US006162772A_ United States Patent 11» [1 Patent Number: 6,162,772 Dounis [45] Date of Patent: Dec. 19, 2000 [54] OILADDITIVES AND COMPOSITIONS 421207 51977 Durand etal 4032489 61077 Crosland etal SSor04 1103 Maldonado et [75] Iaventor: Panagiotis Dounis, Oxon, United (75) ii 5242989 9/1903 Bening ct al Kingdom 5 $pts80 11/1003 Bening etal ssiance: Infineum USA LPs Linden, 53005886 4/1994 Bening ta sosams (73) Assignee: Infineum USA LP, Linden, NJ 5,310,890 5/1904 Struglinsk et al. 252/88, S310814 51904 Struglnshi eta saat [21] Appl. No. 09/3737 5356970 10/1994 Bening et S2st68 3528:128 ‘6/1900. McAleer et a 44459 [23] Fitea 19, 1999 3543409 $1990 Stuglnst etl sasais a eee are Soasass 81999 Suuplnd cat Sate ‘Aug. 20, 1998 [GB] United Kingdom 9818210 FOREIGN PATENT DOCUMENTS ren) oe COCCI 1490863 1/1077 United Kingdom ata 205608 1/1982 United Kingdom (32) US.Cl 5081583; 508/475; 508451; -s_bllen M. Me SRS, 508/475: 508451 Primary Exaniner—Ellen M. McAvoy [58] Field of Search 508/591, 583 [57] ABSTRACT (56) References Cited Use of « hydrogenated diene polymer with a polar group to improve cold flow improver adpack compatibility USS, PATENT DOCUMENTS. “ P ip patibility 3,635,685 1/1972 Sonnenfeld 48 Claims, No Drawings6,162,772 1 OIL ADDITIVES AND COMPOSITIONS ‘This invention relates to oil compositions, primarily to fuel oil compositions, and more especially to fuel oil com- positions susceptible to wax formation at low temperatures, {o additives for use in such fuel oil compositions, andl to the use of the additives to improve the cold flow properties of fuels Fuel oils, whether derived from petroleum or from veg~ ‘lable sources, contain components, e.g, alkanes, that at low temperature tend (0 precipitate as large crystals or spheru- lites of wax in such & way as to form a gel structure which ‘causes the fuel to lose its ability to flow. The lowest temperature at whieh the fuel will sil flow is known as the pour point. ‘AS the temperature of the fuel falls and approaches the pour point, difficulties arise in transporting the fuel through Tines and pumps. Further, the wax erystals tend to plug fuel lines, screens, and filters at temperatures above the pour point, These problems are well recognized in the art, and various additives have been proposed, many of which are in ‘commercial use, for depressing the pour point of fuel oi Similarly, other additives have been proposed and are in ‘commercial use for reducing the size and changing the shape Of the wax crystals that do form. Smaller size erystals are desirable since they are less likely to clog a filter. The wax from a diesel fuel, which is primarily an alkane wax, crystallizes as platelets; certain additives inhibit this and ‘cause the wax fo adopt an acicular habit, the resulting needles being more likely to pass through a filter than are platelets. The additives may also have the effect of retaining in suspension in the fuel the crystals that have formed, the resulting reduced settling also assisting in prevention of blockages. It has previously been proposed, for example in British Specification No. 1 490 563, to use a hydrogenated diene polymer, ¢., 4 homopolymer of butadiene ot a copolymer Of butadiene with a C, to Cy diene, especially isoprene, as a cold flow improver. It has also been proposed t0 use a hydrocarbon wax to the same end, It is common practice to include hydrocarbon polymers, or bydrocatbon-uasaturated ester copolymers, especially ethylene-vinyl acetate ‘copolymers, for the purpose, and it is further common to ‘employ two or more cold flow improvers, such mixtures showing synergy. Unfortunately, it has been found that when two or more ‘cold flow improvers are mixed at high concentrations in a solvent medium, as ia an additive concentrate or “adpack", they may be incompatible, the solution not being stable over a prolonged period. This problem has proved especially severe when hydrogenated diene polymers and ethylene- unsaturated ester polymers are present in the same package, certain combinations producing sediment after storage for ‘only one day at room temperature. ‘The present invention is based on the observation that the inclusion of a polar group, advantageously a terminal polar group, in the hydrogenated diene polymer improves its ‘compatibility in multi-component cold flow additive pack: ages. ‘The present invention accordingly provides a cold flow improver composition comprising (i) « hydrogenated diene polymer having a polar group and (i) a cold flow improver ‘ther than a polymer (i) ‘Advantageously, the hydrogenated diene polymer is an oil-soluble hydrogenated block diene polymer, comprising al least one crystallizable block, obtainable by end-to-end polymerization of a linear diene, and at least one non- 0 as os ss 4s ss 6s 2 crystallizable block, the non-crystallizable block being obiainable by 1,2-configuration polymerization of a linear diene, by polymerization of a branched diene, or by a ‘mixture of such polymerizations. ‘Advantageously, the hydrogenated block copolymer used in the present invention comprises at least one sub- stantially linear erystalizable segment or block and af least ‘one segment or block that is essentially not erystallizable. Without wishing to be bound by any theory, it is believed that when butadiene is homopolymerized with a sufficient proportion of 1,4 (or end-to-end) enchainments to provide substantially linear polymeric structure then on hydrogena- tion it resembles polyethylene and crystallizes rather readily; when a branched diene is polymerized on its own or with butadiene a branched structure will result (eg, & hydroge- rated polyisoprene structure will resemble an ethylene- propylene copolymer) that will not readily form crystalline domains but will confer fuel oil solubility on the block copolymer. “Advantageously, the block polymer before hydrogena- tion comprises units derived from butadiene only or from butadiene and at least one comonomer of the formula (CH =CR'—CR=CH, wherein R! represents a C; to Cy alkyl group and RE represents hydrogen or a C, to Cy alkyl group. Advan- tagcously the total number of carbon atoms in the ‘comonomer is 510 8, and the eomonomer is advanta- seously isoprene. Advantageously, the copolymer eon- ins at least 10% by weight of units derived from butadiene. Alter hydrogenation, the copolymer advantageously con- tains at least 10%, preferably at least 20%, and’ most preferably from 25 to 60%, by weight of at least one cxysalline or erystallizable segment composed primarily of methylene units; 10 this end the erystllizable. segment before hydrogenation advantageously has an average 1,4 of end-to-end enchainment of at least 70 preferably at least 85, mole per cent. The hydrogenated block copolymer com- prises at least one low crystallinity (or difficultly cxystallizable) segment composed of methylene and substi tuted methylene units, derived from one or more alkyl- substituted monomers described above, e.g, isoprene and 2,3-dimelhyIbutadiene. ‘Alternatively, the low crystallinity segment may be derived from butadiene by 1,2 enchainmeat, in which the segment has before hydrogenation an average 1,4 enchain- rent of butadiene of at most 60, preferably at most 50, percent, As a result, the polymer comprises. 14- polybutadiene as one ‘block and 1,2-polybutadiene “as another. Such polymers are obtainable by, e-8. adding a catalyst modifier, as described in International Application WO92/16568, the disclosure of which is incorporated berein by reference ‘A further advantageous block copolymer is a hydroge- nated tapered block or segmented copolymer, advania- zeously of butadiene and at least one other conjugated diene, preferably isoprene. Such a block copolymer may be Obtained ‘by anionically copolymerizing, in. hydrocarbon solution ia, for example, a batch reactor, @ mixture contain- ing butadiene monomer and at least one other conjugated diene monomer to form a precursor copolymer having at least 75 weight percent 1,4-configuration of the butadiene and at least one other conjugated diene and then hydroge- nating said precursor copolymer. During the intial formation of the unhydrogenated pre- cursor copolymer of butadiene and at least one other con-6,162,772 3 jugated diene, butadiene wil be preferentially polymerized ‘The concentration of monomers in solution changes during the course ofthe reation in favour ofthe other conjugated dione asthe butadiene is depleted. The results a precursor ‘copolymer in which the copolymer chain is higher in buta- diene concentration in the chain segments grown near the beginning of the reaction and higher in the other conjugeted diene concentration in the chain segments formed near the tend ofthe reaction, These copolymer chains are accordingly described as tapered in composition. Upon hydrogenation the butadiene rich portion of the polymer becomes rich in methylene units. Therefore, ia each of these hydrogenated generally linear copolymer molecules two longitudinal seg- iments are present, gradually merging ino each other without sharp boundaries. One of the outer segments consists nearly ‘completely of methylene units derived from the hydrogena- tion ofthe butadiene in the 1-configuration and contains only small amounis of substituted methylene units derived from the hydrogenation of the other conjugated diene such a isoprene, The second segment is relatively rich in sub- stituted methylene units derived, for example, from the hhydrogenation ofthe isoprene inthe 1,4-conlguratio, The first segment, which is rich in methylene units, comprises the erysalizable segment, advantageously containing more than 30 mole percent 1,4-polybutadiene. The second outer segment comprises the low crystallinity segment, advanta- geously containing ess than 20 mole percent 1,4- polybutadiene units In these tapered block copolymers the ‘xystalizableseyment typically comprises an average of at least 20 mole percent ofthe copolymer’s chain “The weight percent of the butadiene present in the eac= sion mixture is that effective wo form a tapered segmented or block copolymer having at least one erystallizable block and atleast one non-crytallizable block. Generally this amount ‘of butadiene is from 20 0 90 weight percent. Additionally, the proportion of the 1,4-configuration butadiene present in the precursor copolymer is that effective to form a cxystal- lizable. segment upon hydrogenation of the precursor copolymer. Generally this proportion is atleast 80 weight peteent ‘Aurther advantageous block copolymer isa star copoly- mer having from 3 t0 25, preferably 5 to 15, ams. ‘Advantageous embodiments of block copolymers ate those comprising a single erystllizable block and a single nom-erystallizable block and those comprising «single non- ‘rystalizable block having at each end a single erystalliz~ able block. Other ti and ters-block copolymers are also suitable Tn general, the crystllizable block of blocks willbe the hydrogenation product of the unit resulting from predomi- nantly 14 or end-to-end polymerization of butadiene, while the non-erystalizable block or blocks willbe the hyroge- tation product ofthe unit resulting from 1,2-polymerization fof buladiene or from I--polymerizaion of an alkyl- ‘substituted butadiene. ‘Advantageously the molecular weight, Mo, ofthe bydro- genated block copolymer, measured by GPC, lies in the range of S00 to 100,000, more advantageously 500 to 20,000, preferably 500 to 10,000 and move preferably from 3,000 to 8,000, Advantageously, in a diblock polymer, the molecular _weight of the erstllizable block is from 500 10 20,000, and preferably from 500 to 5,000, and that of the non- xysallizable block is from $00 to 50,000, preferably from 1,000 fo 5,000, In a triblock polymer, the molecular Weight of each erystalizable block is advantageously from 500 to 20,000, advantageously about 5,000, and that of the non- 0 as os ss 4s ss 6s 4 exysiallizable block is from 1,000 t0 20,000, preferably 1,000 to 5,000, ‘The proportion of the total molecular weight of « block copolymer represented by a crystalline block or blocks may be determined by H or C NMR, and the total molecular ‘weight of the polymer by GPC, ‘As indicated in more detail in International Application 'W092/16567, the disclosure of which is incorporated herein by reference, the precursor block copolymers are conve- niently prepared by anionic polymerization, which facili- tates control of structure and molecular weight, preferably using a metallic or organometallic catalyst. Hydrogenation is effected employing conventional procedures, using elevated temperature and hydrogen pressure in the presence of a hydrogenation catalyst, preferably palladium on barium sulphate or calcium carbonate or nickel octanoatetrietbyl aluminium ‘Advantageously, at least 90% of the original unsaturation (as measured by NMR spectroscopy) is removed on hydrogenation, preferably atleast 95%, andl more preferably at least 98%, ‘The polar group in the hydrogenated diene polymer may be, for example a hydroxy or carboxy group. ‘The polar group is advantageously prescat in a molar proportion of 0.4 to 2, preferably 0.6 to 15, and more preferably 0.8 10 12, groups per polymer molecule. In general, the polar groups are advantageously predominantly primary, ie., terminal, groups. ‘The polar group may be introduced into the diene polymer, either after but preferably before hydrogenation, by a method appropriate to the polar group concerned. For example, a hydroxy group may be introduced just before completion of polymerization by reaction with ethylene or propylene oxide in the presence of a basic catalyst (e.g. lithium hydroxide) and subsequent reaction with « proton donor (eg., a carboxylic acid) to form the bydroxide, or by the ethylene oxide treatment deseribed in USS. Pat. No. 3,135,716, the entire disclosure of which is incorporated by reference herein. A further method for introducing a hydroxy group is by polymerizing in the presence of a peroxide, e.g, hydrogen peroxide, as described in US. Pat. No. 3,446,740, the disclosure of which is incorporated by reference herein ‘The hydroxy group may, in turn, provide a site for further reaction yield other polar groups which may improve compatibility or confer other characteristics on the polymer, ‘A carboxy group may be introduced by treatment of the polymer with CO, also as described in U.S. Pat. No. 3,135,716, and if desired may, in the same way as the hydroxy group, be used as a further reaction site. In USS, Pat, No. 3,446,740 there is disclosed the use of hydrogenated diene polymer containing hydroxyl groups as cold flow improver, U.S. Pat, No. 3,635,685 discloses a hydrogenated butadicne-styrene copolymer with hydroxyl, carboxyl and pyridyl groups for the same purpose. In each case, the hydrogenated polymer is the sole cold flow improver present ‘As examples of cold flow improvers other than 4 polymer as defined in (i) there may be mentioned (A) ethylene-unsaturated ester compounds, (B) comb polymers, (©) polar nitrogen compounds, (D) hydrocarbon polymers, (E) hydrocarbyl esters of amine-substituted carboxylic acids, (F) poly(methjacrylate esters, (G) polyoxyalkylene compounds, and