text:
|Publication number
|Publication type
|Application number
|Publication date
|Sep 11, 1984
|Filing date
|Mar 7, 1983
|Priority date
|Mar 7, 1983
|Fee status
|Publication number
|William J. Trepka
|Original Assignee
|Phillips Petroleum Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (14), Referenced by (17), Classifications (20), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
The invention relates to methods to improve the effectiveness of lithiation of hydrogenated copolymers. The invention further relates to lubricating oil and gasoline additives.
In the preparation of nitrogen-containing polymers effective as dispersant viscosity index improvers for lubricating oils, and/or as detergent additives for gasolines, a polymer is prepared by solution polymerization of a monomer or monomers to result in a polymer cement (polymer in hydrocarbon solvent). Coupling may follow. The polymer is hydrogenated, and then treated for hydrogenation catalyst removal. In normal course, the next step is lithiation (metalation) to introduce numerous sites in the polymer for subsequent treatment with a suitably reactive nitrogen-containing organic compound to finally result in a polymer exhibiting effective dispersant and/or detergent properties.
However, a problem developed in the lithiation step. Commercially unacceptably high levels of lithiating agent were being consumed. The relatively high consumption of lithiating agent required use of excessive amounts lithiating agent in order to attain desired level of lithiation. Unless sufficient lithiation is attained, there are not sufficient sites in the polymer to react subsequently with the nitrogen-containing compound and the net result is that the polymer then does not exhibit sufficient dispersant activity or properties.
In order to have a reasonably economical process of producing the nitrogen-containing hydrogenated polymers, and to assure sufficient resulting activity therein, a method was needed to reduce the amounts of lithiating agent required.
I have discovered that in the preparation of dispersant nitrogen-containing hydrogenated copolymers, that the lithiation (metalation) step is greatly improved in effectiveness with much reduced demand for lithiating agent when the polymer cement resulting from the hydrogenation catalyst removal step is first treated with an alkaline wash step prior to the lithiation step. Thus, my process inserts a step into the overall process of solution polymerization--hydrogenation--hydrogenation catalyst removal--alkaline wash--lithiation--treatment with nitrogen-containing organic compound, to poduce a dispersant hydrogenated polymer.
While I do not wish to be bound by theory, it is assumed that some sort of poisons inimical to lithiating agents remain in the polymer cement, scavengers or poisons in the reaction mixture, possibly resulting from the hydrogenation step and/or the hydrogenation catalyst removal step.
The alkaline wash step, since it employs an aqueous dispersion/solution of alkaline material, is followed by a suitable alkaline rinse step to remove traces of alkaline material, and a suitable drying step to remove residue moisture, prior to the subsequent lithiation step.
FIG. 1 illustrates in a block schematic form the placement of my alkaline wash step in the overall process of preparing the dispersant/detergent polymers.
Monomer(s) 1, structure control agent 2, solvent 3, and initiator 4, are contacted under solution polymerization 5 conditions to form a polymer-cement 6. Alternatively, a pre-formed polymer 7 and solvent 8 are admixed 9 for polymer dissolution to form polymer-cement 10.
Polymer cement 11 is contacted with hydrogen 12 and hydrogenation catalyst 13 under hydrogenation conditions 14. This step destroys any remaining active lithium from initiation.
The resulting hydrogenated polymer (still in solution but now containing hydrogenation catalyst residues) 15 is treated 16 for removal of hydrogenation catalyst residues 17.
The hydrogenated polymer (cement) 18, now cleansed of hydrogenation catalyst residues, is treated by an aqueous alkaline wash step 19 wherein the polymer cement is contacted with an aqueous solution/dispersion of an alkaline agent 21. The alkaline wash is separated and removed 22 for recycle or reuse. The cleansed but now wet polymer cement is dried to remove residue water.
The now cleansed and dry polymer cement 23 is contacted with appropriate lithiating agent(s) 24 in lithiation step 25.
The lithiated polymer cement 26 is contacted with an organic nitrogen-containing compound 27 in functionalization step 28.
The organic nitrogen-containing functionalized polymer (cement) 29 is treated in recovery step 31 for separation of the solvent 32 and recovery of the polymer 33 for use in oils or gasolines as desired. Solvent is recovered, normally, for recycle (not shown).
FIG. 2 illustrates in more detail one method of incorporating the alkaline wash and drying step (step 19 in FIG. 1) into the functionalized polymer preparation scheme in accordance with my invention.
A polymer cement from hydrogenation catalyst removal 18 is admixed with aqueous alkaline solution 51, separated 44, and neutralized 53. The substantially neutralized polymer cement 59 is washed with water 61, and again separated 65. The washed polymer cement 74 then is sent to such as a drying column 75 (not shown).
In the process of my invention, a polymer is prepared by solution polymerization, hydrogenated, treated for removal of hydrogenation catalyst residues, and treated by an alkaline wash step. Such step has been found by me to improve the subsequent lithiation (metalation) step. Apparently the alkaline wash removes lithium-poisons or scavengers that otherwise adversely affect the lithiation. Following the alkaline wash treatment, the so-treated polymer cement preferably is substantially neutralized, water washed, and dried. The now cleansed and dried polymer cement then is lithiated, and subsequently treated with any of a variety of nitrogen introducing compounds to result in the dispersant viscosity index improver and/or dispersant gasoline additives, as may be desired.
The feed stream to which the alkaline-wash treatment is applied is a polymer cement (polymer in hydrocarbon solvent) obtained from a hydrogenation catalyst removal step.
The alkaline-wash treatment can be more readily visualized by reference to FIG. 2. In FIG. 2, the polymer cement 18, from hydrogenated catalyst removal, is admixed with aqueous alkaline admixture 51, such as a mild solution of NaOH in water, to form stream 41 which is thoroughly mixed, such as by an in-line motionless mixer 42.
The admixed stream 43 is taken to a first operator 44, such as a coalescer. The alkaline wash settles (separates) to the bottom 45, and the washed polymer cement separates to the upper area 46.
The separated (exhaust) alkaline wash 45 is withdrawn 47. A portion can be removed, if desired, for separate recovery of reuse 48. The remaining exhaust stream augmented as to strength or concentration as may be necessary or desirable by fresh alkaline aqueous admixture 49, to forms recycle stream 51, and is recycled to contact further polymer cement 18 from the hydrogenation catalyst removal step.
The alkaline-washed separated treated polymer cement 46 which, of course, contains some traces of alkaline material treating agent and water, is removed 52, preferably contacted with an acidic H+ agent 53 to form stream 54, preferably thoroughly admixed in such as an in-line mixer 55. The neutralized treated admixed polymer cement stream 56 is allowed to separate, such as in a coalescer 57. Any separated aqueous solution/dispersion is removed 58 as needed for disposal.
The separated treated neutralized polymer cement 59 is admixed with water 61, which may be fresh, recycle, or admixture, and the mixture 62 is thoroughly admixed to wash the polymer cement, such as by an in-line mixer 63. The mixed washed stream 64 is taken to a second separator 65. The water separates (settles) to form lower layer 66. The washed cleansed polymer cement forms upper layer 67.
The separated water bottoms 66 is removed 67. A portion or side-stream usually is withdrawn 68 to waste disposal or purification (not shown) depending on the condition of the withdrawn separated water 66-67 as to salts content and the like.
Fresh or cleansed water 69 is added, as needed, to form water recycle stream 61.
The separated water-washed polymer-cement 67 is withdrawn overhead 71, passed through a de-waterer or settler 72. Any water that separates is removed 73, for disposal or reuse depending on its quality. The de-watered stream 74 sent to polymer drying, such as a suitable drying columns 75 (not shown).
While the process of my invention is applicable to any solution-polymerized polymer system utilized ultimately in preparing dispersant type polymers as described hereinabove, usually the copolymers involved are produced by copolymerizing under solution polymerization methods at least one hydrocarbon conjugated diene with at least one monovinylarene hydrocarbon, presently preferably and typically butadiene and styrene, to produce copolymers. Methods of producing such polymers have been well described and need not be described in great detail here.
Several types of particularly useful copolymers for lube oil and gasoline additives are described in such as my patent U.S. Pat. No. 4,145,298 issued Mar. 20, 1969, and also in patent U.S. Pat. No. 4,238,202 issued Dec. 9, 1980, wherein I am coinventor with Richard J. Sonnenfeld; both of which patents are herein incorporated by reference.
Suitable conjugated diene monomers are those aliphatic hydrocarbon conjugated dienes of four to eight carbon atoms per molecule. Exemplary conjugated dienes include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, piperylene, and the like. Suitable monovinylarene monomers are the hydrocarbon monovinylarenes of eight to fifteen carbon atoms per molecule. Exemplary monovinylarenes include styrene, α-methylstyrene, 3-methylstyrene, 3,5-diethylstyrene, 4-tolylstyrene, and the like.
In my discussions hereinafter for simplicity and convenience I use styrene as representative of as well as the preferred monovinylarene, and 1,3-butadiene as representative of as well as the preferred conjugated diene. Similarly butadiene/styrene copolymers are discussed as representative of the applicable conjugated diene/monovinylarene copolymers generally.
Suitable copolymers will contain about 20 to 70 percent by weight copolymerized styrene, the balance then being copolymerized butadiene, more preferably about 50 to 65 weight percent styrene and the balance butadiene. These copolymers presently preferably are substantially random copolymers, but can contain significant blocks of polystyrene and/or blocks of polybutadiene and/or blocks of random or random tapered butadiene/styrene. These copolymers also can be represented by such as B/A, A-B, and B/A-A, wherein A is a block of polystyrene, B is a block of polybutadiene, and B/A represents either a random copolymer block of butadiene/styrene, or a tapered block of butadiene/styrene, with the realization that B/A also can contain appreciable block structure of polystyrene. The use of the designation B/A when used with reference to tapered random blocks indicates the direction of taper with the B/A blocks. These blocks, while considered random, gradually decrease in content of the first indicated monomer along the block, due to the mode of preparation used. The block polystyrene A content of the random block copolymer B/A-A preferably should be in the range of less than about 35, more preferably less than about 25, weight percent. For most usages, a block polystyrene A content of less than about 5, and preferably less than about 2.5, weight percent is suitable and effective, such as 0.5-5 weight percent.
The butadiene/styrene copolymers employed to prepare gasoline additives should have a number average molecular weight in the approximate range of 1,000 to 10,000, presently preferred about 5,500 to 8,500. The copolymers, as far as the polymerized butadiene portion, should have a vinyl unsaturation content prior to hydrogenation of about 20 to 95 percent, preferably about 20 to 70 percent. (The vinyl unsaturation content refers to the percentage of the total unsaturated bonds in the polymerized butadiene portion of the copolymer which are in the form of vinyl unsaturation). The copolymers are of a type and molecular weight which as finally modified provide significant detergency improving properties to the hydrocarbon fuel, and still have sufficient fuel solubility to be formulated into the hydrocarbon fuel.
The butadiene/styrene copolymers which are employed to prepare lube oil additives should have a number average molecular weight in the approximate range of 20,000 to 300,000, presently preferred about 25,000 to 100,000. The copolymers, as far as the butadiene portion, will have a vinyl content prior to hydrogenation of about 20 to 95 weight percent, preferably about 20 to 70 weight percent. The copolymers are of a type and molecular weight which, as finally modified, provide significant viscosity index improving properties to the oil when so used, have sufficient oil-solubility to be formulated into lubricating oils, and possess significant shear stability in such oil formulations.
Hydrocarbyl monolithium initiators well known in the arts are employed in an amount effective for polymerization of the monomer charge employed to the molecular weight desired. Polymerization is conducted by contacting the monomer charge with the monolithium initiator in a suitable diluent. Diluents employed for the purpose include any of the paraffinic, cycloparaffinic, or aromatic hydrocarbons known to the art, used alone or in admixture, typically of 4 to 10 carbon atoms per molecule in commercial operations. Cyclohexane currently is preferred for ease of handling, high solubility of polymer, and availability.
Polymerization can be carried out at any convenient temperature employed in the solution polymerization arts. Suitable and exemplary temperatures lie in the range of from less than about 0� C. to over 200� C., presently preferred about 40� C. to 100� C., since these temperatures are consistent with obtaining the desired copolymers. The pressures employed can be as convenient, though preferably pressures are employed sufficient to maintain monomers and diluent substantially in the liquid phase. The polymerization times can vary widely as may be convenient, and will, of course, be affected by polymerization temperatures chosen. Time preferably should be chosen such that substantially complete conversion of monomers is obtained.
To prepare the A-B copolymeric structure, either styrene or butadiene can be first polymerized and then the other monomer added and polymerized to result in the A-B copolymer.
Alternatively, a mixture of the butadiene and styrene monomers can be copolymerized in desired proportion under randomizing conditions to produce a B/A copolymer. In another mode, a B/A structure can be first prepared by polymerizing a suitable butadiene/styrene admixture to the desired degree of conversion, and this usually will produce a tapered block since butadiene tends to polymerize somewhat faster to start with, and then subsequently additional styrene can be added to form an A block onto the first formed B/A block. Alternatively, and presently preferred, a mixture in a suitable ratio of butadiene and styrene can be copolymerized, under limited randomizing conditions, and this then permits formation of a preferred B/A-A structure since the faster polymerization of the butadiene exhausts the butadiene, and remaining styrene then block homopolymerizes.
Where a substantially random B/A portion is desired, employment of a randomizing agent can be included at the suitable stage in the polymerization, typically selected from ethers, thioethers, and amines, and others as is known in the art, typically such as tetrahydrofuran, or from the alkali metal alkoxides other than of lithium, typically such as potassium t-butoxide or potassium amyloxide.
The hydrogenation procedure employed should be effective so as to substantially reduce olefinic unsaturation including vinyl unsaturation, while leaving essentially untouched aromatic unsaturation present in the monovinylarene portion of the copolymer.
Hydrogenation can be conveniently conducted directly on the unquenched polymerization reaction admixture from the solution polymerization procedure. Alternatively, where convenient, the polymerization can be quenched, the polymer recovered, and then redissolved in a suitable hydrocarbon solvent for hydrogenation purposes.
Hydrogenation catalysts suitable are such as those described in U.S. Pat. No. 3,531,448. These catalysts comprise reaction products of aluminum alkyl compounds with either nickel or cobalt carboxylates or alkoxides. Typical of the aluminum alkyl compounds are such as triisobutyl aluminum, triethyl aluminum, tri-n-propyl aluminum, and the like. Exemplary nickel or cobalt carboxylates or alkoxides include the nickel and cobalt acetates, propionates, benzoates, octoates, and the butoxides, ethoxides, isopropoxides, and the like.
Methods of hydrogenation are well described in U.S. Pat. No. 3,531,448 and U.S. Pat. No. 4,145,298 and U.S. Pat. No. 4,238,202.
Following hydrogenation, the now hydrogenated polymer (still in hydrocarbon solution as a cement) is treated in a hydrogenation catalyst removal step, such as is described in U.S. Pat. No. 3,023,201 or U.S. Pat. No. 3,531,448. I presently consider the process of the latter patent particularly useful. Therein, the hydrogenated polymer cement is treated with an aqueous phosphate solution resulting in a polymer containing solution (cement) from which the catalyst residues can be readily removed.
In treating the hydrogenated polymers in this manner, any ammonium phosphate, e.g., meta, monobasic, or dibasic, in aqueous solution, or a partially or completely ammonia-neutralized aqueous solution of phosphoric acid, can be used, optionally in the presence of excess ammonia. The pH of the solution used should be greater than about 5, preferably greater than about 6, and the PO4 -3 ion content should be in the range of about 5 to 50 weight percent. For example, commercial phosphate solution such as 9:30:0, or 10:34:0, can be used. These solutions have PO4 -3 contents of about 40 and about 46 weight percent, and NH3 contents of about 11 and about 12 weight percent, respectively, and a pH of about 6.2.
Following the treating of the polymer solutions with the aqueous ammonium phosphate solution, the precipitated catalyst residues are separated from the solution by any means known in the art for the separation of precipitates, such as conveniently by filtration.
Following separation of the hydrogenation catalyst residues, the hydrogenated polymer-cement then is subject to the alkaline wash step in accordance with the process of my invention.
Compounds which can be employed in the alkaline wash step include solutions or dispersions of alkali metal hydroxides or carbonates, alkaline earth metal hydroxides, and/or ammonia or ammonium carbonate or hydroxide, alone or in admixture. Exemplary suitable compounds further include such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; and magnesium hydroxide, and calcium hydroxide. Of course, ammonia can be employed as such in admixture with water resulting in ammonium hydroxide. Other suitable alkaline compounds are such as ammonium carbonate, sodium carbonate, or any of the other substantially water soluble alkali metal carbonates also are employable.
For best handling and ease of subsequent removal, it is presently preferred that the alkaline agent employed be one which is soluble in water, rather than forming a dispersion or suspension of the alkaline material in water. For this reason, the alkaline earth materials are much less preferred.
Because of ease of handling, availability, and economy, sodium hydroxide is a presently preferred alkaline material to be employed.
The concentration of the alkaline material in water can range widely, such as about 0.5 to 50 percent by weight, more usually in the range of about 4 to 10 percent by weight.
The ratio of alkaline wash solution/dispersant relative to the polymer cement can vary widely, though presently I consider that about an equal volume of polymer cement versus alkaline wash to be suitable and convenient. This can, of course, vary such, as plus or minus ten percent, with no difficulty involved. Under these conditions, the amount of alkaline material relative to the feedstream of polymer cement can be expressed in terms of the alkaline compound as being broadly from about 100 to 10,000 ppm, presently preferably about 500 to 1,000 ppm, alkaline compound relative to the feedstream. Thus, utilizing these suggested limitations, one skilled in the art can readily calculate the concentration of alkali material needed in the aqueous solution.
The time employed in the alkaline wash step in accordance with my invention is believed not to be critical, with the only requirement being that good contact or mixing is achieved between the aqueous basic solution and the polymer solution. This good contacting can be readily achieved in equipment such as in-line mixers and the like. The temperature employed is not critical, and typically is in the range of about 5� C. to 150� C., preferably about 25� C. to 50� C. The pressure employed is considered not to be critical, and generally simply will be the autogenous pressure generated by the components of the system.
The polymer solution which has been alkaline-wash treated is separated from the aqueous alkaline treating solution, such as in a settling vessel or coalescer of any convenient and suitable construction in view of the alkaline materials-handling involved. The organic phase containing the polymer dissolved in solvent will contain some traces of aqueous alkaline material.
While adequate water-washing certainly can remove residual retained alkaline substances, less water-washing is involved by employing an intervening H+ neutralization step. Thus, it is preferred to treat the alkaline-washed and separated polymer cement with an acidic reagent, or a reagent producing an acidic result in water, such as carbon dioxide. Such neutralization also avoids or reduces the use of more costly materials of construction in downstream equipment which otherwise might be required if the pH was excessively high. The acidic reagent conveniently can be added to the alkaline polymer solution by means such as an in-line mixer.
The substantially neutralized material then is passed to a coalescing stage in which the aqueous phase remaining in the polymer solution is allowed to separate out for removal from the system. Control of the pH can be conveniently monitored on the water separated from the coalescer (58 in my FIG. 2) to a range of about 3 to 10, preferably about 6 to 8. This aqueous phase usually is discarded since it contains various neutralized salts.
The effluent from the alkaline treatment step, or from pH adjusted where such treatment is employed, is treated with a water-wash step. The water-wash step can be accomplished in essentially the same type of equipment used in the prior alkaline treatment step. The water-wash step while optional, is preferred, and serves to remove any residual alkaline or other water soluble salts remaining in the polymer solution. The effluent from the water-wash step is passed to a coalescing stage wherein the major portion of the water remaining in the water washed polymer solution is removed.
The next step, prior to passing the polymer solution to the metallation (lithiation) reaction zone, is a drying step. The drying of the polymer solution can be carried out by various methods.
For example, the drying column procedure as described in U.S. Pat. No. 4,278,506, incorporated herein by reference, in which dry solvent is added to the polymer solution and flashed overhead to result in a dried polymer solution suitable for the metallation reaction zone. Presently, the preferred method of drying the polymer solution is the drying column as disclosed in U.S. Pat. No. 4,278,506.
A polymer-solvent mixture is passed to a fractionation-stripping zone wherein components lower boiling than the solvent are separated and a purified polymer-solvent mixture is recovered by contacting the polymer-solvent mixture in said zone with dry solvent stripping vapors added to the bottom portion of the fractionation column to act as a stripping agent. The added stripping component can be taken from a source other than the fractionation column, e.g., storage for dry solvent. The polymer-solvent mixture recovered as the fractionation column bottoms is then passed to a subsequent reaction.
In a specific embodiment, hydrogenated butadiene/styrene copolymer in a cyclohexane solvent is passed to a fractionation-stripping column to strip water and any other components boiling at lower temperatures than the solvent from the polymer-in-solvent. Dry cyclohexane, is vaporized and added to the bottom portion of the fractionation column to act as a stripping vapor for the water and any other lower boiling materials. The polymer and solvent are recovered as the bottom product from the fractionation column and passed to a metallation reactor for reaction with n-butyllithium.
Other suitable drying methods include dessicant beds utilizing materials such as alumina, bauxite, or the like. A stream of (dry) nitrogen can be passed through the polymer solution as a drying procedure.
Metallation of the polymer and subsequent reaction of the metallated polymer with a reactive nitrogen-containing organic compound to prepare the dispersant viscosity index improver is carried out according to procedures such as disclosed in U.S. Pat. No. 4,145,298; and for the carburetor detergent additives in accordance with procedures such as described in U.S. Pat. No. 4,238,202.
Examples provided are intended to assist one skilled in the art to a further understanding of the invention, without limiting the proper scope thereof. Particular species, conditions, amounts of materials, ranges of materials, and the like, employed in these examples, are designed to be exemplary and not limitative of the scope of my invention.
Runs were made to examine the effect of various treatments on the n-butyllithium scavenger (poison) level in a hydrogenated polymer solution (cement) (9.3% solids) in cyclohexane. The polymer was a butadiene/styrene (40/60) copolymer which had been hydrogenated by a nickel carboxylate salt/organoaluminum compound catalyst. The catalyst residues were removed by treating the polymer solution with aqueous ammonium phosphate, and then filtering the polymer solution.
The scavenger levels were determined by the following procedure and recipe:
______________________________________Scavenger Recipe______________________________________Hydrogenated polymer, cyclohexane 100 parts by wt.solution (about 9.5% solids)N,N,N',N'--Tetramethylethylenediamine 1.39 parts by wt.(TMEDA)Styrene 3 parts by wt.Temperature, �C. 70______________________________________
The above mixture was titrated with n-butyllithium solution of known concentration until a light yellow color persists. The amount of n-butyllithium required to reach this end point is taken as the scavenger level expressed in parts by weight n-butyllithium per 100 parts by weight of polymer.
The following Runs were conducted at room temperature (about 27� C.). A 400 mL volume of polymer solution was utilized in each Run. When employed, filtration was done on a suction funnel with a 1 inch deep bed of diatomaceous earth (Dicalite) as the filter medium. Results of the Runs are shown in Table I:
TABLE I______________________________________A B C DRun Filtration N2 Purgea, Caustic Water Scavenger,No. Dicalite minutes Washb Washc php nBuLi______________________________________1dYes 5 No No 0.392dYes 5 No No 0.453dYes 30 No No 0.394.sup.No 5 No No 0.635.sup.No 5 No No 0.576.sup.No 30 No No 0.387eYes 5 No Yes 1.208fYes 5 Yes Yes 0.339fYes 5 Yes Yes 0.2810fYes 30 Yes Yes 0.13______________________________________ a Flow rate of about 3L/minute. b Utilized 400 mL of aqueous NaOH, 6% by wt. c Utilized 400 mL of water. d Sequence of treatment: A/B e Sequence of treatment: D/A/B f Sequence of treatment: C/D/A/B
The results in Table I demonstrate that the alkaline wash step provided a significant reduction in scavenger level required by the hydrogenated polymer solution.
Runs were carried out to metalate the hydrogenated polymer, and then to react the metalated polymer with a reactive organic nitrogen compound, p-dimethylaminobenzaldehyde, so as to prepare a nitrogen-containing polymer according to the teaching of U.S. Pat. No. 4,145,298. The hydrogenated polymer solution was treated in various ways to determine the n-butyllithium scavenger level resulting therefrom and the final product was analyzed for resulting N-content as an indication of metalation effectiveness.
The hydrogenated polymer solution subjected to the treatments (all at about 27� C.) described below was the same type as that employed in Example I. After being treated as described below, each solution was subjected to a drying step utilizing azeotropic distillation of added dry cyclohexane. Each dried polymer solution then was utilized in a metalation reaction employing 1.39 php TMEDA and 0.77 php effective n-butyllithium for 1.5 hr at 70� C. Effective n-butyllithium refers to that amount in excess of the scavenger. Each mixture was then reacted with p-dimethylaminobenzaldehyde, 1.79 php, and the products recovered by coagulation of the cyclohexane solutions with isopropyl alcohol. The polymer was redissolved and precipitated twice. The thrice precipitated polymer products were dried under vacuum.
The treatment procedures and the results obtained are shown in Table II:
TABLE II______________________________________ Scav- Poly- C8 enger merRun Treatment Alcohola THFb php N,No. Type ppm ppm nBuLi %______________________________________11 None (as received) 194 483 --e --12 Passed over activated <20 <10 0.16 0.13alumina13 Water washed 220 200 0.96 0.0114 Caustic wash, water 207 <10 0.83 0.14and HCl washedc15 HCl wash, water -- -- 0.90 0.02washd______________________________________ a Suspected poison, 2ethylhexanol, a hydrogenation catalyst byproduct. b THF is tetrahydrofuran, a possible poison for the metalation reaction. c Utilized KOH solution of about 6 wt. % concentration. Emulsions tended to form that finally were broken by adding isopropyl alcohol. d Utilized 10% HCl then water washed until neutral. e Dash indicates not determined.
The results in Table II demonstrate that alumina treatment provides a low scavenger level and low levels of suspected poisons. The product polymer also has an N-content indicating effective metalation, and that the N-content is at a suitably high level for use as a dispersant type viscosity index improver. Even though the scavenger level in Run 14 (alkaline wash) apparently was not reduced to a level comparable to that achieved in Run 12, nevertheless the resulting N-content of the polymers was essentially the same. A water wash or an acid wash (Runs 13 and 15) was not effective as treatment especially in view of the low resulting polymer N-contents.
A five gallon portion of hydrogenated polymer solution which had been filtered free of catalyst residues was washed at about 27� C. with: (1) an approximately equal volume of 6% by weight aqueous sodium hydroxide solution and then (2) an approximately equal volume of water then dried by addition of dry cyclohexane and azeotropic distillation thereof. A portion of the same hydrogenated polymer feedstream was dried in the same manner but without any wash treatment. Scavenger levels of these two dried polymer solutions were determined as in Example I. The results obtained are shown in Table III:
TABLE III______________________________________Run Polymer Solution Scavenger,No. Caustic/Water Washed php N--BuLi______________________________________16 Yes 0.2617 No 0.74______________________________________
The results in Table III demonstrate that the caustic wash/water wash treatment of the instant invention can reduce the scavenger level by 65% in comparison to the absence of any treatment except drying.
Other Runs were conducted to demonstrate the effectiveness of the caustic wash procedure in reducing the scavenger level for hydrogenated polymer solutions used for metalation and subsequent reaction with an organic nitrogen-containing compound. The same type of hydrogenated polymer feedstream as previously employed was used in these runs. After the indicated treatment each polymer solution was dried by azeotropic distillation with added dry cyclohexane as previously described. The dried polymer solutions were subjected to metalation and subsequent reaction with p-dimethylaminobenzaldehyde in a manner similar to that described in Example II. Scavenger levels were determined for each treated polymer solution by the procedure given in Example I, and nitrogen contents of the final polymer products were also determined. The treatments employed and the results obtained are shown in Table IV:
TABLE IV______________________________________ Scav- Poly- C8 enger merRun Alcohola Acida php N,No. Treatment % % nBuLi %______________________________________18 None 0.03 0.06 0.70 0.0519 NaOH washb -- -- 0.31 0.10620 Stored over activatedc -- -- 0.24 0.106alumina21 NaOH washd 0.04 0.002 0.36 0.136______________________________________ a 2Ethylhexanol and 2ethylhexanoic acid are suspected poisons from hydrogenation catalyst as byproducts. b Washed with an equal volume of 5% aqueous NaOH at about 27� C. c Utilized about 20% by volume alumina for 72 hours at about 27� C. d Washed with 1000 ppm NaOH in an equal volume of water at about 21� C. then neutralized with CO2 to a pH of 7.
The results in Table IV demonstrate that the alkaline wash treatments were nearly as effective as activated alumina in reducing scavenger level for metalation reaction, but gave essentially the same results or better in terms of nitrogen content in the final polymer.
My disclosure, including data, has illustrated the value and effectiveness of my invention. The examples, the knowledge and background of the field of the invention an the general principles of chemistry and other applicable sciences have formed the bases from which the broad descriptions of my invention including the ranges of conditions and the generic groups of operant components have been developed and formed the bases for my claims here appended.
|Cited Patent
|Filing date
|Publication date
|Dec 27, 1954
|Jul 7, 1959
|Phillips Petroleum Co
|Process for decolorizing hydrogenated butadiene polymers with a saturated carboxylic acid
|Oct 26, 1955
|Feb 27, 1962
|Phillips Petroleum Co
|Process for removal of catalyst from hydrogenated polymer solutions
|Aug 30, 1965
|Jan 17, 1967
|Phillips Petroleum Co
|Removal of contaminants from unsaturated hydrocarbon-containing mixtures
|Nov 6, 1968
|Sep 29, 1970
|Phillips Petroleum Co
|Process for removal of hydrogenation catalyst from hyrogenated polymers
|Sep 11, 1970
|Oct 3, 1972
|Phillips Petroleum Co
|Hydrogenation process
|Oct 15, 1970
|Aug 7, 1973
|Organolithium-polyamine compositions
|Oct 26, 1970
|Dec 3, 1974
|Phillips Petroleum Co
|Purification of high molecular weight polymers to reduce hydrogenation conditions
|Jan 29, 1976
|Jun 7, 1977
|Mobil Oil Corporation
|Non-aqueous removal of soluble hydrogenation catalyst
|Feb 25, 1977
|Jul 4, 1978
|The Firestone Tire & Rubber Company
|Removal of catalytic residues from hydrogenated thermoplastic or elastomeric polymers
|Aug 22, 1977
|Mar 20, 1979
|Phillips Petroleum Company
|Hydrogenated lithiated copolymers grafted with organic nitrogen compounds as viscosity index improvers having dispersant properties
|Aug 31, 1979
|Dec 9, 1980
|Phillips Petroleum Company
|Hydrocarbon fuels with carburetor detergent properties
|Dec 21, 1979
|Jul 14, 1981
|Phillips Petroleum Company
|Polymer solution purification
|Oct 23, 1981
|Sep 6, 1983
|Phillips Petroleum Company
|Viscosity index improvers with dispersant properties prepared by reaction of lithiated hydrogenated copolymers with 4-substituted aminopyridines
|Oct 23, 1981
|Sep 6, 1983
|Phillips Petroleum Company
|Viscosity index improvers with dispersant properties prepared by reaction of lithiated hydrogenated copolymers with substituted aminolactams
|Citing Patent
|Filing date
|Publication date
|Jul 30, 1987
|Sep 19, 1989
|Shell Oil Company
|Modified block copolymers having carboxyl groups grafted on the alkenyl arene blocks
|Feb 1, 1988
|Nov 21, 1989
|Shell Oil Company
|Modified block copolymers
|May 16, 1988
|Feb 6, 1990
|Shell Oil Company
|Modified block copolymers functionalized in the monoalkenyl aromatic or vinylarene block
|Apr 4, 1988
|Mar 6, 1990
|The University Of Akron
|Method of lithiating a tertiary chloro alkyl compound and the product provided by said method
|Nov 23, 1990
|Feb 18, 1992
|Shell Oil Company
|Removal of hydrogenation catalyst from polymer solutions by contact with activated carbon
|Nov 23, 1990
|Apr 14, 1992
|Shell Oil Company
|Removal of hydrogenation catalyst from polymer solutions by contact with silicates
|Mar 30, 1990
|Apr 27, 1993
|Shell Oil Company
|Functionalized elastomeric polymers
|Jun 14, 1990
|May 18, 1993
|Shell Oil Company
|Removal of hydrogenation catalyst from polymer solutions by catalyzed precipitation
|May 16, 1995
|Aug 6, 1996
|Shell Oil Company
|Concurrent epoxidation and catalyst residue extraction
|Aug 10, 1999
|Mar 27, 2001
|Shell Oil Company
|Removal of hydrogenation catalyst from polymer solutions by treatment with ammonia and carbon dioxide
|Mar 2, 2000
|Apr 24, 2001
|Shell Oil Company
|Treatment of polymer solution with acid and ammonia to improve polymer color
|Feb 9, 2001
|Oct 5, 2004
|Kraton Polymers U.S. Llc
|Process for removing hydrogenation catalyst residue from hydrogenated polymers
|Jun 26, 2001
|Nov 9, 2004
|Asahi Kasei Kabushiki Kaisha
|Method for hydrogenation of polymer
|Jun 26, 2001
|Aug 8, 2002
|Koichi Miyamoto
|Method for hydrogenation of polymer
|Feb 9, 2001
|Jul 24, 2003
|Hofman Adrianus Hendrick
|Process for removing hydrogenation catalyst residue from hydrogenated polymers
|Dec 18, 1992
|May 2, 1995
|Shell Oil Company
|Modified block copolymers functionalized in the monoalkenyl aromatic or vinylarene block
|Feb 9, 2001
|Aug 16, 2001
|Kraton Polymers Research B.V.
|A process for removing hydrogenation catalyst residue from hydrogenated polymers
|U.S. Classification
|525/338, 525/339, 525/366
|International Classification
|Cooperative Classification
|European Classification
|Mar 7, 1983
Owner name: PHILLIPS PETROLEUM COMPANY; A CORP OF DE.
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:TREPKA, WILLIAM J.;REEL/FRAME:004111/0045
Effective date: 19830228
|Sep 25, 1987
|Fee payment
Year of fee payment: 4
|Apr 14, 1992
|Maintenance fee reminder mailed
|Sep 13, 1992
|Lapse for failure to pay maintenance fees
|Nov 17, 1992
|Expired due to failure to pay maintenance fee
Effective date: 19920913
|Nov 24, 1992
|Expired due to failure to pay maintenance fee
Effective date: 19920913


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self-inflicted wound (n): a spectacularly humiliating, and often hilarious, incident entirely of one's own making. see also you did it to yourself.
"Parks and Recreation"actor Nick Offerman shares his humorous fulminations on life, manliness, meat, and much more in his first book.
Mindy Kaling has lived many lives: the obedient child of immigrant professionals, a timid chubster afraid of her own bike, a Ben Affleck-impersonating Off-Broadway performer and playwright, and, finally, a comedy writer and actress prone to starting fights with her friends and coworkers with the sentence "Can I just say one last thing about this, and then I swear I'll shut up about it?"
"Love All the People," a collection of controversial comedian Bill Hicks stand-up routines, notebooks, journals, and letters, traces his evolution from brilliant conventional stand-up to something far more interesting and dangerous: a comic speaking without fear.
Before Liz Lemon, before "Weekend Update," before "Sarah Palin," Tina Fey was just a young girl with a dream: a recurring stress dream that she was being chased through a local airport by her middle-school gym teacher. She also had a dream that one day she would be a comedian on TV.
She has seen both these dreams come true.
Disney meets Lena Dunham in this illustrated humor book featuring your favorite fairy-tale characters dating and finding their way in 21st-century America
The New York Times bestselling writer and comedian Demetri Martin is back with a brand new collection of drawings that urge you to:
From "New York Times" bestselling author, one of America's top cultural critics ("Entertainment Weekly"), and The Ethicist for "The New York Times Magazine, "comes" "a new book of all original pieces on villains and villainy.
"New York Times Book Review" Editors' Choice
A Very Oral History
With a New Introduction by the Author
""We Killed" shines in its details and its anecdotes....Well crafted and entertaining." "The Boston Globe "
From the authors of the "New York Times "bestsellers "Awkward Family Photos "and "Awkward Family Pet Photos "comes a celebration of those special times throughout the year when our families embarrass us the most . . . the holidays.

subset: commoncrawl


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"Hi there! I have been meditating since January 2011 and have seen major transformation and increased inner peace in my life because of it. I am trained to lead..."
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Maltese Articles
- Riflessjonijiet fuq is-suċċess ekonomiku
- Riformi li se Jolqtu x-Xogħol tal-Awdituri
- Sfidi għas-settur bankarju
- Wara l-Panama s-settur finanzjarju tagħna għandu futur?
- Indikaturi ekonomici misturin li jbiddlu l-politika tal-Gvern
- Aktar opportunita' għal pajjiżna
- X'jieħu pajjiżna mill-laqgħat ta' Washington
- Malta hi centru finanzjarju ta' l-ogħla livell
- Ir-Rebbiegħa Għarbija- seba' snin wara
- Għaliex insemmu ċ-Ċina
- More Maltese Articles>>
English Articles
- Looking ahead: Malta's economic outlook for 2016
- Opposition has 'brainwashed' everyone against €360 million loan guarantee
- Two-thirds of my time now spent fighting bureaucracy
- Our interest in Greek saga
- Private sector is driving force
- The '€400m discrepancy'
- Malta's clean bill of health from Brussels
- Regaining Malta's credibility
- Deficit aim 'credible'
- From 'good performer' to laggard
- More English Articles>>
Press Releases
- Lowest January to May deficit on record
- Minister for Finance attends the launch of ACCA-X programme
- EU tax agreement
- Finance Minister Edward Scicluna addresses the Operators of the European Financial Regulated Markets
- Malta Records Highest Employment Growth in the EU for the Second Consecutive Quarter
- Malta Finance Minister addresses ASEM meeting on behalf of the EU Presidency Trio
- Economic Growth in Malta Continues to Impress
- Challenges and Opportunities for the Insurance Industry
- High reduction in the debt-to-GDP ratio in 2015
- Finance Minister receives a courtesy visit from the Algeria-Malta Parliamentary Friendship Group
- More Press Releases>>
Latest News
EC Vice-President Tajani at Malta Business Bureau Meeting
Professor Edward Scicluna MEP was invited to participate in a high profile business breakfast debate organised by the Malta Business Bureau (MBB) on Monday 5th March at the Grand Excelsior Hotel in Floriana. Stakeholders from the Maltese business sector had the opportunity to meet with the European Commission Vice-President Antonio Tajani. Representatives from the Malta Chamber of Commerce, Enterprise and Industry (Malta Chamber) and the Malta Hotels and Restaurants Association (MHRA) discussed issues related industry, entrepreneurship, tourism and SME internationalisation, all forming part of Commissioner Tajani's portfolio within the College of Commissioners. Officials from various EU-offices, Members of Parliament, MEPs and other distinguished guests also participated.
- Gallery -
-Monday, 5th March, 2012
Latest News
- EU Delegation visit to the Ministry for Finance
- Moody's – "Malta to benefit from strong economic growth in 2016-17"
- L-iskema tal-PN turi problemi mal-banek
- On track to reach the deficit target for third year running
- PN confuses basics on pensions
- Imnedija inċentivi għal min jagħżel li jibqa' jaħdem u ma japplikax għall-pensjoni fl-età ta' 61 sena
- Economic momentum upped in 2015
- SME-oriented capital markets platform to be launched soon on the Stock Exchange
- Minister Scicluna discusses financial services safeguards with European Commissioner Jonathan Hill
- MFC Merchant Bank, Sliema
- More Latest News>>


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Recording her first album is a dream come true for New Zealand Got Talent winner Clara van Wel.
"Everything I ever imagined in the shower, and in front of the mirror is suddenly being realised," the 15-year said when Stuff visited her in the studio.
"We started off just having a massive jam session and working out which songs we are going to use, and what we were going to use in terms of musicians in the songs and then layer by layer we built up from drums to bass, to piano, to guitar and now I am just doing the vocals which is fun," she described the recording process.
The singer-songwriter was at times surprised how her own songs turned out in the studio. "I like them all for different reasons. It's still a work in progress, things are still happening and I am still getting surprised by little changes."
The teenager's first single Where Do You Find Love, released in December, reached No 3 in the New Zealand charts.
Her yet unnamed debut album will be released in March. In the meantime van Wel is joining Fat Freddy's Drop, AnikaBoh&Hollie and The Adults (feat. Jon Toogood and Julia Deans) on the 17 date Winery Tour that starts on February 2 at Ascension Wine Estate in Matakana and finishes on March 3 at Mystery Creek in Hamilton.
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The Wayans Brothers come to NZ
Time Lords rally for Sir Peter
Review: Robert Plant and the Sensational Space Shifters
COROnation show: The word on the street
Rihanna adds third Auckland show
Counting Crows a no show - again
Counting Crows counting the years
Government may step in if Auckland doesn't put a new city plan in place
Disoriented man in Britomart tunnel causes Auckland train delays
NZMA staff among those keen to help Auckland window washer
Auckland heart researchers to share $6 million war chest
Millennials struggling to break into Auckland market urged to club together
Arthritis sufferer tackles base camp challenge
Black Caps fans welcome home returning World Cup heroes in Auckland
Tragedy strikes during dune motorbike ride
Lotto winners promise 'random acts of kindness'
Masala restaurants fined for exploiting migrant workers
Crown Lynn pottery museum set to open
New Zealand's most expensive homes for sale
Models used in adverts for homeless charity a 'kick in the guts'
Moko: Hit, kicked, thrown, bitten, stomped and smothered – but prosecutors can't prove couple murdered the boy
Lotto punters strike it lucky - but Powerball still up for grabs
Zilda Williams strips back the botox, boob jobs and touch-ups of glamour modelling
First home buyer angry after Auckland property developer hikes costs by 20 per cent
Small retailers hurt as Auckland CDB rents soar
Study reveals 9 in 10 Auckland children want to walk to school
Sir Peter Snell's singlet raises money for Auckland man's medical treatment
Traffic disruptions following serious crash in north Auckland crash
Marked by their religion – is the threat of homegrown terrorism real?


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Long-time college coach Nick Rapone (ruh-pone) enters his third season with the Cardinals and third year in the NFL after he joined Arizona as defensive backs coach on 2/5/13.
Rapone, a veteran of 36 seasons as a coach, including 30 as a collegiate assistant, joined the Cardinals in 2013 after spending the previous seven years (2006-12) at the University of Delaware as defensive coordinator and defensive backs coach.
Long-time college coach Nick Rapone (ruh-pone) enters his third season with the Cardinals and third year in the NFL after he joined Arizona as defensive backs coach on 2/5/13.
Rapone, a veteran of 36 seasons as a coach, including 30 as a collegiate assistant, joined the Cardinals in 2013 after spending the previous seven years (2006-12) at the University of Delaware as defensive coordinator and defensive backs coach.
Last season, cornerbacks Patrick Peterson and Antonio Cromartie were both selected to the Pro Bowl. It was Peterson's third consecutive Pro Bowl selection at cornerback and Cromartie's third straight Pro Bowl and fourth of his career in his first season in Arizona. The Cardinals defense allowed just 18.7 points per game, the fifth lowest average in the league, while allowing 20 points or fewer in an NFL-high 13 games. Arizona's defense allowed just 299 points, the first time the team has allowed fewer than 300 points in a season since 1994 (267).
With the Cardinals in 2013, Rapone helped a defense that finished as the NFL's sixth-ranked overall unit and forced 30 takeaways, including 20 interceptions which tied for the fifth-best total in the NFL. Peterson made his second consecutive Pro Bowl at cornerback and was also named first-team AP All-Pro.
At Delaware, Rapone was a part of two NCAA national runner-up teams, including the 2010 season when he helped the Blue Hens to a 12-3 record and a share of the Colonial Athletic Association title. For his coaching efforts that season, Rapone was named the 2010 FootballScoop NCAA Division I FCS Coordinator of the Year. That season his defense led the nation in scoring (12.1 ppg), ranked fifth in total defense (280.7 ypg) and was 12th in rushing defense (105.3 ypg). The secondary included four All-CAA performers, including All-American selections Anthony Walters and Anthony Bratton at safety. The Hens also ranked ninth in the nation in passing efficiency (102.7), and the team's 21 interceptions were the third-highest total in the nation at the FCS level.
Rapone helped the Blue Hens to another outstanding season in 2007 when Delaware went 11-4 and advanced to the NCAA Division I FCS title game with quarterback Joe Flacco. The Blue Hens captured the Lambert Cup Trophy as the top team in the East and was named the ECAC Team of the Year.
A native of New Castle, PA, Rapone was an All-State receiver at New Castle High School prior to attending Virginia Tech where he was a four-year letterman for the Hokies (1974-77). While at Virginia Tech, he played with Cardinals head coach Bruce Arians in 1974 when Arians was a senior and Rapone was a freshman. Arians then served as a graduate assistant (1975-76) and running backs coach (1977) while Rapone played for the Hokies.
Rapone began his coaching career as a graduate assistant at the University of Pittsburgh in 1979 where he worked with the secondary for two seasons before serving as defensive backs coach at East Tennessee State (I-AA) from 1981-82. He reunited with Arians as part of his staff at Temple, coaching the Owls secondary for six seasons (1983-88) while also serving as defensive coordinator from 1985-88.
He returned to Pitt as defensive backs coach for four years (1989-92), doubling as defensive coordinator in 1992. Rapone then became the head coach at his alma mater, New Castle High School, for two seasons (1993-94). He returned to the college game in 1995 at then Division I-AA University of Connecticut under head coach Skip Holtz, serving as defensive coordinator and secondary coach for four seasons and helping the Huskies to the I-AA playoffs for the first time in school history in 1998. That squad was ranked No. 7 in the final The Sports Network Top 25 poll and was led by a defense that forced 29 turnovers on the season.
Rapone then returned for his second tenure at Temple and served as defensive backs coach and kickoff coverage coach for seven years (1999-2005). The Owls were one of only eight teams in the nation to rank in the top 20 in total defense in both 2001 and 2002.
He earned his bachelor's degree in Education from Virginia Tech in 1979 and his master's degree in Education from Pittsburgh in 1981. Rapone has two daughters, Johanna and Mary.
Undrafted rookie free agent from Alabama will battle Matt Barkley for roster spot
Cornerback from University of Calgary hoping to turn raw tools into roster spot
Three-day exercise gives first-year players the resources to succeed in the NFL
YouTube agreement will make three of Cards' top games available to all
In secondary, Cardinals have transition after departures of Johnson, Powers
NFL Media's David Carr explains the relationship between QB Carson Palmer and head coach Bruce Arians.
Paul Calvisi talks about offensive coordinator Harold Goodwin's expanding role with the team.
Cardinals wide receiver Larry Fitzgerald is voted the 27th-best player in the NFL by his peers on "Top 100 Players of 2016."
Cardinals safety Tyrann Mathieu is voted the 28th-best player in the NFL by his peers on "Top 100 Players of 2016."


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Featured video and audio clips on Minnesota Timberwolves brought to you by Boston's WEEI Sports Radio.
Kevin McNamara, beat writer for the Providence Journal covering college hoops, joins Nick and Jason to break down the NBA Draft with a particular focus on PC alum Kris Dunn and Ben Bentil.
Boston Celtics select Jaylen Brown with No. 3 overall pick in the 2016 NBA Draft.
It's time to move on. More Celtics Ricky Rubio on Rajon Rondo's return: 'It's hard' Jared Sullinger, Celtics get better of Kevin Love, Timberwolves Danny Ainge's strange summer turns to winter of content Voice of the Brooklyn Nets, Ian Eagle, joins Grande and Max on the Celtics Summer Cooler More ...
Everything's coming up Even ( Brad) Stevens . More Celtics Celtics come up small against Timberwolves ' bigs in blowout loss Blazers blow by defenseless C's Phil Pressey points Celtics to victory Voice of the Brooklyn Nets, Ian Eagle, joins Grande and Max on the Celtics Summer Cooler More from WEEI ...
four games after Rondo's season-ending ACL injury, and the Celtics finished 0-4, including losses to the Bobcats, Timberwolves and Cavaliers . Meanwhile, Stevens is implementing new schemes without the one guy capable of running an effective NBA offense
the fifth overall pick of the NBA Draft by the Minnesota Timberwolves . In order, Joe Smith, Antonio McDyess , Jerry ..... Draft, four teams made selections prior to the Timberwolves : the Golden State Warriors , the Denver Nuggets
matched Phoenix's offer sheet for Eric Gordon and now the Suns have money to spend and their eyes on Mayo and Lee. The Timberwolves may also be in the market for a shooting guard if the Blazers match their offer for Nic Batum. With Brandon Bass, Kevin
Dunn is projected to go to the Denver Nuggets at No. 7, down two from their previous mock that had him going fifth to the Timberwolves . The same draft has the Celtics going with Croatian Dragan Bender with the No. 3 overall pick. For more Celtics news
ESPN reported Monday night that the Timberwolves made it clear to the Bulls that they ..... September, would make sense for the Timberwolves , who recently got a new coach in ..... the league. Although it seems the Timberwolves now have interest in the 2015 Most
third overall pick. Bleacher Report's David Pick reports via twitter that Bender will visit the Celtics, Suns, and Timberwolves in the U.S. The Celtics have already scouted Bender in Israel, where he's playing professionally. Team president of basketball
at her best." — The Warriors' quest for a record 73 wins hit an unexpected obstacle Tuesday in the form of the lowly Timberwolves . Even more surprising, Minnesota's 124-117 overtime victory came in Oakland, where the Warriors had been undefeated
in Monday's 114-90 victory over the Celtics 'NET RESULTS (mobile users, check the website to see the videos): Timberwolves rookie Karl-Anthony Towns finishes with authority against the Suns. A youngster runs on the court to give Knicks star


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Senior Product Owner/Program Manager - API Solutions, Phoenix, AZ
Axway - United States
The Senior Product Owner reports to a Product Line Manager and collaborates closely with development managers, project managers, developers, designers,...
Director Planning & Architecture
Johns Hopkins University - Baltimore, MD
Supervise staff including architects, planners, and landscape architects as well as administrative. Architectural, landscape, and environmental designs,...
CAD Technician
Biohabitats Inc. - Baltimore, MD
Working collaboratively with designers (engineers, scientists, and landscape architects) to develop concept drawings and construction documents for stream and...
Senior Environmental Graphic Designer
Younts Design Inc. - Baltimore, MD
Coordinate with Architects and Interior Designers. Read and understand architectural documents and work within multidisciplinary teams including architecture,...
Architectural Sales Territory Manager
Forms+Surfaces - Baltimore, MD
Ideal candidate will have education and experience (3-5 years) as an Architect, Landscape Architect or Interior Designer who then decided to transition into a...


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- Still to come, The Shield will speak. Back to commercial.
- Back from the break and out comes Seth Rollins, Dean Ambrose and Roman Reigns through the crowd, to the ring.
- Back from the break and out comes Seth Rollins, Dean Ambrose and Roman Reigns through the crowd, to the ring. The Shield talks about breaking down the injustices in WWE since they arrived at Survivor Series. Seth Rollins says not one person has been able to stop them. Rollins says they changed WWE history when they stopped Ryback from becoming WWE Champion. We see a still from Survivor Series. We see stills of The Shield taking out The Rock, Big Show, Sheamus and John Cena. Dean Ambrose says they looked immortality in the face and force fed justice to The Undertaker. Reigns tells Taker to rest in peace. We see a video from SmackDown where The Shield beat up Taker.
Ambrose says justice doesn't care if you're undefeated at WrestleMania, the WWE Champion or what your name is. Rollins says justice has not forgot about Ryback and John Cena. Rollins goes on but 3MB's music hits and out comes Heath Slater, Jinder Mahal and Drew McIntyre on the stage. Slater tells them to shut up. Slater says The Shield has unfinished business with 3MB tonight. Drew says they were seconds from teaching Triple H a lesson but The Shield crashed their party. Mahal says now they're crashing The Shield's party. 3MB surround the ring and enter. A brawl breaks out. The Shield look to be getting the upperhand. Kane's pyro goes off and out he comes with Daniel Bryan. They hit the ring but The Shield retreats through the crowd. Kane and Bryan beat up 3MB and clear the ring of them instead. Kane chokeslams Slater while staring at The Shield. Bryan makes the crowd chant yes and The Shield runs off to the back.
- John Cena is backstage getting his foot taped up. Ryback comes in and says Cena can tape it up all he wants but he's still hurt. Cena says hurt, not injured and he can still go. Cena says he is more effective on one leg than Ryback is two. Ryback says he will take that chance and walks off. Back to commercial.
Dolph Ziggler vs. Kofi Kingston
Cole and Lawler plug Domino's pizza. Out comes World Heavyweight Champion Dolph Ziggler with AJ Lee and Big E Langston by his side. Out next comes his opponent WWE United States Champion Kofi Kingston.
Lots of back and forth to start the match. Kofi goes for SOS but it's blocked. More counters and attempts. We go to commercial mid-match.
Back from the break and Ziggler is in control. Kofi fights out of a hold. Ziggler cuts him off. Ziggler taunts Kofi now. Ziggler with a neckbreaker. Ziggler misses a splash in the corner as Kofi moves out of the way. Ziggler goes back to the attack and beats Kofi down in the corner. Kofi fights him off with kicks and punches. Kofi makes a comeback and nails a big dropkick. Kofi hits the Boom Drop. Ziggler blocks Trouble in Paradise but Kofi catches him. Ziggler counters that with a big DDT. Ziggler with a 2 count. More back and forth. Kofi with SOS for a 2 count. Ziggler misses the leg drop and Kofi nails Trouble in Paradise but AJ puts Ziggler's leg on the bottom rope. Big E helps Ziggler up on the floor but Kofi dives out onto both of them. Kofi brings Ziggler back in and goes to the top. Kofi with a big crossbody for a close 2 count. AJ distracts the referee. Big E gets on the apron but Kofi sends him to the floor. Ziggler rolls Kofi up for 2. Kofi counters with a 2 count. Kofi catches Ziggler again and catapults him into the corner. Kofi misses a big shot from the top rope. Ziggler hits Zig Zag for the win.
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Jimmy "Superfly" Snuka - Who Was Deemed Mentally Incompetent To Stand Trial - Added To WrestleCon
WWE Announcer Working On New Project, WWE - Scooby Doo Trailer, The Brooklyn Brawler (Photos)
Dean Ambrose - Renee Young Swerved Clip, Summer Rae Swimsuit Photo, Bellas Magazine Cover
Former WWE Writer On Vince McMahon Wanting To Make Out With Former Diva On-Screen, Making It Happen
Undertaker Talks Out Of Character In 2002 About Mankind HIAC Match, Taker Vs. Mankind Anniversary
Seth Rollins Trains With Roderick Strong (Photo), Rollins Appearance, Enzo & Cass' RAW Opponents
Jim Ross On If A UFC 200 Loss Hurt's Brock Lesnar's WWE Drawing Power, CM Punk's UFC Debut, Fedor
The Rock In "Fast 8" Photo, ESPN-Owned Site Looks At The Rock's Positively "Absurd" Movie Career
WWE Monday Night RAW Results - The Club And Seth Rollins Stand Tall, Kane Returns, More
WWE Drops Trademark For Top Superstar
Backstage News On WWE NXT Superstars Getting Called Up, More On NXT And The WWE Draft
The Undertaker And Michelle McCool Celebrate Wedding Anniversary (Photo), NXT Wrestler Gets Married
Backstage Simon Gotch WWE Injury Update
News On WWE Having Two World Titles, Luke Gallows And Karl Anderson Talk New Era And Brand Extension
Jim Ross Calls Roman Reigns' WWE Suspension "Embarrassing For The Talent," Talks Working With Reigns
Goldberg Reveals Which Wrestler He Wanted To Put Over During His Streak, WWE Not Being Fun For Him


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Active-duty airman kills self in Target parking lot after...
One dead after Northeast Side highway collision
San Antonio man sentenced to 35 years for murder
Now hiring: Willie Nelson needs you to work for his weed...
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Kevin Durant expected to meet with Spurs' Popovich, Duncan
Family: Texas man battling to keep leg after flesh-eating...
Manziel family was larger than life long before Johnny
Houstonians strip down for the Hot Undies Run
Blood stains, broken glass at dance studio after shooting
Yearly Archive for 2012
Lyons expected to bolster Roadrunners' offensive line
Braden Lyons, an offensive lineman from City College of San Francisco, has committed to play football for the UTSA Roadrunners, his coach in California confirmed Friday. The confirmation came from …
Boerne Champion's McKinney to fortify UTSA offensive line
Boerne Champion offensive lineman Kyle McKinney on Wednesday morning committed to play football for UTSA, Champion coach Danny Threadgill said. "It's a great thing for Kyle and great for UT-San …
El Paso Franklin offensive tackle leaning toward UTSA
The UTSA Roadrunners apparently have become the front-runner in the recruitment of El Paso Franklin offensive tackle Derek Elmendorff, the player's high school coach said Tuesday. Franklin coach Daren …
Blinn safety expected to join Roadrunners in the spring
Safety Tevin Broussard of Blinn Junior College is expected to be a spring semester enrollee at UTSA, a Blinn assistant coach said in an email late Monday night. Broussard is a 6-1, 200-pound …
Linebacker from California commits to Roadrunners
Jens Jeters, a linebacker from Pierce College (Calif.), has committed to play football for the UTSA Roadrunners. Jeters tweeted Monday night that he "just committed to UTSA." He added that, "San …
Triston Wade earns first-team, all conference honors
Safety Triston Wade leads a list of five UTSA football players named on Monday to the All-Western Athletic Conference team. Wade, a sophomore from Tyler John Tyler, made the first team defense. …
C-USA welcomes Middle Tennessee, Florida Atlantic
Middle Tennessee and Florida Atlantic have entered into membership agreements with Conference USA, commissioner Britton Banowsky said in a release Thursday morning. The agreements will begin no later …
Media reports: Middle Tennessee, FAU to Conference USA
Sun Belt Conference members Middle Tennessee and Florida Atlantic are apparently set to announce Thursday that they are joining Conference USA. ESPN.com is reporting that both will link with C-USA to …
Hickey, Coker surprised by C-USA defections
UTSA officials on Tuesday expressed surprise that both Tulane and East Carolina from Conference USA have accepted invitations to join the Big East. "The soap opera continues," UTSA athletic director …
UTSA celebrates on the field after 38-31 victory over Texas State
By Jerry Briggs UTSA Roadrunners fans poured onto the field at the Alamodome Saturday afternoon in celebration of a 38-31 victory over the Texas State Bobcats. A sea of orange engulfed the Roadrunners …


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Million-euro HOK-Elanto bribery case heads to prosecutorThe National Bureau of Investigation says it has completed a massive preliminary investigation into allegations that a former leading member of the business cooperative HOK-Elanto received bribes amounting to one million euros. The results of the ... YLE, 1 month ago
Ex HOK-Elanto official suspected of bribery - Finland Times, 1 month ago
Finland: Million-euro HOK-Elanto bribery case heads to prosecutor - EthiXbase, 1 month ago
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High-tech cheating scandal leads Thai university to cancel exams
LAK HOK, Thailand, May 10 (UPI) -- A university in Thailand cancelled its entrance exams after a small group of students were found using high-tech devices to cheat. A photo from Rangsit University employee Arthit Ourairat showed the combination ...UPI, 1 month ago Thailand student candidates busted for high-tech exam cheating TheStack.com, 1 month ago
All hail Vunivalu, king of the cheapies
CHEAPIES have been everywhere for us this year, but in select positions for the most part — HOK, HFB, 5/8 and FLB. Where we were crying out for a few has been the CTW position (aside from Kerrod Holland). All hail the great Suliasi Vunivalu! ...Perth Now, 1 month ago
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Driftscape, designed by Toronto-based HOK, envisions a mobilized hotel consisting of drone-powered hotel rooms. HOK/Radical Innovation Skift Take: These ideas may seem a bit far-fetched for now, but they point to a future where hospitality can ...Skift, 2 hours ago The Barclay, A NYC Classic, Reopens Travel Market Report, 1 month ago InterContinental New York Barclay Hotel Reopens Following an Extensive $180 Million, 20-Month Renovation PressReleasePoint, 1 month ago New York Barclay Completes Renovation Meetings Focus, 1 month ago
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The American Institute of Architects (AIA) and the Architects Foundation have partnered with architecture firm HOK to research how better design practices can improve public health. Under the terms of a memorandum of understanding, the trio will ...CLAD Global, 1 month ago When Architecture Rivals and Reveres the Art Within Specifier Magazine, 1 month ago AIA and HOK partner to advance Design and Health Research Consortium Building Design Construction, 1 month ago American interior design leader partners with WELL Building Institute to promote health and wellness CLAD Global, 2 weeks ago
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These authors contributed equally to this publication.
Special Issue Paper - Numerical Methods and Applications of Multi-Physics in Biomechanical Modeling
Validation of an open source framework for the simulation of blood flow in rigid and deformable vessels
Version of Record online: 24 JUN 2013
DOI: 10.1002/cnm.2568
Copyright © 2013 John Wiley & Sons, Ltd.
International Journal for Numerical Methods in Biomedical Engineering
Volume 29, Issue 11, pages 1192–1213, November 2013
Additional Information
How to Cite
Passerini, T., Quaini, A., Villa, U., Veneziani, A. and Canic, S. (2013), Validation of an open source framework for the simulation of blood flow in rigid and deformable vessels. Int. J. Numer. Meth. Biomed. Engng., 29: 1192–1213. doi: 10.1002/cnm.2568
Publication History
- Issue online: 5 NOV 2013
- Version of Record online: 24 JUN 2013
- Manuscript Accepted: 16 MAY 2013
- Manuscript Revised: 25 APR 2013
- Manuscript Received: 21 DEC 2012
Funded by
- NSF. Grant Number: DMS-1109189
- NIH. Grant Number: R01 HL70531
- National Science Foundation. Grant Number: OCI-1053575
- Abstract
- Article
- References
- Cited By
- computational fluid dynamics;
- hemodynamics;
- experimental validation;
- fluid–structure interaction
We discuss in this paper the validation of an open source framework for the solution of problems arising in hemodynamics. The proposed framework is assessed through experimental data for fluid flow in an idealized medical device with rigid boundaries and a numerical benchmark for flow in compliant vessels. The core of the framework is an open source parallel finite element library that features several algorithms to solve both fluid and fluid–structure interaction problems. The numerical results for the flow in the idealized medical device (consisting of a conical convergent, a narrow throat, and a sudden expansion) are in good quantitative agreement with the measured axial components of the velocity and pressures for three different flow rates corresponding to laminar, transitional, and turbulent regimes. We emphasize the crucial role played by the accuracy in performing numerical integration, mesh, and time step to match the measurements. The numerical fluid–structure interaction benchmark deals with the propagation of a pressure wave in a fluid-filled elastic tube. The computed pressure wave speed and frequency of oscillations, and the axial velocity of the fluid on the tube axis are close to the values predicted by the analytical solution associated with the benchmark. A detailed account of the methods used for both benchmarks is provided.Copyright © 2013 John Wiley & Sons, Ltd.


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Teddy Wayne's
Unpopular Proverbs
Teddy Wayne is the author of the novels Kapitoil and The Love Song of Jonny Valentine.
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A scalded cat fears cold water—and don't even think about putting Mr. Fluffers into a lukewarm bath, because he'll claw your face. Make sure to feed him twice a day, but alternate the cans; morning's on the left cabinet, night's on the right. My right. Yes. Here's his eye drops—each night, you'll have to hold him down without being, like, aggressive about it, or he'll claw your face, and dispense six drops into each eye or else he's vulnerable to pink eye. If he gets it, you'll basically catch it, too. He wakes up around five, five-thirty, and will start meowing and jumping on the bed and clawing your face, but after you feed him, you can go back to bed, and he won't claw you again till six-thirty, six at the earliest. What else… I think that's it! If there's an emergency, just call us in Thailand anytime using your own phone. No, we don't trim his nails here.
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Wise Guys Free Sports Picks!
Wise Guys Free Sports Picks Record is 133-43-1
Free sports picks are by our top expert TJ Clark.
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Brunel University is offering an MSc in Packaging Technology which can be studied either part- time or by distance learning. more
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Timothy Evans
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IRBsearch LLC
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Pathfinder Society Scenario #5–20: The Sealed Gate (PFRPG) PDF
vs. Monsters PDF
Pathfinder Society Scenario #45: Delirium's Tangle (PFRPG) PDF
Pathfinder Society Scenario #4–12: The Refuge of Time (PFRPG) PDF
The Secrets of Martial Mastery (PFRPG) PDF
Rite Publishing(based on 2 ratings)
Fight with Flair!
Do not just stand there and slug it out with your opponent. Learn to use combat maneuvers! Even if you do not have the feat, you can still try it. You are only going to provoke an attack of opportunity. Hey, didn't that stupid barbarian already use up that dragon's attack of opportunity for the round? You could prevent the dragon from using its breath weapon, or maybe that nasty bite attack. Maybe you want to grapple your opponent, pick him up, and actually throw him into another opponent! In addition, you could pull a rope-a-dope on that charmed friend of yours and then choke or sap him into submission rather than having to kill him. Come and learn at the feet of the Masters of the Arts—learn the Secrets of Martial Mastery.
Author: Steven D. Russell
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Last one to post wins,
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Ancient Lands, Eldritch Secrets, and Vast Riches Await in Pathfinder Adventure Card Game: Mummy's Mask,


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Accounting and management services
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Connect Farmers' Worldwide Inc. (COWAFI)
Better Connections Better Opportunities BACKGROUND COWAFI was established in 2008 in Lira district with aim of engaging rural farmers groups into partnerships to produce crops identified by COFAWI for the different investors based on what is demanded in the market. COFAWI was incorporated...
Child Action Lanka
Child Action Lanka serves over 1500 street and underprivileged children in Sri Lanka. CAL does this through many drop in centres around the island that provide kids with food, clothing education and care. CAL works closely with the communities. It provides them micro credit opportunities and...
Unite for Education (U4EDU)
U4EDU aims to promote the rights to equality and education, with the strong belief that this will enable the poor and working classes to have an equal opportunity in life. Education is an end in itself. Education helps one to understand and claim the full respect of the rights preserved in the...
Kuhamasisha Africa
Kuhamasisha Africa is a Kenyan company that works on business programmes.
Evin School of Management
The Evin School of Management is an organisation in Tanzania that provides organisational development services to the business community.
HELMAR Import & Export Company (Pty) Ltd
HELMAR Import & Export Company (Pty) Ltd is a South African company that aims to provide business advisory services to Micro Small and Medium Enterprises (MSMEs) and implement projects in a range of disciplines,including agribusiness, construction, education and food processing.
Immanuel Business Consulting and Supplies Limited
Immanuel Business Consulting and Supplies Limited is a Kenyan consultancy that works in the area of marketing and development.
CWCC is a professional advisory firm providing a full range of business services in Hong Kong and major cities in mainland China.
Succeed Consult
Succeed Consult is a Ugandan company that offers corporate social responsibility and social accountability training, quality management systems training (ISO 9001:2008) and training in manufacturing operations management.
Sabre Business World Limited
Sabre Business World Limited is a privately owned company is a Zimbabwean company that offers soft skills training in entrepreneurship and business skills development. The company aims to assist in growing the Zimbabwean economy by empowering people through better knowledge of how to do business...


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Methods and systems for conducting live pool and competitive wagering activities
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United States Patent #7942735
Methods and systems for conducting wagers, such as pari-mutuel wagers. In one exemplary embodiment a series of events, such as horse races, dog races, etc., is identified for which a plurality of bettors may each place at least one wager, and a wagering activity thereon is structured as a contest. Bettors may each be provided with a "play money" bankroll for use in wagering, and play against one another competitively to achieve one or more winning outcomes for the contest as defined by the operator. Alternatively, bettors may have their conventional, live wagers entered into the contest. The prize pool for the contest, which may be multi-tiered, is fixed based on the number of participants and allocated to winners independent of the live wager prize pool, thus not affecting odds for the live wager. The contest wagering activity may be run in parallel with live wagering, and utilizing the same wagering system for administration of both. Wagering systems and a wagering network are also disclosed.
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Join us for a lively morning of music from around the world, including new and traditional songs. Clap, dance, and sing to the music!
Groups, please call for reservations.
There is something fun going on at your library every week during the time of the Summer Reading Program.
Upcoming Events
- Asheba
- Saturday, June 25, 2016, 3:00 pmBayview, Bayview Meeting Room
- Six Roses - Jazz Performance
- Wednesday, June 29, 2016, 7:00 pmExcelsior, Excelsior Meeting Room
- Musical Outdoor Storytime
- Tuesday, July 5, 2016, 10:30 am
Upcoming Classes
- Zumba Basics
- Saturday, June 25, 2016, 2:00 pmMission Bay, Mission Bay Program Room
*Funded by Friends of the San Francisco Public Library.


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Tours & Niagara Day Trips
Whether you're a culture vulture, history enthusiast or love food, a variety of fun tours await in Toronto. And take a day trip to the magnificent Niagara Falls.
Find Tours & Niagara Day Trips
Use the filters below to narrow your search.
City Tours – by Boat, Bike, Bus, on Foot or in the Air
There are many fun and efficient ways to see the neighbourhoods and attractions of Toronto in a short period of time.
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Food & Beer Tours
Let your taste buds be your guide with these culinary tours.
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Unique Tours
Fun and quirky ways to tour Toronto.
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Niagara and Region Day Trips
Day trips are a wonderful way to discover the nearby region and there's none more awesome than Niagara Falls. Packed with attractions, dining and adventure, here are some of the ways to enjoy your day trip to the Falls and the Niagara region.
More: Niagara and Region Day Trips.