Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2001-05-04
2003-01-28
Medley, Margaret (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C524S549000, C524S556000, C525S327400, C525S327900, C526S318250, C526S318300, C526S318600
Reexamination Certificate
active
06512055
ABSTRACT:
DESCRIPTION
The present invention relates to novel copolymers I carrying functional groups and comprising
a) 20-60 mol % of at least one monoethylenically unsaturated C
4
-C6-dicarboxylic acid or an anhydride thereof,
b) 10-70 mol % of at least one oligomer of propene or of a branched 1-olefin of 4 to 10 carbon atoms, having an average molecular weight M
w
of from 300 to 5000, and
c) 1-50 mol % of at least one monoethylenically unsaturated compound which is copolymerizable with the monomers a) and b),
and furthermore a process for the preparation of these compounds I. The present invention also relates to oil-soluble reaction products II obtainable from the copolymers I by reaction with an amine, a process for the preparation of said reaction products, the use of the compounds II and fuels and lubricants which contain these compounds.
WO-A 90/03359 describes polymers which are used as additives in lubricating oils and have dispersant properties for sludge particles and solid particles present therein. Moreover, the polymers have viscosity index-improving properties, ie. they ensure that the viscosity of a lubricating oil which contains this compound decreases to a substantially smaller extent than that of oils without such an additive when the temperature is increased.
These polymers are composed of two monomer groups, ie. on the one hand of maleic acid or fumaric acid or derivatives of these compounds and on the other hand of an olefin whose molecular weight is sufficiently large for the polymer prepared from these monomers to be oil-soluble. The olefin must carry at least 20% of alkylvinylidene groups.
The polymers disclosed in the publication have properties which are not satisfactory for all applications; in particular, the viscosity-temperature behavior of lubricating oils which contain these polymers as additives is unsatisfactory.
Furthermore, the dispersing effect of this class of compounds is not satisfactory for all industrial applications.
It is an object of the present invention to provide additives for lubricating oils, which additives do not have these disadvantages.
We have found that this object is achieved by the copolymers defined at the outset.
We have also found a process for their preparation, reaction products II obtainable from these copolymers I by reaction with an amine, a process for the preparation of said reaction products and the use of the reaction products II. We have furthermore found lubricants and fuels which contain these compounds.
The embodiments which are particularly advantageous for the use of the copolymers I as intermediates for the preparation of lubricating oil additives are described below.
Copolymers I are composed of monomers a) to c).
Monomer a)
Suitable monomers a) are monoethylenically unsaturated dicarboxylic acids of 4 to 6 carbon atoms, such as maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride and methylenemalonic anhydride and mixtures of these with one another. Maleic anhydride is preferred.
Monomer b)
Suitable monomers b) are oligomers of propene or of a branched 1-olefin of 4 to 10 carbon atoms. These oligomers are composed of at least 3 olefin molecules. Their average molecular weight M
w
is from 300 to 5000 g/mol. Examples of these are oligomers of propene, of isobutene and of branched isomers of pentene, hexene, octene and of decene, the copolymerizable terminal group of the oligomer being present in the form of a vinyl, vinylidene or alkylvinylidene group. Oligopropenes and oligopropene mixtures of 9 to 200 carbon atoms and in particular oligoisobutenes, as obtainable, for example, according to DE-A 27 02 604, are preferred. Mixtures of the stated oligomers are also suitable. The molecular weights of the oligomers may be determined in a conventional manner by gel permeation chromatography.
Monomer c)
Suitable monomers c) are all those monomers which are copolymerizable with the monomers a) and b).
Examples of these are linear 1-olefins of 2 to 40, preferably 8 to 30, carbon atoms, such as decene, dodecene, octadecene and industrial mixtures of C
20
-C
24
-1-olefins and C
24
-C
28
-1-olefins.
Other suitable monomers c) are monoethylenically unsaturated C
3
-C
10
-monocarboxylic acids, such as acrylic acid, methacrylic acid, dimethacrylic acid, ethylacrylic acid, crotonic acid, allylacetic acid and vinylacetic acid, among which acrylic and methacrylic acid are preferred.
Vinyl and allyl alkyl ethers where the alkyl radical is of 1 to 40 carbon atoms are also suitable, and the alkyl radical may carry further substituents, such as hydroxyl, amino, dialkylamino or alkoxy. Examples are methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-(diethylamino)ethyl vinyl ether, 2-(di-n-butylamino)ethyl vinyl ether, and the corresponding allyl ethers.
A further group of monomers comprises C
1
-C
40
-alkyl esters, amides and C
1
-C
40
-N-alkylamides of monoethylenically unsaturated C
3
-C
10
-mono- or dicarboxylic acids, such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate and the esters of industrial alcohol mixtures of 14 to 28 carbon atoms, ethyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, octadecyl methacrylate, monobutyl maleate, dibutyl maleate, monodecyl maleate, didodecyl maleate, monooctadecyl maleate, dioctadecyl maleate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dibutylaminoethyl methacrylate, acrylamide, methacrylamide, N-tert-butylacrylamide, N-octylacrylamide, N,N′-dibutylacrylamide, N-dodecylmethacrylamide and N-octadecylmethacrylamide.
Vinyl and allyl esters of C
1
-C
30
-monocarboxylic acids may also be copolymerized with the monomers a) and b). Specific examples of these are vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl pivalate, allyl acetate, allyl butyrate and allyl stearate
N-vinylcarboxamides of carboxylic acids of 1 to 8 carbon atoms, such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-methylpropionamide and N-vinylpropionamide, are also suitable. Other examples are N-vinyl compounds of nitrogen-containing heterocycles, such as N-vinylimidazole, N-vinylmethylimidazole, N-vinylpyrrolidone and N-vinylcaprolactam.
Mixtures of the stated monomers are also suitable as building blocks for the copolymers.
Preferred among these monomers are acrylic acid, methacrylic acid, C
16
-olefins, C
20
-C
24
-olefins, C
14
-C
20
-alkyl vinyl ethers and C
14
-C
20
-alkyl esters of monoethylenically unsaturated C
3
-C
6
-mono- and dicarboxylic acids.
The compolymers I contain the monomers a) to c) in amounts of from 20 to 60 mol % of monomer a), from 10 to 70 mol % of monomer b) and from 1 to 50 mol % of monomer c).
The copolymers may be prepared by all known conventional polymerization processes, for example by mass, emulsion, suspension, precipitation and solution polymerization. All stated polymerization processes are carried out in the absence of oxygen, preferably in a nitrogen stream. The conventional apparatuses, for example autoclaves and kettles, are used for all polymerization methods. Mass polymerization of the monomers of groups a) to c) is particularly preferred. It may be carried out at from 80 to 300° C., preferably at from 120 to 200° C., the lowest polymerization temperature to be chosen preferably being at least about 20° C. above the glass transition temperature of the polymer formed. The polymerization conditions are chosen according to the molecular weight which the copolymers are to have. Polymerization at high temperatures gives copolymers having low molecular weights, whereas polymers having higher molecular weights are formed at lower polymerization temperatures.
The copolymerization is preferably carried out in the presence of compounds which for
Denzinger Walter
Günther Wolfgang
Hartmann Heinrich
Mach Helmut
Oppenländer Knut
BASF - Aktiengesellschaft
Medley Margaret
LandOfFree
Copolymers and their reaction products with amines as fuel... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Copolymers and their reaction products with amines as fuel..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Copolymers and their reaction products with amines as fuel... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3045934