US 3816346 A
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United States Patent r191 Coppock et al.
LUBRICANT FOR SPINDLES, NEEDLES OR TWISTER RINGS Inventors: Walter J. Coppock, Wallingford;
James R. Amaroso, Newtown Square, both of Pa.; John Q. Griffith, Ill, Claymont, Del.
Sun Oil Company of Pennsylvania, Philadelphia, Pa.
Filed: Apr. 14, 1972 Appl. No.: 244,274
Related US. Application Data Assignee:
US. Cl 252/32.5, 252/8.6, 252/49.8,
252/49.9, 252/56 R lnt. Cl Cl0m l/46 Field of Search 252/8.6, 49.9, 49.8, 32.5
References Cited UNlTED STATES PATENTS Bretschneider 252/8.6
[ June 11, 1974 2,830,951 4/1958 Bowden et a1. 252/37.2 2,882,231 4/1959 Brennan 252/8.6 X 3,169,923 2/1965 Guarnaccio et a1. 252/32.5 3,562,145 2/1971 Frauz ct a1 208/96 3,666,657 5/1972 Thompson et a1. 208/58 3,684,684, 8/1972 Coleman et a1 208/28 OTHER PUBLlCATlONS Jones, Oil & Gas Jour. Nov. 1, 1954, pages 81-84.
Primary Examiner-W. Cannon Assistant Examiner-W. Cannon v Attorney, Agent, or FirmG. L. Church, Esq.; J. E. Hess, Esq.; B. A. Bisson, Esq. I
 ABSTRACT A composition which does not cause pin hole damage to cotton, and which is useful as a spindle oil, or as a twister ring oil, or as a needle oil, said composition comprising an effective amount of a friction reducing additive and a hydrorefined naphthenic or paraffinic lube or a hydrocracked hydroisomerized paraffinic lube or a hydrogenated polyolefin oil, said additive containing at least one alkyl ester of a carboxylic acid (preferably a methyl ester of a triglyceride of a fatty acid) or an alkyl acid phosphate or alkyl ammonium alkyl acid phosphate (e.g., an alkyl amine-neutralized, alkyl acid phosphate having alkyl groups in the C C range).
4 Claims, No Drawings LUBRICANTFOR SPINDLES, NEEDLES R TWISTER RINGS APPLICATIONS CROSS REFERENCE TO RELATED The following patents and applications are related to the disclosure of the present application in that they disclose additives which are useful in the present composition and/or methods of obtaining hydrorefined naphthenic oils (and other oils) which can be used to i make the textile machinerylubricant oil composition of the present invention.
The disclosure of all of the following applications and patents is hereby incorporated in the present applica- 'tions:
Filing Date US. Pat. No.
Issue Date Title 8-18-69 (now abandoned) 8-18-69 (now abandoned) Clay Treatment of Hydrorefined Cable Oils lvor W. Mills & Glenn R. Dimeler Process for Preparing an Aromatic Oil and Non-discoloring Rubber Composition lvor W. Mills, Glenn R. Dimeler & Merritt C. Kirk, Jr.
Process for Producing Cable Oils by Sequential Refining Steps lvor W. Mills & Glenn R. Dimeler Hydrorefined Transformer Oil and Process of Manufacture lvor W. Mills & Glenn R. Dimeler Catalytic H ydrofinishing of Petroleum Distillates in the Lubricating Oil Boiling Range lvor W. Mills, Merritt C. Kirk, Jr. & Albert T. Olenzak lsomerization of Waxy Lube Streams and Waxes lb Steinmetz & David S. Barmby Blended Hydrocarbon Oil and Process of Manufacture lvor W. Mills & Glenn R. Dimeler Hydrorefined Lube Oil and Process of Manufacture lvor W. Mills & Glenn R. Dimeler Process for Preparing High Viscosity Hydrorefined Cable Oil lvor W. Mi ls, 9 .1 1 3 13-,
Filing Date Uls. Pat. Issue Title 3.68 1.233 AWE-L72 8-3-70 (now abandoned) Dimeler. William. A. Atkinson & David A. Hoffman Oil and Process of Manufacture of Blended Hydrorefined Oil Ivor W. Mills. & Glenn R. Dimeler Light-colored Highly Aromatic Oil and Process of Preparation lvor W. Mills. Glenn R. Dimeler 8t Merritt vC..Kirk. .lr. Hydrorefined Cable Oil and Process of Manufacture lvor W. Mills & .Q s im Hydraulic Oil Composition Containing a Blended Base Stock John Q. Griffith, 111, Edward W. Williams & William H. Reiland, Jr. Hydraulic Oil Composition Containing a Blended Base Stock John O. Griffith 111. Edward S. Williams, William H. Reiland, Jr., lvor W. Mills & Glenn R. Dimeler Polyisobutylene Oil Having a High Viscosity Index Gary L.Driscoll, lrl N. Duling 81. David S. Gates Textile Machinery Lubricant Composition James R. Amaroso & John Q. Griffith, lll Catalytic Hydrofinishing of Lube Oil Product of Solvent Extraction of Petroleum Distillate lvor W. Mills. Merritt C. Kirk, Jr. & Albert T. Olenzak Mist Lubricant Containing Polymeric Additive James R.
Amaroso, Walter J.
Coppock. Thomas D. Newingham & Edward S. Williams Composition Comprising Stabilized Hydrocracked Lube and an Antioxidant Robert B. Bryer, William W. Crouse, Jr., John O. Griffith, 11], Thomas D. Newingham, & William H. Reiland, Jr.
Soap Thickened Hydraulic Oil Composition John Q. Griffith, 111. Edward S. Williams & William H.
. lsilanddrt U.S. Pat. No.
Issue Date Serial No.
Filing Date Title Hydrogenated Ethylene-propylene Copolymer Oils Richard S. Stearns, lrl N. Duling & David itqt aw Hydrorefined Lube Oil and Process of Manufacture lvor W. Mills & Glenn R. Dimeler Improved Textile Machinery Lubricant Composition Walter J. Coppock, James R. Amaroso 8L John Q. Griffith. 111
SUMMARY OF THE INVENTION Novel compositions, which are useful as textilemachinery lubricants, are an improved needle oil, an improved twister ring oil, and an improved spindle oil. These oils have greater oxidation stability, cloth scourability and better antifriction properties than do prior art oils. These oils have little or no tendency to produce pinholes in cotton, which was a problem with prior art oils.
A composition which does not cause pin hole damage to cotton, and which is useful as a spindle oil, as a twister ring oil or as a needle oil, comprises a hydrogenated, hydrocracked or hydroisomerized oil, e.g., a hydrofined'napthenic or paraffinic lube, or a hydroisomerized or hydrocracked paraffinic lube or a hydrogenated polyolefin oil, and an effective amount of a friction reducing additive, said additive containing at least one alkoxy or alkyl phosphate or acid phosphate or at least one alkyl ester of a carboxylic acid, more preferred a triglyceride of a fatty acid. The fatty acid can contain in the range of C -C carbon atoms. The alkyl group is preferably methyl, but can be C to C Preferably, the oil has an SUS viscosity at 100 F. in the range of 60-600 SUS (more preferred, 70-300 SUS) and contains in the range of 5-40 wt. percent aromatic hydrocarbons.
One such friction reducing additive is a surfaceactive organic phosphate ester, as of a linear aliphatic ethoxylated alcohol, (e.g., Ultrophos l 1, Ortholeum 162, etc.) in an amount (e.g., 0.1-10 wt. percent) effective to reduce the static friction of the base oil as measured by the low velocity friction apparatus. Ortholeum 162 consists essentially of dilauryl phosphate and other similar mixed alkyl acid orthophosphates. Preferably, such acid phosphates are neutralized with an alkyl amine before use in the present lubricant. This test method and such phosphate esters are further described in U.S. Pat. Ser. No. 218,394, filed Jan. 17, 1972 of l-laseltine, Jr., Gates and Hagstrom, said application being incorporated herein by reference.
Another useful additive is the synthetic sulfurized oil of U.S. Pat. application Ser. No. 135,466 of Recchuite, filed Apr. 19, 1971 (now abandoned), which is made by heating sulfur and a blend of 30-95 percent lard oil and 70-5 percent of one or a mixture of C -C acyclic monoolefin.
The new, improved needle oil preferably comprises an effective amount of a friction reducing additive in a base oil consisting essentially of hydrorefined or hydrocracked paraffmic lube having a viscosity at 100 F. in the range of -150 SUS (typically -1 15), said hydrorefined or hydrocracked paraffinic lube containing in the range of 4-1 0 percent aromatics (e.g., 8 percent) and typically, having a 260 UVA in the range of 005-04 (e.g., 0.2) and having been obtained by bydrorefining of a 9-15 wt. percent (e.g., 12 percent) aromatic content, solvent refined paraffinic distillate to reduce the 260 UVA by at least 30 percent, or by hy-' drocracking a paraffinic distillate oil (which can be solvent extracted either before or after said hydrocracking). Although a hydrorefined naphthenic oil can be substituted in whole or in part for said hydrorefined paraffinic lube, the lubricant consisting essentially of the hydrorefined paraffinic lube or the hydrocracked paraffinic lube, or a blend of such lubes has better heat resistance. Butylacetate can be used instead of (or to replace part of) the methyl ester of a triglyceride of a fatty acid; however, butylacetate is less preferred because it has a low flash point.
A preferred formulation for such a needle oil (especially for high speed knitting needles for double-knit hosiery) having excellent stability, low drag and which produces little deposit build-up on the needle, is a 90-100 parts by weight (typically 94.5), hydrorefined or hydrocracked paraffinic lube of about (e.g., 1 l0) SUS viscosity at 100 F., l-lO parts of a friction reducing additive (typically 5), one preferred additive being a mixture of methyl esters of mixed triglycerides of fatty acids in the c rcggrange. Further preferred is the product sold by Procter & Gamble Company under the trade designation TE-l618, which contains in the range of 2-6 percent C monounsaturates, 17-24 percent C saturates, 35-45 percent C monounsaturates, has a saponification number in the range of -200, an iodine number in the range of 39-60, a refractive index of about 1.4472, a specific gravity at 88 F. of about 0.86, a melt point of about 15 C., a flash point (open cup) of about 340 F., a pH of about 7, a maximum acid number of 1 (more preferably less than 0.4), and a percent transmission at 460 mm of at least 80. This friction modifier is light in color and, with nylon or cotton, has good detergent scourability and is non-staining, non-abrasive and noncorrosive. 7 V n The needle oil can also contain other additives, such as 0.1-2 parts barium salts of alkylaryl or alkyl polyethylene oxyphosphorus ester acids (e.g., 0.5 parts of the 50 percent active material sold by General Aniline and Film Co. under the trade name Antara LM-505) such a material is light colored and serves as a lubricant or antiwear agent, as an emulsifier or dispersant, inhibits rust, and also provides some detergency and scourability. Typically this additive contains 5-8 percent barium (e.g., 6.2 percent) and l-2 percent phosphorous (e.g., 1.6 percent), has a viscosity at 100 F. of about 1,100 SUS and a flash point of about 350 F.
Also useful in the needle oil arean antioxidant, such as ditertiary butyl para cresol, known as DBPC, (e.g.,
43 lbs. per 1,000 gallons of oil) and an ultraviolet stabi lizer, such as the triazole types (e.g., 0.7 lb. per 1,000 gallon).
Another novel composition, useful in the textile field, is an improved spindle oil, containing l-lO parts (e.g., 3.8) of a friction reducer, such as mixed methyl esters of glycerides of fatty acids, in the range of 85-99 parts hydrogenated oil having an SUS viscosity at 100 F. in
the range of 70-200 (and preferably hydrorefined naphthenic oil, e.g., 87.3 parts of 100 SUS and 5.2 parts of 2500 SUS). The spindle oil can also contain 0.2-1.0 parts of an antioxidant (e.g., 0.6 parts DBPC) and 0.5-5 parts of a rust preventative and detergent,, such as 2.2 parts of the 80 percent active sodium salts of sylfonates of petroleum acids sold by the trade name Shell 80-20 sulfonates (barium salts can also be used).
The novel twister ring oil comprises hydrorefined or hydrocracked paraffinic lube, or a high Vl hydrogenated polyolefin and a friction modifier, preferably an amine salt of an alkyl acid phosphate.
Tables 1, 2 and 3, attached hereto, present typical and a preferred range of properties for, respectively, such a needle oil, such a spindle oil and such a twister ring oil. However, operable products can be formulated which have properties outside these preferred ranges, for example, the viscosity at 100 F. of any of these products could be within the range of 70-300 SUS.
FURTHER DESCRIPTION In general, improved lubricants of the present invention comprise a friction reducing additive and a base oil having an SUS viscosity in the range of 60-600 at 100 F. (more preferably 70-300), consisting essentially of one or more hydrorefined naphthenic oils, hydrogenated polyolefin oils, or hydrocracked or hydrorefined paraffinic oils (or blends of any of these oils) of the lubricating oil viscosity range (e.g., 45-l2,000 SUS at 100 F.)
Preferably, the hydrorefined naphthenic oils have an aniline point in the range of l40-190 F., more preferred l50-l70 F., a viscosity-gravity constant (VGC) in the range of 0820-0899, more preferred 0.850-0.899, and an ultraviolet absorptivity (i.e., UVA) at 260 millimicrons, (i.e., 260 UVA) which is at least 40 percent less than that of an unhydrorefined' naphthenic lube of the same viscosity, viscosity-gravity constant, and boiling range. The hydrocracked or hydrorefined paraffinic oils have a VGC in the range of 0790-0819 and an ASTM viscosity index of at least 90 (typically, at least 95).
Preferably, the UVA of the base oil at 335 millimicrons (i.e., 335 UVA) is in the range of 0.01 to 0.4 (typically 002-02) and the ASTM D1500 initial color is less than 4.0 (more preferably no greater than 2.5). The additives comprise a friction reducing additive and can include viscosity index improvers, antirust, antifoam, antioxidant, etc. In some cases a tackiness agent is added. The preferred tackiness agents are olefin polymers (e.g., atactic polypropylene, or polyisobutylene rubber) and can partially or fully hydrogenated; however, any oil-compatable tackiness agent (e.g., polyacrylates, Al oleate, or natural rubber obtained from dehydrated latex) can be used. The preferred range for the polyisobutylene polymers as commercially available, as indilution with oil (about 50 percent) is about 0.3-6 percent, more preferably 1-3 percent. In any event, the amount used must be sufficient to cause the lubricant to be highly retentive on a hearing (or other part) and to reduce splashing; however,
the amount must be less than that which will cause the lubricant to be stringy.
Preferred acrylates and methacrylates (e.g., the viscosity index improver types can be of the nondispersant type and correspond to the structural formula:
where n is an integer such that the viscosity average 10 molecular weight (VAMW) is in the range of 10,000 to 2,000,000, where R is H, for the acrylates and methyl for the methacrylates. In the copolymer type materials,
R is a single alkyl radical (branched or normal) having a carbon number in the range of six to about 30, preferably eight to 24 (usually an even number). In the terpolymer types of materials at least two different alkyl radicals (in the above carbon number ranges) are present in the polymer chain (e.g., normal octyl and normal .decyl or each of the even numbered normal alcohols in the C -C range). The dispersant type materials can also be used. In the dispersant type, the above noted copolymers or terpolymers have been grafted with .vinyl pyrrolidone. Descriptions of such polymers can be found in U.S. Pat. Nos. 2,091,627; 2,489,671;
3,252,949; 3,417,021 and 3,510,425.
An especially preferred polymethacrylate is that sold by Rohm and Haas under the trade name PL 10190" i (whislthas $919921? Wei ht O about 9010. and is of the same chemical structure as the 700 Series").
} Two operable polyisobutylenes are Paratone N .(which has amolecular weight of about 20,000) and Paratac 108 (which has a molecular weight less than 20,000). A mixture of 10 parts by weight of a 300,000 VAMW methacrylate terpolymer, wherein two or more of the alkyl groups are in the C12-C24 range and 1 to 4 parts by weight of a 150,000 VAMW polyisobutylene is also useful as a polymeric additive. Also useful is the dispersant type polymethacrylate terpolymer sold as 40 Acryloid 9665. A useful acrylic is Acryloid 162. In the twister ring oil and the needle oil the preferred .lubricant base stocks are paraffinic lubes having a viscosity in the range of 70 to 300 SUS at 100 F. Such paraffinic lubes are generally solvent dewaxed and solvent refined and have an ASTM viscosity index in the .range of 90-105. The preferred paraffinic lube is hydrorefined or hydrocracked or hydroisomerized. Blends of such paraffinic lubes with naphthenic lubes of about the same viscosity range or, more preferred, with hydrorefined naphthenic lubes can also be used. In general the naphthenic component is preferred in the spindle oils, and a high V.l. paraffinic oil is generally preferred in the twister ring oils.
Another preferred additive is an antiwear agent .which will not harm textiles, most preferred is 0.3-10 percent of a chlorinated paraffin; however, 0.2-2 per- Icent of tricresyl phosphate or a combination of these two additives can also be used. Optionally, the lubricant can also contain an antifoam (such as 0.5-20 ppm of active silicone antifoam). Generally such an antifoam is used as a dilute solution or suspension containing about 1 percent of the active ingredient.
To further safeguard against discoloration, an antiox- 65 idant such as 0.05-1 percent ditertiarybutyl paracresol (i.e.. DBPC) can also be included.
In general, any additive used in the lubricants of the present invention should have an acid number less than 25 and the total. compounded lubricant should have an acid numbhr less than 0.5 and a neutral pH (preferably, 6.2-7.7, more preferred 6.8-7.2).
The base oil can consist essentially of a single narrow-boiling range, hydrorefined lube of the desired SUS viscosity or the desired viscosity base oil can be obtained from a wider boiling range blend of two or more narrow-boiling range oils (e.g., a 150 SUS base oil can be obtained directly by hydrogenation of a 160 SUS distillate or can be obtained by hydrogenating a blend of 100 and 2500 SUS distillate or, more preferred, the 150 SUS base oil can be obtained by blending a 100 SUS hydrorefined distillate with a 2500 SUS hydrorefined distillate, or with a bright stock"). Processes for obtaining such distillates and such hydrogenated oils are disclosed, for example, in the previously referred to applications and patents. Such oils are available under the trade names Sunthene, Sundex,
Sunpar, Sunpar H, etc.
Although the base oil can have a viscosity at 100 F. in the range of 60-600 SUS, the preferred viscosity range is 70-300 SUS and, more preferred, 100-200 SUS.
To improve such properties as color, flash point and oxidation stability, the base oil can also contain (in addition to a major amount of a hydrorefined, hydrocracked or hydroisomerized oil) in the range of 0.5-25 percent of solvent refined paraffinic oil, naphthenic distillate, naphthenic-acid free naphthenic distillate or polyolefin oils.
The base oils preferably contain less than 80 ppm of basic nitrogen, more preferably less than 30 ppm (in some cases -10 ppm), and can be those described in the previously cited U.S. Pat. application Ser. Nos. 622,398; 636,493; 812,516, and more preferably, are blends of two or more hydrorefined or hydrocracked oils (e.g., a 150 SUS blend ofa 100 SUS at 100 F. hydrorefined naphthenic oil and a 2500 SUS at 100 F. hydrorefined naphthenic oil) or a blend of hydrorefined naphthenic oil and hydrocracked paraffinic oil.
In certain of the lubricants of the present invention, the base oil can have an aniline point in the range of 140-180, and in some cases the preferred aniline point of the base oil is in the range of l50-l 70 F. to enable maintenance of good rubber seal condition, (or in the range of 195-2l5 F. where silicone rubbers are used). Preferably, in such lubricantsthe oil or blend of oils is selected so as to obtain a base with the desired viscosity, an ultraviolet absorptivity at 335 millimicrons (i.e., 335 UVA) in the range of 001-04, more preferred 002-02, and an aniline point in the desired range. The hydrorefined naphthenic oil component of such a base stock will generally have an aniline point in the range of 140-190, more preferred l50l70 F., and the hydrorefined or hydrocracked or hydroisomerized paraffinic oils will be above 190 F. (e.g., 200260 F.).
The phrases severe hydrorefining or hydrogenation refer to processes conducted in the presence of a hydrogenation catalyst at from about 500775 F., with hydrogen of 50-100 percent purity, and from 8003,000 p.s.i. of hydrogen at the reactor inlet (at total pressures from 8006,000 p.s.i.g.) at a fresh feed liquid hourly space velocity (LHSV) of from 0.1-8.0 (usually below 2.0), preferably conducted either in vapor phase or trickle phase. Such hydrogenation or severe hydrorefining is to be distinguished from hydrocracking in that the production of overhead" (i.e., hydrocarbons boiling below 485 F.) is less than 25 percent by volume per pass through the reactor and, typically, less than 10 percent). Product'recycle, for example, as in U. S. Pat. No. 2,900,433, can be used to increase severity. Recycle liquid hourly space velocity can vary from 0 to 20; however, it is preferred to operate at total liquid through-puts that obtain at greater than 25 percent of flooding velocity and more preferably at from 40-98 percent of flooding velocity.
Preferably, the temperature is below that at which substantial cracking occurs, that is, no more than 20 weight percent (preferably less than l0percent) of the feed stock is converted to material boiling below 300 F. in a single pass through the reactor. Although the maximum hydrogenation temperature which will not produce substantial cracking is somewhat dependent upon the space velocity, the type of catalyst and the pressure, generally it is below 750 F. but can be as high as 785 F. To allow a margin of safety, it is preferred to operate below 700 F. (except when it is desired to obtain a hydrogenated oil containing more gel aromatics than are in the charge). At total pressures below about 2,000 p.s.i. the preferred temperature is below about 660 F., since above that temperature the degradation of of oil viscosity can become large.
Typical of such severe hydrorefining methods, when conducted within the aforementioned processing conditions, are those of U.S. Pat. Nos. 2,968,614; 3,993,855; 3,012,963; 3,114,701; 3,144,404; 3,278,420 and 3,642 and those of the previously referred to copending U.S. Pat. applications, Ser. No. 622,398; 652,026; 636,493; 730,999 and 812,516. The terms severely hydrorefined oil or hydrogenated oil include the products, within the lubricating oil boiling range, of such severe hydrorefining or hydrogenation. One characteristic of a severely hydrorefined or hydrogenated oil is that the ratio of monocyclic aromatics to polycyclic aromatics is significantly greater than in hydrotreated oils or conventional distillate oils.
Where the desired hydrorefined oil is to be of the naphthenic class, a preferred charge to the hydrogenation reactor can be obtained by vacuum distillation of naphthenic or mildly aromatic crude oils (as in U. S. Pat. No. 3,184,396), especially those crude oils wherein the l,500-3,000 SUS (at F) distillate fractions have viscosity-gravity constants from 0.84 to 0.92. Preferably, such a charge stock should be substantially free of naphthenic acids prior to the hydrorefining (thus, in some cases distillation in the presence of caustic is advantageous). Usually materials boiling below about 600 F. (including residual H S, Nl-l etc.) are removed from the hydrorefined oils, as by atmospheric distillation (and the viscosity can also be adjusted by choice of distillation end point) prior to clay contacting (if the oils are to be clay finished). Such naphthenic distillate oils are available commercially under the trade name Circosol.
The viscosity of the base oil, or of the final hydrorefined oil, can be adjusted by the addition of other oils of higher or lower viscosity and which are within the lube oil boiling range. Where desired, the basic nitrogen content can be lowered by contacting the charge or hydrogenated oil or the blend of hydrogenated oils with sufficient acidic adsorbent or mineral acid to reduce the basic nitrogen content of the oil, as to below 10 ppm.
By naphthenic distillate, we refer to a distillate fraction (or a mildly acid treated distillate fraction, or a solvent raffinate fraction or an acid-treated raffinate) usually from vacuum distillation, of a crude which is classified as naphthenic (including relatively naphthenic) by the viscosity-gravity constant (VGC) classification method, (see p. 79-80, Plasticizer Technology, Vol. I, p. Bruins, Reinhold Publishing Corp., N. Y., 1965). Preferably, such crudes are Grade A (wax-free), typically Gulf Coastal, and include, for example, Refugio, Mirando, and Black Bayou. The lower VGC oils can be obtained from mid-continental crudes; and can be dewaxed if desired (as by extraction or isomerization). Such naphthenic fractions will have a VGC in the range of 0.820 to 0.899 and, typically, a viscosity in the range of ISO-12,000 SUS at 100 F. (for example, 500-6,000). In some cases the crude (and distillate) can have a VGC as high as 0.94 (such crudes are characterized as mildly aromatic, or higher (e.g., 0.96). Deep furfural extraction (e.g., about 50 percent yield) of a high VGC Grade A crude can be used to produce a wax-free, lower VGC fraction (e.g., 0.83 VGC).
Typically, paraffinic oils are those having a viscositygravity constant (VGC) inthe range of 0.790 to 0.819 (preferably above 0.799). Typical of solvent refined paraffinic lubes are those available commercially under the trade name Sunpar. Typical hydrorefined paraffinic lubes are those available commercially under the trade name Sunpar, H series (e.g., Sunpar 1 H).
Naphthenic oils have a VGC in the range of 0.820 to 0.899 and the preferred hydrorefined naphthenic oils have a VGC in the range of 0.850 to 0.899. l-lydrorefined, relatively aromatic oils, having a VGC in the range of 0.900 to 0.920, can sometimes be used as a whole or partial substitute for the hydrorefined naphthenic lube. Aromatic oils (including hydrorefined or hydroaromat'ized oils) having a VGC in the range of 0.921 to 1.050 and greater, can be useful in minor proportions (e.g., 1-20 percent) for adjusting the aniline point of the base oil, particularly when the base oil contains a high proportion (e.g., percent) of a high VI hydrocracked paraffinic oil.
As an additional component to the hydrorefine naphthenic oils previously described, the lubricant can contain a hydrogenated polyolefin oil (e.g., see U.S. Pat. Ser. No. 220,362 of Stearns et al.; U.S. Pat. Ser. No. 52,301 of Driscoll et al.; Canadian U.S. Pat. No.
842,290; and U.S. Pat. No. 3,598,740) or a high viscosity index, hydrocracked oil or a mixture of such components, (such oils can be dewaxed, if desired). In such blends an aromatic oil or'concentrate rich in aromatic hydrocarbons (e.g., cycle oil) may have to be added to obtain the proper aniline point for seal swelling.
The preferred polyolefin oils are polymers or copolymers of C -C olefin which have a pour point no greater than 35" F., and preferably below 50 F. The hydrogenation can be from 50 to 100 percent of saturation, and, preferably, is to a bromine number no greater than 10, more preferably less than 5. Preferred polyolefins include ethylene-propylene copolymer, polypropylene, polybutene (especially polyisobutylene), and poly( l-octene).
The high VI hydrocracked paraffinic oil component can be obtained by hydrocracking a high viscosity distillate or dewaxed distillate from a paraffinic crude (such as Lago-medio) and typically has a V1 in the range of 90-105 and contains in therange of 3-30 percent of aromatics by clay-gel analysis. The hydrocracked lubes are preferably stabilized (against UV light degradation and sludging) by extraction of the hydrocracked oil with aromatic selective solvents, such as furfural or phenol or by hydrorefining to reduce the 260 UVA at least 30 percent (preferably 40 percent). For examples of such oils see U.S. Pat. Ser. No. 178,193 of Bryer et al. and U. S. Pat. No. 3,579,435 to Olenzak et al.
The preferred stabilized hydrocracked oils (whether extracted or hydrorefined) are characterized by having a D-943 test life (to an increase in acid number of 2.0) which is at least 20 percent lower than the D-943 life of an unstabilized hydrocracked oil but which is at least 20 percent greater than the D-943 life (with the usual amount of inhibitor, e.g., 0.5 percent DBPC) of an unhydrocracked solvent refined paraffinic lube of the same viscosity. Also useful is an isomerized paraffinic oil, as in U. S. Pat. No. 3,658,689.
. ILLUSTRATIVE EXAMPLES EXAMPLE 1 A twister ring oil was made by blending the following:
Wt. Hydrorefined naphthenic oil sus at 100F.) 72.3
Hydrorefined naphthenic oil (2400 SUS at 100F.) 2 NaSuI. BSN (Rust Inhibitor) TE 1618 (Friction modifier) l. 0. 5. Oletac 100 (tacky polypropylene) l.
CCNLII The blend had a viscosity of 207.0 SUS at 100 F. and 46.0 SUS at 210 F an ASTM-Vl of 85, and API gravity of 22.9 and an lFT (interfacial tension) of l 1.0 dynes/cm. The lFT of the base oil was in the'range of 35-40.
When the TE 1618 is replaced by 1.5 wt. percent butyl acetate, the [ET is about 8.
EXAMPLE 2 A twister ring oil (having a viscosity at 100 F. of about 200 SUS) was made by blending the following:
Solvent Refined Paraffinic Oil SUS at 100F.) 65.0 Solvent Refined Paraffinic Oil (510 SUS at 100F.) 3213 Antioxidant (DBPC) 0.6 *Acrylic Polymer additive 1.6 Ortholeum RP-Z (friction reducer and antirust) 0.5 Silicone Antifoam (1% soln.) 0.02
* The acrylic polymer-additive is a viscosity-index improver and is commercially available as Acryloid 772" from Rohm and Haas Co. and has a viscosity at 210 F. in the range of 4300-4800 SUS.
Another useful fatty acid phosphate, useful as a friction modifier, is marketed as Ortholeum 162. When Ortholeum 162 is neutralized with an amine (e.g., trimethylamine), it becomes similar to Ortholeum RP-2.
It is important that a twister ring oil have a high viscosity index; therefore, with the usual paraffinic lubes, a viscosity index improving additive is generally necessary. However, the V1 improver can be reduced or eliminated if a high VI oil (such as the ethylenepropylene copolymer of US. Pat. Ser. No. 220,362) is substituted for the paraffinic lube.
EXAMPLE 3 A needle oil was made by blending the following:
Wt. Hydrorefined naphthenic oil (100 SUS at 100F.) 89.9 Hydrorefined naphthenic oil (2400 SUS at 100F.) 5.0 NaSul BSN 0.1 TE-l618 (Friction modifier) 5.0
The resulting needle oil had a viscosity of 102 SUS at 100 F. and 38.0 SUS at 210 F., an ASTM-V1 of 20, an API- gravity of 24.1 and an interfacial tension (IFT) of l 1.0 dynes/cm (whereas the base oil [FT was in the range of 35-40 dynes/cm.)
The heat stability of this needle oil is greatly improved by replacing the hydrorefined naphthenic oil with a hydrorefined or hydrocracked paraffinic oil (preferable with a pour point of or below) of about the same 100 F. viscosity.
EXAMPLE 4 A spindle 011 was made by blending the following:
Wt. Hydrorefined naphthenic oil (100 SUS at 100F.) I 94.9 NaSul BSN 0.1 TIE-1618 (Friction modifier) 5.0
The blend had a viscosity at 100 F. of 95.0 SUS and 37.5 SUS at 210 F., an ASTM-VI of 18, API gravity 24.4 and IFT of 1 1.0 dynes/cm.
NaSul BSN is a neutral barium sulfonate marketed by The needle oil had a viscosity at 100 F. of 132 SUS and 40 SUS at 210 F., a flash point (D92) of 295 F., a pour point (D97) of less than 50 F., an API gravity (D287) of 23.3, a total acid No. (ASTM D664) of0. 16, an IFT (ASTM D971) of 7.8 dynes/cm, a saponification number (D94) of 3.29 and rated 38-39-3 (20) in the ASTM D1401 demulsibility test.
' EXAMPLES A spindleoil was made blending the following:
Parts by Wt.
Solvent refined paraffinic oil (Sunvis 11) 98.3 Ultraphos ll (Friction modifier) 1.5 NaSul BSN 0.2 DBPC (antioxidant) 0.6 Silicone antifoam (1% soln.) 0.05
The spindle oil had a viscosity at 100 F. of 107 SUS and 40 SUS at 210 F., ASTM-V1 (D567) of 99. flash point of 390 F., 0 F. pour point, API gravity 33.1, IFT of 0.0 dynes/cm, and a surface tension (ASTM D94) of 33.3.
TABLE 1 PROPERTIES OF IMPROVED NEEDLE OIL Preferred Test Method Typical Range Viscosity, SUS/100F D2161 92.0 -1 10 Viscosity, SUS/210F D2161 38.7 Viscosity Index D2270 100 min Viscosity, cSt/l00F D445 18.72 18.1-20.5 Viscosity, cSt/2l0F. D445 3.76 Flash, COC, F. D92 380 340 min Fire, COC, F. D92 430 Color D1500 0.25 0.5 max Gravity, AP1 D287 33.5 32.5-34.5 Appearance visual clear 8;
bright Total Acid No.,
mgKOH/g D664 nil Saponification No.,
mgKOH/g D94 9.3 8.5-10/5 Copper Strip. Class,
3 hrs/212F. D130 LA 1 max Aniline Point, F. D611 207 Sulfated Ash, D874 0.02 Rusting,
Syn. Sea Water D6658 pass Pass 4-Ball Wear Scar. mm 0.40
20 Kg, 1800 RPM, 130F., 1 hr. 1
Barium, 0.036** 0.02-0.06 Phosphorous, 7c D1091 0.008 DBPC, 7c D2668 0.6 0.1-1 .0
TABLE 2 PROPERTIES OF IMPROVED SPINDLE OIL Preferred Test Method" Typical Range Viscosity. SUS/F. D2161 108 90-120 Viscosity, SUS/210F. D2161 38.6 Viscosity Index D2270 20 0-80 Viscosity. cSt/100F. D445 20.4 20.5-24.0 Viscosity. cSt/2 10F. D445 3.73 Flash. COC. F. D92 330 310 min Fire, COC, F. D92 360 Color D1500 1.0 2.0 max Gravity. AP1 D287 23.8 23-25 Total Acid No.,
mgKOH/g D664 Ni1 Saponification No. D94 9.3 8.5-10.5 Copper Strip, Class.
3 hrs/212F. D 1A 1 max Aniline Point, F. D611 Sulfated Ash. 7c D874 0.20 0.18-0.22 Rusting, Syn. Sea Water D6658 Pass 4-Ball Wear Scar, mm 0.40
20 Kg, 1800 RPM. 130F..
Total Sulfur, 7: D129 0.11 DBPC. '7? D2668 0.6
this range, the aniline point will be determined by the given blend.
The invention claimed is:
l. A lubricant composition which does not cause pin hole damage to cotton and which is useful as a lubricant for a spindle, a needle or a twister ring, said lubricant comprising an effective amount of a friction reducing additive and a base oil having an SUS viscosity at 100 F in the range of 60-600 and containing a major amount of at least one member selected from the group consisting of hydrorefined naphthenic petroleum oil, hydrorefined paraffinic petroleum oil, hydrocracked paraffinic petroleum oil, hydroisomerized paraffinic petroleum oil, solvent refined paraffinic petroleum oil and hydrogenated polyolefm oil, said additive containing an effective amount of trimethylamine of dilaurlphosphate.
' 2. The composition of claim 1 wherein said base oil Patent No.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,8163% Dated June 11, 197A Inventor(-s) Walter .J. Coppock, James R. Amaroso 8c John. Q. erigfith It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
- Claim 1, next 'to last line, after "trimethylamine" insert Signed and Seled this 17th" dey of Decer nber 1974.
(SEAL) Attest: V
McCOY M. GIBSON JR. v c. MARSHALL DCANN Attesting Officer Commissioner of Patents