FI93441B - Alkylphenylpoly(oxypropylene)aminocarbamates and lubricating oil compositions and fuel compositions comprising these compounds - Google Patents

Abstract

The invention relates to liquid alkylphenylpoly(oxypropylene)aminocarbamates which do not form wax when they are cooled down to -40degreeC in a 50 percent by weight toluene solution, with the aminocarbamates containing at least one basic nitrogen atom and having a mean molar mass of approx. 600-6000 and in which the alkyl group is an essentially unbranched chain containing 25-50 carbon atoms. The invention also relates to fuel compositions and concentrates which comprise the said alkylphenylpoly(oxypropylene)aminocarbamates.

Description

93441

Alkylphenyl poly (oxypropylene) aminocarbamates and lubricating oil and fuel compositions containing them

The invention relates to novel alkylphenyl poly (oxypropylene-5) aminocarbamates and lubricating oil and fuel compositions containing them.

Hydrocarbon fuels naturally contain numerous scaling constituents. When used in internal combustion engines, these components tend to form scum 10 in and around narrow areas in contact with the fuel. Typical areas that are usually and often severely burdened by karst formation include e.g. carburetor throats, chokes and nozzles, engine intake valves, etc.

15 Scale adversely affects vehicle operation. For example, scale in the carburetor choke and nozzles increases the fuel to air ratio of the gas mixture entering the combustion chamber and thus increases the amount of unburned hydrocarbon and carbon monoxide leaving the chamber. A high fuel-to-20 substance-to-air ratio also reduces the number of miles a vehicle can reach with a certain amount of gasoline.

When the scum on the engine's intake valves becomes large enough, on the other hand, it limits the gas mixture flow: * ·· into the combustion chamber. This limitation prevents air and fuel from entering the engine and results in a reduction in power. Karsta valves also increase the likelihood of valve failures due to combustion and incomplete valve closure. In addition, this scale may come off and enter the combustion chamber, potentially leading to mechanical damage to the piston, piston rings, cylinder head, etc.

. The formation of this scum can be prevented and removed by combining an active detergent with the fuel. These • · m \ 'detergents work to clean such scale-prone areas from harmful scale and thus increase engine performance and age. At present, there are numerous detergent-type gasoline additives that provide these degrees of activity. Three factors make it difficult to use such detergent-type gasoline additives. First, given the car's engines, which require the use of unleaded gasolines (to prevent catalysts used to reduce emissions from becoming useless), it has been found difficult to obtain gasoline with a sufficiently high octane number to prevent knocking and consequent damage. The main problem is in the range formed by the degree of required increase in octane number, which is referred to herein as "0RIM" and which is caused by the scum formed by commercial gasoline.

The basis of ORI's problem is this: each engine requires a new minimum octane fuel to function satisfactorily without squeaking and / or knocking. When the engine is run on any gasoline, this minimum octane number rises, and in most cases, if the engine is run on the same 20 fuels for an extended period of time, it will reach equilibrium. This is apparently caused by the amount of karst in the combustion chamber. Balance is typically achieved when the car has been operating for 5,000 to 15,000 miles.

: ** · The balance of the required increase in the specific engine octane number used in commercial gasolines.1 · 1 25 r octane ranges from 5-6 octane units to as much as 12-15 units, depending on the gasoline compositions, engine design, and type of operation. Thus, the severity of the problem is obvious. A typical car that has been studied to require a new octane «» · 30 Chapter 85 may after a few months of operation. require 97 octane gasoline to operate when • «· **” zero, and unleaded gasoline with this octane number • · · ’·) 1 is scarce. The ORI problem also occurs to some extent with engines running on leaded fuels. U.S. Patent Nos. 3,144,311; 3,146,203; and * • · · • · · ·· 1 · 3 93441 4 247 301 discloses lead-containing fuel compositions having reduced ORI properties.

The GRI problem is combined with the fact that the most common method of increasing the octane number of unleaded gasoline is to increase its aromatic content. However, this ultimately results in an even greater increase in the required octane number. In addition, some of the nitrogen-containing compounds currently used, which are used as karst control additives, and their mineral oil or polymer 10 enrichments can also make a significant contribution to ORI in engines using unleaded fuels.

Therefore, it is particularly desirable to provide scaling control additives that effectively control 15 scales in engine intake systems without themselves ultimately contributing to the problem.

In this regard, hydrocarbyl poly (oxypropylene) aminocarbamates are commercially successful fuel additives that control the combustion chamber Kars-20, thus minimizing ORI.

Another aggravating factor is related to the low temperature properties of fuel and lubricating oil additives. Since exposure of solutions of these additives to cold extremes is not uncommon, it is important that no solids (such as waxes) are formed during handling, storage or actual field use. Once formed, these waxy constituents can clog the filtration equipment normally used in additive distribution systems and in the fuel and lubrication systems of engines currently in operation. Such clogging would be clearly ·· · catastrophic and must be avoided.

• · · V 1 The third aggravating factor is related to the miscibility of the fuel adhesive with the lubricating oil. Because the additives themselves have a higher boiling point than gasoline, they tend to accumulate on the surfaces of the engine combustion chamber. • · ♦ • · · • 1 · * 3441 4. This accumulation of additives eventually enters the engine crankcase lubricating oil during the "Blow-by" process 1 la and / or the "wipe down" process of the cylinder wall / piston ring. In some cases up to 25% to 30% of the non-volatile fuel components, i. including fuel additives, eventually accumulates in the lubricating oil. While the recommended drain interval for some engines can be as high as 7,500 miles or more, such fuel 10 additives can occasionally accumulate in substantial amounts in the lubricating oil. In the event that the fuel additive is not sufficiently mixed with the lubricating oil, the accumulation of fuel additive immiscible with such oil may in fact contribute to the regression of the crankcase Kars-15, as measured by the Sequence VD test.

The immiscibility of certain fuel additives with lubricating oils, i.e. oils containing other additives arises despite the fact that some fuel additives are also known to be dispersants in ointment-20 oil. However, even if these dispersants were used in a fully formulated lubricating oil as a dispersant instead of a fuel additive, their immiscibility with other additives in the lubricating oil will result in increased crankcase heat according to Sequence V-D engine test measurements.

t ·; There are several theories as to the reason for the lack of lubricity of certain fuel / lubricating oil additives. Without wishing to be bound by any theory, it is possible that some of these additives, when found in lubricating oil, will interfere with other additives,. which are present in the lubricating oil and either counteract the effectiveness of these additives; or in fact cause the dissolution of one or more of these additives. In either case, the immiscibility of the additive with other * ··· 35 lubricating oil additives proves to be less * v f • · · - * · »· t« 5 93441 than the sequence VD engine test for the measured crankcase karst is desirable.

In another theory, when using a fuel additive, it is possible that the accumulation of the additive in the lubricating oil during the emptying interval exceeds its maximum solubility in the lubricating oil. In this theory, this excess amount of additive is insoluble in the lubricating oil and is the cause of the increased crankcase scale.

In yet another theory, it is possible that additive 10 decomposes in the lubricating oil during engine operation, and the decomposition products cause increased crankcase scum.

In any case, additives immiscible with lubricating oil are less than desirable insofar as the use of them during engine operation results in increased scum in the crankcase. This problem can be catastrophic.

It has been found that hydrocarbyl poly (oxybutylene) aminocarbamates are substantially more expensive than hydro-carbyl poly (oxypropylene) aminocarbamates. This is because butylene oxide is much more expensive than propylene oxide. At present, the price of butylene oxide (B0) is more than four times the price of propylene oxide (PO) by weight. However, because of this; 25 he by any known hydrocarbyl polyoxypropylene · · · lene) aminocarbamate was not found to be sufficiently miscible • · · · miscible with lubricating oil and non-waxy, it was necessary to use • · '· “1 more expensive hydrocarbyl poly (oxybutylene) aminocarbamate-» · ·' · "1 In addition, it was particularly advantageous to develop hydrocarbyl poly (ok - ..] · 1 cipropylene) aminocarbamates which are miscible with lubricating oil compositions and non-waxy -40.

This invention relates to lubricating oil compositions and • ·. fuel compositions containing a new group of hyd-> · · · * », 35 rocarbyl poly (oxypropylene) aminocarbamates. As fuel additives, these new hydrocarbyl poly (oxyalkylene) aminocarbamates control the combustion chamber scale, thus minimizing ORI, and are miscible in lubricating oil with lubricating oil composition. As a lubricating oil additive 5, these new hydrocarbyl poly (oxyalkylene) aminocarbamates provide dispersibility without being immiscible with the lubricating oil. The novel additives of this invention are also substantially liquids that do not form a wax at -40 ° C in a 50% by weight toluene solution.

Several references disclose hydrocarbyl poly (oxyalkylene) aminocarbamates as fuel additives. These include e.g. the following U.S. Patent Nos. 4,160,648; 4,191,537; 4,197,409; 4,236,020; 4,243,798; 4,270,930; 15 4 274 837; 4,288,612; 4,521, 61C and 4,568,358.

Of particular interest is U.S. Patent No. 4,274,837, which discloses that hydrocarbyl poly (oxyalkylene) aminocarbamates containing certain poly (oxyalkylene) chains, i. oxypropylene, provide a lacquer-like surface in the crankcase 20 when used in fuels used in combination with certain lubricating oils. This reference further discloses that hydrocarbyl poly (oxypropylene) aminocarbamates which are miscible with lubricating oil are improved in use. ; 25 as this poly (oxypropylene) copolymer, which also contains 1 to 5 branched C 1-10 oxyalkylene units.

U.S. Patent No. 4,160,648 discloses a suction control system additive for fuels, the additive being a hydrocarbyl poly (oxyalkylene aminocarbamate, wherein the hydrocarbyl consists of 1 to 30 carbon atoms and comprises alkyl or alkylphenyl groups. Hydrocarbyl groups include tetrapropenylphenyl, olelyl, and mixtures of C16, C18, and C1-4 alkyl groups, as well as U.S. Patent No. 4,283,612 discloses stock control agents for gasoline engines. which additives are hydrocarbyl poly (oxyalkylene aminocarbamates in which the hydrocarbyl group contains 1 to about 30 carbon atoms, including alkylphenyl groups in which the alkyl group is 5 straight or branched chain having 1 to about 24 carbon atoms. U.S. Patent No. 4,568,358 discloses diesel combustion, an additive such as hydrocarbyl poly (oxyalkylene) aminocarbamate the reference discloses hydrocarbyl groups such as 10 alkyl groups having 1 to 30 carbon atoms; aryl groups having 6 to 30 carbon atoms, alkaryl groups having 7 to 30 carbon atoms, etc.

U.S. Patent No. 4,332,595 discloses hydrocarbyl polyol (oxyalkylene) polyamines in which the hydrocarbyl group is a hydrocarbyl radical of 8 to 18 carbon atoms derived from linear primary alcohols.

U.S. Patent Nos. 4,233,168 and 4,329,240, among others, disclose lubricating oil compositions containing a dispersing amount of hydrocarbyl poly (oxyalkylene) aminocarbamate.

Although these prior art references disclose fuel compositions containing C..30 hydro. carbyl poly (oxyalkylene) aminocarbamates used in • · · ·. ; Poly (oxypropylene) polymers, none of these references discloses a specific hydrocarbyl group in accordance with the present invention, and none of these references suggests that the use of this particular hydrocarbyl group * * «'·' This would solve the problem of immiscibility of lubricating oil known in the art, which immiscibility arises when using prior art hydrocarbyl poly (oxypropylene) - * ·: aminocarbamates, and in particular the problem of wax formation at low temperature.

9 9 9 9 9 9 0 9 9 9 9 9 8 93441

The present invention relates to an alkylphenyl poly (oxypropylene) aminocarbamate having the formula

/ \ f ”3 II

5 / O- OtCH ^ HO- ^ C-NHfRjNH1 H

Rm wherein R is a substantially straight chain alkyl group derived from a substantially straight chain α-olefin oligomer of C8.20-α-olefins, and Rt is alkylene of 2 to 6 carbon atoms, m is an integer from 1 to 2, n is an integer such that the compound has a molecular weight of about 600 to 6000, and p is an integer from 1 to 6, and wherein said compound does not form a wax when cooled to -40 ° C in a 50% by weight toluene solution.

The invention also relates to a fuel composition comprising a hydrocarbon boiling in the range of gasoline or diesel and about 30 to 5,000 parts per million of a compound as defined above.

The invention further relates to a fuel concentrate comprising an inert stable oleophilic organic solvent boiling between 150 and 400 eF and 5 to 50% by weight according to any one of claims 1, 2, 3, 4, 5, 6, 7 or 8 defined compounds.

The invention further relates to a lubricating oil composition comprising an oil having a lubricant viscosity and an effective amount of a compound as defined above for dispersion.

The invention further relates to a lubricating oil concentrate comprising about 90 to 50% by weight of an oil having a lubricating viscosity and about 10 to 50% by weight of a compound as defined above.

• · • · · • «· • · · 9 93441

Finally, the invention relates to an alkylphenol in which the alkyl group is derived from an α-olefin oligomer having a substantially unbranched chain of C8.20-α-olefins and which is attached to the phenol ring at least 6 carbon-5 min from the longest chain of the alkyl group.

The novel alkylphenol compounds described above used to prepare these alkylphenyl poly (oxypropylene) aminocarbamates. These novel alkylphenyl intermediates are alkylphenols in which the alkyl-10 group is a substantially straight chain alkyl group of about 25 to 50 carbon atoms attached to the phenol ring at least six carbon atoms from the longest chain of the alkyl group. The alkyl group of the alkylphenol preferably contains from about 28 to 50 carbon atoms, and more preferably from about 30 to 45 carbon atoms.

Among other factors, the present invention is based on the finding that the "distillate" alkylphenyl poly (oxypropylene jaminocarbamates of the present invention having a substantially straight chain alkyl substituent 20 do not form a wax when cooled to -40 ° C at 50% w / w). These non-waxy carbamates do not form any traces of crystalline wax under these conditions.

• I. It is crucial that these aminocarbamates are • r ··· ♦: 25 non-waxy at low temperatures. Fuel additive. and lubricating oil additives must all be pumpable, for example to fuels, and • operate efficiently in cold conditions in places such as • · · · ’Alaska or Wisconsin during the winter. Even very small amounts of wax, e.g. milligrams, clog micron-sized filters with which these additives usually come into contact. Micron-sized filters are present, for example, in additive distribution and mixing systems that prepare additive packages and blends prior to their • ·. 35 deliveries for purchase by the consumer. Also in cars and • · · • · · * * • • 10 93441 diesel engines, where the fuel is filtered before combustion, there are micron-sized filters.

The alkylphenyl poly (oxypropylene) aminocarbamates of this invention consist of an amino group and an alkylphenyl poly (oxypropylene) polymer attached by a carbamate bond, i. -0C (0) N <. The specific alkylphenyl group used in this invention in an alkylphenyl poly (oxypropylene) polymer is critical to achieving lubricating oil miscibility for alkylphenyl poly (oxypropylene) aminocarbamates, while providing a group with excellent alkyl temperature properties. unbranched and formed from 25 to 50 carbon atoms, results in an alkylphenyl poly (oxypropylene) aminocarbamate that is miscible with lubricating oil and non-waxy at low temperatures.

As used herein, the abbreviation "PO" is intended to mean propylene oxide or propylene oxide-derived polymers. Likewise, the abbreviation "BO" is intended to mean butylene oxide or butylene oxide-derived polymers. The term "EDA" is also meant to mean ethylenediamine or ethylenediamine-derived carbamates. Furthermore, the term "DETA" is intended to mean »·« «. : 25 diethylenetriamine or diethylenetriamine-derived carbamates.

** 11 ^ The term "α-olefin" or "simple α-olefin" • · as used herein generally refers to 1-olefins in which • 1 · "· 1 'the double bond is at the alkyl chain terminus, α-olefins 30 are almost always mixtures of isomers, and often also mixtures of compounds in which the carbon numbers vary.

* · · · Low molecular weight α-olefins such as C6, C8, CO, C12 and C14-α-olefins are almost exclusively · 1-olefins. Higher molecular weight olefin fractions, such as C16_ie: =; a; =; a; =; a; or C20_24, have increasing proportions of the double bond isomerized to the internal or vinylidene position; however, these fractions of higher molecular weights are also referred to herein as α-olefins.

The term "α-olefin oligomer (s)" (A00) as used herein means olefin dimers, trimers, tetramers and pentamers prepared from or derived from Ce.20-α-olefins. These AOOs have a barb-like structure consisting primarily of internally di-10 substituted and trisubstituted olefins. The olefin double bond of these A00s is generally located at least n-2 carbon atoms from the end of the longest continuous carbon chain, where n is the number of carbon atoms of the starting α-olefin.

Alkyl Substituent The alkyl substituent of the alkylphenyl moiety of these alkylphenyl poly (oxypropylene) carbamates is a substantially straight chain alkyl group having about 25 to 50 carbon atoms. The term "substantially unbranched" is intended to mean an alkyl group in which more than about 80% of the individual carbon atoms in the alkyl-s-substituent are either primary (CH3-) or secondary (-CH2-) carbon atoms. Preferably, more than 85% of the carbon atoms in the alkyl substituent are primary or secondary carbons.

The alkyl substituent of the alkylphenyl poly (oxy • · · * '** propylene) aminocarbamates of this invention is arranged in a manner referred to herein as "barbed".

• »I

* · * * Configuration. This configuration has been found to be critical to provide the non-stable low temperature properties of aminocarbamates.

By "forced" configuration is meant that the alkyl group is attached to, for example, an aromatic • ·. to a ring position with a significant distance from the end of the longest chain of the ai- ι · «Μ, * 35 cluster group. This results in at least • · «» · * »9 · • · 9 3 4 41 12 two hydrocarbon tails or a crank wing that« dirt near the clinking point. "Significant distance from the end" means at least 6 carbon atoms from the end of the longest chain of the alkyl group, preferably at least 8 carbon atoms towards the center of the chain. Thus, a "barbed" alkylphenol has an alkyl group comprising at least two tails having a length of at least 6 carbon atoms, preferably a length of at least 8 carbon atoms.

Preferred "barbed" compounds useful in this invention are those compounds in which the alkyl substituent has tails which are hydrocarbon radicals having a substantially straight chain.

As described in more detail below, the alkylphenyl-15 substituent of the aminocarbamate of this invention is derived from the corresponding alkylphenol.

The preferred type of alkylphenol is prepared by alkylating 1 and phenol with one or more α-olefin oligomers. Alkylation with α-olefin oligomers such as decene trimer or octene tetramer gives alkyl phenols having "barbed" configurations. Such configurations can be described by structure A as an example of a docene trimer-derived alkylphenol and by structure B as an example of an octene tetramer-derived alkylphenol, as shown below. In these structures, parentheses 9 are meant to denote various alkyl groups of the alkyl group.

• · t * • <M • · »

• I

• ·> · • ft ·

• I I

• · «

• f »I

• · »ta *« a · f '· * »» • «9. * »· · A # • · • * • a ♦» · * «· •« 13 93441 HO - (0) -1 ^ 5 <Γ ~

A

. s 15 The α-olefin oligomers used herein are prepared by methods well known in the art. A preferred method for preparing these oligomers is to use BF3 as an oligomerization catalyst, as described, for example, in U.S. Patent Nos. 4,238,343 and 4,045,507, and Onopchenko, et al., BF3-Catalyzed Oligomerization of Alkanes (Structures, Mechanisms). and Properties). 183. ACS Natl. Meet. (Las Vegas, March 1982).

»·. Ind. Eng. Chem., Prod. Res. Dev., 22 (2), 182-191 (Jun.

• · 1 25 1983).

• · • 1 · The olefinic position of these α-olefin oligomers is ..: at least 75% di- or trisubstituted. For example, the structure of the α-olefin trimer can be represented as follows: rrr »· · • · • · • # where R = n-2, and n is the carbon content of the α-olefin used as starting material. number.

• •• I

· * · • m · ··· 14 93441 α-olefin oligomers are substantially unbranched in terms of the number of branched (i.e., tertiary or quaternary) carbons as a percentage of the total number of carbon atoms. That is, more than 5 to 80 percent of the carbon atoms in the molecule are primary or secondary carbons, preferably more than 85 percent.

The alkyl groups having a substantially unbranched chain are illustrated by the examples in Table A below: • · • · · • · · M »• · • ·» * · · • · ♦ «·« · «·· • · · • · ··· • · · • * · • · ··· · ··· ♦ • · ♦ • · · • · · ♦ • · • ♦ • · · · ♦ • · · · «« • 15 93441 ta ~ t ~ \ C Φ cc 0) -HGM ♦ h: <d ^ M Λ π Ό O n ΜΌ- Ό σ »co G: <tf

ε 3 P

h λ: w

M Φ: rtJ

w ε: n3 m c φ «o V * ™ O fs | g · <"" Λ p M +> g

-, · Η O

• oj »m O io

I V H

(d h

• H * H

-P Λ r — I M

H f * -H x: <O ~ | co ^ _ 3 3 5 s I "s 3 £! 3" "Ή Ή V (rt 2 ζ: ^

S £ Ό + J

tP - * · 00 VO 0)

Zi O / U P W

<«. / Φ -H

, g K - (c tn ρ / Φ \ Φ H: 2 OS_ / C / G P wj

S - \ -H a * / WC

. »X \ / \ <a ό φ gfn \ 2 as_/ ® 3 ta HM ^ \ 4 Ä-( c>;> ·: · 9 Ί - <A h \ -h φ Λί ···· C Ή \ es fj H / n H ifl

: \: 3 8 A Λ c «-JA B

::! ' · § c (¾ \ °) “S3::” 9 oo S ^ 3 c ή p ··· WC jxj «» GO 3 p ··· λ: ® m ua au •::, wp • I -H - H g -h 1 -H -H - c G -P -H ^ <*> Φ β P 3 0> Φ P p φ „G Ή Φ Φ Ή φ · Ρ ΦΦ Q, 4J _.:. H G φ φ -H M P P φ “» dj -H <H S dj φ Φ Λ * g. ^ _ O -P> 1 P Ό φ O § <»· · *: *. P <M Q, P P | g IP <Blrf ·. · * .G Φ O P φ O P <N P ^ m <. au rH P Φ> ro p ro φ ^ ....: P) 004W— u p uv ημπ • · t · · • · · • · · * 16 93441

Preferred α-olefin oligomers (AOOs) are derived from C8.20-α-olefins, more preferably C10-1f-α-olefins. Preferred AOOs are dimers, trimers, tetramers and pentamers. The alkyl group of these carbamates is preferably derived from α-olefin oligomers selected from the group consisting of: C 8 tetramers, C 10 trimers, C 12 trimers, C 14 dimers and trimers, C 8 dimers and trimers, C 1 D dimers and C 2 O dimers. dimeei i t.

As described above, the alkyl substituent of these alkylphenyl pol-10 ly (oxypropylene) aminocarbamates is arranged in a so-called "barbed" configuration. This "barbed" configuration is readily distinguishable from alkyl groups in which the hydrocarbon chains are attached to or near the longest chain end of the alkyl group, i. 1-5 carbon atoms away. Thus, the alkyl groups of aminocarbamates prepared from simple α-olefins (compared to α-olefin oligomers) and their precursors, including phenols and alkylphenyl poly (oxypropylene) alcohols, are in the "terminal" configuration. Compounds having an alkyl group in the terminal configuration are referred to herein as "terminal compounds", for example, C 2 -C 4, 4-terminal alkylphenols and terminal alkyl carbamates.

: ‘·· In terminal compounds, such as terminal alkylphenols, there is .. * · * 25 only 1 main chain starting close to the point of attachment of the alkyl group to the phenol. The terminal compounds are e.g. combines * teas prepared by reacting α-olefins

• »I

with phenol of the earth under typical acid reaction conditions.

»· · 30 Preferred alkylphenyl group. Preferred alkylpheners for use in this invention.

the alkylphenyl group of the phenyl poly (oxypropylene) aminocarbamate is obtained from the corresponding alkylphenol of the formula: **: I below: * 93 · · · · «· *» · 17 93441

OH

R 'm 5 wherein R is a substantially unbranched alkyl group having about 25 to 50 carbon atoms and m is an integer from 1 to 2.

R is preferably a substantially unbranched alkyl group having 28 to 50 carbon atoms. More preferably, R is a substantially unbranched alkyl group having 30 to 45 carbon atoms.

When m is one, alkylphenyl is monoalkylphenyl; while m is two, alkylphenyl is dialkylphenyl.

The alkylphenols of formula I above are prepared by reacting a suitable olefin or olefin mixture with a phenol in the presence of an alkylating catalyst at a temperature of about 60 ° C to 200 ° C, and preferably 125 ° C to 180 ° C, either alone or in a substantially inert solvent at atmospheric temperature. pressure. The preferred alkylating catalyst is a sulfonic acid catalyst such as Amberlyst 15 *, available from Rohm and Haas, Philadelphia, Pennsylvania.

ψ · ·

Molar ratios of reagents can be used. When molar ratios are used, the reaction gives a mixture of dialkylphenol, monoalkylphenol and unreacted phenol.

• · ·

As mentioned above, dialkylphenol and monoalkylphenol can be used to prepare additives for use in the compositions of this invention, while unreacted phenol is preferably removed from the post-reaction mixture by conventional methods. Exchange • · · ·; * ♦ *; alternatively, a molar excess of fencli can be used, *, i.e. 2-2.5 equivalents of phenol for each olefin equivalent, so that the unreacted phenol is recycled. The latter method maximizes the monoal- • · · • · · • · · • 18 93441 alkylphenol. Examples of inert solvents are. mm. benzene, toluene, chlorobenzene and 250 thinner, a mixture of aromatics, paraffins and naphthenes.

The preferred alkylphenyl group is derived from a stable phenol. Violent phenols can be prepared from α-olefin oligomers.

Useful A00-derived alkyl phenols have average molecular weights in the range of 480 to 790, and average alkyl carbon numbers are in the range of 25 to 10, and preferably 28 to 50. More preferred average alkyl carbon numbers are in the range of 30 to 45.

Alternative methods for preparing the alkylphenol compounds used herein have also been investigated. "Concentrated" alkyl phenols can be synthesized by a variety of methods. These methods are typically based on either preforming the entire alkyl group prior to alkylation of the phenol, or first preparing the alkylphenol, which is then further processed and in which the alkyl group has the necessary functionality to further develop into a barbed alkylphenol. Thus, the phenol can be alkylated either with a barbed olefin or a corresponding alcohol or with an alkyl halide,. such as with chloride or bromide.

* ”The exact structure of the final alkylphenol is difficult to predict with certainty. Alkylations using carbonium ions • · ·. 1: lead to atomic transfers during carbonium ion formation and reaction. It is also known that the products of such alkylation systems may also suffer from atomic transfers, dealkylations and re-alkylations under reaction conditions. Thus, various structures are included in this invention.

• · · ·

Particularly preferred monoalkylphenols used in this invention are either ortho-monoalkylphenols of formula II below: «93 * 19

OH

(T °

or para-monoalkylphenols of formula III below:

OH

φ

R

Particularly preferred dialkylphenols for use in this invention are generally 2,4-dialkylphenols of formula IV below:

OH

20 years

R

although it may contain small amounts of 2,6-dialkylphenol,. having the formula V below: • ·

0H

\: 25 ---- v ί Τ ° Γ • · · ... * Preferred poly (oxypropylene) component * ··. · · Alkylphenyl poly (oxypropylene) polymers used in the preparation of the carbamates of this invention · Are monohydroxy compounds, i.e. alcohols, • · J *. often referred to as alkylphenyl "coated" *. poly (oxypropylene) glycols and must be separated from poly- • · · (oxypropylene) glycols (diols) that are not • · ♦ • 35 alkylphenyl-terminated, i.e., not coated.

• · • »·· ··» 934, l 20

Alkyl phenyl poly (oxypropylene) alcohols or the addition of propylene oxide to the alkyl alkyl phenol, m.p. formula I, i.e.

OH

under polymerization conditions wherein R and m are as defined above. In general, the chain lengths of poly (oxypropylene) polymers vary, but their properties closely resemble those of the polymers described in terms of average composition and molecular weight. Each poly (oxypropylene) polymer contains at least 1 oxypropylene unit, preferably 1 to about 100 oxypropylene units, more preferably about 5 to about 50 oxypropylene units, and most preferably about 10 to about 25 oxypropylene units. Methods and properties for preparing these polymers are disclosed in U.S. Patent Nos. 2,841,479 and 2,782,240, which are incorporated herein by reference, and Kirk-Othmer, "Encyclopedia of Chemical Technology", Volume 19, p. 507. Phenyl poly (oxypropylene) for the preparation of polymers having either 1, 2 or 3 oxypropylene units comprises the use of a compound having '**. 25 is CH under formula VI,

Cl (CH 2 CHO) H VT

2 q

* .1 'where q is an integer from 1 to 3. When using formula VI

30, the phenoxide of alkylphenol I / I 'is first prepared and then reacted with a compound of formula VI to give the desired alkylphenyl generation (oxypropylene) polymer having 1 to 3 • ·. oxypropylene units. Compounds of formula VI are commercially available or may be prepared by methods known in the art.

Preferred Amine Component The amine group of the alkylphenyl poly-5- (oxypropylene) aminocarbamate used in this invention is derived from polyamine. The polyamine is preferably reacted with an alkylphenyl poly (oxypropylene) chloroformate to provide alkylphenyl poly (oxypropylene) aminocarbamate additives useful in the present invention. The chloroformate itself is obtained from an alkylphenyl poly (oxypropylene) alcohol by reaction with phosgene. A polyamine comprising diamines yields an alkylphenyl poly (oxypropylene) aminocarbamate having on average at least one basic nitrogen atom per carbamate-15 molecule, i. a nitrogen atom titratable with a strong acid. The ratio of carbonyl carbon to nitrogen is preferably from about 1: 1 to about 10: 1.

Examples of preferred polyamines are e.g. ethylenediamine, diethylenetriamine, di (trimethylene) -20 triamine, dipropylene triamine, triethylenetetranine, tripropylenetetramine, tetraethylenepentamine and Pentaethylenehexamine. Most preferred are C 1-4 alkylene polyamines, especially lower polyalkylene polyamines, e.g. ethylenediamine, diethylenetriamine, propylene diamine, dipropylene triamine, etc.

• · ·. ’·· In many cases, the amine used in the reaction

V

as an agent in the production of the carbamate of this invention, is not a single compound, but a mixture in which one or more compounds predominate and an average composition is reported. For example, tetraethylenepentamine, prepared by polymerizing aziridine or by the reaction of dichloroethylene and ammonia, has both lower and upper amine members, e.g., triethylenetethanol, substituted piperazines, and pentaethylene. amine, but the composition is predominantly tetraethylene pentamine, and the empirical formula of the total amine composition closely resembles the empirical formula of tetraethylene pentamine.

Preferred alkyl phenyl poly (oxypropylene) aminocarbamate

Once the preferred alkylphenyl poly (oxypropylene) component and the preferred polyamine component have been described, the preferred alkylphenyl poly (oxypropylene) aminocarbamate additive of this invention is obtained by joining these components together with a carbamate bond, i.

O

wherein the ether oxygen can be considered as the terminal hydroxyl acid of the alkylphenyl poly (oxypropylene) alcohol component, and the carbonyl group -C (O) - is preferably obtained with a coupling agent, e.g. phosgene.

The alkylphenyl poly (oxypropylene) aminocarbamate used in this invention has at least one basic nitrogen atom per molecule. "Basic nitrogen atom" • ·: “is a nitrogen atom that can be titrated with a strong acid, ... Ϊ 25 e.g. primary, secondary or tertiary amino • nitrogen, separated from, for example, an amide nitrogen, i.e.

9 • · · ···· · «·

O

... „T: -cn <, 30 which is not so titratable. The basic nitrogen is preferably in the primary or secondary amino group.

«» «•% * * · 9 · 9 9 ·· * • · • • 9 9 9 999 9 99 9 9 • · 23 93441 Λ1 The average molecular weight of phenyl Ipoly (oxypropylene) aminocarbamate is preferably 800 to 3,000 and most preferably 1,000 - 2,500.

Hydrophilic-Lipophilic Equilibrium It is important that the relatively hydrophilic propylene oxide polymer backbone be equilibrated with the hydrophobic alkyl carbon 1a of the alkylphenol. The aminocarbamates of this invention must achieve a good hydrophilic-lipophilic balance (HLB) in order for their hydrocarbon-10 solubility in oil to be sufficient and therefore do not behave detrimental to the lacquered surface of the crankcase.

It has been found that in order to achieve good solubility of the lubricant, the number of carbon atoms in the alkyl group must be about twice the number of propylene oxide units. For example, if the average number of propylene oxide units is n, then the alkyl chain attached to the phenoxy radical should have approximately 2n carbon atoms; preferably between 2n to 4 and 2n + 4 20 carbon atoms; most preferably between 2n and 2n + 4 carbon atoms.

Alkyl Phenyl Ipoly (Oxypropylene Preparation of Jaminocarbamate) The additives used in this invention may conveniently be prepared by first reacting the appropriate alkylphenyl poly (oxypropylene alcohol) with phosgene to give the alkylphenyl poly (oxypropylene). ) chloroform, then the chloroformate is introduced

• M

react with a polyamine to give the desired alkylphenyl poly (oxypropylene) aminocarbamate.

• · 4 • ’* 4 · 4 · • * 4 m • * •» *

»· I

• 4 4 «» 4 · 4 4 24 93441

The preparation of aminocarbamates is disclosed in U.S. Patent Nos. 4,160,648; 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 4,566-358, which are incorporated herein by reference. In general, the reaction of a poly (oxypropylene) compound and phosgene is usually carried out using substantially equimolar amounts, although excess phosgene can be used to improve the degree of reaction. The reaction can be carried out at temperatures of -10 ° C to 100 ° C, preferably 10 ° C to 50 ° C. The reaction is usually completed within 1/4 to 5 hours. Reaction times are usually between 2 and 4 hours.

A solvent can be used in the chloroformylation reaction. Suitable solvents include e.g. benzene, toluene, etc.

The reaction of the chloroformate formed with the amine can be carried out neat or, preferably, in solution. Temperatures of -10 ° C to 200 ° C can be used, the desired product can be, washed with water and stripped of any remaining solvent, usually by vacuum.

Polyamine molar ratio of polyether chloroformate. is generally in the range of about 2 to 20 moles of polyamine per mole of chloroformate, and more usually 5 to 15 moles of polyamine per mole of polyamine. Since it is generally desirable to stop polysubstitution of the poly- · V ·: amino, large molar excesses of polyamine are used. In addition, the preferred adduct is a monocarbamate compound, as opposed to bis (carbamate) or a disubstituted amino ether.

The reaction or reactions can be carried out in the presence or absence of a reaction solvent. The reaction solvent is generally used when it is necessary to reduce the viscosity of the reaction product. These solvents should be stable and inert to the reagents and products of the reaction. Depending on the reaction temperature, the chloroformate used, the molar ratios, and the concentrations of the reagents, the reaction time may vary from less than 1 minute. 3 hours.

After allowing the reaction to proceed for a sufficient time, the reaction mixture is extracted with hydrocarbon-water or hydrocarbon-alcohol-water media to release the product from any low molecular weight amine salts formed and any unreacted diamine. The product can then be separated by evaporation of the solvent. Further purification can be performed by column chromatography on silica gel.

Depending on the particular application of the composition of this invention, the reaction may be carried out in the medium in which it will eventually be used, e.g. polyether carriers or in an oleophilic organic solvent or mixtures thereof, and may be formulated to give a detergent composition concentrate. Thus, the final mixture may be in a form in which it can be used directly by blending with fuels.

An alternative process for preparing the alkylphenyl poly (oxypropylene) aminocarbamates used in this invention involves the use of an aryl carbonate intermediate. That is, the alkylphenyl poly (oxypropylene) alcohol is reacted with the aryl chloroformate to form an aryl carbonate, which is then reacted with a polyamine to form the aminocarbamate used in the present invention. Particularly useful aryl chloroformates include e.g.

phenyl chloroformate, p-nitrophenyl chloroformate, j * # 2,4-dinitrophenyl chloroformate, p-chlorophenyl chloroformate. formate, 2,4-dichlorophenyl chloroformate and p-tri- "* fluoromethylphenyl chloroformate. The use of an aryl carbonate product" · 35 l allows the conversion to aminocarbamates, • • ·

• I

• f · »26 93441 which contain an almost theoretical amount of basic nitrogen, although a smaller excess of polyamine is used, i.e. the molar ratio of polyamine to aryl carbonate is generally 1: 1 to about 5: 1, and further avoids the evolution of hydrogen chloride in the reaction in which the aminocarbamate is formed. The preparation of hydrocarbyl-coated polyloxyalkylene) aminocarbamates by an aryl carbonate intermediate is disclosed in U.S. Patent Applications Nos. 586,533 and 689,616, which are incorporated herein by reference.

As will be appreciated by those skilled in the art, the aminocarbamates of this invention are mixtures of many individual compounds.

The alkyl group typically has different amounts of carbon-15 because the olefins used as starting materials are generally not pure compounds, and for any given amount of carbon in the alkyl group, there are many structural isomers. In addition, mono- and dialkylphenols are generally obtained. Also, the number of propylene oxide units is an average number of 20 and different molecules have a somewhat different number of PO units.

Also within the scope of this invention are fully formulated lubricating oils containing an effective amount of an alkylphenyl poly (oxyalkylene) amino-carbamate for dispersion.

* «. '·· The fully formulated composition contains: p * · * 1. alkenyl succinimide, **': dihydrocarbyl dithiophosphorus of a Group 2 metal; acid salt, t 30 3. Neutral or overbased alkali or alkaline earth metal hydrocarbyl sulphonate or mixtures thereof, and !!! 4. Neutral or overbased alkaline or alkaline earth • · • · ’. potassium alkylated phenate or a mixture thereof, a 5. viscosity index (VI) enhancer.

· · · M · • · * · «I« »· 27 93441

Alkenyl succinimide is present to act as a dispersant and to prevent the formation of scum which builds up during engine operation. Alkenyl succinimides are well known in the art. Alkenyl succin-5 quinimides are reaction products of a polyolefin polymer-substituted succinic anhydride and an amine, preferably a polyalkylene polyamine. Polyolefin polymer-substituted succinic anhydrides are obtained by the reaction of a polyolefin polymer or a derivative thereof with maleic anhydride. The succinic anhydride thus obtained is reacted with an amine compound. The preparation of alkenyl succinimides has been described in the art many times. See, e.g., U.S. Patent Nos. 3,390,082; 3,219,666; and 3,172,892, the disclosures of which are incorporated herein by reference. Reduction of the alkenyl-substituted succinic anhydride gives the corresponding alkyl derivative. Alkyl succinimides are intended to be included within the scope of the term "alkenyl succinimide". A product consisting essentially of mono- or bis-succinimide can be prepared by controlling the molar ratios of the reagents. Thus, for example, if one mole of amine is reacted with one mole of alkenyl- or alkyl-substituted succinic anhydride, a predominantly monosuccinimide product is prepared. If 9 · two moles of succinic anhydride are reacted with 25 moles of polyamine, bis-succinimide is produced.

Particularly good results are obtained with the lubricating oil compositions of the present invention when the alkenyl succinimide is a polyisobutylene-substituted succinic anhydride of a polyalkylene polyamine.

30 Polyisobutylene from which polyisobutene sub-: · titrated succinic anhydride is obtained by polymerizing isobutene-. may vary greatly in composition. Average. The number of carbon atoms may be between 30 and less than - * '250 or more, to give an average molecular weight of about 400 or less than - 3,000 or more. Polyisobutylene- 9,. The average number of carbon atoms in the 93441 molecule is preferably from about 50 to about 100, with the average molecular weight of the polyisobutenes being from about 600 to about 1,500. The polyisobutylene molecule has an average number of carbon atoms of about 60 to about 90 and an average molecular weight of from about 800 to about 1. 300. The polyisobutene is reacted with maleic anhydride according to well known methods to give polyisobutene-substituted succinic anhydride.

In the preparation of alkenyl succinimide, the substituted succinic anhydride is reacted with a polyalkylene polyamine to give the corresponding succinimide. Each alkylene radical of a polyalkylene polyamine usually has up to about 8 carbon atoms. The number of alkyl-15 radicals can vary up to about eight. Examples of alkylene radicals include ethylene, propylene, butylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, etc. The number of amino groups is generally, but not necessarily, greater than the number of alkylene radicals present in the amine, i. if the polyalkylene polyamine has 3 alkylene radicals, it usually contains 4 amino radicals. The number of amino radicals can vary up to about 9. The alkylene radical contains ecI. From about 2 to about 4 carbon atoms, and all amine groups • are primary or secondary. In this case

V

the number of amine groups exceeds the number of alkylene groups by one. The polyalkylene polyamine preferably contains: 3-5 amine groups. Specific examples of polyalkylene polyamines include e.g. ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, tripropyl-. lene tetramine, tetraethylenepentamine, trimethylenediamine, pentaethylenehexamine, di (trimethylene) triamine, tri (hexamethylene) tetramine, etc.

29 9 3 4 41

Mold amines suitable for the preparation of alkenyl succinimide useful in this invention include e.g. cyclic amines such as piperazine, morpholine and dipiperazines.

The alkenyl succinimides used in the compositions of this invention preferably have the following formula: ___ .0 R. CH-

| alkylene N ·) · H

10 CH 2 C == 5.0 L

wherein: a) Rt is an alkenyl group, preferably a substantially saturated hydrocarbon prepared by polymerizing aliphatic monoolefins. Rt is preferably made of isobutene, and its average number of carbon atoms and average molecular weight are described above; b) the "alkylene" radical is a substantially hydrocarbyl group containing up to about 3 carbon atoms and preferably containing about 2-4 carbon atoms, as described above; c) A is a hydrocarbyl group, an amine-substituted hydrocarbyl group or a hydrogen. The hydrocarbyl group and the amine-substituted hydrocarbyl groups are generally alkyl and amino-substituted alkyl analogs of the alkylene radicals described above. A is preferably hydrogen; • ·. {. d) n is an integer from about 1 to 10, and preferably · · ·, ···. about 3-5.

The term "alkenyl succinimide" also includes the mo- 1 '30 diffused succinimides disclosed in U.S. Patent No. 4,612,132, which is incorporated herein by reference.

Alkenyl succinimide is present in the lubricating oil compositions of this invention in an effective amount as a dispersant and to prevent scaling of contaminants formed during engine operation. The amount of alkenyl- • · m m · * · • · 1 · · · • · 93441 lisucine imide can vary from about 1% by weight to about 20% by weight of the total lubricating oil composition. Preferably, the amount of alkenyl succinimide present in the lubricating oil composition of this invention is from about 1% to about 10% by weight of the total composition.

Alkali or alkaline earth metal hydrocarbyl sulfonates may mean either petroleum sulfonate, synthetically alkylated aromatic sulfonates or aliphatic sulfonates such as those derived from polyisobutylene. One of the most important functions of sulfonates is to act as a detergent and dispersant. These sulfonates are well known in the art. The number of carbon atoms in the hydrocarbyl group must be sufficient to render the sulfonate molecule oil soluble. The hydrocarbyl moiety preferably has at least 20 carbon atoms and may be aromatic or aliphatic, but is usually alkyl aromatic. Most preferred for use are calcium, magnesium or barium sulfonates which are aromatic in nature.

Certain sulfonates are typically prepared by sulfonating a petroleum fraction having aromatic groups, usually mono- or dialkylbenzene groups, followed by ** formation of a metal salt of a sulfonic acid substance.

.!: * 25 Other starting materials used for these sulfonates t. * ·; manufacture, are e.g. synthetically alkylated benzenes and aliphatic hydrocarbons prepared by polymerizing a mono- or diolefin, for example polyiso- • i *. a butenyl group prepared by polymerizing isobutene. Metal salts are formed directly or by metathesis using well known procedures.

“Sulfonates can be neutral or overbased. with base numbers up to about 400 or more. Carbon dioxide and calcium hydroxide or oxide are the most commonly used substances for the production of basic or overbased sulfonates. Mixtures of neutral and overbased sulfonates can be used. Sulfonates are commonly used so that 0.3 to 10% by weight of the total composition is obtained, the neutral sulfonates are preferably present in an amount of 0.4 to 5% by weight of the total composition, and the overbased sulfonates are present in an amount of about 0.3 to 3% by weight of the total composition.

The phenates used in this invention are conventional products which are alkali or alkaline earth metal salts of alkylated phenols. One of the functions of phenates is to act as detergents and dispersants. Among other factors, it prevents the formation of contaminants in the scum, which is formed when the engine is running at high temperatures. Phenols can be mono-15 or polyalkylated.

The alkyl portion of the alkylphenate is present to impart oil solubility to the phenate. The alkyl moiety can be obtained from naturally occurring or synthetic sources. Naturally occurring sources include e.g. petroleum hydrocarbons such as val-20 oil and wax. Since the hydrocarbon moiety is derived from petroleum, it is a mixture of different hydrocarbyl groups, the specific composition of which depends on the particular petroleum material used as a starting material. Suitable synthetics. sources include e.g. various commercially available alkenes and alkane derivatives which, when reacted with phenol, give alkylphenol. Suitable .1: 1 radicals include e.g. butyl, hexyl, octyl, • · · Decyl, dodecyl, hexadecyl, eicosyl, tricontyl • ·:: and the like. Other suitable synthetic sources of the alkyl radical include e.g. olefin polymers such as polypropylene, polybutylene, polyisobutylene and the like.

··; ·. The alkyl group may have a straight chain or branched chain, it may be saturated or saturated (if unsaturated, it preferably contains * '2 35 up to 2 and generally up to 1 olefinically saturated). · · 1 2 32 93441). Alkyl radicals generally contain from 4 to 30 carbon atoms. In general, when the phenol is monoalkyl substituted, the alkyl radical should contain at least 8 carbon atoms. Phenate can be sulfurized if desired. It can be either neutral or overbased, and if overbased, it has a base number of up to 200-300 or more. Mixtures of neutral and overbased phenates can be used.

Phenates are usually present in the oil at 0.2 to 27% by weight of the total composition. Neutral phenates are preferably present in 0.2 to 9% by weight of the total composition, and overbased phenates are present in 0.2 to 13% by weight of the total composition. Most preferably, the overbased phenates are present in an amount of 0.2 to 5% by weight of the total composition. Preferred metals are calcium, magnesium, strontium or barium.

Sulfurized alkaline earth metal alkyl phenates are preferred. These salts are obtained by various methods, such as by treating the neutralization product of an alkaline earth metal base and an alkylphenol with sulfur. Usually, sulfur in elemental form is added to the neutralization product and reacted at elevated temperatures to give sulfurized alkaline earth metal alkyl phenate.

If more alkaline earth metal base is added during the neutralization reaction than is necessary to neutralize the phenol, a basic sulfurized alkaline earth metal alkylate is obtained. See, e.g., Method Walker et al., U.S. Patent No. 2,680,096. Increased alkalinity can be obtained by adding carbon dioxide to basic sulfurized soil. alkalimetallialkyylifenaattiin. Excess alkaline earth metal base may be added after the sulfurization step, but is suitably added at the same time as the alkaline earth metal base. a base is added to neutralize the phenol.

Carbon dioxide and calcium hydroxide or oxide are the most commonly used agents for the preparation of basic 35 or "overbased" phenates. A process for the preparation of basic sulfurized alkaline earth metal alkylphenates by the addition of carbon dioxide is disclosed in Hanneman, U.S. Patent No. 3,178,368.

The dihydrocarbyldithiophosphorus-5 acid salts of Group II metals have durability, antioxidant and thermal stability properties. Phosphoridithioic acid salts of group II metals have been described previously. See, for example, U.S. Patent No. 3,390,080, columns 6 and 7, which generally describes these compounds and their preparation. The dihydrocarbyldithiophosphoric acid salts of Group II metals useful in the lubricating oil composition of this invention suitably contain from about 4 to about 12 carbon atoms of the hydrocarbon radical, and may be the same or different and may be aromatic, alkyl or cycloalkyl. Preferred hydrocarbyl groups include alkyl groups containing 4 to 8 carbon atoms, such as butyl, iso-butyl, sec-butyl, hexyl, isohexyl, octyl, 2-ethylhexyl and the like. Metals suitable for the formation of these salts include e.g. barium, calcium, strontium, zinc and cadmium, of which zinc is preferred.

The dihydrocarbyldithiophosphorus pole salt of the Group II metal preferably has the following formula: 25 12 ° \ / ··· y ^ * · · y '**: R., 0 ^ S M.

• · • · 30 wherein: e) R2 and R3 independently of one another denote hydrocarbyl radicals as described above, and • f) M. is a group II metal cation as described above.

* • · • · • · · 34 93441

The dithiophosphorus salt is present in the lubricating oil compositions of this invention in an amount effective to inhibit lubricating oil wear and oxidation. The amount is between about 0.1 and about 4% by weight of the total composition. The salt is preferably present in an amount ranging from about 0.2% to about 2.5% by weight of the total lubricating composition. The final lubricating oil composition usually contains 0.025 to 0.25% by weight of phosphorus and preferably 0.05 to 0.15% by weight.

Viscosity index (VI) enhancers are either non-dispersive or dispersive VI enhancers. Non-dispersive VI enhancers are typically hydrocarbyl polymers comprising copolymers and terpolymers. Typical hydrocarbyl copolymers are copolymers of ethylene and propylene. Such non-dispersive VI enhancers are disclosed in U.S. Patent Nos. 2,700,633; 2,726,231; 2,792,288; 2,933,480; 3,000 866; 3,063,973; and 3,093,621, which are incorporated herein by reference for information on their non-dispersive VI enhancers.

Dispersive VI enhancers can be prepared by functionalizing non-dispersive VI enhancers. For example, non-dispersive hydrocarbyl copolymer and terpolymer VI enhancers can be functionalized to produce • aminated oxidized VI enhancers having dispersing properties and an average molecular weight of 1: 500 to 20,000. Such functionalized dispersants • VI enhancers are disclosed in U.S. Patent Nos. 3,864,268; . 3,769,216; 3,326,804 and 3,316,177, which are incorporated. with reference to this for information on such dispersive VI enhancers.

Other dispersing VI enhancers include e.g. amine-grafted acrylic polymers and copolymers in which one monomer contains at least one amino group. Typical compositions are described in GB Patent No. 1,488,382; and 35 U.S. Patent Nos. 4,89,794 and 4,025,452, which are incorporated herein by reference for their information on such dispersive VI enhancers.

Non-dispersing and dispersing VI enhancers are commonly used in 5-20% by weight of the lubricating oil composition.

Fuel Compositions The alkylphenyl poly (oxypropylene) aminocarbamates of this invention are generally used in hydrocarbon distillate fuel. The correct concentration of this additive, which is necessary to achieve the desired detergent and dispersant effect, will vary depending on the type of fuel used, the presence of other detergents, dispersants and other additives, etc. However, 30-5,000 parts by weight mil-15 are generally required. Per line (ppm) and preferably 100 to 500 ppm and more preferably 200 to 300 ppm of alkylphenyl poly (oxypropylene) aminocarbamate per part of base fuel for best results. When other detergents are present, a lower amount of alkylphenyl poly (oxypropylene) aminocarbamate may be used. For use as a gas detergent only, lower concentrations, for example 30 to 70 ppm, may be preferred. Higher concentrations, i.e. 2,000 to 5,000 ppm, can lead to a scaling effect in the combustion chamber.

* · '25 Karst control additives can also be formulated as concentrates using an inert stable oleophilic organic solvent boiling in the range of about 150 ° C to about 400 ° F. Preferably an aliphatic or aromatic hydrocarbon solvent such as benzene, toluene, xylene is used. 30 leen or higher boiling aromatic substances or aromatic diluents Aliphatic alcohols having about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, n-butanol and the like, in combination *: also suitable for use with hydrocarbon solvents ·· 35 detergent In the concentrate, the amount of the additive is usually at least 5% by weight and generally does not exceed 50% by weight, preferably from 10 to 30% by weight.

When using certain alkylphenyl poly (oxypropylene) aminocarbamates of this invention, especially those having more than 1 basic nitrogen, it may be desirable to further add an emulsion disintegrant to the gasoline or diesel fuel composition. These emulsion disintegrants are generally added to 1-15 ppm of the fuel composition. Suitable emulsion disintegrants include, for example, L-1562 ", a high molecular weight glycol coated phenol supplied by Petrolite Corp., Tretolite Division, St. Louis, Missouri, and OLOA 2503Z1 supplied by Chevron Chemical Company, San Francisco, California.

Gasoline fuels may also include other fuel additives such as anti-knock agents, e.g., methylcyclopentadienyl manganese tricarbonyl, tetramethyl, or tetraethyl lead, or other dispersants or detergents, such as various substituted succinimides, amines. aryl halides, e.g. dichlorobenzene or alkyl halides, e.g.

• · · *. ethylene dibromide. In addition, antioxidants, metal deactivators and emulsion disintegrants may be present.

Other well-known additives can be used in diesel fuels, such as pour point depressants, flow improvers, cetane improvers, etc.

30 Lubricating Oil Compositions • j. The alkylphenyl poly (oxy- ·· ♦ ·:... Propylene) aminocarbamates of this invention are useful as dispersing additives when used in lubricating oils. When used in this way, the additive is usually present in an amount of 0.2 to 10% by weight of the total composition, preferably about 0.5 to 8% by weight. by weight and more preferably about 1-6% by weight. The lubricating oil to be used with the additive compositions of this invention may be a mineral oil or a synthetic oil having a lubricant-5 viscosity and is suitable for use in the crankcase of an internal combustion engine. The viscosity of crankcase lubricating oils is usually about 1300 CSt at 0 eF to 22.7 CSt at 210 eF (99 eC). Lubricating oils can be obtained from synthetic or natural sources. The mineral oils used in the base oil according to the present invention are e.g. paraffinic, naphthenic and other oils commonly used in lubricating oil compositions. Synthetic oils include both hydrocarbon synthetic oils and synthetic esters. Useful synthetic hydrocarbon oils include nun. liquid polymers of α-olefins with the correct viscosity. Particularly useful are Hydrogenated liquid oligomers of C6-12 α-olefins, such as 1-decene trimer. Alkylbenzenes of the correct viscosity, such as didodecylbenzene, can also be used. Useful synthetic esters include esters of both monocarboxylic acid and polycarboxylic acids, as well as monohydroxyalkanols and polyols. Typical examples are didodecyl adipate, pentaerythritol tetra-caproate, di-2-ethylhexyl adipate, dilauryl base: * and the like. Complex esters prepared from mixtures of mono- and dicarboxylic acid and mono- and dihydroxyalkanols can also be used.

· «· * ··. Mixtures of hydrocarbon oils with synthetic oils * | · \ are also useful. For example, using • ♦ 30 blends of 10 to 25 weight percent hydrogenated 1-decene trimer and 75 to 90 weight percent 150 SUS (100 ° F) • · · mineral oil provides an excellent lubricating oil base.

• «'Additive concentrates are also included in this invention; ♦ ·; covered by the invention. The concentrates of the present invention ...: 35 usually comprise from about 90 to 50% by weight of oil.

• IM

38 9 3 4 41 having a lubricant viscosity and about 10 to 50 weight percent of the additive of this invention. Concentrates typically contain sufficient diluent to make them easy to handle during transport and storage. Suitable diluents for the concentrates are any inert diluents, preferably an oil having a lubricant viscosity, so that the concentrate can be easily mixed with the lubricating oils to prepare lubricating oil compositions. Suitable lubricating oils that can be used as diluents typically have viscosities ranging from about 35 to about 500 Saybolt Universal Seconds (SUS) at 100 eF (38 eC), although an oil having a lubricant viscosity may be used.

Other additives that may be present in the composition include e.g. rust inhibitors, defoamers, corrosion inhibitors, metal deactivators, pour point depressants, antioxidants, and various otherwise well known additives.

The following examples are presented to specifically illustrate this invention. These examples and presentations should not be construed as limiting the scope of this invention in any way.

. Examples i * ··

*. Example A

• M

Preparation of 25 α-olefin oligomers (C14-derived) • · · '· *! using a sulfonic acid catalyst This example illustrates α-olefin oligomers useful in the present invention. A dry 500 mL * Γ: three-necked round bottom flask equipped with a heating mantle, mechanical stirrer and condenser was charged with 200 grams of CM-α-olefin (Chev- •····. Ron Chemical Co., San Francisco ) and 10 grams of experimental • ·

Alumina supported fluorosulphonic acid catalyst (DOW

** * XUS 40036.07) available from Dow Chemical Company.

· * '* 35 These ingredients were heated and stirred using nitrogen • • 0 9 0 * 99 9 • • 99 • 9 39 9 3 4 41 as a shielding gas for 25 h at 185 eC. During this time, the dark reaction mixture was purified of any residual C14 impurities by heating in vacuo, filtered. The product was analyzed by SFC to reveal an olefin dimer in the 95/5-sac-5 de trimer. This product was used for phenol alkylation without further purification. This product was not allowed to crystallize at low temperatures and was considered as such as waxless.

Example B

Preparation of α-olefin oligomers (C14-derived) using BF3 This example also illustrates α-olefin oligomers useful in this invention. In this example, the C14-α-olefin of Example A was oligomerized using boron trifluoride gas and alcohol as a cocatalyst, as described, for example, in U.S. Patent Nos. 4,238,343 and 4,045,507. An approximately 2 H gallon clear pale yellow liquid was prepared containing approximately 67% dimer, 25% trimer, and 8% tetramer / pentamer-y-20 combination. This mixture, having an average molecular weight of 472, was converted to the barbed alkylphenol without further purification. This product was a non-viscous liquid at room temperature and below, and as such was considered wax-free.

• · ·

25 Example C

Preparation of α-olefin oligomers (C16-derived) This example illustrates oligomers useful in the present invention. The procedure of Example • »'···' A for C16 C16-α-olefin was followed. The product obtained was a mixture of dimers and trimers in a ratio of approximately 95. This product was a non-viscous liquid at and below room temperature and was considered as such as wax-free.

• * · * · · • «· • · ♦ * • · 40 9 3 4 41

Example IA

Preparation of barbed alkyl phenols from the (C14-derived) oligomers of Example B

310 g (0.66 mol) of the BF3-prepared olefin oligomers of Example B were charged to a 1 liter three-necked flask equipped with a heating mantle, a mechanical stirrer and a condenser. The liquid was heated to 85 ° C, during which time 344 grams (3.83 mol) of liquid phenol was added followed by 65 grams of 10 dry Amberlist 15. The reaction mixture was then heated at 150 ° C for 24 hours, during which time the resin was removed by heat filtration. Excess phenol was removed by vacuum distillation to give 343 g of non-viscous amber-colored alkylphenol (343 grams-15 earth; hydroxyl number = 105.4). The average alkyl carbon content of this phenol was 36 carbon atoms. This product was converted to polyoxypropylene alcohol without further purification. This phenol was a non-viscous liquid at room temperature and turned into a thick oil at lower temperatures. No wax formation was observed.

Example IB

Preparation of barbed alkyl phenols from the oligomers of Example C. ·. The C16-derived olefin oligomer of Example C was used to alkylate phenol in a manner similar to T *. as described in Example IA. The average alkyl carbon content of the obtained alkyl-like phenol was 34 carbon atoms.

· · ·

Comparative Example 1C

• ·· ^ ·. · · Preparation of 30 C20.24-terminal alkylphenol To a 5-liter flask equipped with a stirrer, a Dean-Stark trap, a condenser, and a nitrogen inlet and outlet was added 500 g of a mixture of C20_24-α-olefins having a substantially unbranched chain (li-] 35 total olefin content, C18 less than 1%; C20 49%; C22 • · • * * • · • · · «·» ·· • · „93441 41

42%; C24 8%; C26 over 0.1%), in which at least 15 mole% of said olefins in the total olefin fraction contain vinylidene groups (C20_24-α-olefins are available from Chevron Chemical Company, San Francisco, CA), 656 grams of phenol-5 and 75 grams of sulfonic acid cation exchange resin - (polystyrene crosslinked with divinylbenzene) catalyst (Amberlyst 15 ", supplied by Rohm and Haas, Philadelphia, PA). (i.e. mg KOH / g sample) and a para-alkylphenol content of approximately 45% This phenol was a low melting wax at room temperature.

Preparation of C20_2e-terminal alkylphenol To a 2-liter flask equipped with a stirrer, Dean-Stark trap, condenser, and nitrogen inlet and outlet was added 674 g of a substantially unbranched C20_28-α-olefin mixture (olefin-20 : C18 2%; C20 28%; C22 19%; C24 13%; C26 21%; C.8 11%; and C30 more than 6%), in which at least 20 mol% of said olefins in the total olefin fraction contain vinylidine groups (C20-24 α-olefins and C24.28-α-olefins are available from Chevron Chemical Company, San Francisco, CA, and are then mixed in physically equal molar proportions to give a C; 0.28 olefin mixture), 211.5 • · grams of phenol, 43 grams of sulfonic acid cation exchange • M ·. ···. resin (polystyrene crosslinked with divinylbenzene) catalyst (Amber lyst 15 ", supplied by Rohm and Haas, Philadelphia, PA). The reaction mixture was heated at about 140 ° C for 8 hours with stirring and under a nitrogen atmosphere.

··· ··· The reaction mixture was fractionally distilled by heating under vacuum, and the product was filtered hot with diatomaceous earth to give 574 g of C20-28 alkylphenol having a hydroxyl number of 110 to 35 and a para-alkylphenol content of 56%. . Here, the alkylphenol- • · · • · · · · · · • · 42 93441 sa was approximately 26% dialkylphenol and had an average alkyl carbon number of 29. This product was a hard wax at room temperature.

Comparative Example 2B

Preparation of low dialkyl C20-28 terminal alkylphenol The procedure of Example 2A was used except that 966 g of C20-28 α-olefins and 211.5 g of phenol were used. The resulting alkylphenol contained approximately 6% dialkyl-10 phenol and had an average carbon number of 24. This product was a wax at room temperature.

Comparative Example 2C

Preparation of an average C26-terminal alkylphenol In a separate procedure, the low dial-15 C20.24 phenol of Example 2B was re-alkylated using an additional 10% C20-24-α-Chevron olefin (under the conditions described in Example 1C). This reaction thus gave an alkylphenol consisting of approximately 16% dialkylphenol species. The average amount of alkyl carbon was 26. This product was a wax at room temperature.

Comparative Example 3 Preparation of Tetrapropenylphenol To a 2-liter flask equipped with a stirrer, a Dean-Stark trap, a condenser, and a nitrogen inlet and outlet were added 567 grams of tetrapropylene, 540 grams of phenol, 72 grams of sulfonic acid. ·.:. interchangeable resin (polystyrene crosslinked divinylbenzene ··· 1.

. ···. catalyst (Amberlyst 15, edited by Rohm and • · β · | · β Haas, Philadelphia, PA). The reaction mixture was heated to 30,110 ° C for about 3 hours with stirring under a nitrogen atmosphere.

The reaction mixture was partitioned by heating under vacuum, and the product formed was filtered hot over diatomaceous earth to give 626 grams of tetrapropenylphenol having a hydroxyl number of 205 and a para-alkylphenol content of 96%.

* · M m • 9 m • · · • · · 43 93441

Comparative Example 4 Preparation of C20-28 terminal alkylphenyl Ipoly (oxypropylene) alcohol

To a dried 12-liter 3-necked flask was added 3.5 liters of toluene and 2020.5 grams (4.61 moles) of C20-28 terminal alkylphenol prepared in the same manner as in Example 2A under a nitrogen atmosphere. The system was heated to approximately 60 ° C, and 60 grams (1.54 moles) of metallic potassium, cut into small pieces, was added slowly and with vigorous stirring. The temperature of the reaction system was allowed to rise during this addition and reached approximately 100 ° C. After 2 h, all of the metallic potassium was dissolved. The reaction system was then allowed to cool to 60 ° C. 4552 grams (78.37 moles) of propylene oxide was then added to the system via an addition funnel at a rate of addition slow enough to avoid flooding the gas cooling system. The system was then gently refluxed for 72 hours, at which point the temperature rose to 20,110 ° C and held for an additional 3 hours. The system was then cooled to 60 ° C and quenched by the addition of 0.54 liters of 3 N HCl solution. The system was then dried by azeotropic distillation. Sen. then the system was diluted with 10 liters of hexane, which was then extracted three times with mildly basic salt. aqueous solution (pH * 8-9). In each extraction, a • * · 9 9 0 '/ boundary zone was formed between the aqueous solution and the hexane solution. The cut-off area and the aqueous solution were discarded after each extraction. The resulting hexane solution was fractionally distilled and dried at elevated temperature under high vacuum to give 4450 grams of the title compound as a light oil having a molecular weight of approximately 1435 and a hydroxyl number of 39. The product had an average of 17 PO- units. This ’. the procedure was repeated to give the following example I 9 · · · 9 f · · • 0 ·

«» I

> 9999 • · 44 9 3 4 41 ch 13 products listed. This product was a waxy paste at room temperature.

Comparative Example 5A

Preparation of C20-28 alkylphenylphenyl poly (oxypropylene) chloro-5 formate To a 12 liter 3-necked flask was added 3 liters of anhydrous toluene and 3042 grams (2.6 moles) of a C20-2e terminal alkylphenyl poly (oxypropylene) prepared as above. . The system was cooled to 5 ° C with stirring. While stirring, 297 grams (3.0 moles) of liquid phosgene was added all at once to the reaction system. The reaction system was allowed to warm to room temperature and stirred gently for 24 hours. To remove excess phosgene 15 and HCl formed during the reaction, the system was vigorously bubbled with nitrogen. Infrared analysis of the batch gave a strong chloroformate absorption at 1785 cm -1, with no detectable alcohol absorption in 3450 mothers. This product was a waxy paste at room temperature.

Example 5B

Preparation of a barbed alkylphenyl poly (oxypropylene) chloroformate from the poly (oxypropylene) alcohol of Example 32 • · * 25 To a cooled (5 ° C) mechanically stirred solution of the barbed poly (oxypropylene) alcohol of Example 32 (440). g, 0.26 moles) derived from the C ^ oligomer, in 1 liter of dry toluene under a nitrogen atmosphere, was added in one portion 254 ml of a 20% phosphorus solution in toluene ( 242 g). The reaction mixture was allowed to warm to room temperature and stirred gently for 24 hours to remove excess phosgene and HCl formed during the reaction period. Infrared analysis of the batch *. gave a strong chloroformate absorption at 1785 cm'1 • · m m · • • · · i »· * · ·» * * 45 9 3 4 41 and no detectable alcohol (3450 cm * 1) · This product was a liquid at room temperature.

Comparative Example 6 Preparation of C20.2e-alkylphenyl poly (oxypropylene) ethylene -5 diamine (EDA) carbamate

The entire chloroformate / toluene solution of Example 5A was diluted with 4 liters of dry toluene. In a separate vessel, 2565 grams (42.7 moles) of ethylenediamine (EDA) was also diluted with 4 liters of dry toluene. The two solutions were mixed rapidly at room temperature using two variable speed Teflon gear pumps and a 10 inch Kenics static mixer. After 15 minutes, the crude reaction mixture was fractionally distilled, diluted with 12 liters of hex-15, washed successively once with water and three times with slightly basic (pH * 9) brine. The separation of the aqueous brine and hexane solution was improved by adding brine as needed. The hexane solution was separated, dried over anhydrous sodium sulfate, filtered and partitioned to give the title product as a pale yellow liquid which turned to a solid loose paste on cooling with a base value of 30 and 0.75% by weight of basic. this nitrogen. This preparation was repeated to give · * ♦ 25 the product listed as Example 23 below. This product was a waxy paste at room temperature and did not pass the wax test described in Example 45.

»•« f. ···. Comparative Example 7 »9 ~ ~ - • Preparation of C20.28-terminal alkylphenyl poly (oxypropylene) diethyl • · 30-trienetriaminecarbamate

As described in Example 6 above, 2256 grams of earth (1.53 moles) of C2rt_2e ~ terminal alkylphenyl poly (oxypropyl

• 99 * V

9 9 * * * lene) chloroformate prepared in the same manner as in Example 5A above was treated with 2654 grams (25.8 moles) of diethylene tri- • · · · ··· · * · * * · «93441 amine (DETA) to give the title compound having a base value of 56 and 1.4% by weight of basic nitrogen. This preparation was repeated to give the product listed as Example 27 below. This product was a 5 waxy paste at room temperature and did not pass the wax test of Example 45.

Comparative Example 8 Preparation of n-butyl poly (oxypropylene) ethylenediamine carbamate 10,000 grams (0.91 moles) of n-butyl poly (oxypropylene) alcohol were prepared as in Example 4 by substituting n-butanol for C20.28 alkylphenol. The n-butyl poly (oxypropylene) alcohol was then treated with phosgene as in Example 5A to give n-butyl poly-15 (oxypropylene) chloroformate, which was reacted with 1093 grams (18.2 moles) of ethylenediamine as in Example 6 to give the title compound. as a pale yellow liquid with a basic value of 22.5 and containing 0.56% by weight of basic nitrogen. This product was 20 liquids at room temperature and passed the wax test of Example 45.

Comparative Examples 9-17

Other hydrocarbyl poly (oxyalkylene) alcohols were prepared using various hydrocarbyl groups, including the hydrocarbyl groups of Examples 2A and 3; using ♦! * [*; different poly (oxyalkylene) groups with different • · · chain lengths. Examples 9-17 are found below in Table '**' I, which summarizes the various hydrocarbyl poly (oxyalkylene) alcohols thus prepared.

• · * «« m • · · • · · · «« · • · · · · · · · · · · · · 47 93441

Table I

Poly (oxyalkylene) alcohols of formula ΐ1

R, -OfCH., CHO4 · H

5 J 1 n

Phenol- Avg.

source alkyl

Eg R3 e.g. No. Rj n carbons 10 __ _ __ - - - 9 n-butyl - -CH3 approx. 37 s 10 n-butyl - -CH3 approx. 23 4 11 tetrapropenyl-3 -CH3 approx. 20 12 lifenyl 15 12 tetrapropenyl-3 -CH2CH3 ca. 17 12 lifenyl 13 C20-2e-terminus-2A -CH3 ca. 17 29 alkylphenyl 14 C-.28-terminus-2A -CH3 ca. 14 29 20 alkylphenyl approx. 10 29 alkylphenyl 16 C20.28-terminated 2A -CH3 approx. 6 29 alkylphenyl 25 17 C20.2e-terminated 2A -CH2CH3 approx. 17 29 alkylphenyl 29 C20-29-terminated-2B -CH3 approx. 17 24 alkylphenyl 30 C2C.29-terminal 2B -CH3 ca. 13 24 30 alkylphenyl 31 C20-29-terminal 2C -CH3 ca. 14 26. alkylphenyl • '·· 32 α-Cu-derived 1A -CH3 ca. 20 36.:. barbed 35 alkylphenyl 33α-C14 oligomer-1A -CH3n · 16 36 'rialkylphenyl, .t: 1 alkylalkyl, 2 ·. 34 α-Clfc-oligomee- IB -CH3 ca. 17 34 and 40-alkylphenyl: alkylalkylphenyl • · · * · · ♦ • »·» II • · ·> · · · · · · · · · · · * »• · • · • · · · 1 · 2 • · 48 93441

Table 11

Carbamates of formula R. 0

1 II

R30fCH2CH (HnCNHfCH2-NH-CH 2 pH *

5

Phenol- Avg.

source alkyl

Eg R3 eg No. R3 np carbon 10 18 n-butyl - -CH3 n.37 1 4 19 n-butyl - -CH3 n.23 1 4 20 tetrapropenyl-3 -CH3 n.20 1 12 lifenyl 21 tetrapropenyl-3 -C2H5 ca. 17 1 12 15 lifenyl 22 tetrapropenyl-3 -C2H5 n.17 2 12 lifenyl 23 C20-28-terminal 2A -CH3 ca. 17 1 29 alkylphenyl 20 24 C20-28-terminal 2A -CH3 ca. 23 C20-28-terminal 2A -CH3 ca. 10 1 29 alkylphenyl 26 C20-26-terminal 2A -CH3 ca. 6 1 29 25 alkylphenyl 27 C20.28-terminal 2A -CH3 ca. 17 2 29 alkylphenyl 23 C20-28-terminal 2A -CH3 ca. 17 1 29 alkylphenyl 30 35 C20-28 terminal 2B -CH3 ca. 17 1 24 alkylphenyl 36 C20-28 terminal 2B -CH3 ca. 13 1 24 • * ·· alkylphenyl 37 C20.28 terminal 2B -CH3 ca. 13 2 24 ···· 35 alkylphenyl 38 C20-28 terminal- 2C -CH3 ca. 14 1 26 alkylphenyl 39 α-CM-derived IA -CH3 ca. 20 2 36, ***. barbed ”· * 40 alkylphenyl: T: 40 α-C14-derived IA -CH3 ca. 16 2 36 barbed alkylphenyl • j. 41 α-C16-derived IA -CH3 ca. 17 2 34 45 barbed · alkylphenyl »• · • · m m · · • · ♦» * · m • ·

Comparative Examples 18 to 28 49 93441

Other hydrocarbyl poly (oxyalkylene) aminocarbamates were prepared using various hydrocarbyl groups, including the hydrocarbyl-5 groups of Examples 2 and 3, and using poly (oxyalkylene) groups with different chain lengths. Examples 18 to 28 are found in Table II, which summarizes the various hydrocarbyl poly (oxyalkylene) aminocarbamates thus prepared.

10 Comparative Example 29 Preparation of C24-terminal alkylphenyl poly (oxypropylene) alcohol

In the same manner as described in Example 4, 622 g (1.45 moles) of a low dialkyl terminal phenol obtained from C 2 C 3; 3-α-olefin (Example 2B) was converted to 2048 g of poly (oxypropylene) alcohol ( hydroxyl number 40.0; molecular weight 1402) by reaction with approximately 17 moles of propylene oxide. This product was a waxy paste at room temperature.

20 Comparative Example 30

Preparation of an average C24-terminal alkylphenyl poly (oxypropylene) alcohol

The alkylphenol of Example 2B was reacted with • * »· 13 moles of PO as in Example 4 to give the alkylphenyl poly (oxypropylene) alcohol of Example 25.

* »· · · * · · Comparative Example 31 • ♦ · - * · C26-terminal alkylphenyl poly (oxypropylene) alcohol ·» ·. * ··. Iin manufacturing • ·

The alkylphenol of Example 2C was converted to the 14-PO-polymer (determined by Nmr) in the same manner as described in Example 4, but using 14 moles of PO per mole of phenol. This product was a waxy paste at room temperature »·· *.

9 • · • · • 9 · Ψ

»· I

19 * 9 • »·· · • 9 so 93441

Example 32 Preparation of Concentrated Poly (Oxypropylene) Alcohols from the C14 Oligomer-Derived Phenol of Example IA This experiment was performed in a dry 2-liter three-lacquer flask equipped with a heating mantle, a mechanical stirrer, and fitted with a dry ice condenser to maintain an inert nitrogen atmosphere. To a warm solution of a dry toluene solution (250 mL) and 203 grams (0.36 moles) of the concentrated phenol of Example IA with alkylphenol was slowly added potassium metal (5.4 g) in small pieces with vigorous mechanical stirring. The temperature of the vessel rose to approximately 100 ° C during the addition, and after 2 hours all the potassium had dissolved. After cooling to 60 ° C, 585 mL of propylene oxide (486 g, 8.36 moles) was added to avoid flooding the gas cooling system. The reaction solution was gently refluxed for 72 hours, at which time the temperature rose to 110 ° C, and was maintained at that temperature for another 3 hours. After cooling to 60 ° C, the reaction was quenched with 60 mL of 3 N HCl (slight excess) and dried by azeotropic distillation. The crude product was then diluted with hexane (3 liters), extracted three times with slightly basic brine. Each time a boundary region was formed and it ·: 1 25 was discarded. The resulting hexane solution was fractionally distilled and dried under high vacuum to give 670 g of a pale yellow oil having a molecular weight of about · · ♦ · ···. 1725 (by hydroxyl number determination). Spectroscopic analysis (1H- and 13C-Nmr) revealed that this alcohol contained an average of 20 propylene oxide monomer units. This product was a non-viscous liquid at room temperature.

«M

*** and could not be crystallized at low temperature.

* · · * · · • »t • · ·« • »•% 9 · 9 · · * ·». m »1 · m m

Example 33 51 93411 Preparation of barbed alkylphenyl poly (oxypropylene> alcohols

The barbed alkylphenol of Example IA (C14-derived) was converted to the poly (oxypropylene) alcohol by reaction with 16 molar equivalents of propylene oxide in the same manner as described in Example 32.

Example 34 Preparation of barbed alkylphenyl poly (oxypropylene) -10 alcohols

The barbed alkylphenol (C16-derived) of Example IB was converted to a poly (oxypropylene) alcohol by reaction with 17 molar equivalents of propylene oxide in the same manner as described in Example 32.

15 Comparative Example 35 Preparation of low dialkyl C2c_24-terminal carbamate i-EDA

The terminal alkylphenol alcohol of Example 29 was converted to chloroform without further purification as described in Example 5A, except that a 20% by weight toluene solution of phosgene was used instead of concentrated phosgene liquid (for ease of handling and safety). After the reaction, the chloroformate is then bubbled with a molecule, but less with PO. This is shown in Example 36.

Comparative Example 36

Preparation of C24-terminal alkylphenyl poly (oxypropyl-5-yl) -EDA carbamate

In a separate procedure, the "low" di-alkyl terminal phenol of Example 2B was converted to a phenol-coated poly (oxypropylene) alcohol containing 13 PO units using a procedure similar to that described in Example 10. This alcohol was converted to the corresponding chloroform as in Example 5A using phosgene / toluene solution. The chloroformate was degassed and used without further purification.

One batch of this chloroformate was converted to EDA-carbamate as in Example 6 (base value = 37, 0.93% basic nitrogen). 1 product did not pass the wax test of Example 45.

Comparative Example 37 Preparation of C24-terminal alkylphenyl poly (oxypropylene) -DETA-20 carbamate

The remaining chloroformate of Example 36 was converted to the corresponding DETA carbamate (base value = 67.4, 1.69% basic nitrogen) as in Example 7. This product m "did not pass the wax test of Example 45.

25 Comparative Example 38 • · - 1 - • ·. 1: Preparation of average C24-terminal alkylphenyl poly (oxypropylene) -EDA carbamate • · ·

The poly (oxypropylene) alcohol of Example 31 was converted to the corresponding chloroform as in Example 5A, 30 and reacted with EDA to give the desired ethylenediamine carbamate in the same manner as ·; ·. in Example 6 (base value »34.0, 0.85% basic nitrogen).

• »This product did not pass the wax test of Example 45.

• 1 As observed in Examples 24, 35, 36, 37 and 38, the reduction of the number of propylene oxide units in the additive body of the 93441 does not improve the lacquering surface forming properties. not nearly as significant as increasing the amount of alkyl carbons in the alkylphenol. As can be seen from Example 35, an average alkyl carbon content of 24 carbon atoms with PO formulations is insufficient to provide the required lacquered surface and dirt control. Neither by reducing the PO content (Example 36) nor by changing the DETA carbamate mice (Example 37) can the lacquer-like surface forming properties be restored to the level shown in Example 24. However, by increasing the dialkyl content to a higher degree (Example 38), the properties can be restored to baseline. However, none of these examples represents a complete solution to the overall problem, which further requires that these additives be non-waxy at low temperatures and thus pass the experiment of Example 45.

Example 39 Preparation of alkylphenyl poly (oxypropylene) diethylenetriaminecarbamate The chloroformate / toluene solution of Example 5B was diluted to 2 liters with dry toluene. In a separate vessel, 530 grams of diethylenetriamine (5.2 moles) was also diluted to 2 liters with dry toluene. The two solutions were mixed rapidly using two variable speed Teflon tooth-25 wheel pumps and a 10 inch Kenics static mixer. The crude reaction mixture was then fractionally distilled, diluted with 6 • · · L of hexane and washed successively with water (4x),; with basic (pH = 9) water (2x) and water (4x). The separation of the phases was improved by adding isopropanol as needed. The organic layer was then dried: (NaSO 4), filtered and fractionally distilled to give *. a light orange product which remained liquid at -40 ° C (base value ^ 50, 1.25% basic nitrogen). This product * '35 was considered non-waxy on the basis that it passed the wax test of Example 45. This carbamate does not bubble the harmful lacquered surface or dirt into its base oil.

Examples 40-41 Preparation of Aminocarbamates of this Invention The barbed alcohols 33 and 34 were reacted in the same manner as in Examples 5 and 7 to give a Cu-derived DETA barbed carbamate. 1, if -10a had 16 oxypropylene units and an average alkyl carbon number of 34 (Example 40), and a C: 6-derived DETA barbed carbamate having 17 oxypropylene units and an average alkyl carbon number of 36 (Example 41). These products pass the wax test at 15-40 ° C and do not form a harmful li1 <aa or lacquered surface relative to the base oil.

Example 42 Oil Solubility Step Test This procedure was intended to determine the oil solubility / miscibility of various additives in a fully formulated lubricating oil. Because up to 25-30% of a gasoline additive can end up in the crankcase in a "blow-by" manner. and / or the “wipe down” of the cylinder wall / piston ring, this is an important property criterion.

• r • · · • •• 1 25 The lubricating oil composition was formulated to contain: 6% by weight of monopolyisobutenyl succinimide; 20 millimoles per kilogram of highly overbased • · · I '/ · sulfurized calcium phenate; 30 millimoles per kilogram of highly overbased sulfurized calcium hydrocarbyl sulfonate; 22.5 millimoles per kilogram of zinc dithiophosphate; 13% by weight of a commercial non-dispersive viscosity index improver; 5 parts by weight of antifoam in 150N-Exxon base oil gave 10 W of 40 formulated oil.

m • M · 1 • · • · · · • «« · · 55 93441

The oil solubility of the additive was determined as follows:

To a heated solution of the lubricating oil described above (50 grams) was added 50 grams of pure additives. The mixture was then heated to 170 ° F with constant stirring and maintained at this temperature for 15 minutes. Dilutions were then prepared according to the desired solubility test range using fresh hot reference oil as a diluent. In each case, the 10 diluted samples were mixed at 170 eF for 10 minutes to ensure complete mixing. The solutions were then placed in sealed containers and allowed to stand alone in the cool for 1-5 days, typically at room temperature. The oil continuity of each sample was then evaluated visually.

Additives that were barely soluble in this mixture separated as a denser secondary phase and were clearly visible as such without the need for centrifugation. Additives that added to the oil immiscibility problems were inherently oil soluble, however, they tended to displace the component that proved to be a VI (viscosity index) enhancer. This phenomenon resulted in the separation of a less dense VI enhancer than the main oil, which formed a clear 25-thick upper layer. The solubility / miscibility of the petrol additive was thus determined as the highest concentration (based on weight) which did not result in an insoluble lower phase or an insoluble upper VI- · »·. '; to improve the formation of the donkey.

30 Oil solubility (or insolubility) of hydrocarbyl poly (oxyalkylene) aminocarbamates to which amino- ·· · * · *; carbamates include the alkyls of this invention. phenyl poly (oxypropylene) aminocarbamates, is believed to correspond well to precursor hydrocarbyl poly (oxyalkylene)

MM

'' 35 alcohol solubility of alcohol. Accordingly, Table III

»· * · · · I ·· ·> · 56 93441 below contains solubility results for hydrocarbyl poly (oxyalkylene) alcohols. oil solubility is expressed as a percentage by weight of the additive in the lubricating oil composition.

Table III

5 Example No. Oil solubility 9 5 10 8 11 18 12 27 10 13 40 14 50 15 50 16 50 17 50 15 The oil solubility of aminocarbamates is given in Table IV.

Example 43

Sequence V-D test method

Formulated oils containing alkylphenyl lipoly (oxypropylene) aminocarbamate were tested by the sequence V-D test method as were formulated oils containing reference hydrocarbyl poly (oxyalkylene). aminocarbamates. This procedure uses a Ford • 1 2.3-liter four-cylinder Pinto engine. The test method simulates a difficult type of field test performance characterized by • · / / a combination of low speed, low temperature, • · · ·· "stop and drive" urban driving, and moderate road operation. The effectiveness of additives in oil is defined as terms denoting protection against dirt and lacquer scales on a scale of 0-10, so that 0 is: 1 black and 10 means that there is no lacquer or dirt scum. The results of these experiments are shown in Table IV below.

• · ·

The reference composition was formulated to contain: 6% by weight of monopolyisobutenyl succinimide; • · · 57 93441 20 millimoles per kilogram of highly overbased sulfurized calcium phenate; 30 millimoles per kilogram of highly overbased calcium hydrocarbyl sulfonate; 22.5 millimoles per kilogram of zinc dithiophosphate 5; 13% by weight of a commercial non-dispersive viscosity index improver; 5 ppm of antifoam in 150N-Exxon base oil to give a 10 W 40 formulated oil.

Comparisons against this reference composition were made using an oil formulated identically to the reference composition except for an additional amount of additive, as shown in Table IV below: • m 9 9 9 9 9 9 • 99 9 9 ··· 9 9 • 99 9 9 9 • 9 9 • 9 9 9 • • 9 9 • 99 9 9 • 9 • 99 • 99 9 9 9 • 99 9 9 • 9 9 9 9 9 9 9 9 • • · • · · 9 9 9 9 9 • 9 « 1 · · ♦ · »9 99 9 9 9 58 93441

Table IV

Carbamate performance and properties

Crankcase- Crankcase oil- is average. is the average.

5 purchase- Wax e varnish (3) dirt. Avg.

Eg flow (1) -40 ° C (2) 2.5 (4) 5.5 2.5 5.4 HC - ft (5) 18 0.5 no 4.4 9.2 4 10 19 1 no 4 20 7 no 12 21 15 no 5.7 5.5 9.5 9.55 12 22 15 no 12 15 23 16 yes 29 24 20 yes 6.4 7.5 9.6 9.35 29 25 45 yes 29 26 50 yes 29 27 16 yes 29 20 28 16 yes 29 35 18 yes 4.4 9.5 24 36 20 yes 5.4 9.4 24 37 18 yes 7.4 9.2 24 25 38 22 yes 6.2 9.4 26 39 18 no (6) (6) 34 40 18 no (6) (6) 36 41 18 no (6) (6) 34 30 --------------- ------------------------------------------- (1) See, for example, 42 ( 2) See eg 45 ί * '(3) See eg 43 - rating scale »1-10 so that 10 means no lacquered surface or • · J / ·; 35 card no.

• J * (4) Weight percent of additive.

; * '* · (5) Average number of alkyl carbons of the alkylphenyl group • · m (6) These carbamates are not harmful in relation to the base oil of Example 30.

'. * !! Examples 18 to 22 represent prior art hydro-carboxylic poly (oxyalkylene) aminocarbamates. This * * ϊ “ί lock indicates that the alkylphenyls of this invention; nyl poly (oxypropylene) aminocarbamates (Examples 39-9 f I · c

»· I

• · »t t · W t. 'Λ 1' '' Ml J’ 4 1) were less harmful, i.e. gave a strong crankcase karst by means of the surface of the crankcase in the sequence V-D results.

The table also shows that the additives of this invention have lubricating oil miscibility. This is particularly surprising in view of the fact that prior art hydrocarbyl poly (oxypropylene) aminocarbamates are not lubricating oil-miscible, i. examples 18, 19 and 20.

10 Example_44

TGA Stability of Arninocarbamates Thermal acids in fuel can be measured by thermogravimetric analysis (TGA). The TGA procedure used a Du Pont 951 TGA-1 component connected to a microcomputer. Fuel additive samples, approximately 25 milligrams, were heated isothermally at 200 ° C using an air flow of 100 cubic centimeters per minute.The sample weight was monitored as a function of time.Increased weight loss 20 is considered to be a first order process.Kinetic data, i.e. rate constants and half-lives The half-life measured by this procedure is the time that "" elapses when half of the additive decomposes or evaporates. The half-life results correlate with the probability that the additive is an additional cause of "\ 1 'ORI. Lower half-lives represent a more readily degradable product that is less likely to accumulate and form scum in the combustion chamber. All reference carbamates-30 and the carbamate examples of this invention have good TGA performance, i. half-lives of less than 4 hours and therefore promote ORI as little as possible.

60 9 3 4 41

Example 45

Determination of waxiness of the additive

Since it is not uncommon for solutions of these additives to be exposed to extremely cold temperatures, it is important that no solids (typically wax) be formed during handling, storage or actual field use. Once formed, such waxy components can completely clog the piping filter equipment normally used in additive distribution systems and in the fuel or lubrication systems of actual engines in operation. Such blockages would, of course, be catastrophic and must be avoided. The following experimental procedure constitutes a reasonable determination of this low temperature tendency and serves as a crucial distinguishing feature of the present invention when PO oligomers are used as dispersants / detergents.

The test additive (30 g) is dissolved in a weight equivalent amount of reagent grade toluene, cooled to 20-40 ° C and maintained at this temperature for four weeks.

The sample solution is then examined for visual clarity ("brightness"). If anything precipitated solids. occurs or the sample is cloudy, the sample has not passed the test- '. ta. A sample that passes this test is described as "clear and bright", which is very *! a well-known standard used in the industry.

m

Example 46 • · ·

Epoxide Content Measurement: Nmr spectroscopy provides a method for measuring the "epoxide content" of the body of these additives. Ether carbons and related protons are easily separated and "calculated" by anyone.

• · · '^ The "epoxide readings" determined independently of each other from the carbon and proton Nmr spectra are averaged and have good reproducibility and are • · · • · · · · »„ «441 consistent with the experimental molar ratios we used and the mass equilibrium results of the reaction we obtained. The analysis of polyethers can be performed in the alcohol step or later with products.

5 Assays were performed using a Varian VXR-300.

The polyethers were dissolved "as is" in deuteromotylene chloride (30 mg / ml), and the proton FT-Nmr spectrum was determined according to the instrument parameters detailed below.

For the carbon FT-Nmr spectrum, the polyethers were also dissolved in deuteromethylene chloride (400 mg / ml) containing approximately 5 mg of the relaxant Cr (III) tris-acetylacetonate, i. Cr (III) (AcAc) 3: a. All spectra were determined using high performance 5 mm 15 Nmr tubes.

device conditions

Proton Carbon Detection Detection

Frequency 299.944 MHz 75.429 MHz 20 Spectrum width 5000 Hz 20492 Hz

Notification time 1.6 s 0.4 s

Sleep delay 2.0 s 2.0 s. Vibration width 14 '90 ° • · * ”Temperature Environment Environment · * · ϊ 25 Repeats 16 2048 • a

Rotation speed 20 Hz 24 Hz

FT size 16 K 32 K

a ·· Determination of imIntegral values

Proton Nmr Spectra 30 Aromatic protons (6.5 to 7.5 ppm) serve as an internal standard in this assay. When dealing with products derived from "high dialkylated" • * · phenols (20-25%), the integral value of this · * * region of the spectrum is divided by 3.75. This signal value per proton * 35 is then used to estimate the ether carbon proton content • · · • · i • * · 9 • · 6J 93441. Otherwise, this signal is characteristic of four aryl protons (phenols with <10% dialkylation) -

Ether protons of interest range from 3.2 to 4.0 ppm. Shown here is the mass of methylene and methine protons, which protons comprise separate multiplets observed for the first and last epoxide units of these polyethers. Half of the total number of PO-associated protons is detected in this region, while only 10 three-eighths of BO-associated protons are present there.

Carbon NMR spectra

Six aromatic carbons (105-160 ppm) serve as an internal standard in this assay. In this case, there is no need to make any corrections due to the presence of dialkylphenol.

Ether carbons of interest range from 60 to 80 ppm. Bearing in mind that only two-thirds of the detectable PO-associated carbons are calculated from this range (half of the BO polymers), the calculation for the determination of epoxy units is simple.

Example 47. Determination of the nature of the alkylphenyl group • · • · ♦ *. Analytical methods for the determination of the general nature of the alkylphenyl substituent • · · · ···· 25 9 9 9 9 '· 1: can be carried out as follows:

Alkylphenyl poly (oxyalkylene) aminocarbamate sample • (identified by infrared and Nmr spectroscopy)::: hydrolyzed using a strong base to give the corresponding polyoxyalkylene alcohol. Non-oxidative thermal decomposition further removes the polyether moieties, leaving an alkylphenol on the ice. This residue can then be • ♦ ♦ • examined by mass spectroscopy for the presence of tropylium ion particles. Alkylphenols tend to decompose so that the greater of the two (or three) benzyl substituents is eliminated in the formation of the observed phenol ion particles. Thus, tropylium ions evolved from simple α-olefins typically contain 1-3 carbon atoms more than belong to the aromatic ring-5 itself. In comparison, the same ionic particles evolved from the barbed alkyl phenols used in this invention, such as those obtained from the α-olefin oligomer, contain much more carbon atoms due to fragmentation at the benzylic positions. It is important to note that such tropylium ion particles are readily formed from alkylphenols, and high energy collision ionization can be too harsh a method in all cases. As a result, under forced conditions, more detailed information regarding the structure of the alkyl-15 moiety may be lost. In these cases, it is possible to study "low energy" collision ionization, which may be useful in detecting these tropylium ions. In any case, tropylium ions have a remarkable relative stability and appear as a base ion peak more often than not (peak relative intensity peak). See: Silverstein,

Bassler and Morril, Spectrometric Identification of Organic. Compounds. Wiley and Sons (New York, 1974), pp. 19-22.

* · • "Another less preferred but supportive lysis can be performed by carefully controlled oxidations of alkylphenol side chains. This is typically done by aqueous potassium permanganate acid:: * [: decomposition at pH conditions. designed to control the extent of the desired oxidative chain cleavage reactions If the alkylphenol is derived by alkylation with, for example, linear α-olefins, a bimodal distribution of low and high molecular weight alkanoic acids is obtained. However, if the phenol in question is a barbed alkylphenol, and the phenyl ring is attached to the center of the alkyl chain.

• · I

«· * • · 93441 64 ti, it is found that higher molecular weight alkane acids are found, although they do not form most of the products of the oxidation reaction. Thus, it would be expected that from the concentrated alkylphenol derived from the C10-α-ole-5 phenyl oligomer, the corresponding C7-9 alkanoic acids would be detected after decomposition. On the other hand, when the phenol obtained from the simple C20-α-olefin alkylation is studied, high molecular weight acid crystals are also formed and detected, which reflects the existence of these long chains in the original phenol.

It should be noted that due to the general severity of these reaction conditions, only small amounts of these heavier acids can be detected. However, by derivatization, they can be detected chromatographically. Together with other common values such as phenol molecular weight, degree of dialkylation, etc., this method may be informative.

Example 48

Determination of the average alkyl hydrocarbon content of alkylphenols

Chemical method

Once the hydroxyl content of a given phenol (mg KOH / g sample) has been determined, the molecular weight (MW) is calculated: MW = • ·. 56100 / hydroxyl amount, where 56100 is the molecular weight of KOH in the milligram.

• · • '· Since the phenol content of these products corresponds to 91 mass units, the difference (MW - 91) is due to the average hydrocarbon content.

Since these alkyl groups are saturated hydrocarbons, partitioning the fraction by 14 (units of mass of the -CH2 group) gives the center of the alkyl hydrocarbon atoms of the phenol. number.

• · »· · · · # · · ·» · «· · · · · · · · · 65 9 3 4 41

Spectroscopic method

Alternatively, Nmr analysis can be used to determine the average alkyl hydrocarbon content. Nmr analysis of the integrated xH spectra indicates the ratio of aryl-5 hydrogens to aliphatic hydrogens that can be used to estimate the average hydrocarbon content of phenol.

This information can also be obtained using the integrated 13C-Nmr spectra of these products. Thus, 10 numbers of aromatic carbons can be used as an internal standard to measure the average number of saturated carbons in phenol. Usually, the XH and 13C-Nmr results are averaged and are well consistent with the chemical assay.

It is assumed that the average alkyl hydrocarbon content of phenols does not change during the production reaction of alcohols, chloroformates and carbamates.

«• · · ψ ··· ·· ♦ · • 0» ♦ · • ♦ · * · »• I • ··« • ·· m 0 m φ V »·" 00 0 · 0 0 0 000 0 • 000 0 00 "0 · • · * 0 Ψ 0 0 0 0« • 0 0 0 0 0 0 • 00 0 0 0

Claims (15)

An alkylphenyl poly (oxypropylene) aminocarbamate of the formula / - / fl / Q \ - (nCH 2 CHO- ^ C-NHtl ^ NH 2 pH Rm 10 wherein R is a substantially unbranched alkyl group obtained from C 8-20 a substantially unbranched α-olefin oligomer of α-olefins, and R 1 is alkylene of 2 to 6 carbon atoms, m is an integer from 1 to 2, n is an integer such that the compound has a molecular weight of about 600 to 6000, and p is an integer from 1 to 6, and wherein said compound does not form a wax when cooled to -40 ° C in a 50% by weight toluene solution. A compound according to claim 1, characterized in that R is attached to the phenyl ring at least 6 carbon atoms from the end of the longest chain of said group R. • · · *. A compound according to claim 1, characterized in that R is a substantially unbranched • m m * · '! a chain alkyl group having from about 28 to about 50 m carbon atoms. »·· A compound according to claim 3, characterized in that R is a substantially straight chain alkyl group having from about 30 to 45 carbon atoms. atoms. * / · T A compound according to claim 1, characterized in that n is an integer from about 1 to about 100. A compound according to claim 5, characterized in that n is an integer from about 5 to 50. »*. · »« · »· · * V · 93441 A compound according to claim 6, characterized in that n is an integer of about 10 to 25. A compound according to claim 1, characterized in that the compound has an average molecular weight of about 1,000 to 2,500. A fuel composition comprising a hydrocarbon boiling in the range of gasoline or diesel and about 30 to 5000 parts per million of a compound as defined in any one of claims 1, 2, 3, 4, 5, 6, 7 or 8. A fuel concentrate comprising an inert stable oleophilic organic solvent boiling between 150 and 400 eF and 5 to 50 weight percent of a compound as defined in any one of claims 1, 2, 3, 4, 5, 6, 7 or 8. A lubricating oil composition comprising a lubricant viscosity. an oil and a dispersing effective amount of a compound as defined in any one of claims 1, 2, 3, 4, 5, 6, 7 or 8. A lubricating oil concentrate comprising about 20 to 50 weight percent of an oil having a lubricant viscosity and about 10 to 50 weight percent of a compound as defined in any one of claims 1, 2, 3, 4, 5, 6, 7 or 8. • · · ·: 13. Alkylphenol in which the alkyl group is obtained • · *.:! 25 of an α-olefin oligomer having a substantially unbranched chain of ca.20-α-olefins and attached to a phenolic ring at least 6 carbon atoms from the end of the longest chain of the alkyl group. Alkylphenol according to Claim 13, characterized in that the alkyl group contains about v · 28 to 50 carbon atoms. Alkylphenol according to claim 14, characterized in that the alkyl group contains about • ·. 30 to 45 carbon atoms. 35 • · 93441