and component (B) has at least 1300 alkylphenols bonded to a succinic acid group.
At least one substituted succinic acid-based acylating agent having a polyalkylene group having a number average molecular weight of A product obtained by reacting with at least one compound selected from the group in any order, wherein the compound having at least one H-N= group has at least one of 1 to 30
Amines selected from the group consisting of secondary or primary monoamines substituted with hydrocarbon or hydroxyhydrocarbon groups having 5 carbon atoms; heterocyclic amines selected from piperidine, piperazine, and morpholine; alkylene a polyamine; a hydroxyalkylene polyamine; a polyoxyalkylene polyamine; and hydrazine, wherein the organic hydroxy compound is a compound selected from alcohols and hydroxyalkylene compounds having up to 40 carbon atoms, and the reactive metal is sodium, potassium, lithium, barium,
Calcium, magnesium, strontium, cadmium, nickel, chromium, zinc and aluminum, containing 0.3 to 3.0 parts by weight of component (A) per 1 part by weight of component (B); Ingredient (C)
An additive composition for a lubricant containing a proportion of 0.05 to 1.0 by weight. 14. The composition according to claim 13, wherein component (C) is a mixture of basic calcium sulfonate and basic magnesium sulfonate.