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Publication numberUS3637503 A
Publication typeGrant
Publication dateJan 25, 1972
Filing dateJul 28, 1969
Priority dateJul 28, 1969
Publication numberUS 3637503 A, US 3637503A, US-A-3637503, US3637503 A, US3637503A
InventorsJoseph P Giannetti, Robert A Plundo
Original AssigneeGulf Research Development Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Lubricating composition
US 3637503 A
Abstract
A lubricating oil composition having good shear stability is obtained by blending together a mineral lubricating oil and a viscosity index improving amount of a polymer of a normal alpha olefin having from four to 16 carbon atoms per molecule. The polymer is obtained by polymerizing the alpha olefin or alpha olefin mixture in the liquid phase in the presence of aluminum chloride and a nonpolymerizing hydrocarbon diluent at a temperature between about -40 DEG and +70 DEG F. for a time sufficient to produce a polymer having a viscosity of about 40 to about 3000 centistokes at 210 DEG F. The alpha olefin is introduced into the polymerization system at a rate of about 0.6 to about 60 moles of olefin per mole of aluminum chloride per hour. The addition of the olefin is continued until 2 to 200 moles of olefin per mole of aluminum chloride has been added.
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United States Patent Giannetti et al.

Jan. 25, 1972 LUBRICATING COMPOSITION [72] Inventors: Joseph P. Giannetti, Allison Park; Robert A. Plundo, Greensburg, both of Pa.

[73] Assignee: Gulf Research 8! Development Company,

Pittsburgh, Pa.

[22] Filed: July 28, 1969 [211 App]. No.: 845,502

[52] US. Cl ..252/59 [51] Int. Cl. ..C10m 1/16 [58] Field of Search ..252/59; 260/93.74

[56] References Cited UNITED STATES PATENTS 2,525,788 10/1950 Fontana et al. ..252/59 2,697,694 12/1954 Shalit et al. .252/59 2,779,753 l/1957 Garabrant et al ..252/59 X Primary Examiner-Daniel E. Wyman Assistant Examiner-W. J. Shine Attorney-Meyer Neishloss, Deane E. Keith and William H. Deitch [5 7] ABSTRACT A lubricating oil composition having good shear stability is obtained by blending together a mineral lubricating oil and a and +70 F. for a time sufficient to produce a polymer having a viscosity of about 40 to about 3000 centistokes at 210 F.

The alpha olefin is introduced into the polymerization system at a rate of about 0.6 to about 60 moles of olefin per mole of aluminum chloride per hour. The addition of the olefin is continued until 2 to 200 moles of olefin per mole of aluminum chloride has been added.

10 Claims, No Drawings LUBRICATING COMPOSITION This invention relates to a lubricating oil composition and more particularly to a mineral lubricating oil composition having improved viscosity index characteristics.

The viscosity-temperature relationship of a lubricating oil is one of the more important characteristics of an oil in that it is this relationship which is indicative of the relative change in viscosity of an oil at high and low temperatures. As might be expected, the viscosity of most mineral lubricating oils changes rapidly with a change in their temperature. In general, mineral oils tend to become thinner as their temperature increases and thicker as their temperature decreases. The change in viscosity with temperature is greater with some oils than with others. While some change is tolerable, excessive change is undesirable. In motor oils of the type known as crankcase oils, it is desirable for the oil to have a viscosity which is sufficiently high at an elevated temperature to provide adequate lubrication and to prevent excessive oil consumption. On the other hand, the motor oil should have a viscosity which is sufficiently low at ambient temperature to provide ease of engine starting. Increasing the high-temperature viscosity of an oil while decreasing its low-temperature viscosity can be accomplished only by improving the viscositytemperature relationship or, stated differently, by raising the viscosity index of the oil. g

In the past, the viscosity index of a mineral lubricating oil has been improved by subjecting the base oil from which the lubricating oil composition is made to more drastic refining methods and/or by adding a viscosity index improver to the lubricating oil. For example, the viscosity index of some oils has been improved by subjecting the base oil to solvent extraction and treatment with aluminum chloride. Aluminum chloride refined or solvent extracted paraffinic oils, such as the Pennsylvania oils, have provided excellent base oils for many lubricating compositions having improved viscosity indices. Likewise, drastically refined Mid-Continent and Gulf Coastal oils have been widely used as base oils in forming lubricants having high-viscosity indices.

In addition to these refining methods, lubricating oils of improved viscosity indices have been obtained by hydrogenating various charge stocks derived from Pennsylvania, Mid-Continent, West Coast, Middle-East crudes, etc. It is known, for example, that improved viscosity-temperature relationships can be obtained when some lubricating oil stocks are either hydrofinished or hydrotreated. I-Iydrofinishing and hydrotreating some lubricating oil stocks, for example, has resulted in excellent base stocks for multigrade lubricants, i.e., lubricants suitable for use under a wide range of temperatures. Regardless of the treatment to which the various charge stocks are subjected, the viscosity index of the lubricating oil can be improved only up to a certain maximum by refining techniques alone inasmuch as further treatment has only an additional negligible effect on viscosity index characteristics. Further improvement can be effected by adding various types of viscosity index improving additives to the lubricating oil. In improving the viscosity index of lubricating oils by additives, recourse has been made to the introduction of various high molecular weight polymers such as polyisobutylene, polymerized esters of the acrylic acid series and the like. In most instances, the highest increase in viscosity index is obtained with polymers of the greatest molecular weight. While high molecular weight polymers have been generally satisfactory in improving the viscosity-temperature relationship of the oil, these polymers have not been entirely satisfactory inasmuch as their viscosity index improving characteristic in many instances is lost or substantially reduced when the oil in which they are incorporated is subjected to vigorous agitation and high shear rates and stresses.

We have found that a lubricating composition having a high-viscosity index and improved shear stability is obtained by incorporating in a mineral lubricating oil a minor amount, sufficient to improve the viscosity index of said oil, of a polymer of a normal alpha olefin having about four to about 16 carbon atoms per molecule or a polymer of a mixture of normal alpha olefins where the average carbon number of themixture is about four to about l6, said polymer being obtained by the process which comprises polymerizing said olefin in the liquid phase in the presence of aluminum chloride and a nonpolymerizing hydrocarbon diluent, said olefin being introduced into the aluminum chloride-nonpolymerizing hydrocarbon reaction mass at a rate of about 0.6 to about 60 moles of said olefin per mole of aluminum chloride per hour and in an amount of about 2 to about 200 moles of olefin per mole of aluminum chloride, at a temperature of about 40 to about +70 F. for a time sufficient to produce a polymer having a viscosity of about 40 to about 3,000 centistokes at 210 F. We have found that a lubricating composition comprising a major=amount of a mineral lubricating oil and a minor amount of a polymer obtained as described above in addition to being shear stable is also thermally stable.

In accordance with the invention, normal alpha olefins having about four to about 16 carbon atoms per molecule or a blend of normal alpha olefins where the average carbon number of the blend is between about four and about 16 are polymerized in high yield by a process which comprises contacting theolefin or blend of olefins in the liquid phase with aluminum chloride catalyst in a nonpolymerizing hydrocarbon solvent at a temperature of about 40 to about +70 F. under selected and correlated reaction conditions to give a polymer having a viscosity of about 40 to about 3,000 centistokes at 210 F. While we recognize that alpha olefins have been polymerized previously in the presence of aluminum chloride or aluminum bromide, a catalyst promoting agent and a nonpolymerizing hydrocarbon diluent, we have discovered that, by carrying out the polymerization reaction under selected and correlated reaction conditions, shear stable polymers having viscosities of about 40 to about 3,000 centistokes at 210 F. are obtained and that these polymers when added to a mineral lubricating oil in amounts sufficient to improve the viscosity index of the oil produce a lubricating composition having good shear and thermal stability. The polymers obtained in accordance with the present invention not only improve the viscosity index of most mineral lubricating oils but also impart exceptional multiviscosity characteristics to certain hydrotreated mineral lubricating base oils, said multiviscosity characteristics heretofore having been obtained by utilizing compounds or compositions comprising constituents other than hydrocarbons, e.g., polymerized esters of the acrylic acid series.

The polymers obtained in accordance with the present invention can be incorporated in the mineral lubricating oil in any convenient manner. Thus, the polymers as such, can be added directly to the lubricating oil or they can be added in the form of concentrated solutions in a solvent such as a light lubricating oil in order to facilitate blending. If desired, such concentrated solutions also can contain other compatible addition agents designed to improve one or more properties of the oil. In the case of blended lubricating oils, the herein-disclosed polymers can be added to one of the component oils prior to blending. Some stirring, possibly with mild heating may be desirable to facilitate more rapid formation of a homogeneous mixture, but this is not absolutely essential.

Exemplary of the alpha olefins which are used in preparing the polymers according to the invention are butene-l, pentene-l, hexene-l, heptene-l, octene-l, nonene-l, decene-l, undecene-l dodecene-l, tridecene-l, tetradecene-l pentadecene-l, hexadecene-l and mixtures thereof.

In preparing lubricating compositions of the present invention, the polymers are employed in concentrations in the range of about 2 to about 30 percent preferably about 5 to about 25 percent by volume based on the volume of the final lubricating composition, but other proportions can be used provided that the polymer is soluble in the oil to the extent to which it is used. The optimum amount of polymer employed may vary depending upon the characteristics of the particular polymer employed and upon the characteristics of the base oil to which the polymer is to be added. Ordinarily, a polymer having a high viscosity will be used in amounts less than a polymer having a low viscosity. ln any event, the polymer is added to the lubricating oil in an amount sufficient to improve the viscosity index of the oil. An especially shear stable lubricating composition having a high-viscosity index has been obtained by admixing about 8 to 10 percent by volume of a decene-lpolymer having a viscosity of about 380.7 cs. (1770 SUS) at 210 F. with about 90 to 92 percent by volume of a hydrotreated mineral lubricating oil.

In preparing the polymers utilized in the composition of the present invention, the alpha olefin or alpha olefin mixture is introduced into a reaction vessel containing aluminum chloride catalyst and a nonpolymerizing hydrocarbon diluent. Prior to introducing the alpha olefin into the reaction vessel, the mixture of aluminum chloride and nonpolymerizing hydrocarbon diluent is preferably contacted with hydrogen chloride for a short time, usually not more than about 1 to 2 hours, preferably about to 30 minutes. Such contacting can be conducted merely by bubbling gaseous hydrogen chloride through the mixture of aluminum chloride and nonpolymerizing hydrocarbon diluent. The diluent is preferably a paraffin hydrocarbon such as butane. However, other nonpolymerizing hydrocarbon diluents can be used. The amount of the diluent may be the same that is normally used in other olefin polymerization reactions. For example, we may use the nonpolymerizing hydrocarbon diluent in amounts of about 1 to about 15 moles per mole of olefin. Larger or smaller amounts may be employed as desired.

The polymerization reaction is carried out generally with agitation at a temperature of about 40 to about +70 F., preferably at a temperature of about to about +40 F. The pressure should be just sufficient to keep the alpha olefin in the liquid phase. Higher pressures have no advantage. While the rate at which the alpha olefin is introduced into the reaction vessel can vary over wide limits, we prefer to add the olefin to the reaction mixture at a rate of about 0.6 to about 60 moles of olefin per mole of aluminum chloride per hour, preferably about 2 to about 20 moles of alpha olefin per mole of aluminum chloride per hour. The amount of alpha olefin added comprises about 2 to about 200 moles of alpha olefin per mole of aluminum chloride, preferably about l0 to about I50 moles of alpha olefin per mole of aluminum chloride. The reaction time is sufficient to produce a polymer having a viscosity of about 40 to about 3,000 eentistokes at 2l0 F. ln most instances, polymerization o this extent is complete in about I to about 24 hours, and usually in about 3 to about l2 hours. In a preferred embodiment of the invention, a shear stable lubricating composition is obtained by incorporating in a mineral lubricating oil a minor amount, sufficient to improve the viscosity index of the oil, of a polymer of decene-l, said polymer being obtained by the process which comprises polymerizing said decene-lin the liquid phase in the presence of aluminum chloride and butane as a diluent, said decenelbeing introduced into the aluminum chloride-butane reaction mass at a rate of about 2 to about 12 moles of decenelper mole of aluminum chloride per hour and in an amount of about 10 to about I00 moles of decene-lper mole of aluminum chloride, at a temperature of about 25 to about 35 F. for a time sufficient to produce a polymer having a viscosity of about 40 to about 3,000 centistokes at 210 F. Inasmuch as the polymerization reaction is exothermic, means must be provided for removing heat during the polymerization. In a preferred embodiment the heat of reaction is removed by a heat exchanger through which a coolant circulates at about l0 to about 20 F. below the boiling point of the diluent. If desired, evaporative cooling can be effected by vaporization of the diluent from the reaction mass. At the conclusion of the polymerization reaction, the contents of the reaction vessel are emptied into a quantity of water, i.e., about 0.5 to about 20 times the volume of the reaction mass to decompose the catalyst. The polymer is separated from the water and then dried. The dried polymer is subjected to a topping distillation to 700' F. The polymer thus obtained has a viscosity within the range of40 to 3,000 centistokes at 210 F.

The lubricating oil to which the polymerized alpha olefin is added according to the invention is advantageously a highly refined oil derived from a paraffinic, naphthenic or asphalt base oil. Thus, the lubricating oil can be one which has been obtained by conventional aluminum chloride refining and/or by solvent extraction. Aluminum chloride refined or solvent extracted paraffinic base oil, such as Pennsylvania oil, provides an excellent base oil for the composition of the invention. However, drastically refined Mid-Continent and Gulf Coastal oil may also be used. Hydrofinished and hydrotreated mineral oils, because of their improved stability over untreated oils and also their improved viscosity index characteristics are especially preferred lubricating oil bases for preparing multigrade lubricating compositions of the invention. Hydrotreating is distinguished from hydrofinishing in that the latter involves the use of milder hydrogenation conditions. In this regard, we prefer to employ an oil which has been hydrotreated. While hydrotreated oils are excellent base oils from which multigrade lubricants can be prepared according to the invention, we can also obtain multigrade lubricating oils using a hydrofinished or conventionally refined base oil.

Especially preferred hydrotreated oils are obtained when a deasphalted residuum is treated with hydrogen at a temperature within the approximate range of about 650 to about 850 F.; a pressure within the range of 1,500 to about 10,000 p.s.i.g.; a space velocity between about 0.l and about 5 volumes of charge stock per volume of catalyst per hour; and a hydrogen recycle rate between about 2,000 and about 7,500 standard cubic feet per barrel of charge. A preferred set of operating conditions for hydrotreating include a temperature of 700 to 800 F., a pressure of 2,000 to 5,000 p.s.i.g., a space velocity of 0.25 to 2 and a gas circulation rate of 2,500 to 5,000 standard cubic feet of hydrogen per barrel of charge.

The viscosity index improving characteristics and shear stability of lubricating compositions containing the polymers of normal alpha olefins according to the invention will hereinafter be illustrated using various lubricating oil bases. It will be noted that many of the illustrative lubricating compositions satisfy the SAE viscosity requirements of multigrade lubricants.

The preparation of the polymers of C to C, normal alpha olefins utilized in compositions of the invention will be illustrated by the following specific examples.

EXAMPLE I Into a 3-liter, three-necked flask equipped with a stirrer, a condenser and a gas inlet tube was placed 1,465 ml. (15.1 moles) of butane and l 1.0 grams (0.08 mole) of aluminum chloride. Hydrogen chloride gas as a promoter was bubbled through the stirred system for approximately 15 minutes. Decene-l (1,284 ml. [6.78 molesl) was added to the reaction vessel over an 8-hour period. The reaction ratios were as follows:

Moles of deccnc-l per mole of AlCl 84.8 Moles of butane per mole of decenc-l 2.23 Moles of decene-l per mole of MCI, per hour l0.6

The temperature of the reactants was maintained at 30 F. After all the decene-l had been added, the contents of the flask were poured into a vessel containing 1 liter of heptane and 2 liters of water. The butane was removed from the reaction mass by vaporization. After all the butane was removed, the heptane-polymer mixture was washed three times with 1.5 liters of water. The washed product was dried over anhydrous sodium sulfate and then fractionated by distillation. The yield of polymer having an initial boiling point of 700 F. was percent based on the volume of the decene-l charged. The polymer thus obtained had a viscosity of 380.7 cs. (1770 SUS) at 210 F. and a viscosity index of 1 15.

This decene-l polymer was blended with various hydrotreated base oils. lnspections of the physical properties of these blends are shown in table I.

TABLE I Percent by volume of Composition...

TABLE III Percent by volume of Composition I J K L M N Hyd rotreatcd base oil: 5 Deeene-l pol mer 10 15 Acryloid I improver 3 4 5 inspections. Viscosity at 210 F., cs.: y Before sonic shear Stu, Inspgctions; bility test 5-95 4-25 1]. 62 7. 81 8. 56 10.1!) 7. 02

Viscosity t Aiter sonic shear sta- 210 F.,cs 5.60 .10 6.22 380.7 10.79 11.33 9.79 10 il y test 5-95 4.25 9.58 7. 23 7.70 10. 11 6.86 Viscosity i Viscosity index, D567:

D5 7 13 132 135 115 142 140 139 B fo some sh ar sta- Pour point o o 5 0 0 billty test 130 00 136 146 14!; 138 152 After sonic shear stability test 120 90 130 142 143 138 146 Pereent loss in thickening l )1 When 90.0 volume percent of a hydrotreated base oil 15 power 1 31 33 1 designated as hydrotreated base oil 1 was blended with 10 volume percent of the decene-l polymer, the resulting lubricating composition (Composition E) met the viscosity specifications of a multigrade l0W/30 lubricating oil, having a viscosity of 10.79 cs. at 2 10 F. and a viscosity index of 142.

When 90.0 volume percent of a hydrotreated base oil designated as hydrotreated base oil 2 was blended with 10 volume percent of the decene-l polymer, the resulting lubricating composition (Composition F) met the viscosity specifications of a multigrade l0W/30 lubricating oil having a viscosity of 1 1.33 cs. at 2 10 F. and a viscosity index of M0.

When 91.75 volume percent of a hydrotreated base oil designated as hydrotreated base oil 3 was blended with 8.25 volume percent of the decene-l polymer, the resulting lubricating composition (Composition G) met the viscosity specifications of a multigrade l0W/30 lubricating oil having a viscosity of 9.79 cs. at 2 1 0 F. and a viscosity index of 139.

The excellent sonic shear stability of the oils prepared in example l is illustrated using the blend prepared by adding 8.25 volume percent of the decene-l polymer to the hydrotreated base oil designated as hydrotreated base oil 3 (Composition G). In order to illustrate the shear stability of the polymers of the invention, the polymer-base oil blends are subjected to a proposed ASTM test for detennining the shear stability of polymer containing oils. This test is described in ASTM Standards on Petroleum Products. Volume 1, 1961, page l,l60. According to this test, the material to be evaluated is subjected to irradiation in a sonic oscillator for a fixed period of time and the change in viscosity determined. The results ob- An additional hydrotreated base oil as well as a hydrofinished light neutral distillate oil were blended with the decene-l of example 1. For comparison, these oils were also blended with a conventional Acryloid viscosity improving agent. The results obtained are presented in table lll.

TABLE III Percent by volume of- Composition H I J K L M N Hydrotreatcd base oi14..... 100 90 97 06 Hydrofinished light neutral distillateojl, 100 85 05 I V=hlend viscosity at 210 F. after shear test.

Vn=viscosity of base oil at 210 F. before shear test.

where The improved shear stability obtained with the decene-l polymer in accordance with the present invention as compared with a conventional Acryloid viscosity index improver is clearly shown by the illustrative data in table ill. It will be noted that after sonic irradiation, compositions of the invention, i.e., Compositions .l and M, retained their highviscosity indices with very little loss in thickening power. Contrariwise, the hydrotreated and hydrofinished base oils containing the Acryloid" viscosity index improver did not retain their high-viscosity index and lost from 29 to 33 percent of their thickening power. The data thus obtained in the sonic shear stability test indicate that the alpha olefin polymers are surprisingly more stable than conventional Acryloid" viscosity index improvers even when subjected to vigorous agitation and high shear rates and stresses.

The thermal stability of a lubricating composition of the invention is demonstrated by the data in table IV. In order to illustrate the thermal stability of polymers utilized in compositions of the invention, the blends were subjected to a modified London Heat Test. According to this test, the material to be evaluated is heated to l60 F. for 48 hours and the change in color is determined by ASTM D1500.

These-tests were conducted with a hydrofinished light neutral distillate oil and the decene-l polymer of example 1.

.For comparison, an additional composition was prepared utilizing a conventional Acryloid viscosity index improving agent. In these tests, the lubricating composition was subjected to a temperature of 500 F. for 24 hours under an atmosphere of nitrogen.

The improved thermal stability obtained with an olefin polymer in accordance with the present invention as compared with a conventional Acryloid viscosity index improver is clearly shown by the illustrative data in table IV. it will be noted that the oil with the decene-l polymer did not show any viscosity loss or increase in acidity (neutralization number) after exposure to 500 F. for 24 hours in a nitrogen atmosphere. The oil which contained the Acryloid" viscosity index improver lost l2 percent of its thickening power and showed an increase in neutralization number after exposure to the same conditions.

TAB LE IV Percent by volume of Composition I M Tv Hydrofinished light neutral distillate Oil 86 05 Decene-l olymer VI Improver P hysieal characteristics Viscosity at 210 F., cs.:

WHEEL TABLE IV Percent by volume of Composition I M Color, ASTM D1500:

Before heating to 500 F 1. 1. 0 1. After heating to 500 F 1. 1.5 1. Percent loss in thickening power I 0 1 I Loss in thickening powcr=Vr-V I V1-Vl where bicn(1 viscosity at 210 F. before thermal test.

V:blend viscosity at 210 F. after thermal test. vo yiscosity ofl ase oil at 210 F. before thermal test.

recto EXAMPLES 2 to l 1 inspections;

Viscosityat 210 F..es.... 4.25 10.2 10.2 10.2 10.2 10.2 10.2 Viscosity index, D667. J0 133 135 138 13'.) 141 142 Pour point, F 0 +5 +5 0 +10 +20 Sonic shear test (10 minutcs) 210' F. viscosity loss, cs less than 1% of original viscosity Viscosity index loss Less then 1% of original viscosity index otherpror rtieso f Q nposition iii are shown in Tables 111 and 1\".

All the blended oils shown in table Vl are shear stable, i.e., less than i percent loss in viscosity or viscosity index. The blended oils prepared from the polymers where the alpha olefin monomer contained six and eight carbons while having improved viscosity index characteristics were marginal oils with respect to the viscosity index. The blended oils from the polymers where the alpha olefin monomer contained 12 to 16 carbons had high pour points which, however, can be reduced by the use of a pour point depressant. The blended oils containing the decene-l polymer, when both the viscosity index and pour point characteristics are considered, gave the most acceptable l0W/30 multiviscosity oil. it is evident that polymers of the invention made from C to C alpha olefins can be used to produce l0W/30 multiviscosity oil but best e l ser i s! itiit s pel r fr9 .925

TABLE V.-PREPARATION OF POLYMERS Polymer preparation Polymer prop orties, viscosity Tem- Addiat Alpha pera- Moles Moles Moles tion Reaction ratios olefin ture, moncatadilutime 100 F., 210 F., monomer Catalyst Diluent F. omer lyst ent hours A B C cs. cs,

Example:

2 Rescue-1.. 30 2.32 .13 16.1 4 17.8 6. 04 4.45 4,795 206 3.. 30 2. 32 .13 16.1 2 17.8 6. 94 8. 9 3,023 148 4.. 30 11.0 06 16.1 12 183. 3 1. 46 15. 3 1, 540 100 5.. 30 3. 19 08 19. 2 8 39. 9 6. 02 5. 0 2, 450 161 6 30 1. 50 .08 14. 8 8 18. 8 9. 87 2. 3 8, 200 463 7 .do..... 30 1.12 .08 4. 8 6 14.0 13.21 2. 3 3, 450 220 8 Dodecene-l 30 1. 08 15. 1 8 19. 4 9. 74 2. 4 7, 844 531 9 ..do... 30 1.62 .07 16.1 4 23.2 9.94 5.8 1,000 79 10 Tetratiec- 30 1. 36 08 13. 1 8 17. 0 9. 63 2. 1 2,034 161 ene- 11 Hexedlec- .do do. 30 1.35 .08 15.1 8 16.0 11.19 2.1 1,869 157 ene- * HCl bubbled through diluent-catalyst mix for /5 hour prior to monomer addition; A=Moles of alpha olefin per mole of AlCla;

B=Moles of butane per mole of olefin; O=Moles of alpha olefin per mole of A101; per hour.

When l5 percent by volume of polymers prepared from C to C alpha olefins was added to the hydroflnished light neutral distillate oil the resultant blend had viscosities in the range required for l0W/30 multiviscosity oils. The result obtained when blending 15 volume percent of the polymers with arc ul fii lid. were v. tern.

While polymers of normal alpha olefins having from about six to 16 carbon atoms per molecule have been described above with particular reference to their ability to improve the viscosity index of hydrofinished and hydrotreated mineral lubricating oils, it is to be understood that the polymers can also be utilized in improving the viscosity index of other mineral lubricating oils. For example, the polymers can be added to lubricating oils that have been derived from paraffinic, naphthenic or mixed base crude petroleum oils, and that have been subjected to solvent or sulfuric acid treatment, aluminum chloride treatment and other refining treatments. The improved characteristics of other hydrotreated and nonhydrotreated base oils with other polymers of the invention TxBLi'iHiIREsPoNsE OF LIGHT NEUTRAL DIS'IILLA'IE T0 VARIOUS o POLYMERS Composition Percent by volume of Light neutral distillate Cm polymer. Medium Gm Polymer Light On polymer. Inspeciions; Viscosity; cs. at:

F Viscosity index, D567- Meets specifications. After 10 minutes soni es. at:

TABLE VIII.EFFECT OF POLYMER ON VISCOSITY F TABLE Xi l BASE OILS C pltilyniietrz I t t 100 F. 4000 15 Polymer. y as a 01 o Viscosity: cs. at 100 F. 8600 7 5005 0 i V1 ml: "at 210 F. 542 5 iscosity index, D507122 Vl. .osity liirlex, l)567120 viscosity, CS

B... on 250.2% "77551715 Viscosity, (1s. Vls- 5 O m Spoon-l I I l'olynn-r, icoiilty Mlitill llficrllltwn percen F. F. F. D561 cations lww. 0| vu time 0 100 211] nt ex, spec i- H t t rlcsarl itlmi ii-remit. l", |i l U507 cations l0 gt ifgfi fff fli 1 2 i i l 70 mmhlxm V n 14.87 3. 22 88 Extrapolated values.

8.0 a 21. 91 5. 21 143 5W/20 h V 18.0 1, 828 67.89 11.50 143 W/30 e A .M llyitlrotroated 0 24 43 4 91 140 o l 1. t y

1.4 783 27-71 5.41 144 u TABLE XII. EFFECT OF POL! MER ON ISCOSIT} ()F 2.9 804 30.29 5.90 145 5w/20 BASE OIL 11.5 1, 590 59.15 10. 42 145 l0W/30 Ca polymer: lScOSltyI cs. at100 F. 1,215

. o l lqxtriipoluted values. 123321211 351?15%.?11.

Viscosity, es. \is- Polymer, cosity Meets Base oll volume 0 100 210 index. specifi- D O TABLE IX.EFFEOT or POLYMER 0N VISCOSITY 0F descrlpm Percent F. D 1 ations BASE OILS 0 1,695 43. 05 7.02 132 10W/20 Hydrotreated 5.0 1, 780 48. 7.865 132 10W/29 C15 polymer: 25 o l 10.0 2,000 55.6 8.77 132 10W/20 Viscosity: cs. at 100 F. 8,200 15. 0 2,560 65. 8 10.16 134 10W/30 Viscosity: cs. at 210 F. 463 Viscosity index, D567 122 1 Extrapolated values.

Viscosity, cs. Vits- M t V Polymer cosi y ee 5 Base volum O 100 210 index, Specifk The lubricat ng oil compositions of this invention can condescription percent F. F. F. D567 cations tain other addition agents normally added to lubricating OilS for a specific purpose such as an oiliness agent, an extreme 50 Texas ressure a cut, an antioxidant, a corrosion inhibitor, a foam (11 till i 0 228 l) 675 2 34 49 p g S a e 434 22 1 117 1:1: suppressant, a dye, a sludge inhibitor, a pour point depressant 9.8 555 27.55 5.88 159 5W/29 35 and the like. Light neutral 912 157 low/20 While our invention has been described with reference to distillate 0 825 21.8 4.12 07 various specific examples and embodiments it will be un- Wdium new 3 63-85 28 137 10W] 30 I derstood that the invention is not limited to such examples and trril distillate. 8 g, 358 33.3 5.22 .u m embodiments and may be variously practiced within the scope 9. 15.0 s, 529 142. 2 17.14 125 20W 59 40 of the clalms heremafter made- We claim: 6 i; igg'f 3; 1. A lubricating composition comprising a major amount of 9.5 223.1 17. 26 a mineral lubricating oil and a minor amount, sufficient to im- Hm TN 0" n 21 5 3 m prove the viscosity index of said oil, of a polymer of a normal 1.8 1:800 34.7 5. alpha olefin having about four to about 16 carbon atoms per 3 3-33 molecule, said polymer being obtained by the process which comprises polymerizing said olefin in the liquid phase in the 4 "iiiff 2'3: Presence of aluminum chloride and a nonpolymerizing 9:1) 2: 170 54:0 13:47 130 10W/20 hydrocarbon diluent, said olefin being introduced into the alu- 50 minum chloride'nonpolymerizing hydrocarbon reaction mass 100 4 tr ll. 0 20.9 3.80 54 mm m 0 4.9 1, 260 29. 9 5.30 121 1. at a rate of about 0.6 to about moles of said olefin per mole 2-: 551% 2 3 22 5 5838138 of aluminum chloride per hour and in an amount of about 2 to Hydrotmated about 200 moles of olefin per mole of aluminum chloride, at a 011 0 1,34 38-30 low/20 temperature of about 40 to about F. for a time suffi- 5. 2 1, 010 56. 03 0. 07 136 iow zo 55 cient to produce a polymer having a viscosity of about 40 to l t 1 t d I about 3,000 centistokes at 210 F. 5 a ...Y%. 4 2. The lubricating composition of claim 1 wherein said minor amount is about 2 to about 30 ercent b volume of the P Y composition. 60 3. The lubricating composition of claim 1 wherein said TABLE X C I olefin utilized in obtaining said polymer IS hexenel.

0 p0 ymer: l viscosity: w at 5950 4. The lubricating composition of claim 1 wherein said Viscosity: es. at 210 F. 380.7 olefin utilized in obtaining said polymer is octenel. Viscosity lndex' D567115 5. The lubricating composition of claim 1 wherein said Viscosity, cs. Vis- M 5 olefin utilized in obtaining said polymer is decenel. Pol mer coslty eets Base on vgmm 0 100 210 index specify 6. The lubricating composition of claim 1 wherein said description percent F. F. F. D567 cation olefin utilized n obtaining said polymer 1S dodecenel 0 869 5 M0 138 n 7. The lubricating composition of claim 1 wherein said 10. 0 .122 2:1 g g 33 18 6 6128 0 olefin utilized in obtaining said polymer is tetradecene-l. 15.0 2, 7 Hvdmtmated 0 1' 195 4 M0 132 low/20 0. The lubricating composition of claim 1 wherein said oil 10. 0 2,170 59. 54 i1. 33 10W/a0 olefin utilized in obtaining said polymer is hexadecene-l.

8 Mfg gig? &3; i3? $331138 9. The lubricating composition of claim 1 wherein said a. 25 1, 359 59. 25 9. 79 30 low/30 olefin utilized in obtaining said polymer is an alpha olefin mixig m values 75 ture where the average carbon number of said mixture lS about four to about 16.

mass at a rate of about 2 to about l2 moles of decene-l per mole of aluminum chloride per hour and in an amount of about 10 to about l00 moles of decene-l per mole of aluminum chloride, at a temperature of about 25 to about 35 F. for a time sufficient to produce a polymer having a viscosity of about 40 to about 3,000 centistokes at 210 F.

t i i l i

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Referenced by
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Classifications
U.S. Classification585/10, 585/532, 585/13
International ClassificationC10M143/08
Cooperative ClassificationC10M2205/02, C10M2205/026, C10N2220/02, C10M2205/00, C10M2205/028, C10M143/08, C10M2209/084
European ClassificationC10M143/08
Legal Events
DateCodeEventDescription
May 5, 1986ASAssignment
Owner name: CHEVRON RESEARCH COMPANY, SAN FRANCISCO, CA. A COR
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:GULF RESEARCH AND DEVELOPMENT COMPANY, A CORP. OF DE.;REEL/FRAME:004610/0801
Effective date: 19860423
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GULF RESEARCH AND DEVELOPMENT COMPANY, A CORP. OF DE.;REEL/FRAME:004610/0801