Abstract:
A lubricating oil composition having improved dispersancy and viton seal compatibility. the dispersant being prepared by coupling partly glycolated succinimides with an aldehyde and a phenol.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     Internal combustion engines operate under a wide range of temperatures including low temperature stop-and-go service as well as high temperature conditions produced by continuous high speed driving. Stop-and-go driving, particularly during cold, damp weather conditions, leads to the formation of a sludge in the crankcase and in the oil passages of a gasoline or a diesel engine. This sludge seriously limits the ability of the crankcase oil to effectively lubricate the engine. In addition, the sludge with its entrapped water tends to contribute to rust formation in the engine. These problems tend to be aggravated by the manufacturer&#39;s lubrication service recommendations which specify extended oil drain intervals. 
     It is known to employ nitrogen containing dispersants and/or detergents in the formulation of crankcase lubricating oil compositions. Many of the known dispersant/detergent compounds are based on the reaction of an alkenylsuccinic acid or anhydride with an amine or polyamine to produce an alkylsuccinimide or an alkenylsuccinamic acid as determined by selected conditions of reaction. 
     It is also known to chlorinate alkenylsuccinic acid or anhydride prior to the reaction with an amine or polyamine in order to produce a reaction product in which a portion of the amine or polyamine is attached directly to the alkenyl radical of the alkenylsuccinic acid or anhydride. The thrust of many of these processes is to produce a product having a relatively high level of nitrogen in order to provide improved dispersancy in a crankcase lubricating oil composition. 
     With the introduction of four cylinder internal combustion engines which must operate at relatively higher engine speeds or RPM&#39;s than conventional 6- and 8-cylinder engines in order to produce the required torque output, it has become increasingly difficult to provide a satisfactory dispersant lubricating oil composition. 
     Another problem facing the lubricant manufacturer is that of seal deterioration in the engine. All internal combustion engines use elastomer seals, such as Vitron seals, in their assembly. Over time, these seals are susceptible to serious deterioration caused by the lubricating oil composition. A lubricating oil composition that degrades the elastomer seals in an engine is unacceptable to engine manufacturers and has limited value. 
     It is an object of this invention to provide a novel lubricating oil additive. 
     Another object is to provide a novel lubricating oil composition which does not degrade elastomer seals in internal combustion engines. 
     A still further object is to provide a lubricating oil composition which can withstand the stresses imposed by modern internal combustion engines. 
     2. Disclosure Statement 
     U.S. Pat. Nos. 3,172,892 and 4,048,080 disclose alkenylsuccinimides formed from the reaction of an alkenylsuccinic anhydride and an alkylene polyamine and their use as dispersants in a lubricating oil composition. 
     U.S. Pat. No. 2,568,876 discloses reaction products prepared by reacting a monocarboxylic acid with a polyalkylene polyamine followed by a reaction of the intermediate product with an alkenyl succinic anhydride. 
     U.S. Pat. No. 3,216,936 discloses a process for preparing an aliphatic amine lubricant additive which involves reacting an alkylene amine, a polymer substituted succinic acid and an aliphatic monocarboxylic acid. 
     U.S. Pat. No. 3,131,150 discloses lubricating oil compositions containing dispersant-detergent mono- and di-alkyl-succinimides or bis(alkenylsuccinimides). 
     Netherlands Pat. No. 7,509,289 discloses the reaction product of an alkenylsuccinic anhydride and an aminoalcohol, namely a tris(hydroxymethyl)-aminomethane. 
     U.S. patent application, Ser. No. 334,774, filed on Dec. 28, 1981, discloses a hydrocarbyl-substituted succinimide dispersant having a secondary hydroxy-substituted diamine or polyamine segment and a lubricating oil composition containing same. 
     U.S. Pat. No. 4,338,205 discloses alkenyl succinimide and borated alkenyl succinimide dispersants for a lubricating oil with impaired diesel dispersancy in which the dispersant is treated with an oil-soluble strong acid. 
     The disclosures of U.S. Pat. Nos. 3,172,892 and 4,048,080 and of application Ser. No. 334,774 are incorporated herein by reference. 
     SUMMARY OF THE INVENTION 
     The present invention provides a novel additive which improves the dispersancy and viton seal compatibility of a lubricating oil. The lubricating oil composition comprises a major portion of a lubricating oil and a minor dispersant amount of a reaction product prepared by the process which comprises: 
     (a) reacting a polyethylene amine with an alkenyl succinic acid anhydride to form a bis-alkenyl succinimide; 
     (b) acylating said bis-alkenyl-succinimide with glycolic acid to form a partially glycolated bis-alkenyl succinimide; 
     (c) adding an excess of a formaldehyde to said partially glycolated bis-alkenyl succinimide to form an iminium salt of the glycolated bis-alkenyl succinimide; 
     (d) adding a phenol to said iminium salt, thereby forming an acylated Mannich phenol coupled glycamide bis-alkenyl succinimide; and 
     (e) recovering said acylated Mannich phenol coupled glycamide bis-alkenyl succinimide. 
    
    
     DESCRIPTION OF THE INVENTION 
     The charge polyamine compositions which may be employed in practice of the process of this invention according to certain of its aspects may include primary amines or secondary amines. The amines may typically be characterized by the formula ##STR1## 
     In these formulae, a may be an integer of 3 to 8, preferably about 5; and n may be 0 or 1. 
     In the above compound, R&#39; may be hydrogen or a hydrocarbon group selected from the group consisting of alkyl, aralkyl, cycloalkyl, aryl, alkaryl, alkenyl, and alkynyl including such radicals when inertly substituted. When R&#39; is alkyl, it may typically be methyl, ethyl, n-propyl, iso-propyl, n-butyl, i-butyl, sec-butyl, amyl, octyl, decyl, octadecyl, etc. When R&#39; is aralkyl, it may typically be benzyl, beta-phenylethyl, etc. When R&#39; is cycloalkyl, it may typically be cyclohexyl, cycloheptyl, cyclooctyl, 2-methylcyclo-heptyl, 3-butylcyclohexyl, 3-methylcyclohexyl, etc. When R&#39; is aryl, it may typically be phenyl, naphthyl, etc. When R&#39; is alkaryl, it may typically be tolyl, xylyl, etc. When R&#39; is alkenyl, it may typically be allyl, 1-butenyl, etc. When R&#39; is alkynyl, it may typically be propynyl, butynyl, etc. R&#39; may be inertly substituted i.e. it may bear a non-reactive substituent such as alkyl, aryl, cycloalkyl, ether, halogen, nitro, etc. Typically inertly substituted R&#39; groups may include 3-chloropropyl, 2-ethoxyethyl, carboethoxymethyl, 4-methyl, cyclohexyl, p-chlorophenyl, p-chlorobenzyl, 3-chloro-5-methylphenyl, etc. The preferred R&#39; groups may be hydrogen or lower alkyl, i.e. C 1  -C 10  alkyl, groups including eg methyl, ethyl, n-propyl, i-propyl, butyls, amyls, hexyls, octyls, decyls, etc. R&#39; may preferably be hydrogen. 
     R&#34; may be a hydrocarbon selected from the same group as R&#39; subject to the fact that R&#34; is divalent and contains one less hydrogen. Preferably R&#39; is hydrogen and R&#34; is --CH 2  CH 2 . Typical amines which may be employed may include those listed below in Table I. 
     TABLE I 
     propylenediamine (PDA) 
     diethylenetriamine (DETA) 
     triethylenetetramine (TETA) 
     tetraethylenepentamine (TEPA) 
     pentaethylenehexamine (PEHA) 
     The preferred amine may be tetraethylenepentamine. 
     The charge aldehyde which may be employed may include those preferably characterized by the formula R 2  CHO. 
     In the above compound, R 2  may be hydrogen or a hydrocarbon group selected from the group consisting of alkyl, aralkyl, cycloalkyl, aryl, alkaryl, alkenyl, and alkynyl including such radicals when inertly substituted. When R 2  is alkyl, it may typically be methyl, ethyl, n-propyl, iso-propyl, n-butyl, i-butyl, sec-butyl, amyl, octyl, decyl, octadecyl, etc. When R 2  is aralkyl, it may typically be benzyl, beta-phenylethyl, etc. When R 2  is cycloalkyl, it may typically be cyclohexyl, cycloheptyl, cyclooctyl 2-methylcyclo-heptyl, 3-butylcyclohexyl, 3-methylcyclohexyl, etc. When R 2  is aryl, it may typically be phenyl, naphthyl, etc. When R 2  is alkaryl, it may typically be tolyl, xylyl, etc. When R 2  is alkenyl, it may typically be vinyl, allyl, 1-butenyl, etc. When R 2  is alkynyl, it may typically be ethynyl, propynyl, butynyl, etc. R 2  may inertly substituted i.e. it may bear a non-reactive substituent such as alkyl, aryl, cycloalkyl, ether, halogen, nitro, etc. Typically inertly substituted R groups may include 3-chloropropyl, 2-ethoxyethyl, carboethyoxymethyl, 4-methyl cyclohexyl, p-chlorophenyl, p-chlorbenzyl, 3-chloro-5-methylphenyl, etc. The preferred R.sup. 2 groups may be lower alkyl, i.e. C 1  -C 10  alkyl, groups including eg methyl, ethyl, n-propyl, i-propyl, butyls, amyls, hexyls, octyls, decyls, etc. R 2  may preferably be hydrogen. 
     Typical aldehydes which may be employed may include those listed below in Table II. 
     TABLE II 
     formaldehyde 
     ethanal 
     propanal 
     butanal etc. 
     The preferred aldehyde may be formaldehyde employed as its polymer-paraformaldehyde. 
     The charge phenols which may be employed in practice of the process of this invention may preferably be characterized by the formula HR 3  OH. It is a feature of these phenols that they contain an active hydrogen which will be the site for substitution. Poly-phenols (eg compounds containing more than one hydroxy group in the molecule whether on the same ring or not) may be employed. The rings on which the hydroxy groups are sited may bear inert substituents. However, at least two positions, e.g., ortho- and para-, to a phenol hydroxy group, must be occupied by an active hydrogen as this is the point of reaction with the iminium salt group. 
     R 3  may be an arylene group typified by --C 6  H 4  --, --C 6  H 3  (CH 3 )--, or --C 6  H 3  (C 2  H 5 )--. 
     Typical phenols which may be employed may include those listed below in Table III. 
     TABLE III 
     Phenol 
     Bisphenol A 
     Resorcinol 
     Mono-nonyl phenol 
     Beta-naphthol 
     The preferred phenols may be phenol or mono-nonyl phenol. 
     In practice of the process of this invention, the reagents are step wise reacted with a succinic acid anhydride bearing a polyolefin substituent containing residual unsaturation in a &#34;one pot reaction&#34;. 
     The succinic acid anhydride may be characterized by the following formula ##STR2## 
     In the above formula, R may be a residue (containing residual unsaturation) from a polyolefin which was reacted with maleic acid anhydride to form the alkenyl succinic acid anhydride. R may have a molecular weight M n  ranging from about 500 to about 2000, preferably about 1000 to about 1300, and more preferably about 1300. 
     The Mannich phenol coupled glycamide bis-alkenyl succinimide is prepared by the following sequence of steps in a single flask preparation as shown below in Scheme I. The first step of the reaction sequence involves reacting a polyethyleneamine with an alkenyl succinic acid anhydride (ASAA), respectively, in a 1:2 molar ratio to form the bis-alkenyl succinimide (A) intermediate. To this intermediate (A) is added enough glycolic acid to acylate all of the free basic amines except for one or one equivalent amine to form the partially glycolated bis-alkenyl succinimide (B). To this succinimide (B) is added an excess of paraformaldehyde to form the iminium salt of the glycolated bis-alkenyl succinimide (C). Immediately after the addition of formaldehyde (3 min) is added one half of an equivalent of phenol relative to the polyethylenediamine, or any other phenolic compound capable of reacting with a iminium salt twice, to give the derived product of Mannich phenol coupled glycamide bis-alkenyl succinimide (D). 
     The product so obtained may be a 50-80, say 50 wt.% solution of the desired additive in inert diluent; and preferably it is used in this form. ##STR3## 
     The preferred acylating agents which are carboxylic acids may be glycolic acid; oxalic acid; lactic acid; 2-hydroxymethyl propionic acid, or 2,2-bis(hydroxymethyl)propionic acid. The most preferred being glycolic acid. 
     Acetylation may be effected preferably by addition of the acetylating agent (e.g., glycolic acid or oxalic acid) to the reaction product of the polyethyleneamine and the succinic acid anhydride. 
     Acylation is preferably effected by adding the acylating agent (typically oxalic acid or glycolic acid) in an amount of about 0.5 to about 3.0 equivalents per mole of active amine employed. 
     For example, when tetraethylenepentamine (TEPA) is employed, there are 1.7 equivalents of glycolic acid added. Similarly, when triethylenetetramine (TETA) is used, about 0.7 equivalent of glycolic acid is added; and when pentaethylenehexamine (PEHA) is employed, about 2.7 equivalents of glycolic acid are added to the reaction. 
     During acylation, the carboxyl group of the acylating agent bonds to a nitrogen atom to form an amide. Acylation is carried out at 100° C.-180° C., say 160° C. for 2-24 hours, say 8 hours preferably in the presence of an excess of inert diluent-solvent. 
     The partially acylated product may in one of its embodiments be represented by the formula ##STR4## wherein R is polyisobutylene. 
     In order to illustrate the effectiveness of the present compounds, i.e., coupled glycolated succinimides, as dispersants with viton seal compatibility, there are several tests to which the present succinimides have been subjected. These tests include the Bench VC and VD Tests, the Bench Sequence VD Test, the Caterpillar I-G2 Engine Test, and the Daimler-Benz Viton Compatibility Test. These tests are described below in more detail as well as the results of the various tests are provided below in Tables IV, V, VI, and VII. 
     THE BENCH VC TEST (BVCT) 
     This test is conducted by heating the test oil mixed with a synthetic hydrocarbon blowby and a diluent oil at a fixed temperature for a fixed time period. After heating, the turbidity of the resulting mixture is measured. A low percentage turbidity (0 to 10) is indicative of good dispersancy while a high value (20 to 100) is indicative of an oil&#39;s increasingly poor dispersancy. The results obtained with the known and present dispersants are set forth in Table IV below at 6 and 4 percent by weight concentration respectively, in an SAE 10W-40 fully formulated motor oil. 
     THE BENCH VD TEST (BVDT) 
     In the Bench VD Test, (BVDT), oil samples are artificially degraded by bubbling air for six hours through a mixture of test oil and synthetic blowby at 290° F. Every hour, synthetic blowby is added and at the 5th and 6th hour of the test, samples are removed and diluted with SNO-7/20 diluent oil and their turbidity measured. Low turbidity in the BVDT indicates good lubricant dispersancy as related to the Sequence VD Test. The Sequench VD engine correlation work predicts that SF (i.e. satisfactory) quality lubricants should read 60 or less in the BVDT (turbidity units); oils 70 or greater would be predicted to do significantly poorer in the Sequence VD Test. 
     Reference standard: The reference oil standard used in this test has had an average Sequence VD deposit rating of 6.81=Average varnish, 9.56=Average sludge. In the BVDT the 6 hour turbidity should be 55+/-12. The reference oil is included in each BVDT run. The resultant BVDT runs are provided below in Table IV. 
     
                       TABLE IV______________________________________Bench VC.sup.1 and Bench VD.sup.2 Test Results of PhenolicCOUPLED GBSD.sup.3 TYPE DISPERSANTS.sup.4DISPERSANT             BVCT.sup.5,6                           BVDT.sup.5______________________________________1   GBSD (TEPA, H-300 ASAA)                      --       101, 1042   GBSD (TEPA, H-300 ASAA,                      25/33    41    phenol)3   GBSD (TEPA, H-300 ASAA,                       8/11    21    resorcinol)4   GBSD (TEPA, H-300 ASAA,                       9/12    59    bisphenol A)5   GBSD (TEPA, H-300 ASAA,                      10/12    17    thiodiphenol)6   GBSD (TEPA, H-300 ASAA,                       8/11    162, 120    2,6-dimethylphenol)7   GBSD (TEPA, H-300 ASAA,                      11/11     69, 178    2,6 di-t-butylphenol)8   Modified GBSD (PEHA, H-300 ASAA,                      8/6      54    phenol)9   Modified GBSD (PEHA, H-300 ASAA,                      9/6      36    nonyl phenol)10  GBSD (PEHA, H-300 ASAA, phenol                      12/15    2411  GBSD (PEHA, H-100 ASAA, phenol                      23/15    3612  GBSD (PEHA, H-50 ASAA, phenol                      --       --______________________________________ .sup.1 Bench Test for sludge dispersancy performance. .sup.2 Bench Test for varnish dispersancy performance. .sup.3 GBSD is a Glycamide bissuccinimide dispersant (90% bis and 10% mono). .sup.4 These phenolic coupled dispersants were blended at 7.4 wt. % in an SAE 30 SF/CD motor oil. .sup.5 The lower the value, the better is dispersancy. .sup.6 The number to the right of the slash mark represents GBSD used as the good reference. TEPA  Tetraethylenepentamine. PEHA  Pentaethylenehexamine. ASAA  Alkenyl succinic acid anhydride; H50 ASAA (mw≈750); H100 ASAA (mw≈1000); H300 ASAA (mw≈1300). 
    
     SEQUENCE VD TEST 
     Various dispersants including known dispersant and the present dispersants were tested by the Sequence VD gasoline engine test in a fully formulated oil motor at about 5.7 wt.% and gave the results shown below in Table V. 
     The Sequence VD test evaluate the performance of engine oils in terms of the protection provided against sludge and varnish deposits as well as valve train wear. The test was carried out with a Ford 2.3 liter 4 cylinder gasoline engine using cyclic low and mid range engine operating temperatures and a high rate of blowby. 
     
                       TABLE V______________________________________SEQUENCE VD TESTING.sup.1                Treatment Levels______________________________________Dispersants (wt. %)Modified GBSD.sup.2    6.1     --     --(N-300 ASAA, PEHA)Modified GBSD          --      5.7    --(N-300 ASAA, PEHA, phenol/CH.sub.2 O)Modified GBSD          --      --     5.5(N-300 ASAA, PEHA nonyl phenol/CH.sub.2 O)Sequence VDAverage Sludge         9.42    9.67   9.6Average Varnish        5.01    6.40   6.1Piston Skirt Varnish   6.82    7.00   7.0(The higher the values,the better the performance)______________________________________ .sup.1 These dispersant were evaluated in a SAE 30 grade SF/CD motor oil formulation. .sup.2 GBSD is a Glycamide bissuccinimide dispersant (90% bis and 10% mono.) TEPA  Tetraethylenepentamine PEHA  Pentaethylenehexamine ASAA  Alkenyl succinic acid anhydride; H100 ASAA (mw≈1000); H300 ASAA (mw≈1300). 
    
     THE CATERPILLER 1-G2 TEST 
     The diesel engine performance of Example II, as measured by the Caterpiller 1-G2 testing in SAE 30 fully formulated oil formulation using 0.055 wt.% nitrogen from the dispersant gave the results shown below in Table VI. 
     
                       TABLE VI______________________________________Caterpillar 1-G2 Engine Testing.sup.1______________________________________Dispersant, wt. %GBSD.sup.2       6.32      --      --GBSD (PEHA, H-300            --        6.32    --ASAA, Mannich phenol)GBSD (PEHA, H-300            --        --      6.32ASAA, Mannich nonyl phenol)Cat. 1-G2120 hrsTGF (%)          63        61      --WTD              200       156     --480 hrsTGF (%)          80        66      76WTD              208       220     292______________________________________ .sup.1 These dispersants were evaluated in a prototype SAE 30 SF/CD motor oil formulation. .sup.2 GBSD is a Glycamide bissuccinimide dispersant (90% bis and 10% mono). PEHA  Pentaethylenehexamine ASAA  Alkenyl succinic acid anhydride; H100 ASAA (mw 1000); H300 ASAA (mw 1300). TGF  Top grove fill. WTD  Weighted total demerits. 
    
     THE DAIMLER-BENZ VITON COMPATIBILITY TEST 
     An important property of a lubricating oil additive and a blended lubricating oil composition containing additives is the compatibility of the oil composition with the rubber seals employed in the engine. Nitrogen-containing succinimide dispersants employed in crankcase lubricating oil compositions have the effect of seriously degrading the rubber seals in internal combustion engines. In particular, such dispersants are known to attack Viton AK-6 rubber seals which are commonly employed in internal combustion engines. This deterioration exhibits itself by sharply degrading the flexibility of the seals and in increasing their hardness. This is such a critical problem that the Daimler-Benz Corporation requires that all crankcase lubricating oils must pass a Viton Seal Compatibility Test before the oil compostion will be rated acceptable for engine crankcase service. The AK-6 Bend Test is described below and is designed to test the Viton seal compatibility for a crankcase lubricating oil composition containing a nitrogen-containing dispersant. 
     The AK-6 Bend Test is conducted by soaking a sample of Viton AK-6 rubber at an elevated temperature in the oil being tested then determining the bending properties and hardness of the Viton rubber sample against a suitable sample. Specifically, a 38 by 9.5 mm slab of a Viton AK-6 rubber cut with the grain of the rubber is placed in a 30 ml wide-mouth bottle with 20 ml of the test oil. The bottle is sealed and the test sample placed in an oven at 149° C. for 96 hours. The bottle is removed from the oven and the rubber specimen taken from the initial bottle and placed into a second bottle with a new charge of test oil. After 30 minutes in the new oil charge, the rubber specimen is removed from the second bottle and submitted to a Bend Test. This is done by bending the rubber specimen 180°. The degree of cracking is observed and reported as follows: no cracking (NC) surface cracking (SC) or cracking (C). If cracking is observed, the test is terminated on that particular sample. 
     If no cracking has been observed, the rubber specimen is returned to the bottle containing the second oil charge and this bottle is returned to the oven maintained 149° C., the bottle is removed from the oven and the rubber specimens withdrawn and placed into another bottle containing a fresh oil charge for 30 minutes, following which the bend test is repeated. 
     If the rubber specimen continues to pass the bend test, the test is continued for 2 more heat-soak cycles of 96 hours and 72 hours respectively, each heat-soak cycle being followed by the bend test for total test time of 336 hours from the time the specimens were initially put into the oven. 
     Following the above procedure, each rubber specimen is removed from its bottle, washed in naphtha to remove all oil traces and then air dried. The rubber specimens are then submitted to a hardness test according to the procedure described in ASTM D2240 following which a final bend test is made on all specimens. 
     The results of the Daimler-Benz test runs are provided below in Table VII. 
     
                       TABLE VII______________________________________Daimler-Benz Viton Compatibility Test.sup.1                              TensileDispersant.sup.2         Cracking % Elongation                              Strength______________________________________GBSD.sup.3 (H-300,         None     166          9.0ASAA Mannich phenol)               n/mm.sup.2GBSD (H-300, ASAA         None     166         9.0Mannich bisphenol A)GBSD (H-100 ASAA         None     154         8.4Mannich phenol)GBSD (H-50 ASAA,         None     133         6.7Mannich phenol)Good Reference Sample         None     130         7.5______________________________________ .sup.1 All dispersants were evaluated in a single grade SAE 30 SF/CD moto oil formulation at 6.3 wt. %. .sup.2 All dispersants were prepared using PEHA (Pentaethylene hexamine a the amine source). .sup.3 GBSD is a Glycamide bissuccinimide dispersant (90% bis and 10% mono). ASAA  Alkenyl succinic acid anhydride; H50 ASAA (mw≈750); H100 ASAA (mw≈1000); H300 ASAA (mw≈1300). n/mm.sup.2  newton/millimeter.sup.2