Solid anti-friction devices – materials therefor – lubricant or se – Lubricants or separants for moving solid surfaces and... – Compound of indeterminate structure – prepared by reacting a...
Reexamination Certificate
2000-08-29
2002-03-12
Howard, Jacqueline V. (Department: 1764)
Solid anti-friction devices, materials therefor, lubricant or se
Lubricants or separants for moving solid surfaces and...
Compound of indeterminate structure, prepared by reacting a...
C585S266000, C585S266000, C585S452000, C585S541000, C585S522000
Reexamination Certificate
active
06355603
ABSTRACT:
Thermal reaction products of maleic anhydride and oligoalkenes, derivatives of the thermal reaction products with amines or alcohols and use of these derivatives as fuel additives and lubricant additives
The present invention relates to thermal reaction products of maleic anhydride and oligoalkenes obtained from specific linear &agr;-olefins, which have a number average molecular weight of from 700 to 20,000, and a process for the preparation of these thermal reaction products. The present invention furthermore relates to derivatives of the thermal reaction products with amines or alcohols in the form of the corresponding alkenylsuccinamides, alkenylsuccinimides or alkenylsuccinic esters and the use of these derivatives as fuel additives and lubricant additives. The present invention also relates to motor oils which contain these derivatives as additives.
Imides of polyisobutenylsuccinic acids have long been known as ashless dispersants in the form of alkenylsuccinic acid derivatives. However, the polyisobutenyl radical and also other corresponding long-chain radicals known from the prior art do not yet ensure an optimum property spectrum of such dispersants. In particular, viscosity behavior is still unsatisfactory, i.e. a reduction in the low-temperature viscosity is desired.
WO-A 93/24539 (1) discloses poly-1-olefins obtained from C
3
- to C
20
-1-olefins, such as propene, 1-butene, 1-pentene or 1-hexene, having a number average molecular weight of from 300 to 10,000, which are prepared by conventional metallocene catalysis. Said 1-olefins are always used as a mixture with more readily volatile saturated and unsaturated hydrocarbons; for example, an industrial butane/butene stream or industrial isobutene-containing butene stream (“refined product I/II” from the steam cracker) is used. The poly-1-olefins obtained can then be converted by means of maleic anhydride into functionalized products which are used, inter alia, for lubricating oils and as fuel additives.
WO-A 96/28486 (2) relates to copolymers of unsaturated carboxylic acids or their anhydrides and oligomers of 1-olefins of 3 to 14 carbon atoms, which can be prepared by metallocene catalysis. Inter alia, n-decene is also mentioned here as a 1-olefin. The average molecular weight of the olefin oligomers is from 300 to 10,000. The copolymers obtained from the unsaturated dicarboxylic acids (anhydrides) and the olefin oligomers are suitable, after derivatization with amines, as fuel additives and lubricant additives.
WO-A 96/23751 (3) discloses olefin oligomers which are prepared by means of metallocene catalyst systems and are based on linear and cyclic C
2
- to C
12
-olefins, e.g. 1-decene. Their weight average molecular weight ({overscore (M)}
w
) is from 100 to 20,000, with a molecular weight distribution {overscore (M)}
w
/{overscore (M)}
n
(weight average value
umber average value) of from 1.0 to 2.4. Their degree of polymerization is from 2 to 200. These olefin oligomers can be further processed according to (3) by the conventional chemical reactions, such as hydroformylation and/or hydroamination, to give functionalized compounds which are suitable, for example, as fuel additives or lubricant additives.
It is an object of the present invention to remedy the deficiencies of the prior art.
We have found that this object is achieved by thermal reaction products of maleic anhydride and oligoalkenes which are obtainable by oligomerization of linear C
8
- to C
12
-1-alkenes, have a vinylidene double bond content of more than 30%, in particular more than 50%, especially more than 60%, and have a number average molecular weight of from 700 to 20,000.
Suitable linear C
8
- to C
12
-1-alkenes and mixtures thereof are 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene and mixtures thereof. In a preferred embodiment, oligoalkenes which are obtainable by metallocene-catalyzed oligomerization of linear 1-decene are used, it being possible for up to 40 mol %, based on the amount of linear 1-decene, of further linear C
8
- to C
12
-1-alkene to be incorporated as polymerized units.
The essential monomer component in this preferred embodiment is thus linear 1-decene, which may be oligomerized alone or as a mixture with up to 40, in particular up to 20, especially up to 5, mol %, based on the amount of 1-decene, of further linear C
8
- to C
12
-1-alkenes (1-octene, 1-nonene, 1-undecene and/or 1-dodecene).
Said 1-alkene can be used in chemically pure form (purities of, usually, from 99 to 99.9% by weight) or as industrial mixtures in purities of, usually, from 90 to 99% by weight, the remaining components in the industrial mixtures usually being roughly equally volatile, polymerizable or unpolymerizable components (for example unsaturated isomers, homologs or saturated hydrocarbons). As a rule, the 1-alkenes used are virtually free of more highly volatile components, especially free of more highly volatile saturated or unsaturated hydrocarbons, in particular those having less than 8 carbon atoms; virtually free means that at most less than 1, in particular less than 0.5, % by weight of such more highly volatile components may occur.
In the oligomerization of said linear C
8
- to C
12
-1-alkenes, the procedure is carried out in particular under metallocene catalyst, especially in the presence of a titanium, zirconium or hafnium metallocene catalyst and of an activator based on organoaluminum, organoboron or carbocationic compounds.
The systems used for the oligomerization and comprising metallocene catalyst and activator are conventional catalyst systems. By varying the structure of the metallocene, it is possible to adjust the desired molecular weight ranges of the oligoalkenes in a known manner. The oligomerization is carried out as a rule in a suitable medium (reaction mixture), for example an organic solvent, under the conditions usual for this purpose.
The catalyst systems do not have to meet any special requirement, apart from being substantially soluble in the reaction mixture. The reaction mixture is the mixture which is present in the time after the combination of all reaction components up to, at the latest, the destruction of the catalyst system after the end of the oligomerization reaction. The solubility of the catalyst system in the reaction mixture is determined by measuring the turbidity of the reaction mixture analogously to DIN 38404. Substantial solubility of the catalyst system is present if the turbidity number is from 1 to 10, preferably from 1 to 3.
The metallocene component of the catalyst system is a complex of titanium, of zirconium or of hafnium, in which the metal atom M is bonded, in the form of a sandwich, between two unsubstituted or substituted cyclopentadienyl groups, the remaining valences of the central atom M being saturated by readily exchangeable leaving atoms or leaving groups X
1
, X
2
.
Suitable metallocene complexes are those of the formula Cp
2
MX
1
X
2
, where M is titanium, zirconium or hafnium, preferably zirconium.
CP
2
is a pair of unsubstituted or substituted cyclopentadienyl ligands. Here, both cyclopentadienyl ligands or only one of the two may be substituted.
Where the substituents are C
5
- to C
30
-alkyl, the cyclopentadienyl rings are usually symmetrically substituted. This means that the type and number as well as the position of the alkyl substituents of one Cp ring are identical to the type, number and position of the alkyl substituents of the second Cp ring. The number of alkyl groups of the cyclopentadienyl ring is from 1 to 4.
Suitable C
5
- to C
30
-alkyl radicals are the aliphatic radicals pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl and their isomers, for example neopentyl and isooctyl, and the cycloaliphatic radicals cyclopentyl and cyclohexyl. n-Octadecyl is particularly suitable.
The unsubstituted or C
5
- to C
30
-alkyl-substituted cyclopentadienyl units may however also be substituted by 1 or 2 C
4
- to C
10
-alkyl units each which, together with the
Mach Helmut
Rath Hans Peter
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