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Patent US6818601 - Dispersant-viscosity improvers for lubricating oil compositions - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsA composition of matter suitable for use as a dispersant-viscosity improver for lubricating oil compositions comprises the reaction product of reactants comprising (a) hydrocarbon polymer grafted with an α,β-ethylenically unsaturated carboxylic acid or functional derivative thereof; and (b) an amine...http://www.google.com/patents/US6818601?utm_source=gb-gplus-sharePatent US6818601 - Dispersant-viscosity improvers for lubricating oil compositionsAdvanced Patent SearchPublication numberUS6818601 B1Publication typeGrantApplication numberUS 09/599,709Publication dateNov 16, 2004Filing dateJun 22, 2000Priority dateSep 13, 1996Fee statusPaidPublication number09599709, 599709, US 6818601 B1, US 6818601B1, US-B1-6818601, US6818601 B1, US6818601B1InventorsRichard M. LangeOriginal AssigneeThe Lubrizol CorporationExport CitationBiBTeX, EndNote, RefManPatent Citations (18), Non-Patent Citations (3), Referenced by (18), Classifications (13), Legal Events (2) External Links: USPTO, USPTO Assignment, EspacenetDispersant-viscosity improvers for lubricating oil compositions
US 6818601 B1Abstract
What is claimed is: 1. A dispersant-viscosity improver composition for lubricating oil compositions comprising the reaction product of
(a) a hydrocarbon polymer having a number average molecular weight between 20,000 and 500,000 grafted with an α,β-ethylenically unsaturated carboxylic acid or functional derivative thereof containing from 2 to about 20 carbon atoms exclusive of carbonyl carbons and present in the range of about 0.01 to about 10 percent by weight based on the weight of the polymer; and (b) an amine selected from the group consisting of (b-1) a polyamine product having at least one condensable primary or secondary amino group, made by contacting at least one hydroxy-containing material (b-i) having the general formula (R)nYz—Xp—A(OH)q)m (I) wherein each R is independently H or hydrocarbon based group, Y is selected from the group consisting of O, N, and S, X is a polyvalent hydrocarbon based group, A is a polyvalent hydrocarbon based group, n is 1 or 2, z is 0 or 1, p is 0 or 1, q ranges from 1 to about 10, and m is a number ranging from 1 to about 10; with (b-ii) at least one amine having at least one N—H group, and (b-2) an acylated derivative of (b-1) containing at least one condensable N—H group, and optionally, (c) at least one hydrocarbon group substituted carboxylic acid or anhydride. 2. The composition of claim 1 wherein the reaction product further comprises at least one preformed polyester containing at least one condensable hydroxyl group.
(1) hydrogenated polymers of dienes; (2) hydrogenated copolymers of a conjugated diene with one or more vinyl substituted aromatic compounds; (3) polymers of alpha olefins containing from 2 to about 28 carbon atoms; (4) olefin-diene copolymers; and (5) star polymers. 4. The composition of claim 3 wherein the hydrocarbon polymer is (1) a hydrogenated polymer of dienes, wherein the diene is a conjugated diene selected from the group consisting of isoprene, butadiene, and piperylene.
17. The composition of claim 1 wherein grafting of the hydrocarbon copolymer is conducted at about 80� C. to about 200� C. in the presence of a free radical initiator.
Hydrogenated polymers include homopolymers and copolymers of conjugated dienes including polymers of 1,3-dienes of the formula wherein each substituent denoted by R, or R with a numerical subscript, is independently hydrogen or hydrocarbon based, wherein hydrocarbon based is as defined hereinabove. Preferably at least one substituent is H. Normally, the total carbon content of the diene will not exceed 20 carbons. Preferred dienes for preparation of the polymer are piperylene, isoprene, 2,3-dimethyl-1,3-butadiene, chloroprene and 1,3-butadiene.
(A)a-(B)b-(C)c, (A)a-(C)c-(B)b, or (B)b-(A)a-(C)c, wherein the lower case letters a, b and c represent the approximate number of monomer units in the indicated block.
There are numerous commercial sources for lower olefin-diene polymers. For example, Ortholeum� 2052 (a product marketed by the DuPont Company) which is a terpolymer having an ethylene:propylene weight ratio of about 57:43 and containing 4-5 weight % of groups derived from 1-4 hexadiene monomer, and numerous other such materials are readily available. Olefin-dienes copolymers and methods for their preparation are described in numerous patents including the following U.S. Patents:
Azo group containing initiators, such as Vazo� polymerization initiators (DuPont) employed in the grafting process at about 95� C. result in a much higher degree of grafting onto the polymer backbone than do peroxide initiators such as t-butyl peroxide, employed at about 150-160� C. Peresters are particularly effective in the free-radical grafting process.
Examples include 2-alkoxyethanols, members of the “Cellosolve” family of glycol ethers made by Union Carbide Corporation, and 2-(polyalkoxy)ethanol. Other commercially available products of alcohol alkoxylation include Neodol� ethoxylated linear and branched alcohols from Shell Chemical, Alfonic� ethoxylated linear alcohols from Vista Chemical, propoxylated alcohols from ARCO Chemicals, UCON� propoxylated alcohols from Union Carbide, Provol� propoxylated fatty alcohols from Croda Chemical, and Carbowax methoxy polyethylene glycols, such as Carbowax� 350 and 750 from Union Carbide.
As noted hereinabove, polyether monools may also be prepared by condensation of 2 or more different alkylene oxides, in mixtures or consecutively, with alcohols, alkylphenols or amides, Commercially available polyether monools made from reaction of mixtures of ethylene oxide and propylene oxide with butanol are represented by the UCON� 50-HB- and 75-HB-series of functional fluids from Union Carbide, while similar products from mixtures of propylene oxide and higher (e.g., C4-C10) alkylene oxides are sold by BP Chemicals under the Breox� tradename.
wherein R1, R2 and R3 are independently C2-C12 hydrocarbylene, more often ethylene or propylene, and a, b and c are independently zero to about 100, provided that the total of a, b, and c is at least 1. Examples of ether- and polyether-diols are diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 2-(2-hydroxyethyloxy)-1-propanol and 1,2-bis-(2-hydroxypropyloxy)ethane, polyoxyalkylene oxides of the Carbowax� family of polyethylene glycols from Union Carbide, the Pluronic� P-series of polypropylene oxide diols from BASF, polyoxybutylene glycols from Dow Chemical, and the like.
The amine b(ii) contains at least one N—H group. Among the preferred amines making up b(ii) are the alkylene polyamines, including the polyalkylene polyamines. The alkylene polyamines include those conforming to the formula wherein n is from 1 to about 10; each R2 is independently a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted or amine-substituted hydrocarbyl group having up to about 30 atoms, or two R2 groups on different nitrogen atoms can be joined together to form a U group, with the proviso that at least one R2 group is a hydrogen atom and U is an alkylene group of about 2 to 10 carbon atoms. Preferably U is ethylene or propylene. Especially preferred are the alkylene polyamines where each R2 is hydrogen or an amino-substituted hydrocarbyl group with the ethylene polyamines and mixtures of ethylene polyamines being the most preferred. Usually n will have an average value of from 2 to about 7. Such alkylene polyamines include methylene polyamine, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines, heptylene polyamines, etc. The higher homologs of such amines and related amino alkyl-substituted piperazines are also included.
Other useful types of polyamine mixtures are those resulting from stripping of the above-described polyamine mixtures. In this instance, lower molecular weight polyamines and volatile contaminants are removed from an alkylene polyamine mixture to leave as residue what is often termed “polyamine bottoms”. In general, alkylene polyamine bottoms can be characterized as having less than two, usually less than 1% (by weight) material boiling below about 200� C. In the instance of ethylene polyamine bottoms, which are readily available and found to be quite useful, the bottoms contain less than about 2% (by weight) total diethylene triamine (DETA) or triethylene tetramine (TETA). A typical sample of such ethylene polyamine bottoms obtained from the Dow Chemical Company of Freeport, Tex. designated “E-100” showed a specific gravity at 15.6� C. of 1.0168, a percent nitrogen by weight of 33.15 and a viscosity at 40� C. of 121 centistokes. Gas chromatography analysis of such a sample showed it to contain about 0.93% “Light Ends” (most probably DETA), 0.72% TETA, 21.74% tetraethylene pentamine and 76.61% pentaethylene hexamine and higher (by weight). These alkylene polyamine bottoms include cyclic condensation products such as piperazine and higher linear and branched analogs of diethylenetriamine, triethylenetetramine and the like.
The reaction is run at an elevated temperature which can range from 60� C. to about 265� C. Most reactions, however, are ran in the 220� C. to about 250� C. range. The reaction may be run at atmospheric pressure or optionally at a reduced pressure. The degree of condensation of the resultant high molecular weight polyamine prepared by the process is limited only to the extent to prevent the formation of solid products under reaction conditions. The control of the degree of condensation of the product of the present invention is normally accomplished by limiting the amount of the condensing agent, i.e., the hydroxyalkyl or hydroxy aryl reactant charged to the reaction. The resulting product frequently contains the neutralized catalyst and significant amounts by weight, from about 0.1% , often at least 1%, frequently 5% up to 20%, often up to 10%, water.
A reactor is charged with 1000 parts of an ethylene polyamine bottoms identified as HPA-X (Union Carbide) and 613 parts of 40% aqueous tris-hydroxymethylamino-methane (THAM). An N2 purge is started and is maintained throughout processing The materials are heated to 49� C. whereupon 15.9 parts 85% aqueous phosphoric acid are added and the temperature is increased to 177� C. Conditions are adjusted to enable condensation and reflux of the amine while allowing water to be removed from the system. The temperature is then increased to 227� C. and is held at 227-232� C. for 10 hours while refluxing the amines. The mixture is then stripped by heating at 232-238� C. for 6 hours, then is rapidly cooled to 93� C. whereupon 127 parts water are added followed by the addition of 22.1 parts 50% aqueous NaOH. The batch is mixed for 4 hours at 88-93� C. The unfiltered product contains 27% N, 0.35% P, and 11% H2O.
4 A necked, 500-ml, round-bottom flask equipped with glass stirrer, thermowell, subsurface N2 inlet, Dean-Stark trap, and Friedrich condenser is charged with 201 parts of tetraethylenepentamine (TEPA), 151 parts of 40% aqueous THAM, and 3.5 parts of 85% H3PO4. The mixture is heated to 120� C. over 1.0 hour. With N2 sweeping, the mixture is heated to 130� C. over 1 hour and to 230� C. over 2 hours more. The temperature is maintained at 230�-240� C. for 4 hours and at 241�-250� C. for 3 hours. The materials are cooled to 150� C. and filtered.
A 4 necked, 3-1, round-bottom flask equipped with glass stirrer, thermowell, subsurface N2 inlet, Dean-Stark trap, and Friedrich condenser is charged with 1299 parts HPA Taft Amines (amine bottoms), 727 parts 40% aqueous tris(hydroxymethyl)-aminomethane, heated to 60� C. whereupon 23 parts 85% H3PO4 are added. The mixture is heated to 120� C. over 0.6 hr. With N2 sweeping, the mixture is heated to 150� C. over 1.25 hr and to 235� C. over 1 hr. more. The materials are held at 230�-235� C. for 5 hours. The temperature is increased to 240� C. over 0.75 hour and is held at 240�-245� C. for 5 hour. The materials are cooled to 1500� C. and filtered. Yield: 84%.
A 3-liter flask equipped with stirrer, thermowell, below surface N2 inlet and a stripping condenser is charged with 363 parts of THAM and 1200 parts of TEPA. Next are added 16 parts of H3PO4 at 110� C. N2 blowing is commenced at 120 cc/min. The mixture is heated to 220� C. in 0.8 hour and held at 220�-225� C. for 1.2 hour; then heated to 230� C. in 0.2 hour and held at 230� C. for 4.75 hours: 129 parts distillate collected. The mixture is held at 242�-245� C. for 5 hours: 39 parts additional distillate is collected. Temperature is maintained at 246�-255� C. for 1.2 hr: 178 parts material in trap. The mixture is filtered at 155� C.
A 3-liter flask equipped with stirrer, thermowell, below surface N2 inlet and a stripping condenser was charged with 363 parts THAM and 1200 parts TEPA. At 100� C. are added 16 parts H3PO4. N2 blowing is commenced at 95 cc/min. The mixture is heated to 165� C. in 0.4 hour; and to 241� C. in 0.6 hour, then held at 241�-243� C. for 0.3 hour. The contents are further heated to 250� C. for an additional 0.5 hour and held at 250� C. for 5.5 hour: 288 parts distillate are collected in the trap. Materials are filtered at 150� C.
A 1-liter flask equipped with stirrer, thermowell, below surface N2 inlet and Dean-Stark trap was charged with 121 parts THAM and 400 parts TEPA. To this mixture are added 8.2 parts of KH2PO4 at 60� C. N2 blowing is commenced at 70 cc/min. The reaction mixture is heated to 150� C. over 1 hour, and to 230� C., over 1.5 hours. The temperature is held at 230� C.-232� C. for 4.25 hour: 17 parts material collected in trap. The mixture is held at 237� C. for 3.25 hour: 38 parts material collected in trap. The mixture is further heated to 241� C. over 0.75 hour and is held at 241� C.-242� C. for 4.75 hour; 50 parts material collected in trap. The material is held at 250� C. for 5 hour; total of 53 parts material collected in trap. Filter at 150� C.
To a 500 ml flask equipped with stirrer, thermowell, below surface N2 inlet and Dean-Stark trap is charged with 201 parts TEPA and 468 parts glycerol. 2.3 parts H3PO4 are added at 80� C. N2 blowing is commenced at 165 cc/min. The mixture is heated to 220� C. over 2 hours; to 240� C. in 1 hour; to 245� C. in 1.5 hour and to 255� C. in 1 hour. The temperature is held at 255�-252� C. for 2 hours: 12 parts material collected in trap. The mixture is held at 255�-262� C. for 7 hours: 34 parts distillate collected in trap. The temperature of the mixture is held at 255�-260� C. for 1 hour more. A total of 36 parts distillate is collected in trap. Filter at 130� C.
To a 500 ml flask equipped with stirrer, thermowell, below surface N2 inlet and Dean-Stark trap are charged 201 parts TEPA and 45 parts hexaglycerol. To this mixture 3.5 parts H3PO4 are added at 85� C. N2 blowing is commenced at 165 cc/min. The mixture is heated to 245� C. over 0.7 hour and held at 245� C.-260� C. for 1.75 hour. The mixture is held at 260� C.-270� C. for 7.5 hour: total of 27 parts material collected in trap. Filter at 125� C.
The acylated amine (b-2) can be prepared by reacting any of the carboxylic acid acylating agents referred to herein with one or more of the polyamine products (b-1). Procedures for preparing acylated amines are well known in the art and are taught in many patents including U.S. Pat. Nos., 3,172,892; 3,219,666; 3,272,746; 4,234,435; and many others. In a typical process, the amine is heated with the acylating agent, optionally in the presence of a substantially inert, normally liquid organic diluent at temperatures ranging from about 30� C. up to the decomposition temperature of any reactant or product of reaction, more often from about 80� C. up to about 250� C. Relative proportions of amine and acylating agent are chosen such that (b-2) will contain at least one N—H group. Accordingly, a stoichiometric excess of (b-1) is usually employed relative to the acylating agent. The acylated amine product (b-2) is typically an amide, imide or amidine. Accordingly, sufficient (b-1) is used to generate the desired acylated amine which contains unreacted N—H groups. Post treated products are prepared by any of the procedures describe in the art, for example in U.S. Pat. No. 4,234,435.
A reactor is charged with 400 parts mineral oil and 1000 parts of a N2 blown polyisobutenyl ({overscore (M)}n=1000) succinic anhydride while mixing under an N2 purge. The temperature is adjusted to 88� C. followed by addition of 152 parts of the product of Example (b-1)-1 while maintaining 88-93� C. The batch is mixed for 2 hours at 82-96� C., then the temperature is increased to 152� C. over 5.5 hours. At 152� C. the N2 purge is discontinued and submerged N2 is begun. The batch is heated at 149-154� C. until % H2O is no more than 0.30% by weight. The materials are cooled and filtered at 138-149� C. and adjusted with oil to give total oil of about 40% by weight. The product contains 2.15% N.
The procedure of example (b-2)-1 is repeated except that before filtration, the materials are reacted with 28 parts of terephthalic acid at 160� for three hours.
A polybutene having a number average molecular weight=1350 (1000 parts) is reacted with 106 parts maleic anhydride with Cl2 blowing (total Cl2 about 90 parts) to prepare a substituted succinic anhydride. To a reactor containing 1000 parts of the substituted succinic anhydride are added 1050 parts mineral oil, the materials are heated, with mixing, to 120� C., then 70 parts of the product of Example (b-1)-1 are added. The reaction mixture is heated to 155� C. over 4 hours with N2 sparging to remove volatiles then filtered employing a diatomaceous earth filter aid.
A boron containing composition is prepared by reacting a mixture of 275 parts mineral oil, 147 parts of the product of Example (b-1)-1 and 1000 parts of polyisobutene ({overscore (M)}n≈1000) substituted succinic anhydride at 120-125� C. for 2 hours, at 150� C. for 2 hours, then blowing with nitrogen at 150� C. for 5 hours to form an acylated amine. To a slurry of 239 parts boric acid in 398 parts mineral oil there are added 1405 parts of above acylated amine over a period of 2 hours. The mixture is heated to 150� C. for 7 hours and filtered employing a diatomaceous earth filter aid to give a liquid product containing B and N.
A solution of 698 parts mineral oil and 108 parts of the ethylene polyamine of Example (b-1)-1 is prepared and heated to 115� C. To the oil solution is added 1000 parts of the polybutenyl-substituted succinic anhydride of Example (b-1)-3 under N2 followed by heating to 150� C. The reaction is continued at 143-150� C. for 1 hour. The product is then filtered.
3,515,669
Other useful acids include hydrocarbyloxy(polyalkyleneoxy)carboxylic acids. Some examples of the hydrocarbyloxypolyalkyleneoxycarboxylic acids include: isostearyl-O—(CH2CH2O)5CH2CO2H; lauryl-O—(CH2CH2O)2.5—CH2CO2H; lauryl-O—(C3H6O)x(CH2CH2O)yCH2CO2H, wherein x=2-3 and y=1-2, octylphenyl-O—(CH2CH2O)8CH2CO2H; and 2-octadecanyl-O—(CH2CH2O)6CH2CO2H. In one embodiment, the hydrocarbyloxypolyalkyleneoxycarboxylic acid is stearyl, preferably isostearyl, pentaethyleneglycolacetic acid. Some of these acids are available commercially from Sandoz Chemical under the tradename Sandopan� Acids and from Shell Chemical Co. under the tradename Neodox� carboxylic acids. Similar polyoxyalkylene carboxylic acids that have methoxy terminal groups, such as 3,6,9-trioxa-decanoic acid are marketed by Hoechst Chemie.
Non-limiting examples of carboxylic compounds (c) include those in the following examples. Parts in the following examples are, unless otherwise indicated, parts by weight. Temperatures are in degrees Celsius (� C.). Filtrations employ a diatomaceous earth filter aid.
A mixture of 6400 parts (4 moles) of a polybutene comprising predominantly isobutene units and having a number average molecular weight of about 1600 and 408 parts (4.16 moles) of maleic anhydride is heated at 225-240� C. for 4 hours. It is then cooled to 170� C. and an additional 102 parts (1.04 moles) of maleic anhydride is added, followed by 70 parts (0.99 mole) of chlorine; the latter is added over 3 hours at 170-215� C. The mixture is heated for an additional 3 hours at 215� C. then vacuum stripped at 220� C. and filtered through diatomaceous earth. The product is the desired polybutenyl-substituted succinic anhydride having a saponification number of 61.8.
A polybutenyl succinic anhydride is prepared by the reaction of a chlorinated polybutylene with maleic anhydride at 200� C. The polybutenyl radical has a number average molecular weight of 805 and contains primarily isobutene units. The resulting alkenyl succinic anhydride is found to have an acid number of 113 (corresponding to an equivalent weight of 500).
A reactor is charged with 1000 parts of polybutene having a number average molecular weight determined by vapor phase osmometry of about 950 and which consists primarily of isobutene units, followed by the addition of 108 parts of maleic anhydride. The mixture is heated to 110� C. followed by the sub-surface addition of 100 parts C12 over 6.5 hours at a temperature ranging from 110 to 188� C. The exothermic reaction is controlled as not to exceed 188� C. The batch is blown with nitrogen then stored.
A procedure similar to that of Example c-e is repeated employing 1000 parts of polybutene having a molecular weight determined by vapor phase osmometry of about 1650 and consisting primarily of isobutene units and 106 parts maleic anhydride. Cl2 is added beginning at 130� C. and added at a nearly continuous rate such that the maximum temperature of 188� C. is reached near the end of chlorination. The residue is blown with nitrogen and collected.
A reactor is charged with 1000 parts of a polybutene having a number average molecular weight of about 1500 and 47.9 parts molten maleic anhydride. The materials are heated to 138� C. followed by chlorination, allowing the temperature to rise to between 188-191� C., heating and chlorinating until the acid number is between 43 and 49 (about 40-45 parts Cl2 are utilized). The materials are heated at 224-227� C. for about 2.5 hours until the acid number stabilizes. The reaction product is diluted with 438 parts mineral oil diluent and filtered with a diatomaceous earth filter aid.
A substantially hydrocarbon-substituted succinic anhydride is prepared by chlorinating a polybutene having a number average molecular weight of 1000 to a chlorine content of 4.5% and then heating the chlorinated polybutene with 1.2 molar proportions of maleic anhydride at a temperature of 150-220� C. A mixture of 874 grams (2 carbonyl equivalents) of this succinic anhydride and 104 grams (1 mole) of neopentylene glycol is maintained at 240-250� C./30 mm for 12 hours. The residue is a mixture of hydroxy containing polyester resulting from the esterification of one and both hydroxy groups of the glycol. Typical analyses are acid number of 10, a number average molecular weight of 5500 and an average of one free condensable —OH per polyester molecular weight.
A mixture of 3225 parts (5.0 carbonyl equivalents) of the polybutene-substituted succinic acylating agent prepared in Example (d)-1 and 289 parts (8.5 equivalents based on —OH) of pentaerythritol is heated at 224-235� C. for 5.5 hours, with removal of volatiles by nitrogen blowing. Then 5204 parts mineral oil are added followed by mixing. The homogeneous mixture is filtered at 130� C. to yield an oil solution of the desired polyester product.
A mixture of 1000 parts of polybutene having a number average molecular weight of about 1000 and 108 parts (1.1 moles) of maleic anhydride is heated to about 190� C. and 100 parts (1.43 moles) of chlorine are added beneath the surface over a period of about 4 hours while maintaining the temperature at about 185-190� C. The mixture is then blown with nitrogen at this temperature for several hours, and the residue is the desired polybutenyl-substituted succinic acylating agent.
A reactor is charged with 1000 parts of a polybutenyl-substituted succinic acylating agent prepared as in Example (d)-3. At between 160-175� C. are added 121 parts of pentaerythritol. The materials are heated to 200� C. over 8 hours followed by nitrogen blowing at 204-210� C. for 8 hours. Water is removed and is collected. Upon completion of the reaction, the materials are diluted with 872 parts of mineral oil and the solution is filtered with a diatomaceous earth filter aid. Typical analyses are acid number=8. The polyester contains about 1.8 —OH groups per repeating unit.
A reactor charged with 1000 parts of the C18-24 substituted succinic anhydride of Example c-g and 289 parts of pentaerythritol is heated to 200� C. and is held at 200� C. to 235� C. for 5 hours, removing volatiles by N2 blowing. The materials are diluted with 800 parts of mineral oil and filtered.
A reactor is charged with 1000 parts of the product of Example c-f and 464 parts of mineral oil. The materials are heated to 140� C. under N2, 110 parts pentaerythritol are added and the materials are heated to 210� C. over 6 hours while removing water employing a sub-surface N2 sparge. At this point 750 parts oil are added and the batch is cooled to 150� C. and filtered.
A reactor is charged with 1000 parts of a polybutenyl-substituted succinic anhydride prepared essentially as described in Example (d)-3, 109 parts pentaerythritol and 31 parts Polyglycol� 112-3, a polyether polyol obtained by reacting glycerol, propylene oxide and ethylene oxide, having a molecular weight ranging from about 4600 to about 5300. The mixture is heated to 210� C. over 6 hours employing a sub-surface N2 sparge. The materials are cooled to 160� C. and a toluene solution of 19 parts of commercial ethylene polyamine having a % N of about 34 is added over 1 hours followed by heating and N2 sparging at 160� C. for 3 hours. The product is diluted with 800 parts mineral oil and filtered using a diatomaceous earth filter aid.
To the polyester of example (d)-3 are added 857 parts of mineral oil and 19.25 parts (.46 equivalent) of a commercial mixture of ethylene polyamines having an average of about 3 to 10 nitrogen atoms per molecule. The reaction mixture is further stripped of volatiles by heating at 205� C. with nitrogen blowing for 3 hours and filtered. The filtrate is an oil solution (45% 100 neutral mineral oil) of the desired amine-modified carboxylic polyester of about 2850 number average molecular weight which contains 0.35% nitrogen, total base number of 2 and total acid number of 4.
A reactor equipped with a stirrer, condenser with Dean-Stark trap, thermocouple probe and N2 inlet (N2 at 0.5 standard cubic feet/hour (SCFH)) is charged with 1100 parts of a polybutenyl substituted succinic anhydride prepared according to the procedure of Example (d)-3, 146 parts triethanolamine and 125 parts toluene. The mixture is heated to 210� over 4 hours then stirring and heating is continued at this temperature for 26 hours, collecting a clear yellow distillate having pH 7-9 in the Dean-Stark trap. N2 flow is increased to 1.5 SCFH and stirring is continued at temperature for 3 additional hours, cool to 105�, and charge 800 parts mineral oil. The materials are stirred at temperature for 0.5 hour, mixed with a diatomaceous earth filter aid and filtered. The filtrate contains, by analysis, 0.69% N and 0.18% —OH. Total acid no.=1.83; total base no.=22.9.
A reactor is charged with 1000 parts of the polyester of Example (d)-7 and heated to 150� C. A solution of 15 parts of a commercial polyamine having about 34% nitrogen and total base number of 41 in 15 parts toluene is added over 0.5 hour. The materials are stirred for 2 hours at 160� C. with N2 sparging, 550 parts mineral oil is added and the solution is filtered.
A reactor equipped with a stirrer, gas inlet, wide-mouth addition funnel, thermowell and condenser is charged with 5950 parts of hydrotreated 100 neutral paraffinic oil. The oil is heated, under nitrogen sweep at 190 cc/min to 160� C. At this temperature, 1050 parts of an ethylene-propylene copolymer (52% ethylene, 48% propylene, by weight) having {overscore (M)}w of 210,000 and {overscore (M)}w/{overscore (M)}n of 1.8, is added as small pieces (about �-{fraction (-3/8)}″ cubes) over 3 hours. After 4 hours at 160� C. all polymer appears to have dissolved, but the mixture is stirred 16 hours more at 160� C.
The solution is cooled to 130� C., nitrogen flow is reduced to 23-47 cc/min. and 15.3 parts maleic anhydride is charged followed by stirring for 0.25 hours. A solution of 15.3 parts of tertiary butyl peroxybenzoate in 20 parts of toluene is added dropwise over one hour followed by mixing 3 hours at 130-135� C. The temperature is increased to 160� C. and the reaction mixture is nitrogen stripped at 943 cc/min. for 4 hours to remove toluene and residual maleic anhydride. Saponification number=1.7; viscosity (100� C.)=7258 centistokes.
A reactor equipped with stirrer, gas inlet, addition funnel, thermowell, Dean-Stark trap, and condenser is charged with 2500 parts of the product of Example 1-B and 1750 parts mineral oil (Shell HVI 100N) and heated, with stirring and N2 sparging, to 125� C., at which time 750 parts of the product of Example (b-2)-1 are added over 0.1 hour followed by heating to 150� C. over 0.5 hour. The N2 flow is increased and the materials are heated for 3 hours at 150� C. to 160� C. The materials are cooled to 100� C. and filtered. Filtrate contains 0.36% N, total acid no=1.13 and total base no =5.2.
A reactor equipped with a stirrer, thermometer, water-cooled condenser and gas inlet is charged with 6912 parts of mineral oil (100 Neutral, Sun Oil). A nitrogen purge is begun and is maintained throughout the process. Hydrogenated styrene-isoprene copolymer having a molecular weight measured by gel permeation chromatography of about 180,000 (Shellvis 40, Shell Chemical Company), 768 parts, is added over 0.5 hours. The temperature is increased to 157� C. and is maintained at 157-160� C. for 3 hours, until the polymer is completely dissolved.
To the oil solution of Part A of this Example are added 19.2 parts of maleic anhydride, the materials are stirred for 0.25 hour then 19.2 parts ditertiary butyl peroxide are added over 1 hour. The materials are held at 159� C. for 1 hour, then the temperature is increased to 163� C. and the N2 flow is increased. The reaction is held at 163�-166� C. for 3 hours, collecting a small amount of distillate. N2 flow is decreased and 1920 parts diphenylalkane are added. The temperature is maintained at 150� C. for 0.5 hour.
A reactor is charged with 250 parts of the product of Part B of this example, and is heated to 100� C. with N2 purge. To this solution are added 88 parts of the product of Example (b-2)-2 and the materials are heated to 160� C., maintaining N2 purge, then maintained at 160� C. for 2 hours. The materials are the product.
A reactor is charged with 1336 parts of the product of Part A of this example and 570 parts of the product of example (b-2)-2. Materials at 65� C. A nitrogen purge is maintained throughout the process. The materials are heated to 151� C. over 6 hours and are held at 151� C. for 1 hour. The materials are cooled to 93� C. and collected.
A reactor is charged with 1336 parts of the product of Example 3, Part A and 280 parts mineral oil, N2 purging is begun, and the temperature is increased to 151� C. over 0.5 hour. The materials are held at 151� C. for 0.5 hour whereupon 401 parts of the product of Example (b-2)-2 are added, the temperature dropping to 140� C. The temperature is increased to 151� C. and is maintained at 150-155� C. for 2 hours, collecting about 0.5 parts distillate. The materials are cooled to 93� C. and collected.
A three liter flask equipped with a stirrer, reflux condenser, thermowell, and subsurface nitrogen sparging tube is charged with 1950 parts of 11.5 weight percent solution of Ortholeum 2052 a terpolymer containing about 48 weight percent ethylene units, 48 weight percent propylene units and 4 weight percent 1,4-hexadiene units, (E.I. DuPont DeNemours and Company) in 100 neutral solvent extracted diluent oil, containing additionally 3 weight percent of fumarate-vinyl acetate polymeric pour point depressant and 0.12 weight percent phenolic antioxidant. The solution is heated to 80� C. under a slow nitrogen sparge followed by addition of 21.8 parts of maleic anhydride. Stirring is continued while the reaction mixture is heated to 220� C. The mixture is held at this temperature for 8 hours, then blown with nitrogen at an increased rate to remove volatile materials. The solution is cooled to 150� C. and filtered using a diatomaceous earth filter aid yielding 1918 parts of viscous product having a total acid number (TAN) of 2.4.
A solution of 150 parts Ortholeum 2052 and 850 parts of 100N hydrotreated paraffinic oil is prepared under 135� C. under a nitrogen atmosphere. The solution is cooled to 90� C., 5 parts of maleic anhydride is added and the solution is heated to 135� C. under a nitrogen atmosphere. The solution is held at that temperature while a solution of 2 parts tertiary-butyl peroxide in 10 parts xylene is added over a one hour period with rapid stirring. The solution is held at 135� C. for an additional 2 hours then slowly heated to 155� C. over the next hour. The solution is blown with nitrogen over one hour at 155� C. to remove volatile materials (none collected), then cooled to yield a polymer solution containing 15% active agent having a TAN of 2.0.
A reactor is charged with 700 parts of the product of part A of this example, 120 parts of 100 neutral (100N) mineral oil and 350 parts of the product of Example (b-2)-2. The materials are heated to 150� C. and are held there, under N2, for 1 hour then filtered.
A reactor equipped with thermowell, condenser, stirrer and subsurface N2 inlet is charged with 2420 parts mineral oil. Over 0.5 hours are added, with stirring, 427 parts of a copolymer containing, by analysis, ethylene a weight ratio of 57:43, containing 1.4% by weight units derived from dicyclopentadiene and propylene units in and having polydispersity ({overscore (M)}w/{overscore (M)}n=2.2. N2 sparging is at 94 cc/min. The material are heated to 160� C. and held at 160� C. overnight to dissolve the polymer. To this solution are added 4.3 parts maleic anhydride. The materials are stirred to dissolve maleic anhydride and the condenser is washed with about 5 parts toluene. Over 1 hour, at 160� C. are added, dropwise, 4.3 parts t-butyl peroxide. The reaction is held at 160� C. for 2 hours the N2 sparging is increased to 700 cc/min. for 3 additional hours to remove volatiles. The product contains about 15% weight polymer and has TAN of 1.8.
A reactor is charged with 1000 parts of the product of Part A of this example, 700 parts 100N oil, and 300 parts of the product of Example (b-2)-2. The materials are heated to 150� C. and are held there, under N2, for 1 hour, then filtered.
A reactor equipped with a stirrer, condenser, thermowell and sub-surface N2 inlet is charged with 6375 parts mineral oil, then with stirring, 1125 parts Ortholeum 2052 are added over 0.5 hour. N2 sparging is at 94 cc/min. The materials are heated to 157� C. and held at 157-160� C. for 6 hours to dissolve the polymer. To the solution are added 11.5 parts maleic anhydride, stirring is continued until the maleic anhydride is dissolved, then, over 1 hour, 11.5 parts di-tertiary-butyl peroxide are added. The reaction is held at 157-160� C. for 1 hour, then N2 is increased to 470 cc/min, removing volatiles at 163-166� C. The product contains about 15% weight polymer and TAN of 6.0.
A reactor is charged with 1000 parts of the product of Part A of this example, 200 parts 100N oil and 350 parts of the product of Example (b-2)-2. The materials are heated to 150� C. and are held there, under N2, for 1 hour, then filtered.
Maleic acid modification of Ortholeum 2052 is carried out in a Brabender twin-screw extruder having three heated zones, 125� C., 150� C. and 170�, over the length of the feeding screws. The screw configurations are set for feeding, mastication (using a different thread pitch to increase back pressure on the reactants and slow extrusion at atmospheric pressure. The polymer (97.5 parts, is cut into small pieces and fed into the extruder at a constant screw rotation rate of 50 revolutions per minute (RPM) while separate solutions of 2 parts maleic anhydride in 10 parts warm toluene and 1 part di-tertiary butyl peroxide in 10 parts toluene are fed in simultaneously, dropwise over the same time. The masticated mixture passes through the heated zones and is slowly extruded as a thin thread which is passed through a cold water bath and is subsequently chopped into small pellets. The solid product has TAN=10.
A reactor is charged with 700 parts 100N oil and 100 parts of the product of Part A of this example. The materials are heated to 135� C. under N2 and held at temperature until the mixture is homogeneous. The solution is cooled to 100� C. whereupon 200 parts of the product of Example (b-2)-2 are added, with stirring. The temperature is increased to 150� C. and held for 1 hour with good stirring and N2 sparging. The materials are filtered.
A reactor is charged with 750 parts of the solution of Ortholeum 2052 of Example 13, the temperature is increased to 170� C., 2 parts acrylic acid are added dropwise over 0.25 hour followed by the dropwise addition of a solution of 2 parts ditertiary butyl peroxide in 10 parts toluene. The reaction is continued, under N2 for 2 hours at 165-170� C. while volatiles are removed.
A reactor is charged with 800 parts of the maleic anhydride grafted Ortholeum 2052 described in Example 13 and 200 parts of polyalphaolefin oil having viscosity at 100� C. of 4.5 centistokes. The solution is heated to 125� C. with stirring under a N2 purge whereupon 200 parts of the product of Example (b-2)-1 are added rapidly. The temperature is increased to 150� C. and is held at temperature for 1 hour, followed by cooling to 120� C. and filtration.
A solution of 800 parts of hydrogenated styrene-butadiene random block copolymer (Glissoviscal 5260, supplied by BASF) in 4200 parts 100N oil (Sun Oil) is prepared by adding the solid polymer to the mineral oil in a 12-liter, 4-necked reaction flask equipped with a stirrer, thermometer, subsurface nitrogen purge tube, solids addition funnel and water cooled condenser, at 160� C. over 1.25 hours with stirring. The mixture is held at 160� C. for 2.75 hours to obtain solution of the solids. A slow, subsurface nitrogen sparge is maintained during the processing steps. The temperature is reduced to 130� C., 50 parts maleic anhydride are added followed by dropwise addition over 1.5 hours, of a solution of 20 parts ditertiary butyl peroxide in 100 parts toluene. The materials are reacted for 2 hours at 140� C. with N2 sparging, removing volatile materials. To the residue are added 200 parts diphenyl alkane and the mixture is homogenized at 125� C.
A reactor is charged with 800 parts of the product of Part A of this example and 200 parts of the product of Example (b-2)-2 followed by heating, under N2, to 150� C. The temperature is maintained at 150� C. for 1 hour then filtered.
A solution of 200 parts of a hydrogenated styrene-isoprene radial copolymer (Shellvis 250, Shell Chemical) in 1000 parts mineral oil is prepared. The temperature is adjusted to 135� C. whereupon 10 parts maleic anhydride are added followed by the dropwise addition over 1 hour of a solution of 2.5 parts ditertiarybutyl peroxide in 10 parts toluene. The reaction is continued for 2 hours at 140� C. using N2 sparge to remove volatile materials. The product has theory TAN of 3.3.
A reactor is charged with 1000 parts of the maleinated polymer of Part A of this example and 200 parts of 100N oil, the temperature is adjusted to 100� C. under N2, whereupon 300 parts of the product of Example (b-2)-2 are added followed by heating to 150� C. The temperature is maintained for 1.5 hours.
A solution of 150 parts 120,000 molecular weight polyisobutylene-polymer containing about 4% by weight diene monomer segments in 850 parts hydrotreated 100N oil is prepared as in Example 2. The temperature is adjusted to 90� C., 5 parts maleic anhydride are added and the temperature is increased to 135� C. under N2. A solution of 2.5 parts ditertiarybutyl peroxide in 10 parts toluene is added over 1 hour, then the materials are heated for an additional 2 hours at 140� C.
A reactor is charged with 1000 parts of the product of Part A of this example and 200 parts 100N oil. The temperature is raised to 100� C. under N2, 300 parts of the product of Example (b-2)-2 are added, the materials are heated to 150� C. and are held at temperature for 1.5 hours, removing volatiles with N2 sparging.
A reactor is charged with 800 parts of the product of Part A of this example and 300 parts poly(alphaolefin) oil having viscosity of 4.5 centistokes at 100� C., the temperature is increased to 125� C. and 300 parts of the product of Example (b-2)-1 are charged followed by heating to 150� C. The materials are heated at 150� C. for 2 hour, removing volatiles with N2 sparging the filtered.
A reactor is charged with 1000 parts of the product of part A of this example and 200 parts of diphenyl alkane having viscosity of 3.8 centistokes at 100� C. The temperature is increased to 125� C., 300 parts of the product of Example (b-2)-1 are charged, the temperature is increased to 155� C., and held at temperature for 1 hour, removing volatiles with N2 sparging. The product has viscosity of 1085 centistokes at 100� C.
A reactor is charged with 250 parts of the maleinated ethylene-propylene copolymer of Example 1-B, 200 parts 100N oil, and 50 parts of a polyisobutene ({overscore (M)}n=1000) substituted succinic anhydride. The materials are heated to 150� C. whereupon 7.6 parts of the polyamine product of Example (b-1)-1 are added, dropwise, over 1 hour. The materials are heated at 150� C. for 1 hour, and collected.
A reactor is charged with 1000 parts of the product of Example 2 and 50 parts of the product of Example (d)-1. The materials are mixed and heated for 1.5 hours at 140-160� C.
Polybutene ({overscore (M)}n ˜1300) subst.
Ca overbased MR ˜1.1) S-coupled
Ca overbased (MR ˜3.5) S-
Di-(nonyl phenyl) amine
Zinc salt of di-mixed isopropyl-
Ca overbased (MR ˜1.2) alkyl
Mg overbased (MR 14.7) alkyl
Product of Example 1-C
Ca overbased (MR ˜2.3)
Ca overbased (MR ˜11) alkyl
Polybutene ({overscore (M)}n ˜1000) substituted
t-Butyl-propylene tetramer
Polymethacrylate Pour Point
Alkylphenoxypolyethoxy ethanol
Polybutene ({overscore (M)}n ˜1000) subst.
H3BO3 post treated polybutene
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(1980), pp. 119-150.Referenced byCiting PatentFiling datePublication dateApplicantTitleUS7651987 *Oct 12, 2004Jan 26, 2010The Lubrizol CorporationTartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereofUS7700684 *Dec 9, 2004Apr 20, 2010Afton Chemical CorporationGraft functionalized olefin polymer dispersant and uses thereofUS7739968Jul 25, 2007Jun 22, 2010General Vortex Energy, Inc.System, apparatus and method for combustion of metals and other fuelsUS7807611 *Feb 6, 2006Oct 5, 2010The Lubrizol CorporationTartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereofUS8133290Feb 3, 2011Mar 13, 2012The Lubrizol CorporationTartaric acid derivatives in fuel compositionsUS8148307May 17, 2010Apr 3, 2012The Lubrizol CorporationTartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparations thereofUS8198222Mar 16, 2010Jun 12, 2012The Lubrizol CorporationTartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparations thereofUS8778854Jul 6, 2010Jul 15, 2014The Lubrizol CorporationDispersant viscosity modifiersUS20060079413 *Oct 12, 2004Apr 13, 2006The Lubrizol Corporation, A Corporation Of The State Of OhioTartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereofUS20060128875 *Dec 9, 2004Jun 15, 2006Bradley Joseph SGraft functionalized olefin polymer dispersant and uses thereofUS20060183647 *Feb 6, 2006Aug 17, 2006Jody KocsisTartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereofUS20100160196 *Dec 23, 2008Jun 24, 2010Clarke Dean BPower Transmission Fluids with Improved Viscometric PropertiesUS20100173812 *Jul 8, 2010The Lubrizol CorporationTartaric Acid Derivatives as Fuel Economy Improvers and Antiwear Agents in Crankcase Oils and Preparations ThereofUS20100222245 *May 17, 2010Sep 2, 2010Th Lubrizol CorporationTartaric Acid Derivatives as Fuel Economy Improvers and Antiwear Agents in Crankcase Oils and Preparations ThereofUS20100227784 *May 17, 2010Sep 9, 2010Th Lubrizol CorporationTartaric Acid Derivatives as Fuel Economy Improvers and Antiwear Agents in Crankcase Oils and Preparations ThereofUS20100251946 *Jun 17, 2010Oct 7, 2010General Vortex Energy, Inc.System, Apparatus and Method For Combustion of Metals and Other FuelsUS20110131868 *Jun 9, 2011Th Lubrizol CorporationTartaric Acid Derivatives in Fuel CompositionsWO2011005740A1 *Jul 6, 2010Jan 13, 2011The Lubrizol CorporationDispersant viscosity modifiers* Cited by examinerClassifications U.S. Classification508/240, 525/382, 508/508, 525/64, 508/507, 525/381International ClassificationC10M149/00, C10M133/52Cooperative ClassificationC10N2230/04, C10M133/52, C10M149/00European ClassificationC10M149/00, C10M133/52Legal EventsDateCodeEventDescriptionApr 28, 2008FPAYFee paymentYear of fee payment: 4Apr 26, 2012FPAYFee paymentYear of fee payment: 8RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services