Source: http://www.google.com/patents/US6472353?dq=6246862
Timestamp: 2017-10-24 03:22:52
Document Index: 126958016

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Patent US6472353 - Dispersant-viscosity improvers for lubricating oil compositions - Google Patents
Graft copolymers useful as a dispersant-viscosity improver for lubricating oil compositions comprise a hydrocarbon polymer having graft polymerized thereon at least two nitrogen containing units, at least one of the nitrogen containing units being derived from at least one of a neutral N-(lower hydrocarbyl...http://www.google.com/patents/US6472353?utm_source=gb-gplus-sharePatent US6472353 - Dispersant-viscosity improvers for lubricating oil compositions
Publication number US6472353 B1
Application number US 09/856,040
PCT number PCT/US2000/025173
Publication number 09856040, 856040, PCT/2000/25173, PCT/US/0/025173, PCT/US/0/25173, PCT/US/2000/025173, PCT/US/2000/25173, PCT/US0/025173, PCT/US0/25173, PCT/US0025173, PCT/US025173, PCT/US2000/025173, PCT/US2000/25173, PCT/US2000025173, PCT/US200025173, US 6472353 B1, US 6472353B1, US-B1-6472353, US6472353 B1, US6472353B1
Inventors John C. Smoggie, Richard M. Lange
Patent Citations (20), Non-Patent Citations (1), Referenced by (16), Classifications (39), Legal Events (3)
US 6472353 B1
1. A graft copolymer comprising a hydrocarbon polymer having graft polymerized thereon at least two nitrogen containing units, at least one of the nitrogen containing units being derived from at least one of N-methyl-, N-ethyl-, N,N-dimethyl-, N,N-diethyl-, and N-propyl-(meth)acrylamide, and at least one of the nitrogen containing units being derived from at least one vinylic nitrogen containing heterocyclic compound.
2,973,344 3,488,049 3,799,877
3,278,550 3,513,095 3,842,010
3,311,558 3,563,960 3,864,098
3,312,619 3,598,738 3,864,268
3,326,804 3,615,288 3,879,304
3,403,011 3,637,610 4,033,889
3,404,091 3,652,239 4,051,048
3,445,389 3,687,849 4,234,435
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. At least one substituent is H. Preferably, when R3 is hydrocarbyl, R and R1 will both be hydrogen, and when R2 is hydrocarbyl, then R4 and R5 will both be hydrogen. Most preferably, R1, R2, R3 and R4 will all be hydrogen. Normally, the total carbon content of the diene monomer 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.
where a and b are as described hereinbelow. Techniques vary for the preparation of these “A-B-A” and “B-A-B” triblock polymers, and are described in the literature for anionic polymerization.
(A)a(B)b(A)c, or (B)a(A)b(B)c, or (A)a(B)b(C)c
where (C) represents a segment of a third monomer. Several configurations are possible depending on how the homopolymer segments are arranged with respect to each other. For example, linear triblock copolymers of monomers (A), (B) and (C) can be represented by the general configurations:
Examples of suitable regular diblock copolymers as set forth above include SHELLVIS® 40, and SHELLVIS® 50, both hydrogenated styrene-isoprene linear diblock copolymers, manufactured by Shell Chemical.
Examples of commercially available random block and tapered random block copolymers include the various GLISSOVISCAL® block copolymers manufactured by BASF. A previously available random block copolymer was Phil-Ad viscosity improver, manufactured by Phillips Petroleum.
Polymerization using coordination catalysis is generally conducted at temperatures ranging between 20° and 300° C., preferably between 30° and 200° C., often up to about 100° C. Reaction time is not critical and may vary from several hours or more to several minutes or less, depending upon factors such as reaction temperature, the monomers to be copolymerized, and the like. One of ordinary skill in the art may readily obtain the optimum reaction time for a given set of reaction parameters by routine experimentation. Preferably, the polymerization will generally be completed at a pressure of 1 to 40 MPa (10 to 400 bar).
3,513,096 4,068,057
3,551,336 4,081,391
3,562,160 4,089,794
3,607,749 4,098,710
3,634,249 4,113,636
3,637,503 4,132,661
3,992,310 4,137,185
4,031,020 4,138,370
4,068,056 4,144,181
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-diene copolymers and methods for their preparation are described in numerous patents including the following U.S. Patents:
Star polymers are commercially available, for example as SHELLVIS® 200 sold by Shell Chemical Co.
The grafting process is typically conducted at an elevated temperature, generally from about 85° C. up to the lowest decomposition temperature of reactants or product, preferably from about 100° C. to about 165° C. and more preferably from about 120° C. to about 145° C. Considerations for determining reaction temperatures include reactivity of the system and the half-life of the initiator at a particular temperature.
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 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.
The following examples are intended to illustrate several compositions of this invention as well as means for preparing same. Unless indicated otherwise, all parts are parts by weight, temperatures are in degrees Celsius (° C.), and pressures are atmospheric. When referring to parts by volume, the relationship is as parts by weight in grams to parts by volume in milliliters. Filtrations are conducted using a diatomaceous earth filter aid. All analytical values are by analysis. Viscosity is measured using ASTM-D445 procedure. It is to be understood that these examples are only intended to illustrate compositions and procedures of the invention and are not intended to limit the scope of the invention.
A reactor equipped with a stirrer, thermometer, water cooled reflux condenser and sub-surface gas inlet is charged with 3000 parts of a 10% by weight in mineral oil (PetroCanada 100N, ˜100% saturated) solution of an ethylene-propylene-dicyclopentadiene copolymer having {overscore (M)}n 89,000 and {overscore (M)}w 200,000 comprising 51 weight % ethylene units and 2 weight % dicyclopentadiene units. The materials are heated, under N2 to 130° C. To one addition funnel are added a mixture of 7.5 parts N-vinyl imidazole and 15 parts N,N-dimethyl acrylamide in 50 parts by volume toluene and to a second addition funnel are added 15 parts t-butyl peroxybenzoate in 25 parts by volume toluene. While maintaining N2, the two toluene solutions are added dropwise, simultaneously, over 2 hours. After the additions are completed, the materials are heated while maintaining N2, at 130° C. for 4 hours, stripped to 150° C. then vacuum stripped to 150° C. at 20 mm Hg pressure. The residue is filtered providing a product containing 0.158% N, total base number=1.28 and kinematic viscosity (100° C.) 2830 centistokes.
A mixture of 610 parts of the product of Example 1 and 6.1 parts of an 85% active primary straight chain alkyl benzene sulfonic acid are stirred, under N2, at 130° C. for 2 hours. Kinematic viscosity (100° C.)=4200 centistokes.
A reactor equipped with a stirrer, thermometer, water cooled reflux condenser and sub-surface gas inlet is charged with 1000 parts of 9% by weight in mineral oil (Exxon 100N, ˜75% saturated) solution of an ethylene-propylene-dicyclopentadiene copolymer having {overscore (M)}n 140,000 and {overscore (M)}w 330,000 comprising 51 weight % ethylene units and 2 weight % dicyclopentadiene units. The materials are heated, under N2, to 130° C. To a first addition funnel are charged 1.5 parts 1-vinylimidazole, 3 parts N,N-dimethylacrylamide and 14 parts toluene. To a second addition funnel are charged 4.5 parts t-butyl peroxybenzoate and 14 parts toluene. While maintaining N2 throughout the reaction, dropwise addition of the peroxybenzoate is begun followed 0.1 hour later by dropwise addition of the monomers. Dropwise addition from the two addition funnels is carried out for 1.25 hours then the batch is held at 135° C. for 2.5 hours. The apparatus is then set up for stripping. The materials are purged with N2 and heated to 145° C. while collecting 10.3 parts distillate. The product contains 0.07% N.
The procedure of Example 3 is repeated with 1000 parts of the polymer solution, 1.5 parts 1-vinylimidazole, 3 parts N,N-dimethylacrylamide and 4.5 parts t-butyl peroxybenzoate. The additions are completed in 0.7 hour. After the initial 2.5 hour heating period, an additional 0.5 part t-butyl peroxybenzoate is added and heating at 135° C. is continued for 3 more hours. The product contains 0.09% N.
A reactor equipped with a stirrer, thermowell, water cooled reflux condenser and sub-surface gas inlet is charged with 1000 parts of 10% by weight in mineral oil (150N, ˜88% saturated) solution of a hydrogenated styrene-butadiene random block copolymer having molecular weight determined by GPC of about 120,000 (GLISSOVISCAL® 5260, BASF). The materials are heated, under N2, to 130° C. To a first addition funnel are charged 1.67 parts 1-vinylimidazole, 3.33 parts N,N-dimethylacrylamide and 15 parts toluene. To a second addition funnel are charged 5.5 parts t-butyl peroxybenzoate and 15 parts toluene. While maintaining N2 throughout the reaction, dropwise addition of the peroxybenzoate is begun followed 0.1 hour later by dropwise addition of the monomers. Dropwise addition from the two addition funnels is carried out simultaneously and is completed in 1.3 hours. After addition is completed, the batch is heated to 135° C. and is held for 2 hours. An additional 1 part t-butyl peroxybenzoate is added and the batch is maintained at 135° C. for 2 hours, N2 blown at 145C for 3 hours collecting 10 parts distillate, then filtered. The material contains 0.09% N.
A reactor equipped with a stirrer, thermowell, water cooled reflux condenser and sub-surface gas inlet is charged with 1000 parts of 10% by weight in mineral oil (PetroCanada 100N, ˜100% saturated) solution of the hydrogenated copolymer of Example 7. The materials are heated, under N2, to 130° C. To a first addition funnel are charged 1.67 parts 1-vinylimidazole, 3.33 parts N,N-dimethylacrylamide and 15 parts toluene. To a second addition funnel are charged 5.5 parts t-butyl peroxybenzoate and 15 parts toluene. While maintaining N2 throughout the reaction, dropwise addition of the peroxybenzoate is begun followed 0.1 hour later by dropwise addition of the monomers. Dropwise addition from the two addition funnels is carried out simultaneously and is completed in 1.25 hours. After addition is completed, the batch is heated to 135° C. and is held for 3.5 hours, then is heated to 145° C. and N2 blown for 2 hours, collecting 11 parts distillate. The product contains 0.09% N.
A reactor equipped with a stirrer, thermowell, water cooled reflux condenser and sub-surface gas inlet is charged with 1000 parts of 9% by weight in mineral oil (100N, ˜78% saturated) solution of a hydrogenated styrene-butadiene linear tapered block copolymer having molecular weight determined by GPC of about 140,000 (GLISSOVISCAL® SGH, BASF). The materials are heated, under N2, to 130° C. To a first addition funnel are charged 1.5 parts 1-vinylimidazole, 3.0 parts N,N-dimethylacrylamide and 15 parts toluene. To a second addition funnel are charged 5.0 parts t-butyl peroxybenzoate and 15 parts toluene. While maintaining N2 throughout the reaction, dropwise addition of the peroxybenzoate is begun followed 0.1 hour later by dropwise addition of the monomers. Dropwise addition from the two addition funnels is carried out simultaneously and is completed in 1.25 hours. After addition is completed, the batch is heated to 135° C. and is held for 2.5 hours followed by N2 blowing at 145° C. for 3 hours while collecting 5 parts distillate. The batch contains 0.077% N.
A reactor equipped with a stirrer, thermowell, water cooled reflux condenser and sub-surface gas inlet is charged with 1000 parts of 7% by weight in mineral oil (100N, ˜79% saturated) solution of a hydrogenated styrene-isoprene linear diblock copolymer having molecular weight determined by GPC of about 200,000 (SHELLVIS® 40 Shell Chemical Co.). The materials are heated, under N2, to 130° C. To a first addition funnel are charged 1.17 parts 1-vinylirnidazole, 2.33 parts N,N-dimethylacrylamide and 15 parts toluene. To a second addition funnel are charged 4.5 parts t-butyl peroxybenzoate and 15 parts toluene. While maintaining N2 throughout the reaction, dropwise addition of the peroxybenzoate is begun followed 0.1 hour later by dropwise addition of the monomers. Dropwise addition from the two addition funnels is carried out simultaneously and is completed in 1.25 hours. After addition is completed, the batch is heated at 135° C. for 2.5 hours then is N2 blown at 145° C. for 3 hours. The product contains 0.062% N.
A reactor equipped with a stirrer, thermowell, water cooled reflux condenser and sub-surface gas inlet is charged with 1000 parts of 14% by weight in mineral oil (100N, ˜79% saturated) solution of a hydrogenated isoprene radial copolymer having molecular weight determined by GPC using polystyrene standard of about {overscore (M)}n=414,000 and {overscore (M)}w=541,000, (SHELLVIS® 250, Shell Chemical. Co.). The materials are heated, under N2, to 130° C. To a first addition funnel are charged 2.33 parts 1-vinylimidazole, 4.67 parts N,N-dimethylacrylamide and 15 parts toluene. To a second addition funnel are charged 7 parts t-butyl peroxybenzoate and 15 parts toluene. While maintaining N2 throughout the reaction, dropwise addition of the peroxybenzoate is begun followed 0.1 hour later by dropwise addition of the monomers. Dropwise addition from the two addition funnels is conducted simultaneously for 1.25 hours then the batch is heated at 135° C. for 2.5 hours then N2 blown at 145° C. for 2 hours while collecting 5 parts distillate. The residue is filtered. The product contains 0.12% N.
The procedure of Example 11 is repeated employing 900 parts of a 14% by weight in mineral oil (PetroCanada 100N, ˜100% saturated) solution of Shellvis 250 polymer, 2.10 parts 1-vinylimidazole, 4.20 parts N,N-dimethylacrylamide, 6.3 parts t-butyl peroxybenzoate and, in each addition funnel, 15 parts toluene. After addition of monomers and initiator, the material are heated at 130° C. for 4 hours then N2 purged at 145° C. for 2 hours while collecting 12 parts distillate. The product contains 0.14% N.
A reactor equipped with a stirrer, thermometer, water cooled reflux condenser and sub-surface gas inlet is charged with 1000 parts of 14.5% by weight in mineral oil (Exxon 100N, ˜75% saturated) solution of an ethylene-propylene-dicyclopentadiene copolymer having {overscore (M)}n 140,000 and {overscore (M)}w 330,000 comprising 51 weight % ethylene units and 2 weight % dicyclopentadiene units and 350 parts of the Exxon 100N mineral oil. The solution is heated, under N2, to 80° C. whereupon 150 parts toluene and 2.5 parts n-dodecyl mercaptan. To a first addition funnel is charged 10 parts N-vinylimidazole dissolved in 25 parts toluene. To a second addition funnel is charged 7.5 parts t-butyl peroxybenzoate dissolved in 25 parts toluene. The temperature is increased to 130° C. then while maintaining N2 throughout the reaction, simultaneous dropwise addition of the peroxybenzoate and the N-vinylimidazole from the two addition funnels is carried out for 1.5 hours then the batch is held at 130° C. for 2.5 hours while maintaining N2. The apparatus is then set up for stripping. The materials are vacuum stripped to 145° C. and 20 mm Hg, diluted with an additional Exxon 100N oil and filtered distill. The product contains 0.043% N.
10  <1
12  6
3,163,603 3,399,141 3,574,101
3,184,474 3,415,750 3,576,743
3,215,707 3,433,744 3,630,904
3,219,666 3,444,170 3,632,510
3,271,310 3,448,048 3,632,511
3,272,746 3,448,049 3,697,428
3,281,357 3,451,933 3,725,441
3,306,908 3,454,607 4,194,886
3,311,558 3,467,668 4,234,435
3,316,177 3,501,405 4,491,527
3,340,281 3,522,179 5,696,060
3,341,542 3,541,012 5,696,067
3,346,493 3,541,678 5,779,742
3,351,552 3,542,680 RE 26,433
3,381,022 3,567,637
Additive concentrates are prepared by mixing together the desired components, often at elevated temperatures, usually less than 150° C., often no more than about 130° C., frequently no more than about 100° C.
Product of Example 1 2
Product of Example/(pbw) 4/8.0 6/9.0
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U.S. Classification 508/221, 525/282, 525/296, 508/543, 525/279, 525/281
International Classification C08L51/00, C08F297/04, C08F255/02, C08F257/02, C08F279/02, C10M149/10, C08F287/00, C08F291/00, C08F255/06, C08F255/10, C08L51/06
Cooperative Classification C10M149/10, C08F255/06, C08F257/02, C08L51/06, C08F255/02, C08F255/10, C08F297/04, C08F287/00, C08F279/02, C08L51/003, C08F291/00
European Classification C08L51/06, C08L51/00B, C08F255/06, C08F257/02, C08F291/00, C08F255/02, C08F287/00, C08F297/04, C10M149/10, C08F279/02, C08F255/10