Fuel and related compositions – Liquid fuels – Containing organic -c
Reexamination Certificate
2000-11-01
2004-04-20
Toomer, Cephia D. (Department: 1714)
Fuel and related compositions
Liquid fuels
Containing organic -c
C044S412000
Reexamination Certificate
active
06723141
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to additive concentrates, gasoline compositions containing additive concentrates, the preparation of gasoline compositions, and the operation of spark-ignition internal combustion engines.
BACKGROUND OF THE INVENTION
EP-A-534551 provides a gasoline composition comprising a major amount of a gasoline and from 5 ppmw to 1,000 ppmw based on the gasoline composition of a mixture of (a) an oil soluble polyamine selected from the group consisting of (i) an aliphatic alkylene polyamine containing at least one olefinic polymer chain attached to a nitrogen atom and/or a carbon atom of the alkylene radical(s) connecting the amino nitrogen atoms and said polyamine having a number average molecular weight in the range from 600 to 10,000, (ii) a Mannich polyamine comprising the condensation product of a high molecular weight sulphur-free alkyl-substituted hydroxyaromatic compound wherein the or each alkyl group has a number average molecular weight in the range from 600 to 10,000, an amine which contains an amino group having at least one active hydrogen atom, and an aldehyde, wherein the respective molar ratio of reactants is 1:0.1-10:0.1-10, and (iii) mixtures of (i) and (ii); and (b) an oil soluble hydrocarbyl poly(oxyalkylene) aminocarbamate having a number average molecular weight in the range from 600 to 10,000 having at least one basic nitrogen atom wherein said hydrocarbyl group contains from 1 to 30 carbon atoms, and wherein the weight ratio of said polyamine (a) to said hydrocarbyl poly(oxyalkylene) aminocarbamate (b) ranges from 3:1 to 1:2.
The aliphatic alkylene polyamines of type (a)(i) necessarily contain at least two amino nitrogen atoms. The general formula (I) for preferred polyamines as given on page 3, provides for the polyamine to be a diamine when x in the formula is zero. Exemplified in EP-A-534551 is a composition comprising an N-polyisobutenyl-N′-N′-dimethyl-1,3-diamino propane having a molecular weight of 1050 (M
n
). There is no mention whatsoever in EP-A-534551 of an aliphatic alkylene additive of type(a)(i) having just one amino nitrogen atom.
WO91/12303 describes a fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and about 400 to 1,200 parts per million of a fuel additive composition comprising:
a) a dispersant comprising a hydrocarbyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen atom and an average molecular weight of about 1,000 to about 3,000;
b) an injector detergent comprising a branched chain hydrocarbyl amine having at least one basic nitrogen atom and an average molecular weight of about 300 to about 700, wherein the hydrocarbyl moiety is derived from polymers of C
2
to C
6
olefins;
c) a fuel demulsifier which is homogeneous with the other components of said fuel additive composition; and
d) a natural or synthetic carrier fluid.
It is said that the fuel additive compositions will in general contain about 10 to 70 weight percent amino carbamate dispersant, about 1 to 10 weight percent of the hydrocarbyl amine injector detergent, about 0.5 to 5 weight percent of the fuel demulsifier and about 25 to 80 weight percent of the carrier fluid (page 12 lines 21 to 26).
On page 18, at lines 6 to 8, of WO 91/12303 it is indicated that the branched chain hydrocarbyl amine having an average molecular weight of about 300 to 700, will in general contain from about 20 to 40 carbon atoms, which corresponds to a molecular weight range from about 280 to about 560.
The molecular weight range of the branched chain hydrocarbyl amines is described as being narrow and peaked near the indicated molecular weight (page 18, lines 12-14). From this it can be deduced that the term “molecular weight” as used in WO 91/12303 means number average molecular weight (M
n
)
While the amino component of the branched chain hydrocarbyl amines may be either a monoamine or a polyamine, and this component embodies a broad class of amines having from 1 to 10 amine nitrogen atoms and from 2 to 40 carbon atoms and with a carbon to nitrogen ratio of between about 1:1 and 10:1 (page 18, lines 16 to 12), it is specifically stated that a particularly preferred branched-chain hydrocarbyl amine is polyisobutylene diamine (page 19, lines 1 and 2).
Indeed the only hydrocarbyl amine injector detergent used in the working examples of WO 91/12303 is a polyisobutylene ethylene diamine prepared by the stepwise reaction of a C
30
polyisobutylene having a molecular weight of approximately 420 with chlorine and ethylene diamine (page 23, lines 21 to 27).
The favourable effect of using this hydrocarbyl amine injector detergent is demonstrated in Example 9, wherein a fuel additive composition containing this hydrocarbyl amine injector detergent is shown to contribute to the octane requirement of a gasoline composition significantly less than an additive composition comprising an additive package containing a heavy polybutene ethylene diamine made from a polybutene containing on average 100 carbons per molecule and having an average molecular weight of about 1450.
From the teaching of WO 91/12303 the person skilled in the art would be led to conclude that if an injector detergent is to be used in combination with a hydrocarbyl poly(oxyalkylene) aminocarbamate, it should have a relatively low molecular weight below about 700, and preferably about 420, and that it should desirably be a polyamine.
One important property for an additive concentrate to possess is storage stability over a broad range of temperatures, e.g. temperatures as low as −20° C. and as high as 40° C.
SUMMARY OF THE INVENTION
It has now surprisingly been found possible to prepare an additive concentrate containing an hydrocarbyl poly(oxyalkylene) aminocarbamate together with a relatively high molecular weight monoamine, resulting in advantageous storage stability characteristics when compared with similar concentrates based on hydrocarbyl polyamines (e.g. a concentrate corresponding to those in EP-A-534551)
Accordingly, the present invention provides an additive concentrate which comprises an oil soluble hydrocarbyl poly(oxyalkylene) aminocarbamate having a number average molecular weight (M
n
) in the range 600 to 10,000 having at least one basic nitrogen atom wherein said hydrocarbyl group contains 1-30 carbon atoms, and an oil soluble hydrocarbyl amine of formula R—NH
2
wherein R represents a group R′ or a group R′—CH
2
—, wherein R′ represents a hydrocarbyl group having a number average molecular weight (M
n
) in the range 750 to 6,000.
DETAILED DESCRIPTION OF THE INVENTION
In the description which follows, all molecular weight values are number average molecular weights (M
n
), unless otherwise indicated.
As described in EP-A-534551, the amine component of the oil soluble hydrocarbyl-terminated poly(oxyalkylene) aminocarbamate is preferably derived from a polyamine having from 2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms. The polyamine is preferably reacted with a hydrocarbyl poly(oxyalkylene) chloroformate to produce the hydrocarbyl poly(oxyalkylene) aminocarbamate component. The chloroformate is itself derived from hydrocarbyl poly(oxyalkylene) alcohol by reaction with phosgene. The polymer, encompassing diamines, provides the product poly(oxyalkylene) aminocarbamate with, on average, at least one basic nitrogen atom per carbamate molecule, i.e., a nitrogen atom titratable by strong acid. The polyamine preferably has a carbon-to-nitrogen ratio in the range from 1:1 to 10:1. The polyamine may be substituted with substituents selected from hydrocarbyl groups having from 1 to 10 carbon atoms, acyl groups having from 2 to 10 carbon atoms, and monoketone, monohydroxy, mononitro, monocyano, alkyl and alkoxy derivatives of hydrocarbyl groups having from 1 to 10 carbon atoms. It is preferred that at least one of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen. Examples of suitable polyamines are those described in U.S. Pat. No. 4,191,537.
Hydrocarbyl, as used in de
Shell Oil Company
Toomer Cephia D.
LandOfFree
Additive concentration does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Additive concentration, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Additive concentration will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3240871