text:
[Eurocreme] Skinny Boys
Slender, slim, smooth and skinny, these are the freshest, youngest boys from Eurocreme, with the flattest stomachs, smallest waists and tightest asses! Watch these skinny little fuckers get down and dirty with hung studs and other twinks, all of whom are desperate to fuck their peachy little bubblebutts and worships their throbbing cocks!
File size: 1.5 GB
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Skinny bitch fucked in tight anus
Lounging on the couch, skinny cutie tyrannizing his narrow anal finger tight. The guy looked at it a perversion, and decided to help a skinny ass, gently vdul in tight anal. Great pleasure, having broken only ass, cum in anal, bubbles, groans, and bliss.
Directed by: Anal
Description: Skinny bitch fucked in tight anus, anal cum.
Length: 00:12:47 min.
Translation: English
Format: WMV
Quality: DVDRip
Video: Windows Media Video 9 720x576 (4:3) 25.00fps 1562Kbps
Audio: Windows Media Audio 44100Hz stereo 160Kbps
File size: 155.1 MB
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Skinny hooker enjoys double penetration
Skinny whore highly passionate, moaning like a snake. Oral anal fuck pussy, fuck the two members simultaneously in two tight holes. Sweet skinny whore best fuck in the anal and mouth.
Directed by: Tight Anal
Description: Shelbee Myne tight anal
Length: 00:17:24 min.
Format: WMV
File size: 110.8 MB
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Roxy Red and Zack Mason
Photographer Zach Roxy shoved his big dick
Genre: gay, asian, white, teen, student, interracial, anal, oral, anal, skinny, babyface, barely legal
Duration: 00:23:04
File size: 140.7 MB
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Roxy Red and Zack Mason
Photographer Zach Roxy shoved his big dick. And it's cool happened, it seems like everyone! Enjoy!
Genre: gay, asian, white, teen, student, interracial, anal, oral, anal, skinny, babyface, barely legal
Duration: 00:23:04
File size: 140.7 MB
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The skinny threesome
Studio: Punani Films
Video language: English
Skinny and long haired dude gets to fuck two skinny hotties at once in an amazing threesome. Watch and get freaky with the gorgeous babes getting driven to a paradise of pleasures for intense orgasms to occur.
Format: mp4
Duration: 4:56
Video: 640x480, AVC (H.264), 3661kbps
Audio: 125kbps
File size: 136.8 MB
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Mohawk Stud Reamed In The Ass By His Skinny Twink Boyfriend
Release Year: 2012
Studio: Alfa Red
Cast: Sale, Mateya
Genres: Gay, Cumshots, Anal Sex, Blowjobs, Cum Swapping, Ass To Mouth
Video language: English
In this video, slightly older stud Sale gets banged in the ass by his skinny twink boyfriend Mateya. Mateya lies back and doesn't have to do a thing because Sale is willing to put in all the work! Sale, who is wearing nothing more than a mohawk hairstyle, gobbles down his boyfriend's surprisingly big dick, rubbing the base with one hand while he grips the balls with the other. Then the mohawk stud lies on his side, with his skinny boyfriend sliding in behind him and easing his prick into his tight ass with minimal lube. It's lucky that Sale drooled all over the cock, otherwise his ass would be extremely sore as it gets busted open!
Format: lavfpref
Duration: 19:52
Video: 720x480, AVC (H.264)
Audio: 125kbps
File size: 572.3 MB
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Skinny model fucked during a photoshoot
Skinny beauty shot for the portfolio, and so the photographer wanted to attach your dick in her tight little holes that he did not restrain their desires and hot bitch fuck ...
Format: mp4
Duration: 26:00
Video: 960x544, AVC (H.264), 1762kbps
Audio: 148kbps
File size: 365.3 MB
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Skinny Asian Brazil Fuck
Studio: Ladyboy Player
Dani Alencar is the third in our series of hardcore Brazilian ladyboy sets. As a skinny pre-teen Asian boy Dani loved cock and so became girl which attracted a constant supply of throbbing brown Brazilian dick. On this day she has lured a shirtless dark well built stud back to her room and she wastes no time in pulling down his sweats and underwear. When she sees his already hard tan tool she quickly strips and gives him a blowjob. The guy returns the favor and is happy to see that despite her emaciated frame that her shedick is big and long. This drives her nuts and she once again attacks his cock with her mouth and a hand while showing us her gaping asshole as she stokes her swollen dink and balls with the other hand. Now she is rock hard and ready to fuck some ass so she pulls the dudes legs open and rams him hard as he jerks himself. He then fucks this skinny white Asian bitch the same way until he pulls out and squirts his creamy load on her stomach. But she isn't satisfied until she cums too which she does by licking every drop of jizz off his cock which makes her dick ejaculate all over the back of her thighs.
Format: Windows Media
Duration: 21:33
Video: 1280x720, Windows Media Video 9, 3958kbps
Audio: 62kbps
File size: 638.0 MB
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Skinny blonde has developed a tight ass
Cast: Ava Mendes
Skinny babe first difficulty is pushed her tight ass on a thick dick guy, but as galloping, her ass calmly accepts a huge club ...
Format: mp4
Duration: 27:05
Video: 960x544, AVC (H.264), 1753kbps
Audio: 148kbps
File size: 378.5 MB
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Stuffed ballerina in skinny ass
Cast: Stoya
It was a ballerina at the barre, legs pulled, twisted ass yes. Ass, I must say, for an amateur (very skinny). And such is found. Took cover in the nook, ripped her clothes and his hefty babe all holes by a dick cleared.
Format: mp4
Duration: 19:20
Video: 720x404, AVC (H.264), 1843kbps
Audio: 114kbps
File size: 277.7 MB
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Skinny babe loves anal
The guy rubbed his skinny ass girlfriend and started to push first tuna is an anal plug, the anal beads, and then shoved his big dick and fuck passionately and powerfully in the final cumshot in the anus ...
Format: flv
Duration: 15:56
Video: 1024x576, VP6F, 3000kbps
Audio: 256kbps
File size: 321.5 MB
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In a tight ass skinny babe
Cast: Lyla Storm
Cute skinny babe twisted before the guy showing off their charms, and tighten until the guy strung her tight ass on his thick dick.
Format: mp4
Duration: 26:27
Video: 720x404, AVC (H.264), 1293kbps
Audio: 89kbps
File size: 269.2 MB
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Matt Hughes & Luckas Layton (Mar 25, 2014)
Release Year: 2014
Genres: Anal, Oral Sex, Big Dick, Blow Job, Cumshots, Facial
Confessing his crush, skinny blond twink Luckas lets Matt in on his secret, and he's totally flattered. Moving out, there's nothing to lose with a bit of big dick fun, and Luckas gladly obliges!! Matt's rock hard dick proves just what a weapon it is as he lets loose on Luckas and fucks his ass as hard as ever, slamming it home again and again, flipping the boy over and over as he gets his fill of ass, and Luckas gets filled with dick! Spurting whilst Matt grinds hard, his face is then the target of streams of cum.
Format: mp4
Duration: 13:06
Video: 1920x1080, AVC (H.264), 4915kbps
Audio: 62kbps
File size: 478.0 MB
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Skinny blonde gives in the ass
Cute skinny blonde with pleasure sucks big dick and then takes it in his ass ...
Format: mp4
Duration: 14:39
Video: 640x480, AVC (H.264), 1118kbps
Audio: 74kbps
File size: 128.3 MB
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He's a skinny little twink boy who has never been with a black dude (2014)
Release Year: 2014
Cast: Drew Stiles
Genres: Interracial
... Well, well...you know he's come to the right place. Drew is meeting Intrigue at the local public pool...too bad it couldn't gop down right there in broad daylight. LOL! Anyways...they meet up and head back to the fuckpad. Intrigue puts Drew right to the test and sticks his big black dick right in his very eager mouth and let me tell you, Drew is loving every inch of it. He's sucking that black cock like he's in love with it. Once the dick sucking comes to an end the ass fucking must begin...and it sure does. Don't be fooled by Drew being a skinny guy...his whole is the biggest thing on him. It opens up wide for Intrigue's big ass hard black cock to just slide right up in there...all the way without any problem. Intrigue pumps that white ass full of his black meat log, stroke after deep stroke and Drew just moans with delight. Now that's how a white boy should act when fucked with a nice black dick!
Format: Windows Media
Duration: 21:57
Video: 1280x720, Microsoft MPEG-4 Video Codec V3
Audio: 54kbps
File size: 722.8 MB
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Skinny busty slut hard in all holes
Cast: Olga Petronovic
Skinny busty slut fucks guy hard, driving his big dick turns her in all holes.
Format: avi
Duration: 11:15
Video: 608x448, DivX 5, 1153kbps
Audio: 125kbps
File size: 108.1 MB
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A Tan Guy Sucks A Dick Then Gets It In The Ass
Release Year: 2012
Studio: Alfa Red
Cast: Mateya, Aco
Genres: Gay, Cumshots, Anal Sex, Blowjobs, Cum Swapping, Ass To Mouth
Video language: English
In this video, slightly older stud Sale gets banged in the ass by his skinny twink boyfriend Mateya. Mateya lies back and doesn't have to do a thing because Aco is willing to put in all the work! Sale, who is wearing nothing more than a mohawk hairstyle, gobbles down his boyfriend's surprisingly big dick, rubbing the base with one hand while he grips the balls with the other. Then the mohawk stud lies on his side, with his skinny boyfriend sliding in behind him and easing his prick into his tight ass with minimal lube. It's lucky that Aco drooled all over the cock, otherwise his ass would be extremely sore as it gets busted open!
Format: lavfpref
Duration: 19:19
Video: 720x480, AVC (H.264)
Audio: 125kbps
File size: 550.1 MB
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Skinny crumbs stuffed in tight ass
Hot guy fucks his cute skinny girlfriend ruthlessly moaning babe will drive huge size dick in a tight ass maiden.
Format: Windows Media
Duration: 22:59
Video: 860x480, Windows Media Video 9, 2500kbps
Audio: 46kbps
File size: 430.6 MB
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BulldogPIT - Benjamin ONeil and Philip Tiger
Cruising in the bar, butch Ben eyes up skinny twinky Phil, tracks in his hair and a slim defined body which a hit meaty dick, perfect for fucking!! With plenty of cock sucking and mutt munching, Ben is soon fucked into the sofa, he ass being exposed to the full width of Phil's fat dick, slamming as deep as he can into Ben's wet and hairy crack. Riding like a cowboy at the bronco, Ben really works that dick into his ass, jerking himself senseless as he splatters his spunk, both loads dribbling down their sweat soaked bodies.
Length: 486 MiB Duration: 21mn 57s 818ms
Video: MPEG-4 Visual at 2 988 Kbps, Aspect: 720 x 480 (1.773) at 29.970 fps
Audio: AAC at 99.8 Kbps, Infos: 2 channels, 48.0 KHz
File size: 485.9 MB
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text:
Lubricating oil compositions for internal combustion engines having unexpectedly wide temperature operating characteristics, contain a combination of 2-block copolymer comprising a first polymer block of an alkenyl arene, e.g., styrene and a second essentially completely hydrogenated polymer block of isoprene and certain pour point depressants in a lubricant base stock having a viscosity index of at least 85. The compositions have excellent shear stability and can be formulated to pass a number of the ASTM and SAE engine oil performance and engine service classifications.
Claims available in
Description (OCR text may contain errors)
United States Patent [1 1 St. Clair et al.
[ Nov. 13, 1973 LUBRICATING COMPOSITIONS [75] Inventors: David J. St. Clair, Bethalto, 111.;
Donald D. Evans, Burlington, Ontario, Canada [52] [1.8. CI. 252/32.7 E, 252/51.5 A, 252/56 R,
252/59 [51] Int. Cl. C10m 1/48, ClOm l/16 [58] Field of Search 252/32.7 E, 33.4, 252/5l.5 A, 59, 56 R; 260/879 [56] References Cited UNITED STATES PATENTS 2,889,282 6/1959 Lorensen et al. 252/5l.5 A 3,438,897 4/1969 Henderson 3,554,911 l/1971 Schiff et a1 252/59 FOREIGN PATENTS OR APPLICATIONS 769,281 3/1957 Great Britain 252/59 Primary Examiner-Patrick P. Garvin Assistant Examiner-Andrew H. Metz Att0rneyWilliam I-I. Myers et a1.
[5 7] ABSTRACT Lubricating oil compositions for internal combustion engines having unexpectedly wide temperature operating characteristics, contain a combination of 2-block copolymer comprising a first polymer block of an alkenyl arene, e.g., styrene and a second essentially completely hydrogenated polymer block of isoprene and certain pour point depressants in a lubricant base stock having a viscosity index of at least 85. The compositions have excellent shear stability and can be formulated to pass a number of the ASTM and SAE engine oil performance and engine service classifications.
9 Claims, 1 Drawing Figure PAIENTEDIIIII I3 I975 HVI 250M MAY I HVI 80N MUST BE ADDED TO +I BE ADDED TO 3 FORMULATION FORMULATION h I I I N I N ,-I- o I F E I I :0 I O (I! A 9 I u. 0 I o I O m 4 1. (\I m I w a; I I: (I) o I O o m I 2 m 7,, I v m I 9 J, l 3 m I I E: O o (\l I m I I w I 0 I I BASE I BLEND I I SAE 5w SAE IOW SAE 20w I2p 24p VISCOSITY AT 0 F BASE BLEND CONTAINS ALL HVI MENTAL ADDITIVE PACKAGE WITHOUT VI IMPROVER.
IOON PLUS A COMPLETE SUPPLE- LUBRICATING COMPOSITIONS BACKGROUND OF THE INVENTION 1. Field of Invention This invention relates to novel lubricating compositions and the like, containing a critically defined combination of certain block copolymers and pour point depressants. Unless otherwise indicated, the terms lubricant, lubricating oil or lubricating composition refer to lubricating oils for internal combustion engines.
2. Description of the Prior Art a The art of lubricating oil formulation has become increasingly complex with the ever more stringent demands made by the developing automotive industry. One of the primary requirements is to provide an economical petroleum lubricant which can be utilized over a wide range of operating conditions, especially insofar as temperature variations are concerned. At the same time, the formulated lubricant must also possess an ability to impart oxidative stability, detergency, disper sancy, wear inhibition and corrosion inhibition during its use as well as during storage. Furthermore, the auto motive industry desireslubricants which will stay in their SAE viscosity grades'fora substantial length of time again under both use and storage conditions.
By multi-grade lubricants is meant lubricants which meet a F viscosity specification and a 210F viscosity specification, such as is shown for motor oils by the following table derived from SAE, 1300a taken from the SAE Handbook for 1969:
Viscosity at SAE Viscosity at SAE Oil Grade 0"F, poises Oil Grade 210F, SUS Spec. vSpec.
20 45-58 SW 12 maximum 30 5870 10W 12-24 40 7085 20W 24-96 50 According to the table, for example, an SAE l0W/50 oil must have a viscosity at0F between 12 and 24 poises and a viscosity at 210F of between 85 and 110 SUS.
The art has evolved a number of multi-grade oils such as SAE l0W/30 and SAE 20W/40 oils but with few exceptions has not been able to formulate wider multigrade oils such as SAE l0W/50 having low oil consumption and high shear stability. Commercially, such formulations should be economically feasible, capable of large scale production, versatile in regard to the base stock and preferably resistant to degradation under conditions of high shear.
A large variety of polymeric additives have been employed primarily as thickening agents, viscosity index (VI) improvers andpour point depressants. A common limitation of essentially all of these is shear sensitivity. This is not unexpected, since most of the these polymers are'relatively high molecular weight materials and consequently are readily subject to shear degradation. On the other hand, relatively low molecular weight polymeric materials, at least up to the present time, have proven to be relatively ineffective as thickeners or VI improvers in automotive engine lubricants, even Pat. No. 3,509,056 issued Apr. 28, 1970, shows the use though they may have reasonably good shear stability.
of styrene-olefin copolymers prepared by Ziegler catalysts as lubricating oil additives. These have proven to be surprisingly ineffective as thickening agents and VI improvers. A number of block polymers of the tapered type have been investigated such as those prepared by copolymerization of alpha methyl styrene and ethylene. For some unexplained reason, as shown in Anderson U.S. Pat. No. 3,290,414, issued Dec. 6, 1966, the tapered or random copolymerization as in the case of styrene-butadiene random copolymerization results in an unsatisfactory composition.
Certain styrene-hydrogenated butadiene block copolymers have been employed as pour point depressants or thermal degradation stabilizers in pertroleum fuels as shown in Streets U.S. Pat. No. 3,419,365 issued Dec. 31, 1968. However, since they were employed as fuel additives, they-were used in frictional percentages which were too small to appreciably affect the thickening of the oil or the viscosity index thereof. Moreover, as will be developed later, block copolymers containing hydrogenated polybutadiene blocks show essentially no response to supplementary pour point depressants, especially if the 1,2-content is low.
Fully formulated multi-grade oils of the SAE l0W/30 type are shown in Henderson U.S. Pat. No. 3,438,897 issued Apr. 15, 1969. However, the combination of lubricating oil additives disclosed by this patent, while useful for relatively narrow multi-grade oils, such as SAE 10W/30, does not provide for the possibility of compounding wider multi-grades such as SAE 5W/20, 5W/30, 10W/40, 10W/50 or SAE 20W/50.
SUMMARY OF THE INVENTION It is an object of the present invention to provide improved lubricating compositions. It is another object of the present invention to provide improved multi-grade lubricants. It is a particular object of the invention to provide wide multigrade compositions which will exhibit lower oil consumption due to volatility than the same viscosity multigrade oil made with conventional VI improvers. Other objects will become apparent during the following detailed description of the invention.
Now, in accordance with the present invention hydrocarbon lubricating compositions are provided comprising the following components:
a. a hydrocarbon lubricating oil having a viscosity index of at least b. a minor but effective amount of pour point depressant for said oil; and g c. 01-10 percent by weight of a block copolymer comprising 1 I. a single polymer block A, at least 75 percent of which is condensed alkenyl arene units, no more than 5 percent of the aromatic unsaturation being reduced by hydrogenation of the block copolymer, said block A having an average molecular weight between about 10,000 and about 55,000; and 2. a single hydrogenated polymer block B, said block, priorto hydrogenation, being a polyisoprene block; at least percent of the olefinic unsaturation of block B being reduced by hydrogenation of the block copolymer; same block B having an average molecular weight between about 20,000 and about 100,000;
the weight ratio of block A to block B being between about 0.45:l and 0.8:1;
remaining blocks C, if any, in the block copolymer having a total average molecular weight not exceeding about 7,500 and being selected from alkenyl arene polymer blocks, conjugated diene polymer blocks and copolymer blocks of alkenyl arenes and conjugated dienes, each having the hydrogenation limitations of blocks A and B.
DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with this invention it has been found that block copolymers having the above limitations, when combined with a high viscosity index hydrocarbon lubricant containing a pour point depressant, exhibit outstanding physical characteristics not possessed by any other polymeric thickener investigated to date. Preferably, the block copolymer has the simple structure A-B. However, as pointed out above, it may have the alternative structure A-B-C wherein C is the relatively low molecular weight polymer block referred to above. It is preferred that each of blocks A and B be homopolymeric blocks. Moreover, it is preferred that polymer block A be essentially aromatic, e.g. less than 5 percent hydrogenated while polymer block B be at least 99 percent saturated insofar as its original olefinic unsaturation is concerned.
The monoalkenyl arenes, particularly a-alkenyl arenes, which may be used in the preparation of the subject class of block copolymers comprise styrene and methyl styrenes such as alpha methyl styrene, vinyl toluene and other ring methylated styrenes. Styrene is the preferred monomer. Mixtures of these alkenyl arenes may be used if desired.
Polyisoprene is the conjugated diene employed in preparing the precursor of block B. Preferably the polyisoprene block should have at least about 80 percent l,4 structure which may be either cis or trans and still more preferably it should have at least about 88 percent 1,4 structure.
The block copolymers may be prepared by conventional methods using lithium-based initiators, preferably lithium alkyls such as lithium butyls or lithium amyls. Polymerization is usually conducted in solution in an inert solvent such as cyclohexane or alkanes such as butanes or pentanes and mixtures of the same. The first monomer to be polymerized (which may be either mono alkenyl arene or isoprene) is injected into the system and contacted with the polymerization initiator which is added in an amount calculated to provide the predetermined average molecular weight. Subsequent to obtaining the desired molecular weight and depletion of the monomer, the second monomer is then injected into the living polymer system and block polymerization occurs, resulting in the formulation of the living block copolymer poly(alkenyl arene)- polyisoprene which is then killed, e.g., by the addition of methanol.
This precursor is then subjected to selective hydrogenation such as by the method shown in Wald et al. U.S. Pat. No. 3,595,942 issued July 27, 1971, to form the block copolymers used in the lubricating compositions of this invention. Preferably hydrogenation is conducted in the same solvent in which the polymer was prepared, utilizing a catalyst comprising the reaction product of aluminum alkyl and a nickel or cobalt carboxylate or alkoxide. A favored catalyst is the reaction product formed from triethyl aluminum and nickel octoate.
The temperatures and pressures employed in the hydrogenation step are adjusted such as shown in the last referred-to patent to cause essentially complete hydrogenation of the polyisoprene block with essentially no effective hydrogenation of the monoalkenyl arene polymer block.
The polymer may be isolated from its solvent after its hydrogenation and dispersed in lubricating oil. This may be effected, for example, by adding a lubricating oil to the solution of hydrogenated polymer and thereafter evaporating the relatively volatile solvent.
It is convenient to prepare concentrates of the hydrogenated block copolymer in lubricating oil. Such concentrates suitably contain up to about 20 percent by weight of the hydrogenated block copolymer and preferably between about 2.5 and 15 percent by weight depending on polymer molecular weight.
Wherein the present specification and claims, reference is made to molecular weights of the block copolymers, these are meant to refer to number average molecular weights as determined, for example, by tritium counting techniques or osmotic pressure methods.
Preparation of the block copolymers by anionic solution polymerization results in the desired relatively very narrow molecular weight spread as contrasted to the broad spectrum of species which results from the use of Ziegler polymerization catalysts. Broad spectrum (Ziegler) polymers, containing a substantial proportion of high molecular weight fractions, exhibit excessive shear degradation.
Preferably the polymer blocks A have molecular weights between about 25,000 and 50,000 and the polymer blocks B have molecular weights between about 35,000 and 80,000. Still more preferably, the weight ratio of A:B is from 0.521 to 0.721.
The pour point depressants utilized in accordance with the present invention and in conjunction with the block polymers as defined above are employed primarily for their pour point depressing effect although many of them may act as viscosity index improvers or thickeners. However, since they are employed in minor (pour point depressing) amounts, e.g., 0.l2.5 percent by weight preferably 0.l50.7 percent by weight, their proportion is normally too small to have an appreciable effect upon oil properties other than pour point. It is essential that the pour point depressant be present, however, since the block copolymers defined above exhibit essentially no effective pour point depressant function. On the other hand, one of the prime characteristics of the above class of block copolymers is their effective response to added pour point depressants such as high molecular weight compolymers of alkyl acrylates or alkyl methacrylates as well as nitrogen containing acrylic esters. By the term acrylic esters" is meant esters of acids of the acrylic acid series including both acrylic acid and methacrylic acid.
The nitrogen-containing acrylic ester polymers as defined can be prepared by any suitable means such as described in Hughes et al. US. Pat. No. 3,215,632 issued Nov. 2, 1965, and can be illustrated by the following examples: Nitrogen-containing polymers, namely, copolymers of vinyl pyridine and C alkyl methacrylates, having a molecular weight range of from 1,500 to 2,000,000, preferably between 200,000 and 850,000 include (1) copolymer of 25 percent 2-methyl -vinyl pyridine and 75 percent stearyl methacrylate, molecular weight 200,000; (2) copolymer of 30 percent stearyl methacrylate, 51 percent lauryl methacrylate, 14 percent methyl methacrylate and 5 percent 2-methyl-5- vinyl pyridine, molecular weight 600,000; (3) copolymer of 14 percent methyl methacrylate, 54 percent lauryl methacrylate, 27 percent stearyl methacrylate and 5 percent 2-methyl-5-vinyl pyridine in weight ratio molecular weight 830,000; (4) copolymer of lauryl methacrylate, stearyl methacrylate and 2-methyl-5-vinyl pyridine in the weight ratio of 602355, molecular weight 810,000; (5) copolymer of 2-methyl-5-vinyl pyridine, lauryl methacrylate and stearyl methacrylate in the weight ratio of 75:58:34.5, molecular weight 31,000; (6) N-vinyl pyrrolidone-alkyl acrylate copolymers; and (7) N,N-dimetyl-aminoethyl acrylate-alkyl acrylate copolymers.
The oil component of the lubricating compositions according to the present invention is especially designed for the preparation of multi-grade lubricants although single grade lubricants may be compounded as well. Still more specifically, the present combination of block copolymer and pour point depressant is especially beneficial in Wax-containing lubricating oil cuts such as found in Mid Continent oils, West Texas Ellenburger crudes, East Texas crudes, Oklahoma crudes, Pennsylvania crudes and California crudes and similar waxy crudes which may be referred to as paraffin base crudes, naphthenic crudes or mixed base crudes as distinguished from asphalt base crudes. While lubricating oils of any viscosity may be used as the base for the present compositions, the preferred oils are referred to as High Viscosity Index (HVl) 100 Neutral, HVI 250 Neutral and PW! Bright Stock as well as combinations of the same. Also included in this general term l-lVI for the purpose of this description, are very high viscosity index (VHVl) oils such as those prepared via hydrocracking of poor quality oils, such as low viscosity index (LVI) oils. More volatile oils may be employed for special purposes such as(HVI) 80N. These neutral oils are produced by well-known refining methods, such as distillation, dewaxing, deasphalting, dearomatizing, etc, as may be needed, dependant largely on the crude oil used. Typical properties of these HVI oils are the following:
PROPERTIES OF BASE OILS HVI HVI HVI HVI VHVI Designation 80 N 100 N 250 N 150 BS 100 N VlS 210F (SUS) 38.0 39.8 50.0 157 38.6 VIS 100F (SUS) 82 107 265 2775 32.7 VI 103 93 93 95 126 Gravity (lb/gal) 7.08 7.20 7.33 7.44 7.21 Four Point (F) 5' 20 20 0 Flash Point (F) 360 405 430 575 400 Aniline Cloud Point 203 213 220 260 226 ll: Aromatics by UV 15 l1 14 27-40 5 w S 0.05 0.09 0.05 0.16 0.05 ASTM Color L05 L0.5 L10 L45 L05 The present invention, in part, comprises the discovery that the block polymers as defined hereinbefore are only effective in hydrocarbon lubricants having a viscosity index of at least and preferably of at least as defined by ASTM test D227064. Data given hereinafter will establish the criticality of the present invention in this respect by showing the block copolymers of the invention either have little or no effect on Vl on low and medium VI oils, or actually reduce the VI in such oils.
One of the primary aspects of the present invention comprises the discovery of the unique capability of these compositions for the provision of wide multigrade lubricants having relatively low tendency toward oil consumption during use. It has been wellestablished that oil consumption is directly related to the relative volatility of the lubricant base. With most thickeners and VI improvers as well as most pour point depressants it is essential to formulate an SAE l0W/50 lubricant containing a substantial amount of relatively high volatility oils such as 80N or even lighter. This is due to the basic fact that most polymers alter the viscosity/temperature slope to only a moderate degree. However, as shown by FIG. I forming a part of this specification, it will be seen that the block copolymers of the present invention have an unexpected effect in providing a unique viscosity/temperature slope between 210F and 0F. The practical result of this is that multi-grade oils such as SAE l0W/30, l0W/4O and 10W/50 oils may be compounded with the present combination of additives utilizing as the oil base the relatively heavier oils, e.g., fractions having a viscosity at 100F of at least about SUS such as HV] or heavier, rather than resorting to thinning the composition with the more volatile lubricants. The second commercially important implication of this is that a single mixture of relatively heavy lubricant base stocks may be kept in storage for the preparation of a number of multi-grade oils which may be prepared simply by varying the block copolymer concentration. Thus, by the use of the present invention it is possible not only to simplify manufacturing requirements but also to reduce oil consumption during engine operation.
As will be seen in the working examples which follow, other types of polymers which may provide a certain degree of oil thickening or VI improving at temperature between 100+F and 210F, do not have the unique and strong effect upon the viscosity/temperature slope between 0F and 210F as is experienced with the particular'block copolymers of this invention. The unexpectedly low viscosities at 0F of the SAE l0W/50 compositions of this invention are unique and cannot be achieved with other polymers. The working examples furthermore demonstrate that even within the area of polymers having the structure polystyrenehydrogenated polyisoprene, the block molecular weights and weight proportions of thetwo blocks must be within the limits specified hereinbefore if the block copolymer is to impart a substantial increase inviscosity index.
The present invention not only provdes wide range multigrade lubricant compositions but also provides compositions having relatively low ash content, e.g. less than about 1 percent by weight sulfated ash, which are especially suitable for gasoline engines.
The basic composition as described above may be used as such but preferably is modified by the presence of supplementary additives combined with the block copolymer and pour point depressant to provide the necessary stability, detergency, dispersancy,antiwear and anticorrosion properties required of modern lubricants according to increasingly severe automotive specifications.
Among such supplementary additives are polymeric succinic acid derivatives used as detergent-dispersants. These can be made by the process described in U.S. Pat. Nos. to Hughes 3,215,632 issued Nov. 2, 1965; to Rense 3,215,707 issued Nov. 2, 1965; to Stuart et a1. 3,202,678 issued Aug. 24, 1965, or Le Suer et al. Canadian 681,235 issued Mar. 3, 1964, and can be illustrated by examples (1) succinimide of mono(polyisobutylene) succinic anhydride and tetraethylene pentamine, the polyiso-butylene radical having a molecular weight of about 1,000, (2) amine derivative of polyisobutyl monocarboxylic acid and tetraethylene pentamine having a molecular weight of about 1,000, (3) succinimide of mono(polypropylene)succinic anhydride and diethylene triamine, the polypropylene radical having a molecular weight of 800-1,500, (4) diimide of mono(polyisobutylene)succinic anhydride and tetraethylene pentamine, the polyisobutylene radical having a molecular weight of 800-1500.
The most preferred ashless dispersants to be used in the lubricants of the present invention are achieved by providing oil-soluble compositions prepared by reacting under esterification conditions (A) at least one substituted poly carboxylic acid acylating agent containing an average of at least about 30 aliphatic carbon atoms per substituent with (B) at least one polyhydric alcohol in amounts such that there is at least one equivalent of polyhydric alcohol for each equivalent of substituted carboxylic acid acylating agent to form an estercontaining first reaction mixture and thereafter intimately contacting this first reaction mixture with (C) from about 0.025 to about 0.15 equivalent of at least one hydroxy-substituted primary amine per equivalent of (A). These reaction products and their preparation are described in Widmer et a1. U.S. Pat. No. 3,576,743, issued Apr. 27, 1971. Still more preferably, (A) is further characterized in that it is a substantially saturated acylating agent produced by reacting ethylenically unsaturated carboxylic acidic reactant of the formula Itocoon or the corresponding carboxylic acid halides, anhydrides, and esters where R is characterized by the presence of at least one ethylenically unsaturated carbonto-carbon covalent bond and n is an integer of two to six, with an ethylenically unsaturated hydrocarbon or chlorinated hydrocarbon containing at least thirty aliphatic carbon atoms at a temperature within the range of l00-300C with the proviso that said acylating agent may contain polar substituents to the extent that such polar substituents do not exceed percent by weight of the hydrocarbon portion of the acylating agent excluding the weight of the carboxylic acid groups. The use of such detergents results in a substantial reduction (e.g., -50 percent) in the ash level compared to the use of other detergents which may otherwise be effective and satisfactory, such as the succinimides of high molecular weight mono(polyolefin)- succinic anhydride and polyalkylene polyamines.
Alkaline earth metal overbased petroleum sulfonates also may be employed. The highly basic alkaline earth metal (Mg, Ca and/or Ba) petroleum sulfonate can be made by suitable means known in the art such as described in British Patents 790,471 and 818,323 or Ellis et a1. U.S. Pat. No. 2,865,956 issued Dec. 23, 1958. The basic calcium petroleum sulfonates (M.W. 300-800) are preferred. By basic sulfonate is meant that the end product has a basicity in excess of 20 percent and up to 1,800 percent and preferably between 40 percent and 1,400 percent in excess of that normally required to neutralize the acid to produce the normal salt. Other types of sulfonic acids in the molecular weight range of 350 to 800 and derived from olefinic polymers, alkyl aromatic compounds, e.g., alkylated benzene, or alkylated naphthalene also can be used in forming the basic magnesium, calcium and/or barium sulfonate salt, such as basic calcium diwax benzene sulfonate, basic diwax naphthalene sulfonate and the like, the basicity being in excess of about 50-180 percent and the molecular weight of the compound between 450 and 750. Similar alkaline earth metal alkyl phenates and alkyl salicylates also are useful.
Furthermore, dithiophosphates may be included as supplementary additives, e.g., Ca, Zn, Pb salts of alkylthiophosphates, as well as their thio derivatives, Zn bis (2-ethylhexyl)dithiophosphate, Zn dioctyl dithiophosphate Zn bis(alkylphenyl)dithiophosphate, P 8 terpene reaction product, phosphonates such as dibutyl methane phosphate, dibutyl trichloromethane phosphonate, dibutyl monochloromethane phosphate, dibutyl chlorobenzene phosphonate, and the like. The full esters of pentavalent phosphorus acids may be used, such as triphenyl, tricresyl, trilauryl and tristearyl orthophosphates or potzlssium salt of P S -terpene reaction products or zinc above, like Zn di(C alkyl)dithiophosphate, e.g., Zn bis(2-ethylhexyl)- dithiophosphate, Zn bis(alkylphenyl)dithiophosphate. Corresponding dithiocarbamates, preferably zinc salts, also may be employed.
Anti-foaming agents such as silicone polymers, e.g., dimethyl silicone polymer, can also be used.
When desired, additional improvements with respect to oxidation stability and scuffing inhibition can be imparted to the oil compositions of the invention by incorporating small amounts (0.01 %2%, preferably 0.1%-1%) of phenolic antioxidants such as alkylphenols, e.g., 2-6-ditert.butyl-4-methylphenol or p,p'- methylene bisphenols such as 4,4-methylene-bis(2,6- ditert.butylphenol) or arylamines such as phenylalphanaphthylamine; dialkyl sulfides and mixtures thereof, e.g., dibenzyl disulfide or didodecyl sulfide. Anti-scuffing agents include esters of metal salts or organic phosphites, phosphates, phosphonates and their thio derivatives, such as C trialkyl phosphites, or phosphonates, e.g., tributyl-, trioctyl-, trilauryl-, tristearyl-, tricyclohexyl-, tribenzyl-, tricresylor triphenyl phosphites or phosphates.
A preferred formulation incorporating the present invention is as follows:
Components by Weight Block Copolymer 0.1-10 Pour Point Deprcssant 0.1-5 Oil Soluble Metal Thiophosphate 0.01-0.11 Ashless detergent 0.1-8.5 Overbased alkaline earth metal alkaryl sulfonate (Basis sulfated ash) 0.0S-3.5 Oil Balance EXAMPLE 1 Response of Various Block Polymers to Pour Point Depressants The basic compounded oil in this example was a W base oil (47 SUS at 210F) containing sufficient acrylic pour point depressant to reduce its pour point to -F; the VI of the base oil (including acrylic additive) was 117 (Sample A in Table I). The acrylic pour point depressant was a copolymer of cetyl methacrylate (50%w), lauryl methacrylate (%w) and octyl methacrylate (25%w), used in amount of 0. 1 7%w), based on the oil.
The block polymers tested are identified in Table I. The polymer column identifies the types of blocks and the mol wt column shows the molecular weight of each block.
When the polymers of Table I were tested in the uncompounded base oil'they showed no pour point depressant effect. The polymers must therefore be used in combination with a pour point depressant to be useful as low temperature lubricant compositions.
In the tests recorded in Table I, the amount of each polymer employed was that required to thicken the oil blend from 47 SUS to 65 SUS at 210F. Table I summarizes the data obtained:
(Samples C, D, F and G) had substantially higher pour points than that of the compounded base oil without block copolymer. Further data indicate that this pour point problem may be solved by randomly copolymerizing styrene with the butadiene block or by including higher 1,2-content (about 70 percent) in the butadiene block. Both remedies, however, have an adverse effect on the thickening efficiency of the polymer and thus require either higher polymer concentrations to thicken the oil or higher polymer molecular weights.
EXAMPLE II Comparison of Polymers TABLE I Polymer Mol wt conc. Polymer x 10- percentw point, P V1 None 20 l 17 Polystyrene-hydrogenated polyisoprene..... 28-44 1.2 -20 171 Polystyrene-hydrogenated polybutadiene 23-53 1.0 +20 147 Hydrogenated polystyrene-hydrogenated 23-53 1.4 +25 146 polybutadiene. Hydrogenated polystyrene-hydrogenated 21-107 1.0 25 147 polyisoprene Hydrogenated polybutadiene-polystyrene- 61-140-61 1.4 15 160 hydrogenated polybutadiene. Polystyrene-(styrenelhydrogenated buta- 19-(35/10) 1.5 +25 102 diene random copolymer). Hydrogenated polystyrene-hydrogenated 13-70-13 1.3 147 polyisoprene-hydrogenated polystyrene.
TABLE II Sonic shear Conc. Visc. percent Mol wt (percent at 0 F, loss at Sample Polymer X 10 w) VI poises 210 A None B Hydrogenated polyisoprene. 88 1.95 C Polystyrene-hydrogenated po y opren 21-21 4.0 D ..d 19-51 2.6 21-107 1.75 F 28-44 1.85 G 29-51 1.70 11.. Polystyrene-hydrogenated polybutadiene 16-47 4.0 I Hydrogenated polystyrene-hydrogenated 20-(25/25) 7 4,6
(butadicne/styrene)-copolymer J Ethylene/propylene copolymer 1.2 173 14.8
The above screening comparison illustrates several points: Ethylene/propylene random copolymer (Sample I) had poor shear stability. This particular ethylene/propylene copolymer was chosen for investigation because of its moderately good low temperature flow properties. In general, ethylene/propylene random copolymers are very poor in low temperature flow. The hydrogenated block polymer containing a styrene/- butadiene random copolymer block (Sample I) had 11 poor thickening efficiency, less than the desired effect on V1 and relatively high viscosity. The block copolymer including a hydrogenated polybutadiene block (prepared by 72 percent 1,2 addition) (Sample H) showed virtually no VI enhancement effect. The set of Other block copolymers, e.g., a 3-block copolymer having the structure:
hydrogenated polystyrene-hydrogenated polyisoprene-hydrogenated polystyrene did not show this critical feature, being about equally effective in all types of lubricants regardless of V1. However, as the Figure shows, such 3-block copolymers requires the addition ofa relatively light lubricant (80N) in order to meet broad spectrum multi-grade viscosity requirements, such as SAE l0W/50.
EXAMPLE IV Oil Base Stock Requirements for Multigrade Oils the two types of blocks and the molecular weights come within the limits specified for this invention The primary objective, as discussed hereinbefore, (Samples F and G), then the lubricating oil composiwas to design a multgrade lubricant having relatively tion exhibits high polymer thickening efficiency and low volatility. The Figure shows graphically the effect high VI response. of a number of types of polymers upon the oil base stock allowable for multigrade oils. All polymers were EXAMPLE added to a base blend containing HVI 100N plus a rep- Rheological Properties: Relationship to Base Oil resentative additive combination. At a given viscosity The viscosity index was determined for lubricating at 2100}?! h lower the viscosity 00F measured i the compositions comprising a block copolymer (same as cold crahklhg slmulamrg the h f y the 011 me polymer of Sample F, Table II of Example [1), ployed for a given multigrade oil. It is readily apparent 02%, of a pour point depressant (Same as used in from the Figure that the polymers fall into two classes, ample II), and four lubricating oils differing in VI. those cohtalhlhg Polystyrene and thos cohtalhlhg y- Table n presents the results obtained: drogenated polystyrene or no styrene at all. It 15 also apparent that the polystyrene-containing polymers TABLE show a steeper slope in the Figure and thus show superior performance. gr: at glg at 3, 1 These data have been converted into actual polymer Base Oil SUS SUS v1 concentrations and base oil compositions allowed in LVl 100M 0 38.2 106 6 Lvl 100M L0 456 2M 70 SAE 1OW/50 motor oils. Results are shown in Table LVl 100N 2.0 55.4 564 19 IV. The lettered curves on the Figure refer to the corre- LVl WON sponding samples listed in Table IV. It is apparent from Mvl lOON 0 38.2 100 38 My 100M 20 591 638 35 these data that polystyrene-hydrogenated polyisoprene MVI MON 30 98.2 2092 33 is the only polymer which can be used to make an ac- :gg: 8 32% g; :28 ceptable SAE 10W/50 lubricant. The ethylene propyl- HVI 100N 2.0 75.9 423 176 ene random copolymer is much too susceptible to deg- HVI WON 1246 186 radation by shear to remain an SAE 1OW/5O under norvHvt IOON 0 38.7 84 129 VHVI WON L0 483 I58 184 mal service. Except with polystyrene-hydrogenated VHVl IOON 2.0 0.2 39 205 polyisoprene polymers, in order to obtain an SAE 2120 200+ l0W/50 lubricant it was necessary to use substantial As the above data show, the present invention applies am u of HVI 80 Oil in the blend 0f higher to the use of high viscosity index, including very high amounts of polymer. If an 80 neutral oll IS requ viscosity index lubricating oils, since the polystyrene- Inmate result 15 g 011 cohshmphoh dunhg hhydrogenated polyisoprene block polymers were either f a l g amount Ph y needed, the 'hp ineffective or even detrimental in low or medium VI 15 at ah ecohomlc dlsadvahtage compared Wlth the oils. more efficient polymers.
TABLE IV Conc. Ratio Ratio (percent HVI HVI Sample Polymer Mn X 10- w) 100 N 250 N A Hydrogenated polyisoprene 41 P S- sible B ..do 98 2.4 10/90 C.... ..do 2.1 25/75 D... Polystyrene-hydrogenated polyisoprene..... 29-51 1.9 75/25 15.... ..do 32-54 1.7 75/25 F.... ..do 38-70 1.5 72/28 6.... ..do 40-69 1.8 77/23 H Hydrogenated polystyrene-hydrogenated 21-107 2.7 25/75 polyisoprene. l ..do 38-70 3.1 lO/90 J ..do 40-69 3.2 10/90 K Hydrogenated polystyrene-hydrogenated 13-70-13 2.8 25/75 polyisoprene-hydrogenated polystyrene. L Ethylene/propylene random copolymer 1.5 70/30 M Polymethacrylate 6.8 35/65 From comparison, an expert in lubricating oil formulation can see that only the polystyrene-hydrogenated polyisoprene block copolymers are the suitable choice: 1) they are effective at relatively low concentrations; 2) they do not require any high volatility (80 neutral) oil; and 3) a range or oils (e.g. SAE 10W/30, 10W/40 and 10W/50) can be made from the same oil base by varying the polymer concentration.
EXAMPLE V Effect of Partial Hydrogenation of Aromatic Block TABLE V Aromatic Polymer Viscosity Saturation Concentration at 210F (sus) V1 Unexpectedly, these data show that even a small degree of aromatic hydrogenation renders the polymer less desirable as a V1 improver.
EXAMPLE V1 Performance Features of Fully Formulated SAE W/50 Motor Oil A representative SAE 10W/50 lubricating oil formulation in accordance with this invention is shown herewith:
Component %w HVl 100 neutral oil (Mid-Continent 65.66 l-lVl 250 neutral oil (Mid'Continent) 21.89 Polystyrene-hydrogenated polyisoprene (29,000-5l,000 mol wt) 1.95 Zince dialkyl dithiophosphate 2.00 Polyisobutylene succinimide (0.34% total nitrogen. Basic nitrogen nil) 7.00 overbased Ca petroleum sulfonate (1400% excess basicity as CaCO;,) 1.00 Copolymer of 2-methyl-5-vinyl pyridine (5%),
lauryl methacrylate) (60%) and stearyl methacrylate (35%) 810,000 mol wt) 0.50 Dimethyl silicone, ppm 10 Typical properties for this formulation are the following:
Tested Oil Viscosity at 210F, SUS 108.8 Viscosity at 100F, SUS 756.0 Viscosity at 0F (cold cranking 21.2
' simulator), poise Viscosity index 174 Pour Point, F -30 Flash Point, F 405 TBN-E Total Base Number electrometric 5.15 TAN-E Total Acid Number electrometric 2.60 Initial pH 7.5 Sulfated Ash, %w 0.89
Gravity, AP1 29.1 Zinc, %w 0 Phosphorus, %w 5 Calcium, %w 0.17 Magnesium, %w N ASTM Foam Test, ml Sequence 1 1 0/0 Sequence 2 :10/0 (Foam Tendency/Foam Stability Sequence 3 0/0 The formulation was subjected to the series of tests designated ASTM-SE, which were set as standard to satisfy automotive requirements. Reference to these tests may be found in the ASTM special Technical Publication No. 315-E. The set of engine tests are those proposed as additions to Technical Report .1183 of the 1971 SAE Handbook. The more important results of the tests, all of which were passed by the above formulation, are summarized as follows:
Sequence 111 C This is an oxidation thickening test, designed to simulate conditions such as those encountered by a car pulling a trailer at mph.
SE Requirement Tested Oil Average Sludge (10=clean) 9.0 min. 9.8 Average Piston Skirt Varnish (l0=clean) 9.5 min. 9.8 Average Ring Land Varnish (10=c1ean) 6.0 min. 8.3 Viscosity Increase at F,
at 40 hours 400 max. 4 at 64 hours Must complete 18 Cam and Lifter Wear, in.
Average 0.0010 0.0006 Maximum 0.0020 0.0013
Sequence VC This is a low temperature sludge and varnish test to indicate effect of the oil formulation on engine cleanliness.
SE Requirement Tested Oil AverageSludge (l0=clean) 8.5 min. 9.6
Average Varnish (10qrlean) 8.0 min. 8.7 Average Piston Skirt Varnish (l0=clean) 8.7
Oil Screen Clogging, 5 max. 0
Oil Ring Clogging, 5 max. 0
Compression Ring Sticking None None L-38 This is a high temperature test to indicate copperlead bearing corrosion under operating conditions.
Bearing weight loss, mg at 40 hours 40 max. 12.2
Sequence 118 This test is designed to establish the rust protection properties of the oil formulation under dynamic operating conditions.
Average Engine Rust (10=clean) 8.9 min. 8 9
Summarizing the above formulation and engine test results, the SAE 10W/50 formulation having low base stock volatility and low oil consumption in service is made possible by the unique thickener, polystyrenehydrogenated polyisoprene. The low temperature properties are enhanced by the vinyl pyridinemethacrylate copolymer, while oxidation inhibition and anti-wear protection are obtained by the dithiophosphate. Anti-rust and engine cleanliness are promoted by the overbased calcium sulfonate and the ashless dispersant (polybutylene succinimide). The entire formulation typically has only 0.8 percent sulfated ash.
As shown by the engine test results, the above formulation provides excellent sludge, varnish and wear control as indicated by the Sequence 111C, VC and L-38 tests. The rust rating in the Sequence 118 test assures adequate rust protection under the most severe operating conditions.
In addition to these laboratory engine test results which should assure excellent performance in the field, the oil satisfies current shear stability requirements: that is, it stays within the SAE 10W/50 viscosity grade after (a) 1,000 simulated miles in a Ford 302-C1D shear stability test (60 mph for 17 hours) and (b) 10 hours in the L-38 engine test.
An additional advantage of the present invention lies in the ease of hot starting, enabled by the use of, for example, a lW/50 oil of this invention. It is a fairly common occurrence that cars experience, hot starting problems when, for example, after a high speed trip on a freeway they are stopped to refill the gas tank. A comparison was made between the SAE 10W/50 oil of Example VI and a SAE 10W/30 oil as described in the Henderson patent US. Pat. No. 3,438,897. The tests were carried out on a 1972 Chevelle with a 307-CID V-8 engine to determine cranking speed as a function of coolant temperature in the jacket next to the inder wall. Results of this comparison clearly indicated at least a 10F increase in the temperature at which the engine could be started when using the SAE 10W/50 oil of this invention over the [OW/30 oil of the Henderson patent.
EXAMPLE VII In order to determine if three-block polymers having terminal polystyrene blocks attached to a hydrogenated rubber center block could be used in the compositions of the present invention, the gelling tendencies of such polymers in lubricating oils were examined.
Polystyrene-hydrogenated polybutadienepolystyrene polymers having the block molecular weights as shown below, were dispersed in I-IVI 100 neutral lubricating oil at 2%w concentration and observed at room temperature.
Sample Block Mol WtXlO" Room Temp. Gel Results A 3534 no gel B 5255 no gel gelled Anti-Rust Characteristics of Formulated Oil %w 100 HVl neutral 65.24 250 HVl neutral 21.75 Block copolymer 1.85 Zinc dialkyl dithiophosphate 1.5 Polyisobutylene succinimide of trimethylolaminomethane 7.00 Overbased magnesium sulfonates 2.16 Vinyl pyridine-acrylate copolymer 0.50 Dimethyl silicone, ppm Total sulfated ash, %w 1.0
The above SAE l0W/50 formulation was run in the Sequence I18 and gave an engine rust rating of 9.0. The above formulation had essentially the same components in different concentrations as the formulation of Example V1, except that magnesium sulfonates (800 percent overbased) were used in place of calcium sulfonates.
EXAMPLE IX Diesel Cleanliness of Formulated Oil %w 100 l-IVl Neutral 34.0 250 HVl Neutral 29.0 150 HVI Bright Stock 14.0 Polystyrene-hydrogenated polyisoprene Block Copolymer 0.8 Tetraethylene pentamine derivative of polyisobutylene 6.0 Zinc diaryl dithiophosphate 3.4 Overbased calcium salicylate 1 1.7 Acrylate polymer 0.1 Isooctyl phenoxytetraethoxyl ethanol 1.0 Silicone fluid, ppm +10 Total sulfated ash, %w 1.8
The above SAE 20W/40 formulation was run in the Caterpillar l-G test for 240 hours. The results were excellent with very little top-ring groove carbon filling (2 percent) and very little lacquer deposit. This performance is almost identical to an SAE 30 oil with the same additive package except without the block copolymer. A comparable oil containing a polymethacrylate polymer gave poorer clenliness ratings with about 25 percent top-ring groove filling.
We claim as our invention:
1. A lubricating oil composition comprising a. a major amount of a mineral lubricating oil having a viscosity index of at least b. a minor but effective pour point depressing amount of a pour point depressant for said oil of the group consisting of copolymers of alkyl acrylates, copolymers of alkyl methacrylates and copolymers of nitrogen-containing esters of the acrylic acid series; and
c. 0.1 l0 percent by weight of a block copolymer comprising 1. a single polymer block A, at least about 75 percent of which is condensed alkenyl arene units, no more than about 5 percent of the aromatic unsaturation being reduced by hydrogenation, said block A having an average molecular weight between about 10,000 and 55,000;
2. a single hydrogenated polymer block B, said block, prior to hydrogenation, being a polyisoprene block; at least about percent of the olefinic unsaturation of block 13 being reduced by hydrogenation; said block B having an average molecular weight between about 20,000 and about 100,000; the weight ratio of block A to block B being between about 0.45:1 and about 0.8:1; any remaining blocks in the block copolymer having a total average molecular weight not exceeding about 7,500, being selected from alkenyl arene polymer blocks and conjugated diene polymer blocks each having the monomer identity and hydrogenation limitations recited for blocks A and B.
2. A lubricating oil composition according to claim 1 comprising a. a major amount of a mineral lubrication oil;
b. a minor but effective amount of a pour point depressant for said oil; and
0. 0.1-10 percent by weight of a block copolymer having the structure wherein l. A is a polymer block comprising at least about 75 percent by weight of condensed styrene units, no more than 25 percent of the aromatic unsaturation in said block being reduced by hydrogenation; and 2. B is hydrogenated polymer block comprising, prior to hydrogenation, at least 75 percent by weight of condensed isoprene units, at least 95 percent of the olefinic unsaturation in said block being reduced by hydrogenation.
3. A lubricating oil composition according to claim 2 wherein the pour point depressant is an oil-soluble copolymer of (l) a monovinyl-substituted pyridine of the group consisting of pyridines substituted on one of the ring carbon atoms with, as the sole substituted substituent, a vinyl group, and derivatives of the aforedescribed vinyl pyridines having a lower alkyl group substituted on a ring carbon atom and (2) a mixture of a C to C alkyl ester of an acrylic acid of the group consisting of acrylic acid and methacrylic acid and a C to C alkyl ester of an acrylic acid of the group consisting of acrylic acid and methacrylic acid in mole ratios varying from 1:4 to 4:1, said copolymer having the monoviiiyl pyridine and the combined acrylic acid esters in a mole ratio varying from 1:2 to 1:10, respectively, and a molecular weight from 5 X to 2.5 X 10.
4. A lubricating oil composition according to claim 3 wherein the block copolymer has the structure AB wherein 1. A is a homopolymer block of styrene having an av- I erage molecular weight between about 25,000 and about 50,000.
2. B is a hydrogenated homopolyisoprene block having an average molecular weight between about 35,000 and about 80,000; the weight ratio of A18 being between 0.511 and 0.721.
5. A lubricating oil composition according to claim 3 wherein the pour point depressant is a copolymer of 2-methyl-5-vinyl pyridine, lauryl methacrylate and stearyl methacrylate.
6. A lubricating oil composition according to claim 1 wherein the composition has a viscosity of less than 24 poises at 0F and more than 58 SUS at 210F.
7. A lubricating oil composition according to claim 6 wherein the composition has a viscosity more than SUS at 210F.
8. A lubricating oil composition according to claim 6 wherein the lubricating oil consists essentially of fractions having a viscosity of at least about SUS at i 9. A composition according to claim 7, which comprises in addition:
a. 0.1-3.0 percent oil-soluble metal thiophosphate;
b. 0.18.5 percent oil-soluble essentially ashless detergent; and
c. a rust-inhibiting amount of an oil-soluble basic alkaline earth metal hydrocarbon sulfonate.
Patent Citations
Referenced by
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USDA Mortgages: Take Advantage of These Low-Rate Mortgage Loans to Buy a New Home
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After riding high on the original's success for years, PopCap is finally narrowing down the release window for Plants... Read More
The App Store is about to hit a major milestone with 50 billion downloads across the platform. The countdown has passed... Read More


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Children of Barton County living with cancer will benefit from a new fundraiser hosted by Kans for Kids Fighting Cancer Foundation. The organization has announced that a Shrimp Boil will be held on Saturday, Nov. 5 at the Hoisington Knights of Columbus Hall. The evening will kick off with a social hour from 5:30 to 6:30 p.m. with live music provided by Tony Rubio and friends.
HOISINGTON - Hoisington Main Street, Inc.'s (HMSI) Board of Directors has approved a $10,000 loan to Kindscher's Mule Barn from its local Revolving Loan Fund. Kindscher's Mule Barn will be opening March 1, 2012 and will provide a variety of products including animal care, lawn and garden, tools, hardware, plumbing, electrical, farm supplies, automotive, paint and cleaning supplies. The business will open in the building Duckwall previously occupied.
Great Bend Regional Hospital provided a financial donation to Sunflower Diversified Services Inc., for the Invest in Kids Programs.
The mini-grants recently awarded by the Foundation at St. Rose Ambulatory & Surgery Center were earmarked for a variety of needs. The grant total came to $8,973 for four different areas of St. Rose.
Holiday menus for parties and dinners can seem like landmines for those with diabetes. They know the season is chock full of goodies that can wreck their diets.
The Golden Belt Community Concert Association will present the Water Coolers, an award-winning musical comedy troupe, at 7:30 p.m. Tuesday, Oct. 25, at the Great Bend Municipal Auditorium, Lakin and Stone.
The Kansas Department of Health and Environment (KDHE) samples recreational bodies of water for blue-green algae when the agency is alerted to a potential algae bloom. When harmful algal blooms are present, KDHE, in cooperation with the Kansas Department of Wildlife, Parks and Tourism (KDWPT), responds by informing the public of these conditions.
USD 495 calendar
Instrumentalist Ed Huffman ("Sanctified Sax") of Maize and bass soloist David Arasmith of Topeka will perform a concert of gospel music and message at 10:30 a.m. on Sunday at the First Congregational United Church of Christ, 3400 21st Street in Great Bend. The public is invited.
At 7 p.m. on Nov. 6, American Baptist International Missionary in Laos and Thailand, Matt Mann, will talk about his work among street children who are victims of human trafficking. The service will take place at Central Baptist Church, corner of Lakin and Harrison. Human Trafficking is an urgent issue that many churches around the world are fighting. Human Trafficking plagues our own country as well. Matt is a second generational missionary whose parents served in Thailand since 1959. Matt's brother, Mike, also serves as a missionary in Thailand in tribal economic development. Come and learn what we ...
A Hoisington Middle School student, Kylie Crawford, has made the middle school district honor band. She will be traveling to Dodge City on Nov. 5 to perform in the KMEA Southwest District Middle School Honor Band.
HOISINGTON - Clara Barton Hospital auxiliary will have its annual memorial Christmas ornaments for sale to benefit CBH. Memorials will be accepted from Oct. 1. through Nov. 30.
The Principles of Agriculture Economics class at Barton Community College is currently exploring consumer choices and how they make those choices when selecting foodstuffs at the store. This discussion also includes the direct buyers of crops and livestock off the farm and ranch. It is helpful to remember that while economics is rife with numbers, charts, and statistics, economics is at its core a social science trying to explain and predict human behavior. This week's column explains how these choices made. Next week - how does agriculture respond?


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Infectious Disease Specialist (virus, bacteria, parasites)
27 years of experience
27 years of experience
North Ironbound
230 Jefferson St
Newark, NJ 07105 Phone number & directions
230 Jefferson St
Newark, NJ 07105 Phone number & directions
License & Identifications
A medical license is required for a doctor to practice medicine in a particular state. Requirements vary by state but most require, at a minimum, post-graduate training in the doctor's specific specialty. An NPI number is a national identifier unique to an individual health care provider and is managed by the Center for Medicare & Medicaid Services (CMS).
Learn more about Dr. Ana Rodriguez-Diaz:
View the full profile to get information on:
- Qualifications
- What's important to you
View full profile
Patient Reviews
No reviews yet…
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be the first!
Specialties & Research
- She has special expertise in 1 area:
- AIDS/HIV (Acquired Immunodeficiency Syndrome)
Education & Awards
Dr. Rodriguez-Diaz graduated from Univ De Valencia.
Dr. Rodriguez-Diaz has 5 hospital affiliations:
- Clara Maass Medical Center
- St. James Hospital Cathedral
- Spanish
Home > Find an Infectious Disease Doctor > NJ > Newark Infectious Disease Doctors > Dr. Ana Rodriguez-Diaz, MD
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- Additional Information
- Dr. Ana Rodriguez-Diaz MD is a female Infectious Disease Specialist, has 27 years of experience and practices in Infectious Disease.
- Where does Dr. Ana Rodriguez-Diaz practice?
- Dr. Ana Rodriguez-Diaz has 1 office location.
Dr. Ana Rodriguez-Diaz practices Infectious Disease near Newark, NJ.
See Newark Infectious Disease Doctors.


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Houses to rent near Tewkesbury Close, Loughton IG10
£1,495 pcm (£345 pw)
3 bed end terrace house to rentRoding Road, Loughton IG10
A three bedroom end of terrace property with two reception rooms, modern bathroom and large rear garden. Walking distance to Loughton Station and nearby shopping amenities. Unfurnished and available now. More details
Note: Distances are straight line measurements
- Loughton (0.2 miles)
- Debden (1.1 miles)
Marketed by Michael Stevens Estates, IG10. Call 020 3544 2561£1,775 pcm (£410 pw)
4 bed end terrace house to rentWitham Close, Loughton IG10
Churchill Estates are pleased to offer this Four Bedroom House located close to Loughton's central line station. The property is presented is very good decorative order with modern kitchen and modern bathroom. The property further benefits from double ... More details
Note: Distances are straight line measurements
- Loughton (0.2 miles)
- Buckhurst Hill (0.9 miles)
Marketed by Churchill Estates - Loughton, IG10. Call 020 3318 7575
Latest Tewkesbury Close, Loughton IG10 houses to rent
Zoopla is one of the UK's leading property portals, helping you to find property for sale and to rent and make smarter decisions when buying and renting homes in the UK. Discover information on homes in Tewkesbury Close, Loughton IG10 by researching Tewkesbury Close, Loughton IG10 property values, Tewkesbury Close, Loughton IG10 house prices paid, our Tewkesbury Close, Loughton IG10 property market overview and find Tewkesbury Close, Loughton IG10 agents.


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News from WTOP
News from the AP
Mike Causey
Shows & Panels
- Agency of the Month
- Business of Government Hour
- The CFO Agenda: Delivering value from financial transparency and audit efforts in the public and private sector
- CXO Surveys
- Federal News Countdown
- Government Perspectives on Mobility and the Cloud
- Reducing Risk in the Cloud
- Reimagining the Next Generation of Government
Shows & Panels
- AFCEA Answers
- American Readiness: Renewable Power and Efficiency Technologies
- Ask the CIO
- Delivering the Digital Government Mission
- Federal Executive Forum
- Federal News Radio's National Cyber Security Awareness Month Special Panel Discussion
- Federal Tech Talk
- The Future of Government Data Centers
- Government Perspectives on Mobility and the Cloud
- Mitigating Insider Threats in Virtual & Cloud Environments
- Moving Agency Applications to the Cloud with PaaS
- Reducing Risk in the Cloud
- Security in the Age of Targeted Attacks
- Air Traffic Management Transformation Report
- Cloud First Report
- General Dynamics IT Enterprise Center
- Gov Cloud Minute
- Government in Technology Series
- Homeland Security Cybersecurity Market Report
- The Intersection: Where Technology Meets Transformation
- Modern Mission Critical Series
- National Cybersecurity Awareness Month
- Technology Insights
- The Cyber Security Report
- The Next Generation Cyber Security Experts
Shows & Panels
New alliance in the battle for cybersecurity
Wednesday - 2/17/2010, 4:44pm EST
There is a new alliance in the battle for cybersecurity. Though neither side has confirmed it, The Washington Post recently reported that Google has asked the NSA to help investigate the mid-December cyber attack against its networks "to better defend Google - and its users - from future attack." This partnership demonstrates the increasing interdependencies between the public and private sector in defending against cyber threats.


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The Top 10 In Action Sports
01This British Council Is Trying To Make Skateboarding A Crime...
02Want To Escape The UK And Surf Every Day? This Is The Place To Go…
03Snowfall In New York Has Been So Deep, People Can't Get Out Of Their Houses
04What Do You Get If You Cross A Zip-Wire With A Roller Coaster?
0523 #FirstWorldProblems People Encounter When Skiing
067 Awkward Moments Every Brit Experiences When Surfing Abroad
07'Has Skiing Made Me Bald?' - What Do You Contemplate When You're On The Chairlift?
08This Squaw Valley Ski Edit Is Not To Be Missed...
09This 22 Year Old Student Took Three Years To Make This Adventure Film. The Result Is Truly Beautiful…
10From Small Photo To Breathtaking Reality: This Ski Trip Is One Of The Best We've Seen...
Fred & Vince - Soul Flying
The Soul Flyers Fred Fugen, Vince Reffet and Jean-Phi Teffaud are back in Norway for some FreeFly BASE Action. From a 3280 feet cliff in Norway, Fred Fugen and Vince Reffet, 3X Freefly world champions, impress with their jumps and combos ... Once again, they push the limits of "Freefly Base" with some technical prowess and exceptional tricks!
What Do You Think?
Get the best in action sports straight to your inbox


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Hot answers tagged email
You can use any email you want to register for apps. Use the forum one to keep app spam off the serious one. Remember, purchased apps are still on the primary Google account, no matter what other address you register the app account with.
Only top voted, non community-wiki answers of a minimum length are eligible


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Hollyear Hotel Xiangke
No availability found through our partners. Please contact the business directly or check some of our recommended alternatives.
TripAdvisor Reviews Hollyear Hotel Xiangke Changsha
Travel Blogs from Changsha
Chapter 11 - The Calm and The Storm
... the 4 Christmas Dinners (another reason why I've started Ti Chi).
I'm writing this entry quite late at night. Tomorrow I'm off to the Zhangjiajie Mountains better known for being the home of certain blue men and women (no not the smurfs!) and I have a 5 hour train Journey to take so I will leave it at that. Next time there will be lots of stories to tell and pictures to share so until then, Goodbye.
From Your Stupid Boy,
Chapter 10 A mountain to climb
... at. Crystal chandeliers dangling above every table, golden ornaments lining the walls and a huge fish tank with a fully grown sea turtle inside. When I first saw it though, I was worried. In most restaurants that serve fish, they display the fish you want to eat in a tank, remove and kill the fish in front of you and serve it. However I was informed that this turtle is a pet (who keeps a sea turtle as a pet!!). I have to say the food was brilliant. Name a type of sea animal and I ...
Chapter 9 - Fireworks and Moon Cake
... 30+ degree heat), I have been getting used to living in my own apartment. It doesn't quite feel like home yet but I am getting there slowly but surely.
I am even getting used to the constant humidity and hot food. According to one of the teachers I work with, Changsha is known as "The City of Fire" due to the climate and the hot food. The flavors though are simply incredible. So much so it almost makes English food dull in comparison.
What I really ...
Chapter 8 - That Journey & First Impressions
... Beijing. I mentioned in my last blog that I went out the last night before I traveled. Well I woke up fresh as a daisy (much to the annoyance of those with bad heads). I wasn't due to leave the hotel till 14:00 (keep a track on time here) so decided to go for one last walk around the area. It was a beautiful sunny day (for once no smog). I found a huge lake nearby which I wondered round. In places it was very much like walking round the pinewoods near my ...
You'll be in your way
... are dissatisfied. Apart from the evident health repercussions, a person could also practical experience some psychological and emotional dilemmas if he is overweight. You dont really need to undergo any more. You requested, What am i able to do to deal with my constipation? plus the respond to is straightforward, look at this report and abide by thes . In these kinds of time, a ideal sweet sixteen celebration is really an occasion that shouldnt be skipped. ...
Other places to stay in Changsha
Crowne Plaza Changsha City CentreWuyi Square, Changsha | 4 star hotelfrom $119
Zidongge Huatian HotelRailway Station, Changsha | Hotelfrom $49
Dolton HotelRailway Station, Changsha | 5 star hotelfrom $103
Sheraton Changsha HotelWuyi Square, Changsha | 4 star hotelfrom $172
Xiangquan HotelWuyi Square, Changsha | 5 star hotelfrom $48
Huatian HotelHelong Stadium, Changsha | Hotelfrom $91
Mingcheng International HotelXingsha, Changsha | Hotelfrom $81
Wandai HotelWuyi Square, Changsha | Hotelfrom $56
Xiaoxiang Huatian HotelWuyi Square, Changsha | Hotelfrom $261
Hollyear HotelYuhua District, Changsha | Hotelfrom $68
Jolly HotelHelong Stadium, Changsha | Hotelfrom $94
New Empire Hotel ChangshaYuelu District, Changsha | 4 star hotelfrom $68
Vaya International HotelNo.81 Wanjiali Middle Road, Yuhua District, Changsha | Hotelfrom $56
Changsha Hiyi International HotelWuyi Square, Changsha | Hotelfrom $17
Hunan Bestride HotelHelong Stadium, Changsha | 5 star hotelfrom $55
Gold Source HotelHelong Stadium, Changsha | Hotelfrom $71
Furama Hotel ChangshaWuyi Square, Changsha | 4 star hotelfrom $64
Wu Hua HotelHelong Stadium, Changsha | 1 star hotelfrom $56
Country Garden Phoenix Hotel ChangshaXingsha, Changsha | Hotelfrom $86
Lotus Huatian HotelRailway Station, Changsha | Hotelfrom $38
Vienna International Hotel Changsha Furong SquareNo.540 First Section, Furong Middle Road, Furong District, Changsha | 5 star hotelfrom $54
Royal Seal (Tian Xi) HotelHelong Stadium, Changsha | Hotelfrom $53
Jasmine International HotelHexi College Zone, Changsha | 4 star hotelfrom $61
Gaoyuanhong HotelWuyi Square, Changsha | Hotelfrom $58
Xinshikong Conifer HotelNo.398 Furong Midddle Road, 3 Section, Tianxin District, Changsha | 4 star hotelfrom $46


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Sebonic Financial - Worst experience ever!
- 1 day ago 2014-11-25 14:32:16
Sebonic Financial
Sebonic Financial is a division of Cardinal Financial Company, a full service mortgage banking firm which has been in operation since 1987. The company is an approved seller/servicer for Fannie Mae, Freddie Mac and Ginnie Mae. Cardinal is also an approved lending institution for the Department of Housing and Urban Development/Federal Housing Administration and the Department of Veteran Affairs/Veterans Administration with FHAs Direct Endorsement and VA Automatic Lender Authority. Cardinal Financial Company is an authorized lender for the USDA/Rural Housing Program, the Pennsylvania Housing Finance Agency and the New Jersey Mortgage Housing Finance Agency. It is licensed by the Departments of Banking in many states, mainly in the eastern and southeastern United States. Its retail and wholesale divisions originate first mortgage loans for qualified borrowers.3701 Arco Corporate Drive Suite 415 Charlotte NC 28273
- Loans and Mortgages
- Cupertino, California
- Mortgage Refinance
- 44
Several delays in processing the loan despite proof that the loan docs were sent via fax. There were many many delays from the firm about my loans. The email from the manager said that she would respond but she was overloaded because all of her team was on vacation. On the day before the loan closing, they told me about a problem and that it would cost $3000. They basically had my back to the... Read more ›Was this review helpful? 1 0 5


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DEFINITION of 'Shareholder Activist'
A person who attempts to use his or her rights as a shareholder of a publicly-traded corporation to bring about social change. Some of the issues most often addressed by shareholder activists are related to the environment, investments in politically sensitive parts of the world and workers' rights (sweatshops).
The term can also refer to investors who believe that a company's management is doing a bad job and who attempt to gain control of the company and replace management for the good of the shareholders.
INVESTOPEDIA EXPLAINS 'Shareholder Activist'
Shareholder activism is a way in which shareholders can influence a corporation's behavior by exercising their rights as owners. Although shareholders don't run a company, there are ways for them to influence the board of directors and management. These can range from dialogue with management to voice their concerns about a particular issue to formal proposals that are voted on by all shareholders at a company's annual meetings.
ShareholderAny person, company or other institution that owns at least one ...
Sin StockA stock of a company that is either involved in or associated ...
Activist InvestorAn individual or group that purchases large numbers of a public ...
Dissenters' RightsState legislation that allows shareholders of a corporation the ...
Annual General Meeting - AGMA mandatory, public yearly gathering of a publicly traded company's ...
Socially Responsible Investment ...An investment that is considered socially responsible because ...
How Your Vote Can Change Corporate Policy
Green Investors Get Heard
Fundamental Analysis
Carl Icahn's Investing Strategy
Personal Finance
Go Green With Socially Responsible Investing


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HBO Go Now Compatible With Google's Chromecast, Just In Time For The Holidays (video)
Just in time for holiday couch potato all stars, HBO Go is now compatible with Google's Chromecast. Yes, you read that right. In addition to Netflix, Hulu Plus, and YouTube support, you can now stream HBO Go from any iOS or Android devices to your TV's Chromecast.
You'll of course need an HBO subscription with your cable or satellite provider. If not, then you're kind of screwed. However, and there are of course no guarantees, there is a good chance you've got a buddy who is willing to share their HBO login. So far HBO hasn't cracked down on the sharing of HBO logins, and trust me when I say that it's rampant.
If you don't own a Google Chromecast, you can pick one up for as little as $35 on Amazon or direct from Google. Sure, it's not as robust as an Apple TV, but it's about a third of the cost and plugs into your TV's HDMI port – just make sure you've got a spare USB port to power it.
If you do own a Chromecast, you'll likely need to update the iOS or Android app. Once you've done so, you should see a little beam symbol, similar to the one you see in YouTube, within the HBO Go app, after you select your video.
Christen Costa
Grew up back East, got sick of the cold and headed West. Since I was small I have been pushing buttons - both electronic and human. With an insatiable need for tech I thought "why not start a blog focusing on technology, and use my dislikes and likes to post on gadgets."
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iPad mini Retina drops $70, Dre Beats Mixr Headphones only $129
Deals: Curved Sony HDTV Gets Whopping $700 Off Coupon


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Wu-Tang Clan's RZA has responded Jay Electronica's recent claims that he made ignorant comments about the south.
RZA claimed he was merely referencing the unbalanced level of education in the country.
"I was speaking on the education level in the South, how brothers drop out … in the sixth grade — some of them because they have to go to work, some of them because of the poverty, some because they're not interested in the education system… I was speaking on the education level in the South, how brothers drop out … in the sixth grade — some of them because they have to go to work, some of them because of the poverty, some because they're not interested in the education system…If anybody got a question of what I say, they can ask me. I fear no man. I fear no MC's talent," he said. "But I definitely know when you young, you feel a certain way. At one point, we as Wu-Tang was like, 'The whole industry is wack besides Wu-Tang.' That was our energy, our spirit." (MTV)
Electronica made his issues with RZA public during an interview last month.
"Particularly, RZA, I love RZA and I love the Wu-Tang, but I remember RZA — he said some real ridiculous stupid, ignorant things about the South," Jay explained in an interview. "And he's from Ohio or something like that about New York from another place. I don't give a f*ck where you're from, whether you were born and raised in Brooklyn, where's your grandparents from? Where's your great grandparents from? He was saying something to the effect of like, they were talking about the down South music and I think Lil Jon was big at the time — he was talking about the lyricism and quality of music. He was saying, 'Yeah, we were doing this a long time ago,' but then when you start talking about the intelligence level, which is a very unwise thing to do and is very disrespectful, because you're running around saying all these things — this is the first time I'm ever saying this publicly too, peace on RZA he's a great brother [but] also, RZA, you said some crazy wild sh*t…I put it in a record called 'I Feel Good' which I did a long, long time ago." (The Most Influential)
This also caused a minor spark with New York radio personality DJ Kay Slay.
"What happened in the past happened and the South is eating now and you got on," Slay said. "Why you keep bringing up old foolishness and keep throwing New York up? I'm taking offense because when Ludacris came around before his first album dropped, he came to my crib to freestyle. T.I. when he first came out came to my crib to freestyle; he asked me to bring him on BET his first time around. 8Ball's first time when he came to New York, I took him through Harlem. You're using these people like no one in New York supported the South and everybody was dogging them [and] that never was the case." (All Hip Hop)
The deejay later wrote via Twitter denying his comments were meant to encourage a beef.
"Why yall internet n*gga act like yall dont know the difference Between BEEF and cats SPEAKING THEIR MIND. No threats no shots fired!!"
"@JayElectronica Its all Good Sun.. it aint nothin but grown man convo… These 85%ers are takin it somewhere else…peace." (DJ Kay Slay's Twitter)
Check out Jay Electronica speaking on RZA below:


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Rhyming slang for soup.
Could I have a bowl of that chicken hairy hoop please, and some bread. thanks.
by Vegas_Malone March 05, 2008
10 Words Trending Now
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The family of Dr. Myles and Pastor Ruth Munroe held a press conference in the ballroom at the Grand Lucayan Hotel on November 12th, just three days after the fatal plane crash. Continue reading
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Rance Allen Talks About the Meaning of New Hit Song
The Rance Allen Group's hit radio single "A Lil' Louder (Clap Your Hands)" has listeners across the country groovin' along to its driving bassline and catchy hook. Though the group wants you to dance, they also want to ensure that fans truly get the song's true meaning. With the goal to be an inspiration and share their wisdom, they are excited about sharing this time in praising God. They want the dancers to dance and the praisers to praise, all for our Father. Continue reading
J. Moss Loses Everything in House Fire, Speaks for the First Time
Grammy Award Winning producer and Stellar Award Winning artist J. Moss speaks on the recent loss of his families home due to fire. Continue reading
Ricky Dillard Talks About Almost Quitting Gospel
Choir master┬ĀRicky Dillard┬Āseems to be an anomaly on radio airwaves during a time when many of his kind have been replaced by more modern sounding gospel music artists. Continue reading
Purpose Driven Life Pastor Rick Warren Shares ŌĆ£Why I Do What I Do ŌĆō The Theme of My LifeŌĆØ
Best-selling author and Pastor Rick Warren shared on Friday that his dad,┬ĀPastor Jimmy Warren, who would have celebrated his 95th birthday this week, helped shape his destiny with his final, dying words. Continue reading
Beyonce's Dad MATHEW KNOWLES Says He's Running for Mayor!
Music mogul Mathew Knowles told Houston's 97.9 that he's considering running for mayor. After discussing a playful theory on what caused the rift between Knowles and daughter Beyonce, the interview turned serious as Mathew outlined his motive for running for one of Houston's top offices. Continue reading
Lecrae Announces New Book as Album "Anomaly" Hits Stores
Your local Christian book store will stock more Lecrae content than music soon enough. Continue reading
DEITRICK HADDON Responds Harshly to Ex-Wife DAMITA Breaking Her Silence on Divorce
Deitrick Haddon has now responded to the exclusive interview Path MEGAzine brought to you about a month ago with ex-wife Damita. Deitrick responded confidently to Damita finally breaking her silence on infidelity during their 15 year courtship and marriage. Continue reading
Smokie Norful Talks About Declining Gospel Album Sales
Smokie Norful has went gold twice, but seeing those kind of numbers arenŌĆÖt as easy now as they were before. The ŌĆ£I Need You NowŌĆØ singer knows he has to take a different approach to be successful this time around, and after working on his newly released album for five years he wants it to be worth the effort. Continue reading
Dr. Bobby Jones Remembers the Late Bishop Al Hobbs
Today, the Gospel community is in Indianapolis remembering one of their fallen laborers of the faith. Perhaps no one knew Bishop Al Hobbs better than the legendary Dr. Bobby Jones. Continue reading


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Florida > Naples Yellow Pages > Automotive > Vehicle Service and Repair > Brakes: Brake Lines Naples
Summit Automotive Inc
(239) 206-2509
3784 Domestic Ave, Naples, FL| Map
Nissan and Toyota specialists. - Looking for the highest quality automotive services? Come to Summit Automotive Inc. We offer comp... More>
Matching: Brake Lines
European Motors
(239) 300-2049
1989 Trade Center Way, Naples, FL| Map
Specializing in Mercedes-Benz and BMW - Welcome to European Motors of Naples, Florida. At European Motors, we provide our customers with... More>
Matching: Brake Lines
Chet's Courtesy Automotive
(239) 330-4179
1863 Tamiami Trail North, Naples, FL| Map
Your One Stop Auto Repair Shop. - Chet's Courtesy Auto is a car repair shop serving Naples, FL and the surrounding areas. Specializ... More>
Matching: Brake Lines
Rocky's Auto & Tire Center
(239) 330-1618
12525 Collier Blvd, Naples, FL| Map
We now do custom exhaust systems - We know how inconvenient waiting for your car to be fixed can be. This is why we take every step ... More>
Matching: Brake Lines
Pine Ridge Imports Of Naples Inc
Experience Expert Service From A Family Owned Business.
Johnny Myers Discount Tires & Service Center
Committed to Service Excellence at a Fair Price.
North Trail RV Center
Helping Create Fond Family Memories For Over 25 Years.
(239) 732-5571
3032 Davis Blvd, Naples, FL| Map
AutoWorks is a family operated business that has been providing quality service to many customers... More>
Matching: Brake Lines
Tuffy Auto Service Centers
(239) 596-1668
9401 Tamiami Trl N, Naples, FL| Map
Mission StatementTo Provide the Best Automotive Repair Service in the IndustryThrough a Continu... More>
Matching: Brake Lines
Duff's Auto Repair Service
(239) 244-5931
2380 Pine St, Naples, FL| Map
Duff's Auto Repair Service is a full-service auto repair and preventive maintenance center servi... More>
Matching: Brake Lines
T & D Automotive Service
(239) 597-6001
1986 J & C Blvd, Naples, FL| Map
T & D Automotive Service is located in Naples, Florida and serves the surrounding communities. Is... More>
Matching: Brake Lines
(239) 598-2932
2425 J AND C BLVD, Naples, FL| Map
Cars and More Cars Tech located in Naples, FL. Offers Auto Repair & transmission Repair Services ... More>
Matching: Brake Lines
Express Towing Inc
(239) 290-4100
4384 Progress Ave, Naples, FL| Map
Don't stay stuck on the side of the road! Express Towing Inc . will tow your car, truck, RV, trai... More>
Matching: Brake Lines
Collier Tire Truck Division
(239) 643-7676
3906 Exchange Ave, Naples, FL| Map
Collier Tire Truck Division of Naples, FL is proud to say service is our business. Family owned a... More>
Matching: Brake Lines
Mike's Topline Auto Repair
(239) 300-4088
2072 Davis BLVD, Naples, FL| Map
My name and integrity is important to me and is very influential when choosing where you have yo... More>
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Johnny Myers Discount Tires & Service Center
(239) 791-7084
4248 Fowler St
Fort Myers, FL 33901
Fort Myers, FL 33901
Committed to Service Excellence at a Fair Price.
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RepoCydia.com Setup Files and icons.
Korean TenKey, one-hand keyboard layout
networks list shows all wifi access points
use vertical animations for app switching
Download straight into your ringtones folder. Now Includes S
Extensible Toggle Platform
timer & stopwatch available from anywhere
SpringBoard, the way you want it. All over again.
SMS experience you can't live without
Brings substance to your Lockscreen
dims screen after certain amount of time
perform useful actions at battery % levels


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-dromeSyllabification: -drome
Definition of -drome in English:
from Greek dromos 'course, running'.
Definition of -drome in:
- British & World English dictionary
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Word of the day verbose
Pronunciation: vəːˈbəʊs
using more words than are needed…


text:
: Prospect Info:
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Left Of The Dial
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Join Date: Jul 2005
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Polling the consensus
gives Gaunce, Hertl, Skjei, Vasilevski, and Lindholm from 20-24.
Vasilevski's a goalie and Hertl has skating issues, so I would be surprised if either of those guys were on the Pens radar. Lindholm sounds like an Erik Karlsson type, high-risk/high-reward, raw offensive defenseman (I wonder how much his stock is being helped by Karlsson's play).
Gaunce brings size, intangibles, and packs a solid scoring punch. I would be surprised if he were around at 22ish. Skjei sounds like he was made in a Ray Shero wet dream: American defenseman with high-end skating ability, but doesn't use his size as well as he should.
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