Hydrocarbon oil compositions

Abstract: Hydrocarbon oil compositions, containing a paraffinic hydrocarbon oil and as additives: a) one or more linear polymers of carbon monoxide with one or more olefins consisting at least in part of α-olefins having at least 10 carbon atoms per molecule (C₁₀+ α-olefins) in which polymers on the one hand the units originating from carbon monoxide and on the other hand the units originating from the olefins occur in a substantially alternating way, and moreover one or more polymers selected from: b) polymers of one or more olefinically unsaturated compounds consisting at least in part of alkyl acrylates or alkyl methacrylates having at least eight carbon atoms in the alkyl group (C₈+ alkyl esters), and c) polymers of ethene with one or more vinyl esters of saturated aliphatic monocarboxylic acids.

Description: The invention relates to novel hydrocarbon oil compositions containing a hydrocarbon oil and polymeric additives. Hydrocarbon oils such as gas oils, diesel oils, lubricating oils and crude oils can contain considerable amounts of paraffins. When such oils are stored, transported and used at low temperature, problems can occur as a result of crystallization of these paraffins. In order to meet these problems, it is customary to add certain polymers to the paraffinic hydrocarbon oils. A class of polymers which is very suitable for this purpose is formed by linear polymers of carbon monoxide with one or more olefins consisting at least in part of α-olefins having at least 10 carbon atoms per molecule (hereinafter referred to as C₁₀+ α-olefins), in which polymers on the one hand the units originating from carbon monoxide and on the other hand the units originating from the olefins occur in a substantially alternating way. A second class of polymers which is very suitable for this purpose is formed by polymers of one or more olefinically unsaturated compounds consisting at least in part of alkyl acrylates or alkyl methacrylates having at least eight carbon atoms in the alkyl group (hereinafter referred to as C₈+ alkyl esters). A third class of polymers which is likewise suitable for this purpose is formed by polymers of ethene with one or more vinyl esters of saturated aliphatic monocarboxylic acids. GB-A-1272614 relates to additives for hydrocarbon oil compositions being olefin/carbon monoxide copolymers obtainable by free radical catalyzed polymerization. Such polymers are branched copolymers having a relatively modest carbon monoxide content, e.g. up to 20% mol as illustrated in the working examples. CH-A 572969 relates to paraffinic crude oil compositions comprising as additive polymers or copolymers comprising heterocyclic rings mixturs and aliphatic substituents having at least 10 carbon atoms. US-A 4175926 relates to mineral oil compositions comprising as pour point depressing additives copolymers of ethylene and vinylesters of saturated carboxylic acids. An investigation performed by the Applicant into the use of polymers as additives in paraffinic hydrocarbon oils for improving the properties of these oils at low temperature has disclosed that mixtures of polymers of the first class with polymers of the second and/or third class, which polymers each possess activity per se to reduce the pour point (PP), the cloud point (CP) and/or the cold filter plugging point (CFPP) of these oils, display a synergistic activity. This means that when the mixture is used in a given concentration a stronger PP, CP and/or CFPP reduction is obtained than when each of the polymers is used individually in the same concentration, or that the mixture can produce the same PP, CP and/or CFPP reduction at a lower concentration. The present patent application therefore relates to novel hydrocarbon oil compositions characterized in that they contain a paraffinic hydrocarbon oil and as additives: a) linear polymers of carbon monoxide with one or more olefins consisting at least in part of C₁₀+ α-olefins in which polymers on the one hand the units originating from carbon monoxide and on the other hand the units originating from the olefins occur in a substantially alternating way, and moreover one or more polymers selected from b) polymers of olefinically unsaturated compounds consisting at least in part of C₈+ alkyl esters, and c) polymers of ethene with one or more vinyl esters of saturated aliphatic monocarboxylic acids. As paraffinic hydrocarbon oils the low-temperature properties of which can be improved according to the invention, mention may be made inter alia of gas oils, diesel oils, lubricating oils and crude oils. Very favourable results are achieved inter alia with the use of the present polymer mixtures in paraffinic gas oils and crude oils. The molecular weight of the polymers which are eligible for use in the hydrocarbon oil compositions according to the invention can vary within wide limits. For preference, additives are used having a weight average molecular weight ( M w ) between 10³ and 10⁶ and in particular between 10⁴ and 10⁶. Both the C₁₀+ α-olefins which are used as monomers in the preparation of the polymers mentioned in a) and the alkyl groups present in the C₈+ alkyl esters which are used as monomers in the preparation of the polymers mentioned in b) should preferably be unbranched. Both the C₁₀+ α-olefins and the alkyl groups present in the C₈+ alkyl esters, if present, preferably contain fewer than 40 and in particular fewer than 30 carbon atoms. The preference for a given molecular weight of the polymers and for a given number of carbon atoms in the C₁₀+ α-olefins and in the alkyl groups of the C₈+ alkyl esters which are used as monomers in the preparation of the polymers is largely determined by the nature of the paraffins present in the hydrocarbon oil. In the preparation of the polymers mentioned in a), besides C₁₀+ α-olefins, olefins with fewer than 10 carbon atoms can also be used such as ethylene, propylene, butene-1 and cyclopentene. Preferably, in the preparation of the polymers mentioned in a), exclusively C₁₀+ α-olefins are used as olefins. The monomer mixture from which the polymers mentioned in a) are prepared may contain in addition to carbon monoxide both one and more C₁₀+ α-olefins. As an example of a copolymer with which very favourable results were achieved according to the invention, mention may be made of a carbon monoxide/1-octadecene copolymer. As an example of a terpolymer which is very suitable for the present purpose, mention may be made of a carbon monoxide/1-tetradecene/1-octadecene terpolymer. Polymers of carbon monoxide with a mixture of unbranched α-olefins having 20-24 carbon atoms per molecule were also found to be very suitable for use in the present polymer mixtures. As has been noted hereinbefore, as regards the polymers mentioned in a) there is a preference for polymers based on carbon monoxide with one or more C₁₀+ α-olefins which polymers possess an M w above 10⁴. An investigation into these polymers recently performed by the Applicant disclosed an attractive method of preparation. This preparation method consists basically of contacting the monomers at elevated temperature and pressure and in the presence of a diluent consisting for more than 90 %v of an aprotic liquid with a catalyst composition containing a Group VIII metal and a phosphorus bidentate ligand having the general formula (R¹R²P)₂R, where R¹ and R² represent identical or different optionally polar substituted aliphatic hydrocarbyl groups and R a bivalent organic bridging group containing at least two carbon atoms in the bridge linking the two phosphorus atoms. There is a preference for the use of catalyst compositions which contain 0.75-1.5 mol of a phosphorus bidentate ligand per gram atom of Group VIII metal where the groups R¹ and R² are identical alkyl groups having not more than six carbon atoms and which moreover per gram atom of Group VIII metal contain 2-50 mol of an anion of an acid having a pKa below 2 and optionally 10-1,000 mol of an organic oxidant. Special preference exists for catalyst compositions based on palladium acetate, 1,3-bis(di-n-butylphosphino)propane, 1,4-naphthoquinone and trifluoroacetic acid or nickel perchlorate. The preparation of the polymers is preferably performed at a temperature of 30-130°C, a pressure of 5-100 bar and a molar ratio of the olefins relative to carbon monoxide of 5:1 to 1:5 and with the use of such a quantity of catalyst composition as to contain 10⁻⁶ to 10⁻³ gram atom of Group VIII metal per mol of olefin to be polymerized. The polymerization is preferably performed in a diluent which contains a small quantity of a protic liquid. A very suitable diluent for the present polymerization is a mixture of tetrahydrofuran and methanol. In the preparation of the polymers mentioned in b), besides C₈+ alkyl esters other olefinically unsaturated compounds can also be used such as alkyl acrylates and alkyl methacrylates having fewer than eight carbon atoms in the alkyl group, olefinically unsaturated aromatic compounds such as styrene and olefinically unsaturated heterocyclic compounds such as vinyl pyridines. The monomer mixture from which the polymers mentioned in b) are prepared can contain both one and more C₈+ alkyl esters. As examples of terpolymers with which very favourable results can be achieved according to the invention, mention may be made of a 1-dodecyl methacrylate/1-octadecyl methacrylate/2-vinylpyridine terpolymer and a 1-octadecyl acrylate/1-eicosyl acrylate/1-docosyl acrylate terpolymer. As examples of polymers with which likewise very favourable results were achieved according to the invention, mention may be made of polymers of 4-vinylpyridine with a mixture of n-alkyl acrylates having 18-22 carbon atoms in the alkyl groups, polymers of mixtures of n-alkyl acrylates having 12-15 carbon atoms in the alkyl groups, and polymers of methylacrylate with a mixture of n-alkyl acrylates having 12-15 carbon atoms in the alkyl groups. Examples of polymers mentioned in c) with which advantageous results are obtained are copolymers of ethene with vinyl propionate or acetate, especially the latter give good results. They are obtainable commercially in a variety of molecular weights and weight distributions, specially formulated for ready addition to hydrocarbon oils. In the hydrocarbon oil compositions according to the invention, both one or more of the polymers mentioned in a) and one or more of the polymers mentioned in b) and c) may be present. Preference exists for hydrocarbon oil compositions which contain only two additives: only one of the polymers mentioned in a) and only one of the polymers mentioned in b) and c). Besides the present polymer mixtures, the hydrocarbon oil compositions may also contain other additives such antioxidants, corrosion inhibitors and metal deactivators. The quantity of polymer mixture which is taken up in the paraffinic hydrocarbon oils according to the invention and the relative ratio of the polymers in the polymer mixture can vary between wide limits. For preference, 0.1-10,000 and in particular 1-1,000 mg of the polymer mixture is taken up per kg of hydrocarbon oil. The polymer mixture used preferably contains 1-90 %w and in particular 10-75 %w of the polymers mentioned in a), and thus preferably 10-99, in particular 25-90 %w, of the polymers mentioned in b) and c) together. The invention will now be illustrated with reference to the following examples: Example 1 A carbon monoxide/1-octadecene copolymer was prepared as follows. In a stirred autoclave with a capacity of 250 ml which contained 100 ml of tetrahydrofuran and 40 g of 1-octadecene in a nitrogen atmosphere, a catalyst solution was introduced, containing: 5 ml methanol, 0.1 mmol palladium acetate, 0.5 mmol nickel perchlorate, 0.12 mmol 1,3-bis(di-n-butylphosphino)propane, and 6 mmol 1,4-naphthoquinone. After injection of carbon monoxide to a pressure of 40 bar, the contents of the autoclave were heated to 50 °C. After 30 h, the polymerization was terminated by cooling the reaction mixture to ambient temperature and depressuring. After the addition of acetone to the reaction mixture, the polymer was filtered off, washed with acetone and dried. The yield was 40 g of copolymer having an M w of 20,300. Example 2 A carbon monoxide/1-tetradecene/1-octadecene terpolymer was prepared in substantially the same manner as the carbon monoxide/1-octadecene copolymer in Example 1, but with the following differences: a) the autoclave contained 30 g of 1-octadecene instead of 40 g and moreover 30 g of 1-tetradecene, b) the reaction temperature was 35 °C instead of 50 °C, and c) the reaction time was 20 instead of 30 h. The yield was 41 g of terpolymer having an M w of 78,000. Example 3 A polymer of carbon monoxide with a mixture of linear α-olefins having 20-24 carbon atoms per molecule was prepared in substantially the same manner as the carbon monoxide/1-octadecene copolymer in Example 1, but with the following differences: a) the autoclave contained 40 g of a mixture of linear α-olefins having 20-24 carbon atoms per molecule instead of 1-octadecene, b) carbon monoxide was injected into the autoclave to a pressure of 70 instead of 40 bar, and c) the reaction time was 15 instead of 30 h. The yield was 38 g of polymer having an M w of 22,700. Example 4 : A carbon monoxide/1-hexadecene copolymer was prepared in substantially the same manner as the carbon monoxide/1-octadecene copolymer in Example 1, but with the following differences: a) the autoclave contained 38 g of 1-hexadecene instead of 40 g of 1-octadecene, b) carbon monoxide was injected into the autoclave to a pressure of 70 instead of 40 bar, and c) the reaction time was 15 instead of 30 h. The yield was 40 g of copolymer having an M w of 35,000. Example 5 A carbon monoxide/1-tetradecene/1-hexadecene/1-octadecene quaterpolymer was prepared in substantially the same manner as the carbon monoxide/1-octadecene copolymer in Example 1, but with the following differences: a) the autoclave contained 38 g of an n-C₁₄/n-C₁₆/n-C₁₈ α-olefin mixture having a molar ratio of 1:2:1 instead of 40 g of 1-octadecene, b) carbon monoxide was injected into the autoclave to a pressure of 70 instead of 40 bar, and c) the reaction time was 15 instead of 30 h. The yield was 42 g of quaterpolymer having an M w of 22,000. Example 6 The following polymers were tested as additives in two crude oils (A and B) and in two gas oils (C and D) to reduce the PP of these oils. Additive 1: The copolymer prepared according to Example 1. Additive 2: The terpolymer prepared according to Example 2. Additive 3: The polymer prepared according to Example 3. Additive 4: A 1-dodecyl methacrylate/1-octadecyl methacrylate/2-vinylpyridine terpolymer having an M w of 66,000. Additive 5: A 1-octadecyl acrylate/1-eicosyl acrylate/1-docosyl acrylate terpolymer having an M w of 220,000. Additive 6: A polymer of 4-vinylpyridine with a mixture of n-alkyl acrylates having 18-22 carbon atoms in the alkyl groups and having an M w of 135,000. Additive 7: A polymer of a mixture of n-alkyl acrylates having 12 to 15 carbon atoms in the alkyl groups and having an M w of 160,000. Additive 8: A polymer of methyl acrylate with a mixture of n-alkyl acrylates having 12-15 carbon atoms in the alkyl groups and having an M w of 224,000. The polymers were introduced into the oil in the form of a solution of 50 %w of solid matter in toluene. The results of the experiments are given below in Table I, in which the PP is reported after preheating to the stated temperature (50 or 90 °C) and, if applicable, adding at 50 °C the stated amount of polymer solution expressed as mg of polymer solution per kg of paraffinic oil. All mixtures of additives had a weight ratio of 1:1, except the mixture of test 5, which had a weight ratio of 1:2. The PPs were determined in accordance with standard method ASTM D97. The sixteen polymer mixture-containing hydrocarbon oil compositions as described above and tested for their PP are compositions according to the invention. The synergism which occurs when a mixture of a polymer listed under a) with a polymer listed under b) is used, is readily apparent from a comparison of the results of the experiments performed with either additive 1 (tests 17-19) or additive 4 (tests 20-22) with a 1:1 mixture of additives 1 and 4 (tests 23-25). This synergism also emerges clearly upon comparison of the results of tests 26-29 performed with gas oil D. Example 7 The following polymers were tested as additives in a gas oil (E) to reduce the CFPP of this oil. Additive 9: the copolymer prepared according to Example 4. Additive 10: the copolymer prepared according to Example 5. Additive 11: a copolymer of ethene and vinyl acetate, commercially available as a solution under the trademark PARAMIN ECA 5920. Additive 12: a copolymer of ethene and vinyl acetate, commercially available as a solution under the trademark PARAMIN PARAFLOW 214. Additive 13: a copolymer of ethene and vinyl acetate, commercially available as a solution under the trademark PARAMIN ECA 8182. Additives 9 and 10 were introduced into the oil in the form of a solution of 50 %w of solid matter in toluene. Additives 11-13 were introduced into the oil in the form of their commercial solutions. The results of the experiments are given below in Table II, in which the CFPP is reported after preheating to 50 °C and, if applicable, adding at 50 °C the stated quantity of polymer solution expressed as mg of solution per kg of gas oil. All mixtures of additives had a weight ratio of 1:1. The CFPPs were determined according to standard method IP 309. The six polymer mixture-containing hydrocarbon oil compositions as described above and tested for their CFPP are compositions according to the invention. The synergism which occurs when a polymer listed under a) is mixed with a polymer listed under c), is readily apparent from mutual comparison of the results of tests 31-33, of tests 34, 35 and 37, of tests 34, 39 and 41, of tests 31, 42 and 43, of tests 35, 44 and 45, or of tests 45-47. Examples 1-5, in which the preparation is described of the polymers used as additives in Examples 6 and 7, fall outside the scope of the invention. By means of ¹³C-NMR analysis, it was determined that these polymers were constructed of linear chains in which on the one hand the units originating from carbon monoxide and on the other hand the units originating from the C₁₀+ α-olefins occurred in an alternating way. In the polymers prepared from monomer mixtures containing two or more C₁₀+ α-olefins, the units originating from the various C₁₀+ α-olefins occurred in random sequence relative to one another.

Claims: Claims for the following Contracting States : BE, DE, FR, GB, IT, NL Hydrocarbon oil compositions, characterized in that they contain a paraffinic hydrocarbon oil and as additives: a) one or more linear polymers of carbon monoxide with one or more olefins consisting at least in part of α-olefins having at least 10 carbon atoms per molecule (C₁₀+ α-olefins) in which polymers on the one hand the units originating from carbon monoxide and on the other hand the units originating from the olefins occur in a substantially alternating way, and moreover one or more polymers selected from: b) polymers of one or more olefinically unsaturated compounds consisting at least in part of alkyl acrylates or alkyl methacrylates having at least eight carbon atoms in the alkyl group (C₈+ alkyl esters), and c) polymers of ethene with one or more vinyl esters of saturated aliphatic monocarboxylic acids. Hydrocarbon oil compositions as claimed in claim 1, characterized in that the additives possess a weight average molecular weight ( M w ), between 10³ and 10⁶. Hydrocarbon oil compositions as claimed in claim 1 or 2, characterized in that both the C₁₀+ α-olefins and the alkyl groups present in the C₈+ alkyl esters, if present, contain fewer than 40 carbon atoms. Hydrocarbon oil compositions as claimed in any one or more of claims 1-3, characterized in that exclusively C₁₀+ α-olefins are used as olefins in the preparation of the polymers mentioned in a). Hydrocarbon oil compositions as claimed in any one or more of claims 1-4, characterized in that they contain polymers mentioned in a) based on carbon monoxide with one or more C₁₀+ α-olefins which polymers possess an M w above 10⁴ and which polymers are obtainable by contacting the monomers, at elevated temperature and pressure and in the presence of a diluent consisting for more than 90 %v of an aprotic liquid, with a catalyst composition containing a Group VIII metal and a phosphorus bidentate ligand having the general formula (R¹R²P)₂R, where R¹ and R² represent identical or different optionally polar substituted aliphatic hydrocarbyl groups and R a bivalent organic bridging group containing at least two carbon atoms in the bridge linking the two phosphorus atoms. Hydrocarbon oil compositions as claimed in any one or more of claims 1-5, characterized in that they contain polymers mentioned in b) selected from n-dodecyl methacrylate/n-octadecyl methacrylate/2-vinyl pyridine terpolymers, n-octadecyl acrylate/n-eicosyl acrylate/n-docosyl acrylate terpolymers, polymers of 4-vinyl pyridine with a mixture of n-alkyl acrylates having 18-22 carbon atoms in the alkyl groups, polymers of mixtures of n-alkyl acrylates having 12-15 carbon atoms in the alkyl groups, and polymers of methylacrylate with a mixture of n-alkyl acrylates having 12-15 carbon atoms in the alkyl groups. Hydrocarbon oil compositions as claimed in any one or more of claims 1-6, characterized in that they contain polymers mentioned in c) selected from copolymers of ethene with vinyl propionate or acetate. Hydrocarbon oil compositions as claimed in any one or more of claims 1-7, characterized in that they contain only one of the polymers mentioned in a) and only one of the polymers mentioned in b) and c). Hydrocarbon oil compositions as claimed in any one or more of claims 1-8, characterized in that they contain 0.1-10,000 mg of polymer mixture per kg of hydrocarbon oil. Hydrocarbon oil compositions as claimed in any one or more of claims 1-9, characterized in that the polymer mixture used contains from 1-90 %w of the polymers mentioned in a). Claims for the following contracting State : ES A process for preparing hydrocarbon oil compositions, characterized in that a paraffinic hydrocarbon oil is admixed with the following additives: a) one or more linear polymers of carbon monoxide with one or more olefins consisting at least in part of α-olefins having at least 10 carbon atoms per molecule (C₁₀+ α-olefins) in which polymers on the one hand the units originating from carbon monoxide and on the other hand the units originating from the olefins occur in a substantially alternating way, and moreover one or more polymers selected from: b) polymers of one or more olefinically unsaturated compounds consisting at least in part of alkyl acrylates or alkyl methacrylates having at least eight carbon atoms in the alkyl group (C₈+ alkyl esters), and. c) polymers of ethene with one or more vinyl esters of saturated aliphatic monocarboxylic acids. Process as claimed in claim 1, characterized in that the additives possess a weight average molecular weight ( M w ), between 10³ and 10⁶. Process as claimed in claim 1 or 2, characterized in that both the C₁₀+ α-olefins and the alkyl groups present in the C₈+ alkyl esters, if present, contain fewer than 40 carbon atoms. Process as claimed in any one or more of claims 1-3, characterized in that exclusively C₁₀+ α-olefins are used as olefins in the preparation of the polymers mentioned in a). Process as claimed in any one or more of claims 1-4, characterized in that they contain polymers mentioned in a) based on carbon monoxide with one or more C₁₀+ α-olefins which polymers possess an M w above 10⁴ and which polymers are obtainable by contacting the monomers, at elevated temperature and pressure and in the presence of a diluent consisting for more than 90 %v of an aprotic liquid, with a catalyst composition containing a Group VIII metal and a phosphorus bidentate ligand having the general formula (R¹R²P)₂R, where R¹ and R² represent identical or different optionally polar substituted aliphatic hydrocarbyl groups and R a bivalent organic bridging group containing at least two carbon atoms in the bridge linking the two phosphorus atoms. Process as claimed in any one or more of claims 1-5, characterized in that they contain polymers mentioned in b) selected from n-dodecyl methacrylate/n-octadecyl methacrylate/2-vinyl pyridine terpolymers, n-octadecyl acrylate/n-eicosyl acrylate/n-docosyl acrylate terpolymers, polymers of 4-vinyl pyridine with a mixture of n-alkyl acrylates having 18-22 carbon atoms in the alkyl groups, polymers of mixtures of n-alkyl acrylates having 12-15 carbon atoms in the alkyl groups, and polymers of methylacrylate with a mixture of n-alkyl acrylates having 12-15 carbon atoms in the alkyl groups. Process as claimed in any one or more of claims 1-6, characterized in that they contain polymers mentioned in c) selected from copolymers of ethene with vinyl propionate or acetate. Process as claimed in any one or more of claims 1-7, characterized in that they contain only one of the polymers mentioned in a) and only one of the polymers mentioned in b) and c). Process as claimed in any one or more of claims 1-8, characterized in that they contain 0.1-10,000 mg of polymer mixture per kg of hydrocarbon oil. Process as claimed in any one or more of claims 1-9, characterized in that the polymer mixture used contains from 1-90 %w of the polymers mentioned in a).

Inventors: BODT DUCO, REYNHOUT MARINUS JOHANNES, TOMASSEN HENRICUS PAULUS MARIA, BODT, DUCO, REYNHOUT, MARINUS JOHANNES, TOMASSEN, HENRICUS PAULUS MARIA
Applicants: SHELL INT RESEARCH, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1991
Main classification: C10M157
IPC codes: C07C11, C10L1, C08L91, C10M145, C10M169, C10L10, C07C7, C07C9, C10N40, C10M157, C10N30