Solid anti-friction devices – materials therefor – lubricant or se – Lubricants or separants for moving solid surfaces and... – Organic sulfur compound – wherein the sulfur is single bonded...
Reexamination Certificate
1999-06-03
2001-03-20
Howard, Jacqueline V. (Department: 1721)
Solid anti-friction devices, materials therefor, lubricant or se
Lubricants or separants for moving solid surfaces and...
Organic sulfur compound, wherein the sulfur is single bonded...
C508S391000
Reexamination Certificate
active
06204226
ABSTRACT:
The present invention relates to a mixture of alkyl phenyl sulfonates of alkaline earth metals, its application as detergent/dispersant additives for lubricating oils, and methods for preparing said mixture.
BACKGROUND OF THE INVENTION
In prior art, methods are known for preparing weakly or strongly superalkalinized sulfonates from sulfonic acids obtained by the sulfonation of different alkyl aryl hydrocarbons and from an excess of alkaline earth base.
The alkyl aryl hydrocarbons subjected to the sulfonation reaction are obtained by alkylation via the Friedel and Craft reaction of different aryl hydrocarbons, particularly aromatic, with two different types of olefin:
Branched olefins obtained by the oligo-polymerization of propylene to C
15
to C
42
hydrocarbons, particularly the propylene tetrapolymer dimerized to a C
24
olefin, and
Linear olefins obtained by the oligo-polymerization of ethylene to C
14
to C
40
hydrocarbons.
It is easy to obtain a good dispersion in the medium of the alkaline earth base not fixed in the form of salt if the sulfonic acid is derived from a hydrocarbon obtained by alkylation of an aryl hydrocarbon with a branched olefin. It is difficult if the alkylation is effected with a linear olefin. It is particularly difficult for the alkylation of an aryl hydrocarbon where a high percentage of the alkylaryl hydrocarbon has the aryl substituent on positions 1 and 2 of the linear alkyl chain, due to the formation of a skin in the open air.
This poor dispersion is especially pronounced if the medium also contains a high proportion of sulfonate, that is if it corresponds to a low Base Number (between 3 and 60), hence to a low content of free lime and the absence of carbon dioxide and carbonate.
In fact, during the alkylation reaction with benzene or another aromatic or aryl hydrocarbon, 25 mole % of the alkylaryl hydrocarbon has the aryl substituent on positions 1 and 2 of the linear alkyl chain.
When prepared by the method described, for example in French Patent No. 2,564,830, this high proportion of alkyl aryl hydrocarbon having an aryl radical on position 1 or 2 of the linear alkyl chain results in a sulfonate that exhibits hygroscopic properties such that a superficial ‘skin’ is formed. This ‘skin’ makes this product unacceptable as an additive for lubricating oil.
Furthermore, the formation of this superficial skin is generally accompanied by a very low filtration rate, a high viscosity, a low incorporation of calcium, a deterioration of anti-rust performance, and an undesirable turbid appearance, or even sedimentation, when the sulfonate thus prepared is added at the rate of 10% by weight to a standard lubricating oil and stored for examination.
The Applicant has carried out chromatographic analyses to identify each of the different isomers differing by the position of the aryl radical on the carbon atom of the linear alkyl chain, and examined their respective influence on the properties of the corresponding alkyl aryl sulfonates of alkaline earth metals obtained from these different isomers.
The Applicant has thus discovered that he could overcome the aforementioned drawbacks, inasmuch as the mole % of the aryl hydrocarbon, other than benzene, having the aryl substituent on positions 1 or 2 of the linear alkyl chain was between 0 and 13%, and preferably between 5 and 11%, and more particularly between 7 and 10%.
This discovery was the subject of a French Patent Application filed Mar. 8, 1995 under No. 95 02,709 by the Applicant.
Yet the Applicant had not succeeded in obtaining satisfactory results when the aryl hydrocarbon was benzene, because, heretofore, he had never been able to prevent the formation of the skin with the use of this aromatic hydrocarbon, even if the hydrocarbon was alkylated with a very long chain linear mono olefin so that the mole % of the aryl hydrocarbon having the aryl substituent on positions 1 or 2 of the linear alkyl chain was between 0 and 13%, and preferably between 5 and 11%, and more particularly between 7 and 10%.
As a result of more intensive studies, the Applicant had discovered that the aforementioned drawbacks could be overcome by using a mixture of alkyl aryl sulfonates of superalkalinized alkaline earth metals comprising:
(a) from 50% to 85% of a linear mono-alkyl phenyl sulfonate in which the linear alkyl chain contains between 14 and 40 carbon atoms, and between 0 and 13 mole % of the phenyl sulfonate radical of the alkaline earth metal is fixed on position 1 or 2 of the linear alkyl chain, and
(b) from 15% to 50% of a heavy alkyl aryl sulfonate selected from:
(i) dialkyl aryl sulfonates wherein both alkyl substituents are linear alkyl chains, of which the sum of the carbon atoms is from 16 to 40, or
(ii) mono or polyalkyl aryl sulfonates wherein the alkyl substituent or substituents are branched chains, wherein the sum of the carbon atoms is from 15 to 48 carbon atoms.
This mixture of alkyl aryl sulfonates has a maximum of 10 mole % of the phenyl sulfonate radical of the alkaline earth metal fixed on position 1 or 2 of the linear alkyl chain. This mixture has no skin formation after three days of storage in an open jar at room temperature. It has good calcium incorporation, a low viscosity, good solubility, and good performances. This discovery was the subject of a French Patent Application filed Sep. 5, 1996 under No. 96 10,833 by the Applicant.
According to that process, the linear mono-alkyl phenyl sulfonates should have no more than 13% attachment in position 1 or 2. Such low levels of attachment in the 1 or 2 position is possible using a staged HF catalyst alkylation reaction (two reactors in serial; low molar excess of benzene in the first reactor, large molar excess in the second), but it is not possible if only one reactor is available.
SUMMARY OF THE INVENTION
The present invention provides a mixture of alkyl phenyl sulfonates of alkaline earth metals having low color and no skin formation even after three days of storage in an open jar at room temperature.
That mixture is characterized in that it comprises from 20% to 70% by weight of a linear mono alkyl phenyl sulfonate and from 30% to 80% by weight of a branched mono alkyl phenyl sulfonate. This mixture is useful as a detergent/dispersant additive for lubricating oils. Preferably, the Base Number of this mixture is between 3 and 60, and more preferably it is between 10 and 40.
The linear mono alkyl substituent of the linear mono alkyl phenyl sulfonate contains from 14 to 40 carbon atoms, preferably from 20 to 24 carbon atoms. The mole % of the phenyl sulfonate radical fixed on position 1 or 2 of the linear alkyl chain is between 10% and 25%, preferably between 13% and 20%.
The branched mono alkyl substituent of the branched mono alkyl phenyl sulfonate contains from 14 to 18 carbon atoms. The resulting molecular weight of the starting alkylate is low, 300 or less. Preferably, the branched mono alkyl phenyl sulfonate is derived from a polymer of propylene.
One method for preparing this mixture of alkyl aryl sulfonates of alkaline earth metal is by the mixing of the corresponding linear mono alkyl phenyl and branched mono alkyl phenyl, the sulfonation of the mixture of mono alkyl phenyls, and the reaction of the resulting sulfonic acids with an excess of alkaline earth base.
Another method for preparing this mixture of alkyl aryl sulfonates of alkaline earth metal is by the separate preparation of each of the alkyl aryl sulfonic acids, their mixing, and their reaction with an excess of base.
A third method for preparing this mixture of alkyl aryl sulfonates of alkaline earth metal is by the separate preparation of each of the alkyl aryl sulfonates entering into the composition of the mixtures and their mixing in the requisite proportions.
DETAILED DESCRIPTION OF THE INVENTION
In its broadest aspect, the present invention involves a mixture of alkyl phenyl sulfonates of alkaline earth metals, its application as detergent/dispersant additives for lubricating oils, and methods for preparing said mixture.
Prior to discussing the invention in further d
Clement Olivier Pascal Marie
Coent Jean-Louis Le
Guellec Amedee
King William Frank
Lockett Steven G.
Chevron Oronite S.A.
Howard Jacqueline V.
Stumpf Walter L.
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