Note: Descriptions are shown in the official language in which they were submitted.
)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 -
:. . . . .. . , ~ . . .. ... :. :.
~ 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 '>'~ ~
OH NH2CCH2H
~```` ~20 ~ X ~;
1 ~ ~R ~ 3 K2O
:~ "
~, /
f~ ' N~ X
. ~1 ' ~ '.
y :'
1 0
`.: . '.': ` ' ' '' ~''` ' '
' :`
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
CH2 - CH2
,. . .
~ 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: ~
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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
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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
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`~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
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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).
EXAMPLE 2
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
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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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1 EXAMRLE 3
,
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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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.
EXAMPLE 5
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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EXAMPLE 6
The process of Example 5 was carried out except that
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^-~ 20 ~ the 0.05 moles of tetraethylene pentamine was replaced by 0.05 moles
of diethylene triamine.
` EXAMP_E 7
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The process of Example 5 was carried out except that
the 0.05 moles of tetraethylene pentam~ne was replaced by 0.05 moles
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'~ ~ of diethylene glycol.
Infrared analysis of the products of Examples 5 and 6
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showed the presence of the oxazoline ring at substantially the same ~ -
;1 level and disappearance of the ester linkage extant in said mono-oxa-
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~ 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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* Trade Mark
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