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The current underwater search for missing Malaysia Airlines Flight MH370, focused on a tight 10 km (6.2 mile) circle of the sea floor, could be completed within a week, Australian search officials said on Saturday.
Malaysia said the search was at a "very critical juncture" and asked for prayers for its success. A U.S. Navy deep-sea autonomous underwater vehicle (AUV) is scouring a remote stretch of the Indian Ocean floor for signs of the plane, which disappeared from radars on March 8 with 239 people on board.
After almost two months without a sign of wreckage, the current underwater search has been narrowed to a small area around the location in which one of four acoustic signals believed to be from the plane's black box recorders was detected on April 8, officials said.
"Provided the weather is favourable for launch and recovery of the AUV and we have a good run with the serviceability of the AUV, we should complete the search of the focused underwater area in five to seven days," the Joint Agency Coordination Centre told Reuters in an email.
Officials did not indicate whether they were confident that this search area would yield any new information about the flight, nor did they state what steps they would take in the event that the underwater search were to prove fruitless.
More than two dozen countries have been involved in the hunt for the Boeing 777 disappeared from radar shortly into a Kuala Lumpur to Beijing flight in what officials believe was a deliberate act.
Weeks of daily sorties have failed to turn up any trace of the plane, even after narrowing the search to an arc in the southern Indian Ocean, making this the most expensive such operation in aviation history.
"It is important to focus on today and tomorrow. Narrowing of the search area today and tomorrow is at a very critical juncture," Malaysian Acting Transport Minister Hishammuddin Hussein told a media conference in Kuala Lumpur, asking for people to pray for success.
Malaysia was asking oil companies and others in the commercial sector to provide assets that might help in the search, Hishammuddin added, after earlier saying more AUVs might be used.
After almost two weeks without picking up any acoustic signals, and long past the black box battery's 30-day life expectancy, authorities are increasingly reliant on the $4 million U.S. Bluefin-21 drone, which on Saturday was expected to have dived to unprecedented depths.
Because visual searches of the ocean surface have yielded no concrete evidence, the drone, with its ability to search deep beneath the ocean surface with "side scan" sonar, has become the focal point of the search 2,000 km (1,200 miles) northwest of the Australian city of Perth. …continued »


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Articles tagged bienvenido
14 Mar 2008 // 4:10 AM
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Today PopMatters launches Moving Pixels, which will analyze gaming in ways that go beyond the product reviews that our multimedia coverage has until now been limited to.READ more
//Mixed media
Colette Carr "Static" (video) (Premiere) // Music
House of Blondes "First of July" (audio) (premiere) // Music
Digisaurus 'No More Room For Love' (EP stream) // Music
Eszter Balint 'Airless Midnight' (album stream) (premiere) // Music
//Pm Picks
PopMatters is on a short summer publishing break. We resume Monday, July 6th.
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"PopMatters is on a short summer publishing break. We resume Monday, July 6th.READ the article

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- Striker Agrees Personal Terms With Chelsea Ahead Of Proposed Move
- Liverpool Deploy Scouts To Watch Tottenham Target As Rodgers Eyes Swoop
- Blues Ready To Battle Arsenal & Man Utd For £52m-Rated Duo
- Chelsea Eye Swoop On Liverpool After Midfielder Rejects New £80k Deal
- Man Utd Ready To Hijack Arsenal's Bid To Land €17m German Star
- Double Injury Boost For Arsenal Ahead Of QPR Game
[Video] Individual Highlights Of Luis Alberto's Superb Hat-Trick Display For U-21′s
Liverpool under-21′s came from 2-0 down to beat Sunderland 5-2 on Tuesday at Anfield thanks to an inspired second-half display from summer signing Luis Alberto.
The 20-year-old arrived on Merseyside from Sevilla in June and has been turning out for the reserves in a bid to impress first team boss Brendan Rodgers and he certainly did that by bagging a hat-trick against the Black Cats.
Rodgers was in the stands to watch the Spanish youngster in action and he may now give him a chance in the first team, particularly after Philippe Coutinho was ruled out for 6 weeks with a shoulder problem.
You can watch match highlights here or watch individual highlights of Alberto's display and all his goals below:
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WATCH: 'The Devil's Carnival: Alleluia!' – TICKETS NOW ON SALE! [Video]
Published: July 7, 2015 in Tech N9ne
ALLELUIA! THE DEVIL'S CARNIVAL is the second installment in a musical-horror-fantasy film series by director Darren Lynn Bousman and writer/actor Terrance Zdunich, the fellows behind the cult smash REPO! THE GENE ...Read more.


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Play Video
Maximus Thor Plays Hide & Go Seek
Posted by Charlie01 on Apr. 29, 2013
Break celebrates 4th of July the American Way: by laying the smack down on ...
With the 4th of July around the corner, we celebrate the most kick-ass USA ...
Dude, are you drunk AND high? Or are you just being PRANKED?!
Posted by Charlie01 on Apr. 29, 2013


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1950 Plymouth Custom 4dr deluxe, Beautiful driver. 85 year old owner must abandon restoration. Moving to Daughter in Whitefish MT. Car will stay in... More
Here is a real time capsule on wheels this 1952 PLYMOUTH CAMBRIDGE 4door sedan is in terrific condition all original with the exception of... More
Body off restoration on rust-free CA car, 1969 dual quad 426 Hemi engine. Built 727 transmission, 9" Currie positrac 355 rear end. Radio heater... More
LMC is proud to offer for sale this wonderful 1957 Plymouth Fury. The Plymouth Fury was produced by Chrysler from 1956 to 1978. The... More
Very original well maintained car that runs and drives perfectly. Other than an aluminum radiator for improved cooling, this car is all stock and... More
1958 Plymouth. Recently completed body-off restoration. Was fitted with a modern 5.7L Dodge Hemi motor with electronic fuel injection and drive-by wire gas pedal.... More
Heres a chance to own a car like one owned by Neil Young. This car is complete, with CA black plates, and ready to... More
1950 Plymouth 2 door fastback Frame off restoration rebuilt engine all new cloth wiring new interior and carpet runs and drives well 65 mph... More
1957 Plymouth Belvedere ConvertibleThe Plymouth Belvedere is a absolutely beautiful car.The Belvedere is a convertible which is very rare because there are only 9866... More
1950 Plymouth Special DeluxeThis Plymouth from 1950 is a really nice classic oldtimer. The 6 cylinder engine runs excellent and the manual gearbox shifts... More
1959 Plymouth Fury 2D Hardtop CoupeThese Plymouth still comes from the time with the beautiful big tail fins that give the car an elegant... More
1957 Plymouth Belvedere 4dr HardtopThe Plymouth Belvedere 1957 has an appearance that is very similar to the Belvedere from 1958 which was used for... More
1956 Plymouth Fury SavoyThis Plymouth Savoy is a very beautiful classic oldtimer. A true American classic car from the 50s with the amazing V8... More
Meet "Reagan". The wonderful and fully restored "demon free" 1959 Plymouth Sport Fury. Reagan's story begins in sunny Arizona, where she led a quality,... More
Plymouth 1952 Cambridge. Runs well, many new parts: carburator, brakes, master cylinder, wheel cylinders. Nice exterior. Seats in good condition. 74,000. Owner/Shop Manual included,... More


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A Springfield man who went on a crime spree last spring has been sentenced in connection with numerous break-ins at businesses in Shelby County.
Robert Eugene Weathers, 40, was sentenced to 15 years in prison on Monday by Shelby County Circuit Judge Charles Hickman on 11 counts of third-degree burglary.
Weathers' crime spree had included Shelby and surrounding counties.
The small exterior structure fire that ignited a wood furnace and the building's contents, Monday afternoon should serve as a reminder to Spencer County residents this winter.
Chief Nathan Nation, of the Taylorsville-Spencer County Fire Department, said extra care should be taken with heating sources.
"We've been lucky so far, but there have been several fire fatalities in the region," Nation said.
Two business owners added their names to those hoping to profit from November's wet vote this week, by publicizing their intent to apply for alcohol sales licenses with the Alcohol Beverage Commission. One hopes to open a packaged beer, wine and liquor store in Taylorsville. The other wants to offer beer sales to golfers.
O'Driscoll's Spirits will be a new venture for Mic-Zee's Video store manager Michaela Russell. After working several years for her father, Mike Driscoll, Russell said she is looking forward to running her own business.
John Riley (R) filed his intent to run for Spencer County judge executive Tuesday afternoon, joining a list of five other candidate hopefuls.
Riley will be the second sitting magistrate attempting to claim the county's highest elected position in the 2010 election. Campbranch Magistrate Bill Drury will be vying for the Democratic ticket along with business owner Carmin Gaines. Riley, magistrate for Elk Creek, will be facing off in the primary against Republicans Bill Karrer and David Hesse.
Superintendent Chuck Adams is somewhat perplexed by the governor's plans to give $30 to $40 million in "excess education funds" to Kentucky school districts – but he will gladly accept Spencer County's share.
"Right now, anything is better than nothing," said Adams, who has seen several cuts to his budget in recent years.
In a celebration of hometown heroes, six Spencer Countians were inducted into the Signature HealthCare Hall of Fame last Tuesday. The second annual event provided an evening of reflection into how seemingly ordinary individuals can positively impact the lives of others.
The Taylorsville-Spencer County Fire Department responded to a working barn fire in the 1000 block of Love Lane in Western Spencer County Dec. 16.
The first unit on the scene found about 75 percent of the building engulfed in flames.
Fire Chief Nathan Nation said the fire originated with a wood stove in the barn.
Three engines and three tankers assisted in putting out the flames.
ROBIN BASS/The Spencer Magnet
Ummm...barbecue. Don't the words just make the stomach growl?
Joel and Susan Solinger were greeted with local officials one recent morning to celebrate the opening of their new business in Elk Creek. Barrell Smoked BBQ is located at 4802 Taylorsville Rd next to Wayne's Farm Machinery. They feature dine-in, carry out and catering services with a full menu of barbecue pork, brisket, ribs and homemade sides.
The family owned business is open Tues. through Sat. for lunch and dinner.
The lunch crowd at the Bluegrass Country Depot in Clay Village enjoyed a visit by U.S. Representative Brett Guthrie (R-Bowling Green) last Tuesday, who dropped by the store on his way to file for re-election for a second term in Congress.
"I came here during my campaign and met some really great people, and they've got good food and good people to eat with and have good conversation," Guthrie said, glancing around at the crowded table.
"Well, he sure is a wonderful talker," said Neal Raizor, as everyone laughed.
Aimee Barr takes her children Lauren, 6, and Dawson, 4, to the Spencer County Public Library at least once a week.
Hardly through the door, Lauren and Dawson will race for their favorite books. Dawson loves 'the dump truck book,' and Lauren has to have Junie B. Jones.
"She likes to read those to me. Sometimes she'll read to Dawson," Barr said. "There have been times when we walk out of there with 10 books, and very rarely do we not read them all."
Copyright © 2015
The Spencer Magnet is your source for local news, sports, events, and information in Spencer County, KY and the surrounding area.


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Worst place we stayed in throughout our Europe trip. Worse than any hostel. Bathroom is tiny - I'm a size 8 & my arm was rubbing off the sink when sitting on the toilet. Walls were filthy. Had to kill mosquitos before we went to bed. Very few plug sockets. The whole 'hotel' smelled really bad. Elevator is tiny too. Location - close to Duomo but hard to find as its down a back street & road right in front of front door with no paths. Breakfast wasn't great not much selection. Would not recommend
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No-Dig Down Under will be returning in 2015 for the 11th conference and exhibition of the Australasian Society for Trenchless Technology (ASTT). The event will be held at the impressive Gold Coast Convention and Exhibition Centre from 8 – 11 September 2015.
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Three major social events, including opening cocktails sponsored by HOBAS, boat cruise and the prestigious ASTT Gala Dinner and Awards Evening sponsored by Ditch Witch.
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A catalyst system comprising (i) a bulky ligand catalyst compound; and (ii) a novel borate activator is active for olefin polymerization. The novel borate contains at least one chelating (divalent) ligand and contains at least one fluorine atom. Preferred borate activators are provided as anilinium or carbonium salts. Highly preferred borate salts contain two perfluorinated alkoxy chelating ligands. The catalyst system may be used to produce polyethylene for "end use" applications such as polyethylene film and molded polyethylene goods.
1. A process for the polymerization of at least one C2 to C8 alpha olefin monomer in the presence of a catalyst system comprising:
(i) a catalyst compound; and
(ii) an activator defined by the formula:
X1 and X2 are selected from the group consisting of O, NR1, S;
Y1 and Y2 are selected from the group consisting of CR2R3, SiR4R5; and
Z is selected from the group consisting of a bond, CR6R7, SiR8R9, NR10, and PR11, wherein each of R1 to R11 is selected from the group consisting of i) a C1 to C20 hydrocarbyl group and ii) a perfluorinated C1 to C20 hydrocarbyl group with the proviso that at least one of Y1 and Y2 contains at least one fluorine atom; and each
L is independently fluorinated alkyl, fluorinated aryl, fluorinated alkoxy, fluorinated aryloxy, alkoxy or aryloxy ligand;
n=0, 2, m=2, 1;
2m+n=4; and
[Cat]+ is a non-interfering cation.
2. The process according to
3. The process according to
4. The process according to
5. The process according to
6. The process according to
7. The process according to
8. The process according to
This invention relates to a novel boron activator for olefin polymerization.
Aluminum alkyls are well known as cocatalysts for conventional Ziegler Natta catalysts. More recently, many new catalysts for olefin polymerization have been invented. These new catalysts are, in general, well defined organometallic compounds with bulky ligands (whereas, in contrast, the prior art Ziegler Natta catalysts are, in general, simple transition metal halides). Numerous cocatalysts or activators have been proposed for these new catalysts, including methyl aluminoxane (or "MAO") and ionic boron activators. These cocatalysts/activators provide high activity but are expensive to synthesize.
An elegant family of alkoxy aluminates are disclosed In U.S. Pat. No. 5,895,771 (Epstein et al.) but the data reported in this patent illustrate that these aluminates are not particularly active.
We have now discovered a simple chelating borate which provides excellent activity for olefin polymerization.
The present invention provides a process for the polymerization of at least one C2 to C8 alpha olefin monomer in the presence of a catalyst system comprising:
(i) a catalyst compound; and
(ii) an activator defined by the formula:
X1 and X2 are selected from the group consisting of O, NR1, S;
Y1 and Y2 are selected from the group consisting of CR2R3, SiR4R5; and
Z is selected from the group consisting of a bond, CR8R7, SiR8R9, NR10, and PR11, wherein each of R1 to R11 is selected from the group consisting of i) a C1 to C20 hydrocarbyl group and ii) a perfluorinated C1 to C20 hydrocarbyl group with the proviso that at least one of Y1 and Y2 contains at least one fluorine atom; and each
L is independently fluorinated alkyl, fluorinated aryl, fluorinated alkoxy, fluorinated aryloxy, alkoxy or aryloxy ligand;
n=0, 2, m=2, 1;
2m+n=4; and
[Cat]+ is a non-interfering cation.
As used herein, the phrase "catalyst system" includes at least one "catalyst compound" and the novel "activator" which characterizes this invention, both of which are described further herein. The catalyst system may also include other components, such as supports, poison scavengers, etc.
As used herein, the phrase "catalyst compound" includes any compound that, once appropriately activated, is capable of catalyzing the polymerization or oligomerization of olefins. The catalyst compound comprises at least one Group 3 to Group 15 atom (preferably a Group 4 to 12 transition metal) or lanthanide or actinide atom, and optionally at least one leaving group bound thereto.
As used herein, the phrase "leaving group" refers to one or more chemical moieties bound to the metal center of the catalyst compound that can be abstracted from the catalyst compound, thus producing a species active towards olefin polymerization or oligomerization.
As used herein, in reference to Periodic Table "Groups" of Elements, the "new" numbering scheme for the Periodic Table Groups are used as in the CRC HANDBOOK OF CHEMISTRY AND PHYSICS (David R. Lide ed., CRC Press 81st ed. 2000).
As used herein, a "hydrocarbyl" includes aliphatic, cyclic, olefinic, acetylenic and aromatic radicals (i.e., hydrocarbon radicals) comprising hydrogen and carbon that are deficient by one hydrogen. A "hydrocarbylene" is deficient by two hydrogens.
As used herein, an "alkyl" includes linear, branched and cyclic paraffin radicals that are deficient by one hydrogen. Thus, for example, a —CH3 group ("methyl") and a CH3CH2— group ("ethyl") are examples of alkyls.
As used herein, an "alkenyl" includes linear, branched and cyclic olefin radicals that are deficient by one hydrogen; alkynyl radicals include linear, branched and cyclic acetylene radicals deficient by one hydrogen radical.
As used herein, "aryl" groups includes phenyl, naphthyl, pyridyl and other radicals whose molecules have the ring structure characteristic of benzene, naphthylene, phenanthrene, anthracene, etc. For example, a C6H5 − aromatic structure is an "phenyl", a C6H4 2− aromatic structure is an "phenylene". An "arylalkyl" group is an alkyl group having an aryl group pendant therefrom, examples of which include benzyl, phenethyl, tolylmethyl and the like; an "alkylaryl" is an aryl group having one or more alkyl groups pendant therefrom, examples of which include tolyl, xylyl, mesityl, cumyl and the like.
As used herein, an "alkylene" includes linear, branched and cyclic hydrocarbon radicals deficient by two hydrogens. Thus, —CH2— ("methylene") and —CH2CH2— ("ethylene") are examples of alkylene groups. Other groups deficient by two hydrogen radicals include "arylene" and "alkenylene".
As used herein, the phrase "heteroatom" includes any atom other than carbon and hydrogen that can be bound to carbon. A "heteroatom-containing group" is a hydrocarbon radical that contains a heteroatom and may contain one or more of the same or different heteroatoms. In one embodiment, a heteroatom-containing group is a hydrocarbyl group containing from 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur. Non-limiting examples of heteroatom-containing groups include radicals of imines, amines, oxides, phosphines, ethers, ketones, oxoazolines heterocyclics, oxazolines, thioethers, and the like.
As used herein, "heterocyclic" refers to ring systems having a carbon backbone that comprise from 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur, unless the heteroatom (non carbon atom) is described.
As used herein, an "kylcarboxylate", "arylcarboxylate", and "alkylarylcarboxylate" is an alkyl, aryl, and alkylaryl, respectively, that possesses a carboxyl group in any position. Examples include C6H5CH2C(O)O−, CH3C(O)O−, etc.
As used herein, "non-interfering" means that the ligand (or cation) being referred to does not interfere with olefin polymerization (i.e. that it does not reduce the activity of olefin polymerization by more than 50% in comparison to a polymerization conducted in the absence of the ligand or cation).
As used herein, the term "substituted" means that the group following that term possesses at least one moiety in place of one or more hydrogens in any position, the moieties selected from such groups as halogen radicals (esp., Cl, F, Br), hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl groups, C1 to C10 alkyl groups, C2 to C10 alkenyl groups, and combinations thereof. Examples of substituted alkyls and aryls includes, but are not limited to, acyl radicals, alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- and dialkylcarbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals, and combinations thereof.
As used herein, structural formulas are employed as is commonly understood in the chemical arts; lines ("—") used to represent associations between a metal atom ("M", Group 3 to Group 15 atoms) and a ligand or ligand atom (e.g., cyclopentadienyl, nitrogen, oxygen, halogen ions, alkyl, etc.), as well as the phrases "associated with", "bonded to" and "bonding", are not limited to representing a certain type of chemical bond, as these lines and phrases are meant to represent a "chemical bond"; a "chemical bond" defined as an attractive force between atoms that is strong enough to permit the combined aggregate to function as a unit, or "compound".
Unless stated otherwise, no embodiment of the present invention is herein limited to the oxidation state of the metal atom "M" as defined below in the individual descriptions and examples that follow. The ligation of the metal atom "M" is such that the compounds described herein are neutral, unless otherwise indicated.
Catalyst Compound
In general, any catalyst compound which is activated by methyl aluminoxane (MAO) is particularly suitable for use In the present invention. An extensive discussion of such catalysts is provided in U.S. Pat. No. 6,720,396 (Bell et al.; assigned to Univation Technologies) and the references cited therein (disclosure to all of which is incorporated herein by reference). A general (non-limited) overview of such catalyst compounds follows. Such catalysts typically contain a "bulky" ligand.
The bulky ligands are generally represented by one or more open, acyclic, or fused ring(s) or ring system(s) or a combination thereof. The ring(s) or ring system(s) of these bulky ligands are typically composed of atoms selected from Groups 13 to 16 atoms of the Periodic Table of Elements. Preferably the atoms are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum or a combination thereof. Most preferably the ring(s) or ring system(s) are composed of carbon atoms such as but not limited to those cyclopentadienyl ligands or cyclopentadienyl-type ligand structures or other similar functioning ligand structure such as a pentadiene, a cyclooctatetraendiyl or an imide ligand. The metal atom is preferably selected from Groups 3 through 15 and the lanthanide or actinide series of the Periodic Table of Elements. Preferably the metal is a transition metal from Groups 4 through 12, more preferably Groups 4, 5 and 6, and most preferably the transition metal is from Group 4.
In one embodiment, catalyst compounds are represented by the formula:
Independently, each LA and LB may be unsubstituted or substituted with a combination of substituent groups R. Non-limiting examples of substituent groups R include one or more from the group selected from hydrogen, or linear, branched alkyl radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight, branched or cyclic, alkylene radicals, or combination thereof. In a preferred embodiment, substituent groups R have up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, that can also be substituted with halogens or heteroatoms or the like. Non-limiting examples of alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, including all their isomers, for example tertiary butyl, isopropyl, and the like. Other hydrocarbyl radicals include fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstituted boron radicals including dimethylboron for example; and disubstituted heteroatom radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide. Non-hydrogen substituents R include the atoms carbon, silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and the like, including olefins such as but not limited to olefinically unsaturated substituents including vinyl-terminated ligands, for example but-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two R groups, preferably two adjacent R groups, are joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron or a combination thereof. Also, a substituent group R group such as 1-butanyl may form a carbon sigma bond to the metal M.
Other ligands may be bonded to the metal M, such as at least one leaving group Q. As used herein the term "leaving group" is any ligand that can be abstracted from a bulky ligand catalyst compound to form a bulky ligand catalyst species capable of polymerizing one or more olefin(s). In one embodiment, a is a monoanionic labile ligand having a sigma-bond to M. Depending on the oxidation state of the metal, the value for n is 0, 1 or 2 such that formula (I) above represents a neutral bulky ligand catalyst compound.
Non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides or halogens and the like or a combination thereof. In another embodiment, two or more Q's form a part of a fused ring or ring system. Other examples of Q ligands include those substituents for R as described above and including cyclobutyl, cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like.
In another embodiment, the catalyst compound is represented by the following formula:
These compounds represented by formula (II) are known as bridged, ligand catalyst compounds. LA, LB, M, Q and n are as defined above. Non-limiting examples of bridging group A include bridging groups containing at least one Group 13 to 16 atom, often referred to as a divalent moiety such as but not limited to at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom or a combination thereof. Preferably bridging group A contains a carbon, silicon or germanium atom, most preferably A contains at least one silicon atom or at least one carbon atom. The bridging group A may also contain substituent groups R as defined above including halogens and iron. Non-limiting examples of bridging group A may be represented by R′2C, R′2Si, R′2Si R′2Si, R′2Ge, R′P, where R′ is independently, a radical group which is hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, substituted chalcogen, or halogen or two or more R′ may be joined to form a ring or ring system. In one embodiment, the bridged, ligand catalyst compounds of formula (II) have two or more bridging groups A.
In one embodiment, the catalyst compounds are those where the R substituents on the bulky ligands LA and LB formulas (I) and (II) are substituted with the same or different number of substituents on each of the bulky ligands. In another embodiment, the bulky ligands LA and LB of formulas (I) and (II) are different from each other.
In one embodiment, catalyst compounds useful in the invention include bridged heteroatom, mono-bulky ligand compounds. These types of catalysts and catalyst systems are described in U.S. Pat. No. 5,057,475.
In another embodiment, the catalyst compound is represented by the formula:
In formula (III) J is a heteroatom containing ligand in which J is an element with a coordination number of three from Group 15 or an element with a coordination number of two from Group 16 of the Periodic Table of Elements. Preferably J contains a nitrogen, phosphorus, oxygen or sulfur atom with nitrogen being most preferred.
In another embodiment, catalyst compound is a complex of a metal, preferably a transition metal, a bulky ligand, preferably a substituted or unsubstituted pi-bonded ligand, and one or more heteroallyl moieties, such as those described in U.S. Pat. No. 5,527,752.
In another embodiment, the catalyst compounds are represented by the formula:
In formula (IV), L and M are as defined above for formula (I). Q is as defined above for formula (I), preferably Q is selected from the group consisting of —O—, —NR—, —CR2— and —S—. Y is either C or S. Z is selected from the group consisting of —OR, —NR2, —CR3, —SR, —SiR3, —PR2, —H, and substituted or unsubstituted aryl groups, with the proviso that when Q is —NR— then Z is selected from one of the group consisting of —OR, —NR2, —SR, —SiR3, —PR2 and —H; R is selected from a group containing carbon, silicon, nitrogen, oxygen, and/or phosphorus, preferably where R is a hydrocarbon group containing from 1 to 20 carbon atoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is an integer from 1 to 4, preferably 1 or 2; X is a univalent anionic group when n is 2 or X is a divalent anionic group when n is 1; preferably X is a carbamate, carboxylate, or other heteroallyl moiety described by the Q, Y and Z combination.
In another embodiment of the invention, the catalyst compounds are heterocyclic ligand complexes where the bulky ligands, the ring(s) or ring system(s), include one or more heteroatoms or a combination thereof. Non-limiting examples of heteroatoms include a Group 13 to 16 element, preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorous and tin. Examples of these bulky ligand catalyst compounds are described in U.S. Pat. No. 5,637,660.
In one embodiment, the catalyst compounds are represented by the formula:
It is also within the scope of this invention, in one embodiment, that the catalyst compounds include complexes of Ni2+ and Pd2+ described in U.S. Pat. No. 5,852,145. These complexes can be either dialkyl ether adducts, or alkylated reaction products of the described dihalide complexes that can be activated to a cationic state by the activators of this invention described below.
Also included as catalyst compounds are those diimine based ligands of Group 8 to 10 metal compounds.
Other suitable catalyst compounds are those Group 5 and 6 metal imido complexes described in U.S. Pat. No. 5,851,945, which is incorporated herein by reference. In addition, bulky ligand catalyst compounds include bridged bis(arylamido) Group 4 compounds, bridged bis(amido) catalyst compounds and catalysts having bis(hydroxy aromatic nitrogen ligands).
It is also contemplated that in one embodiment, the catalyst compounds of the invention described above include their structural or optical or enantiomeric isomers (meso and racemic isomers) and mixtures thereof.
Other catalyst compounds useful in this invention are disclosed in the aforementioned U.S. Pat. No. 6,720,396 (and references therein), reference to all of which is incorporated herein.
Novel Activator
The borate anion is preferably provided in the form of a simple salt represented by the formula:
The borate anion (i.e. [BA]− above) is defined by the formula:
When m is 1, L may be a single, non-interfering divalent ligand.
It is preferred that m=2. When m=1, it is preferred than n=2 and that each L is a monovalent ligand selected from the group consisting of fluorinated alkyl, fluorinated aryl, fluorinated alkoxy, fluorinated aryloxy, alkoxy or aryloxy ligands.
As noted above, it is preferred that m=2—i.e. that the boron contains two divalent chelating ligands. While not wishing to be bound by theory, it is believed that the chelating ligands are more stable under polymerization conditions (i.e. less prone to decomposition) than the analogous monovalent alkoxy ligands of the prior art.
The chelating divalent ligand of this invention must be fluorinated (in that each of Y1 and Y2 must contain at least one fluorine atom). It is highly preferred that each of Y1 and Y2 is perfluorinated (and especially that each of Y1 and Y2 is a perfluorinated, non-cyclic group having from 3 to 5 carbon atoms).
It is most highly preferred that:
m is 2;
each X is oxygen;
each Y is a perfluorinated hydrocarbyl having 3 carbon atoms;
and Z is a bond (and the synthesis of lithio and trityl salts of this most preferred species is disclosed in the examples).
It is most highly preferred that X is oxygen and that each of Y1 and Y2 is defined by the formula:
In general, the activator and catalyst compounds are used in mole ratios of boron (activator) to transition metal of from 0.3:1 to 10:1, especially from 0.8:1 to 5:1.
Polymerization Process
Polymerization processes suitable for this include solution, gas phase, slurry phase and a high pressure process or a combination thereof.
In one embodiment, the process of this invention is directed toward a solution, high pressure, slurry or gas phase polymerization process of one or more olefin monomers having from 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. The invention is particularly well suited to the polymerization of two or more olefin monomers of ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and decene-1.
Other monomers useful in the polymerization process of the invention include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins. Non-limiting monomers useful in the invention may include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene.
In the most preferred embodiment of the process of the invention, a copolymer of ethylene is produced, where with ethylene, a comonomer having at least one alpha-olefin having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8 carbon atoms, is polymerized in a solution polymerization process.
In another embodiment of the process of the invention, ethylene or propylene is polymerized with at least two different comonomers, optionally one of which may be a diene, to form a terpolymer.
In one embodiment, the invention is directed to a polymerization process for polymerizing propylene alone or with one or more other monomers including ethylene, and/or other olefins having from 4 to 12 carbon atoms. Polypropylene polymers may be produced using the particularly bridged bulky ligand catalyst compounds as described in U.S. Pat. Nos. 5,296,434 and 5,278,264, both of which are herein incorporated by reference.
Typically in a gas phase polymerization process a continuous cycle is employed where in one part of the cycle of a reactor system, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization. This heat is removed from the recycle composition in another part of the cycle by a cooling system external to the reactor. Generally, in a gas fluidized bed process for producing polymers, a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer. (See for example U.S. Pat. No. 4,543,399, incorporated herein by reference.)
The reactor pressure in a gas phase process may vary from about 100 psig (690 kPa) to about 500 psig (3,448 kPa), preferably in the range of from about 200 psig (1,379 kPa) to about 400 psig (2,759 kPa), more preferably in the range of from about 250 psig (1,724 kPa) to about 350 psig (2,414 kPa).
The reactor temperature in a gas phase process may vary from about 30� C. to about 120� C., preferably from about 60� C. to about 115� C., more preferably in the range of from about 70� C. to 110� C., and most preferably in the range of from about 70� C. to about 95� C.
Other gas phase processes contemplated by the process of the invention include series or multistage polymerization processes.
In a preferred embodiment, the reactor utilized in the present invention is capable and the process of the invention is producing greater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1,000 lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4,540 Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500 Kg/hr).
A slurry polymerization process generally uses pressures in the range of from about 1 to about 50 atmospheres and even greater and temperatures in the range of 0� C. to about 120� C. In a slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomers and often hydrogen along with catalyst are added. The suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor. The liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane. The medium employed should be liquid under the conditions of polymerization and relatively inert. When a propane medium is used the process must be operated above the reaction diluent critical temperature and pressure. Preferably, a hexane or an isobutane medium is employed.
A preferred polymerization technique of the invention is referred to as a particle form polymerization, or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution. Such technique is well known in the art, and described in for instance U.S. Pat. No. 3,248,179, which is fully incorporated herein by reference. Other slurry processes include those employing a loop reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof. Non-limiting examples of slurry processes include continuous loop or stirred tank processes. Also, other examples of slurry processes are described in U.S. Pat. No. 4,613,484, which is herein fully incorporated by reference.
In an embodiment the reactor used in the slurry process of the invention is capable of and the process of the invention is producing greater than 2,000 lbs of polymer per hour (907 Kg/hr), more preferably greater than 5,000 lbs/hr (2,268 Kg/hr), and most preferably greater than 10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactor used in the process of the invention is producing greater than 15,000 lbs of polymer per hour (6,804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).
Examples of solution processes are described in U.S. Pat. Nos. 6,372,864 and 5,589,555, which are fully incorporated herein by reference.
These solution processes for olefin (co)polymerization are well known in the art. The processes are conducted in the presence of a C5 to C12 hydrocarbon solvent such as pentane, methyl pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, naptha, or mixtures thereof. The solvent may contain chlorinated hydrocarbons. An example of a suitable solvent is ISOPAR E (aliphatic solvent, Exxon Chemical Co.).
The polymerization temperature is typically fro about 30� C. to 350� C., preferably from 80� C. to 250� C. In a preferred process, two reactors in series are used. The first reactor operates at a temperature of from 80 to 180� C. and the second at a temperature of up to 250� C. Preferred operating pressures are from about 2,000 to 4,000 psig (about 14,000 to 28,000 kiloPascals).
Part A: Chelating Borate Synthesis
The sodium salt of the bis(perfluoropinacolato)borate was reported in 1968 (M. Allan, A. F. Janzen and C. J. Willis, Can. J. Chem. 1968, 46, 3671). A new synthesis (described generally by the following three formulae) is reported as follows.
LiOC(CF3)2C(CF3)2OLi: n-BuLi (7.75 mL, 12.4 mmol) was added dropwise to a pr oled mixture of hexafluoro-2,3-bis(trifluoromethyl)-2,3-butanediol (perfluoropinacol) (2.07 g, 6.19 mmol) in pentane. The reaction became turbid, which was stirred overnight and filtered. The solid was washed with pentane and was dried under vacuum. Isolated 1.9 g, 89% yield, analysis by Proton Nuclear Magnetic Resonance ("NMR") (1H NMR (THF-d8)) lacked the OH peak at 8.21 ppm (singlet). Analysis by fluorine NMR showed 19F NMR (THF-d8, with C6F6 capillary insert)-70.45 ppm (singlet).
Li(OEt2) B[OC(CF3)2C(CF3)2O]2: LiOC(CF3)2C(CF3)2OLi (1.02 g, 2.96 mmol) was dissolved in ether and cooled to −78� C. To this, boron trichloride (8.45 mL, 0.174 M solution in ether) was added dropwise. After warming up to room temperature overnight with constant stirring, a white precipitate was present. The solvent was evaporated under vacuum and the resultant solid was extracted with hot toluene. The toluene solution was filtered when hot and the filtrate was chilled at −40� C. The white crystalline solid was separated from toluene by decantation, washed with pentane and was dried under vacuum. 19F NMR in THF-d8 showed the compound was pure at this stage. Sublimation at 75� C., 80 mtorr gave X-ray quality crystals. 1H NMR (THF-d8) 1.11 ppm (triplet, 6H), 3.38 ppm (quartet, 4H). 19F NMR (THF-d8, with C6F6 capillary insert)-68.41 ppm (singlet).
As shown in
[Ph3C]+[B{OC(CF3)2C(CF3)2O}2]−: Trityl chloride (0.114 g, 0.409 mmol) was added to Li(OEt2) B[OC(CF3)2C(CF3)2O]2 (0.306 g, 0.405 mmol) in dicholoromethane. Reaction immediately turned bright yellow in color. After being stirred at room temperature for 5 hours, the reaction was filtered to remove LiCl. The yellow filtrate was pumped to dryness to give crystalline solid (in quantitative yield). 1H NMR (CD2Cl2) 7.9 ppm (broad multiplet). 19F NMR (CD2Cl2, C6F6 capillary insert)-68.50 ppm (singlet).
An Oak Ridge Thermal Ellipsoid Plot (or "ORTEP") diagram which illustrates the solid-state structure of the lithio salt is provided as
Important bond lengths and bond angles are reported in Table A.1.
All the polymerization experiments described below were conducted on a continuous solution polymerization reactor. The process is continuous in all feed streams (solvent, monomers and catalyst) and in the removal of product. All feed streams were purified prior to the reactor by contact with various absorption media to remove catalyst killing impurities such as water, oxygen and polar materials as is known to those skilled in the art. All components were stored and manipulated under an atmosphere of purified nitrogen.
All the examples below were conducted in a reactor of 71.5 cc internal volume. In each experiment the volumetric feed to the reactor was kept constant and as a consequence so was the reactor residence time.
The catalyst solutions were pumped to the reactor independently and there was no pre-contact between the activator and the catalyst. Because of the low solubility of the catalysts, activators in xylene and methylaluminoxane (MAO) in cyclohexane, solutions were prepared in purified xylene. The catalyst was activated in situ (in the polymerization reactor) at the reaction temperature in the presence of the monomers. The polymerizations were carried out in cyclohexane at a pressure of 1,500 psi. Ethylene was supplied to the reactor by a calibrated thermal mass flow meter and was dissolved in the reaction solvent prior to the polymerization reactor. Under these conditions the ethylene conversion is a dependent variable controlled by the catalyst concentration, reaction temperature and catalyst activity, etc.
The internal reactor temperature is monitored by a thermocouple in the polymerization medium and can be controlled at the required set point to +/−0.5� C. Downstream of the reactor the pressure was reduced from the reaction pressure (1,500 psi) to atmospheric. The solid polymer was then recovered as a slurry in the condensed solvent and was dried by evaporation followed by oven drying before analysis.
The ethylene conversion was determined by a dedicated on-line gas chromatograph by reference to propane which was used as an internal standard. The average polymerization rate constant was calculated based on the reactor hold-up time, the catalyst concentration in the reactor and the ethylene conversion and is expressed in l/(mmol*min). Average polymerization rate (kp)=(Q/(100−Q)).times.(1/[TM]).times.(1/HUT), where:
Q is the percent ethylene conversion;
[TM] is the catalyst concentration in the reactor expressed in mM; and
HUT is the reactor hold-up time in minutes.
A series of ethylene homopolymerizations were then conducted using tri(tertiary butyl) phosphinimine titanium dimethyl (CpTiNP(tBu)3Me2, wherein tBu is tertiary butyl and Me is methyl) as the catalyst compound and the trityl salt of the chelating borate from Part A (i.e. [Ph3C]+[B{OC(CF3)2C(CF3)2O}2]−) as the activator.
A commercially available MAO (MMAO-7, from Albemarie) was used to scavenge poisons. A hindered phenol (2,6-di-tertiary butyl-4-ethyl phenol) was added to the MAO at an Al/OH ratio of about 3.3/1. The MAO was added to the polymerization reactor so as to provide an aluminum concentration of about 14.5 micromoles per liter for experiments 14 and about 6.3 micromoles per liter for experiment 5. (It will be appreciated by those skilled in the art that MAO is (itself) an activator for bulky olefin polymerization catalysts. However, the concentrations of MAO used in these experiments were not high enough to provide commercially useful rates of polymerization, given the impurity levels in the monomers and solvents used in these experiments.)
Catalyst and activator concentrations for experiments 1 to 5 are reported in Table B.1.
The total solution feed rate to the reactor was about 26 milliliters per minute for all experiment, with an ethylene flow of about 1.0 grams per minute. As shown in Table 1, ethylene conversions of between 80.9 and 97.9% were observed. A Kp (polymerization constant, as defined above) of 30,800 was observed for experiment 4 which illustrates the excellent performance of the activator used in the process of this invention.
The data in Table 1 show that the activator of this invention did not function in a "stoichiometric" manner under the polymerization conditions of these experiments (i.e. the activity increased as the boron/titanium ratio was increased from 1/1 to 3/1 in experiments 1 to 4).
In experiment 5, the concentration of MAO in the reactor was reduced but the molar B/Ti ratio was increased to 4/1. The polymerization activity of experiment 5 was observed to decrease (in comparison to experiment 4). This may indicate that the level of MAO was insufficient to scavenge the impurities/poisons in the monomers/solvent (or alternatively, it may indicate that the activity may be maximized by optimizing a boron to MAO ratio).
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SEC Wants 'Level Playing Field' Regarding Camps, Transfers
The Southeastern Conference wants a level playing field.
Former Duke Guard Rasheed Sulaimon Transferring To Maryland
Former Duke guard Rasheed Sulaimon will play his final season at Maryland.
Dantonio On Rivalry With Michigan: 'It Is As It Is'
Michigan State head coach Mark Dantonio has never shied away from fanning the rivalry flames between Michigan State and Michigan.
No. 6 Wisconsin Rallies To Beat Michigan State 80-69 In OT
Michigan State led 57-46 after going on a 17-5 run midway through the second half, only to have Wisconsin come back.
Spartans Rally Past Maryland, 62-58, To Reach Big Ten Championship Game
Travis Trice scored 20 points as Michigan State rallied to beat No. 8 Maryland, 62-58, on Saturday in the Big Ten semifinals.
Michigan State Beats Ohio State, 76-67, To Advance To Big Ten Semifinals
Travis Trice scored 15 of his 18 points in the second half as the Spartans (22-10) advanced to the Big Ten semifinals for the fifth straight year.
Dawkins Scores 31, Michigan Beats Rutgers, 79-69
The Wolverines (15-15, 8-10 Big Ten) finished a disappointing regular season on a positive note, winning for only the second time in their last nine games.
Michigan State Holds Off Indiana's Late Rally, 74-72
The Spartans (21-10, 11-6) have won two straight and six of eight as they try to earn the No. 3 seed in the Big Ten tournament.
No. 6 Wisconsin Wins Big 10 Title By Beating Minnesota 76-63
Wisconsin wasn't about to let up after clinching at least a tie for the Big Ten title last weekend.
No. 5 Wisconsin Beats Michigan State 68-61
No. 5 Wisconsin clinched at least a share of the Big Ten regular-season title with a 68-61 victory Sunday over Michigan State.


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- Kevin Seifert, NFL Nation
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GREEN BAY -- Let's hit a few quick items as the Packers hold on for a 28-26 victory:
What it means: The Green Bay Packers were on the ropes for most of the second half because their defense couldn't get off the field on third down, leading to a tremendous time of possession deficit and few chances for their offense. Oh, and the Lions played a rugged and spirited game as well. The Lions converted 10 of 17 third down attempts and held the ball for 37 minutes and 37 seconds. But ultimately they lost their 19th consecutive regular season game in the state of Wisconsin because the Packers ran off the final 6:32.
Run-down: Converted fullback John Kuhn did exactly what you would hope he could do in the fourth quarter: Help the Packers run down the clock in a close game. I had him for 34 rushing yards [updated] on the final possession, which also included a smart 16-yard run from quarterback Aaron Rodgers. In this league, the one time you need a powerful running game is at the end of the game. And for 6:32, at least, the Packers had one.
Tomorrow's talker: Lions quarterback Shaun Hill threw for 331 yards, completing 34 of 51 passes, which are certainly nice numbers. But Hill also showed his mobility by rushing for 53 yards, including a 40-yarder -- no, that's not one of my many typos -- in the third quarter. Hill took advantage of a wide-open middle of the field to convert a 3rd-and-6 -- and then some. Some people probably forget that Hill often ran the option at the University of Maryland.
Still kicking: Lions place-kicker Jason Hanson was short on a 55-yard attempt just before halftime but drilled four field goals, including conversions from 52 and 49 yards.
What's next: The Packers play at the Washington Redskins and the Lions host the St. Louis Rams. Both games are next Sunday.
For Lions to be elite, it starts with Matthew Stafford
2dBen Goessling
NFC North Q&A: What would it take to supplant the Packers in the division?
3dMichael Rothstein
Lions' defensive line, other than Haloti Ngata and Ziggy Ansah, are unknowns
8dMichael Rothstein
Vikings will be thorough with Trae Waynes
9dBen Goessling
Rapid Reaction: Packers 28, Lions 26


text: Dzhokar Tsarnaev / FBI Photo Tsarnaev Due In Court Thursday By Associated Press December 18, 2014 Boston Marathon bombing suspect Dzhokhar Tsarnaev has not been seen in public since he was arraigned on 30 federal charges in July 2013, when he still bore signs of the bloody standoff with police that led to his capture and the death of his older brother, Tamerlan Read More|Comment Category: Articles, Crime, News, Southcoast News Tags: 260 injured, Boston Marathon Bombings, Defense Attorneys, Federal Court, pre-trial conference, Tamerlan, Three Dead, tsarnaev Send to a friend! Share on Facebook Share on Twitter Pin it! Reddit This! Share on Tumblr!


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Kickboxer Records Brutally Vicious Knockout … of Himself [VIDEO]
This guy is definitely not ready for UFC, MMA or any other acronym-based organization that endorses extreme fighting.
This guy is definitely not ready for UFC, MMA or any other acronym-based organization that endorses extreme fighting.
Baseball has always had its fair share of quirky characters and this promising prospect is doing his part to keep that tradition.
The man known for the four corners offense is now known for the $200 gift.
Hopefully, Nigel Hayes' timing is better the next time he's on the court.
The last sign up for Lapeer Sharks Youth Football and Cheer is this Sunday March 29, from 3-6 pm at River Ridge Mobile Home Park club house in Lapeer located at 25 Pine Ridge Drive. Lapeer Sharks football is open to 6-12 years of age and cheer 4-12. The cost is $125 for cheer and football ages 7 and under and $175 for football 8-12. Everyone gets awesome Shark jersey with their name on it to keep.
March Madness has more than its fair share of memorable moments. Heck, memorable moments are what make March Madness so irresistible.
Charles Barkley usually gets attention for what he says, not for what he wears. Or, more precisely, for what he doesn't wear.
Sixteen men's college basketball teams remain hopeful of making the 2015 Final Four in Indianapolis. Regional semifinals are set for Thursday and Friday, with the winners playing in the regional finals on Saturday and Sunday, respectively. Here's a preview of the Sweet 16 matchups.
March Madness is a time for the improbable upsets and a chance for the best of the best to rise to the occasion. Sadly, it's also a time for several schools to watch from their couches.
We are smack in the middle of the phenomenon known as March Madness where the titans of the sport duke (not Duke) it out for the title of national champion, as a field of 68 will be whittled down to one.
RayC's Harley-Davidson of Lapeer Relay For Life Team and Polar Palace Arena present 5th Annual Guns & Hoses charity hockey game at Polar Palace in Lapeer on Saturday, March 28th at 6pm.
College basketball fans have spent most of the last week gorging themselves on a buffet of hoops action, as the NCAA tournament field went from 68 to 16. Here's what we've learned.


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Then all we would need is a "reformer" willing to carry through.
But so has President Obama, and we should expect him to nominate a man who will carry through on his commitment.
Can we expect that to carry through as the theme of the season?
early 14c., from Anglo-French carier "to transport in a vehicle" or Old North French carrier "to cart, carry" (Modern French charrier), from Gallo-Romance *carrizare, from Late Latin carricare, from Latin carrum (see car).
Meaning "take by force" is from 1580s. Sense of "gain victory in an election" is from 1610s. Of sound, "to be heard at a distance" by 1896. Carrying capacity is attested from 1836. Carry on "continue to advance" is from 1640s; carryings-on "questionable doings" is from 1660s. Carry-castle (1590s) was an old descriptive term for an elephant.
c.1600, "vehicle for carrying," from carry (v.). U.S. football sense attested by 1949.
[fr the 1920s phrase carry iron, ''to be armed'']


text:
Last Dogma - Crowning of our Mother - Dr. Miravalle: Mcasts120
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Uploaded by AirMaria on Jan 12, 2012
In this episode Dr. Mark Miravalle continues from the previous episode on the same message from the Lady of All Nations (Oct 11, 1953). After the messages cease, the great work will begin of Crowning Our Lady by proclaiming the Dogma of Mary Coredemptrix, Mediatrix, and Advocate and so prevent these worldwide calamities. This proclamation will be brought about by praying the Prayer to Our Lady of All Nations which directly asks to bring these things about. To get a prayer card for the prayer of the Lady of All Nations: Call 740-937-2277 email us at"¦ email@example.com, or Write to us.. 313 High St., Hopedale, OH 43976 To ask questions regarding Mary, email Dr Mark Miravalle: firstname.lastname@example.com Ave Maria! To Download Audio go to http://airmaria.com?p=19737
Blessed Virgin Mary
All Nations Lady
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