CA1063611A

CA1063611A - Additive useful in oleaginous compositions

Info

Publication number: CA1063611A
Application number: CA242,514A
Authority: CA
Inventors: Jack Ryer; James Zielinski; Harold N. Miller; Stanley J. Brois
Original assignee: Exxon Research and Engineering Co
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 1975-01-23
Filing date: 1975-12-22
Publication date: 1979-10-02
Also published as: FR2298559A2; FR2298559B2; BE837843R; GB1547980A; IT1054792B

Abstract

ABSTRACT OF THE DISCLOSURE
Amine or polyol or alkylene oxide derivatives of Oxazoline reaction products of hydrocarbon substituted dicarboxylic acid, ester or anhydride, for example octadecenylsuccinic anhydride and polyisobutenyl-succinic anhydride with 2,2-disubstituted-2-amino-1-alkanols, such as tris-hydroxymethylaminomethane (THAM) are useful additives in oleaginous compositions, such as sludge dispersants for lubricating oil, or anti-rust agents for gasoline.

Description

)63~
~ACKGRO~ND OF THE INVENTION AND PRIOR AR~
During the past decade, ~shless sludge dispersants have become increasingly important, primarily in improving the performance of lubricants and gasoline in keeping the engine clean of deposits, and permitting extended crankcase oil drain periods. Most commercial ashless dispersants fall into several general categories. In one category, an amine or polyamine is attached to a long chain hydro-carbon polymer, usually polyisobutylene, obtained by the reaction of halogenated olefin polymer with polyamine as in U.S. Patents 3,275,554; 3,565,592; 3,565,804. In another category, a polyamine is linked to the polyisobutylene through an acid group, such as long chain monocarboxylic acid, e.g., see U.S. Patent 3,444,170 or long chain dicarboxylic acid such as polyisobutenylsuccinic anhydride, by forming amide or imide linkages, such as described in U.S. Patents ` 3,172,892; 3,219,666; etc. More recently, non-nitrogen ashless dis-., .
persants have been formed by esterifying long chain dicarboxylic acids; such as the polyisobutenylsuccinic anhydride, with polyols, such as pentaerythritol, as in U.S. Patent 3,381,022, Reaction products of hydrocarbon substituted succinic anhyd-ride, e.g., the aforesa;d polyisobutenylsuccinic anhydride, with com-pounds contain~ng both an am~ne group and a hydroxy group have been suggested or investigated in the prior art. For example, U.S. Patent 3,272,746 teaches the reaction of ethanolamine and diethanolamine, as well as~various hydroxyalkyl substituted alkylene amines, such as N- -(2-hydroxyethyl) ethylene dlamine, N,N'-bis(2-hydroxyethyl) ethylene diamine, with alkenyl succinic anhydride to obtain ashless dispersants for lube oil. A hydroxy amine~, such as diethanolamine, is reacted -~ ,with a long chain alkenylsuccinic anhydride in U.S. Patent 3,324,033 to form a mixture of esters ;~

2 --............ :, . ., , . i .~ , . , . , , .. ~ . . .

- "` lQ63~1~
.nd amides, wherein some of the diethanolamine reacts through a hydroxy group to give an ester linkagè, which another portion of the diethanolamine forms an amide linkage. U.S. Patent 3,364,001 teaches a tertiary alkanolamine reacted with an alkenyl succinic anhydride to form an ester useful as a ~asoline additive. U.S. Patent

3,~48,049 teaches dispersants, corrosion inhibitors and antiwear agents in lubricants and fuels by esterifying alkenyl succinic anhyd-ride with a hydroxy compound made by reacting an alkanolamine with an unsaturated ester, amide or nitrile.~ U.S. Patent 3,630,904 teaches reacting a hydroxy amine, with both short and long chain dicarboxylic acid. U.S. Patent 3,484,374 teaches the polymeric condensation pro-ducts of polycarboxylic acid or anhydride with various alkanolamines~
such as aminoethylethanolamine, N-methyldiethanolamine, etc. United Kingdom Specification 809,001 teaches corrosi~n inhibitors compElsing ;~ a multiple salt complex derived from the reaction product of hydro-carbyl substitut~d dicarboxylic acids and hydroxy amines (inc-luding 2-amino-2-methyl-1, 3-propanediol CAMP~ and tris hydroxy-methylamino-; . .
methane ~THAr~-) further complexed with mono- and polycarboxylic acids (see Examples 17-lg)-.
.
~20 U~S~ Patent 3,576,743``teaches reacting polyisobutenylsuccinic anhydride with a polyol, such as pentaerythritol, followed by reac-..
tion with THAM,~ ~see Example 1). U.S. ~atent 3,632, 511~teaches ~! polyisobutenylsuccinic anhydride with both a polyamine and polyhydric ~ alcohol including THAM. U.S. Patent 3,697,428 (Example 11) teaches `~ reacting polyisobutenylsuccinic anhydride with a mixture of penta-~ erythritol and T~AM. United Kingdom ~pecification 984,409 teaches `~ ashless, amide/imide/ester type lubricant additives prepared by re-acting an alkenyl succinic anhydride, said alkenyl group having 30 to 700 carbon atoms, with a hydroxy amine including r~HAM.
~`
: : ' - :

:. . . . .. . , ~ . . .. ... :. :.

~ 3~ ~
~ ,.. .

1 ~9~
2 A~ no~ed above, the prior art teaches dispersants 3 formed ~rom hydrocarbyl substituted dicarboxylic acid mater~

4 ial, usually alkenyl succinic anhydride, reacted with ~arious amino or hydroxy compounds either through an amida,imide or 6 ester linkage. In contrast to most of the prior art, the 7 present invention is based upon the discovery that reaction 8 of hydrocarbyl dicarboxylic acid material~ i.e. a,cid or ;9 anhydride, or ester, with certain classes of amino alcohols, under certain conditions, will result in a heterocycLic ring 11 Qtructure namely an oxazoline ring, a~d that materials with : .
:` . 12 this oxazoline ring including derivatives thereof can bè
`.: 13 tailored or various functions, such as anti-rust agents, - .
14 detergen~s, or dispersants. for oleaginous compositions in-cluding lube oil, gasoline, turbine oils and oils for drilling ..
. 16 applications~
"~. 17 : The derivative compounds of the inven~ion have at :~-. .
18 least 8 carbons in the subs~antially saturated aliphatio 19 hydrocarbyl group and at leas~ one carboxylic acid group con-. . . . .
verted into an oxazoline~ring as a result of the reac~ion o~
21 ~at least equimolar amounts of said~hydrocarbon substituted ~-22 - C~-clo mono-unsaturated dicarboxylic acid material and a 2,2- ~
.. . -. . . .
23 di.subs~ituted-2~am~no-1-al~anol having 2 to:3 hydroxy groups :~:
24 ~nd containing a total of 4 to 8 carbons followed by reac~ion ~.
: 25 with a third reactant ~o ~form th derivative, said reac~an~s ~:
6 including: amines; alkylene oxides; and glycols which react :;~X7 with~said oxazoline~containing compound whereby the ~multl-~ -28 functionality of the additive compound o the invention can be :~ 29 better tailored to its requlsi~e use.~ . -;~ .
`~:; 30 31 The:hydrocarbyl substituted dicarboxylic acid m~ter~
. ~. .
.
. .
...
~ ~ - . .. . .
. ',` .

. .

.. ... . .

" 1~6~61~
al, i.e., acid or anhydride, or ester, used in the invention in-cludes alpha-beta unsaturated C4 to C10 dicarboxylic acid, or anhyd-rides or esters thereof, such as fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, dimethyl fumarate, etc., which are substituted with a hydrocarbon chain containing at least 8 carbons, preferably a long hydrocarbon chain of at least 50 carbons (branched or unbranched) e.g. an olefin polymer chain.
In general, these hydrocarbyl substituted dicarboxylic acid materials and their preparation are well known in the art as wel~
as being commercially available, e.g., 2-octadecenylsuccinic anhydrid~
and polyisobutylenesuccinic anhydride.
The hydrocarbyl portion optlonally should average from at least about 16 carbon atoms per dicarboxylic acid group and be substantially saturated. Usually no more than 10 mole %, and prefer-ably 5 mole ~ or less of the total carbon to carbon linkage will be unsaturated, as excessive unsaturation in the final product will tend to oxidize and unduly form gums and resins in the engine. Further descriptions and examples of the hydrocarbyl substituent portion are ~ set forth in U.S. Patent 3,272,746, column 2, line 35 to column 4, ;`' 20 line 10. Further examples of the hydrocarbyl substituent portion are " set forth in U.S. Patent 3,458,444 which shows such dicarboxylic acids reacted wlth tertiary`amines to produce rust and sludge inhibitors.
Frequently these hydrocarbyl substituted dicarboxylic ` àcid materials are prepared by reacting the unsaturated dicarboxylic acid material, usually maleic anhydride with a~l-olefin, e.g. an ole-~i; fin polymer of at least 30 carbons still retaining a terminal un-saturatlon.
:: :
~` ~
1 , , ! :
. ., ~

, :

1`: : :

~ 5 -~ ~
!'. _ , .

f -- ~0~3~
rhe olefin polymer can, if desirt!d, be first halogenated, for exam-ple, chlorinated or brominated t-o about 2 to 5 wt. % chlorine, or about 4 to 8 wt. ~i bromine, based on the weight of polymer, and then reacted with the maleic anhydride (seé U.S. Patent 3,444,170).
In some cases, the olefin polymer may be completely saturated, for example an ethylene-propylene copolymer made by a Ziegler-Natta synthesis using hydrogen as a moderator to control molecular weight. In the case of such saturated polymers, then the polymer can be halogenated to make it reactive so it can be condensed with the unsaturated dicarboxylic acid material which is then random-ly added along the polymer chain.
Preferred olefin polymers for reaction with the unsatur-ated dicarboxylic acids are polymers comprising a ma~or molar amount f C2 to C5 monoolefin, e.g., ethylene, propylene, butylene, isobuty-lene and pentene. The polymers can be homopolymers such as polyiso-butylene, as well as copolymers of two or more of such olefins such as copolymers of~ ethylene and propylene; butylene and isobutylene;
propylene and isobutylene; etc. Other copolymers include those in which a minor molar amount of the copolymer monomers, e.g., 1 to 20 -mole ~i is a C4 to C18 non-conjugated diolefin, e.g., a copolymer of isobutylene and butadiene; or a copolymer of ethylene, propylene and .
`` 1,4-hexadiene; etc. ~
, ~ The olefin polymers will usually have number average - ~
` molecular weights within the range of about 750 and about 200,000, ;
; - more usually between about 1000 and about 20,000. Partlcularly use-~ ful olef~n polymers have number average molecular weights within the -~ range of about 900 and about 3000 with approximately one terminal 3 double bond per polymer chain~ An especially valuable starting mat-eria1 for a highly potent ,~

~ 6 ; .~ ' . ~.. . .... . .

~ispersant additive made in accordance with this inven-tion is poly-isobutylene.
Especially useful when it is desired that the dispersant additives also possess viscosity index improviny properties are 10,000 to 200,000, e.g., 25,000 to 100,000 number average molecular weight polymers. An especially preferred example of such a V.I.
improving polymer is a copolymer of about 30 to 85 mole % ethylene, about 15 to 70 mole ~ C3 to C5 mono-alpha-olefinl preferably propy lene, and 0 to 20 mole ~ of a C4 to C14 non-conjugated diene.
These ethylene-propylene V.I. improving copolymers or terpolymers are usually prepared by Ziegler-Natta synthesis methods, e.g., see U.S. Patent 3,551,336.
~.
Other halogenation techniques for attaching the dicar-boxylic acid material to a long hydrocarbon chain, involve first `
halogenating the unsaturateddicarboxylic acid material and then reacting with the olefin polymer, or by blowing halogen gas, e.g., chlorine, through a mixture of the polyoléfin and unsaturated dicar-boxylic acid material, then heating to 150 to 220C. in order to remove HCl gasj e.g., see U.S. Patents 3,381,'022 and 3,565,'804.

2 0 THE AMINO ALCOHOL : .
; ~ ~ The amino alcohol used to make the oxazoline dispersant ":: .
~ is a 2,2-disubstituted-2-amino'l-alkanol, having 2 to 3 hydroxy .,, :
~ ~ groups, containing a total of 4 to 8 carbon atoms, and which can be .: - ~
~ represented by the formula:`
~ ,: X
NH - C - CH OH
2 , 2 .~ , X
., ~
, `

i . . . .
~: .....

, , - 7 - ~-:~ .
~, ' ' ':

' ; ,`.' .. ' . ' ' ', " ' ' ' ~ ' ' ~ , ' , ', ' , ' ' ', .... ,. , ; ' . , ', .. ' ' ', " " ' ., ' ' ', ' ' . ' ' ' ,, ' ' :
' .~herein X is an ~lkyl, or hydrox~ alkyl group, with at least one of . the X substituents, and preferab3y both of the X substituents, being a hydroxy alkyl group of the structure -(CH2)nOH, wherein n is 1 to 3.
Examples of such 2,2-disubstituted amino alkanols, in-clude 2-ami.no-2-methyl-1,3-propanediol, 2-amino-2-thydroxy-methyl)-1,3-propanediol (also known~as tris-hydroxyaminomethane or THAM), 2-amino-2-ethyl-1,3-propanediol, etc. Because of its effectiveness, availability, and cost, the THAM is particularly prefer~red.
THE OXAZOLINE REACTION CONDITIONS
The formation of the novel oxazoline materials, in a fairly higher yield, can be effected by adding about 1 to 2 mole.
` equivalent of the aforesaid 2,2-disubstituted-2-amino-1-alkanol per . ~
mole equiva-lent of the dicarboxylic acid material, with or without an ~:
inert diluent, and heating the mixture at 140-240C~., preferably 170-~ 220C. or 1~2 to 24, more us.ually 2 to 8 hs.urs, followed by deriva-` ti.zation.
Although not`necessary, the presence of small amounts, such as .01-to 2 wt~. %, preferably 0.1 to 1 wt. %, based on the weight ~ ~ .
~, 20 of the reactants, of a metal salt can be used in the reaction mixture "~ as catalyst to shorten the reaction times. The metal catalyst can ~;~ later be removed by filtration or by washing a hydrocarbon solution -,. .of the product with a lower alcohol, such as methanol, ethanol, iso-~. propanol, etc., or an alcohol/water solution.
:
Alternatively, the metal salt can be left in the reaction mixture, as it appears to become stably dispersed, or dissolved, in i the reactlon product, and~depending on the 'i . ~ ' .'~ , ' ' :~ ' , .

~636~
.netal, it may even con-tribute pe,formance benefits to the oil or gas-oline. This is believed to occur with the use of zinc catalysts in lubricants.
Inert solvents which may be used in the above reaction include hydrocarbon oils, e.g., mineral lubricating oil, kerosene, neutral mineral oils, xylene, halogenated hydrocarbons, e.g., carbon tetrachloride, dichlorobenzene, tetrahydrofuran, etc.
Metal salts that may be used as catalysts in the inven-tion include carboxylic acid salts of Zn, Co, Mn and Fe. Metal catalysts derived from strong acids (HCl, sulfonic acid, H2SO4, HNO3, etc.) and bases, tend to diminish the yield of the oxazoline products and lnstead favor imide or ester formation. For this reason, these strong acid catalysts or basic catalysts are not preferred and usually will be avoided. The carboxylic acids used to prepare the desired catalysts, includé Cl to C18, e.g., Cl to C-8, acids, such as the saturated or unsaturated mono and dicarboxylic aliphatic hydrocarbon acids, particularly fatty acids. Specific examples of such desired .:
carboxylic acid salts include zinc acetate,~zinc formate, zinc pro-.
pionate, zinc stearate, manganese (ous) acetate, iron tartrate, cobalt (ous) acetate, etc. Completion of the oxazoline reaction càn .'`.' ~ , ~- be readily ascertained by using periodic infrared spectral analysis . ~i ` ~ for following the oxazoline formation (oxazoline peak forms at 6.0 ' ~ microns), or by the cessation of water evolution.
; ~
`~ ~ RE~CTION MECHANISM OF THE OXAZOLINE FORM~TION

While not known with complete certainty, but based on ; . :
experimental evidence, it is believed that the reaction of the hydro-~ . . .
carbyl substituted dicarboxylic acid material, e.g., a substituted succinic anhydride, with the amino alcohol of the invention, e.g., . ,....................................................................... ~ .
~ two equivalents of 2,2-disub-,.. _ g _ ....

~(36~

stituted-2-aminoethanol such as tris-hydroxymethylamino-methane (THAM), glves oxazoline, e.g., bis-oxazolines, via the intermedi-acy of several discrete reaction species. If an acid anhydride-is used, the initial transformation appears to involve the scission of the anhydride by the amino function of one mole of the amino alcohol to yield an amic acid. Addition of another mole equivalent of amino alcohol is believed to form the amic acid amine salt, which then upon further heating, undergoes cyclo-dehydration to the final bis-oxazoline product. The catalyst effect of metal salts, such as zinc acetate (ZnAc2), on oxazoline formation is very likely ascribable to the favourable polarization of the amide group by the zinc ion towards attack by the hydroxy function of the amino alcohol reactant. These reactions can be typified as follows in the case of bis-oxazoline:

\~ ' 2NH2C~ 2K \~NH '>'~ ~

~```` ~20 ~ X ~;

1 ~ ~R ~ 3 K2O
:~ "
~, /
f~ ' N~ X
. ~1 ' ~ '.

y :' `.: . '.': ` ' ' '' ~''` ' ' ' :`

where R is the hydrocarbyl group of the succinic anhydride, and each X in this case of using tris-hydroxymethylamino-methane (THAM) represents a -CH2OH group.
In contrast to the above oxazoline formation using the disubstituted amino alcohol, if the amino alcohol has no sub-stituents as in 2-aminoethanol, or has only one substituent in the 1- or 2-position as in 2-amino-1-propanol, 2-amino-1-butanol, and related mono-substituted 2-amino-ethanols, the amino alcohol fails to undergo the aforesaid oxazoline forming reaction.
Instead, these other amino alcohols will react with the sUccinic anhydride to give almost exclusively succinimide products as ; illustrated in the following reaction:

~ + NH2CHcH2oH > \~GNCHCH20H

R ~R R\ ~ ~ X
r ~ ~ NCH CHOH
~ + 2NH2CH2CHOH ~ ~ 2 -wherein R and X are as previoùsly defined. In experiments on the -above reactions, in no instance were discernible amounts of bis-oxazoline products found.
Condensation of about 1 mole equivalent of the disub-st~tuted alkanol per mole equivalent of said dicarboxylic acid .
material affords the mono-oxazoline ester.
- The reaction products of said alkanol and said dicar-boxylic acids, wherein the molar equivalent of the former in the react~on ranges from at least one to about two,~pre~erably .. ~ ` ' ;," ~

,~ - 1 1 - , '-, ~ , , . .:

: .
3~1~

dbout one, per mole equivalent, c,f the latter results in products which can be usefully reacted wi~:h reactants including amines, alky-lene oxides and polyols to produce the derivatives of the invention.
AMINES
Useful amine compounds for derivatization of the oxazo~
line additives according to this invention include amines of about 2 to 60, e.g. 3 to 20, total carbon atoms and about 1 to 12, e.g., 1 to 6 nitrogen atoms in the molecule, which amines rnay be hydrazines, or may include other groups, e.g., 1 to 4 hydroxyl groups, alkoxy ` 10 groups, amido groups, imidazoline groups and the like.
Preferred amines are aliphatic, saturated amines, and include those of the general formulae:
.,.
R-~-R" and R-N-(CH2)s~CN (C~l2)s ~t , ` R' R' ~ R' R' ; wherein R, R' and R" are independently selected from the group con-sisting of hydrogen; Cl to C12 straight or branched chain alkyl rad-icals; Cl to C12 alkoxy substituted C2 to C6 alkylene radicals; C2 to -~ C12 hydroxy or-~amino alkylene radicals; and Cl to C12 alkylamino substltuted C2 to C6 alkylene radicals; s is~-2~to 6, preferably 2 to 4; and t is 0 to 10, preferably 2 to 6.
` Examples of suitable amine compounds represented by the above include: n-octyl amine; n-dodecyl amine; di-(2-ethylhexyl) amine; 1,3-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane;
-diaminohexane; diethylene triamine; triethylene tetramine; tetra-ethylene penta-amine; 1,2-propylene diamine; di-(1,2-propylene) tri-. . , ~ amine; di(l,3-propylene) triamine; N,N-dimethyl-1,3~diaminopropane;
'~'`'.! N,N-di-(2-amino-ethyl) ethylene diamine; N,N-di-(2-hydroxyethyl)-1,3-propylene diamine`; 3-dodecyl oxy propylamine; N-dodecyl,1-3-propane diamine; diethanol amine; morpholine; trishydroxymethylamino-: ~, ' , , ' - 12 -:~ ;

'''' " . '' . ~ ~ ' . ' ;36~
ethane (THAM); diisopropanol am:irle; etc.
Still other useful c~mine compounds include: alicyclic diamines such as 1,4-di(aminomethyl) cyclohexane and he-terocyclic nitrogen compounds such as imidazolines and N-aminoalkyl piperazines of the genera] formula:
j H - CH
2 ( 2)p \ / N-G

,. . .
~ wherein G is independently selected from the group consisting of hydrogen and _f~ _-aminoalkylene radicals of from 1 to 3 carbon atoms; and p is an integer of from 1 to 4. Non-limiting examples include 2-pentadecylimidazoline; N-(2-amino-ethyl) piperazine; N~(3-aminopropyl) piperazine; and N,N' di(2-aminoethyl) piperazine.
~ Other alkylene amino compounds that can be used include dialkylaminoalkyl amine such as dimethylaminoethylamine, dimethylamino-propylamine, methylpropylaminoamylamine, etc. These may be character-; ized by the formula:
- R

H N - R - N~

~ \ R3 ; ~ wherein Rl is an alkylene radical, e.g., an ethylene, propylene, or butylene radical, and R2 and R3 are Cl to C5 alkyl radicals.
;~ Commercial mixtures of amine compounds may advantageously . ~, , be used for the preparation of the polyamino compositions of this invention. For example, one process for preparing alkyIene amines -. .~ , ~ , .
involves the reacti'on of an alkylene dihalide (such as ethylene,di-~, ~ - chloride or propylene dichloride) with ammonia, which results in a complex mixture of alkylene amines wherein pairs of nitrogens are ~-, joined by alkylene groups, forming such co~pounds as diethylene tri-S

,j . .. . . .. . . . . .

~ 6~61~
amine, triethylene tetramine, tetraethylene penta amine and :`' ~'., .; :, :: .
:'' ~ , ' : '' ' . . .
:: .
` ' , . ~ .
, :;, .
. .~
:~ . .
... . .
~ : :
: . ., ,;
~ ": ~: : ~ : .
. ' .. : .-:;~. ~: , . .
. ~ .
. ,~
.
: .~ .. , ~ : , ~ .
.:3 ., .

~ 3a -, isomeric piperazines. Low cost poly(ethylene amines) compounds having a composition approximating tetraethylene petamine are avail-able commercially under the trade names Polyamine H and Polyamine 400 (PA-400). A similar-mixture sold as Polyamine 500 (PA-500) is marketed by Jefferson Chemical Co., New York, N.Y. Similar materials may be made by the polymerization of aziridïne, 2-methylaziridine and azetidine.
; The more important alkylene polyamine or aliphatic poly-amine compound, used in this invention, can be broadly characterized as an alkylene amino compound containing from 2 to 12 nitrogen atoms where pairs of nitrogen atoms are joined by alkyléne groups of from 2 to 4 carbon atoms.
Reaction of the amine compound with the oxazoline addi-tive readily takes place in an inert solvent containing both compounds at a temperature in the range of about 400C. to 300C., preferably at a temperature in the range of 100C to 200C. Useful amine salts~
can be prepared by mixing the reactants at room temperature.
ALKYLENE OXIDES
~ .
: ~ . . . .
Oxazoline products~ with remaining carboxylic acid ` 20 groups, can be further reacted with 1 to 30, e.g. 1 to 10, moles of . ,~-, . . .
a C2 to C3 alkylene oxide, i.e. ethylene oxide or propylene oxide.

Generally, the reaction is carried out by adding the `

' alkylene oxide portionwise to the oxazoline additive at somewhat ele-vatéd temperatures. Temperatures within the range of 50 to 100C., . ,.~ ~ . .for example, are generally satisfactory and the alkylene oxide may be added conveniently beneath the surface, of a solution of oxazoline in inert solvent. The alkylene oxide reacts immediateIy as it is added, ~ I : . . .
~ and when it has all been added, the reaction is essentially complete.

Z It is be-, . . . ... . ..
. j. , .

`Z ~ ~ - 14 ~

3~ 1~

1 lieved that the alkylene oxides, particularly, can be usefully 2 reacted with the bis~oxazoline product.

4 The oil soluble oxazoline reaction products of this invention can be incorporated in a wide variety of oleaginous 6 compositions, They can be used in lubricating oil composi-7 t~ons, such as automotive crankcase lubrica~ing oils, automatic 8 transmission ~luids, etc. in concentrations generally within 9 the range o~ about 0.01 to 20 weigh~ percent, e.g.~ 0.1 to 10 weight percent, pre~erably .3 to 3.0 weight percen~, of the 11 total composition. The lubricants to which the oxazoline 12 products can be added include not only ~ydrocarbon olls de-13 rived from petroleum, but also include synthetic lubricating 14 oils such as poLyethylene oils; alkyl esters of dicarboxylic ~cid; complex esters of dica~boxylic acid, polyglycol and al~
16 cohol; alkyl esters o~ carbonic or phosphoric acids; poly-17 silicones; 1uorohydrocarbon oils; mixtures of mineral lubri~
18 cating oil and synthetic oils in any proportion, e~c.
19 When the products o~ this invention are used as multifunctional additi~es having detergents, anti-rus~ proper-" . i ~ 21 ties in petroleum fuels such as gasoline~ kerosene, diesel `; 22 uels, No. 2 ~uel oil and other middle distillates, a concentra-23 tion of the additi~e in the fuel in the range of 0.001 to 0.5 - 24 weight percent, based on the weight of the total composition9 .
`~ ~ 25 will usually be employed ..... .
`~ 26 - When used as an anti~oulant in oil ~treams in re~
27 inery operations to preven~ fouling of~process equipment such 28 as heat exohangers or in turbine oils, about 0.001 to 2 wt, ~/0 29 will generally be used, . ~ . , .
-` 30 The additive m~y be convenicntly dispensed as a con-31 cen~rate comprising a m~nr)r proportion Oe the additlve, e.g~
32 2 ~o ~5 parts by wel~ht, dissolve~in a m~r p~opo~t~on o~ a .,;~ . .
` - 15 -~ 36 ~ ~

1 mineral lubricating oil, e g., 98 ~o 45 parts by weight, 2 with or withou~ other additives being present.
3 In the above compositions or concentrates, other ; 4 conventional addLti~es n~y also ~e present inclwding dyes, pour point depressants, antiwcar agents such as tricresyl 6 phosphate or æinc dialkyldithiophosphates of 3 to 8 carbon 7 atoms in each alkyl group, antloxidants, such as N-phenyl 8 o~ -naphthylamine, tert-octylphenol sulfide, 4,4'-methylene 9 bis(2,6-di-tert-butyl phenol), viscosity index impro~7ers 0 such as ethylene-propylene copolymers, polymethacryliates, ll polyisobutyl~n~, alkyl fumarate-vinyl acetate copolymers and .:
12 the like, de-emulsifiers such as polysiloxanes, ethoxylated 13 polym~rs and the like. ;~
14 This invention will be further understood by reference to the following e~amples~ which include preferred 16 embodlments of the invention.
17 EX~MPLE 1 18 ~ ~ A mono-oxazoline o~ octadecenylsuccinic anhydride 19 and~tris-hydroxymethylaminomethane ~I~AM) was prepared as follows: ~
.. ~ , . :
21 ~ A mixture of 87.8 gm. (0~25 moles) of 2-octadecenyl~
22 ~ succinic~anhydr~de, 0.~5 gm. of zinc acetate dihydrate;
23 ~(ZnAc2.2H20) as a catalyst and 30. 75 gm. (0..25 mole~ o~ t _ -24 ~ hydroxymethylaminomethane (THAM) was charged into a laborato~y , i ~ , .
glass 1 liter reaction ~lask, equipped with a bottom draw-off, 26 a thermometer, a charging funnel, a nitrogen bleed, and an over-27 head condenser equipped with a Deane-Starke water trap. The 28 f~lask wss~heated in an oil bath. When the resction temperature ,.1 ~ , :
`~t ,;~ 29~ had risen~to 210C. the reaction was continued at this temper-- 30 ature until the evolution of~water ceased. A sample of the~
31 product was recrystallized from acetone/hexane solution and - 16 - ~ ~
;~ . : . -:
... .. . ..
. j . . . .
' .,i: ` ,;. .: '' -....

; ' ' ' ~ " ' ' ' ' . . ! ' . .

~6361~
submitted to elemental analysis ~hich showed 71.00 wt. % carbon (calculated 71.68 wt. %); 10.33 wt:. % hydrogen (calculated 10.41 wt.
%); and 4.12 wt. % nitrogen (calculated 3.22 wt. %). The calculation was based on C26H45NO4. The infrared spectrum of the product featur-ed strong ester and oxazoline absorption and at 5.75 and 6.0 microns, respectively. The molecular weight of the product by osmometry was ~ound to be 2324 (vapor phase osmometry).

Approximately 0.2 mole of polyisobutenylsuccinic anhyd-ride (Saponification No. 80) was charged into a reactor and heated to 205C. under a nitrogen blanket. To the stirred reactant were added 0.2 mole (2~.2 g;)-of tris-hydroxymethylaminomethane, in portions over an hour period. Thereafter, the mixture was stirred at 205C. for about 3 hours while water distilled from the reactor. Upon cooling, half of the reaction mixture was dissolved in an equal weight percent of Solvent 150 Neutral oil. The resulting oil solution was then di-luted with 500 ml. of hexane and the resulting hexane solution was washed three times, each with a 250 ml. portion of methanol. Roto-evaporation of the hexane layer afforded a concentrate which analyzed for 0.50 wt. % nitrogen and 2.37 wt. ~ oxygen, and featured a TAN
(total acid number)-of 0.16. The experimentally found O/N ratio of ~.7 was in excellent agreement with the theoretical O/N ratio of ~.6.
Furthermore, a strong absorption band at 6.0 microns in infrared .,^ , ; .
spectrum of the product indicated a mono-oxazoline structure formed.
Another strong absorption band at 5.75 micron indicated an ester struc-ture had also formed, which is believed to be between one of the hyd- -roxy groups extending from an oxazoline ring with a carboxy group of the polyisobutenylsuccinic anhydride.

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, 2 1335 ~rams of polyisobutenylsuccinic anhydride 3 havirlg a Sap. No. of about 80 was charged into a 1 liter 4-4 necked flask, and hea~ed to 205C. The reactant was stirred S under a nitrogen sparge and blanket and 121 grams of tris-6 hydroxymethylaminomethane were added over a 1 hour period, `7-~ being careful to avoid foaming. The course o~ reaction was 8 monitored by infrared-spectroscopy, which indicated that the 9 reaction was essentially complete after eight hours. The neat product analyzed for 1.12 wt. % nitrogen and ~eatured a num-11 ber average molecular weight of 3034 (by vapor pressure osmom- -12 etry). The infrared spectrum of the product showed the ~x-13 pected ester and oxazolin~ bands at 5.75 and 6.02 microns, re~
14 spectively.
EXAMPT.E _ 16 53.4 pounds of polyisobutenylsuccinic anhydride 17 (PIBSA) with a Sap. No. of about 80 W2S charged into a reac-18 tor and heated to 435F. The PIBSA reactant ~7as stirred and 19 sparged with nitrogen, and 4.84 pounds of t _ -hydroxymethyl- -20 ~aminomethane were added over an hour period. Reaction was con 2~ tinued until water evolution had ceased. The product was di-22 luted with an equal weight o Solven~ 150 Neutral Oil and ~3 8ho~ed ester and oxazoline a~sorptions in the infrared. The oil 24 80lution analyzed or 0.51 wt.~/~ nitro~en and by infrared measurement ~ndicated that about 99% o~ the I~M had been con~
26 verted into the o~azoline structure. Similarly the products 27 o~ Examples 1, 2 and 3 upon infrared measurement indicated 28 that about 100%, 95% and 98% of the T~M, respect~vely, had 29 been converted~lnto the oxazoline s~ructure.
In Example5 2-4 the PIBSA had been prepared by con-31 vent~onal techniques, namely the reactLon o chLorinated poly~

~32 isobutylene h~ving a chlorine content o~ abo-t 3.8 wt. %, baseci ,~

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63tj~1 on the weight of chlorinated pol~isobutylene, and an average o~ 70 carbon atoms in the polyisobutylene group, with maleic anhydride at about 200C. The resulting polyisobutylenesuccinic anhydride showed a saponification number of 80 m~ KOH/gm. The molecular weight of the polyisobutylene group of said PIBSA was 980 as measured by vapor phase osmometry.

Approximately 0.05 moles (71 grams) of the mono-oxazoline reaction product of polyisobutenylsuccinic anhydride (0.2 mole) and lQ tris-hydroxymethylaminomethane (0.2 mole) was dissolved in 50 ml.` of xylene using a 500 ml. 4-necked flask. To this solution was added 0.05 moles (9.5 grams) of tetraethylene pentamine (a commercially available polyamine containing 32.38 wt. % of nitrogen) designated as Polyamine E-100 and sold by Dow Chemical. Reflux was carried out at 145C. for 3 hours utilizing a Dean Starke trap. The xylene was removed after which the product was heated to 190C. for 1.5 hours and thereafter recovered.
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The process of Example 5 was carried out except that : , .
^-~ 20 ~ the 0.05 moles of tetraethylene pentamine was replaced by 0.05 moles of diethylene triamine.
` EXAMP_E 7 ., ~
The process of Example 5 was carried out except that the 0.05 moles of tetraethylene pentam~ne was replaced by 0.05 moles : .^, '~ ~ of diethylene glycol.
Infrared analysis of the products of Examples 5 and 6 . ~ '. ', . .
showed the presence of the oxazoline ring at substantially the same ~ -;1 level and disappearance of the ester linkage extant in said mono-oxa-, .
~ zoline reaction products.
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The products of Examples 5, 6 and 7 were tested for their effectiveness as gasoline anti-rust agents. Each product :
was first dissolved in xylene, and the solution was added to the gasoline to incorporate the additiveat a treat rate of 12 pounds of oxazoline additive per thousand barrels of gasoline. The gaso-line so treated was then tested for rust according to ASTM-D-665M
rust test. In brief, this test is carried out by observing the :
amount of rust that forms on a steel spindle after rotating for an hour in a water-gasollne mixture. In each case, the oxazoline treated gasoline gave no rust indicating that each product was very effective as an anti-rust additive since the untreated gaso-line will give rust over the entire surface of the spindle.
The oxazoline reaction products of the invention which . are primarily useful as an anti-rust additive and/or detergent for - .
gasoline will generally have hydrocarbyl substituents numbering . from about 12 to about 49 carbons (preferred is about 18 as exemp-.~ lified by 2-octadecenyl); whereas, for applications as a disper-, sant or detergent ln lubrlcants it is preferred that the hydro-carbyl substituents number from:at least 30 carbons, e.g., at least 45 carbons.:
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Thé chemical structure, number of the oxazoline rings and character of the derivative have an influence on the function-ality.of the.additive compounds of the invention.
In summary,.effective additives for oleaginous compo-sitions~can be prepared by reaction of a hydrocarbon substituted dicarboxylic acid mater~ial with a 2,2-disubstituted-2-amino 1- .:
. alkanol under conditions such that formation of simple esters,imides ~ :
:1 or amides `is elimated, or at leàst minimized, so that a substantial -.~
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proportion of the amino alkanol is converted into oxazoline rings.
Infrared spectrum on some of the aforesaid Examples indicate that a major proportion, i.e. from about 90% to about all of the amino-alkanol was converted to oxazoline rings.
As evidenced by the Example 7, it is seen that ester derivatives oE the oxazoline reaction products can be produced.
In a~dition to the diethylene glycol of Example 7 other polyols such as pentaerythritol, trimethylol propane, ethylene glycol, propylene glycol, cellosolve*, carbitol, etc. can be used to prepare the ester derivatives.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A hydrocarbon-soluble derivative of the oxazoline reaction product of a substantially saturated aliphatic hydrocarbyl-substituted C4-C10 dicarboxylic acid material selected from the group consisting of acids, acid anhydrides and esters having at least about 8 carbon atoms in said hydrocarbyl group with from about 1 to about 2 mole equivalent, per mole equivalent of said dicarboxylic acid material, of a 2,2-disubstituted-2-amino-1-alkanol having 2 to 3 hydroxy groups and containing a total of 4 to 8 carbons, and which is represented by the formula:

wherein X is an alkyl or hydroxyl alkyl group, with at least one of the X
substituents being a hydroxyl alkyl group of the structure - (CH2)nOH
wherein n is 1 to 3, said reaction conditions being at a temperature of from about 140 to 240°C for from ? to 24 hours whereby at least one carboxylic acyl group is converted into an oxazoline ring, said reaction product being derivatized by reaction with (a) an aliphatic, saturated amine containing 2 to 60 carbon atoms and 1 to 12 nitrogen atoms and having the general formulae or wherein R, R' and R" are independently selected from the group consisting of hydrogen; C1 to C12 straight or branched chain alkyl radicals; C1 to C12 alkoxy substituted C2 to C6 alkylene radicals; C2 to C12 hydroxy or amino alkylene radicals; and C1 to C12 alkylamino-substituted C2 to C6 alkylene radicals; s is 2 to 6 and, t is 0 to 10, or (b) a polyol or (c) an alkylene oxide.

2. The derivative according to claim 1 wherein said oxazoline reaction product is the monooxazoline product of an alkenyl-succinic anhydride or acid which has been reacted with about one mole equivalent of trishydroxymethylaminomethane, said alkenyl substitutent having a number average molecular weight within the range of about 1000 to about 20,000.

3. The derivative according to claim 1 wherein said oxazoline reaction product is the monooxazoline product of hydrocarbon-substituted succinic anhydride reacted with about one mole equivalent of tris-hydroxy-methylaminomethane, said monooxazoline being further derivatized by reaction with about a molar proportion of an alkylene polyamine containing 2 to 12 nitrogen atoms, and wherein pairs of nitrogen atoms are joined by alkylene groups of 2 to 4 carbon atoms.

4. The derivative according to claim 3 wherein said alkylene polyamine is tetraethylene pentamine.

5. The derivative according to claim 3 wherein said alkylene polyamine is diethylene triamine.

6. The derivative according to claim 1 wherein said hydrocarbon-substituted succinic anhydride is octadecenyl succinic anhydride.

7. The derivative according to claim 1 wherein said hydrocarbon-substituted succinic anhydride is polyisobutenyl succinic anhydride having a number average molecular weight in the range of 900 to 3000.

8. The derivative according to claim 1 wherein said reaction product comprises a monooxazoline further derivatized by reaction with said amine or polyol.

9. A derivative according to claim 8 wherein said monooxazoline is further reacted with a polyol selected from the group consisting of diethylene glycol, pentaerythritol, trimethylol propane, ethylene glycol or propylene glycol.

10. A derivative according to claim 1 wherein said alkylene oxide is a C2 to C3 alkylene oxide.

11. An oleaginous composition comprising a major amount of an oily material and a minor amount of the derivative of claim 1.

12. An oleaginous composition comprising a major amount of an oily material and a minor amount of the derivative of claim 2.

13. An oleaginous composition comprising a major amount of an oily material and a minor amount of the derivative of claim 3.

14. An oleaginous composition comprising a major amount of an oily material and a minor amount of the derivative of any one of claims 4, 5 or 6.

15. An oleaginous composition comprising a major amount of an oily material and a minor amount of the derivative of any one of claims 7, 8 or 9.

16. An oleaginous composition according to any one of claims 11, 12 or 13 wherein said oily material is a mineral lubricating oil, and the amount of said derivative is in the range of about 0.01 to 10 wt.% based on the total weight of said composition.

17. An oleaginous composition according to any one of claims 11, 12 or 13 wherein said oily material is a hydrocarbon fuel containing about .001 to 0.5 wt.%, based on the weight of the total composition, of said derivative.

18. An oleaginous composition according to any one of claims 11, 12 or 13 wherein said oily material is a gasoline containing about 0.001 to 0.5 wt.%, based on the weight of the total composition, of said derivative.