CA1341005C - Fuel compositions and lubricating oil compositions containing very long chain alkylphenyl poly(oxyalkylene) aminocarbamate - Google Patents
Fuel compositions and lubricating oil compositions containing very long chain alkylphenyl poly(oxyalkylene) aminocarbamateInfo
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- CA1341005C CA1341005C CA000580895A CA580895A CA1341005C CA 1341005 C CA1341005 C CA 1341005C CA 000580895 A CA000580895 A CA 000580895A CA 580895 A CA580895 A CA 580895A CA 1341005 C CA1341005 C CA 1341005C
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Abstract
Disclosed are alkylphenyl poly(oxyalkylene) aminocarbamates having at least one basic nitrogen and an, average molecular weight of about 800 to 6,000 and wherein the alkyl group contains at least 40 carbon atoms. Also disclosed are lubricating oil compositions and concentrates containing said alkylphenyl poly(oxyalkylene) aminocarbamates.
Also disclosed is a fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from about 30 to about 5,000 parts per million of a fuel-soluble alkylphenyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen and an average molecular weight of about 800 to 6,000 and wherein the alkyl group contains at least 40 carbon atoms. The instant invention is based on the discovery that use of the unique hydrocarbyl group, i.e., an alkylphenyl group wherein the alkyl group contains at least 40 carbon atoms provides for improved lubricating oil compatibility.
Also disclosed is a fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from about 30 to about 5,000 parts per million of a fuel-soluble alkylphenyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen and an average molecular weight of about 800 to 6,000 and wherein the alkyl group contains at least 40 carbon atoms. The instant invention is based on the discovery that use of the unique hydrocarbyl group, i.e., an alkylphenyl group wherein the alkyl group contains at least 40 carbon atoms provides for improved lubricating oil compatibility.
Description
O1 FUEL COMPO:~ITION:i AND LUBRICATING OIL COMPOSITIONS
03 PC1LY ( OX'.~tALKYLENE ) AMINOCARBAMATES
06 1. Field of then Invention 08 Numerous deposit;-form:ing substances are inherent in hydro-09 carbon fuels. ~'hese :substances when used in internal combustion engines tend to form deposits on and around 11 constricted areas of ithe engine contacted by the fuel.
12 Typical areas commonly and sometimes seriously burdened by 13 the formation of: depo:aits include carburetor ports, the 14 throttle body and venituries, engine intake valves, etc.
16 Deposits adversely af:Eect the operation of the vehicle. For 17 example, deposits on ithe carburetor throttle body and ven-18 turies increase the fuel to air ratio of the gas mixture to 19 the combustion c;hambe:r thereby increasing the amount of unburned hydrocarbon and carbon monoxide discharged from the 21 chamber. The high final-air ratio also reduces the gas 22 mileage obtainable from the vehicle.
24 Deposits on the engine intake valves when they get suffi-ciently heavy, on the other hand, restrict the gas mixture 26 flow into the combustion chamber. This restriction, starves 27 the engine of ai.r and fuel and results in a loss of power.
28 Deposits on the valves also increase the probability of 29 valve failure due to lburning and improper valve seating. In addition, these deposits may break off and enter the com-31 bustion chamber possilbly resulting in mechanical damage to 32 the piston, pisi:on rings, engine head, etc.
O1 The formation of these' deposits can be inhibited as well as 02 removed by incorporating an active detergent into the fuel.
03 These detergents. function to cleanse these deposit-prone 04 areas of the harmful deposits, thereby enhancing engine per-05 formance and longevity. There are numerous detergent-type 06 gasoline additives cui:rently available which, to varying 07 degrees, perform theses functions.
09 Two factors comp~licatEa the use of such detergent-type gasoline additives. First, with regard to automobile 11 engines that reqyire t:he use of nonleaded gasolines (to 12 prevent disablement of: catalytic converters used to reduce 13 emissions), it h.as been found difficult to provide gasoline 14 of high enough octane to prevent knocking and the con-comitant damage which it causes. The chief problem lies in 16 the area of the degree of octane requirement increase, 17 herein called "O~RI", which is caused by deposits formed by 18 the commercial gasoline.
The basis of the ORI problem is as follows: each engine, 21 when new, requires a certain minimum octane fuel in order to 22 operate satisfactorily without pinging and/or knocking. As 23 the engine is operated on any gasoline, this minimum octane 24 increases and, in most: cases, if the engine is operated on the same fuel far a prolonged period, will reach an 26 equilibrium. This is apparently caused by an amount of 27 deposits in the combu:ction chamber. Equilibrium is typi-28 cally reached after 5,000 to 15,000 miles of automobile 29 operation.
31 The octane requirement: increase in particular engines used 32 with commercial gasoli.nes will vary at equilibrium from 5 to 33 6 octane units to as high as 12 or 15 units, depending upon _2_ I)1 the gasoline compositions, engine design and type of opera-I)2 tion. The seriousness of the problem is thus apparent. A
I)3 typical autamobi:Le witlh a research octane requirement of 85, I)4 when new, may afl:er a few months of operation require 97 I)5 research octane c)asoline for proper operation, and little I)6 unleaded gasoline' of t'.hat octane is available. The ORI
I)7 problem also exists in some degree with engines operated on I)8 leaded fuels. U.S. Patent Nos. 3,144,311; 3,146,203; and I)9 4,247,301 disclose lead-containing fuel compositions having :LO reduced ORI properties.
:l 1 :L2 The ORI problem :is compounded by the fact that the most :l3 common method fo;r increasing the octane rating of unleaded :l4 gasoline is to increase its aromatic content. This, how-:l5 ever, eventually causes an even greater increase in the :L6 octane requirement. Moreover, some of presently used :l7 nitrogen-containing compounds used as depositcontrol addi-:l8 tives and their mineral oil or polymer carriers may also :l9 significantly contribute to ORI in engines using unleaded :20 fuels.
:21 :22 it is, therefore, particularly desirable to provide deposit :23 control additives which effectively control the deposits in :24 intake systems of engines, without themselves eventually :25 contributing to the problem.
.26 :27 In this regard, hydrocarbyl poly(oxyalkylene) aminocarba-:28 mates are commercially successful fuel additives which :29 control combustion chamber deposits thus minimizing ORI.
31 The second complicating factor relates to the lubricating 32 oil compatibility of the fuel additive. Fuel additives, due 33 to their higher boiling point over gasoline itself, tend to 34 accumulate on surfaces. in the combustion chamber of the O1 engine. This accumulation of the additive eventually finds 02 its way into the lubricating oil in the crankcase of the 03 engine via a "blow-by''' process and/or via cylinder 04 wall/piston ring "wipes down". In some cases, as much as 05 25~-30~ of the nonvolatile fuel components, i.e., including 06 fuel additives, will eventually accumulate in the lubri-07 eating oil. Insofar as the recommended drain interval for 08 some engines may be asp much as 7,500 miles or more, such 09 fuel additives can accumulate during this interval to sub-stantial quantities in the lubricating oil. In the case 11 where the fuel additive is not sufficiently lubricating oil 12 compatible, the accumulation of such an oil-incompatible 13 fuel additive many actually contribute to crankcase deposits, 14 i.e., varnish and sludge, as measured by a Sequence V-D
test.
17 The incompatibility of certain fuel additives in lubricating 18 oils, i.e., oil:; which contain other additives, arises in 19 spite of the fact thai:. some fuel additives are also known to be lubricating c>il dispersants.
22 Several theorie:c exist as to the cause of the lubricating 23 oil incompatibility o:E certain fuel additives. Without 24 being limited to any theory, it is possible that some of these fuel additives when found in the lubricating oil 26 interfere with other additives contained in the lubricating 27 oil and either counterbalance the effectiveness of these 28 additives or actually cause dissolution of one or more of 29 these additives including possibly the fuel additive itself.
In either case, the incompatibility of the fuel additive 31 with other addii:ives in the lubricating oil demonstrates 32 itself in less i~han desirable crankcase deposits as measured 33 by Sequence V-D engine tests.
O1 In another theory, it is possible that the accumulation of 02 the fuel additive into the lubricating oil during the drain 03 interval period surpasses its maximum solubility in the 04 lubricating oil. In this theory, this excess amount of fuel 05 additive is insoluble in the lubricating oil and is what 06 causes increased. cranl~:case deposits.
08 In still another theory, it is possible that the fuel addi-09 tive will decom~~ose in the lubricating oil during engine operation and th.e decomposition products are what cause 11 increased crankcase dEaposits.
13 In any case, lut~ricati.ng oil incompatible fuel additives are 14 less than desirable insofar as their use during engine operation will result in increased deposits in the crank-16 case. This prot~lem can be severe. Accordingly, it would be 17 particularly adv~antage~ous to develop a good deposit control 18 fuel additive which does not contribute to ORI and which 19 additionally possesse:> lubricating oil compatibility.
21 The instant invention is directed to fuel compositions con-22 taining a novel class of alkylphenyl poly(oxyalkylene) 23 aminocarbamates which as a fuel additive controls combustion 24 chamber deposit:, thus minimizing ORI and in lubricating oil have improved compatibility in the lubricating oil composi-26 tion. The novel. addii:ives of this invention are very long 27 chain alkylphen~~l poly(oxyalkylene) aminocarbamates having a 28 molecular weight: of about 800 to 6,000 wherein the alkyl 29 group of said al.kylphf~nyl group contains at least 40 carbon atoms.
32 This invention i.s also directed toward dispersants compat-33 ible in lubricating o:il. In particular, this invention is 34 directed toward dispe:rsant additives possessing improved O1 compatibility in lubricating oil which are alkylphenyl 02 poly(oxyalkylene) aminocarbamates having at least one basic 03 nitrogen and wherein the alkyl group of said alkylphenyl 04 poly(oxyalkylene) aminocarbamate contains at least 40 carbon 05 atoms.
07 The incompatibility of certain dispersant additives in 08 lubricating oil, i.e., oils which contain other additives, 09 is recognized in the art and arises in spite of the fact that certain of these additives are known lubricating oil 11 dispersants.
13 Several theories exist as to the cause of the lubricating 14 oil incompatibility of certain additives. Without being limited to any theory, it is possible that some of these 16 additives interfere with other additives contained in the 17 lubricating oil and either counterbalance the effectiveness 18 of these additives or actually cause dissolution of one or 19 more of these additives, including possibly the dispersant additive itself.
22 In another theory, it is possible that the additive will 23 decompose in the lubricating during engine operation and the 24 decomposition products are what cause increased crankcase deposits.
27 In still another theory, it is also possible that the 28 incompatibility of the additive is related to its oil 29 solubility.
31 Lubricating oil incompatibla additives are less than desir-32 able insofar as their use during engine operation will 33 result in increased crankcase deposits, i.e., varnish and O1 sludge, in the crankcase as measured by Sequence V-D engine 02 tests. This problem can be severe.
04 The instant invention is directed to a novel class of very 05 long chain alkylphenyl poly(oxyalkylene) aminocarbamates 06 which provide improved. compatibility in lubricating oil 07 compositions. The novel additives of this invention are 08 alkylphenyl poly(oxyalkylene) aminocarbamates having a 09 molecular weight of about 800 to 6,000 wherein the alkyl group of said alkylphe~nyl poly(oxyalkylene) aminocarbamate 11 contains at least 40 carbon atoms.
13 2. Prior Art Numerous references disclose C1 to C30 hydrocarbyl poly(oxy-16 alkylene) aminocarbamates as fuel additives. These include 17 the following U.S. Patients Nos.:
19 4,160,648; 4,243,798; 4,521,610; and 4,191,537; X1,270,930; 4,568,358.
21 4,197,409; 4,274,837;
22 4,236,020; 4,288,612;
24 Of particular rerlevanc:e is U.S. Patent No. 4,274,837 which discloses that hydrocarbyl poly(oxyalkylene) aminocarbamates 26 containing certain po:ly(oxyalkylene) chains, i.e., oxypro-27 pylene, when used in :Fuels employed in combination with 28 certain lubricating oils, produce crankcase varnish. This 29 reference further discloses that lubricating oil compatible hydrocarbyl pol5~(oxypropylene) aminocarbamates are improved 31 by employing the poly(oxypropylene) as a copolymer having 1 32 to 5 C9 to C30 oxyalk;ylene units.
_7_ O1 U.S. Patent No. 4,160,648 discloses an intake system deposit 02 control additive for fuels which is a hydrocarbyl poly(oxy-03 alkylene) aminocarbama.te wherein the hydrocarbyl group is 04 from 1 to 30 carbon atoms including alkyl or alkylphenyl 05 groups. Specifically disclosed hydrocarbyl groups include 06 tetrapropenylphenyl, olelyl and a mixture of C16, C18 and 07 C20 alkyl groups. Lil~:ewise, U.S. Patent No. 4,288,612 08 discloses deposit control additives for gasoline engines 09 which are hydrocarbyl poly(oxyalkylene) aminocarbamates wherein the hydrocarbyl group contains from 1 to about 30 11 carbon atoms including alkylphenyl groups wherein the alkyl I2 group is straight or branched chain of from 1 to about 24 13 carbon atoms. tt.S. Patent No. 4,568,358 discloses diesel 14 fuel compositions containing an additive such as a hydro-carbyl poly(oxy~~lkylene) aminocarbamate. This reference 16 discloses hydro<:arbyl groups such as alkyl groups of 1 to 30 17 carbon atoms; aryl groups of 6 to 30 carbon atoms, alkaryl 18 groups of 7 to :30 carbon atoms, etc.
U.S. Patent No. 4,332,595 discloses hydrocarbyl poly(oxy-21 alkylene) polyamines wherein the hydrocarbyl group is a 22 hydrocarbyl radical of 8 to 18 carbon atoms derived from 23 linear primary alcohols.
U.S. Patent Nos. 4,233,168 and 4,329,240 among others 26 disclose lubricating oil compositions containing a 27 dispersant amount of a hydrocarbyl poly(oxyalkylene) 28 aminocarbamate.
While these prior art: references disclose fuel compositions 31 containing C1 to C30 hydrocarbyl poly(oxyalkylene) amino-32 carbamates, nor..e of i:hese references disclose the unique 33 alkylphenyl group of this invention nor do any of these 34 references suggest that use of this unique alkylphenyl group _g_ (!1 would provide improved compatibility in lubricating oil (12 compositions.
OS
06 The instant invention is directed toward a novel class of 07 alkylphenyl poly(oxyalkylene) aminocarbamates which possess !)8 improved compatibility with lubricating oil compositions.
09 In particular, the instant invention is directed toward an :LO alkylphenyl poly(oxyalkylene) aminocarbamate having at least :Ll one basic nitrogen and an average molecular weight of about :l2 800 to 6.000 and wherein the alkyl group of said alkylphenyl :L3 poly(oxyalkylene) aminocarbamate contains at least 40 carbon :L4 atoms and the pol.y(oxy<~lkylene) polymer is derived from C2 :LS to C5 oxyalkylene~ units with the proviso that if the :L6 poly(oxyalkylene;~ polymer is a homopolymer of oxyethylene :L7 then the poly(ox~rethyl~ene) polymer does not contain more :18 than 25 oxyethyle~ne units. The instant invention is based ;19 on the discovery that ruse of the unique alkylphenyl group, .20 i.e., an alkylphe~nyl group wherein the alkyl group contains :21 at least 40 carbon atoms, imparts to the alkylphenyl poly-22 (oxyalkylene) am:lnocar'.bamate improved lubricating oil 23 compatibility.
25 The compounds of this invention are useful dispersants in 26 lubricating oil. Thus, in its composition aspect, the 27 instant invention is directed toward a lubricating oil 28 composition comprising an oil of lubricating viscosity and a 29 dispersant effective amount of an alkylphenyl poly(oxy-30 alkylene) aminoc.~rbamate of this invention.
32 The instant invention is also directed toward a fuel compo-33 sition containing a novel class of alkylphenyl poly-3q (oxyalkylene) aminocarbamates which as a fuel additive _g_ controls combustion c;hamber deposits thus minimizing ORI
and in lubricating oi.I provide improved compatibility with the lubricating oil composition. In particular, the instant invention is directed toward a fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from about 30 to about 5,000 parts per million of a fuel soluble alkylphenyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen and an average molecular weight of about 800 to 6,000 and wherein the alkyl group of said alkylphenyl poly(oxyalkylene) ami.nocarbamate contains at least 40 carbon atoms and the poly(oxyalkylene) polymer is derived from CZ to C5 ox:yalky7_ene units with the proviso that if the poly(oxyalkylene) polymer is a homopolymer of oxyethylene then the poly(oxyethylene) polymer does not contain more than 25 oxyethylene units. The instant invention is based on the discovery that use of the unique alkylphenyl group, i.e., an alkylphenyl group wherein the alkyl group contains at least 40 carbon atoms, imparts to the: alkylphenyl poly(oxyalkylene) aminocarbamate improved lubricating oil compatibility without contributing to ORI.
According to an aspeca of the present invention, an alkylphenyl poly(oxya.lkylene) aminocarbamate having at least one basic nitrogen and an average molecular weight of about 800 to 6,000 and wherein the alkyl group of said alkylphenyl poly(oxya.lkylene) aminocarbamate contains from 40 to 200 carbon. atoms and the poly(oxyalkylene) polymer is derived from C2 to C5 oxyalkylene units with the proviso that if the poly(oxyalkylene) polymer is a homopolymer of oxyeth.ylene then the poly(oxyethylene) polymer does not contain more than 25 oxyethylene units.
~B
According to a furthear aspect of the present invention, a compound of Formula V
CH2CH;nOC-NHER2NH~QH
R,~
V
wherein R is am alkyl. group having from 40 to 200 carbon atoms; R~ is hydrogen or alkyl of from 1 to 3 carbon atoms; R2 is al:kylene of from 2 to 6 carbon atoms; m is an integer from 1 to 2; n is an integer such that the molecular weight of t:he compound is from about 800 to 6,000; and p is an integer from 1 to 6 and with the proviso that if R~ is hydrogen then n is an integer from 1 to 25.
According to another aspect of the present invention, a lubricating oil composition comprising an oil of lubricating viscosity and a dispersant effective amount of an alkylphenyl pol.y(oxyalkylene) amino carbamate having at least one basic nitrogen and an average molecular weight of about 800 to 6,000 and wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 40 to 200 carbon atoms and the poly(oxyalkylene) polymer is derived from C2 to C5 (oxyalkylene) units with the proviso that if the poly(oxyalkylene) polymer is a homopolymer of (oxyethylene) then tree poly(oxyethylene) polymer does not containing more than 25 (oxyethylene) units.
According to another aspect of the present invention, a fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from about 30 to about 5,000 parts per million of a fuel soluble alkylphenyl poly(oxyalkylene) ami.nocarbamate having at least one basic nitrogen and an average molecular weight of about loa fB
800 to 6,000 and wherein the alkyl group of said alkyphenyl poly(oxyalkylene) aminocarbamate contains from 40 to 200 carbon atoms and the poly(oxyalkylene) polymer is derived from C2 to C5 oxyalkylene units with the proviso that if the p~oly(oxyalkylene) polymer is a homopolymer of oxyeth.ylene then the poly(oxyethylene) polymer does not contain more than 25 oxyethylene units.
DETAILED DESCRIPTION OF THE INVENTION
The alkylphenyl poly(oxyalkylene) aminocarbamates of the present invention consist of an amino moiety and an alkylphenyl pol;y(oxyalkylene) polymer bonded through a carbamate linkage, i.e., -OC(O)N<. The specific alkylphenyl group employed in the instant invention in the alkylphenyl poly(oxyalkylene) polymer is critical to achieving improved lubricating oil compatibility for the alkylphenyl pol:y(oxyalkylene) aminocarbamates. In particular, it lhas been found that employing the alkylphenyl group of this invention wherein the alkyl group contains .at least 40 carbon atoms 10b O1 results in an alkylphenyl poly(oxyalkylene) aminocarbamate 02 which has improved lubricating oil compatibility.
04 The Preferred Alkylphenyl Group 06 The preferred alkylphenyl group of the alkylphenyl 07 poly(oxyalkylene) aminocarbamate employed in this invention 08 is derived from the corresponding alkylphenol of Formula I
09 below:
m 16 wherein R is an alkyl group of at least 40 carbon atoms and 17 m is an integer from 1 to 2.
19 Preferably, m i;~ one.
21 Preferably R is an alkyl group of from 50 to 200 carbon 22 atoms. More preferably, R is an alkyl group of from 60 to 23 100 carbon atom: .
When m is one, l:he alkylphenyl is a monoalkylphenyl; whereas 26 when m is two, i:he alkylphenyl is a dialkylphenyl.
2g The alkylphenol:a of Formula I above are prepared by reacting 2g the appropriate olefin or olefin mixture with phenol in the presence of an ~~lkylating catalyst at a temperature of from 31 about 60°C to 2i)0°C, and preferably 125°C to 180°C either 32 neat or in an e~;sentially inert solvent at atmospheric 33 pressure: Preferred alkylating catalysts are a sulfonic 34 acid catalyst such as Amberlyst 1~ available from Rohm and O1 Haas, Philadelphia, Pennsylvania, or boron trifluoride (or 02 an etherate of boron t:rifluoride). Molar ratios of reac-03 tarts can be employed. when molar ratios are employed, the '04 reaction yields a mixture of dialkylphenol, monoalkylphenol '05 and unreacted phenol. As noted above, dialkylphenol and '06 monoalkylphenol can be used to prepare the additives used in the compositions of this invention whereas the unreacted '08 phenol is preferably removed from the post reaction mixture X09 via conventional techniques. Alternatively, molar excess of :10 phenol can be employed, i.e., 2 to 2.5 equivalents of phenol :11 for each equivalent of: olefin with unreacted phenol :12 recycled. The latter process maximizes monoalkylphenol.
:13 Examples of inert solvents include benzene, toluene, chloro-:14 benzene and 250 thinner which is a mixture of aromatics, :15 paraffins and na.phthenes.
:l6 :17 Particularly preferred alkylphenols employed in this :18 invention are monoalkylphenols represented by Formula II
:19 below:
a1 OH
:Z 2 a3 II
a4 a5 :Z 6 R
wherein R is as defined above.
a8 'Z9 A particularly preferred class of olefins for use in preparing alkyli~henols useful in this invention are 31 polyolefin polymers. Polyolefin polymers are polymers 32 comprising a major amount of C3 to C5 monoolefin, e.g., :33 ethylene, propy:Lene, butylene, isobutylene and pentene.
.34 The polymers can be homopolymers such as polyisobutylene as well as copolymers of two or more such olefins such as copolymers of: ethylene and propylene, butylene, and isobutylene, etc. Other copolymers include those in which a minor amount of the copolymer monomers, e.g., 1 to 20 mole percent is a C4 to C8 nonconjugated diolefin, e.g., a copolymer of isobutylene and butadiene or a copolymer of ethylene, propylene and 1,4-hexadiene, etc.
The polyolefin polymer usually contains at least 40 carbon atoms, although preferably 50 to 200 carbon atoms and more preferably 60 to 100 carbon atoms.
A particularly preferred class of olefin polymers com-prises the polybutenes, which are prepared by polymer-ization of one or more of 1-butene, 2-butene and isobutene. Especially desirable are polybutenes con-taining a substantial proportion of units derived from isobutene. The polybutene may contain minor amounts of butadiene which may or may not be incorporated in the polymer. Most often the isobutene units constitute 80%, preferably at least 90%, of the units in the polymer.
These polybutenes are readily available commercial mate-rials well known to those skilled in the art. Disclosures thereof will be found, for example, in U.S. Patents Nos. 3,215,707; 3,231,587; 3,515,669; and 3,579,450, as well as U.S. Patent No. 3,912,764.
In addition to the reaction of a polyolefin with phenol, many other alkylating hydrocarbons may likewise be used with phenol to produce alkylphenol. Other suitable alkyl-ating hydrocarbons include cyclic, linear, branched and internal or alpha olefins having molecular weights of at O1 least about 560. For example, alpha olefins obtained from 02 the ethylene growth process gives even number carbon ole-03 fins. Another source of olefins is by the dimerization of 04 alpha olefins over an appropriate catalyst such as the 05 well-known Ziegler catalyst. Internal olefins are easily 06 obtained by the isomerization of alpha olefins over a 07 suitable catalyst such as silica.
09 Preferred Poly(oxyalkylene) Component 11 The alkylphenyl poly(oxyalkylene) polymers which are 12 utilized in preparing the carbamates of the present inven-13 tion are monohyd~roxy compounds, i.e., alcohols, often 14 termed alkylpher,~yl "capped" poly(oxyalkylene) glycols and are to be distir.~guishe~d from the poly(oxyalkylene) glycols 16 (diols), which acre noi: alkylphenyl terminated, i.e., not 17 capped. The alk.ylphenyl poly(oxyalkylene) alcohols are 18 produced by the addition of lower alkylene oxides, such as 19 ethylene oxide, propylene oxide, the butylene oxides, or the pentylene~ oxidE~s to the alkylphenol of Formula I, 21 i.e., I , m 29 under polymerization conditions, wherein R and m are as defined above. Preferred poly(oxyalkylene) polymers are 31 those derived from C3 to C4 oxyalkylene units; more prefer-32 ably C3 oxyprop;~lene 'units. Methods of production and 33 properties of these polymers are disclosed in U.S. Patent 34 Nos. 2,841,479 and 2,782,240 and Kirk-Othmer's "Encyclopedia O1 of Chemical Technology", Volume 19, p. 507. In the polymer-02 ization reaction, a single type of alkylene oxide may be 03 employed, e.g., propylene oxide, in which case the product 04 is a homopolymer, e.g., a poly(oxypropylene) propanol.
05 However, copolymers are equally satisfactory and random 06 copolymers are readily prepared by contacting the hydroxyl-07 -containing compound with a mixture of alkylene oxides, such OS as a mixture of propylene and butylene oxides. Block 09 copolymers of oxyalkyl.ene units also provide satisfactory poly(oxyalkylene) polymers for the practice of the present 11 invention.
13 Homopolymers of poly(oxyethylene) polymers are much more 14 hydrophilic than homopolymers of C3-C5 poly(oxyalkylene) polymers. Accordingly, when homopolymers of poly(oxy-16 ethylene) polymers area employed, the amount of poly(oxy-17 ethylene) must be limited so as to ensure fuel 18 dispersency/detergency and lubricating oil compatibility of 19 the final carbam.ate. In general, this is accomplished by limiting the poly(oxyethylene) polymer to about 25 oxy-21 ethylene units or les:~; although preferably about 10 oxy-22 ethylene units or les:>~ and most preferably about 5 23 oxyethylene units or less.
Likewise, copolymers containing a mixture of oxyethylene 26 units and C3-C5 oxyal~:ylene units are formulated to ensure 27 that the copolymer possesses fuel solubility and lubricating 28 oil compatibility.
In general, the poly(oxyalkylene) polymers are mixtures of 31 compounds that differ in polymer chain length. However, 32 their properties; closely approximate those of the polymer 33 represented by t:he average composition and molecular weight.
O1 In general, the very long chain alkylphenyl terminating 02 group on the alkylphe;nyl poly(oxyalkylene) aminocarbamates 03 of this invention allow for use of less oxyalkylene units in 04 the poly(oxyalkylene) polymer to ensure fuel dispersancy/-05 detergency solubility and lubricating oil compatibility than 06 are necessary in prior art carbamate fuel additives. Accor-07 dingly, while longer poly(oxyalkylene) polymers are func-08 tional in this i.nvent:ion, such longer polymers are not 09 necessary. Therefore, each poly(oxyalkylene) polymer utilized in thi:~ invention contains at least 1 oxyalkylene 11 unit, preferably from 1 to about 100 oxyalkylene units, more 12 preferably from about 1 to about 25 oxyalkylene units, even 13 more preferably from about 1 to about 10 oxyalkylene units, 14 and most preferably about 5 oxyalkylene units or less. It is understood that if the poly(oxyalkylene) polymer is a 16 homopolymer of poly(oxyethylene), the polymer length is 17 governed by the constraints discussed above.
19 An alternative method for preparing alkylphenyl poly(oxy-alkylene) polymers ha~~ing 1, 2 or 3 oxyalkylene units 21 involves employing a compound of Formula III below:
24 C;1(CH2CH0)qH III
26 wherein q is an integer from 1 to 3 and R1 is hydrogen or 27 a C1 to C3 alkyl group. When employing the compound of 28 Formula III, the phenoxide of the alkylphenol, I, is first 29 prepared and then reacted with the compound of Formula III
to yield the desired a~lkylphenol poly(oxyalkylene) polymer 31 having from 1 to 3 oxyalkylene units. Compounds of 32 Formula III are either' commercially available or can be 33 prepared by art recognized methods.
O1 Preferred Amine Component 03 The amine moiety of th,e alkylphenyl poly(oxyalkylene) 04 aminocarbamate employed in this invention is preferably 05 derived from a polyamine having from 2 to about 12 amine 06 nitrogen atoms and from 2 to about 40 carbon atoms. The 07 polyamine is preferably reacted with an alkylphenyl poly-08 (oxyalkylene) chlorofcrrmate to produce the alkylphenyl 09 poly(oxyalkylene) aminocarbamate additives finding use within the scope of the present invention. The chloro-11 formate is itself derived from alkylphenyl poly(oxy-12 alkylene) alcohol by reaction with phosgene. The 13 polyamine, encom~.passing diamines, provides the product 14 alkylphenyl poly(oxya7.kylene) aminocarbamate with, on average, at least about one basic nitrogen atom per 16 carbamate molecuale, i,.e., a nitrogen atom titratable by a 1~ strong acid. The polyamine preferably has a carbon-to-18 nitrogen ratio of frorn about 1:1 to about 10:1.
The polyamine may be substituted with substituents 21 selected from (A) hydrogen, (B) hydrocarbyl groups of from 22 1 to about 10 ce~rbon atoms, (C) acyl groups of from 2 to 23 about 10 carbon atoms, and (D) monoketo, monohydroxy, 24 mononitro, monoc:yano, lower alkyl and lower alkoxy derivatives of I:B) and (C). "Lower", as used in terms 26 like lower alky7~ or lower alkoxy, means a group containing 27 from 1 to about 6 carbon atoms. At least one of the 28 substituents on one of the basic nitrogen atoms of the 29 polyamine is hydrogen, e.g., at least one of the basic nitrogen atoms of the polyamine is a primary or secondary 31 amino nitrogen ~~tom.
33 Hydrocarbyl, as used in describing all the components of 34 this invention, denotes an organic radical composed of '341005 O1 carbon and hydrogen which may be aliphatic, alicyclic, 02 aromatic or combinations thereof, e.g., aralkyl. Prefer-03 ably, the hydrocarbyl group will be relatively free of 04 aliphatic unsaturation, i.e., ethylene and acetylenic, 05 particularly acetylenic unsaturation. The substituted 06 polyamines of the present invention are generally, but not 07 necessarily, N-substituted polyamines. Exemplary hydro-08 carbyl groups and substituted hydrocarbyl groups include 09 alkyls such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, etc., alkenyls such as propenyl, 11 isobutenyl, hexe:nyl, octenyl, etc., hydroxyalkyls, such as 12 2-hydroxyethyl, 3-hydroxypropyl, hydroxyisopropyl, 13 4-hydroxybutyl, ~etc., ketoalkyls, such as 2-ketopropyl, 14 6-ketooctyl, etc., alkoxy and lower alkenoxy alkyls, such as ethoxyethyl, ~ethoxypropyl, propoxyethyl, propoxypropyl, 16 2-(2-ethoxyethox:~)ethyl, 2-(2-(2-ethoxyethoxy)ethoxy)-17 ethyl, 3,6,9,12-tetraoxatetradecyl, 2-(2-ethoxyethoxy) 18 hexyl, etc. The acyl groups of the aforementioned (C) 19 substituents are such as propionyl, acetyl, etc. The more preferred substi~tuents are hydrogen, Cl-C4 alkyls and 21 Cl-C4 hydroxyalk~~ls.
23 In a substituted polya:mine the substituents are found at 24 any atom capable of receiving them. The substituted atoms, e.g., substituted nitrogen atoms, are generally 26 geometrically inE~quivalent, and consequently the sub-27 stituted amines ~:inding use in the present invention can 28 be mixtures of mono- a:nd poly-substituted polyamines 29 with substituent groups situated at equivalent and/or inequivalent atoms.
32 The more preferred pol~yamine finding use within the scope 33 of the present invention is a polyalkylene polyamine, 34 including alkylene diamine, and including substituted ~ 34~ 005 O1 polyamines, e.g., alkyl and hydroxyalkylsubstituted poly-02 alkylene polyamine. Preferably, the alkylene group con-03 tains from 2 to 6 carbon atoms, there being preferably 04 from 2 to 3 carbon atoms between the nitrogen atoms. Such 05 groups are exemplified by ethylene, 1,2-propylene, 2,2-di-06 methylpropylene trimethylene, 1,3,2-hydroxypropylene, etc.
07 Examples of such polya.mines include ethylene diamine, 08 diethylene triamine, dli(trimethylene)triamine, dipropylene 09 triamine, triethylene tetramine, tripropylene tetramine, tetraethylene pentamir~e, and pentaethylene hexamine. Such 11 amines encompass isomers such as branchedchain polyamines 12 and the previously mentioned substituted polyamines, 13 including hydroxy- and hydrocarbylsubstituted polyamines.
14 Among the polyalkylene~ polyamines, those containing 2-12 amine nitrogen atoms and 2-24 carbon atoms are especially 16 preferred, e.g., ethy7Lene diamine, propylene diamine, 17 butylene diaminE~, pentylene diamine, hexylene diamine, 18 diethylene triamine, dipropylene triamine, and the C2-C3 19 alkylene polyami.nes are most preferred, in particular, the lower polyalkylene po:lyamines, e.g., ethylene diamine, 21 diethylene triamine, propylene diamine, dipropylene 22 triamine, etc.
24 The amine component of the alkylphenyl poly(oxyalkylene) aminocarbamate also may be derived from heterocyclic 26 polyamines, hetE~rocyclic substituted amines and substi-27 tuted heterocyc:lic compounds, wherein the heterocycle 28 comprises one or more 5-6 membered rings containing oxygen 29 and/or nitrogen. Such heterocycles may be saturated or unsaturated and substituted with groups selected from the 31 aforementioned (A), (B), (C) and (D). The heterocycles 32 are exemplified by piperazines, such as 2-methylpiper-33 azine, N-(2-hydroxyethyl)piperazine, 1,2-bis-(N-pipera-34 zinyl)ethane, and N,N~bis(N-piperazinyl)piperazine, 34? 005 2-methylimidazoline, 3-aminopiperidine, 2-aminopyridine, 2-(3-aminoethyl)3-~pyrro:line, 3-aminopyrrolidine, N-(3-aminopropyl)morpho:Line, etc. Among the heterocyclic compounds, the piperazines are preferred.
Another class of :~uitab:le polyamines are diaminoethers represented by Formula :IV
H2N-X.1 f 0X2 ~ rNH2 I V
wherein X1 and X2 are independently alkylene from 2 to about 5 carbon atoms and r is an integer from 1 to about 10. Diamines of Formula IV are disclosed in U.S. Patent No. 4,521,610.
Typical polyamine:; that can be used to form the compounds of this invention by reaction with a poly(oxyalkylene)-chloroformate incJ.ude the following: ethylene diamine, 1,2-propylene diamine, :1,3-propylene diamine, diethylene triamine, triethyl.ene tetramine, hexamethylene diamine, tetraethylene pent:amine, dimethylaminopropylene diamine, N-(beta-aminoethyl.)piperazine, N-(beta-aminoethyl)piper-idine, 3-amino-N-eathylpiperidine, N-(beta-aminoethyl)-morpholine, N,N'-di(bet;a-aminoethyl)piperazine, N,N'-di(beta-aminoethylimidazolidone-2; N-(beta-cyano-ethyl)ethane-1,2-diamin~e, 1-amino-3,6,9-triazaoctadecane, 1-amino-3,6-diaza--9-oxadecane, N-(beta-aminoethyl)-di-ethanolamine, N'-acetyl-N'-methyl-N-(beta-aminoethyl)-ethane-1,2-diaminE~, N-acetonyl-1,2-propanediamine, N-(beta-nitroethy:L)-1,3-propane diamine, 1,3-dimethyl-5-(beta-aminoethyl)hexahydrotriazine, N-(beta-amino-ethyl)hexahydrotr:iazine, 5-(beta-aminoethyl)-1,3,5-d '' , ~ 3'~~ 005 O1 dioxazine, 2-(2-aminoe~thylamino)-ethanol, 2[2-(2-amino-02 ethylamino)ethylamino]-ethanol.
04 The amine component of: the alkylphenyl poly(oxyalkylene) 05 aminocarbamate may al:~o be derived from an amine-contain-06 ing compound which is capable of reacting with an alkyl-07 phenyl poly(oxyalkylene) alcohol to produce an alkylphenyl 08 poly(oxyalkylene) aminocarbamate having at least one basic 09 nitrogen atom. For ea:ample, a substituted aminoiso-cyanate, such as (R3)~,NCH2CH2NC0, wherein R3 is, for 11 example, a hydrocarby7L group, reacts with the alcohol to 12 produce the amir.~ocarbamate additive finding use within the 13 scope of the prersent :invention. Typical aminoisocyanates 14 that may be used to form the fuel additive compounds of this invention t>y reaction with a hydrocarbylpoly(oxy-16 alkylene) alcohol inc:Lude the following: N,N-(dimethyl)-17 aminoisocyanatoe~thane, generally, N,N-(dihydrocarbyl)-18 aminoisocyanatoalkane, more generally, N-(perhydrocarbyl)-19 isocyanatopolyal_kylen~e polyamine, N,N-(dimethyl)aminoiso-cyanatobenzene, etc.
22 In many instancE~s the amine used as a reactant in the 23 production of the carbamate of the present invention is 24 not a single compound but a mixture in which one or several compounds, predominate with the average composi-26 tion indicated. For example, tetraethylene pentamine 27 prepared by the polymerization of aziridine or the 28 reaction of dichloroethylene and ammonia will have both 29 lower and higher amine members, e.g., triethylene tetramine, substituted piperazines and pentaethylene 31 hexamine, but the composition will be mainly tetraethylene 32 pentamine and the empirical formula of the total amine 33 composition will closely approximate that of tetraethylene 34 pentamine. Finally, in preparing the compounds of this 1341 00~
Ol invention, where the various nitrogen atoms of the poly-02 amine are not geometrically equivalent, several substitu-03 tional isomers are possible and are encompassed within the 04 final product. Methods of preparation of amines, iso-05 cyanates and their reactions are detailed in Sidgewick's 06 "The Organic Chemistry of Nitrogen", Clarendon Press, 07 Oxford, 1966; Hollers' "Chemistry of Organic Compounds", 08 Saunders, Philadelphia, 2nd Ed. 1957; and Kirk-Othmer's 09 "Encyclopedia of Chemical Technology", 2nd Ed., especially Volume 2, pp. 99-116.
12 Preferred Alkylphenyl 13 Pol (y oxyalkylene) Aminocarbamate Having described the preferred alkylphenyl poly(oxy-16 alkylene) component and the preferred polyamine component, 17 the preferred alkylphenyl poly(oxyalkylene) aminocarbamate 18 additive of the present invention is obtained by linking 19 these components together through a carbamate linkage i.e., 24 -0-C-N<
26 wherein the ether oxygen may be regarded as the terminal 27 hydroxyl oxygen of the alkylphenyl poly(oxyalkylene) 28 alcohol component, and the carbonyl group -C(0)- is 29 preferably provided by the coupling agent, e.g., phosgene.
31 The alkylphenyl poly(oxyalkylene) aminocarbamate employed 32 in the present invention has at least one basic nitrogen 33 atom per molecule. A "basic nitrogen atom" is one that is 34 titratable by a strong acid, e.g., a primary, secondary, O1 or tertiary amino nitrogen, as distinguished from, for 02 example, an amido nitragen, i.e., -CN< , 09 which is not so titratable. Preferably, the basic nitrogen is in a primary or secondary amino group.
12 The preferred al:kylphenyl poly(oxyalkylene) aminocarbamate 13 has an average m~~lecular weight of from about 800 to 14 6,000; preferably an average molecular weight of from 800 to 3,000; and most preferably an average molecular weight 16 of from 1,000 to 2,500.
18 A preferred clas;~ of alkylphenyl poly(oxyalkylene) amino-19 carbamate can be described by the following Formula V
~<~fOCH2CH~nOCNH~R2NH~pH V
Rm 26 wherein R is an <~lkyl group containing at least 40 carbon 27 atoms; R1 is hyd~:ogen or alkyl of 1 to 3 carbon atoms; R2 28 is alkylene of f~:om 2 to about 6 carbon atoms; m is an 29 integer from 1 to 2; n is an integer such that the molecular weight of the compound is from about 800 to 31 6,000; and p is an integer from 1 to about 6 and with the 32 proviso that if Rl is 'hydrogen then n is an integer from 1 33 to 25.
Preparation of the Alkylphenyl PoT. ox alkylene) Aminocarbamate The additives employed in this invention can be most conveniently prepared by first reacting the appropriate alkylphenyl poly(oxyalkylene) alcohol with phosgene to produce an alky:lphenyl poly(oxyalkylene) chloroformate.
The chloroformaite is then reacted with the polyamine to produce the desired alkylphenyl poly(oxyalkylene) aminocarbamate.
Preparation of ~~minocarbamates are disclosed in U.S.
Patent Nos. 4,150,648; 4,191,537; 4,197,409; 4,236,020:
4,243,798 4,270,930; 4,274,837; 4,288,612: 4,512,610;
and 4,568,358. In general, the reaction of the poly(oxyalkylen~~) compound and phosgene is usually carried out on ;gin essentially equimolar basis, although excess phosgene can be used to improve the degree of reaction. The :reaction may be carried out at temperatures from -10°C to 100°C., preferably in the range of 0°C to 50°C. The reaction will usually be complete within 1/4 to 5 hours. Times of reaction will usually be in t:he range of from 2 to 4 hours.
A solvent may b~e used in the chloroformylation reaction.
Suitable solvents include benzene, toluene, etc.
The reaction of the resultant chloroformate with the amine may be carried out neat or preferably in solution.
Temperatures of from -10°C to 200°C may be utilized, the desired product may b~e obtained by water and stripping usually be the aid of vacuum, of any residual solvent.
The mol ratio of polyamine to polyether chloroformate will generally be in the range from about 2 to 20 mols of N
;~::a~ a. ,.,'~~'.~' O1 polyamine per mol of c:hloroformate, and more usually 5 to 15 02 mols of polyamin.e per mole of chloroformate. Since suppres-03 lion of polysubstituti.on of the polyamino is usually 04 desired, large molar excesses of the polyamine will be used.
05 Additionally, th.e preferred adduct is the monocarbamate 06 compound, as opposed t:o the bis(carbamate) or disubstituted 07 aminoether.
09 The reaction or reactions may be conducted with or without the presence of a reac:tion solvent. A reaction solvent is 11 generally employed whenever necessary to reduce the vis-12 cosity of the reaction product. These solvents should be 13 stable and inert. to the reactants and reaction product.
14 Depending on the temperature of the reaction, the particular chloroformate used, the mol ratios, as well as the reactant 16 concentrations, the reaction time may vary from less than 1 17 minute to 3 hours.
19 After the reaction has been carried out for a sufficient length of time, the reaction mixture may be subjected to 21 extraction with a hydrocarbonwater or hydrocarbonalcohol-22 water medium to free t:he product from any lowmolecularweight 23 amine salts which havE~ formed and any unreacted diamine.
24 The product may then be isolated by evaporation of the solvent. Further purification may be effected by column 26 chromatography on silica gel.
28 Depending on they particular application of the composition 29 of this invention, the reaction may be carried out in the medium in which it will ultimately find use, e.g., polyether 31 carriers or an oleoph:ilic organic solvent or mixtures 32 thereof and be formed at concentrations which provide a 33 concentrate of a detergent composition. Thus, the final mixture may be in a form to be used directly for blending in fuels.
An alternative process for preparing the alkylphenyl poly-(oxyalkylene) aminocarbamates employed in this invention involves the use of an arylcarbonate intermediate. That is to say, the alkylphenyl poly(oxyalkylene) alcohol is reacted with an aryl chloroformate to form an arylcarbonate which is then reacted with the polyamine to form the aminocarbamate employed in this invention. Particularly useful aryl chloroformates include phenyl chloroformate, p-nitrophenyl chloroformate, 2,4-dinitrophenyl chloroformate, p-chloro-phenyl chloroformate, 2,4-dichlorophenyl chloroformate, and p-trifluoromethylphenyl chloroformate. Use of the aryl carbonate intermediate allows for conversion to amino-carbamates containing close to the theoretical basic nitrogen while employing less excess of polyamine, i.e., molar ratios of generally from 1:1 to about 5:1 of polyamine to the arylcarbonate, and additionally avoids the generation of hydrogen chloride in the reaction forming the aminocarba-mate.
Also included within the scope of this invention are fully formulated lubricating ails containing a dispersant effec-tive amount of an alkylp~henyl poly(oxyalkylene) aminocar-bamate. Contained in th,e fully formulated composition is:
1. an alkenyl succinimide, 2. a Group II metal salt of a dihydrocarbyl dithiophosphoric acid, x, 1341005 ' 3. a neutral or overbased alkali or alkaline earth metal hydrocarbyl sulfonate or mixtures thereof, and 4. a neutral or overbased alkali or alkaline earth metal alky:lated phenate or mixtures thereof.
03 PC1LY ( OX'.~tALKYLENE ) AMINOCARBAMATES
06 1. Field of then Invention 08 Numerous deposit;-form:ing substances are inherent in hydro-09 carbon fuels. ~'hese :substances when used in internal combustion engines tend to form deposits on and around 11 constricted areas of ithe engine contacted by the fuel.
12 Typical areas commonly and sometimes seriously burdened by 13 the formation of: depo:aits include carburetor ports, the 14 throttle body and venituries, engine intake valves, etc.
16 Deposits adversely af:Eect the operation of the vehicle. For 17 example, deposits on ithe carburetor throttle body and ven-18 turies increase the fuel to air ratio of the gas mixture to 19 the combustion c;hambe:r thereby increasing the amount of unburned hydrocarbon and carbon monoxide discharged from the 21 chamber. The high final-air ratio also reduces the gas 22 mileage obtainable from the vehicle.
24 Deposits on the engine intake valves when they get suffi-ciently heavy, on the other hand, restrict the gas mixture 26 flow into the combustion chamber. This restriction, starves 27 the engine of ai.r and fuel and results in a loss of power.
28 Deposits on the valves also increase the probability of 29 valve failure due to lburning and improper valve seating. In addition, these deposits may break off and enter the com-31 bustion chamber possilbly resulting in mechanical damage to 32 the piston, pisi:on rings, engine head, etc.
O1 The formation of these' deposits can be inhibited as well as 02 removed by incorporating an active detergent into the fuel.
03 These detergents. function to cleanse these deposit-prone 04 areas of the harmful deposits, thereby enhancing engine per-05 formance and longevity. There are numerous detergent-type 06 gasoline additives cui:rently available which, to varying 07 degrees, perform theses functions.
09 Two factors comp~licatEa the use of such detergent-type gasoline additives. First, with regard to automobile 11 engines that reqyire t:he use of nonleaded gasolines (to 12 prevent disablement of: catalytic converters used to reduce 13 emissions), it h.as been found difficult to provide gasoline 14 of high enough octane to prevent knocking and the con-comitant damage which it causes. The chief problem lies in 16 the area of the degree of octane requirement increase, 17 herein called "O~RI", which is caused by deposits formed by 18 the commercial gasoline.
The basis of the ORI problem is as follows: each engine, 21 when new, requires a certain minimum octane fuel in order to 22 operate satisfactorily without pinging and/or knocking. As 23 the engine is operated on any gasoline, this minimum octane 24 increases and, in most: cases, if the engine is operated on the same fuel far a prolonged period, will reach an 26 equilibrium. This is apparently caused by an amount of 27 deposits in the combu:ction chamber. Equilibrium is typi-28 cally reached after 5,000 to 15,000 miles of automobile 29 operation.
31 The octane requirement: increase in particular engines used 32 with commercial gasoli.nes will vary at equilibrium from 5 to 33 6 octane units to as high as 12 or 15 units, depending upon _2_ I)1 the gasoline compositions, engine design and type of opera-I)2 tion. The seriousness of the problem is thus apparent. A
I)3 typical autamobi:Le witlh a research octane requirement of 85, I)4 when new, may afl:er a few months of operation require 97 I)5 research octane c)asoline for proper operation, and little I)6 unleaded gasoline' of t'.hat octane is available. The ORI
I)7 problem also exists in some degree with engines operated on I)8 leaded fuels. U.S. Patent Nos. 3,144,311; 3,146,203; and I)9 4,247,301 disclose lead-containing fuel compositions having :LO reduced ORI properties.
:l 1 :L2 The ORI problem :is compounded by the fact that the most :l3 common method fo;r increasing the octane rating of unleaded :l4 gasoline is to increase its aromatic content. This, how-:l5 ever, eventually causes an even greater increase in the :L6 octane requirement. Moreover, some of presently used :l7 nitrogen-containing compounds used as depositcontrol addi-:l8 tives and their mineral oil or polymer carriers may also :l9 significantly contribute to ORI in engines using unleaded :20 fuels.
:21 :22 it is, therefore, particularly desirable to provide deposit :23 control additives which effectively control the deposits in :24 intake systems of engines, without themselves eventually :25 contributing to the problem.
.26 :27 In this regard, hydrocarbyl poly(oxyalkylene) aminocarba-:28 mates are commercially successful fuel additives which :29 control combustion chamber deposits thus minimizing ORI.
31 The second complicating factor relates to the lubricating 32 oil compatibility of the fuel additive. Fuel additives, due 33 to their higher boiling point over gasoline itself, tend to 34 accumulate on surfaces. in the combustion chamber of the O1 engine. This accumulation of the additive eventually finds 02 its way into the lubricating oil in the crankcase of the 03 engine via a "blow-by''' process and/or via cylinder 04 wall/piston ring "wipes down". In some cases, as much as 05 25~-30~ of the nonvolatile fuel components, i.e., including 06 fuel additives, will eventually accumulate in the lubri-07 eating oil. Insofar as the recommended drain interval for 08 some engines may be asp much as 7,500 miles or more, such 09 fuel additives can accumulate during this interval to sub-stantial quantities in the lubricating oil. In the case 11 where the fuel additive is not sufficiently lubricating oil 12 compatible, the accumulation of such an oil-incompatible 13 fuel additive many actually contribute to crankcase deposits, 14 i.e., varnish and sludge, as measured by a Sequence V-D
test.
17 The incompatibility of certain fuel additives in lubricating 18 oils, i.e., oil:; which contain other additives, arises in 19 spite of the fact thai:. some fuel additives are also known to be lubricating c>il dispersants.
22 Several theorie:c exist as to the cause of the lubricating 23 oil incompatibility o:E certain fuel additives. Without 24 being limited to any theory, it is possible that some of these fuel additives when found in the lubricating oil 26 interfere with other additives contained in the lubricating 27 oil and either counterbalance the effectiveness of these 28 additives or actually cause dissolution of one or more of 29 these additives including possibly the fuel additive itself.
In either case, the incompatibility of the fuel additive 31 with other addii:ives in the lubricating oil demonstrates 32 itself in less i~han desirable crankcase deposits as measured 33 by Sequence V-D engine tests.
O1 In another theory, it is possible that the accumulation of 02 the fuel additive into the lubricating oil during the drain 03 interval period surpasses its maximum solubility in the 04 lubricating oil. In this theory, this excess amount of fuel 05 additive is insoluble in the lubricating oil and is what 06 causes increased. cranl~:case deposits.
08 In still another theory, it is possible that the fuel addi-09 tive will decom~~ose in the lubricating oil during engine operation and th.e decomposition products are what cause 11 increased crankcase dEaposits.
13 In any case, lut~ricati.ng oil incompatible fuel additives are 14 less than desirable insofar as their use during engine operation will result in increased deposits in the crank-16 case. This prot~lem can be severe. Accordingly, it would be 17 particularly adv~antage~ous to develop a good deposit control 18 fuel additive which does not contribute to ORI and which 19 additionally possesse:> lubricating oil compatibility.
21 The instant invention is directed to fuel compositions con-22 taining a novel class of alkylphenyl poly(oxyalkylene) 23 aminocarbamates which as a fuel additive controls combustion 24 chamber deposit:, thus minimizing ORI and in lubricating oil have improved compatibility in the lubricating oil composi-26 tion. The novel. addii:ives of this invention are very long 27 chain alkylphen~~l poly(oxyalkylene) aminocarbamates having a 28 molecular weight: of about 800 to 6,000 wherein the alkyl 29 group of said al.kylphf~nyl group contains at least 40 carbon atoms.
32 This invention i.s also directed toward dispersants compat-33 ible in lubricating o:il. In particular, this invention is 34 directed toward dispe:rsant additives possessing improved O1 compatibility in lubricating oil which are alkylphenyl 02 poly(oxyalkylene) aminocarbamates having at least one basic 03 nitrogen and wherein the alkyl group of said alkylphenyl 04 poly(oxyalkylene) aminocarbamate contains at least 40 carbon 05 atoms.
07 The incompatibility of certain dispersant additives in 08 lubricating oil, i.e., oils which contain other additives, 09 is recognized in the art and arises in spite of the fact that certain of these additives are known lubricating oil 11 dispersants.
13 Several theories exist as to the cause of the lubricating 14 oil incompatibility of certain additives. Without being limited to any theory, it is possible that some of these 16 additives interfere with other additives contained in the 17 lubricating oil and either counterbalance the effectiveness 18 of these additives or actually cause dissolution of one or 19 more of these additives, including possibly the dispersant additive itself.
22 In another theory, it is possible that the additive will 23 decompose in the lubricating during engine operation and the 24 decomposition products are what cause increased crankcase deposits.
27 In still another theory, it is also possible that the 28 incompatibility of the additive is related to its oil 29 solubility.
31 Lubricating oil incompatibla additives are less than desir-32 able insofar as their use during engine operation will 33 result in increased crankcase deposits, i.e., varnish and O1 sludge, in the crankcase as measured by Sequence V-D engine 02 tests. This problem can be severe.
04 The instant invention is directed to a novel class of very 05 long chain alkylphenyl poly(oxyalkylene) aminocarbamates 06 which provide improved. compatibility in lubricating oil 07 compositions. The novel additives of this invention are 08 alkylphenyl poly(oxyalkylene) aminocarbamates having a 09 molecular weight of about 800 to 6,000 wherein the alkyl group of said alkylphe~nyl poly(oxyalkylene) aminocarbamate 11 contains at least 40 carbon atoms.
13 2. Prior Art Numerous references disclose C1 to C30 hydrocarbyl poly(oxy-16 alkylene) aminocarbamates as fuel additives. These include 17 the following U.S. Patients Nos.:
19 4,160,648; 4,243,798; 4,521,610; and 4,191,537; X1,270,930; 4,568,358.
21 4,197,409; 4,274,837;
22 4,236,020; 4,288,612;
24 Of particular rerlevanc:e is U.S. Patent No. 4,274,837 which discloses that hydrocarbyl poly(oxyalkylene) aminocarbamates 26 containing certain po:ly(oxyalkylene) chains, i.e., oxypro-27 pylene, when used in :Fuels employed in combination with 28 certain lubricating oils, produce crankcase varnish. This 29 reference further discloses that lubricating oil compatible hydrocarbyl pol5~(oxypropylene) aminocarbamates are improved 31 by employing the poly(oxypropylene) as a copolymer having 1 32 to 5 C9 to C30 oxyalk;ylene units.
_7_ O1 U.S. Patent No. 4,160,648 discloses an intake system deposit 02 control additive for fuels which is a hydrocarbyl poly(oxy-03 alkylene) aminocarbama.te wherein the hydrocarbyl group is 04 from 1 to 30 carbon atoms including alkyl or alkylphenyl 05 groups. Specifically disclosed hydrocarbyl groups include 06 tetrapropenylphenyl, olelyl and a mixture of C16, C18 and 07 C20 alkyl groups. Lil~:ewise, U.S. Patent No. 4,288,612 08 discloses deposit control additives for gasoline engines 09 which are hydrocarbyl poly(oxyalkylene) aminocarbamates wherein the hydrocarbyl group contains from 1 to about 30 11 carbon atoms including alkylphenyl groups wherein the alkyl I2 group is straight or branched chain of from 1 to about 24 13 carbon atoms. tt.S. Patent No. 4,568,358 discloses diesel 14 fuel compositions containing an additive such as a hydro-carbyl poly(oxy~~lkylene) aminocarbamate. This reference 16 discloses hydro<:arbyl groups such as alkyl groups of 1 to 30 17 carbon atoms; aryl groups of 6 to 30 carbon atoms, alkaryl 18 groups of 7 to :30 carbon atoms, etc.
U.S. Patent No. 4,332,595 discloses hydrocarbyl poly(oxy-21 alkylene) polyamines wherein the hydrocarbyl group is a 22 hydrocarbyl radical of 8 to 18 carbon atoms derived from 23 linear primary alcohols.
U.S. Patent Nos. 4,233,168 and 4,329,240 among others 26 disclose lubricating oil compositions containing a 27 dispersant amount of a hydrocarbyl poly(oxyalkylene) 28 aminocarbamate.
While these prior art: references disclose fuel compositions 31 containing C1 to C30 hydrocarbyl poly(oxyalkylene) amino-32 carbamates, nor..e of i:hese references disclose the unique 33 alkylphenyl group of this invention nor do any of these 34 references suggest that use of this unique alkylphenyl group _g_ (!1 would provide improved compatibility in lubricating oil (12 compositions.
OS
06 The instant invention is directed toward a novel class of 07 alkylphenyl poly(oxyalkylene) aminocarbamates which possess !)8 improved compatibility with lubricating oil compositions.
09 In particular, the instant invention is directed toward an :LO alkylphenyl poly(oxyalkylene) aminocarbamate having at least :Ll one basic nitrogen and an average molecular weight of about :l2 800 to 6.000 and wherein the alkyl group of said alkylphenyl :L3 poly(oxyalkylene) aminocarbamate contains at least 40 carbon :L4 atoms and the pol.y(oxy<~lkylene) polymer is derived from C2 :LS to C5 oxyalkylene~ units with the proviso that if the :L6 poly(oxyalkylene;~ polymer is a homopolymer of oxyethylene :L7 then the poly(ox~rethyl~ene) polymer does not contain more :18 than 25 oxyethyle~ne units. The instant invention is based ;19 on the discovery that ruse of the unique alkylphenyl group, .20 i.e., an alkylphe~nyl group wherein the alkyl group contains :21 at least 40 carbon atoms, imparts to the alkylphenyl poly-22 (oxyalkylene) am:lnocar'.bamate improved lubricating oil 23 compatibility.
25 The compounds of this invention are useful dispersants in 26 lubricating oil. Thus, in its composition aspect, the 27 instant invention is directed toward a lubricating oil 28 composition comprising an oil of lubricating viscosity and a 29 dispersant effective amount of an alkylphenyl poly(oxy-30 alkylene) aminoc.~rbamate of this invention.
32 The instant invention is also directed toward a fuel compo-33 sition containing a novel class of alkylphenyl poly-3q (oxyalkylene) aminocarbamates which as a fuel additive _g_ controls combustion c;hamber deposits thus minimizing ORI
and in lubricating oi.I provide improved compatibility with the lubricating oil composition. In particular, the instant invention is directed toward a fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from about 30 to about 5,000 parts per million of a fuel soluble alkylphenyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen and an average molecular weight of about 800 to 6,000 and wherein the alkyl group of said alkylphenyl poly(oxyalkylene) ami.nocarbamate contains at least 40 carbon atoms and the poly(oxyalkylene) polymer is derived from CZ to C5 ox:yalky7_ene units with the proviso that if the poly(oxyalkylene) polymer is a homopolymer of oxyethylene then the poly(oxyethylene) polymer does not contain more than 25 oxyethylene units. The instant invention is based on the discovery that use of the unique alkylphenyl group, i.e., an alkylphenyl group wherein the alkyl group contains at least 40 carbon atoms, imparts to the: alkylphenyl poly(oxyalkylene) aminocarbamate improved lubricating oil compatibility without contributing to ORI.
According to an aspeca of the present invention, an alkylphenyl poly(oxya.lkylene) aminocarbamate having at least one basic nitrogen and an average molecular weight of about 800 to 6,000 and wherein the alkyl group of said alkylphenyl poly(oxya.lkylene) aminocarbamate contains from 40 to 200 carbon. atoms and the poly(oxyalkylene) polymer is derived from C2 to C5 oxyalkylene units with the proviso that if the poly(oxyalkylene) polymer is a homopolymer of oxyeth.ylene then the poly(oxyethylene) polymer does not contain more than 25 oxyethylene units.
~B
According to a furthear aspect of the present invention, a compound of Formula V
CH2CH;nOC-NHER2NH~QH
R,~
V
wherein R is am alkyl. group having from 40 to 200 carbon atoms; R~ is hydrogen or alkyl of from 1 to 3 carbon atoms; R2 is al:kylene of from 2 to 6 carbon atoms; m is an integer from 1 to 2; n is an integer such that the molecular weight of t:he compound is from about 800 to 6,000; and p is an integer from 1 to 6 and with the proviso that if R~ is hydrogen then n is an integer from 1 to 25.
According to another aspect of the present invention, a lubricating oil composition comprising an oil of lubricating viscosity and a dispersant effective amount of an alkylphenyl pol.y(oxyalkylene) amino carbamate having at least one basic nitrogen and an average molecular weight of about 800 to 6,000 and wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 40 to 200 carbon atoms and the poly(oxyalkylene) polymer is derived from C2 to C5 (oxyalkylene) units with the proviso that if the poly(oxyalkylene) polymer is a homopolymer of (oxyethylene) then tree poly(oxyethylene) polymer does not containing more than 25 (oxyethylene) units.
According to another aspect of the present invention, a fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from about 30 to about 5,000 parts per million of a fuel soluble alkylphenyl poly(oxyalkylene) ami.nocarbamate having at least one basic nitrogen and an average molecular weight of about loa fB
800 to 6,000 and wherein the alkyl group of said alkyphenyl poly(oxyalkylene) aminocarbamate contains from 40 to 200 carbon atoms and the poly(oxyalkylene) polymer is derived from C2 to C5 oxyalkylene units with the proviso that if the p~oly(oxyalkylene) polymer is a homopolymer of oxyeth.ylene then the poly(oxyethylene) polymer does not contain more than 25 oxyethylene units.
DETAILED DESCRIPTION OF THE INVENTION
The alkylphenyl poly(oxyalkylene) aminocarbamates of the present invention consist of an amino moiety and an alkylphenyl pol;y(oxyalkylene) polymer bonded through a carbamate linkage, i.e., -OC(O)N<. The specific alkylphenyl group employed in the instant invention in the alkylphenyl poly(oxyalkylene) polymer is critical to achieving improved lubricating oil compatibility for the alkylphenyl pol:y(oxyalkylene) aminocarbamates. In particular, it lhas been found that employing the alkylphenyl group of this invention wherein the alkyl group contains .at least 40 carbon atoms 10b O1 results in an alkylphenyl poly(oxyalkylene) aminocarbamate 02 which has improved lubricating oil compatibility.
04 The Preferred Alkylphenyl Group 06 The preferred alkylphenyl group of the alkylphenyl 07 poly(oxyalkylene) aminocarbamate employed in this invention 08 is derived from the corresponding alkylphenol of Formula I
09 below:
m 16 wherein R is an alkyl group of at least 40 carbon atoms and 17 m is an integer from 1 to 2.
19 Preferably, m i;~ one.
21 Preferably R is an alkyl group of from 50 to 200 carbon 22 atoms. More preferably, R is an alkyl group of from 60 to 23 100 carbon atom: .
When m is one, l:he alkylphenyl is a monoalkylphenyl; whereas 26 when m is two, i:he alkylphenyl is a dialkylphenyl.
2g The alkylphenol:a of Formula I above are prepared by reacting 2g the appropriate olefin or olefin mixture with phenol in the presence of an ~~lkylating catalyst at a temperature of from 31 about 60°C to 2i)0°C, and preferably 125°C to 180°C either 32 neat or in an e~;sentially inert solvent at atmospheric 33 pressure: Preferred alkylating catalysts are a sulfonic 34 acid catalyst such as Amberlyst 1~ available from Rohm and O1 Haas, Philadelphia, Pennsylvania, or boron trifluoride (or 02 an etherate of boron t:rifluoride). Molar ratios of reac-03 tarts can be employed. when molar ratios are employed, the '04 reaction yields a mixture of dialkylphenol, monoalkylphenol '05 and unreacted phenol. As noted above, dialkylphenol and '06 monoalkylphenol can be used to prepare the additives used in the compositions of this invention whereas the unreacted '08 phenol is preferably removed from the post reaction mixture X09 via conventional techniques. Alternatively, molar excess of :10 phenol can be employed, i.e., 2 to 2.5 equivalents of phenol :11 for each equivalent of: olefin with unreacted phenol :12 recycled. The latter process maximizes monoalkylphenol.
:13 Examples of inert solvents include benzene, toluene, chloro-:14 benzene and 250 thinner which is a mixture of aromatics, :15 paraffins and na.phthenes.
:l6 :17 Particularly preferred alkylphenols employed in this :18 invention are monoalkylphenols represented by Formula II
:19 below:
a1 OH
:Z 2 a3 II
a4 a5 :Z 6 R
wherein R is as defined above.
a8 'Z9 A particularly preferred class of olefins for use in preparing alkyli~henols useful in this invention are 31 polyolefin polymers. Polyolefin polymers are polymers 32 comprising a major amount of C3 to C5 monoolefin, e.g., :33 ethylene, propy:Lene, butylene, isobutylene and pentene.
.34 The polymers can be homopolymers such as polyisobutylene as well as copolymers of two or more such olefins such as copolymers of: ethylene and propylene, butylene, and isobutylene, etc. Other copolymers include those in which a minor amount of the copolymer monomers, e.g., 1 to 20 mole percent is a C4 to C8 nonconjugated diolefin, e.g., a copolymer of isobutylene and butadiene or a copolymer of ethylene, propylene and 1,4-hexadiene, etc.
The polyolefin polymer usually contains at least 40 carbon atoms, although preferably 50 to 200 carbon atoms and more preferably 60 to 100 carbon atoms.
A particularly preferred class of olefin polymers com-prises the polybutenes, which are prepared by polymer-ization of one or more of 1-butene, 2-butene and isobutene. Especially desirable are polybutenes con-taining a substantial proportion of units derived from isobutene. The polybutene may contain minor amounts of butadiene which may or may not be incorporated in the polymer. Most often the isobutene units constitute 80%, preferably at least 90%, of the units in the polymer.
These polybutenes are readily available commercial mate-rials well known to those skilled in the art. Disclosures thereof will be found, for example, in U.S. Patents Nos. 3,215,707; 3,231,587; 3,515,669; and 3,579,450, as well as U.S. Patent No. 3,912,764.
In addition to the reaction of a polyolefin with phenol, many other alkylating hydrocarbons may likewise be used with phenol to produce alkylphenol. Other suitable alkyl-ating hydrocarbons include cyclic, linear, branched and internal or alpha olefins having molecular weights of at O1 least about 560. For example, alpha olefins obtained from 02 the ethylene growth process gives even number carbon ole-03 fins. Another source of olefins is by the dimerization of 04 alpha olefins over an appropriate catalyst such as the 05 well-known Ziegler catalyst. Internal olefins are easily 06 obtained by the isomerization of alpha olefins over a 07 suitable catalyst such as silica.
09 Preferred Poly(oxyalkylene) Component 11 The alkylphenyl poly(oxyalkylene) polymers which are 12 utilized in preparing the carbamates of the present inven-13 tion are monohyd~roxy compounds, i.e., alcohols, often 14 termed alkylpher,~yl "capped" poly(oxyalkylene) glycols and are to be distir.~guishe~d from the poly(oxyalkylene) glycols 16 (diols), which acre noi: alkylphenyl terminated, i.e., not 17 capped. The alk.ylphenyl poly(oxyalkylene) alcohols are 18 produced by the addition of lower alkylene oxides, such as 19 ethylene oxide, propylene oxide, the butylene oxides, or the pentylene~ oxidE~s to the alkylphenol of Formula I, 21 i.e., I , m 29 under polymerization conditions, wherein R and m are as defined above. Preferred poly(oxyalkylene) polymers are 31 those derived from C3 to C4 oxyalkylene units; more prefer-32 ably C3 oxyprop;~lene 'units. Methods of production and 33 properties of these polymers are disclosed in U.S. Patent 34 Nos. 2,841,479 and 2,782,240 and Kirk-Othmer's "Encyclopedia O1 of Chemical Technology", Volume 19, p. 507. In the polymer-02 ization reaction, a single type of alkylene oxide may be 03 employed, e.g., propylene oxide, in which case the product 04 is a homopolymer, e.g., a poly(oxypropylene) propanol.
05 However, copolymers are equally satisfactory and random 06 copolymers are readily prepared by contacting the hydroxyl-07 -containing compound with a mixture of alkylene oxides, such OS as a mixture of propylene and butylene oxides. Block 09 copolymers of oxyalkyl.ene units also provide satisfactory poly(oxyalkylene) polymers for the practice of the present 11 invention.
13 Homopolymers of poly(oxyethylene) polymers are much more 14 hydrophilic than homopolymers of C3-C5 poly(oxyalkylene) polymers. Accordingly, when homopolymers of poly(oxy-16 ethylene) polymers area employed, the amount of poly(oxy-17 ethylene) must be limited so as to ensure fuel 18 dispersency/detergency and lubricating oil compatibility of 19 the final carbam.ate. In general, this is accomplished by limiting the poly(oxyethylene) polymer to about 25 oxy-21 ethylene units or les:~; although preferably about 10 oxy-22 ethylene units or les:>~ and most preferably about 5 23 oxyethylene units or less.
Likewise, copolymers containing a mixture of oxyethylene 26 units and C3-C5 oxyal~:ylene units are formulated to ensure 27 that the copolymer possesses fuel solubility and lubricating 28 oil compatibility.
In general, the poly(oxyalkylene) polymers are mixtures of 31 compounds that differ in polymer chain length. However, 32 their properties; closely approximate those of the polymer 33 represented by t:he average composition and molecular weight.
O1 In general, the very long chain alkylphenyl terminating 02 group on the alkylphe;nyl poly(oxyalkylene) aminocarbamates 03 of this invention allow for use of less oxyalkylene units in 04 the poly(oxyalkylene) polymer to ensure fuel dispersancy/-05 detergency solubility and lubricating oil compatibility than 06 are necessary in prior art carbamate fuel additives. Accor-07 dingly, while longer poly(oxyalkylene) polymers are func-08 tional in this i.nvent:ion, such longer polymers are not 09 necessary. Therefore, each poly(oxyalkylene) polymer utilized in thi:~ invention contains at least 1 oxyalkylene 11 unit, preferably from 1 to about 100 oxyalkylene units, more 12 preferably from about 1 to about 25 oxyalkylene units, even 13 more preferably from about 1 to about 10 oxyalkylene units, 14 and most preferably about 5 oxyalkylene units or less. It is understood that if the poly(oxyalkylene) polymer is a 16 homopolymer of poly(oxyethylene), the polymer length is 17 governed by the constraints discussed above.
19 An alternative method for preparing alkylphenyl poly(oxy-alkylene) polymers ha~~ing 1, 2 or 3 oxyalkylene units 21 involves employing a compound of Formula III below:
24 C;1(CH2CH0)qH III
26 wherein q is an integer from 1 to 3 and R1 is hydrogen or 27 a C1 to C3 alkyl group. When employing the compound of 28 Formula III, the phenoxide of the alkylphenol, I, is first 29 prepared and then reacted with the compound of Formula III
to yield the desired a~lkylphenol poly(oxyalkylene) polymer 31 having from 1 to 3 oxyalkylene units. Compounds of 32 Formula III are either' commercially available or can be 33 prepared by art recognized methods.
O1 Preferred Amine Component 03 The amine moiety of th,e alkylphenyl poly(oxyalkylene) 04 aminocarbamate employed in this invention is preferably 05 derived from a polyamine having from 2 to about 12 amine 06 nitrogen atoms and from 2 to about 40 carbon atoms. The 07 polyamine is preferably reacted with an alkylphenyl poly-08 (oxyalkylene) chlorofcrrmate to produce the alkylphenyl 09 poly(oxyalkylene) aminocarbamate additives finding use within the scope of the present invention. The chloro-11 formate is itself derived from alkylphenyl poly(oxy-12 alkylene) alcohol by reaction with phosgene. The 13 polyamine, encom~.passing diamines, provides the product 14 alkylphenyl poly(oxya7.kylene) aminocarbamate with, on average, at least about one basic nitrogen atom per 16 carbamate molecuale, i,.e., a nitrogen atom titratable by a 1~ strong acid. The polyamine preferably has a carbon-to-18 nitrogen ratio of frorn about 1:1 to about 10:1.
The polyamine may be substituted with substituents 21 selected from (A) hydrogen, (B) hydrocarbyl groups of from 22 1 to about 10 ce~rbon atoms, (C) acyl groups of from 2 to 23 about 10 carbon atoms, and (D) monoketo, monohydroxy, 24 mononitro, monoc:yano, lower alkyl and lower alkoxy derivatives of I:B) and (C). "Lower", as used in terms 26 like lower alky7~ or lower alkoxy, means a group containing 27 from 1 to about 6 carbon atoms. At least one of the 28 substituents on one of the basic nitrogen atoms of the 29 polyamine is hydrogen, e.g., at least one of the basic nitrogen atoms of the polyamine is a primary or secondary 31 amino nitrogen ~~tom.
33 Hydrocarbyl, as used in describing all the components of 34 this invention, denotes an organic radical composed of '341005 O1 carbon and hydrogen which may be aliphatic, alicyclic, 02 aromatic or combinations thereof, e.g., aralkyl. Prefer-03 ably, the hydrocarbyl group will be relatively free of 04 aliphatic unsaturation, i.e., ethylene and acetylenic, 05 particularly acetylenic unsaturation. The substituted 06 polyamines of the present invention are generally, but not 07 necessarily, N-substituted polyamines. Exemplary hydro-08 carbyl groups and substituted hydrocarbyl groups include 09 alkyls such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, etc., alkenyls such as propenyl, 11 isobutenyl, hexe:nyl, octenyl, etc., hydroxyalkyls, such as 12 2-hydroxyethyl, 3-hydroxypropyl, hydroxyisopropyl, 13 4-hydroxybutyl, ~etc., ketoalkyls, such as 2-ketopropyl, 14 6-ketooctyl, etc., alkoxy and lower alkenoxy alkyls, such as ethoxyethyl, ~ethoxypropyl, propoxyethyl, propoxypropyl, 16 2-(2-ethoxyethox:~)ethyl, 2-(2-(2-ethoxyethoxy)ethoxy)-17 ethyl, 3,6,9,12-tetraoxatetradecyl, 2-(2-ethoxyethoxy) 18 hexyl, etc. The acyl groups of the aforementioned (C) 19 substituents are such as propionyl, acetyl, etc. The more preferred substi~tuents are hydrogen, Cl-C4 alkyls and 21 Cl-C4 hydroxyalk~~ls.
23 In a substituted polya:mine the substituents are found at 24 any atom capable of receiving them. The substituted atoms, e.g., substituted nitrogen atoms, are generally 26 geometrically inE~quivalent, and consequently the sub-27 stituted amines ~:inding use in the present invention can 28 be mixtures of mono- a:nd poly-substituted polyamines 29 with substituent groups situated at equivalent and/or inequivalent atoms.
32 The more preferred pol~yamine finding use within the scope 33 of the present invention is a polyalkylene polyamine, 34 including alkylene diamine, and including substituted ~ 34~ 005 O1 polyamines, e.g., alkyl and hydroxyalkylsubstituted poly-02 alkylene polyamine. Preferably, the alkylene group con-03 tains from 2 to 6 carbon atoms, there being preferably 04 from 2 to 3 carbon atoms between the nitrogen atoms. Such 05 groups are exemplified by ethylene, 1,2-propylene, 2,2-di-06 methylpropylene trimethylene, 1,3,2-hydroxypropylene, etc.
07 Examples of such polya.mines include ethylene diamine, 08 diethylene triamine, dli(trimethylene)triamine, dipropylene 09 triamine, triethylene tetramine, tripropylene tetramine, tetraethylene pentamir~e, and pentaethylene hexamine. Such 11 amines encompass isomers such as branchedchain polyamines 12 and the previously mentioned substituted polyamines, 13 including hydroxy- and hydrocarbylsubstituted polyamines.
14 Among the polyalkylene~ polyamines, those containing 2-12 amine nitrogen atoms and 2-24 carbon atoms are especially 16 preferred, e.g., ethy7Lene diamine, propylene diamine, 17 butylene diaminE~, pentylene diamine, hexylene diamine, 18 diethylene triamine, dipropylene triamine, and the C2-C3 19 alkylene polyami.nes are most preferred, in particular, the lower polyalkylene po:lyamines, e.g., ethylene diamine, 21 diethylene triamine, propylene diamine, dipropylene 22 triamine, etc.
24 The amine component of the alkylphenyl poly(oxyalkylene) aminocarbamate also may be derived from heterocyclic 26 polyamines, hetE~rocyclic substituted amines and substi-27 tuted heterocyc:lic compounds, wherein the heterocycle 28 comprises one or more 5-6 membered rings containing oxygen 29 and/or nitrogen. Such heterocycles may be saturated or unsaturated and substituted with groups selected from the 31 aforementioned (A), (B), (C) and (D). The heterocycles 32 are exemplified by piperazines, such as 2-methylpiper-33 azine, N-(2-hydroxyethyl)piperazine, 1,2-bis-(N-pipera-34 zinyl)ethane, and N,N~bis(N-piperazinyl)piperazine, 34? 005 2-methylimidazoline, 3-aminopiperidine, 2-aminopyridine, 2-(3-aminoethyl)3-~pyrro:line, 3-aminopyrrolidine, N-(3-aminopropyl)morpho:Line, etc. Among the heterocyclic compounds, the piperazines are preferred.
Another class of :~uitab:le polyamines are diaminoethers represented by Formula :IV
H2N-X.1 f 0X2 ~ rNH2 I V
wherein X1 and X2 are independently alkylene from 2 to about 5 carbon atoms and r is an integer from 1 to about 10. Diamines of Formula IV are disclosed in U.S. Patent No. 4,521,610.
Typical polyamine:; that can be used to form the compounds of this invention by reaction with a poly(oxyalkylene)-chloroformate incJ.ude the following: ethylene diamine, 1,2-propylene diamine, :1,3-propylene diamine, diethylene triamine, triethyl.ene tetramine, hexamethylene diamine, tetraethylene pent:amine, dimethylaminopropylene diamine, N-(beta-aminoethyl.)piperazine, N-(beta-aminoethyl)piper-idine, 3-amino-N-eathylpiperidine, N-(beta-aminoethyl)-morpholine, N,N'-di(bet;a-aminoethyl)piperazine, N,N'-di(beta-aminoethylimidazolidone-2; N-(beta-cyano-ethyl)ethane-1,2-diamin~e, 1-amino-3,6,9-triazaoctadecane, 1-amino-3,6-diaza--9-oxadecane, N-(beta-aminoethyl)-di-ethanolamine, N'-acetyl-N'-methyl-N-(beta-aminoethyl)-ethane-1,2-diaminE~, N-acetonyl-1,2-propanediamine, N-(beta-nitroethy:L)-1,3-propane diamine, 1,3-dimethyl-5-(beta-aminoethyl)hexahydrotriazine, N-(beta-amino-ethyl)hexahydrotr:iazine, 5-(beta-aminoethyl)-1,3,5-d '' , ~ 3'~~ 005 O1 dioxazine, 2-(2-aminoe~thylamino)-ethanol, 2[2-(2-amino-02 ethylamino)ethylamino]-ethanol.
04 The amine component of: the alkylphenyl poly(oxyalkylene) 05 aminocarbamate may al:~o be derived from an amine-contain-06 ing compound which is capable of reacting with an alkyl-07 phenyl poly(oxyalkylene) alcohol to produce an alkylphenyl 08 poly(oxyalkylene) aminocarbamate having at least one basic 09 nitrogen atom. For ea:ample, a substituted aminoiso-cyanate, such as (R3)~,NCH2CH2NC0, wherein R3 is, for 11 example, a hydrocarby7L group, reacts with the alcohol to 12 produce the amir.~ocarbamate additive finding use within the 13 scope of the prersent :invention. Typical aminoisocyanates 14 that may be used to form the fuel additive compounds of this invention t>y reaction with a hydrocarbylpoly(oxy-16 alkylene) alcohol inc:Lude the following: N,N-(dimethyl)-17 aminoisocyanatoe~thane, generally, N,N-(dihydrocarbyl)-18 aminoisocyanatoalkane, more generally, N-(perhydrocarbyl)-19 isocyanatopolyal_kylen~e polyamine, N,N-(dimethyl)aminoiso-cyanatobenzene, etc.
22 In many instancE~s the amine used as a reactant in the 23 production of the carbamate of the present invention is 24 not a single compound but a mixture in which one or several compounds, predominate with the average composi-26 tion indicated. For example, tetraethylene pentamine 27 prepared by the polymerization of aziridine or the 28 reaction of dichloroethylene and ammonia will have both 29 lower and higher amine members, e.g., triethylene tetramine, substituted piperazines and pentaethylene 31 hexamine, but the composition will be mainly tetraethylene 32 pentamine and the empirical formula of the total amine 33 composition will closely approximate that of tetraethylene 34 pentamine. Finally, in preparing the compounds of this 1341 00~
Ol invention, where the various nitrogen atoms of the poly-02 amine are not geometrically equivalent, several substitu-03 tional isomers are possible and are encompassed within the 04 final product. Methods of preparation of amines, iso-05 cyanates and their reactions are detailed in Sidgewick's 06 "The Organic Chemistry of Nitrogen", Clarendon Press, 07 Oxford, 1966; Hollers' "Chemistry of Organic Compounds", 08 Saunders, Philadelphia, 2nd Ed. 1957; and Kirk-Othmer's 09 "Encyclopedia of Chemical Technology", 2nd Ed., especially Volume 2, pp. 99-116.
12 Preferred Alkylphenyl 13 Pol (y oxyalkylene) Aminocarbamate Having described the preferred alkylphenyl poly(oxy-16 alkylene) component and the preferred polyamine component, 17 the preferred alkylphenyl poly(oxyalkylene) aminocarbamate 18 additive of the present invention is obtained by linking 19 these components together through a carbamate linkage i.e., 24 -0-C-N<
26 wherein the ether oxygen may be regarded as the terminal 27 hydroxyl oxygen of the alkylphenyl poly(oxyalkylene) 28 alcohol component, and the carbonyl group -C(0)- is 29 preferably provided by the coupling agent, e.g., phosgene.
31 The alkylphenyl poly(oxyalkylene) aminocarbamate employed 32 in the present invention has at least one basic nitrogen 33 atom per molecule. A "basic nitrogen atom" is one that is 34 titratable by a strong acid, e.g., a primary, secondary, O1 or tertiary amino nitrogen, as distinguished from, for 02 example, an amido nitragen, i.e., -CN< , 09 which is not so titratable. Preferably, the basic nitrogen is in a primary or secondary amino group.
12 The preferred al:kylphenyl poly(oxyalkylene) aminocarbamate 13 has an average m~~lecular weight of from about 800 to 14 6,000; preferably an average molecular weight of from 800 to 3,000; and most preferably an average molecular weight 16 of from 1,000 to 2,500.
18 A preferred clas;~ of alkylphenyl poly(oxyalkylene) amino-19 carbamate can be described by the following Formula V
~<~fOCH2CH~nOCNH~R2NH~pH V
Rm 26 wherein R is an <~lkyl group containing at least 40 carbon 27 atoms; R1 is hyd~:ogen or alkyl of 1 to 3 carbon atoms; R2 28 is alkylene of f~:om 2 to about 6 carbon atoms; m is an 29 integer from 1 to 2; n is an integer such that the molecular weight of the compound is from about 800 to 31 6,000; and p is an integer from 1 to about 6 and with the 32 proviso that if Rl is 'hydrogen then n is an integer from 1 33 to 25.
Preparation of the Alkylphenyl PoT. ox alkylene) Aminocarbamate The additives employed in this invention can be most conveniently prepared by first reacting the appropriate alkylphenyl poly(oxyalkylene) alcohol with phosgene to produce an alky:lphenyl poly(oxyalkylene) chloroformate.
The chloroformaite is then reacted with the polyamine to produce the desired alkylphenyl poly(oxyalkylene) aminocarbamate.
Preparation of ~~minocarbamates are disclosed in U.S.
Patent Nos. 4,150,648; 4,191,537; 4,197,409; 4,236,020:
4,243,798 4,270,930; 4,274,837; 4,288,612: 4,512,610;
and 4,568,358. In general, the reaction of the poly(oxyalkylen~~) compound and phosgene is usually carried out on ;gin essentially equimolar basis, although excess phosgene can be used to improve the degree of reaction. The :reaction may be carried out at temperatures from -10°C to 100°C., preferably in the range of 0°C to 50°C. The reaction will usually be complete within 1/4 to 5 hours. Times of reaction will usually be in t:he range of from 2 to 4 hours.
A solvent may b~e used in the chloroformylation reaction.
Suitable solvents include benzene, toluene, etc.
The reaction of the resultant chloroformate with the amine may be carried out neat or preferably in solution.
Temperatures of from -10°C to 200°C may be utilized, the desired product may b~e obtained by water and stripping usually be the aid of vacuum, of any residual solvent.
The mol ratio of polyamine to polyether chloroformate will generally be in the range from about 2 to 20 mols of N
;~::a~ a. ,.,'~~'.~' O1 polyamine per mol of c:hloroformate, and more usually 5 to 15 02 mols of polyamin.e per mole of chloroformate. Since suppres-03 lion of polysubstituti.on of the polyamino is usually 04 desired, large molar excesses of the polyamine will be used.
05 Additionally, th.e preferred adduct is the monocarbamate 06 compound, as opposed t:o the bis(carbamate) or disubstituted 07 aminoether.
09 The reaction or reactions may be conducted with or without the presence of a reac:tion solvent. A reaction solvent is 11 generally employed whenever necessary to reduce the vis-12 cosity of the reaction product. These solvents should be 13 stable and inert. to the reactants and reaction product.
14 Depending on the temperature of the reaction, the particular chloroformate used, the mol ratios, as well as the reactant 16 concentrations, the reaction time may vary from less than 1 17 minute to 3 hours.
19 After the reaction has been carried out for a sufficient length of time, the reaction mixture may be subjected to 21 extraction with a hydrocarbonwater or hydrocarbonalcohol-22 water medium to free t:he product from any lowmolecularweight 23 amine salts which havE~ formed and any unreacted diamine.
24 The product may then be isolated by evaporation of the solvent. Further purification may be effected by column 26 chromatography on silica gel.
28 Depending on they particular application of the composition 29 of this invention, the reaction may be carried out in the medium in which it will ultimately find use, e.g., polyether 31 carriers or an oleoph:ilic organic solvent or mixtures 32 thereof and be formed at concentrations which provide a 33 concentrate of a detergent composition. Thus, the final mixture may be in a form to be used directly for blending in fuels.
An alternative process for preparing the alkylphenyl poly-(oxyalkylene) aminocarbamates employed in this invention involves the use of an arylcarbonate intermediate. That is to say, the alkylphenyl poly(oxyalkylene) alcohol is reacted with an aryl chloroformate to form an arylcarbonate which is then reacted with the polyamine to form the aminocarbamate employed in this invention. Particularly useful aryl chloroformates include phenyl chloroformate, p-nitrophenyl chloroformate, 2,4-dinitrophenyl chloroformate, p-chloro-phenyl chloroformate, 2,4-dichlorophenyl chloroformate, and p-trifluoromethylphenyl chloroformate. Use of the aryl carbonate intermediate allows for conversion to amino-carbamates containing close to the theoretical basic nitrogen while employing less excess of polyamine, i.e., molar ratios of generally from 1:1 to about 5:1 of polyamine to the arylcarbonate, and additionally avoids the generation of hydrogen chloride in the reaction forming the aminocarba-mate.
Also included within the scope of this invention are fully formulated lubricating ails containing a dispersant effec-tive amount of an alkylp~henyl poly(oxyalkylene) aminocar-bamate. Contained in th,e fully formulated composition is:
1. an alkenyl succinimide, 2. a Group II metal salt of a dihydrocarbyl dithiophosphoric acid, x, 1341005 ' 3. a neutral or overbased alkali or alkaline earth metal hydrocarbyl sulfonate or mixtures thereof, and 4. a neutral or overbased alkali or alkaline earth metal alky:lated phenate or mixtures thereof.
5. A viscosity index (VI) improver.
The alkenyl succinimide is present to act as a dispersant and prevent formation of deposits formed during operation of the engine. The alkenyl succinimides are wellknown in the art. The a:Lkenyl succinimides are the reaction product of a po:Lyolefin polymersubstituted succinic anhydride with ~~n amine, preferably a polyalkylene polyamine. The polyolefin polymersubstituted succinic anhydrides are obtained by reaction of a polyolefin polymer or a derivative thereof with malefic anhydride.
The succinic anlZydride thus obtained is reacted with the amine compound. The preparation of the alkenyl succinimides ha;s been described many times in the art.
See, for example, U.S. Patents Nos. 3,390,082; 3,219,666;
and 3,172,892. Reduction of the alkenyl substituted succinic anhydride yields the corresponding alkyl derivative. The alkyl succinimides are intended to be included within the scope of the term "alkenyl succinimide". .~ product comprising predominantly mono or bissuccinimide can be prepared by controlling the molar ratios of the reactants. Thus, for example, if one mole of amine is reacted with one mole of the alkenyl or alkyl substituted succinic anhydride, a predominantly monosuccinimide product will be prepared. If two moles of the succinic anhydride are reacted per mole of polyamine, a bissuccinimide will be prepared.
x T, O1 Particularly good results are obtained with the lubricating 02 oil compositions of this invention when the alkenyl succi-03 nimide is a polyisobutenesubstituted succinic anhydride of a 04 polyalkylene polyamine.
06 The polyisobutene from which the polyisobutenesubstituted 07 succinic anhydride is obtained by polymerizing isobutene can 08 vary widely in its compositions. The average number of 09 carbon atoms can range from 30 or less to 250 or more, with a resulting number average molecular weight of about 400 or 11 less to 3,000 or more. Preferably, the average number of 12 carbon atoms per polyisobutene molecule will range from 13 about 50 to about 100 with the polyisobutenes having a num-14 ber average molecular weight of about 600 to about 1,500.
More preferably, the average number of carbon atoms per 16 polyisobutene molecule ranges from about 60 to about 90, and 17 the number average molecular weight ranges from about 800 to 18 1,300. The polyisobutene is reacted with malefic anhydride 19 according to wellknown procedures to yield the polyiso-butene-substituted succinic anhydride.
22 In preparing the alkenyl succinimide, the substituted 23 succinic anhydride is reacted with a polyalkylene polyamine 24 to yield the corresponding succinimide. Each alkylene radical of the polyalkylene polyamine usually has from 2 up 26 to about 8 carbon atoms. The number of alkylene radicals 27 can range up to about 8. The alkylene radical is exem-28 plified by ethylene, propylene, butylene, trimethylene, 29 tetramethylene, pentamethylene, hexamethylene, octa-methylene, etc. The number of amino groups generally, but 31 not necessarily, is one greater than the number of alkylene 32 radicals present in the amine, i.e., if a polyalkylene 33 polyamine contains 3 alkylene radicals, it will usually 34 contain 4 amino radicals. The number of amino radicals can O1 range up to about 9. Preferably, the alkylene radical 02 contains from about 2 to about 4 carbon atoms and all amine 03 groups are primary or secondary. in this case, the number 04 of amine groups exceeds the number of alkylene groups by 1.
05 Preferably the holyal)cylene polyamine contains from 3 to 5 06 amine groups. ~~pecif:ic examples of the polyalkylene poly-07 amines include e~thylenediamine, diethylenetriamine, tri-08 ethylenetetramine, propylenediamine, tripropylenetetramine, 09 tetraethylenepentamincs, trimethylenediamine, pentaethylene-hexamine, di(tri.methy:lene)triamine, tri(hexamethylene)tetra-11 mine, etc.
13 Other amines suitable for preparing the alkenyl succinimide 14 useful in this i.nvent:ion include the cyclic amines such as piperazine, morpholine and dipiperazines.
17 Preferably the alkeny:l succinimides used in the compositions 18 of this invention have the following formula 22 Rl-C;H-C
~~N~-Alkylene-N~ H
23 C:H2-C~ ~ n wherein:
27 a. R1 represents an alkenyl group, preferably a substan-28 tially saturated hydrocarbon prepared by polymerizing 29 aliphatic mono-olefins. Preferably R1 is prepared from isobutene ~~nd has an average number of carbon atoms and 31 a number average molecular weight as described above;
33 b, the "alkyl~~ne" radical represents a substantially 34 hydrocarbyl group containing from 2 up to about 8 carbon atoms and preferably containing from about 29 carbon atoms as described hereinabove;
c. A represents a hydrocarbyl group, an amine-substituted hydrocarbyl group, or hydrogen. The hydrocarbyl group and the amine-substituted hydrocarbyl groups are gener-ally the alkyl and amino-substituted alkyl analogs of the alkylene radicals described above. Preferably A
represents hydrogen;
d. n represents an integer of from 1 to about 8, and preferably from about 3-5.
Also included within the term alkenyl succinimide are the modified succinimides which are disclosed in U.S. Patent No. 4,612,132.
The alkenyl succinimide is present in the lubricating oil compositions of the invention in an amount effective to act as a dispersant and prevent the deposit of contaminants formed in the oil during operation of the engine. The amount of alkenyl succinimide can range from about 1 percent to about 20 percent weight of the total lubricating oil composition. Preferably the amount of alkenyl succinimide present in the lubricating oil composition of the invention ranges from about :1 to about 10 percent by weight of the total composition.
The alkali or alka:Line earth metal hydrocarbyl sulfonates may be either petroleum sulfonate, synthetically alkylated aromatic sulfonate;a, or aliphatic sulfonates such as those derived from polyi;sobutylene. One of the more important functions of the s,~lfonates is to act as a detergent and dispersant. These sulfonates are wellknown in the art. The ;° ;
.._ 1341 005 O1 hydrocarbyl group must: have a sufficient number of carbon 02 atoms to render the sulfonate molecule oil soluble. Prefer-03 ably, the hydrocarbyl portion has at least 20 carbon atoms 04 and may be aromatic or aliphatic, but is usually alkylaroma-05 tic. Most preferred i:or use are calcium, magnesium or 06 barium sulfonate~s which are aromatic in character.
08 Certain sulfonat:es area typically prepared by sulfonating a 09 petroleum fraction haring aromatic groups, usually mono- or dialkylbenzene groups,, and then forming the metal salt of 11 the sulfonic acid material. Other feedstocks used for 12 preparing these sulfomates include synthetically alkylated 13 benzenes and aliphatic hydrocarbons prepared by polymerizing 14 a mono- or diolefin, Eor example, a polyisobutenyl group prepared by pol5rmerizing isobutene. The metallic salts are 16 formed directly or by metathesis using well-known 17 procedures.
19 The sulfonates may be neutral or overbased having base num-bers up to abouit 400 or more. Carbon dioxide and calcium 21 hydroxide or oxide are the most commonly used material to 22 produce the ba sic or overbased sulfonates. Mixtures of 23 neutral and overbased sulfonates may be used. The sulfo-24 nates are ordinarily used so as to provide from 0.3% to 10%
by weight of the total composition. Preferably, the neutral 26 sulfonates are present from 0.4% to 5% by weight of the.
27 total composition and the overbased sulfonates are present 28 from 0.3% to 3% by weight of the total composition.
The phenates for use in this invention are those conven-31 tional products which are the alkali or alkaline earth metal 32 salts of alkylated phenols. One of the functions of the 33 phenates is to act as. a detergent and dispersant. Among 34 other things, it prevents the deposition of contaminants ~Dl formed during hi~3h temperature operation of the engine. The ~D2 phenols may be mono- or polyalkylated.
~D 3 ~D4 The alkyl portion of the alkyl phenate is present to lend ~D5 oil solubility t~~ the phenate. The alkyl portion can be ~D6 obtained from naturally occurring or synthetic sources.
~D7 Naturally occurring sources include petroleum hydrocarbons ~D8 such as white oil and wax. Being derived from petroleum, ~D9 the hydrocarbon moiety is a mixture of different hydrocarbyl :10 groups, the specific composition of which depends upon the :ll particular oil stock which was used as a starting material.
:L2 Suitable synthetic sources include various commercially :L3 available alkenes and alkane derivatives which, when reacted :l4 with the phenol, yield an alkylphenol. Suitable radicals :L5 obtained include butyl, hexyl, octyl, decyl, dodecyl, hexa-:L6 decyl,.eicosyl, tricontyl, and the like. Other suitable :l7 synthetic sources of the alkyl radical include olefin poly-:l8 mers such as polypropylene, polybutylene, polyisobutylene :L9 and the like.
:20 :21 The alkyl group can be straight-chained or branch-chained, :22 saturated or unsaturated (if unsaturated, preferably :23 containing not more than 2 and generally not more than 1 :24 site of olefinic unsat.uration). The alkyl radicals will :25 generally contain from 4 to 30 carbon atoms. Generally when :26 the phenol is monoalkylsubstituted, the alkyl radical should :27 contain at least 8 carbon atoms. The phenate may be sul-:28 furized if desired. I:t may be either neutral or overbased :29 and if overbased will have a base number of up to 200 to 300 :30 or more. Mixtures of neutral and overbased phenates may be 31 used.
33 The phenates are ordinarily present in the oil to provide 34 from 0.2% to 27% by weight of the total composition.
O1 Preferably, the neutral phenates are present from 0.2% to 9%
02 by weight of the total composition and the overbased 03 phenates are present from 0.2 to 13% by weight of the total 04 composition. Mast preferably, the overbased phenates are 05 present from 0.2% to 5% by weight of the total composition.
06 Preferred metals are calcium, magnesium, strontium or 07 barium.
09 The sulfurized alkaline earth metal alkyl phenates are pre-ferred. These salts acre obtained by a variety of processes 11 such as treating the neutralization product of an alkaline 12 earth metal base and an alkylphenol with sulfur. Conven-13 iently the sulfur, in elemental form, is added to the 14 neutralization product: and reacted at elevated temperatures to produce the sulfuri.zed alkaline earth metal alkyl 16 phenate.
18 If more alkaline earth metal base were added during the 19 neutralization reaction than was necessary to neutralize the phenol, a basic sulfurized alkaline earth metal alkyl 21 phenate is obtained. See, for example, the process of 22 Walker et al, U.S. Pai:ent No. 2,680,096. Additional 23 basicity can be obtained by adding carbon dioxide to the 24 basic sulfurizecl alkaline earth metal alkyl phenate. The excess alkaline earth metal base can be added subsequent to 26 the sulfurization step but is conveniently added at the same 27 time as the alkaline earth metal base is added to neutralize 28 the phenol.
Carbon dioxide and calcium hydroxide or oxide are the most 31 commonly used material to produce the basic or "overbased"
32 phenates. A process wherein basic sulfurized alkaline earth 33 metal alkylphenates are produced by adding carbon dioxide is 34 shown in Hanneman, U.S. Patent No. 3,178,368.
O1 The Group II metal sa7.ts of dihydrocarbyl dithiophosphoric 02 acids exhibit wear, antioxidant and thermal stability 03 properties. Group II metal salts of phosphorodithioic acids 04 have been described previously. See, for example, U.S.
05 Patent No. 3,390,080, columns 6 and 7, wherein these com-06 pounds and their preparation are described generally. Suit-07 ably, the Group II metal salts of the dihydrocarbyl 08 dithiophosphoric acid:> useful in the lubricating oil compo-09 sition of this invention contain from about 4 to about 12 carbon atoms in each of the hydrocarbyl radicals and may be 11 the same or different and may be aromatic, alkyl or cyclo-12 alkyl. Preferred hydrocarbyl groups are alkyl groups con-13 taining from 4 to 8 carbon atoms and are represented by 14 butyl, isobutyl, sec.butyl, hexyl, isohexyl, octyl, 2-ethylhexyl and the like. The metals suitable for forming 16 these salts include barium, calcium, strontium, zinc and 17 cadmium, of which zinc: is preferred.
19 Preferably, the Group II metal salt of a dihydrocarbyl dithiophosphoric acid has the following formula:
22 R2G~
P
23 R3~./ \S M1 27 wherein:
28 e. R2 and R3 each independently represent hydrocarbyl 29 radicals as described above, and 31 f' M1 represents a Group II metal cation as described 32 above.
34 The dithiophosphoric :.alt is present in the lubricating oil compositions of this invention in an amount effective to inhibit wear and oxidation of the lubricating oil. The amount ranges from about 0.1 to about 4 percent by weight of the total composition, preferably the salt is present in an amount ranging from about: 0.2 to about 2.5 percent by weight of the total lubricating oil composition. The final lubri-cating oil composition will ordinarily contain 0.025 to 0.25% by weight phosphorus and preferably 0.05 to 0.15% by weight.
Viscosity index (VI) improvers are either non-dispersant or dispersant VI impravers. Nondispersant VI improvers are typically hydrocart~yl po7.ymers including copolymers and terpolymers. Typically hydrocarbyl copolymers are copolymers of ethylene and propylene. Such nondispersant VI
improvers are disclosed i.n U.S. Patents Nos. 2,700,633;
2,726,231; 2,792,288; 2,933,480; 3,000,866; 3,063,973; and 3,093,621.
Dispersant VI impro~vers c;an be prepared by functionalizing nondispersant VI im~provens. For example, nondispersant hydrocarbyl copolymer anal terpolymer VI improvers can be functionalized to ~~roduce~ aminated oxidized VI improvers having dispersant ~~ropert:ies and a number average molecular weight of from 1,500 to 20,000. Such functionalized dispersant VI impro~vers are disclosed in U.S. Patents Nos. 3,864,268; 3,769,21E>; 3,326,804 and 3,316,177.
Other dispersant VI improvers include amine-grafted acrylic polymers and copolymers wherein one monomer contains at least one amino group. 7eypical compositions are described in British Patent rlo. 1,488,382; and U.S. Patents AI
Nos. 4,089,794 and 4,025,452.
Nondispersant and dispersant VI improvers are generally employed at from ~~ to 20 percent by weight in the lubricating oil composil~ion.
Lubricai:ing Oil Compositions The alkylphenyl poly(oxyalkylene) aminocarbamates of this invention are useful as dispersant additives when employed in lubricating oils. When employed in this manner, the additive is usually present in from 0.2 to 10 percent by weight to the total composition, preferably at about 0.5 to 8 percent by weight and more preferably at about 1 to 6 percent by weight. The lubricating oil used with the additive compositions oil this invention may be mineral oil or synthetic oils of lubricating viscosity and preferably suitable for use in the crankcase of an internal combustion engine. Crankcases lubricating oils ordinarily have a viscosity of about. 1300 CSt 0°F to 22.7 CSt at 210°F
(99°C).
The lubricating oils may be derived from synthetic or natural sources. Mineral oil for use as the base oil in this invention includes paraffinic, naphthenic and other oils that are ordinaril~t used in lubricating oil composi-tions. Synthetic oils :include both hydrocarbon synthetic oils and synthetic: esters. Useful synthetic hydrocarbon oils include liquid pol~tmers of alpha olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of C6 ito C12 alpha olefins such as 1-decene trimer. Likewise, alkyl benzenes of proper viscosity such as didodecyl benzene, can be used. Useful synthetic esters include the estera of both monocarboxylic acid and xi ~a ;~
O1 polycarboxylic acids as well as monohydroxy alkanols and 02 polyols. Typical examples are didodecyl adipate, 03 pentaerythritol tetracaproate, di-2-ethylhexyl adipate, 04 dilaurylsebacate and the like. Complex esters prepared from 05 mixtures of mono and dicarboxylic acid and mono and 06 dihydroxy alkanols can also be used.
08 Blends of hydrocarbon oils with synthetic oils are also 09 useful. For example, blends of 10 to 25 weight percent hydrogenated 1-decene trimer with 75 to 90 weight percent 11 150 SUS (100°F) mineral oil gives an excellent lubricating 12 oil base.
14 Additive concentrates are also included within the scope of this invention. The concentrates of this invention usually 16 include from about 90 to 50 weight percent of an oil of 17 lubricating visc~~sity and from about 10 to 50 weight percent 18 of the additive of this invention. Typically, the concen-19 trates contain s~.~fficient diluent to make them easy to :20 handle during shipping and storage. Suitable diluents for 21 the concentrates include any inert diluent, preferably an :22 oil of lubricating viscosity, so that the concentrate may be 23 readily mixed with lubricating oils to prepare lubricating :24 oil compositions. Suitable lubricating oils which can be :25 used as diluents typically have viscosities in the range :26 from about 35 to about 500 Saybolt Universal Seconds (SUS) :27 at 100°F (38°C), although an oil of lubricating viscosity :28 may be used.
:29 30 Other additives iahich may be present in the formulation 31 include rust inhibitors, foam inhibitors, corrosion 32 inhibitors, metal deactivators, pour point depressants, 33 antioxidants, and a variety of other well-known additives.
1 341 00~
O1 Fuel Compositions '03 The alkylphenyl poly(oxyalkylene) aminocarbamates of this invention will g~anerally be employed in a hydrocarbon ~D5 distillate fuel. The proper concentration of this additive '06 necessary in ord~sr to achieve the desired detergency and dispersancy varies depending upon the type of fuel employed, the presence of ether detergents, dispersants and other additives, etc. Generally, however, from 30 to 5,000 weight :LO parts per million (ppm), and preferably 100 to 500 ppm and :~1 more preferably 200 to 300 ppm of alkylphenyl poly(oxy-:~2 alkylene) aminoc.arbamate per part of base fuel is needed to :L3 achieve the best results. When other detergents are present, a less amount of alkylphenyl poly(oxypropylene) ~~5 aminocarbamate may be used. For performance as a carburetor :l6 detergent only, lower concentrations, for example 30 to 100 :L7 ppm may be preferred. Higher concentrations, i.e., 2,000 to :l8 5,000 ppm may result in a clean-up effect on combustion :l9 chamber deposits as well as the entire intake system.
a0 al The deposit control additive may also be formulated as a 22 concentrate, using an inert stable oleophilic organic 23 solvent boiling in the range of about 150 to 400°F. Prefer-24 ably, an aliphatic or an aromatic hydrocarbon solvent is 25 used, such as benzene, toluene, xylene or higherboiling :~6 aromatics or aromatic thinners. Aliphatic alcohols of about :~7 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, 28 n-butanol and the like, in combination with hydrocarbon 29 solvents are also suitable for use with the detergent-dis-:30 persant additive. In the concentrate, the amount of the :31 additive will be ordinarily at least 5 percent by weight and :32 generally not e~s:ceed 50 percent by weight, preferably from :33 10 to 30 weight percent.
:34 _3$_ O1 When employing certain of the alkylphenyl poly(oxyalkylene) 02 aminocarbamates of this invention, particularly those having 03 more than 1 basic nitrogen, it can be desirable to addi-04 tionally add a demulsifier to the gasoline or diesel fuel 05 composition. These demulsifiers are generally added at from 06 1 to 15 ppm in the fuel composition. Suitable demulsifiers 07 include for instance L-1562?, a high molecular weight glycol 08 capped phenol available from Petrolite Corp., Tretolite 09 Division, St. Louis, Missouri, and OLOA 2503 available from Chevron Chemical Company, San Francisco, California.
12 In gasoline fuels, other fuel additives may also be included 13 such as anti-knock agents, e.g., methylcyclopentadienyl 14 manganese tricar:bonyl, tetramethyl or tetraethyl lead, tertbutyl methyl peroxide or other dispersants or detergents 16 such as various substituted succinimides, amines, etc. Also 17 included may be .Lead scavengers such as aryl halides, e.g., 18 dichlorobenzene ~~r alkyl halides, e.g., ethylene dibromide.
19 Additionally, antioxidants, metal deactivators and demulsifiers may be present.
22 In diesel fuels, other well-known additives can be employed 23 such as pour point depressants, flow improvers, cetane 24 improvers, etc.
26 The following ex<~mples are offered to specifically illus-27 trate this inven~~ion. These examples and illustrations are 28 not to be construed in any way as limiting the scope of this 29 invention.
~ 34~ 005 02 Example 1 04 Preparation of C65 to C70 Alkylphenyl 05 Poly(oxypropylene) Alcohol 07 To a dried 5-liter, 3-neck flask under a nitrogen atmo-08 sphere was added 1.5 liters of dry toluene and 1125 grams 09 H-1008 (an alkyl;phenol, prepared from polybutene-24, having a hydroxyl number of approximately 34, and a number 11 average of approximately 65-70 carbon atoms in the alkyl 12 portion of the alkylphenol. H-100? also contains approxi-13 mately onethird (1/3) inactive compounds. H-1008 is 14 available from Amoco Petroleum Additives Company, Clayton, Missouri). The system was warmed to approximately 60°C
16 and 5.5 grams (0.14 moles) of metallic potassium cut into 17 small pieces was slowly added with vigorous stirring. The 18 temperature of the reaction system was allowed to increase 19 during this addition and reached approximately 105°C.
After 2-1/2 hours, a:ll of the metallic potassium was 21 dissolved. The reaction system was then allowed to cool 22 to 40°C. Afterwards, 131.5 grams (about 5 equivalents per 23 equivalent of alkylphenol) of propylene oxide was added to 24 the system by an addition funnel at an addition rate slow enough to avoid flooding of the vapor condensing system.
26 The system was then gently refluxed for 13 hours at which 27 point the temperature increased to 113°C and was held 2g there for an addition 3.5 hours. The system was then 2g cooled to 60°C and the reaction quenched by the addition of 0.075 liter of 2N HC1 solution. The system was then 31 dried by azeotropic distillation to yield a toluene 32 solution of the crude product. The system was then 33 diluted with 1 liter of toluene.
iExample 2 Preparation of C65 to C70 Alkylphenyl Poly( os;yprop:Ylene ) Chloroformate The toluene solution containing the product of Example 1 above in a 5-liter, 3-neck flask under a nitrogen atmo-sphere was cooled t:o about 5°C with stirring. While stirring, 301 grams of a 20~ solution of phosgene in toluene was added all at once to the reaction system. The reaction system was allowed to warm to room temperature and stirred gently for 2~4 hours. In order to remove excess phosgene as well as HC1 formed during the reaction, the system was vigorously sparged with nitrogen. After completion of the reaction, an infrared analysis of an aliquot revealed a stron<3 chloroformate absorption at 1785 cm 1 and no detectable alcohol absorption at 3450 cm 1.
Example 3 Preparation of C65 to C70 Alkylphenyl Poly(oxypropylene) Ethylene Diamine Carbamate The entire chloroformate,itoluene solution of Example 2 was diluted with 4 liters of dry toluene. In a separate flask, 487 grams of: ethylene diamine (8.1 moles) approxi-mately 20 equivalents pe:r equivalent of chloroformate, Was also diluted with ~! lite:rs of dry toluene. At room tem-perature, these two solutions were rapidly mixed using two variable speed Teflon gear pumps and a 10-inch KenicvNi static mixer. After fifteen minutes, the crude reaction mixture was strippead, diluted with 10 liters of hexane, and washed successively once with water and three times with a slightly ba:>ic (p1H =9) brine solution. Phase i.
,.y,,~y O1 separation of the aqueous brine solution and the hexane 02 solution was improved by adding isopropanol as needed.
03 The hexane solution was separated, dried over anhydrous 04 sodium sulfate, filtered and stripped to afford the title 05 product as a thick orange liquid having an alkalinity 06 value of 17.7 and 0.44 weight percent basis nitrogen.
OS Example 4 Preparation of C65 to C70 Alkylphenol 11 Poly(oxypropylene) Diethylene Triamine Carbamate 13 In the manner described in Example 3 above, a C65 to C70 14 alkylphenyl poly(oxypropylene) chloroformate (prepared from 1168 grams of H-1.00? alkylphenol, 0.73 moles) pre-16 pared similarly to the' methods described in Examples 1 and 17 2 above was treated with 814 grams (7.89 moles), approxi-18 mately 20 equivalents per equivalent of chloroformate, of 19 diethylene triamine to afford the title compound having~an alkalinity values of 2!i.7 and 0.64 weight percent basic 21 nitrogen.
23 Re:Eerence Example A
Preparation of Tetrapropenylphenol 27 To a 2-liter flask, equipped with stirrer, Dean Stark 28 trap, condensor,, and :nitrogen inlet and outlet was added 29 567 grams of te~:.rapropylene, 540 grams of phenol, 72 grams of a sulfonic a~:id ration exchange resin (polystyrene 31 crosslinked with divinylbenzene) catalyst (Amberlyst 15R
32 available from Rohm and Haas, Philadelphia, Pennsylvania).
33 The reaction mixture was heated to about 110°C for about 3 34 hours with stirring under a nitrogen atmosphere. The O1 reaction mixture was :.tripped by heating under vacuum and 02 the resulting product filtered hot over diatomaceous earth 03 to afford 626 grams of: tetrapropenylphenol and with a 04 hydroxyl number of 205 and with 96~ paraalkylphenol 05 content.
07 Reference alkylphenyl poly(oxyalkylene) aminocarbamates 08 were prepared from the' tetrapropenyl alkylphenol of 09 Reference Example A in a manner similar to Examples 1-4 above. Reference Examples B through D found in Table I
11 below summarizes the different tetrapropenylphenyl 12 poly(oxyalkylene) aminocarbamates so prepared.
:17 :18 R1 0 ~19 R3 f OCH2CH~nOCINH~-R2NH~pH
;2 0 21 Example R3 R1 R2 n p 23 B tetrapropeny:lphenyl -C2H5 -CH2CH2- 17 1 24 C tetrapropeny:lphenyl -CH3 -CH2CH2- 20 1 D tetrapropeny:lphenyl -CH3 -CH2CH2- 5 1 26 3 C65 to C70 a:lkylphenyl -CH3 -CH2CH2- 5 1 a7 4 C65 to C70 a:lkylphenyl -CH3 -CH2CH2- 5 2 ;Z 8 ,Z9 Example 5 31 Oil Solubility Bench Test :32 This procedure was designed to determine the oil solubil-.34 ity/compatibili~~y of different additives in a fully formulated lubricating oil. Insofar as up to 25-30$ of a gasoline additive can enter into the crankcase via "blow-by" and/or cylinder wall/piston ring "wipe down", this is an import~~nt performance criteria.
The lubricating oi.l composition was formulated to contain:
The alkenyl succinimide is present to act as a dispersant and prevent formation of deposits formed during operation of the engine. The alkenyl succinimides are wellknown in the art. The a:Lkenyl succinimides are the reaction product of a po:Lyolefin polymersubstituted succinic anhydride with ~~n amine, preferably a polyalkylene polyamine. The polyolefin polymersubstituted succinic anhydrides are obtained by reaction of a polyolefin polymer or a derivative thereof with malefic anhydride.
The succinic anlZydride thus obtained is reacted with the amine compound. The preparation of the alkenyl succinimides ha;s been described many times in the art.
See, for example, U.S. Patents Nos. 3,390,082; 3,219,666;
and 3,172,892. Reduction of the alkenyl substituted succinic anhydride yields the corresponding alkyl derivative. The alkyl succinimides are intended to be included within the scope of the term "alkenyl succinimide". .~ product comprising predominantly mono or bissuccinimide can be prepared by controlling the molar ratios of the reactants. Thus, for example, if one mole of amine is reacted with one mole of the alkenyl or alkyl substituted succinic anhydride, a predominantly monosuccinimide product will be prepared. If two moles of the succinic anhydride are reacted per mole of polyamine, a bissuccinimide will be prepared.
x T, O1 Particularly good results are obtained with the lubricating 02 oil compositions of this invention when the alkenyl succi-03 nimide is a polyisobutenesubstituted succinic anhydride of a 04 polyalkylene polyamine.
06 The polyisobutene from which the polyisobutenesubstituted 07 succinic anhydride is obtained by polymerizing isobutene can 08 vary widely in its compositions. The average number of 09 carbon atoms can range from 30 or less to 250 or more, with a resulting number average molecular weight of about 400 or 11 less to 3,000 or more. Preferably, the average number of 12 carbon atoms per polyisobutene molecule will range from 13 about 50 to about 100 with the polyisobutenes having a num-14 ber average molecular weight of about 600 to about 1,500.
More preferably, the average number of carbon atoms per 16 polyisobutene molecule ranges from about 60 to about 90, and 17 the number average molecular weight ranges from about 800 to 18 1,300. The polyisobutene is reacted with malefic anhydride 19 according to wellknown procedures to yield the polyiso-butene-substituted succinic anhydride.
22 In preparing the alkenyl succinimide, the substituted 23 succinic anhydride is reacted with a polyalkylene polyamine 24 to yield the corresponding succinimide. Each alkylene radical of the polyalkylene polyamine usually has from 2 up 26 to about 8 carbon atoms. The number of alkylene radicals 27 can range up to about 8. The alkylene radical is exem-28 plified by ethylene, propylene, butylene, trimethylene, 29 tetramethylene, pentamethylene, hexamethylene, octa-methylene, etc. The number of amino groups generally, but 31 not necessarily, is one greater than the number of alkylene 32 radicals present in the amine, i.e., if a polyalkylene 33 polyamine contains 3 alkylene radicals, it will usually 34 contain 4 amino radicals. The number of amino radicals can O1 range up to about 9. Preferably, the alkylene radical 02 contains from about 2 to about 4 carbon atoms and all amine 03 groups are primary or secondary. in this case, the number 04 of amine groups exceeds the number of alkylene groups by 1.
05 Preferably the holyal)cylene polyamine contains from 3 to 5 06 amine groups. ~~pecif:ic examples of the polyalkylene poly-07 amines include e~thylenediamine, diethylenetriamine, tri-08 ethylenetetramine, propylenediamine, tripropylenetetramine, 09 tetraethylenepentamincs, trimethylenediamine, pentaethylene-hexamine, di(tri.methy:lene)triamine, tri(hexamethylene)tetra-11 mine, etc.
13 Other amines suitable for preparing the alkenyl succinimide 14 useful in this i.nvent:ion include the cyclic amines such as piperazine, morpholine and dipiperazines.
17 Preferably the alkeny:l succinimides used in the compositions 18 of this invention have the following formula 22 Rl-C;H-C
~~N~-Alkylene-N~ H
23 C:H2-C~ ~ n wherein:
27 a. R1 represents an alkenyl group, preferably a substan-28 tially saturated hydrocarbon prepared by polymerizing 29 aliphatic mono-olefins. Preferably R1 is prepared from isobutene ~~nd has an average number of carbon atoms and 31 a number average molecular weight as described above;
33 b, the "alkyl~~ne" radical represents a substantially 34 hydrocarbyl group containing from 2 up to about 8 carbon atoms and preferably containing from about 29 carbon atoms as described hereinabove;
c. A represents a hydrocarbyl group, an amine-substituted hydrocarbyl group, or hydrogen. The hydrocarbyl group and the amine-substituted hydrocarbyl groups are gener-ally the alkyl and amino-substituted alkyl analogs of the alkylene radicals described above. Preferably A
represents hydrogen;
d. n represents an integer of from 1 to about 8, and preferably from about 3-5.
Also included within the term alkenyl succinimide are the modified succinimides which are disclosed in U.S. Patent No. 4,612,132.
The alkenyl succinimide is present in the lubricating oil compositions of the invention in an amount effective to act as a dispersant and prevent the deposit of contaminants formed in the oil during operation of the engine. The amount of alkenyl succinimide can range from about 1 percent to about 20 percent weight of the total lubricating oil composition. Preferably the amount of alkenyl succinimide present in the lubricating oil composition of the invention ranges from about :1 to about 10 percent by weight of the total composition.
The alkali or alka:Line earth metal hydrocarbyl sulfonates may be either petroleum sulfonate, synthetically alkylated aromatic sulfonate;a, or aliphatic sulfonates such as those derived from polyi;sobutylene. One of the more important functions of the s,~lfonates is to act as a detergent and dispersant. These sulfonates are wellknown in the art. The ;° ;
.._ 1341 005 O1 hydrocarbyl group must: have a sufficient number of carbon 02 atoms to render the sulfonate molecule oil soluble. Prefer-03 ably, the hydrocarbyl portion has at least 20 carbon atoms 04 and may be aromatic or aliphatic, but is usually alkylaroma-05 tic. Most preferred i:or use are calcium, magnesium or 06 barium sulfonate~s which are aromatic in character.
08 Certain sulfonat:es area typically prepared by sulfonating a 09 petroleum fraction haring aromatic groups, usually mono- or dialkylbenzene groups,, and then forming the metal salt of 11 the sulfonic acid material. Other feedstocks used for 12 preparing these sulfomates include synthetically alkylated 13 benzenes and aliphatic hydrocarbons prepared by polymerizing 14 a mono- or diolefin, Eor example, a polyisobutenyl group prepared by pol5rmerizing isobutene. The metallic salts are 16 formed directly or by metathesis using well-known 17 procedures.
19 The sulfonates may be neutral or overbased having base num-bers up to abouit 400 or more. Carbon dioxide and calcium 21 hydroxide or oxide are the most commonly used material to 22 produce the ba sic or overbased sulfonates. Mixtures of 23 neutral and overbased sulfonates may be used. The sulfo-24 nates are ordinarily used so as to provide from 0.3% to 10%
by weight of the total composition. Preferably, the neutral 26 sulfonates are present from 0.4% to 5% by weight of the.
27 total composition and the overbased sulfonates are present 28 from 0.3% to 3% by weight of the total composition.
The phenates for use in this invention are those conven-31 tional products which are the alkali or alkaline earth metal 32 salts of alkylated phenols. One of the functions of the 33 phenates is to act as. a detergent and dispersant. Among 34 other things, it prevents the deposition of contaminants ~Dl formed during hi~3h temperature operation of the engine. The ~D2 phenols may be mono- or polyalkylated.
~D 3 ~D4 The alkyl portion of the alkyl phenate is present to lend ~D5 oil solubility t~~ the phenate. The alkyl portion can be ~D6 obtained from naturally occurring or synthetic sources.
~D7 Naturally occurring sources include petroleum hydrocarbons ~D8 such as white oil and wax. Being derived from petroleum, ~D9 the hydrocarbon moiety is a mixture of different hydrocarbyl :10 groups, the specific composition of which depends upon the :ll particular oil stock which was used as a starting material.
:L2 Suitable synthetic sources include various commercially :L3 available alkenes and alkane derivatives which, when reacted :l4 with the phenol, yield an alkylphenol. Suitable radicals :L5 obtained include butyl, hexyl, octyl, decyl, dodecyl, hexa-:L6 decyl,.eicosyl, tricontyl, and the like. Other suitable :l7 synthetic sources of the alkyl radical include olefin poly-:l8 mers such as polypropylene, polybutylene, polyisobutylene :L9 and the like.
:20 :21 The alkyl group can be straight-chained or branch-chained, :22 saturated or unsaturated (if unsaturated, preferably :23 containing not more than 2 and generally not more than 1 :24 site of olefinic unsat.uration). The alkyl radicals will :25 generally contain from 4 to 30 carbon atoms. Generally when :26 the phenol is monoalkylsubstituted, the alkyl radical should :27 contain at least 8 carbon atoms. The phenate may be sul-:28 furized if desired. I:t may be either neutral or overbased :29 and if overbased will have a base number of up to 200 to 300 :30 or more. Mixtures of neutral and overbased phenates may be 31 used.
33 The phenates are ordinarily present in the oil to provide 34 from 0.2% to 27% by weight of the total composition.
O1 Preferably, the neutral phenates are present from 0.2% to 9%
02 by weight of the total composition and the overbased 03 phenates are present from 0.2 to 13% by weight of the total 04 composition. Mast preferably, the overbased phenates are 05 present from 0.2% to 5% by weight of the total composition.
06 Preferred metals are calcium, magnesium, strontium or 07 barium.
09 The sulfurized alkaline earth metal alkyl phenates are pre-ferred. These salts acre obtained by a variety of processes 11 such as treating the neutralization product of an alkaline 12 earth metal base and an alkylphenol with sulfur. Conven-13 iently the sulfur, in elemental form, is added to the 14 neutralization product: and reacted at elevated temperatures to produce the sulfuri.zed alkaline earth metal alkyl 16 phenate.
18 If more alkaline earth metal base were added during the 19 neutralization reaction than was necessary to neutralize the phenol, a basic sulfurized alkaline earth metal alkyl 21 phenate is obtained. See, for example, the process of 22 Walker et al, U.S. Pai:ent No. 2,680,096. Additional 23 basicity can be obtained by adding carbon dioxide to the 24 basic sulfurizecl alkaline earth metal alkyl phenate. The excess alkaline earth metal base can be added subsequent to 26 the sulfurization step but is conveniently added at the same 27 time as the alkaline earth metal base is added to neutralize 28 the phenol.
Carbon dioxide and calcium hydroxide or oxide are the most 31 commonly used material to produce the basic or "overbased"
32 phenates. A process wherein basic sulfurized alkaline earth 33 metal alkylphenates are produced by adding carbon dioxide is 34 shown in Hanneman, U.S. Patent No. 3,178,368.
O1 The Group II metal sa7.ts of dihydrocarbyl dithiophosphoric 02 acids exhibit wear, antioxidant and thermal stability 03 properties. Group II metal salts of phosphorodithioic acids 04 have been described previously. See, for example, U.S.
05 Patent No. 3,390,080, columns 6 and 7, wherein these com-06 pounds and their preparation are described generally. Suit-07 ably, the Group II metal salts of the dihydrocarbyl 08 dithiophosphoric acid:> useful in the lubricating oil compo-09 sition of this invention contain from about 4 to about 12 carbon atoms in each of the hydrocarbyl radicals and may be 11 the same or different and may be aromatic, alkyl or cyclo-12 alkyl. Preferred hydrocarbyl groups are alkyl groups con-13 taining from 4 to 8 carbon atoms and are represented by 14 butyl, isobutyl, sec.butyl, hexyl, isohexyl, octyl, 2-ethylhexyl and the like. The metals suitable for forming 16 these salts include barium, calcium, strontium, zinc and 17 cadmium, of which zinc: is preferred.
19 Preferably, the Group II metal salt of a dihydrocarbyl dithiophosphoric acid has the following formula:
22 R2G~
P
23 R3~./ \S M1 27 wherein:
28 e. R2 and R3 each independently represent hydrocarbyl 29 radicals as described above, and 31 f' M1 represents a Group II metal cation as described 32 above.
34 The dithiophosphoric :.alt is present in the lubricating oil compositions of this invention in an amount effective to inhibit wear and oxidation of the lubricating oil. The amount ranges from about 0.1 to about 4 percent by weight of the total composition, preferably the salt is present in an amount ranging from about: 0.2 to about 2.5 percent by weight of the total lubricating oil composition. The final lubri-cating oil composition will ordinarily contain 0.025 to 0.25% by weight phosphorus and preferably 0.05 to 0.15% by weight.
Viscosity index (VI) improvers are either non-dispersant or dispersant VI impravers. Nondispersant VI improvers are typically hydrocart~yl po7.ymers including copolymers and terpolymers. Typically hydrocarbyl copolymers are copolymers of ethylene and propylene. Such nondispersant VI
improvers are disclosed i.n U.S. Patents Nos. 2,700,633;
2,726,231; 2,792,288; 2,933,480; 3,000,866; 3,063,973; and 3,093,621.
Dispersant VI impro~vers c;an be prepared by functionalizing nondispersant VI im~provens. For example, nondispersant hydrocarbyl copolymer anal terpolymer VI improvers can be functionalized to ~~roduce~ aminated oxidized VI improvers having dispersant ~~ropert:ies and a number average molecular weight of from 1,500 to 20,000. Such functionalized dispersant VI impro~vers are disclosed in U.S. Patents Nos. 3,864,268; 3,769,21E>; 3,326,804 and 3,316,177.
Other dispersant VI improvers include amine-grafted acrylic polymers and copolymers wherein one monomer contains at least one amino group. 7eypical compositions are described in British Patent rlo. 1,488,382; and U.S. Patents AI
Nos. 4,089,794 and 4,025,452.
Nondispersant and dispersant VI improvers are generally employed at from ~~ to 20 percent by weight in the lubricating oil composil~ion.
Lubricai:ing Oil Compositions The alkylphenyl poly(oxyalkylene) aminocarbamates of this invention are useful as dispersant additives when employed in lubricating oils. When employed in this manner, the additive is usually present in from 0.2 to 10 percent by weight to the total composition, preferably at about 0.5 to 8 percent by weight and more preferably at about 1 to 6 percent by weight. The lubricating oil used with the additive compositions oil this invention may be mineral oil or synthetic oils of lubricating viscosity and preferably suitable for use in the crankcase of an internal combustion engine. Crankcases lubricating oils ordinarily have a viscosity of about. 1300 CSt 0°F to 22.7 CSt at 210°F
(99°C).
The lubricating oils may be derived from synthetic or natural sources. Mineral oil for use as the base oil in this invention includes paraffinic, naphthenic and other oils that are ordinaril~t used in lubricating oil composi-tions. Synthetic oils :include both hydrocarbon synthetic oils and synthetic: esters. Useful synthetic hydrocarbon oils include liquid pol~tmers of alpha olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of C6 ito C12 alpha olefins such as 1-decene trimer. Likewise, alkyl benzenes of proper viscosity such as didodecyl benzene, can be used. Useful synthetic esters include the estera of both monocarboxylic acid and xi ~a ;~
O1 polycarboxylic acids as well as monohydroxy alkanols and 02 polyols. Typical examples are didodecyl adipate, 03 pentaerythritol tetracaproate, di-2-ethylhexyl adipate, 04 dilaurylsebacate and the like. Complex esters prepared from 05 mixtures of mono and dicarboxylic acid and mono and 06 dihydroxy alkanols can also be used.
08 Blends of hydrocarbon oils with synthetic oils are also 09 useful. For example, blends of 10 to 25 weight percent hydrogenated 1-decene trimer with 75 to 90 weight percent 11 150 SUS (100°F) mineral oil gives an excellent lubricating 12 oil base.
14 Additive concentrates are also included within the scope of this invention. The concentrates of this invention usually 16 include from about 90 to 50 weight percent of an oil of 17 lubricating visc~~sity and from about 10 to 50 weight percent 18 of the additive of this invention. Typically, the concen-19 trates contain s~.~fficient diluent to make them easy to :20 handle during shipping and storage. Suitable diluents for 21 the concentrates include any inert diluent, preferably an :22 oil of lubricating viscosity, so that the concentrate may be 23 readily mixed with lubricating oils to prepare lubricating :24 oil compositions. Suitable lubricating oils which can be :25 used as diluents typically have viscosities in the range :26 from about 35 to about 500 Saybolt Universal Seconds (SUS) :27 at 100°F (38°C), although an oil of lubricating viscosity :28 may be used.
:29 30 Other additives iahich may be present in the formulation 31 include rust inhibitors, foam inhibitors, corrosion 32 inhibitors, metal deactivators, pour point depressants, 33 antioxidants, and a variety of other well-known additives.
1 341 00~
O1 Fuel Compositions '03 The alkylphenyl poly(oxyalkylene) aminocarbamates of this invention will g~anerally be employed in a hydrocarbon ~D5 distillate fuel. The proper concentration of this additive '06 necessary in ord~sr to achieve the desired detergency and dispersancy varies depending upon the type of fuel employed, the presence of ether detergents, dispersants and other additives, etc. Generally, however, from 30 to 5,000 weight :LO parts per million (ppm), and preferably 100 to 500 ppm and :~1 more preferably 200 to 300 ppm of alkylphenyl poly(oxy-:~2 alkylene) aminoc.arbamate per part of base fuel is needed to :L3 achieve the best results. When other detergents are present, a less amount of alkylphenyl poly(oxypropylene) ~~5 aminocarbamate may be used. For performance as a carburetor :l6 detergent only, lower concentrations, for example 30 to 100 :L7 ppm may be preferred. Higher concentrations, i.e., 2,000 to :l8 5,000 ppm may result in a clean-up effect on combustion :l9 chamber deposits as well as the entire intake system.
a0 al The deposit control additive may also be formulated as a 22 concentrate, using an inert stable oleophilic organic 23 solvent boiling in the range of about 150 to 400°F. Prefer-24 ably, an aliphatic or an aromatic hydrocarbon solvent is 25 used, such as benzene, toluene, xylene or higherboiling :~6 aromatics or aromatic thinners. Aliphatic alcohols of about :~7 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, 28 n-butanol and the like, in combination with hydrocarbon 29 solvents are also suitable for use with the detergent-dis-:30 persant additive. In the concentrate, the amount of the :31 additive will be ordinarily at least 5 percent by weight and :32 generally not e~s:ceed 50 percent by weight, preferably from :33 10 to 30 weight percent.
:34 _3$_ O1 When employing certain of the alkylphenyl poly(oxyalkylene) 02 aminocarbamates of this invention, particularly those having 03 more than 1 basic nitrogen, it can be desirable to addi-04 tionally add a demulsifier to the gasoline or diesel fuel 05 composition. These demulsifiers are generally added at from 06 1 to 15 ppm in the fuel composition. Suitable demulsifiers 07 include for instance L-1562?, a high molecular weight glycol 08 capped phenol available from Petrolite Corp., Tretolite 09 Division, St. Louis, Missouri, and OLOA 2503 available from Chevron Chemical Company, San Francisco, California.
12 In gasoline fuels, other fuel additives may also be included 13 such as anti-knock agents, e.g., methylcyclopentadienyl 14 manganese tricar:bonyl, tetramethyl or tetraethyl lead, tertbutyl methyl peroxide or other dispersants or detergents 16 such as various substituted succinimides, amines, etc. Also 17 included may be .Lead scavengers such as aryl halides, e.g., 18 dichlorobenzene ~~r alkyl halides, e.g., ethylene dibromide.
19 Additionally, antioxidants, metal deactivators and demulsifiers may be present.
22 In diesel fuels, other well-known additives can be employed 23 such as pour point depressants, flow improvers, cetane 24 improvers, etc.
26 The following ex<~mples are offered to specifically illus-27 trate this inven~~ion. These examples and illustrations are 28 not to be construed in any way as limiting the scope of this 29 invention.
~ 34~ 005 02 Example 1 04 Preparation of C65 to C70 Alkylphenyl 05 Poly(oxypropylene) Alcohol 07 To a dried 5-liter, 3-neck flask under a nitrogen atmo-08 sphere was added 1.5 liters of dry toluene and 1125 grams 09 H-1008 (an alkyl;phenol, prepared from polybutene-24, having a hydroxyl number of approximately 34, and a number 11 average of approximately 65-70 carbon atoms in the alkyl 12 portion of the alkylphenol. H-100? also contains approxi-13 mately onethird (1/3) inactive compounds. H-1008 is 14 available from Amoco Petroleum Additives Company, Clayton, Missouri). The system was warmed to approximately 60°C
16 and 5.5 grams (0.14 moles) of metallic potassium cut into 17 small pieces was slowly added with vigorous stirring. The 18 temperature of the reaction system was allowed to increase 19 during this addition and reached approximately 105°C.
After 2-1/2 hours, a:ll of the metallic potassium was 21 dissolved. The reaction system was then allowed to cool 22 to 40°C. Afterwards, 131.5 grams (about 5 equivalents per 23 equivalent of alkylphenol) of propylene oxide was added to 24 the system by an addition funnel at an addition rate slow enough to avoid flooding of the vapor condensing system.
26 The system was then gently refluxed for 13 hours at which 27 point the temperature increased to 113°C and was held 2g there for an addition 3.5 hours. The system was then 2g cooled to 60°C and the reaction quenched by the addition of 0.075 liter of 2N HC1 solution. The system was then 31 dried by azeotropic distillation to yield a toluene 32 solution of the crude product. The system was then 33 diluted with 1 liter of toluene.
iExample 2 Preparation of C65 to C70 Alkylphenyl Poly( os;yprop:Ylene ) Chloroformate The toluene solution containing the product of Example 1 above in a 5-liter, 3-neck flask under a nitrogen atmo-sphere was cooled t:o about 5°C with stirring. While stirring, 301 grams of a 20~ solution of phosgene in toluene was added all at once to the reaction system. The reaction system was allowed to warm to room temperature and stirred gently for 2~4 hours. In order to remove excess phosgene as well as HC1 formed during the reaction, the system was vigorously sparged with nitrogen. After completion of the reaction, an infrared analysis of an aliquot revealed a stron<3 chloroformate absorption at 1785 cm 1 and no detectable alcohol absorption at 3450 cm 1.
Example 3 Preparation of C65 to C70 Alkylphenyl Poly(oxypropylene) Ethylene Diamine Carbamate The entire chloroformate,itoluene solution of Example 2 was diluted with 4 liters of dry toluene. In a separate flask, 487 grams of: ethylene diamine (8.1 moles) approxi-mately 20 equivalents pe:r equivalent of chloroformate, Was also diluted with ~! lite:rs of dry toluene. At room tem-perature, these two solutions were rapidly mixed using two variable speed Teflon gear pumps and a 10-inch KenicvNi static mixer. After fifteen minutes, the crude reaction mixture was strippead, diluted with 10 liters of hexane, and washed successively once with water and three times with a slightly ba:>ic (p1H =9) brine solution. Phase i.
,.y,,~y O1 separation of the aqueous brine solution and the hexane 02 solution was improved by adding isopropanol as needed.
03 The hexane solution was separated, dried over anhydrous 04 sodium sulfate, filtered and stripped to afford the title 05 product as a thick orange liquid having an alkalinity 06 value of 17.7 and 0.44 weight percent basis nitrogen.
OS Example 4 Preparation of C65 to C70 Alkylphenol 11 Poly(oxypropylene) Diethylene Triamine Carbamate 13 In the manner described in Example 3 above, a C65 to C70 14 alkylphenyl poly(oxypropylene) chloroformate (prepared from 1168 grams of H-1.00? alkylphenol, 0.73 moles) pre-16 pared similarly to the' methods described in Examples 1 and 17 2 above was treated with 814 grams (7.89 moles), approxi-18 mately 20 equivalents per equivalent of chloroformate, of 19 diethylene triamine to afford the title compound having~an alkalinity values of 2!i.7 and 0.64 weight percent basic 21 nitrogen.
23 Re:Eerence Example A
Preparation of Tetrapropenylphenol 27 To a 2-liter flask, equipped with stirrer, Dean Stark 28 trap, condensor,, and :nitrogen inlet and outlet was added 29 567 grams of te~:.rapropylene, 540 grams of phenol, 72 grams of a sulfonic a~:id ration exchange resin (polystyrene 31 crosslinked with divinylbenzene) catalyst (Amberlyst 15R
32 available from Rohm and Haas, Philadelphia, Pennsylvania).
33 The reaction mixture was heated to about 110°C for about 3 34 hours with stirring under a nitrogen atmosphere. The O1 reaction mixture was :.tripped by heating under vacuum and 02 the resulting product filtered hot over diatomaceous earth 03 to afford 626 grams of: tetrapropenylphenol and with a 04 hydroxyl number of 205 and with 96~ paraalkylphenol 05 content.
07 Reference alkylphenyl poly(oxyalkylene) aminocarbamates 08 were prepared from the' tetrapropenyl alkylphenol of 09 Reference Example A in a manner similar to Examples 1-4 above. Reference Examples B through D found in Table I
11 below summarizes the different tetrapropenylphenyl 12 poly(oxyalkylene) aminocarbamates so prepared.
:17 :18 R1 0 ~19 R3 f OCH2CH~nOCINH~-R2NH~pH
;2 0 21 Example R3 R1 R2 n p 23 B tetrapropeny:lphenyl -C2H5 -CH2CH2- 17 1 24 C tetrapropeny:lphenyl -CH3 -CH2CH2- 20 1 D tetrapropeny:lphenyl -CH3 -CH2CH2- 5 1 26 3 C65 to C70 a:lkylphenyl -CH3 -CH2CH2- 5 1 a7 4 C65 to C70 a:lkylphenyl -CH3 -CH2CH2- 5 2 ;Z 8 ,Z9 Example 5 31 Oil Solubility Bench Test :32 This procedure was designed to determine the oil solubil-.34 ity/compatibili~~y of different additives in a fully formulated lubricating oil. Insofar as up to 25-30$ of a gasoline additive can enter into the crankcase via "blow-by" and/or cylinder wall/piston ring "wipe down", this is an import~~nt performance criteria.
The lubricating oi.l composition was formulated to contain:
6 percent by weight of a mono-polyisobutenyl succinimide;
20 millimoles per kilogram of a highly overbased sul-furized calcium phenate;; 30 millimoles per kilogram of a highly overbased :;ulfurized calcium hydrocarbyl sulfonate;
22.5 millimoles peer kilogram of a zinc dithiophosphate; 13 weight percent of a commercial nondispersant C2-C3 copolymer viscosity index improver; 5 parts per million of a foam inhibitor in 150tJ ExxoriN'base oil to give a 10 W 40 formulated oil.
The oil solubility of the additive was determined as follows:
To a heated solution (50 grams) of the above-described fully formulated lubricating oil was added 50 grams of the neat additive. The mixi:ure was then heated with constant stirring to 170°F and maintained at that temperature for 15 minutes. Dilut.ions were then prepared according to the desired solubility test range using fresh hot reference oil as the diluent.. In each case, the diluted samples were stirred to 1T0°F for 10 minutes to insure complete mixing. The solutions were then sealed and left to cool undisturbed for from 1-5 days typically at room tempera-ture. Each sample was i:hen rated visually for oil continuity.
Additives that were marginally soluble in this blend separated as a denser secondary phase, and were clearly visible as such without the need for centrifugation.
Additives which gave rise to oil incompatibility probe ~ 1 were inherently oil soluble, however, they tended to displace what appears to be the VI improver. This phenomenon resulted in the separation of the VI improver which is less dense than the bulk oil forming a clear thick upper layer. The solubility/compatibility of a gasoline additive was thereby defined as the highest con-centration (on a, weight basis) which did not result in the formation of either an insoluble lower additive phase or an insoluble upper VI improver phase.
Table II below contains compatibility data for the hydrocarbyl poly(oxyaT_kylene) aminocarbamate. Oil compatibility is repoi:ted as weight percent of additive in the lubricating oil composition.
manr.~ r r Example Oil Compatibility (Wt %) The above data demonstrates that the additives of the instant invention pos:~ess improved oil compatibility over prior art compounds.
20 millimoles per kilogram of a highly overbased sul-furized calcium phenate;; 30 millimoles per kilogram of a highly overbased :;ulfurized calcium hydrocarbyl sulfonate;
22.5 millimoles peer kilogram of a zinc dithiophosphate; 13 weight percent of a commercial nondispersant C2-C3 copolymer viscosity index improver; 5 parts per million of a foam inhibitor in 150tJ ExxoriN'base oil to give a 10 W 40 formulated oil.
The oil solubility of the additive was determined as follows:
To a heated solution (50 grams) of the above-described fully formulated lubricating oil was added 50 grams of the neat additive. The mixi:ure was then heated with constant stirring to 170°F and maintained at that temperature for 15 minutes. Dilut.ions were then prepared according to the desired solubility test range using fresh hot reference oil as the diluent.. In each case, the diluted samples were stirred to 1T0°F for 10 minutes to insure complete mixing. The solutions were then sealed and left to cool undisturbed for from 1-5 days typically at room tempera-ture. Each sample was i:hen rated visually for oil continuity.
Additives that were marginally soluble in this blend separated as a denser secondary phase, and were clearly visible as such without the need for centrifugation.
Additives which gave rise to oil incompatibility probe ~ 1 were inherently oil soluble, however, they tended to displace what appears to be the VI improver. This phenomenon resulted in the separation of the VI improver which is less dense than the bulk oil forming a clear thick upper layer. The solubility/compatibility of a gasoline additive was thereby defined as the highest con-centration (on a, weight basis) which did not result in the formation of either an insoluble lower additive phase or an insoluble upper VI improver phase.
Table II below contains compatibility data for the hydrocarbyl poly(oxyaT_kylene) aminocarbamate. Oil compatibility is repoi:ted as weight percent of additive in the lubricating oil composition.
manr.~ r r Example Oil Compatibility (Wt %) The above data demonstrates that the additives of the instant invention pos:~ess improved oil compatibility over prior art compounds.
Claims (100)
1. An alkylphenyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen and an average molecular weight of about 800 to 6,000 and wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 40 to 200 carbon atoms and the poly(oxyalkylene) polymer is derived from C2 to C5 oxyalkylene units with the proviso that if the poly(oxyalkylene) polymer is a homopolymer of oxyethylene then the poly(oxyethylene) polymer does not contain more than 25 oxyethylene units.
2. An alkylphenyl poly(oxyalkylene) aminocarbamate according to Claim 1 wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from about 50 to about 200 carbon atoms.
3. An alkylphenyl poly(oxyalkylene) aminocarbamate according to Claim 2 wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from about 60 to 100 carbon atoms.
4. An alkylphenyl poly(oxyalkylene) aminocarbamate according to Claim 1 wherein the poly(oxyalkylene) polymer is derived from C3 to C4 oxyalkylene units.
5. An alkylphenyl poly(oxyalkylene) aminocarbamate according to Claim 1 wherein the poly(oxyalkylene) group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 1 to about 100 oxyalkylene units.
6. An alkylphenyl poly(oxyalkylene) aminocarbamate according to Claim 5 wherein the poly(oxyalkylene) group of said alkylphenyl poly(oxyalkylene) amino-carbamate contains from 1 to about 25 oxyalkylene units.
7. An alkylphenyl poly(oxyalkylene) aminocarbamate according to Claim 6 wherein the oxyalkylene group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 1 to about 10 oxyalkylene units.
8. An alkylphenyl poly(oxyalkylene) aminocarbamate according to Claim 1 wherein the aminocarbamate group of said alkylphenyl poly(oxyalkylene) aminocarbamate is derived from a polyamine having 2 to 12 amino nitrogen atoms and 2 to 40 carbon atoms.
9. An alkylphenyl poly(oxyalkylene) aminocarbamate according to Claim 8 wherein the polyamine is a polyalkylene polyamine having 2 to 12 amino nitrogen atoms and 2 to 24 carbon atoms.
10. An alkylphenyl poly(oxyalkylene) aminocarbamate according to Claim 9 wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, butylene diamine, pentylene diamine, hexylene diamine, diethylene triamine and dipropylene triamine.
11. An alkylphenyl poly(oxyalkylene) aminocarbamate according to Claim 10 wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, diethylene triamine and dipropylene triamine.
12. An alkylphenyl poly(oxyalkylene) aminocarbamate according to Claim 1 wherein said alkylphenyl poly(oxyalkylene) aminocarbamate has an average molecular weight of from about 1,000 to about 2,500.
13. A compound of Formula V
wherein R is an alkyl group having from 40 to 200 carbon atoms; R1 is hydrogen or alkyl of from 1 to 3 carbon atoms; R2 is alkylene of from 2 to 6 carbon atoms; m is an integer from 1 to 2; n is an integer such that the molecular weight of the compound is from about 800 to 6,000; and p is an integer from 1 to 6 and with the proviso that if R1 is hydrogen then n is an integer from 1 to 25.
wherein R is an alkyl group having from 40 to 200 carbon atoms; R1 is hydrogen or alkyl of from 1 to 3 carbon atoms; R2 is alkylene of from 2 to 6 carbon atoms; m is an integer from 1 to 2; n is an integer such that the molecular weight of the compound is from about 800 to 6,000; and p is an integer from 1 to 6 and with the proviso that if R1 is hydrogen then n is an integer from 1 to 25.
14. A compound according to Claim 13 wherein R is an alkyl group of from about 50 to about 200 carbon atoms.
15. A compound according to Claim 14 wherein R is an alkyl group of from about 60 to about 100 carbon atoms.
16. A compound according to Claim 13 wherein R1 is methyl or ethyl.
17. A compound according to Claim 13 wherein n is an integer from 1 to about 100.
18. A compound according to Claim 17 wherein n is an integer from 1 to about 25.
19. A compound according to Claim 18 wherein n is an integer from 1 to about 10.
20. A compound according to Claim 13 wherein the compound of Formula V has an average molecular weight of from about 1,000 to 2,500.
21. A lubricating oil composition comprising an oil of lubricating viscosity and a dispersant effective amount of an alkylphenyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen and an average molecular weight of about 800 to 6,000 and wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 40 to 200 carbon atoms and the poly(oxyalkylene) polymer is derived from C2 to C5 oxyalkylene units with the proviso that if the poly(oxyalkylene) polymer is a homopolymer of oxyethylene then the poly(oxyethylene) polymer does not contain more than 25 oxyethylene units.
22. A lubricating oil composition according to Claim 21 wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from about 50 to about 200 carbon atoms.
23. A lubricating oil composition according to Claim 22 wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from about 60 to 100 carbon atoms.
24. A lubricating oil composition according to Claim 21 wherein the poly(oxyalkylene) polymer is derived from C3 to C4 oxyalkylene units.
25. A lubricating oil composition according to Claim 21 wherein the poly(oxyalkylene) group of said alkyl-phenyl poly(oxyalkylene) aminocarbamate contains from 1 to about 100 oxyalkylene units.
26. A lubricating oil composition according to Claim 25 wherein the poly(oxyalkylene) group of said alkyl-phenyl poly(oxyalkylene) aminocarbamate contains from 1 to about 25 oxyalkylene units.
27. A lubricating oil composition according to Claim 26 wherein the poly(oxyalkylene) group of said alkyl-phenyl poly(oxyalkylene) aminocarbamate contains from 1 to about 10 oxyalkylene units.
28. A lubricating oil. composition according to Claim 21 wherein the aminocarbamate group of said alkylphenyl poly(oxyalkylene) aminocarbamate is derived from a polyamine having 2 to 12 amino nitrogen atoms and 2 to 40 carbon atones.
29. A lubricating oil composition according to Claim 28 wherein the polyamine is a polyalkylene polyamine having 2 to 12 amino nitrogen atoms and 2 to 24 carbon atoms.
30. A lubricating oil composition according to Claim 29 wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, butylene diamine, pentylene diamine, hexylene diamine, diethylene triamine and dipropylene triamine.
31. A lubricating oil composition according to Claim 30 wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, diethylene triamine and dipropylene triamine.
32. A lubricating oil composition according to Claim 21 wherein said alkylphenyl poly(axyalkylene) aminocarbamate has an average molecular weight of from about 1,000 to about 2,500.
33. A lubricating oil composition comprising an oil of lubricating viscosity and a dispersant effective amount of a compound of Formula V
wherein R is an alkyl group having from 40 to 200 carbon atoms; R1 is hydrogen or alkyl of from 1 to 3 carbon atoms; R2 is alkylene of from 2 to 6 carbon atoms; m is an integer from 1 to 2; n is an integer such that the molecular weight of the compound is from about 800 to 6,000; and p is an integer from 1 to 6 and with the proviso that if R1 is hydrogen then n is an integer from 1 to 25.
wherein R is an alkyl group having from 40 to 200 carbon atoms; R1 is hydrogen or alkyl of from 1 to 3 carbon atoms; R2 is alkylene of from 2 to 6 carbon atoms; m is an integer from 1 to 2; n is an integer such that the molecular weight of the compound is from about 800 to 6,000; and p is an integer from 1 to 6 and with the proviso that if R1 is hydrogen then n is an integer from 1 to 25.
34. A lubricating oil composition according to Claim 33 wherein R is an alkyl group of from about 50 to about 200 carbon atoms.
35. A lubricating oil composition according to Claim 34 wherein R is an alkyl group of from about 60 to about 100 carbon atoms.
36. A lubricating oil composition according to Claim 33 wherein R1 is methyl or ethyl.
37. A lubricating oil composition according to Claim 33 wherein n is an integer from 1 to about 100.
38. A lubricating oil composition according to Claim 37 wherein n is an integer from 1 to about 25.
39. A lubricating oil composition according to Claim 38 wherein n is an integer from 1 to about 10.
40. A lubricating oil composition according to Claim 33 wherein the compound of Formula V has an average molecular weight of from about 1,000 to 2,500.
41. A lubricating oil concentrate comprising from about 90 to 50 weight percent of an oil of lubricating viscosity and from about 10 to 50 weight percent of an alkylphenyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen and an average molecular weight of about 800 to 6,000 and wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 40 to 200 carbon atoms and the poly(oxyalkylene) polymer is derived from C2 to C5 oxyalkylene units with the proviso that if the poly(oxyalkylene) polymer is a homopolymer of oxyethylene then the poly(oxyethylene) polymer does not contain more than 25 oxyethylene units.
42. A lubricating oil concentrate according to Claim 41 wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from about 50 to about 200 carbon atoms.
43. A lubricating oil concentrate according to Claim 42 wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from about 60 to 100 carbon atoms.
44. A lubricating oil concentrate according to Claim 41 wherein the poly(oxyalkylene) polymer is derived from C3 to C4 oxyalkylene units.
45. A lubricating oil concentrate according to Claim 41 wherein the poly(oxyalkylene) group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 1 to about 100 oxyalkylene units.
46. A lubricating oil concentrate according to Claim 45 wherein the poly(oxyalkylene) group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 1 to about 25 oxyalkylene units.
47. A lubricating oil concentrate according to Claim 46 wherein the poly(oxyalkylene) group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 1 to about 10 oxyalkylene units.
48. A lubricating oil concentrate according to Claim 41 wherein the aminocarbamate group of said alkylphenyl poly(oxyalkylene) aminocarbamate is derived from a polyamine having 2 to 12 amino nitrogen atoms and 2 to 40 carbon atoms.
49. A lubricating oil concentrate according to Claim 48 wherein the polyamine is a polyalkylene polyamine having 2 to 12 amino nitrogen atoms and 2 to 24 carbon atoms.
50. A lubricating oil concentrate according to Claim 49 wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, butylene diamine, pentylene diamine, hexylene diamine, diethylene triamine, and dipropylene triamine.
51. A lubricating oil concentrate according to Claim 50 wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, diethylene triamine and dipropylene triamine.
52. A lubricating oil concentrate according to Claim 41 wherein said alkylphenyl poly(oxyalkylene) amino-carbamate has an average molecular weight of from about 1,000 to about 2,500.
53. A lubricating oil concentrate comprising from about 90 to 50 weight percent of an oil of lubricating viscosity and from about 10 to 50 weight percent of a compound of Formula V
wherein R is an alkyl group having from 40 to 200 carbon atoms; R1 is hydrogen or alkyl of from 1 to 3 carbon atoms; R2 is alkylene of from 2 to 6 carbon atoms; m is an integer from 1 to 2; n is an integer such that the molecular weight of the compound is from about 800 to 6,000; and p is an integer from 1 to 6 and with the proviso that if R1 is hydrogen then n is an integer from 1 to 25.
wherein R is an alkyl group having from 40 to 200 carbon atoms; R1 is hydrogen or alkyl of from 1 to 3 carbon atoms; R2 is alkylene of from 2 to 6 carbon atoms; m is an integer from 1 to 2; n is an integer such that the molecular weight of the compound is from about 800 to 6,000; and p is an integer from 1 to 6 and with the proviso that if R1 is hydrogen then n is an integer from 1 to 25.
54. A lubricating oil concentrate according to Claim 53 wherein R is an alkyl group of from about 50 to about 200 carbon atoms.
55. A lubricating oil concentrate according to Claim 54 wherein R is an alkyl group from about 60 to about 100 carbon atoms.
56. A lubricating oil concentrate according to Claim 53 wherein R1 is methyl or ethyl.
57. A lubricating oil concentrate according to Claim 53 wherein n is an integer from 1 to about 100.
58. A lubricating oil concentrate according to Claim 57 wherein n is an integer from 1 to about 25.
59. A lubricating oil concentrate according to Claim 58 wherein n is an integer from 1 to about 10.
60. A lubricating oil concentrate according to Claim 53 wherein the compound of Formula V has an average molecular weight of from about 1,000 to 2,500.
61. A fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from about 30 to about 5,000 parts per million of a fuel soluble alkylphenyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen and an average molecular weight of about 800 to 6,000 and wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 40 to 200 carbon atoms and the poly(oxyalkylene) polymer is derived from C2 to C5 oxyalkylene units with the proviso that if the poly(oxyalkylene) polymer is a homopolymer of oxyethylene then the poly(oxyethylene) polymer does not contain more than 25 oxyethylene units.
62. A fuel composition according to Claim 61 wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from about 50 to about 200 carbon atoms.
63. A fuel composition according to Claim 62 wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from about 60 to about 100 carbon atoms.
64. A fuel composition according to Claim 61 wherein the poly(oxyalkylene) group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 1 to about 100 oxyalkylene units.
65. A fuel composition according to Claim 64 wherein the poly(oxyalkylene) group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from about 1 to about 25 oxyalkylene units.
66. A fuel composition according to Claim 65 wherein the poly(oxyalkylene) group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 1 to about 10 oxyalkylene units.
67. A fuel composition according to Claim 61 wherein the poly(oxyalkylene) polymer is derived from C3 to C4 oxyalkylene units.
68. A fuel composition according to Claim 61 wherein the aminocarbamate group of said alkylphenyl poly(oxyalkylene) aminocarbamate is derived from a polyamine having 2 to 12 amino nitrogen atoms and 2 to 40 carbon atoms.
69. A fuel composition according to Claim 68 wherein the polyamine is a polyalkylene polyamine having 2 to 12 amino nitrogen atoms and 2 to 24 carbon atoms.
70. A fuel composition according to Claim 69 wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, butylene diamine, pentylene diamine, hexylene diamine diethylene triamine, and dipropylene triamine.
71. A fuel composition according to Claim 70 wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, diethylene triamine and dipropylene triamine.
72. A fuel composition according to Claim 61 wherein said alkylphenyl poly(oxyalkylene) aminocarbamate has an average molecular weight of from about 1,000 to about 2,500.
73. A fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from about 30 to about 5,000 parts per million of a fuel soluble compound of Formula V
wherein R is an alkyl. group having from 40 to 200 carbon atoms; R1 is hydrogen or alkyl of from 1 to 3 carbon atoms; R2 is alkylene of from 2 to 6 carbon atoms; m is an integer from 1 to 2; n is an integer such that the molecular weight of the compound is from about 800 to 6,000; and p is an integer from 1 to 6 and with the proviso that if R1 is hydrogen then n is an integer of from 1 to 25.
wherein R is an alkyl. group having from 40 to 200 carbon atoms; R1 is hydrogen or alkyl of from 1 to 3 carbon atoms; R2 is alkylene of from 2 to 6 carbon atoms; m is an integer from 1 to 2; n is an integer such that the molecular weight of the compound is from about 800 to 6,000; and p is an integer from 1 to 6 and with the proviso that if R1 is hydrogen then n is an integer of from 1 to 25.
74. A fuel composition according to Claim 73 wherein R
is an alkyl group of from about 50 to about 200 carbon atoms.
is an alkyl group of from about 50 to about 200 carbon atoms.
75. A fuel composition according to Claim 74 wherein R
is an alkyl group of from about 60 to about 100 carbon atoms.
is an alkyl group of from about 60 to about 100 carbon atoms.
76. A fuel composition according to Claim 73 wherein n is an integer from 1 to about 100.
77. A fuel composition according to Claim 76 wherein n is an integer from 1 to about 25.
78. A fuel composition according to Claim 77 wherein n is an integer from 1 to about 10.
79. A fuel composition according to Claim 73 wherein R1 is methyl or ethyl.
80. A fuel composition according to Claim 73 wherein the compound of Formula V has an average molecular weight of from about 1,000 to 2,500.
81. A fuel concentrate comprising an inert stable oleophilic organic solvent boiling in the range of 150° to 400°F and from about 5 to 50 weight percent of a fuel soluble alkylphenyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen and an average molecular weight of about 800 to 6,000 and wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 40 to 200 carbon atoms and the poly(oxyalkylene) polymer is derived from C2 to C5 oxyalkylene units with the proviso that if the poly(oxyalkylene) polymer is a homopolymer of oxyethylene them the poly(oxyethylene) polymer does not contain more than 25 oxyethylene units.
82. A fuel concentrate according to Claim 81 wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from about 50 to about 200 carbon atoms.
83. A fuel concentrate according to Claim 82 wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from about 60 to about 100 carbon atoms.
84. A fuel concentrate according to Claim 81 wherein the poly(oxyalkylene) group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 1 to about 100 oxyalkylene units.
85. A fuel concentrate according to Claim 84 wherein the poly(oxyalkylene) group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from about 1 to about 25 oxyalkylene units.
86. A fuel concentrate according to Claim 85 wherein the poly(oxyalkylene) group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains from 1 to about 10 oxyalkylene units.
87. A fuel concentrate according to Claim 81 wherein the poly(oxyalkylene) polymer is derived from C3 to C4 oxyalkylene units.
88. A fuel concentrate according to Claim 81 wherein the aminocarbamate group of said alkylphenyl poly(oxyalkylene) aminocarbamate is derived from a polyamine having 2 to 12 amino nitrogen atoms and 2 to 40 carbon atoms.
89. A fuel concentrate according to Claim 88 wherein the polyamine is a polyalkylene polyamine having 2 to 12 amino nitrogen atoms and 2 to 24 carbon atoms.
90. A fuel concentrate according to Claim 89 wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, butylene diamine, pentylene diamine, hexylene diamine, diethylene triamine, and dipropylene triamine.
91. A fuel concentrate according to Claim 90 wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, diethylene triamine and dipropylene triamine.
92. A fuel concentrate according to Claim 81 wherein said alkylphenyl poly(oxyalkylene) aminocarbamate has an average molecular weight of from about 1,000 to about 2,500.
93. A fuel concentrate comprising an inert stable oleophilic organic solvent boiling in the range of 150°
to 400°F and from about 5 to 50 weight percent of a fuel soluble compound of Formula V
wherein R is an alkyl group having from 40 to 200 carbon atoms; R1 is hydrogen or alkyl of from 1 to 3 carbon atoms; R2 is alkylene of from 2 to 6 carbon atoms: m is an integer from 1 to 2; n is an integer such that the molecular weight of the compound is from about 800 to 6,000; and p is an integer from 1 to 6 and with the proviso that if R1 is hydrogen then n is an integer of from 1 to 25.
to 400°F and from about 5 to 50 weight percent of a fuel soluble compound of Formula V
wherein R is an alkyl group having from 40 to 200 carbon atoms; R1 is hydrogen or alkyl of from 1 to 3 carbon atoms; R2 is alkylene of from 2 to 6 carbon atoms: m is an integer from 1 to 2; n is an integer such that the molecular weight of the compound is from about 800 to 6,000; and p is an integer from 1 to 6 and with the proviso that if R1 is hydrogen then n is an integer of from 1 to 25.
94. A fuel concentrate according to Claim 93 wherein R is an alkyl group of from about 50 to about 200 carbon atoms.
95. A fuel concentrate according to Claim 94 wherein R is an alkyl group of from about 60 to about 100 carbon atoms.
96. A fuel concentrate according to Claim 93 wherein R1 is methyl or ethyl.
97. A fuel concentrate according to Claim 93 wherein n is an integer from 1 to about 100.
98. A fuel concentrate according to Claim 97 wherein n is an integer from 1 to about 25.
99. A fuel concentrate according to Claim 98 wherein n is an integer from 1 to about 10.
100. A fuel concentrate according to Claim 93 wherein the compound of Formula V has an average molecular weight of from about 1,000 to 2,500.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/112,901 US4881945A (en) | 1987-10-23 | 1987-10-23 | Fuel compositions containing very long chain alkylphenyl poly(oxyalkylene) aminocarbonates |
| US112,902 | 1987-10-23 | ||
| US112,901 | 1987-10-23 | ||
| US07/112,902 US4933485A (en) | 1987-10-23 | 1987-10-23 | Lubricating oil compositions containing very long chain alkylphenyl poly (oxyalkylene) aminocarbamates |
| PCT/US1988/003775 WO1990004582A1 (en) | 1987-10-23 | 1988-10-25 | Fuel compositions and lubricating oil compositions containing very long chain alkylphenyl poly(oxyalkylene) aminocarbamates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1341005C true CA1341005C (en) | 2000-05-30 |
Family
ID=33422449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000580895A Expired - Fee Related CA1341005C (en) | 1987-10-23 | 1988-10-21 | Fuel compositions and lubricating oil compositions containing very long chain alkylphenyl poly(oxyalkylene) aminocarbamate |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1341005C (en) |
-
1988
- 1988-10-21 CA CA000580895A patent/CA1341005C/en not_active Expired - Fee Related
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