U.S. patent number 3,859,318 [Application Number 05/222,671] was granted by the patent office on 1975-01-07 for products produced by post-treating oil-soluble esters of mono- or polycarboxylic acids and polyhydric alcohols with epoxides.
This patent grant is currently assigned to The Lubrizol Corporation. Invention is credited to William M. Lesuer.
United States Patent |
3,859,318 |
Lesuer |
January 7, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
PRODUCTS PRODUCED BY POST-TREATING OIL-SOLUBLE ESTERS OF MONO- OR
POLYCARBOXYLIC ACIDS AND POLYHYDRIC ALCOHOLS WITH EPOXIDES
Abstract
A process for post-treating oil-soluble esters of mono- or
polycarboxylic acids and polyhydric alcohols with organic epoxides.
The acyl moiety of the esters is derived from mono- or
polycarboxylic acids containing at least about fifty aliphatic
carbon atoms exlusive of the carboxyl carbon atoms. The products
are useful as lubricant and fuel additives. A typical example of
the process would be the post-treatment of a diester of
polyisobutenyl1-substituted succinic acid and sorbitol with
propylene oxide.
Inventors: |
Lesuer; William M. (Cleveland,
OH) |
Assignee: |
The Lubrizol Corporation
(Wickliffe, OH)
|
Family
ID: |
26917034 |
Appl.
No.: |
05/222,671 |
Filed: |
February 1, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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826015 |
May 19, 1969 |
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712606 |
Mar 13, 1968 |
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567052 |
Jul 22, 1966 |
3522179 |
Jul 28, 1970 |
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567320 |
Jul 22, 1966 |
3381022 |
Apr 30, 1968 |
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567052 |
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274905 |
Apr 23, 1963 |
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567320 |
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274905 |
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Current U.S.
Class: |
560/198; 554/149;
554/150; 554/172; 554/226; 560/200; 508/223; 536/115; 554/151;
554/223; 554/227 |
Current CPC
Class: |
C10M
129/95 (20130101); C08G 65/2615 (20130101); C10L
1/1817 (20130101); C10L 1/198 (20130101); C10M
2209/084 (20130101); C10M 2225/00 (20130101); C10M
2213/00 (20130101); C10M 2213/04 (20130101); C10M
2207/404 (20130101); C10M 2209/109 (20130101); C10M
2219/044 (20130101); C10N 2010/04 (20130101); C10M
2225/02 (20130101); C10M 2225/041 (20130101); C10M
2209/105 (20130101); C10M 2217/023 (20130101); C10M
2207/40 (20130101); C10M 2219/024 (20130101); C10M
2205/026 (20130101); C10M 2207/34 (20130101); C10M
2223/047 (20130101); C10M 2209/104 (20130101); C10M
2213/06 (20130101); C10M 2209/106 (20130101); C10M
2223/045 (20130101); C10M 2207/282 (20130101) |
Current International
Class: |
C10L
1/198 (20060101); C10M 129/95 (20060101); C08G
65/26 (20060101); C08G 65/00 (20060101); C10L
1/18 (20060101); C10L 1/10 (20060101); C10M
129/00 (20060101); C07c 069/32 (); C07c 069/40 ();
C10m 003/20 () |
Field of
Search: |
;260/408,485G,410.6
;252/56S,56D |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gotts; Lewis
Assistant Examiner: Rivers; Diana G.
Attorney, Agent or Firm: Adams, Jr.; J. Walter Hoback; Karl
F.
Parent Case Text
This is a continuation of copending application Ser. No. 826,015
filed May 19, 1969 now abandoned which, in turn is a division of
application Ser. No. 712,606 filed Mar. 13, 1968, now abandoned,
which is a continuation-in-part of my earlier filed applications
Ser. No. 567,052 and 567,320 filed on July 22, 1966, these being,
respectively, a continuation-in-part and a continuation of
application Ser. No. 274,905, filed Apr. 23, 1963, and now
abandoned. Ser. No. 567,320 has issued Apr. 30, 1968, as U.S. Pat.
No. 3,381,022, and Ser. No. 567,052, issued July 28, 1970, as U.S.
Pat. No. 3,522,179. Lubricants and fuels containing the
compositions of this invention are the subject of application Ser.
No. 866,084 filed Oct. 3, 1969, now U.S. Pat. No. 3,579,450; Ser.
No. 866,084 being a continuation of Ser. No. 712,606.
Claims
What is claimed is:
1. An oil-soluble reaction product produced by a process comprising
contacting at a temperature of from about 25.degree.C. up to about
the decomposition temperature (A) at least one oil-soluble ester of
a mono- or polycarboxylic acid and a polyhydric alcohol having at
least three hydroxyl groups wherein the carboxylic acid moiety of
the ester is characterized by a substantially saturated, aliphatic
hydrocarbon radical, which is substantially free of
oil-solubilizing pendent groups and has at least about 50 aliphatic
carbon atoms exclusive of the carboxyl carbon atoms, and the
alcohol moiety contains up to about 40 aliphatic carbon atoms; with
(B) at least one organic epoxide having up to about 40 carbon atoms
and corresponding to the formula ##SPC2##
where each R is independently hydrogen or an aliphatic,
cycloaliphatic or aromatic radical; the amount of (A) and (B) in
the reaction mixture being such that the ratio of equivalents of
alcohol present in the ester to equivalents of epoxide is about
1:0.05 to about 1:5.
2. An oil-soluble reaction product according to claim 1 where (A)
and (B) are contacted at a temperature within the range of about
50.degree.-250.degree.C. and (B) is at least one organic epoxide
wherein each R is independently hydrogen, alkyl, haloalkyl,
cycloalkyl, halocycloalkyl, aryl, haloaryl where the haloalkyl,
halocycloalkyl, and haloaryl groups have no more than one halogen
radical for every 3 carbon atoms.
3. An oil-soluble reaction product according to claim 2 where (B)
is at least one aliphatic epoxide containing 2 to 8 carbon
atoms.
4. An oil-soluble reaction product according to claim 3 where (B)
is at least one terminal aliphatic epoxide.
5. An oil-soluble reaction product according to claim 4 where (A)
is at least one ester of a monocarboxylic acid and (A) and (B) are
contacted at a temperature of about 70.degree.-200.degree.C.
6. An oil-soluble reaction product according to claim 5 where (A)
is an ester of a polyhydric aliphatic alcohol of up to 10 carbon
atoms, and characterized by the presence of at least three hydroxyl
groups.
7. An oil-soluble reaction product according to claim 6 wherein the
polyhydric aliphatic alcohol is a polyhydric alkanol of up to 6
carbon atoms, the aliphatic epoxide is ethylene oxide or propylene
oxide, and said ratio of equivalents is about 1:0.1 to about
1:2.
8. An oil-soluble reaction product according to claim 7 wherein the
polyhydric aliphatic alcohol is selected from the class comprising
glycerol, erythritol, pentaerythritol, mannitol, and sorbitol.
9. An oil-soluble reaction product according to claim 4 where (A)
is at least one ester of a dicarboxylic acid and (A) and (B) are
contacted at a temperature of about 70.degree.-200.degree.C.
10. An oil-soluble reaction product according to claim 9 where (A)
is an ester of a hydrocarbon-substituted or chlorinated
hydrocarbon-substituted succinic acid wherein the substituent is
substantially saturated and contains at least about fifty aliphatic
carbon atoms.
11. An oil-soluble reaction product according to claim 10 where (A)
is a diester of a polyolefin-substituted succinic acid wherein the
polyolefin substituent has a molecular weight of about 700 to about
5000 and not more than about 5% of the carbon-to-carbon covalent
linkages in this substituent are unsaturated linkages.
12. An oil-soluble reaction product according to claim 11 where (A)
is a diester of a polyhydric aliphatic alcohol up to 10 carbon
atoms which alcohol is characterized by the presence of at least
three hydroxyl groups.
13. An oil-soluble reaction product according to claim 12 wherein
the polyhydric aliphatic alcohol is a polyhydric alkanol of up to 6
carbon atoms, the aliphatic epoxide is ethylene oxide or propylene
oxide, and said ratio of equivalents is about 1:0.1 to about
1:2.
14. An oil-soluble reaction product according to claim 13 where (A)
is a diester of polyisobutene-substituted succinic acid with a
polyhydric alkanol selected from the class consisting of glycerol,
erythritol, pentaerythritol, mannitol, and sorbitol.
15. An oil-soluble reaction product according to claim 4 produced
by contacting (A) with (B) where (A) is at least one ester of a
mono- or polycarboxylic acid where the acyl moiety of said mono- or
polycarboxylic acid corresponds to the acyl moiety derived from the
reaction at a temperature within the range of about
100.degree.-300.degree.C. of (1) an unsaturated carboxylic acid of
the formula R.sub.o -(COOH).sub.n or the corresponding acyl halides
or anhydrides where R.sub.o is characterized by the presence of at
least one ethylenically unsaturated carbon-to-carbon covalent bond
in an .alpha.,.beta.-position with respect to at least one carboxyl
function and n is an integer of one to six with (2) an
ethylenically unsaturated hydrocarbon containing at least about
fifty aliphatic carbon atoms or a chlorinated hydrocarbon
containing at least about 50 aliphatic carbon atoms, wherein (A)
and (B) are contacted at a temperature of about
70.degree.-200.degree.C.
16. An oil-soluble reaction product according to claim 15 where the
acyl moiety is derived from the reaction of (1) an unsaturated
carboxylic acid of the formula R.sub.o --(COOH).sub.n or its
corresponding acyl halides or anhydrides where R.sub.o is
characterized by the presence of at least one ethylenically
unsaturated carbon-to-carbon covalent bond in an
.alpha.,.beta.-position with respect to at least one carboxyl
function, n is one or two and the total number of carbon atoms in
R.sub.o --(COOH).sub.n does not exceed 10 with (2) polymerized
1-monoolefins or chlorinated polymerized 1-monoolefins.
17. An oil-soluble reaction product according to claim 16 where (A)
is at least one ester of a polyhydric aliphatic alcohol of up to 10
carbon atoms characterized by the presence of at least three
hydroxyl groups.
18. An oil-soluble reaction product according to claim 17
containing about 0.5% to about 10% by weight of the composition
produced by contacting (A) with (B) wherein the total number of
carbon atoms in R.sub.o --(COOH).sub.n does not exceed six and
where (2) is polyisobutylene or chlorinated polyisobutylene.
19. An oil-soluble reaction reaction product according to claim 18
where (A) is at least one ester of a polyhydric alkanol of up to 6
carbon atoms and (B) is selected from the group consisting of
ethylene oxide or propylene oxide, the ratio of equivalents of (A)
to (B) being about 1:0.1 to about 1:2.
Description
This invention relates to a process for treating carboxylic acid
esters, to the compositions of matter resulting from this process,
and to lubricants and fuels containing these compositions of
matter. In particular, the invention is concerned with the
post-treatment of esters of high molecular weight carboxylic acids
with organic epoxides, the compositions of matter which results
from treating the esters with the epoxides, and to lubricants and
fuels containing these compositions.
The prior art discloses many esters of high molecular weight
carboxylic acids as useful additives in fuel and lubricant
compositions, for example, French Pat. No. 1,396,645; British Pat.
Nos. 981,850 and 1,055,337; and U.S. Pat. Nos. 3,255,108;
3,311,558; 3,331,776; and 3,346,354. The present invention is
directed to a process for post-treating esters of this general type
with at least one organic epoxide to provide novel compositions of
matter also useful as additives in lubricant and fuel
compositions.
In accordance with the foregoing, it is a principal object of this
invention to provide a novel chemical process.
A further object of the invention is to provide a process for
post-treating certain esters with organic epoxides.
An additional object is to provide novel compositions of matter
resulting from the post-treatment of certain carboxylic acid esters
with organic epoxides.
A still further object is to provide lubricants and fuels
containing compositions produced by post-treating certain esters
with organic epoxides.
These and other objects of this invention are accomplished by
providing a process comprising contacting (A) at least one
oil-soluble ester of a mono- or polycarboxylic acid and a
polyhydric alcohol where the carboxylic acid moiety of the ester is
characterized by at least about fifty aliphatic carbon atoms
exclusive of the carboxyl carbon atoms and the alcohol moiety
contains up to about 40 aliphatic carbon atoms with (B) at least
one organic epoxide, the amount of (A) to (B) in the reaction
mixture being such that the ratio of equivalents alcohol present in
the ester to equivalents of epoxide is about 1:0.05 to about 1:5.
The compositions produced by this process, the process, and
lubricants and fuels containing the compositions are described in
more detail hereinafter.
The esters to be post-treated with the organic epoxides according
to the process of the present invention are esters of mono- and
polycarboxylic acids containing at least about fifty aliphatic
carbon atoms exclusive of the carboxyl carbon atoms. The alcohol
moiety of the esters contemplated is derived from a polyhydric
alcohol containing up to about 40 aliphatic carbon atoms. These
esters are known in the prior art or can be readily prepared from
available intermediates according to conventional procedures. Since
the foregoing enumerated patents disclose many esters of this type
and various processes for their preparation, these patents are
incorporated herein for the sake of brevity.
For the most part, these patents are directed to esters of
substituted succinic acids and aliphatic polyhydric alcohols.
However, the present invention contemplates the post-treatment of
similar esters prepared from monocarboxylic acids as well as
polycarboxylic acids other than succinic acids. Such esters can be
prepared from these mono- and polycarboxylic acid acylating agents
and the appropriate aliphatic alcohols by following the same
general procedure as used in the preparation of the succinic acid
esters in the above patents.
The acyl radical of the esters to be treated by the process of this
is derived from a mono-or polycarboxylic acid. One particularly
important characteristic of the acyl radical is its size. Thus, the
radical should contain at least about 50 aliphatic carbon atoms
exclusive of the carboxyl carbon atoms. This limitation is based
upon both oil-solubility considerations and the effectiveness of
the compositions as additives in lubricants and fuels. Another
important aspect of the acyl radical is that it preferably should
be substantially saturated, i.e., at least about 95% of the total
number of the carbon-to-carbon covalent linkages therein preferably
should be saturated linkages. In an especially preferred aspect of
the invention, at least about 98% of these covalent linkages are
saturated. Obviously, all of the covalent linkages may be
saturated. A greater degree of unsaturation renders the esters more
susceptible to oxidation, degradation, and polymerization and this
lessens the effectiveness of the final products as lubricant and
fuel additives.
In addition, the acyl radical of the esters should be substantially
free from oil-solubilizing pendant groups, that is, groups having
more than about six aliphatic carbon atoms. Although, some such
oil-solubilizing pendant groups may be present, they preferably
will not exceeds one such group for every 25 aliphatic carbon atoms
in the principal hydrocarbon chain of the acyl radical.
The acyl radical may contain polar substituents provided that the
polar substituents are not present in proportions sufficiently
large to alter significantly the hydrocarbon character of the
radical. Typical suitable polar substituents are halo, such as
chloro and bromo, oxo, oxy, formyl, sulfonyl, sulfinyl, thio,
nitro, etc. Such polar substituents, if present, preferably will
not exceed 10% by weight of the total weight of the hydrocarbon
portion of the carboxylic acid radical exclusive of the carboxyl
group.
Carboxylic acid acylating agents suitable for preparing the esters
are well-known in the art and have been described in detail, for
example, in U.S. Pat. Nos. 3,087,936; 3,163,603; 3,172,892;
3,189,544; 3,219,666; 3,272,746; 3,288,714; 3,306,907; 3,331,776;
3,340,281; 3,341,542; and 3,346,354. In the interest of brevity,
these patents are incorporated herein for their disclosure of
suitable mono- and polycarboxylic acid acylating agents which can
be used for the preparation of the esters used as starting
materials in the present invention.
As disclosed in the foregoing patents, there are several processes
for preparing the acids. Generally, the process involves the
reaction of (1) an ethlenically unsaturated carboxylic acid, acid
halide, or anhydride with (2) an ethylenically unsaturated
hydrocarbon containing at least about 50 aliphatic carbon atoms or
a chlorinated hydrocarbon containing at least about 50 aliphatic
carbon atoms at a temperature within the range of about 100.degree.
- 300.degree. C. The chlorinated hydrocarbon or ethylenically
unsaturated hydrocarbon reactant can, of course, contain polar
substituents, oil-solubilizing pendant groups, and be unsaturated
within the general limitations explained hereinabove. It is these
hydrocarbon reactants which provides most of the aliphatic carbon
atoms present in the acyl moiety of the final products.
When preparing the carboxylic acid acylating agent according to one
of these two processes, the carboxylic acid reactant usually
corresponds to the formula R.sub.o -- (COOH).sub.n, where R.sub.o
is characterized by the presence of at least one ethylenically
unsaturated carbon-to-carbon covalent bond and n is an integer from
one to six and preferably one or two. The acidic reactant can also
be the corresponding carboxylic acid halide, anhydride, ester, or
other equivalent acylating agent and mixtures of one or more of
these. Ordinarily, the total number of carbon atoms in the acidic
reactant will not exceed 10 and generally will not exceed six.
Preferably the acidic reactant will have at least one ethylenic
linkage in an .alpha., .beta. -position with respect to at least
one carboxyl function. Exemplary acidic reactants are acrylic acid,
methacrylic acid, maleic acid, maleic anhydride, fumaric acid,
itaconic acid, itaconic anhydride, citraconic acid, citraconic
anhydride, mesaconic acid, glutaconic acid, chloromaleic acid,
aconitic acid, crotonic acid, methylcrotonic acid, sorbic acid,
3-hexenoic acid, 10-decenoic acid, and the like. Due to
considerations of economy and availability, these acid reactants
usually employed are acrylic acid, methacrylic acid, maleic acid,
and maleic anhydride.
As is apparent from the foregoing discussion, the carboxylic acid
acylating agents may contain cyclic and/or aromatic groups.
However, the acids are essentially aliphatic in nature and in most
instances, the preferred acid acylating agents are aliphatic mono-
and polycarboxylic acids, anhydrides, and halides.
The substantially saturated aliphatic hydrocarbon-substituted
succinic acid and anhydrides are especially preferred as acylating
agents in the preparation of the esters used as starting materials
in the present invention. These succinic acid acylating agents are
readily prepared by reacting maleic anhydride with a high molecular
weight olefin or a chlorinated hydrocarbon such as a chlorinated
polyolefin. The reaction involves merely heating the two reactants
at a temperature of about 100.degree.-300.degree.C., preferably,
100.degree.-200.degree.C. The product from such a reaction is a
substituted succinic anhydride where the substituent is derived
from the olefin or chlorinated hydrocarbon as described in the
above cited patents. The product may be hydrogenated to remove all
or a portion of any ethylenically unsaturated covalent linkages by
standard hydrogenation procedures, if desired. The substituted
succinic anhydrides may be hydrolyzed by treatment with water or
steam to the corresponding acid and either the anhydride or the
acid may be converted to the corresponding acid halide or ester by
reacting with phosphorus halide, phenols, or alcohols.
The ethylenically unsaturated hydrocarbon reactant and the
chlorinated hydrocarbon reactant used in the preparation of the
acylating agents are principally the high molecular weight,
substantially saturated petroleum fractions and substantially
saturated olefin polymers and the corresponding chlorinated
products. The polymers and chlorinated polymers derived from
mono-olefins having from 2 to about 30 carbon atoms are preferred.
The especially useful polymers are the polymers of 1-mono-olefins
such as ethylene, propene, 1-butene, isobutene, 1-hexene, 1-octene,
2-methyl-1-heptene, 3-cyclohexyl-1-butene, and
2-methyl-5-propyl-1-hexene. Polymers of medial olefins, i.e.,
olefins in which the olefinic linkage is not at the terminal
position, likewise are useful. These are exemplified by 2-butene,
3-pentene, and 4-octene.
The interpolymers of 1-mono-olefins such as illustrated above with
each other and with other interpolymerizable olefinic substances
such as aromatic olefins, cyclic olefins, and polyolefins, are also
useful sources of the ethylenically unsaturated reactant. Such
interpolymers include for example, those prepared by polymerizing
isobutene with styrene, isobutene with butadiene, propene with
isoprene, propene with isobutene, ethylene with piperylene,
isobutene with chloroprene, isobutene with p-methyl-styrene,
1-hexene with 1,3-hexadiene, 1-octene with 1-hexene, 1-hexene,
1-heptene with 1-pentene, 3-methyl-1-butene with 1-octene,
3,3-dimethyl-1-pentene with 1-hexene, isobutene with styrene and
piperylene, etc.
For reasons of oil-solubility and stability, the interpolymers
contemplated for use in preparing the acylating agents of this
invention should be substantially aliphatic and substantially
saturated, that is, they should contain at least about 80% and
preferably about 95%, on a weight basis, of units derived from
aliphatic mono-olefins. Preferably, they will contain no more than
about 5% olefinic linkages based on the total number of the
carbon-to-carbon covalent linkages present.
The chlorinated hydrocarbons and ethylenically unsaturated
hydrocarbons used in the preparation of the acylating agents can
have molecular weights of from about 700 up to about 100,000 or
even higher. The preferred reactants are the above described
polyolefins and chlorinated polyolefins having an average molecular
weight of about 700 to about 5,000. When the acylating agent has a
molecular weight in excess of about 10,000, the acylated nitrogen
composition also possess viscosity index improving qualities.
In lieu of the high molecular weight hydrocarbons and chlorinated
hydrocarbons discussed above, hydrocarbons containing activating
polar substituents which are capable of activating the hydrocarbon
molecule in respect to reaction with an ethylenically unsaturated
acid reactant may be used in the above-illustrated reactions for
preparing the acylating agents. Such polar substituents include
sulfide and disulfide linkages, and nitro, mercapto, carbonyl, and
formyl radicals. Examples of these polar-substituted hydrocarbons
include polypropene sulfide, di-polyisobutene disulfide, nitrated
mineral oil, di-polyethylene sulfide, brominated polyethylene,
etc.
The acylating agents may also be prepared by halo-genating a high
molecular weight hydrocarbon such as the above described olefin
polymers to produce a poly-halogenated product, converting the
poly-halogenated product to a poly-nitrile, and then hydrolyzing
the poly-nitrile. They may be prepared by oxidation of a high
molecular weight polyhydric alcohol with potassium permanganate,
nitric acid, or a similar oxidizing agent. Another method for
preparing such poly-carboxylic acids involves the reaction of an
olefin or a polar-substituted hydrocarbon such as a
chloropolyisobutene with an unsaturated poly-carboxylic acid such
as 2-pentene-1,3,5-tricarboxylic acid prepared by dehydration of
citric acid. Mono-carboxylic acid acylating agents may be obtained
by oxidizing a mono-alcohol with potassium permanganate or by
reacting a halogenated high molecular weight olefin polymer with a
ketene. Another convenient method for preparing mono-carboxylic
acid involves the reaction of metallic sodium with an acetoacetic
ester or a malonic ester of an alkanol to form a sodium derivative
of the ester and the subsequent reaction of the sodium derivative
with a halogenated high molecular weight hydrocarbon such as
brominated wax or brominated polyisobutene.
Mono-carboxylic and poly-carboxylic acid acylating agents can also
be obtained by reacting chlorinated mono- and poly-carboxylic
acids, anhydrides, acyl halides, and the like with ethylenically
unsaturated hydrocarbons or ethylenically unsaturated substituted
hydrocarbons such as the polyolefins and substituted polyolefins
described hereinbefore in the manner described in U.S. Pat. No.
3,340,281.
The mono-carboxylic and poly-carboxylic acid anhydrides are
obtained by dehydrating the corresponding acids. Dehydration is
readily accomplished by heating the acid to a temperature above
about 70.degree.C., preferably in the presence of a dehydration
agent, e.g. acetic anhydride. Cyclic anhydrides are usually
obtained from poly-carboxylic acids having acid radicals separated
by no more than three carbon atoms such as substituted succinic or
glutaric acid, whereas linear anhydrides are obtained from
poly-carboxylic acids having the acid radicals separated by four or
more carbon atoms.
The acid halides of the mono-carboxylic and poly-carboxylic acids
can be prepared by the reaction of the acids on their anhydrides
with a halogenating agent such as phosphorus tribromide, phosphorus
pentachloride, or thionyl chloride.
The esters which are to be post-treated are generally prepared by
reacting the carboxylic acid acylating agent, preferably the acid
per se, its acyl chloride, or an anhydride thereof, with an
aliphatic polyhydric alcohol containing up to about 40 aliphatic
carbon atoms according to conventional processes for preparing
carboxylic acid esters. These alcohols are characterized by two to
10 hydroxyl groups and can be quite diverse in structure and
chemical composition. Typical alcohols are alkylene glycols such as
ethylene glycol, propylene glycol, trimethylene glycol, butylene
glycol, and poly glycols such as diethylene glycol, trienthylene
glycol, tetraethylene glycol, dipropylene glycol, tripropylene
glycol, dibutylene glycol, tributylene glycol, and other alkylene
glycols and polyalkylene glycols in which the alkylene radical
contains from 2 to about 8 carbon atoms. Other useful polyhydric
alcohols include glycerol, monomethyl ether of glycerol,
penthaerythritol, 9,10-dihydroxystearic acid, the ethyl ester of
9,10-dihydroxy-stearic acid, 3-chloro-1,2-propanediol,
1,2-butanediol, 1,4-butanediol, 2,3-hexanediol, 2,4-hexanediol,
pinacol, erythritol, arabitol, sorbitol, mannitol,
1,2-cyclohexanediol, 1,4-cyclo-hexanediol,
1,4-(2-hydroxyethyl)-cyclohexane, 1,4-dihydroxy-2-nitro-butane,
1,4-di(2-hydroxyethyl)-benzene, the carbohydrates such as glucose,
ramnose, mannose, glyceraldehyde, and galactose, and the like,
amino alcohols such as di(2hydroxyethyl)amine,
tri-(3-hydroxypropyl)amine, N,N'-di(hydroxyethyl)ethylenediamine,
copolymer of allyl alcohol and styrene, etc.
Included within this group of aliphatic alcohols are those
polyhydric alcohols containing at least three hydroxyl groups, at
least one of which has been esterified with a mono-carboxylic acid
having from eight to about 30 carbon atoms such as octanoic acid,
oleic acid, stearic acid, linoleic acid, dodecanoic acid, or tall
oil acid. Examples of such partially esterified polyhydric alcohols
are the mono-oleate of sorbitol, the mono-oleate of glycerol, the
glycerol, the di-stearate of sorbitol, and the di-dodecanoate of
erythritol.
A preferred class of esters are those prepared from aliphatic
alcohols containing up to 10 carbon atoms, and especially those
containing 3 to 10 carbon atoms. This class of alcohols includes
glycerol, erythritol, pentaerythritol, gluconic acid,
glyceraldehyde, glucose, arabinose, 1,7-heptanediol,
2,4-heptanediol, 1,2,3-hexanetriol, 1,2,4-hexanetriol,
1,2,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-butanetriol
1,2,4-butanetriol, quinic acid,
2,2,6,6-tetrakis-(hydroxymethyl)-cyclohexanol, 1,10-decanediol,
digitalose, and the like. The esters prepared from aliphatic
alcohols containing at least three hydroxyl groups and up to 10
carbon atoms are particularly preferred.
An especially preferred class of polyhydric alcohols for preparing
the esters used as starting materials in the present invention are
the polyhydric alkanols containing 3 to 6 carbon atoms and having
at least three hydroxyl groups. Such alcohols are exemplified in
the above specifically identified alcohols and are represented by
glycerol, erythritol, pentaerythritol, mannitol, sorbitol,
1,2,4-hexanetriol, and the like.
The organic epoxides used in the post-treatment of the esters can
have up to about forty carbon atoms and may be represented by the
formula ##SPC1##
where each R is independently hydrogen or an aliphatic,
cyclo-aliphatic, or aromatic radical. Normally R will be hydrogen
or an alkyl, haloalkyl, cycloalkyl, halocycloalkyl, aryl, or
haloaryl radical having no more than one halogen radical for every
3 carbon atoms. The lower alkylene and haloalkylene epoxides,
including the cycloalkylene epoxides, containing from 2 to 8 carbon
atoms are especially preferred for post-treating the esters. The
arylene and haloarylene epoxides contemplated are those containing
from one to two resonant ring structures such as phenyl, naphthyl,
or substituted phenyl and naphthyl such as alkyl phenyl or
halophenyl (e.g., tolyl, cresyl, xylyl, methyl naphthyl,
chlorophenyl, etc.). Phenyl and halophenyl radicals are the
preferred R groups among the aryl epoxides. The epoxides in which
at least one of the carbon atoms attached to the oxygen in the
oxirane ring is also attached to two hydrogen atoms are especially
preferred. Those epoxides are designated as terminal epoxides.
Specific examples of the organic epoxides useful in the process of
this invention are ethylene oxide, propylene oxide,
1,2-epoxybutane, 1,2-epoxy-3-butane, 1,2-epoxypentane,
1,2-epoxyheptane, 1,2-epoxydodecane, 2,3-epoxybutane,
1,2epoxy5-hexane, 1,2-epoxycyclohexane, 2,3-epoxyheptane,
1,2-epoxyoctane, epichlorohydrin, 1,2-epoxy-4-chlorobutane, styrene
oxide, p-methyl-styrene oxide, p-chloro-styrene oxide, epoxidized
soyabean oil, methyl ester of 9,10-epoxy-stearic acid, and
epoxidized fatty acid esters in which the fatty acid radical has up
to about 30 aliphatic carbon atoms and the alcohol radical is
derived from an aliphatic alcohol having up to about 8 carbon
atoms. Ethylene oxide, propylene oxide and epichlorohydrin are
particularly preferred for post-treating the esters.
The post-treatment process involves contacting the ester or mixture
of esters with an epoxide or mixture of epoxides, usually in the
presence of an inert diluent, while maintaining a temperature of
about 25 .degree.C. up to the decomposition temperature of the
ester or epoxide involved and usually at a temperature within a
range of about 50.degree.-250.degree.C. Good results are achieved
when the post-treatment is conducted at a temperature of about
70.degree.-200.degree.C. The esters and epoxides are easily brought
into contact simply by mixing them in any convenient manner. It is
usually desirable to employ some type of mechanical agitation to
faciltate thorough contact of the esters and epoxides.
Any substantially inert organic liquid can be used as a diluent.
Suitable diluents include the aliphatic, cycloaliphatic, and
aromatic hydrocarbons and their chlorinated analogs exemplified by
pentane, hexane, heptane, cyclohexane, benzene, toluene, xylene,
chlorobenzene, chlorohexanes, and the like. Mineral oils, naphthas,
ligroin, and the like may also be used as a diluent. In many
instances, the ester are prepared as oil-solutions and these
oil-solutions can be used in the post-treating process, the oil
functioning as a diluent.
The precise means by which this process improves the dispersancy
characteristics of the esters is not known. The epoxides are
believed to react with nonesterified hydroxyl groups although they
may also react with any free carboxyl groups present. In a
preferred aspect of the invention, the esters will be substantially
free from unreacted carboxyl groups, for example, the diesters of
the succinic acids as opposed to the monoesters. This can be
achieved by using a stoichiometric equivalent or an excess of
alcohol in preparing the esters. An ester is considered
substantially free from free carboxyl groups when not more than
about 10% of the number of carboxyl functions present are free
carboxyl groups, i.e., --COOH. Ordinarily the number of free
carboxyl groups will be less than about 5% of the total number in
the ester composition being treated in this preferred aspect of the
invention. When free carboxyl groups are present, the amount of
epoxide employed can be increased to provide up to about one
equivalent of epoxide for each equivalent of free carboxyl group in
addition to that used for post-treating the ester.
The esters and epoxides should be contacted in an amount such that
the ratio of equivalents of alcohol present in the ester to the
equivalents of epoxide will be about 1:0.05 to about 1:5 and
preferably 1:0.1 to about 1:2. For purposes of using this ratio,
the equivalent weight of an alcohol is deemed to be its molecular
weight divided by the number of hydroxyl groups present whether or
not they are esterified. Similarly, the equivalent weight of an
epoxide is deemed to be the molecular weight of the epoxide divided
by the number of oxirane rings v,15/5
present in the epoxy molecule.
By way of example, if the ester to be treated contains one mole of
pentaerythritol in the alcoholic moiety, the ester contains four
equivalents of alcohol. According to the present process, such an
ester would be contacted with 0.2 to 20, preferably 0.4 to 8
equivalents of epoxide. This equivalent ratio is offered merely as
a guideline to define the effectived ratios of ester and epoxide
and is in no way intended to imply that all the epoxide used will
react with the ester. However, within this ratio, it is possible to
determine the optimum ratio of ester and epoxide for any given
ester or combination of esters and any given epoxide or combination
of epoxides through routine evaluation.
The following examples illustrate the preferred embodiments of this
invention. As used in these examples and elsewhere in the
specification and claims, "percentage," and "parts" refer to
percent by weight and parts by weight unless otherwise
indicated.
EXAMPLE 1
An ester is prepared by reacting 600 parts of
polyisobutenyl-substituted succinic anhydride (average molecular
weight-1100) with 230 parts of polypropylene glycol (average
molecular weight -- 425) in the presence of 547 parts of a mineral
oil for about 17 hours at 150.degree.-160.degree.C. while blowing
the reaction mixture with nitrogen. Then 32.8 parts of an acidified
clay (commercially available as Super Filtrol from Filtrol
Corporation) is added and the mixture heated to about 200.degree.C.
for an additional 11 hours with hydrogen blowing and subsequently
filtered. The filtrate is an oil solution of the desired ester.
To the filtrate there is added 43.2 parts of propylene oxide and
this mixture is heated at 85.degree.-90.degree.C. for 17 hours. The
reaction mixture is then stripped to 85.degree.C. at a pressure of
80 mm. (Hg). The resulting material is an oil solution of the
desired propylene oxide treated ester.
EXAMPLE 2
A. A carboxylic acid ester is prepared by slowly adding 3,240 parts
of a high molecular weight carboxylic acid (prepared by reacting
chlorinated polyisobutylene and acrylic acid in a 1:1 equivalent
ratio and having an average molecular weight of 982) to a mixture
of 200 parts of sorbitol and 1000 parts of diluent oil over a
1.5-hour period while maintaining a temperature of
115.degree.-125.degree.C. Then 400 parts of additional diluent oil
are added and the mixture is maintained at about
195.degree.-205.degree.C. for 16 hours while blowing the mixture
with nitrogen. An additional 755 parts of oil are then added the
mixture cooled to 140.degree.C., and filtered. The filtrate is an
oil solution of the desired ester.
B. The above ester is post-treated wsith propylene oxide by adding
108 parts of propylene oxide to 5,105 parts of the filtrate and 25
parts of pyridine while maintaining a temperature of
80.degree.-90.degree.C. Then the mixture is heated to
110.degree.-120.degree.C. for 2 to 3 hours and stripped to
170.degree.C. at a pressure of 15 mm. (Hg). The stripped product is
the desired epoxide treated product.
EXAMPLE 3
a. An ester is prepared by heating 658 parts of a carboxylic acid
having an average molecular weight of 1,018 (prepared by reacting
chlorinated polyisobutene with acrylic acid) with 22 parts of
pentaerythritol while maintaining a temperature of about
180.degree.-205.degree.C. for about 18 hours during which time
nitrogen is blown through the mixture. The mixture is then cooled
to about 90.degree.C. and maintained at 90.degree.-100.degree.C.
for about 2 hours while 14 parts of ethylene oxide are slowly
added. The mixture is subsequently heated to about
190.degree.-200.degree.C. for about 4.5 hours while slowly adding
an additional 16 parts of ethylene oxide to the mixture. This
mixture is then maintained at this latter temperature for an
additional 2 hours, then stripped to 150.degree.C. at a pressure of
18 mm. (Hg), and filtered. The filtrate is an oil solution of the
desired ethylene oxide treated ester.
B. The ester of A is post-treated with epichlorohydrin following
the same general procedure but substituting an equivalent amount of
epichlorohydrin for the ethylene oxide.
EXAMPLE 4
A. An ester is prepared by heating 3,318 parts of
polyisobutenyl-substituted succinic anhydride (average molecular
weight -- 1100), 408 parts of pentaerythritol, and 2,445 parts of
diluent oil at 150.degree.C. for 5 hours and thereafter at
200.degree.-210.degree.C. for an additional 5 hours. The reaction
mixture is then filtered, the filtrate being an oil solution of the
desired ester.
B. The foregoing ester is post-treated with an epoxide by heating
2500 parts of the filtrate to about 80.degree.C. and thereafter
adding 123 parts of propylene oxide over a period of 4 hours while
maintaining a temperature at 80.degree.-90.degree.C. Upon
completion of the addition of the propylene oxide, the resulting
mixture is heated an additional 3 hours at a temperature of
80.degree.-90.degree.C. and subsequently stripped to 150.degree.C.
at a pressure of 20 mm (Hg). The residue of this stripping step is
an oil solution of the desired propylene oxide-treated ester.
EXAMPLE 5
Following the procedure of Example 1, a polyisopropenyl-substituted
succinic anhydride (where the polyisopropenyl substituent has an
average molecular weight of about 750) is reacted with mannitol in
an equivalent ratio of anhydride to mannitol of 1:3. An oil
solution containing 1,000 parts of the ester is post-treated with
145 parts of butylene oxide.
EXAMPLE 6
Following the general procedure at Example 3(A), the ester
post-treated with an equivalent amount of styrene oxide in lieu of
ethylene oxide.
EXAMPLE 7
Following the general procedure of Example 4, an ester is prepared
by reacting one mole of polyisobutenyl-substituted succinic
anhydride (average molecular weight -- 3200) simultaneously with
one-half mole of glycerol and one-half mole of pentaerythritol and
the resulting ester (1,000 parts in a 40% oil solution) is
post-treated with 58 parts of propylene oxide.
EXAMPLE 8
An ester is prepared by reacting 2,000 parts of the carboxylic acid
of Example 2(A), 1,200 parts of the anhydride of Example 1, and 300
parts of sorbitol in 1,400 parts of oil following the general
procedure of Example 2(A). Thereafter, the filtrate is post-treated
with 300 parts of propylene oxide following the general procedure
of Example 2(B).
EXAMPLE 9
An ester is prepared from 1,000 parts of the acid of Example 2(A)
and 92 parts of glycerol and thereafter post-treated with 180 parts
of propylene oxide following the general procedure of Example
2(A).
EXAMPLE 10
The ester of Example 4(A) is post-treated with 100 parts of
propylene oxide and 25 parts of epichlorohydrin following the
general procedure of Example 4.
EXAMPLE 11
A mixture of 340 grams (0.3 mole) of alcohol (prepared by
copolymerizing equi-molar proportions of styrene and allyl alcohol
to a copolymer having a molecular weight of 1,150 and containing an
average of 5 hydroxyl radicals per mole), 1.5 moles of a
polyisobutene-substituted succinic anhydride as described in
Example 1, and 500 grams of xylene is heated at
80.degree.-115.degree.C., diluted with mineral oil, heated to
remove xylene, and filtered. The filtrate is post-treated with
propylene oxide (about one equivalent per equivalent of alcohol
used) at 70.degree.-150.degree.C. under reflux. The product is
diluted with oil to an oil solution having an oil content of
40%.
As mentioned before, the post-treated esters produced by the
process of this invention are useful as additives in lubricants and
fuels in the same manner as the ester starting materials. They
function effectively as sludge-dispersants in both lubricants and
fuels. When employed as lubricating oil additives they are usually
present in amounts of from about 0.0l % to about 30% by weight in
the final lubricating composition. Ordinarily, when used as
additives for lubricating oil compositions, the post-treated esters
will be present in amounts of from about 0.5% to about 10% by
weight although under unusally adverse conditions, such as in the
operation of certain diesels, they may comprise up to about
30percent by weight of the lubricant. The products are particularly
useful as dispersants in lubricating oil compositions used in the
crankcase of various internal combustion engines.
When employed in lubricating oils, the post-treated esters may be
used alone or in combination with other dispersants or detergents.
In addition, the lubricating composition may contain rust
inhibitors, oxidation inhibitors, viscosity index improving agents,
extreme pressure additives, and the like. Typical examples of these
additional additives are contained in the above-identified patents
disclosing the carboxylic acid acylating agents useful in preparing
the products of the present invention. The post-treated esters can
be used effectively in both mineral oil-based lubricating
compositions (i.e., petroleum distillates of lubricating oil
viscosity) and synthetic oil-based lubricating compositions
although they will probably find greater use in the former since
mineral oil lubricating compositions are more prevalent.
In fuels, the post-treated esters serve to promote engine
cleanliness by reducing or eliminating harmful deposits in the fuel
system, engine, and exhaust system. They are primarily intended for
use in the normally liquid petroleum distillate fuels, that is, the
petroleum distillates which boil in the range characteristic of
petroleum fuels such as gasolines, fuel oils, diesel fuels,
aviation fuels, kerosene, and the like. When employed in fuels,
they are generally employed in lower concentrations than in
lubricants, for example, in amounts of from about 0.001% to about
2% by weight and generally in amounts of from about 0.01% to about
1% by weight. As in the case of lubricants, other conventional
additives can be present in the fuel compositions contemplated by
the present invention. Additional additives include lead
scavengers, deicers, antiscreen clogging agents, demulsifiers, and
the like.
The following are examples of the lubricating and fuel compositions
contemplated by the present invention.
Example A
SAE 20 mineral oil containing 1% of the product of Example 1.
Example B
SAE 30 mineral oil containing 0.4% of the product of Example 2(B)
and 0.15% of the zinc salt of an equimolar mixture of
di-cyclohexylphosphorodithioic acid and
di-isobutylphosphorodithioic acid.
Example C
SAE 10W-30 mineral lubricating oil containing 4percent of the
product of Example 3(A).
Example D
SAE 10W-30 mineral lubricating oil containing 1.5% of the product
of Example 4(B), 0.075% of phosphorus as the adduct obtained by
heating di-nonylphosphorodithioate with 0.25 mole of 1,2-hexene
oxide at 100.degree.C., a sulfurized methyl ester of tall oil acid
having a sulfur content of 15%, 6% of a polyisobutene viscosity
index improver having an average molecular weight of about 100,000,
0.005% of poly-(alkylmethacrylate) anti-foam agent, and 0.5% lard
oil.
Example E
SAE 20 mineral lubricating oil containing 2.5% of the product of
Example 4, 0.75% of phosphorus as the dioctylphosphorodithioate, 2%
of a barium detergent prepared by neutralizing with barium
hydroxide a hydrolyzed reaction product of a propylene (molecular
weight 2,000) with one mole of phosphorus pentasulfide and one mole
of sulfur, 3% of a barium sulfonate detergent prepared by
carbonating a mineral oil solution of mahogany acid and a 5%
stoichiometrically excess amount of barium hydroxide in the
presence of octylphenol as the promoter at 180.degree.C., 3% of a
supplemental ashless dispersant prepared by copolymerizing a
mixture of 95% by weight of decylmethacrylate, 5% by weight of
diethylaminoethyl acrylate.
Example F
A di-2-ethylhexyl sebacate lubricating composition comprising 0.25%
of the product of Example 2(B).
Example G
Diesel fuel containing 0.2% of the product of Example 4.
Example H
Kerosene containing 0.15% of the product of Example 1.
Example I
Gasoline containing 0.003% of the product of Example 4.
The foregoing compositions illustrate types of compositions
contemplated by the present invention. Many additional compositions
apparent to those skilled in the art are available simply by
replacing all or part of the high-molecular weight esters used in
fuels and lubricants described in the above-patents with an equal
amount of the post-treated esters of the present invention.
Obviously, optimum amounts for any application will depend upon the
particular additive or additive combination selected and the
specific environment in which the fuel or lubricant is to be used.
These optimum amounts can be ascertained through conventional
evaluation techniques commonplace in the industry.
The foregoing examples are illustrative of the present invention
and in no way are intended to be limiting as many other obvious
modifications and embodiments will be obvious to those skilled in
the art.
* * * * *