US3723460A

US3723460A - Polymeric succinimides and their derivatives as fuel and motor oil additives

Info

Publication number: US3723460A
Application number: US00865497A
Authority: US
Inventors: W Brannen; R Watson
Original assignee: Standard Oil Co
Current assignee: BP Corp North America Inc
Priority date: 1969-10-10
Filing date: 1969-10-10
Publication date: 1973-03-27
Anticipated expiration: 1990-03-27

Abstract

The disclosure describes reaction products useful as multipurpose fuel and motor oil additives which are reaction products of about equal molar portions of (1) an intermediate product produced by the condensation reaction between about equal molar portions of a compound selected from the group consisting of an alkenyl substituted succinic acid, an alkenyl substituted succinic anhydride and an alkenyl substituted succinimide or metal salt thereof, said compound having an average molecular weight from about 350 to about 1,000, and a second compound selected from the group consisting of ammonia gas, ammonium hydroxide and hydrazine, and (2) a third compound selected from the group consisting of basic metal compounds, compounds with displaceable halogens, acid halides, alkylene oxides, acid anhydrides, thio anhydrides, triethyl phosphite, boric acid and acrylonitrile. The intermediate product was itself found to be useful as a fuel and motor oil additive.

Description

Waited Patent 1 Brannon ct a1.

[ 51 Mar. 27, 1973 Ohio; Roger W. Watson, Highland, Ind.

[73] Assignee: Standard Oil Company, Chicago, Ill.

[22] Filed: Oct. 10, 1969 [21] Appl. No.: 865,497

[52] US. Cl. ..260/326.5 1F, 44/63, 44/70, 44/71, 252/464, 252/34, 252/49.7, 252/49.8, 252/49.9, 252/515, 260/326.3

[51] Int. Cl. ..C07d 27/10 [58] Field of Search ..260/326.5 F

[56] References Cited UNITED STATES PATENTS Primary Examiner-Alex Mazel Assistant ExaminerJoseph A. Narcavage Attorney-Arthur G. Gilkes, William T. McClain and John J. Connors [57] ABSTRACT The disclosure describes reaction products useful as multipurpose fuel and motor oil additives which are reaction products of about equal molar portions of 1) an intermediate product produced by the condensation reaction between about equal molar portions of a compound selected from the group consisting of an alkenyl substituted succinic acid, an alkenyl substituted succinic anhydride and an alkenyl substituted succinimide or metal salt thereof, said compound having an average molecular weight from about 350 to about 1,000, and a second compound selected from the group consisting of ammonia gas, ammonium hydroxide and hydrazine, and (2) a third compound selected from the group consisting of basic metal compounds, compounds with displaceable halogens, acid halides, alkylene oxides, acid anhydrides, thio anhydrides, triethyl phosphite, boric acid and acrylonitrile. The intermediate product was itself found to be useful as a fuel and motor oil additive.

1 Claim, N0 Drawings POLYMERIC SUCCINIMIDES AND THEIR DERIVATIVES AS FUEL AND MOTOR OIL ADDITIVES BACKGROUND OF THE INVENTION It has been determined that rough idling and loss of power are primarily due to the accumulation of deposits in the throttle bore area of an engines carburetor. As the deposits build up, the throttle plate is m prevented from functioning properly whereby the amount of gasoline for a given amount of air may either be greatly reduced, resulting in the air-fuel mixture becoming too lean thereby causing rough idling and loss of power, or the amount of air for a given amount of gasoline may be greatly reduced, resulting in the airfuel mixture becoming too rich for efficient engine operation. Frequent adjustments of the carburetor are needed to compensate for this build up and finally it becomes necessary to replace or overhaul the carburetor. Many additives have been devised which will clean the carburetor, but may themselves, deposit further along the induction system of the engine. (The term induction system", as used herein, is intended to mean the path that the incoming air follows in an automobile engine, through the air cleaner, carburetor, and intake manifold, into the cylinders. This air, is of course, an air-gasoline mixture after passing through the carburetor.) The problem is, then, to find a gasoline fuel additive that will be effective as a carburetor detergent, yet will not itself deposit further along the induction system of the engine. The need for an effective carburetor detergent has increased since positive crankcase ventilation (PCV) systems have come into general use. Such a system circulates crankcase vapors into the induction system rather than venting them into the air. These vapors maybe introduced either in front of or behind the air cleaner; in either case they pass through the carburetor where they tend to accumulate and increase the normal deposit. Such vapors have two major components, (1) vaporized oil from the crankcase, and (2) exhaust gases containing uncombusted hydrocarbons (this second component is commonly referred to as blow-by, since, it reaches the crankcase of the engine by blowing past the piston rings). Most of the uncombusted hydrocarbons of the exhaust gases are oil insoluble, and therefore tend to form deposits in the crankcase and on the various moving parts of the engine as well as in the carburetor. For the purpose of preventing such deposits on the moving parts and in the crankcase of the automobile, various additives are used in the lubricating oil composition. These oil additives keep the uncombusted hydrocarbons highly dispersed in the oil; such a condition is unfavorable for deposition on metal surfaces.

Generally, then, two additives are used, a detergent in the gasoline to prevent deposit build up of the uncombusted hydrocarbons as the recirculated crankcase vapors pass through the engine induction system, and a detergent in the oil to keep the uncombusted hydrocarbons of the crankcase vapors from depositing on the metal surfaces in the crankcase area. Gasoline detergents are required to be strong enough to keep the carburetor surfaces clean and low enough in molecular weight so that they are carried along the fuel gases and do not build up in the induction system prior to ignition in the cylinders. Yet, some strong detergents will promote a dispersion of water in gasoline, causing carburetor icing and stalls, or they may promote a gasoline-in-water emulsion that wastes gasoline and additives and causes problems in disposing of storage tank water bottoms containing high concentrations of gasoline.

Previously some gasoline and oil additives have been of the general formula:

wherein R is a polyisobutylene radical of from 30 to 200 carbon atoms, R is a divalent alkylene of from 1 to 3 carbon atoms, R and R are alky] radicals of from 1 to 3 carbon atoms, and R, R and R combined contain a total of no more than 10 carbon atoms. Generally, the oil additives have long R groups upward from 30 carbon atoms, and, consequently, high molecular weights, so they cannot be used as gasoline additives. Gasoline additives have shorter R groups and longer R and R groups; they are too expensive to be used as oil additives.

SUMMARY OF THE INVENTION We have now discovered an additive which functions as either a fuel or lubricating oil additive. This additive is of sufficient detergent strength to clean and maintain clean, an automobile engine induction system. This additive is also of such detergent strength that when small amounts of it are blown past the piston rings into the crankcase, it keeps the metal surfaces clean in the crankcase area. Nevertheless, the additive is not such a strong detergent that it promotes the formation of gasoline-in-water emulsions or dispersions of water in gasoline. The new additive is of sufficient detergent strength to function as a carburetor cleaner, yet, surprisingly, when trace amounts of it are blown by the pistons into the crankcase it functions as an oil additive and decreases, by about one-half, the need for other oil detergent additives.

Briefly, our additive is described as the reaction product of about equal molar portions of 1) an intermediate product produced by the condensation reaction between about equal molar portions of a compound selected from the group consisting of alkenyl substituted succinic anhydrides, alkenyl substituted succinic acids, alkenyl substituted succinimides and metal salts of alkenyl substituted succinimides, said compound having an average molecular weight from about 350 to about 1,000, and a second compound selected from the group consisting of ammonium hydroxide, hydrazine and ammonia gas under conditions removing by-product water and (2) a third compound selected from the group consisting of basic metal compounds, compounds with displaceable halogens, acid halides, alkylene oxides, acid anhydrides, thio anhydrides, triethyl phosphite, boric acid and acrylonitrile. Generally, the intermediate or its derivatives, the reaction products of this invention, are

present in hydrocarbon fuels, such as gasoline, or lubricating oil in a concentration of between about 0.000] percent and about percent based upon the weight of gasoline hydrocarbon or lubricating oil respectively. In fuels such as gasoline, they are present in amounts ranging from about 0.0001 percent to about 0.5 percent and preferably about 0.005 percent based on the weight of gasoline hydrocarbon. In lubricating oils they are present in amounts ranging from about 0.1 percent to about 10 percent, preferably about 0.50 percent based on the weight of lubricating oil.

The intermediate is further reacted with various reactive compounds to give reaction products which are also useful as multipurpose gasoline and oil additives. Such reactive compounds can be generally grouped as basic metal compounds, compounds with displaceable halogens, acid halides, alkylene oxides, acid anhydrides, thio anhydrides, triethyl phosphite, boric acid and acrylonitrile.

Basic metal compounds may include such compounds as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, barium oxide and sodium hydrogen sulfide.

Compounds with displaceable halogens may include antimony chloride, antimony bromide, arsenic chloride, arsenic bromide, silicon chloride, silicon bromide, lead chloride, lead bromide, mercuric chloride, mercurous chloride, mercuric bromide, mercurous bromide, tin chloride, tin bromide, zinc chloride and zinc bromide.

Acid halides may include ethyl dichloroformate, acetyl chloride, p-toluenesulfonyl chloride, ethyl chloroformate, steroyl chloride and bromsteroyl bromide.

Alkylene oxides may include ethylene oxide, propylene oxide, butadiene monoxide, epoxides of unsaturated fats including such fats as glycerides of linoleic acid, epoxides of cracked wax olefins such olefins having from five to thirty carbon atoms such as hexadecyl ethylene oxide (18 carbon atoms).

Acid anhydrides may include polymeric succinic anhydrides, propionic anhydride, maleic anhydride, itaconic anhydride and acetic anhydride.

Thio anhydrides may include carbon disulfide, silicon disulfide, phosphorous sulfides such as P 8 P 8 P 8 and P 8,, and arsenic sulfides such as AS285, As S and AS282.

PREFERRED EMBODIMENTS For simplicity in the following Examples, the designations below shall mean a polyisobutenyl radical, attached to the succinic acid, anhydride or imide structure at the No. 2 position, having its double bond between the second and the third carbon atoms from the point of attachment and having an average molecular weight and average number of carbon atoms as follows:

Designation Average Molecular Average Number Weight of Carbon Atoms L-lO 320 23 H-lOO 920 66 EXAMPLEI Polymeric succinimides are prepared by reacting polymeric succinic acids (PSAcid), or anhydrides (PSA) with hydrazine, ammonium hydroxide, or ammonia gas in the presence of small amounts of water. The general procedure is to react the hydrazine, ammonium hydroxide or ammonia gas in the presence of small amounts of water with an equal molar amount of PSA, or PSAcid for from 6 to 12 hours at a temperature in the range of about F. to about 300F. to produce an intermediate compound. When ammonium hydroxide is reacted a 5 mole excess is preferred. When ammonia gas is reacted the amount of water present is from 5 to 10 percent based on the weight of PSA, or PSAcid. Typical results from this reaction are as follows:

With-Ammonia Gas or Ammonium Hydroxide Starting PSA N, (Found) N, (Theoretical) L-4-PSA 3.39 3.22

L-lO-PSA 2.19 3.39

L-SO-PSA 1.46 1.38

H-lOO-PSA 0.83 0.78

With Hydrazine Starting Material Reactant N, (Found) L-4-PSAcid N H, 8.86

L-lO-PSA N,H, 7.42

Alkali metal salts of the intermediate, formed with ammonium hydroxide or ammonia gas is reacted with polymeric succinic acids, or anhydrides, can be formed by reacting about equal molar quantities of the intermediate with an alkali metal hydroxide for from about one-half to about ten hours at a temperature in the range of about 150F. to about 300F. It has been found that such alkali metal salts are preferably reacted with metal compounds with displaceable halogens, acid halides and alkylene oxides to form useful additives.

It has been found that it is preferable to react the intermediate formed when ammonium hydroxide or ammonia gas is reacted with polymeric succinic acids, anhydrides or imides with basic metal compounds, compounds with displaceable halogens, acid halides, acid anhydrides, thio anhydrides, alkylene oxides, triethyl phosphite and boric acid to form useful additives.

It has also been found that it is preferable to react the intermediate formed when hydrazine is reacted with polymeric succinic acids or anhydrides with compounds with displaceable halogens, acid halides, alkylene oxides, acid anhydrides, thio anhydrides, boric acid and acrylonitrile to form useful additives.

EXAMPLE 11 intermediate product of Example I prepared by reacting polymeric succinic acids, or anhydrides, with ammonium hydroxide or ammonia gas can be further reacted for about one-half to 10 hours at a temperature in the range of from about 150F. to about 300F. in approximately equal molar amounts with the following reactants to yield products which are useful multipurpose gasoline and lubricating oil additives.

Reactant Elemental Analyses Yield PCI, P=0.98,%Cl=0.02 41 SnCl, Sn 6.2, CI 6.4 34" Bu,SnCI, Sn 11.0, CI 3.8 65 H 80, B 0.3 12

SiS, %S1=0.7,%S=07 21 BaO Ba 7.4 70 CaO Ca 2.4 100 KOH K 4,7 (3) (C,H,O) P P 3.82 69" C5,, BuBr S 6.9 60

(l) Assumed products contain only one mole of tin per mole of PSImide (2) Infrared spectrum shows presence of carbonyl groups (3) Products diluted with benzene (4) Infrared spectrum shows no ring opening and phosphate or phosphate groupings EXAMPLE III Intermediate product of Example I prepared by reacting polymeric succinic acids, anhydrides or imides with hydrazine can be further reacted for about onehalf to hours at a temperature in the range of about 150F. to about 300F. in approximately equal molar amounts with the following reactants to yield products which are useful multipurpose gasoline and lubricating oil additives.

T-4-N-Aminosuccinimide The alkali metal salts of the intermediate product of Example I can be further reacted for about one-half to l0 hours at a temperature in the range of about 150F. to about 300F. in approximately equal molar amounts with the following reactants to yield products which are useful multipurpose gasoline and lubricating oil additives.

Reactant Elemental Analyses Yield S,Cl, S=3.3,%Cl=0.7 50" SnCl, Sn 2.8, CI 1.4 16" PCI, P 1.3 57" SnCl, Sn 1.2 Ethylene Oxide (l) Assumed 2 moles of PSImide reacted with one mole of reactant (2) Assumed 3 moles of PSImide reacted with one mole of reactant (3) LR. indicates reaction EXAMPLE V In the Black Iron Rust Test additives prepared in Examples II, III and IV showed excellent antirust properties. The test is conducted as follows: Two black iron strips are polished with emery paper until bright and then with steel wool to a satin finish. One hundred milliliters of the sample (light oil or gasoline containing the additive) is placed into a tall 4 ounce bottle. A polished black iron strip is wiped clean with cleansing tissue and immersed in the sample. It is allowed to stand for 30 minutes then 10 mls. of water are pipeted into the bottle, being careful that the water stream does not hit the iron strip. The bottle is stoppered and rolled on its side for 1 minute. It is then stood on end and taped several times to dislodge water globules adhering to the strip and side of the bottle. The strip when standing in the upright tube is contacted by two liquid layers, a water layer on the bottom and a lighter immiscible gasoline or oil layer on the top. The bottle is then set aside and the condition of the strip is observed and rated after 4 and after 24 hours.

The type of rusting as well as the rusted area is considered. Light staining or slight discoloration in the water phase is not defined as rust. The additive is rated by observing the strip in the gasoline and water layers. The most important rating is from observing the strip in the water layer. That rating is based upon the percent of the strip that is covered with a film of rust. The following table shows the rust inhibition of the abovementioned additives. The test was run on base gasoline, which is gasoline that contains no additive whatsoever, and gasoline containing the various additives of the invention.

Rust Inhibition Concentration in pounds per thousand Static Black Iron Rust Additive barrels (PTB) Test (in Rust) 4 hr. 24 hr. Base Gasoline 100 50 N-Amino-L-lO-PSlmide 5 0 40 N-Amino-L-4-PSImide 3 0 l0 N-Amino-L-4-PSImide HCHO 5 25 50 +Acrylonitrile 30 1O 10 +Ethylchloroformate 30 0 30 +Acetic Anhydride 30 O 20 L--PSImide 3 0 25 L-SO-PSlmide 5 0 0 L-4-PSImide H 130 3 0 0 PCl, 3 0 O SiS, 3 0 KOl-I 3 0 0 ClCH,COCl 5 0 S,Cl, 3 0 0 (C,H,O) P 5 10 50 Current Rust Inhibitor EXAM PLE VI In a static rust test additives prepared in Examples II, III and IV showed excellent antirust properties in motor oils. The test used is a standard test to measure rust inhibition in motor oils designated as ASTM D-665 rust test with 0.1 normal I-ICl. Intermediates are also shown.

Rust Inhibition Motor Oils ASTM D-665 Rust Test with 0.1 N HCl Wt. Rating Compound (10 perfect) L-4-PSlmide 1.0 9 L-lO-PSImide 1.0 10 L-SO-PSImide 1.0 9 H-lOO-PSImide 1.0 7 L-4-PSImide Bao 1.0 8 H 80, 1.0 9 Ethylene Oxide 1.0 6 L-4-Polymeric Succinic Anhydride 1.0 0 (L-4-PSA) N-Amino-L-lO-PSImide 1.0 10 N-Amino-L-SO-PSImide L0 8 N-Amino-L-4-PSlmide (at 0.5 wt.

EXAMPLE v11 Additives prepared in Examples II, III and IV have very little tendency toward stabilization of emulsions at gasoline-water interfaces. An emulsion test was run wherein 90 ml of gasoline and 10 ml of water were shaken in a stoppered graduated cylinder for 1 minute. The volume of interfacial emulsion was measured after 0.25, 4 and 24 hours. (A 20 percent by volume emulsion after 1 hour is acceptable.) The test was run on base gasoline which is gasoline that contains no additive whatsoever and gasoline containing the various additives of the invention. The results are shown below.

Additive (in pounds per thousand barrels (PTB), Concen- H,O emulsion volume based on weight of gasoline tration k based on amount of hydrocarbon) in PTB water 0.25 hr. 4 hr. 24 hr. Base Gasoline 30 0 0 N-Amino-L-4-PSlmide 20 Trace Trace N-Amino-L-lO-PSlmide 30 40 30 20 N-Amino L-4-PSlmide 30 [0 Acrylonitrilc l0 Trace Trace Ethyl Chloro formate 20 Trace Trace Acetic Anhydride 20 Trace Trace L-4-Polymeric Succinic Anhydride (L-4-PSA) l0 Trace Trace Tosyl Chloride l0 Trace Trace Ethylene Oxide 0 0 0 L-4-PSlmide 0 0 L-4-PSImide 20 20 Trace L-4-PSlmide H,BO, 0 0 PCI, l0 SiS, 0 0 ClCH,COCl 0 0 S,Cl, 0 0 (C,I-l,O),P 0 O EX AM PLE VIII In addition to other properties, additives prepared in Examples II, III and IV show de-icer properties. Engines were run at low temperature (about 40F.) and high humidity (about 50 percent Relative Humidity) to promote carburetor icing and consequent engine stalls. The following table shows the effectiveness of the various concentrations of the above-mentioned additives.

Additive Stalls Base Fuel, no additive 5 L-4-PSlmide 3 lsopropanol l formate N-Amino-L-4-PSlmide +Acetic Anhydride N-Amino-L-4-PSlmide succinic anhydride (L-4-PSA) N-Amino-L-4-PSlmide +Ethylene Oxide EXAMPLE IX The extreme pressure properties of lubricating oils containing the additives prepared in Examples II, III and IV were measured. The test used was the Steel Falex Test (ASTM No. D-250966T). The concentration of additive used was 1 percent by weight of lubricating oil. The results of the test are shown below. Improvement over the blank Jaw Load Failure is desirable.

Additive Jaw Load Failure (in lb.)

Blank 2000 Present Additive 3250 N-Amino-L-4-PSlmide SnCI, 2750 N-Amino-L-4-PSlmide CS, Butyl Bromide 2500 N-Amino-L-4-PSlmide Acrylonitrile 2250 L-4-PSImide CS, Butyl Bromide 2500 L-4-PSImide Pcl, 2000 L-4-PSlmide Bu,SnCl, 2250 The results in Jaw Load Failure are acceptable in all cases.

EXAMPLE X The rouge suspension properties of gasoline containing various additives described in Examples II, III and IV are shown below. The test is conducted by suspending finely divided particles in the gasoline containing the additive. The least suspension of the particles indicates the most desirable gasoline additive since the rouge has a density very similar to rust (Fe o The rating was done by visual inspection. The concentration of additive was 30 pounds per thousand barrels (PTB) in each case. The object in using the rouge suspension test is to obtain an indication of the suspending properties of the gasoline and additive. Rouge is added to the gasoline containing the additive in a ratio of ml of gasoline to 0.1 grams rouge particles. The mixture of rouge particles and gasoline is placed in a graduated cylinder and shaken for 1 minute and allowed to stand for 24 hours. Ratings are recorded at 0.25 hours, 4 hours and 24 hours. The evaluations are either poor, fair or good. A poor rating being suspension of rouge particles in a major portion of the graduated cylinder. Fair is a suspension of rouge particles only in the lower 25 ml region. A good rating is suspension of rouge particles in the lower 10 ml particle region. The following table shows the various additives and the ratings.

Additive Concen- Rouge Suspension tration (Visual Appearance) PTB 0.25 hr. 4 hr. 24 hr. Base 30 Good Good Good N-Amino-L-lO-PSlmide Fair Fair Fair N-Arnino-L-4-PSImide Fair+ 600d H +Acrylonitrile Fair+ Good Good H H +EthylChloro- Fair+ Good Good formate +Acetic Anhydride u H +L-4-Polymeric H succinic anhydride (L-4-PSA) +Tosyl Chloride u +Ethylene Oxide L-4-PSlmide 20 Fair Good L-SO-PSlmide Fair- Good L-4'PSlmide-H BO Fair+ (iood .p Fair+ Good -SiS, Fair+ Good -ClCH,COCl Fair+ Good .5 Cl Fair+ Good u .(C H O)- P u Good Good EXAMPLE XI L-4-PSlmide in a concentration of 0.3% based upon the weight of the hydrocarbon gasoline was examined in a Sequence Ila" engine test as a supplemental rust inhibitor (ASTM STP 315b, ASTM, 1966). The test is conducted to promote condensation in the engine. The rating is done by disassembling the engine after the test and visually inspecting the parts.

The L-4-PSlmide was found to give an identical rust rating compared to the base blend itself, the rating being 8.7 in both cases (10 is perfect). However, there were no stuck lifters using the PSImide while there were two stuck lifters with the base blend.

$22 33 um'rnn STATES PATENT UFFICE V CERTIFICATE 0i QQRR'EQTEQN Patent No. 317233160 Dated March 7, 973

Inventmfg) William I. Brannen and Roger Wo Watson It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, lines ram: "-blow-by" should be --"blowby" Column Example I table: Under N2 (Theoretical) the second number down is "3.39"; should be 2.39--

Column 5, Example III table: Heading "T-h-N. should be --L- +-N-- Column 6, Example V table: First item, "Base gasoline" the number "50" has been omitted in second column, but shows but of I place after the third column last item, 'YCurrent rust inhibitor" numbers have been omitted in all three columns; should be -l---, --30-- and "To".

Column 6, Ebrample VI table: Last item, under listing of "compounds" parenthesis omitted (at O5 Win71 Column 7, Eiample ,VII table: Second column of numbers, heading "0.25 hr., is somewhat out of place, appearing more under heading "Concentration in PTB" than under proper heading, "H2O emulsion.

Signed and sealed this 19th day of February 1971;...

(SEAL) Attest EDWARD M.FLETCHER,JR. MARSHALL ANN Attesting Officer, Commissioner of Patents