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About John Brennan
John Brennan has been covering sports business — with a focus on the Meadowlands Sports Complex — since 2002 and has worked for The Record since 1983.
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John Brennan on sports business news, including horse racing and casinos
Category Archives: Red Bulls
Heineken signs deals with Red Bulls, NYC FC
Heineken today announced partnership agreements with the New York Red Bulls, Yankee Stadium expansion team New York City FC, and five other Major League Soccer (MLS) clubs starting January 1. The other are the Chicago Fire, Columbus Crew, D.C. United, … Continue reading
Where to watch U.S.-Germany World Cup soccer in North Jersey
We posted colleague Andy Vasquez's excellent list of North Jersey soccer-centric bars (and some in that big 'burb in that other state,too) before the World Cup started – now it's time to bring it back on the eve of Thursday's … Continue reading
Cosmos win battle of New York vs New Jersey over Red Bulls, 3-0
We'll pass along the review from the victors last night, after you check out this context story here: "The New York Cosmos defeated the New York Red Bulls, 3-0, Saturday night at Shuart Stadium behind two goals from forward Mads … Continue reading
North Jersey hot spots to watch the U.S. World Cup game vs. Ghana Monday
The U.S. begins its rugged World Cup soccer schedule on Monday at 6 p.m. against Ghana – the same African nation that bounced them out of the last two World Cups. Where in North Jersey is a good place to … Continue reading
NYCFC Major League Soccer expansion team reportedly to play first three seasons at Yankee Stadium
New York City F.C., an expansion Major League Soccer franchise that joins the league next March for the 2015 season, will announce next week that it will play its first three seasons at Yankee Stadium, according to The New York … Continue reading
Red Bulls valued at $114 million by Forbes
Forbes today came out with its first Major League Soccer team valuations since 2008, and the valuations range from $64 million for Chivas USA to $175 million for the Seattle Sounders. According to the story (click the link for more), … Continue reading
Jersey fresh: Red Bulls fans to be paid to not be obscene, report says
Even back in their days as the MetroStars in cavernous Giants Stadium, the New Jersey Major League Soccer franchise always has had a hardy band of supporters who stuck with the team through thick and – well, mostly thin. They … Continue reading
Shades of 2006: Red Bulls criticized, again, for not having "New Jersey" in their name
State Assemblyman Patrick Diegnan of Middlesex County has announced that since New York City has been announced as the home to a 20th Major League Soccer franchise, it's high time that the Red Bulls be called "New Jersey" and not … Continue reading
breaking: Manchester City, Yankees teaming up to create new MLS team, NYCFC
Major League Soccer Commissioner Don Garber announced on Tuesday that Manchester City FC and the New York Yankees have teamed up to create the league's 20th team. The new team will be named New York City Football Club (NYCFC) and … Continue reading
Cosmos – from the Meadowlands back to Long Island, after all these years?
[updates with notes from Wednesday's formal press release] A state Senator from Long Island on Tuesday announced that the New York Cosmos – very much a Meadowlands Matter from 1976-84 at Giants Stadium – were among the potential developers of … Continue reading


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Crude-oil futures fell in Asia as fears about additional Middle Eastern supply constraints subsided after Saudi officials denied reports of a pipeline explosion.
Crude-oil futures fell in Asia as fears about additional Middle Eastern supply constraints subsided after Saudi officials denied reports of a pipeline explosion.
Brent crude oil futures sank more than 2% on Monday, as concerns of an imminent strike on Syria eased, and traders reduced positions that had reflected fears of oil supply disruption in the Middle East.
Brent crude oil sank to its lowest mark in one week, narrowing its premium over the U.S. crude oil contract which did not fall by as much.
Professor Jim Hamilton nailed it again when he wrote that the OPEC announcement was "largely irrelevant".From the NY Times: Saudi Arabia Defies OPEC and Raises Oil Output
One can see that while the traditional 6:00 AM USDJPY buy program is just duying to resume aggressive upward momentum ignition, futures are still leery and confused by the recent post-open high beta selloffs. Then again, things like yesterday's ridiculous no news 3:30pm ramp happen and confused them even more just as momentum is about to take a downward direction.
Global oil demand in 2014 will be higher than previously forecast, after consumption in the U.S. rebounded to its strongest level in five years, the International Energy Agency said.
As oil production swells, demand falters and prices slide, the global oil market appears on the verge of a pivotal shift from an era of scarcity to one of abundance.
Oil prices have fallen as much as 20% since June, despite a host of rising supply risks, leading more investors and traders to consider whether 2015 is the year in which the U.S. shale oil boom finally tips the world into surplus.
Brent crude fell below $108 per barrel (bbl) following a one-day humanitarian truce between Hamas and Israel. Similarly, West Texas Intermediate (WTI) also hit its lowest point in the week on the back of rising gasoline inventories.
As of 7:05 am EDT, front-month futures of Brent crude were down 0.87% to $107.46 on the International Commodity Exchange (ICE). Meanwhile, front month future of WTI is down 0.6% to $101.48.
Late yesterday, after Nobel peace prize-winning president Obama revealed his latest military incursion, years of pent up can-kicking almost caught up with futures, which dared to tumble by a whopping 0.7%, a move which hit Europe far more than the US, and shortly after Europe's open, the Euro Stoxx 50 Index dropped 10% from its 2014 high, marking an official correction in Europe where the Dax continues to be the key risk indicator, and which dropped as low as 8,903 before recovering to a drop of only 0.9% while German Bunds continues to print record highs day after day on f
HONG KONG (Reuters) - Brent crude futures climbed near $100 a barrel on Monday and Asian stocks fell, hit by fears of unrest throughout the Middle East sparked by deadly protests in Egypt.
Bullfax.com - Market News & Analysis 2008-2011 Contact Us | About Us | Terms & Conditions

subset: commoncrawl


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Miguel Torres said the Tristar Gym where he's gone for virtually every fight camp in his recent career is usually packed.
These days, it's a traffic jam. He estimates there are at least five fighters training for the upcoming UFC 154, which takes place Nov. 17 in Montreal, and another 10 fighting in gym head Firas Zahabi's new event 13 days later. Another 10 or 12 are competing elsewhere.
Hence, Zahabi wasn't available to corner Torres for his next fight, which takes place Saturday at read news >>
With Saturday's successful World Series of Fighting debut show, the organization has its first fight for its second offering.
As expected, with an upset win over former WEC champ Miguel Torres, Marlon Moraes now will meet fellow bantamweight Tyson Nam at WSOF 2.
WSOF 2 is likely to take place in late January in Las Vegas, though a date and venue haven't been finalized.
read news >>
Miguel Torres still is signing the praises of trainer Firas Zahabi eight months after he packed up his things and went to work with him at Tristar Gym in Montreal.
Torres, a former WEC bantamweight champion who makes his UFC debut Saturday at UFC 126, said it took but 15 minutes for Zahabi to win him over, and the trainer has influenced not only his fighting philosophies but his personal ones, as well.
But fighting is what he's here to do, and Torres said the most important of Zahabi's c read news >>
Legacy Fighting Championship has added UFC, WEC and WSOF veteran Miguel Torres to its kickboxing roster. read news >>
Pablo Alfonso enters today's WSOF 11 event with a three-fight winning streak, but what is likely his most impressive and important victory to date came in his most recent bout.Filed under: News, Videos, WSOF read news >>
WSOF contender Pablo Alfonso tells Bloody Elbow that his win over Miguel Torres was just the beginning. WSOF 11, set for July 5th at Daytona, Florida, has already undergone a series of matchmaking changes, and has lost the allure of its original line up, which was to feature welterweight champion Rousimar Palhares defending against fellow former UFC veteran Jon Fitch. One fight on the main card which is flying under the radar is the opening scrap between former TUF contestant Cody 'Bam Bam' Boll read news >>
It appears that World Series of Fighting will make good on its promise to book Miguel Torres once again. Now it's just a question of who his opponent will be. read news >>
Bantamweight Miguel Torres' recent bust for marijuana possession hasn't deterred his promoter's plans for his career. read news >>
MMAjunkie.com Radio today welcomes to the studio WSOF 1 fighters Miguel Torres, Anthony Johnson and Gesias "JZ" Cavalcante. Travis Bartlett also calls in.
We also talk to RFA executive Ed Soares and MMA fan/comedian Joey "CoCo" Diaz. We're also giving away tickets to RFA 4, WSOF 1 and Diaz's comedy show in Ontario, Calif.
MMAjunkie.com Radio airs from noon to 2 p.m. ET (9-11 a.m. PT) live from Mandalay Bay Resort & Casino in Las Vegas. Listen to and watch a video stream of the two- read news >>
Miguel Torres' second release from the UFC immediately brought speculation that the fighter's tweets had again gotten him in trouble.
But Torres today told MMAjunkie.com Radio that he's a little smarter than that.
"I thought that was kind of funny that (people would think) I would make the same joke," Torres said. "That's what people want to say, that's what people want to think, (but) I just know that I'm fighting for the World Series of Fighting."
read news >>
World Series of Fighting (WSOF) today
officially launches its efforts to become
Las Vegas' newest successful
MMA promotion.
And it will
announce that former WEC bantamweight champion
and four-time UFC veteran Miguel Torres will
headline its first major show, a person
familiar with the deal told USA TODAY
Sports and MMAjunkie.com.
The promotion is expected to reveal
the headliner at a news conference today in Las Vegas.
read news >>


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See Didn't i Promise To Giveaways Even Tho Im Busy
Comment And Get[Closed Winner Anounced]Out of everyone who comments below 1 Person Gets A Chance To Win 7
THE WINNER IS : Forgotton-Souls
Get 10 Points For First 11 CommentersFeatured User : Fluka
Out Of First 11 Commenter's 1 Lucky Dude Will Get 10 (tomorrow I Will Give The Points Too Lazy To Transfer It From My Main Account To This One Right Now)
First Make Sure To Leave A Comment Below XD
1- Fav Stuff From The Featured User
2-Leave A Comment On Her Work
3-One Person Out Of The First 11 Comenters Will Get 10 Points
4-Admit These Rule's Are Interesting :3
100 points giveaway Just [Closed]Yeah so just comment below to participate and one lucky winner will get 100
-i'd really appreciate if you made a journal about this giveaway its not compulsory but will help a lot
Guys please help my friend
-Guys my friend ethereal--studio has hosted a contest in his group here :anime-fanx.deviantart.com/jour…
- he has only got one contest entry for the contest he hosted guys please help out in the contest by joining it
-as a promote i will give 1000 to first place winner XD so go join it
Introducing New Kind Of Giveaways !!!As The Title Says Im Going To Introduce New Kinds Of Giveaways Below Is The List Of Em !!
First Comment First Get
In These Kinds Of Giveaways I Would Upload A Journal Saying The First Person To Comment On It Will Get Something... Comment On It And You May Win About 10 to 100 Or Other Amazing Prizes
First Answer First Get
In These Kinds Of Giveaways I Would Post A Journal Asking People Some Questions The First Person To Answer The Questions And Send The Correct Answers In A Note To Me Will Get 5 to 100
The Last Comment I See Gets It
In These Kinds Of Giveaways I Would Post A Journal And After A Certain Period Of Time Example About Thirty Minutes Later I Will Check Who Has Given It The Newest Comment And He/She Will Get 5 to 100
Bored And Want To Listen To Som
Guys Im Stupid !Guys I'm Stupid I Have More Than 10000 + Points And I Dont Have A Premium Membership Can You Guess Why ?
FREE ! commission for you hey guys just put a link to your OC's below and :iconethereal--studio: will draw one lucky guys OC for him for Absoulutely FREEEE !
-So just put a link to your OC's Below
6k Point Giveaway Winner AnnouncementHere Are The Winners
1st- ethereal--studio 4000
2nd- 1000 - Winner Requested To Be Anonymous ( i can see why .... he didnt wont beggers :3 )
3rd-Hetalia-AnimeFTW 50
4th-Fluka 50
5th-micchan-star 50
6th-Flomixi 50
Guys Just Because You Won It Does Not Mean You Have To Delete The 6k Giveaway Journal ( This Means You ethereal--studio )
500 Point Giveaway #14: May (CLOSED)Winners
200 points
50 points
10 points
How to participate:
1. Add this journal to your favs
2. Write a new journal about this giveaway, and include a Mention of me so that I receive a notification of your journal.
3. Include what I do at dATrade. For example:
:icondatrade: is holding a 500 point giveaway! http://fav.me/d7h98s6
At :devdatrade:, you can donate points for an easy way to receive watches, llamas, favs, comments, and critiques!
10 points = 5 critiques / 10 comments / 10 watches / 40 llamas / 50 favs
Go check it out today!
The Prizes:
There will be
Points and Premium Membership Giveaway! (CLOSED)So my birthday is coming up and I keep getting asked what I'd like to do for it...
Instead of expecting a present from someone,
I'm going to give away a 3 Month Premium Membership and 1000 Points because I like doing nice things for others~!
So here goes the prizes!:
One will win a 3 Month Premium Membership! :iconlawooplz:
One will win 400 Points!
One will win 300 Points!
One will win 200 Points!
One will win 100 Points!
You do NOT have to watch+ me, but I'd be terribly glad if you did ;u; <3
(and if you did you'll be updated with other future giveaways!)
1. Simply fave this journal for a number,
2. Make a journal about this giveaway to spread the word around,
leave a link to the journal about this giveaway here on this journal and leave a friendly comment stating you would like to enter for the chance to win!
Free Gift Commissions :> Since I have hit a large amount of pageviews and watchers in a short span of time, I have decided to open a few slots for free commissions.
I will do anything from journal skins, to literature, to drawings... You name it, and I can do it!
3 Month Premium Membership and Outfits Raffle!Thanks for joining everyone! Here are the winners, congratulations!!!
GRAND PRIZE goes to Hinako29!!!
FIVE OUTFIT PRIZES goes to : TheShadowEmpress , MissKirkland15, kadeox , lauraypablo and
500 Point Giveaway #13 (Closed)Winners
200 points
50 points
10 points
How to participate:
1. Add this journal to your favs
2. Write a new journal about this giveaway, and include a Mention of me so that I receive a notification of your journal.
3. Include what I do at dATrade. For example:
:icondatrade: is holding a 500 point giveaway! http://fav.me/d7dxyqi
At :devdatrade:, you can donate points for an easy way to receive watches, llamas, favs, comments, and critiques!
10 points = 5 critiques / 10 comments / 10 watches / 40 llamas / 50 favs
Go check it out today!
The Prizes:
There will be a total of
May 300 points Giveaway Winners!The winners are:
Congratulations, each will receive 100 points!
Hello everybody, time for another point Giveaway!
I´ll give 100 points to 3 lucky winners.
The rules are simple, as always:
- Add this Journal to your favorites, to enter. That´s all you have to do.
- This Giveaway ends on May the 24th.
- The winner will be chosen via random.org
Good luck to everyone!
Watchers Feature + Point Giveaway! *CLOSED/WINNER!Commission Me!
Hey guys! I'm about to hit 2600 watchers (wow!) and I thought I'd go ahead and
give a little back to ya'll by featuring some of your works and giving away some points!
Art Trade~ Fire Wolf by Smaoi Uncolored fox girl (lineart) by Bunnyrabbitluv Arashi by MimiStars Lum-chan by Lalaibeii Friends Forever by WinxMewGirl Madness?? by adamexe20a Lord Death In Office by The-Lost-Hope
500pts GIVEAWAY! (CLOSED)
hosted by me
1st : 100 :iconemimieko: (249)
2nd : 100 :icontacoeating: (115)
3rd : 100 :iconmrkapre: (312)
4th : :100 :iconfrogman2009: (57)
5th : 50 :iconhowling-dark-wolf: (563)
6th : 50 :iconeggroll-cat: (480)
congratulations to them!
If you didn't win, don't be discouraged! There will be another giveaway soon!
to participate, YOU MUST :
be a watcher
[Bullet; Orange] favourite this journal [Bullet; Orange]
THAT'S ALL1st : 100 [Points]
2nd : 100 [Points]
3rd : 100 [Points]
4th : 100 [Points]
5th : 50 [Points]
6th :50 [Points]i will use RANDOM.O
My Very First Contest (3-month membership)!! :D{EDIT} -- Please watch CreepyPonyLover238!! She gave me enough points to change it to a THREE-month!! :"D <3 I thank you very much for your help!!
Yep! You read it right!! My first one omfg I'm so excited!! :"D
Whoever wins will receive a free one-month premium membership THREE-month premium membership from me!
~If you don't read, don't enter~
How do I enter legally?
+Favorite this journal.
Create your own journal about this contest. This is so it can be viewed more and spread around to anymore potential participants; the more the merrier!
Link back to your own journal in the comments on this one. ^^
It's that simple!! (:
Next Kiriban 100 Points to winNext Kiriban to be announced
The one, which sends me a screenshot of ..... pageviews on my site first, wins 100 DA points.
Please send the screenshot only via note.
Good Luck~
Winner of the 33333 Kiriban: minthe-sama
Winner of the 40000 Kiriban HotCakes77
Winner of the 44444 Kiriban Megeroni
Winner of the 50000 Kiriban Shatiel85
Winner of the 55555 Kiriban Lil-Hawk
Winner of the 60000 Kiriban Lil-Hawk <--- two times in a row
CLOSED:2,000 Point Giveaway!! Plus BONUS Points!!*CLOSED*
Thank you all so much for all the support so far! Here's where we're at:
We have 76 new Subscribers! That means we have 124 slots left!
We have 54 new Facebook "Likes!" That means we have 146 slots left!
Make sure you share this with everyone! As soon as we fill all the slots everyone will get
You can receive bonus too. This means you can get even more than 10! Here's how:
Every friend you get to subscribe to Life with Superheroes, you get an extra 1
Every friend you get to "Like" Life with Superheroes on Facebook, you get an extra 1
Then you just note me
Comment GuidelinesGetting Comments
10 = 10
Include "comment" in your donation message
If you'd like to receive comments, just include the word comment somewhere in your donation message.
All comments will contain 25+ words of constructive feedback
Alice only gives credit for comments that are 25+ words long. Duplicate or plagiarized comments will not be counted against your balance.
Giving Comments
1 = 1.0
You may only give 15 comments at a time.
Once you give 15 comments, you must comment on my page and wait for Alice to check your comments. Once the comments have been checked, you can give up to 15 more comments.
Comment on any artwork in the Featured Deviant's gallery.
You will NOT be given any credit for comments on the deviant's gallery page. You must comment on an actual artwork. You can a
Make More Sunthralls Contest/and GiveawaySo, this newest contest will be about creating your very own sunthrall. A sunthrall is basically the opposite of a vampire. It is a creature that freezes without sun or firelight and is holy almost always to the point of being overzealous. Characteristics of a sunthrall include bright yellow eyes and most of them have the ability to summon floating balls of light.
This is a sunthrall.There is more info about them here.
1st 1500 points
2nd 700 points
3rd 300 points
3 random people will be given 100 points at the end of the contest just for entering.
Contest starts now and ends on June 10th
All sunthralls have to have bright yellow eyes.
Expose other deviants to the sunthrall. Invite 3 other people to join if you do. And list on your deviation who you invited. (now optional, but it would be great if you did invite people)
Picture must be a new one created for this contest.
500 points giveaway !! (CLOSED) AND the winner issss ......
Draco-Flight !!! congrats , ill send the points to you c:
hi !!
that's it, 500 that i'm giving away, there will only be one winner !
to enter you must :
favorite this journal
you must advertise this video
and you must advertise this journal !
please comment below and link me the journal you made !
i will pick a winner the 6th of april !! also please watch the video, and you can even leave a comment there if you want c:
good luck to you all !
5000 points GiveawayHelp me break 1000 daily page views and I will do a 5000 giveaway in the next 7 days.
All you have to do is go to my profile, come back to this journal entry and tell me you viewed it. (Please be honest because honestly its not hard to go to my profile and back)
I will then pick 5 people out of the comments to receive 1000
Remember this is only if I hit 1000 page views today.
The deadline is 4:00pm PDT
Reminder : You need to comment "Viewed" after you view my profile for me to be able to pick you. I can't see who viewed my profile since I started this giveaway so please remember that.
(10:25am PDT - 553 views)
(10:35am PDT - 598 views)
(10:45am PDT - 632 views)
(11:00am PDT - 667 views)
(11:30am PDT - 802 views)
(12:00pm PDT - 955 views)
(12:06pm PDT - 1000 views)
(12:30pm PDT - 1126 views)
(1:00pm PDT - 1337 views)
Final update and last
Congratulated to Neroholic and KirCorn <3. You both win a three month PM.
Thank you all who have joined. Sit tight for another round <3.
Edit: update IIV
Today is the last day people can join. This giveaway will be closing tonight. The two winners will be announced in the first week of May.
Thank you all who have joined.
I will make another journal to announce May's give away <3.
Edit: update II
Very important update! Please read if you joined my giveaway!
Jazmin-Jazz was kind enough to bring this matter to my attention. DA used to have an option were you could give someone a 6 month PM. However this seemed to have changed. Of course I c
Open for Cash and Points Commission
ello everyone! I'm open for commission. Please send me a note if you are interested. Thank you very much.
Pencil Sketch*
Head Shot: $5-10 (+$5 for additional character) or corresponding
Half Body: $10-20 (+$10 for additional character) or corresponding
Full Body: $15-40 (+$15 for additional character) or corresponding
*maximum of 2 characters
Line Art*
Head Shot: $10-20 (+$10 for additional character) or corresponding
Half Body: $15-35 (+$15 for additional character) or corresponding
Full Body: $30-50 (+$20 for additional character) or corresponding
*maximum of 2 characters<b>
|Sta.sh Submit


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We, the undersigned, do hereby petition to silence nuisance barking dogs in the county of Kauai by amending the current Animal Control and Police laws of this said county. A provisional clause should also be implemented into the current "Noise Ordinance", "Disturbing the Peace" and/or "Disorderly Conduct" laws to include an instituted amendment of a just law to make dog owner(s) liable for their pets at all times to include excessive barking when it becomes a public nuisance. A dog that barks constantly is directly disturbing the peace of its surrounding neighbors. Such an infraction should be mediated by Animal Control and/or Peace Officers of the county at a further level as described in further detail below. Kauai Police law currently has zero authority to handle such barking dog complaints. The Police Department currently can only advise of contacting the Animal Control Department for such infractions. These procedures are unequaled in the same sense of a loud stereo or other constant and repetitive noises being produced by a neighbor and therefore need to be ratified. This petition will implement a law that dog owners be liable for their pets behavior at all times as the law states under such Disturbing the Peace doctrines. Circumstantial preludes of evidential conduct of such infractions are to be necessary as in any crime to prove the dog as a habitual offender such as; Contact with the dogs' owner(s) as either written or verbal shall be necessary to prove a fair attempt had been made to arbitrarily reconcile such matters; A documented time line of occurrences shall be made, along with official documents by the appropriate county Animal Control department, along with recorded video and audio of such offenses. This will regulate the authenticity of such complaints and to ease court cases from unnecessary "Due Process of Law" constituents. This is an attempt to change policy among Kauai Animal Control and Kauai Police Law to enforce and recognize the county citizens' civil law rights and peaceful living conditions as determined by the United States Constitution. No person appreciates the sound of a neighbor's dog constantly barking for endless hours while inside or outside their own homes. Understandably, dogs do bark. Yet, there are plenty of alternatives on the market both electronic and otherwise that can help an owner manage their nuisance dog(s) which thus, makes it truly unreasonable and careless to ignore it. Help make peaceful habitability a part of your community. Mahalo for your support
Nolan Ahn
My neighbor's dog barks incessantly when the owners are absent. They are apologetic but at a loss for a solution. Train, take the dog with them, or get rid of it are the only reasonable options.
William Peterson
We need a law that addresses this issue and is enforceable. It needs to have teeth!
Please include caged birds in this Petition, because Dogs are not the only "pets" that are a severe nuicence to people that have to listen to them constantly, for months and sometimes years, without any options.
Recent signatures
William Peterson2 weeks ago Comments: We need a law that addresses this issue and is enforceable. It needs to have teeth!
Lisa Squire1 month ago Comments: -
Tona Chacon2 months ago Comments: Living next door to several little dogs and speaking with the owners about the constant barking at all hours of the day and night (in which the neighbors even stated they do not know how to train their dogs - which leads me to believe that they should not have that many (7) in the first place) can be emotionally and physically straining. Yes, your pets become family, but treating them and referring to them as your 'children' when speaking about continuous barking and letting them bark at all hours of the day - well, I'm sure you would find ways to work with your child as to not have them scream ALL day. It becomes tiring. For those of us with dogs, we know it takes hours upon hours of training. This petition and law is necessary as to not just make owners liable, but become educated on obedience training for ALL kinds of dogs. Contrary to popular belief, small dogs can be trained...
Petition highlights
There are no highlights yet.


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One King West Hotel & Residences
1 King Street West, Toronto, Ontario, Canada, M5H 1A1
- Recommended for:
- Business travellers, Couples, Families with teenagers, Families with younger children, Foodies, Design and architecture, Great views / scenery, Live entertainment, Nightlife, Sightseeing
Expert review of One King West Hotel & Residences
I just LOVE this one. I relish every detail from the minute I troop into the soaring two-storey Grand Banking Hall, with its pillars and panels, to the second I'm reluctantly torn from the gorgeous high-floor suites, this hotel in its gorgeous turn-of-the-century building and its modern "Sliver" tower does everything in style.
Brilliant: right on one of the busiest corners of downtown, the old Dominion Bank Building (it was the HQ of the Dominion bank for 126 years), steps from King Street subway station and streetcar stops. Right beside an entrance to the underground PATH system.
Gorgeous: I love having a kitchen (or mini-kitchen, depending on room) at my disposal, plus the washer and dryer are always a bonus. Rooms vary significantly between those in the old 19th century, 12-storey building and the gleaming 51-storey condo tower, nicknamed "The Sliver."
Check availability and compare prices for One King West Hotel & Residences
The lobby has scatters of armchairs, a bar area, cream marble and the usual off-white colour scheme. For those of us who don't have "proper jobs," it's a shame so many of the really cool old banking areas are kept for meetings.
There's a smorgasbord of eating and drinking venues on offer — Henri's Bar in the lobby, the sleek Bistro on King (great buffet breakfast, by the way) and Petite Thuet, an acclaimed sandwich/salad/patry option is off the lobby.
The 17th floor rooftop fitness centre has some great lake views. The terrace is gorgeous once the snows melt in April, right through till it gets chilly in October. There are two saunas, a hot tub and the curiously named "resistance pool", which I seem to have absolutely no resistance to getting into.
Excellent: they really go out on a limb for you here and seem to be on top of everything. Impressive.
Check availability and compare prices for One King West Hotel & Residences
Businesspeople and Ontario couples on city breaks and romantic weekends.
Parking is a fairly standard $30 a night. In-room Internet is wired only, so leave the Mac Book Air at home, and comes at $9.99 a day. It's comped in the lobby and other public areas, though, if you don't have to be online much.
More information on One King West Hotel & Residences:
- Type:
- Aparthotel
- Address:
- 1 King Street West, Toronto, Ontario, Canada, M5H 1A1
- Amenities:
- Business Centre, Fitness Centre, High-Speed Internet, Parking, Restaurant, Room Service, Swimming Pool
- Neighbourhood:
- Downtown


text:
The 20/20 Experience World Tour is back for its last leg! Here are photos from the show in Oakland, CA at the Oracle Arena!
#MeetTheTNKids: Tonight's the night! The 20/20 Experience World Tour will be kicking off its final leg in Portland, Oregon. Today, meet Zenya Bashford - our fantastic backgound vocalist with moves.
Tomorrow - Nov 20 - to kick off the last leg of The 20/20 Experience World Tour, we are dedicating the day to The Ultimate #JT2020Tour Finale Giveaway for you, the fans!!!!!
#MeetTheTNKids: 1 day and we're back! Today get to know Nicole Hurst - our dynamic background singer.


text:
View from the Bleachers
This weekly blog is humor writer Tim Jones' personal search for signs of intelligent life in the universe and his neighborhood. He's still searching. See what he discovered this week.
Posts filtered on Category
My fun weekend at the Royal Wedding with Willy and Kate
I had the best time this past weekend. You see, it was the weekend of the much hyped Royal Wedding of His Royal Highness Prince William of Wales & the newly proclaimed Catherine Middleton, Duchess of Cambridge, at Westminster Abbey. Prince William – or Willy, as he prefers me to call him – is really […] [Read More]
Watson vs. Palin in mock presidential debate – Who will win?
Last week I told you about the phenomenal Watson Super Computer from IBM. Watson appeared on the TV quiz show Jeopardy! and completely dominated the competition against his two human opponents, the two most successful champions in the quiz show's history. As a result, I told you about Republican plans to vet Watson as a […] [Read More]
GOP eyes Watson the Computer as front-runner candidate for 2012 election
Last month, the nation was introduced to the world's smartest computer: the IBM Watson. Watson is an example of the incredible strides made in artificial intelligence (A.I.). With four terabytes of storage capacity, including all of Wikipedia. Watson knows the answer to virtually any question, from Lady Macbeth to Lady Gaga. Even more impressive than […] [Read More]
VFTB Exclusive: Breaking News! Sheen and Gaddafi agree to a job swap
In recent weeks, the situation in the chaotic, volatile region of the world has turned increasingly tense. The mood of his fractured nation has become more volatile with each passing day. Images on TV show streets filled with shouting, angry protestors, crying out for an end to the insanity. Meanwhile the intransigent tyrant refuses to […] [Read More]
View from the Bleachers' Annual Predictions Issue – 2041 Edition
[For a look back at my 2010 predictions for the year 2011, click here. You will be amazed at the accuracy of some of my prognostications.] [Read More]
Why does Montana hate me?
I'll admit it. There are many mysteries in this world I will never be able to grasp. Like, when did time begin? How big is the universe? Is there life after death? Why does a loving God let good people suffer? How can I get the flashing "12:00″ on my VCR set to the correct time? [Read More]
A Preview of TV's Mid-season Reality Shows
Whoever opined that "television is a vast wasteland" never watched an episode of Pimp My Ride or the equally thought-provoking Lingerie Football. If you ask me, the quality of television has never been better. [Read More]
World Cup Special Offer from VFTB: Vuvuzela music lessons – Kids half price!
Life is pretty stressful at times. When I'm feeling a bit overwhelmed, I like to find a comfortable couch, close my eyes and listen to a relaxing sound. And no sounds are more soothing to me than the rhythmic sound of the ocean waves crashing into the shore or the gentle gurgling of a babbling brook or the soothing hum of 35,000 rabid South African soccer fanatics at the FIFA World Cup, blowing their lungs out with their plastic 4 dollar and 95 cent vuvuzelas. If you still haven't heard of a vuvuzela … [Read More]
My fleeting friendship with an Internet Scammer – Conclusion
Welcome back to the thrilling conclusion of my true, unedited story about my brief fleeting friendship with an Internet Scammer named Mr. Chris. If you were with us last week, you know that it all started when I received the following unusual email in my SPAM mail folder. [Read More]
My fleeting friendship with an Internet Scammer
Recently, I made a new friend across Cyberspace: a very nice man named Mr. Chris. Well, at least I thought he was a friend. For a week, it looked like we were going to become best buddies. But sadly this story of fleeting friendship has a heart-breaking ending. [Read More]
Show More


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Summer Hours (English Subtitled) 2009
Amazon Instant Video
|Drama, International, Kids & Family
|Olivier Assayas
|Juliette Binoche, Charles Berling
|Supporting actors
|Jérémie Renier, Edith Scob, Dominique Reymond, Valérie Bonneton, Isabelle Sadoyan, Kyle Eastwood, Alice de Lencquesaing, Emile Berling, Jean-Baptiste Malartre, Gilles Arbona, Eric Elmosnino, Marc Voinchet, Sara Martins, Christian Lucas, Philippe Paimblanc, Luc Bricault, Arnaud Azoulay, Marine Decroix
|IFC Films
|MPAA rating
|NR (Not Rated)
|Captions and subtitles
|English Details
|Rental rights
|48 hour viewing period. Details
|Purchase rights
|Stream instantly and download to 2 locations Details
|Amazon Instant Video (streaming online video and digital download)
Just not very good. Not enough happened, and I don't feel like this movie really said anything. It almost had the casual, insignificant feel of a reality TV show. Read morePublished 2 months ago by samspennell
boot-legged copy......not distributer copy, but still pleased to have any versionPublished 4 months ago by Bobbie
In my opinion, this is an Accurate portrayal of the logistics, interactions and emotions between siblings in the death of a parentPublished 5 months ago by Amazon Customer
This never gelled for the three of us watching ti - we do NOT recommend, but if you're looking for something to put you to sleep, this is the one.Published 6 months ago by CC
'Summer Hours' is a film that takes us to the present. The mother of this family is celebrating her 75th birthday at their summer place outside of Paris. Read morePublished 6 months ago by prisrob
This is a more or less "plotless" film about three generations of a French family. The matriarch is arranging for the disposal of her valuable art collection and the family is just... Read morePublished 6 months ago by Joanna Daneman
Well-dine story about family and losing a loved one. Tasteful and Honest and Real. This would be great for anyone interested in Art and small French towns.Published 6 months ago by Michael L. Draper


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Barack Obama Comes to Family Guyby Free Britney at . Updated at . Comments
Sundat on Family Guy, Quahog's school assignment was to write an essay on hope, with the winner earning an exquisite honor of introducing the President.
Chris stole Meg's essay and won, but like a good brother, they ended up sharing in reading it and presenting Barack Obama at James Woods High School.
Then, of course, Obama appeared in a skintight leather outfit and sang a song for no apparent reason. This sort of thing tends to happen on Family Guy ...
Is that Elvis? Evil Kenevil? Oh, wait, that's just the President of the U.S. Follow this link for the best Family Guy quotes from last night and EVERY episode!
it was actually 23,000 per season. idiot
Typical of the libtards at Family Guy to try to portray the Liar in Chief as a rock star. That is the only thing explains his Ozombies who follow him no matter how he screws up the country.
For the non-musical watching writer--the president was singing a song from the musical "Bye-Bye Birdie" (a tongue in cheek reference made earlier by the principal about lousy plays). The "Elvis" style musician in the musical simply sings and people go crazy--very irrational in their reverence and pied-piper-like obeisance. Perhaps this was what the Family Guy creators were referencing. Sly and subtle humor, indeed.
I think the joke was aimed at Barrack Obama's rock star status, for he has certainly become an ever-present figure in popular media (i.e. "Mythbusters"). However, it may be that only the creators of "Family Guy" truly know. Still loved the episode.
Thought this was a great episode. Really dug the Charles in Charge bit, how the sweater budget for the show was 200 grand. I actually just watched this on my lunch break here at DISH where I work. I have TV Everywhere with my 922 receiver and am able to watch my DVR'd events right on iphone. It's awesome!


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Fix A Broken Zipper In 30 Min. or Less
My favorite jeans. Busted zipper.
Both have been in my drawer for about a year waiting for me to address the problem. I've replaced zippers before and it's just not fun. This time I took a different approach and both were done in 30 minutes:
You will need:
- Scissors
- seam ripper, if you have one
- needle
- thread
- a few pins
See the Tutorial
World Peace Healing
"World Peace Healing"
is my latest big project commissioned by Nora, a Reike Healer from Illinois, USA.
It started with an order for an Intention Quilt back in January or February. Then she ordered some pouches. Then she came to me with this idea about Oneness, World Peace, Healing, the Arts and Arch Angel Michael. She also wanted to incorporate a charm collection that was growing fast.
This quilt is specifically for her healing space at her practice.
We started by making a board for her project on Pinterest.
This is a wonderful tool for getting an idea what someone likes and wants! You can invite others to post in the board and there is the option to leave comments with the pictures. This is a good way to communicate ideas for a project like this that's long distance.
An Unusual Animal Rescue and Sanctuary
b.z.threads has donated this art quilt, Seeds of Change, to Misty Haven Farm Go Fund Me campaign.
More about this below… but first the farm's story:
Silk Treasure Pouches Make A Beautiful Gift
My new Etsy Shop item for this holiday season: Silk Treasure Drawstring Pouches.
Find Treasure Pouches in the Useful Things Section. Prices range from $10 to $25.
Use for Tarot Cards, Crystals, Gifts, Tip Money, Jewelry, Keepsakes, Lingerie, and other Treasures.
Tweaking Doll Patterns
I've been working with a few patterns I designed for dolls for a while now. They have all been tweaked here and there as I learned more about how certain curves will behave.
An Old Idea for Symmetry and Bobbin Sewing.
I thought I'd show how I got this design drawn up. It's simple and I probably learned it in elementary school. It's one of my favorite techniques. At the end, you can see how this sewing technique is done.


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You are here: News. Archive.
Cutting Edge 2012 event to explore the research behind sailing
Cutting Edge 2012 event to explore the research behind sailing03/05/2012
Sailing fans are being invited to explore the research behind the sport at a free event in the run up to the Olympic Games. The Cutting Edge: Behind Sailing event on Thursday 24 May at the Weymouth and Portland Sailing Academy will feature Professor Steve Haake, double Olympic medalist Simon Hiscock, and top sports scientists in an interactive session with demonstrations of technology and sport.
The chance to question scientists & athletes
The event will give attendees the chance to question both the scientists who develop the cutting-edge technology behind sport, and the high-achieving athletes who use it. Professor Steve Haake, one of the UK's top sports scientists, will be joined by Professor Glen McHale, who develops extremely water repellent high tech surfaces that can help to reduce drag in boats, and Dr Judith Wolf, an expert in coastal modeling of tides and currents and the brains behind Team GB's gold medal at the Seoul Olympics. Dr David James will also take part, leading the discussion on how far research and new technologies should be used in the quest to win gold.
Interactive sessions with demonstrations
The Cutting Edge 2012 event series consists of six sessions in total, all themed around a different sport, and will feature a range of sports stars and top scientists in an interactive session with demonstrations. The evening events are an initiative by Research Councils UK (RCUK), and are an opportunity to question both cutting-edge researchers and high-achieving athletes.
Look behind the scenes at what it takes to win Gold
Professor Steve Haake, head of Sports Engineering Research at Sheffield Hallam University and Chair of the event commented: "Cutting Edge is a chance for the general public to look behind the scenes at what it takes to win Gold at the Olympics. Elite sport needs elite support and the Cutting Edge series showcases some of the key expertise provided by the UK's academics and practitioners helping our athletes get the competitive edge needed to come first. These skills include engineering, technology, physiology and psychology as well as elite athletes themselves. Our audiences will be encouraged to ask questions and we will not shy away from the difficult ones - in return we may just ask some searching questions of the audience themselves."
Homepage: rigb.org
Source: bymnews.org & wpnsa.org.uk
More watersports news ...
More informations and functions
Latest Sailing News
Third in Rhum Class in La Route du Rhum-Destination Guadeloupe
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Gusts of up to 35 knots send fleet off to flyer
read more...
Gabart finished first in IMOCA 60 Class
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Team Brunel take second, Team SCA third
read more...
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start Boatfinder...


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Long Island Now
The latest community buzz and updates. | Sign up for community newsletters.
BloggersDenise M. Bonilla Sophia Chang Tara Conry Carl Corry Erin Geismar Scott Eidler Mackenzie Issler Carl MacGowan Deborah S. Morris Amy Onorato Ted Phillips David Reich-Hale Candice Ruud Nicholas Spangler Joshua Stewart
ArchivesMore »
Insurance assistance for storm victims in Copiague
Representatives of the state Department of Financial Services will be in Copiague Wednesday to offer assistance to those with insurance issues stemming from superstorm Sandy.
The agency will be at the Tanner Park Senior Center from 11 a.m. to 7 p.m. to help homeowners, renters and business owners.
Department representatives will help citizens contact their insurers if they have been unable to do so and answer questions about insurance coverage.
PHOTOS: LI damage | Then and now | Aerial views
VIDEOS: Recovery still in progress | Desperate for buyout
DATA: Federal aid to victims | Storm damage | Infrastructure proposals | LI storm damage | How LI reps voted on Sandy funding
MORE: Year after Sandy interactive | Complete coverage
Those who are unable to go to the center are encouraged to call the department's storm hotline at 800-339-1759, staffed from 8 a.m. to 8 p.m., Monday through Friday, and from 10 a.m. to 5 p.m. on Saturday and Sunday. Insurance information is also available on the department's website, dfs.ny.gov.


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A taught Masters which trains psychology graduates to become competent practitioners in applied psychology for children, young people and families.
|MSc in Applied Psychology for Children and Young People
|Start date
|February 2015
|Length of study
|1 Year, Full-time only
|Programme Director
|Dr Rebekah Lwin
The application process for February 2015 intake has now closed.
For further details about the programme, please see the Applicant Handbook below.
The deadline for submission of the Application Form was 12 noon on Friday, 15th August 2014.
For those applications received, you will be advised by email no earlier than 15th October 2014 whether you have been short-listed for interview. Please do not contact us before 16th October 2014, as we will not be able to respond.
Interviews will take place in Edinburgh during the week beginning 3rd November 2014.
Please refer to the "Apply Now" button for information regarding references.
Please note that only candidates invited to interview may be given feedback on their application.
Delivered over one year full-time, this closed programme offers a combination of academic and clinical skills teaching with a full year clinical placement in a Scottish NHS Child and Adolescent Mental Health Service.
The MSc combines academic teaching with clinical practice training in the area of applied psychology for children and young people. It offers an interesting opportunity to develop knowledge and competences in the delivery of evidence-based psychological interventions for this client group.
The programme was developed in close partnership with NHS Education for Scotland, NHS Greater Glasgow and Clyde and NHS Scotland. Students on the programme will be employed as trainees in one of 11 Scottish Health Boards on full time contracts for the duration of their training.
In addition to the essential elements for applied psychologists in health (e.g. assessment, formulation and evaluation) and Child and Adolescent Mental Health professionals (e.g. recognition of child abuse, developmental impairments and delays), there is a particular focus on the early years and early intervention across a variety of settings.
There is also a strong emphasis on parenting and supporting parents through evidence-based models of parent-focused intervention. The clinical experience gained on placement facilitates the linkage of psychological theory to practice and fosters development of professional skills necessary for post-qualification practice.
This article was published on Oct 3, 2014


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Uses of syndiotactic/atactic block polypropylene are provided in which the molecular weight thereof is preferably at least 120kD. The syndiotactic/atactic block polypropylene may be used as a polypropylene modifier, a component in an adhesive composition, a shock absorber component, a waterproof membrane component, a packaging film or component thereof, a shapable composition component, and an acoustic absorbent material component, a composition for moulding into a footwear component, a bitumen modifier, a compatibiliser, an emulgator or an emulsifier, as a viscosity improver, and as a spilled oil absorber.
1. An article or material comprising at least one of (a)-(u), wherein at least a portion of said at least one of (a)-(u) includes a syndiotactic/atactic block polypropylene component, wherein the molecular weight of the syndiotactic/atactic block polypropylene is at least 120 kD, and wherein (a)-(u) includes:
(a) a polyolefin modifier;
(b) an adhesive material;
(c) a shock absorber;
(d) a waterproof membrane;
(e) a packaging film;
(f) a drawn fiber, film or thread;
(g) a shapable material;
(h) an acoustic absorbent;
(i) a foam material;
(j) an oil spill absorbent;
(k) footwear;
(l) a gamma irradiation stable material;
(m) a shapable composition;
(n) a composition for molding into a footwear component
(o) a bitumen modifier;
(p) at least one of a compatibilizer, an emulgator and an emulsifier;
(q) a coextrudate;
(r) a viscosity enhancer;
(s) a plastics recycle material;
(t) motor oil; and
(u) a thermoplastic elastomer gel.
2. The article or material of
3. A polyolefin modified with the polyolefin modifier of
4. The polyolefin of
5. The polyolefin of
6. The article or material of
7. The article or material of
8. The article or material of
9. The article or material of
10. The article or material of
11. The article or material of
12. The article or material of
13. The article or material of
14. The foam material of
15. The foam material of
16. The article or material of
17. The article or material of
18. A bitumen composition comprising bitumen blended with the bitumen modifier of
19. The bitumen composition of
20. The article or material of
21. The article or material of
22. The article or material of
23. The article or material of
24. The article or material of
25. The article or material of
26. An article or material comprising at least one of (a)-(u), wherein at least a portion of said at least one of (a)-(u) includes a syndiotactic/atactic block polypropylene component having a fraction of syndiotactic triads (rr) of at least 70% as determined by 13C NMR and has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of at least 120,000, and wherein (a)-(u) includes:
(a) a polyolefin modifier;
(b) an adhesive material;
(c) a shock absorber;
(d) a waterproof membrane;
(e) a packaging film;
(f) a drawn fiber, film or thread
(g) a shapable material;
(h) an acoustic absorbent;
(i) a foam material;
(j) an oil spill absorbent;
(k) footwear;
(l) a gamma irradiation stable material;
(m) a shapable composition;
(n) a composition for molding into a footwear component;
(o) a bitumen modifier;
(p) at least one of a compatibilizer, an emulgator and an emulsifier;
(q) a coextrudate;
(r) a viscosity enhancer;
(s) a plastics recycle material;
(t) motor oil; and
(u) a thermoplastic elastomer gel.
This application is a division of U.S. patent application Ser. No. 09/233,829, filed Jan. 20, 1999, and entitled Polyolefins and Uses Thereof, now U.S. Pat. No. 6,348,272.
The present invention relates to polyolefins, especially polypropylenes and their uses.
As known in the art, syndiotactic polymers have a unique stereochemical structure in which monomeric units having enantiomorphic configuration of the asymmetrical carbon atoms follow each other alternately and regularly in the macromolecular main chain. Syndiotactic polypropylene was first disclosed by Natta et al. in U.S. Pat. No. 3,258,455. The Natta group obtained syndiotactic polypropylene by using a catalyst prepared from titanium trichloride and diethyl aluminum monochloride. A later patent to Natta et al., U.S. Pat. No. 3,305,538, discloses the use of vanadium triacetylacetonate or halogenated vanadium compounds in combination with organic aluminum compounds for producing syndiotactic polypropylene.
U.S. Pat. No. 3,364,190 to Emrick discloses a catalyst system composed of finely divided titanium or vanadium trichloride, aluminum chloride, a trialkyl aluminum and a phosphorus-containing Lewis base as producing syndiotactic polypropylene. U.S. Pat. No. 4,892,851 disclosed a metallocene catalyst for producing highly crystalline syndiotactic polyolefins.
As disclosed in these patent references and as known in the art, the structure and properties of syndiotactic polypropylene differ significantly from those of isotactic polypropylene. The isotactic structure is typically described as having the methyl groups attached to the tertiary carbon atoms of successive monomeric units on the same side of a hypothetical plane through the main chain of the polymer, e.g., the methyl groups are all above or below the plane. Using the Fischer projection formula, the stereochemical sequence of isotactic polypropylene is described as follows:
In contrast to the isotactic structure, syndiotactic polymers are those in which the methyl groups attached to the tertiary carbon atoms of successive monomeric units in the chain lie on alternate sides of the plane of the polymer. Using the Fischer projection formula, the structure of a syndiotactic polymer is designated as:
The percentage of r dyads in the chain determines the degree of syndiotacticity of the polymer. Syndiotactic polymers are crystalline and, like the isotactic polymers, are insoluble in xylene.
This crystallinity distinguishes both syndiotactic and isotactic polymers from an atactic polymer that is soluble in xylene. Atactic polymer exhibits no regular order of repeating unit configurations in the polymer chain and forms essentially a waxy product. While it is possible for a catalyst to produce all three types of polymer, it is desirable for a catalyst to produce predominantly syndiotactic or isotactic polymer with some atactic block fractions.
PCT/EP97/03649 (filed on 10th July 1997) of the present applicants describes a new syndiotactic/atactic block homopolyolef in and particularly a new syndiotactic/atactic block homopolypropylene. PCT/EP97/03649 also describes a catalyst and process for preparing syndiotactic/atactic block polyolef ins, and more particularly syndiotactic/atactic block polypropylene. The catalyst and process can each be adapted to produce a polymer with differing syndio-/atactic block ratios.
The present invention provides use of syndiotactic/atactic block polypropylene whereby the properties thereof, especially the mechanical properties, are exploited. The syndiotactic/atactic block polypropylene has a combination of plastic properties conferred by the syndiotactic block and elastomeric properties conferred by the atactic block and may be regarded as a member of the �thermoplastic elastomer� family of polymers.
In one aspect, the present invention provides use of syndiotactic/atactic block polypropylene as a modifier of a polyolefin, such as isotactic and/or copolymeric polypropylene and/or other polyolefins. The modified polyolefin or polypropylene formed thereby may be capable of moulding, for example by extrusion, injection or compression and can be used, for example, in high impact resistance applications such as automobile parts, electronic appliances, packaging and sports goods. Accordingly, there is further provided a high impact resistance polyolefin such as a polypropylene, comprising a dispersion of syndiotactic/atactic block polypropylene in a continuous phase comprising isotactic and/or copolymeric polypropylene. Preferably, the amount of syndiotactic/atactic block polypropylene is in the range 3 to 50% preferably 5 to 15% by weight of the polypropylene. It is thought that the syndiotactic/atactic block polypropylene forms discrete dispersed particles in the continuous phase. In this way, the syndiotactic/atactic block polypropylene functions in the same way as rubber or elastomers in high impact polystyrene or as EPDM (ethylene propylene diene monomer such as a 1,4-hexadiene, or dicyclopentadiene or 5-ethylidene norbornene) particles in polypropylene.
In a further aspect, the present invention provides use of syndiotactic/atactic block polypropylene as a component in an adhesive composition. There is further provided an adhesive composition comprising a syndiotactic/atactic block polypropylene and at least one component selected from a wax, and a tackifying and/or reinforcing resin such as HERCOTAC 205 or MBG 212 (both from Hercules). Such adhesive compositions may be used, for example, in book binding applications. In such applications it is preferred that the components of the adhesive are selected so as to give a storage modulus G′ in the range 3�106 to 5�107 and a soft phase glass transition temperature in the range 5 to 30� C.
In a further aspect the present invention provides use of a syndiotactic/atactic block polypropylene as a component in a shock absorber. There is further provided a shock absorber comprising syndiotactic/atactic block polypropylene. In this application, the syndiotactic/atactic block polypropylene exhibits elasticity without rebound. It is found that rebound decreases as the molecular weight of the polypropylene increases. The syndiotactic/atactic block polypropylene appears to act in an analogous way to butyl rubber and could therefore be used in its place, wherever mechanical properties are concerned. The chemical properties of syndiotactic/atactic block polypropylene differ from those of butyl rubber. In particular, syndiotactic/atactic block polypropylene requires no further vulcanization during processing.
The shock absorber may further comprise other components known by those skilled in this art for use therein, such as carbon black, oils, inorganic fillers, organic fillers, other polymers and foaming and processing agents. Typical applications of such shock absorbers include footwear soles, silent-block (noise absorber or damper) and any absorber or damper required between vibrating parts.
Preferably, the shock absorber is for use at room temperature, for example 20� C., and above.
In a further aspect, the present invention provides use of a syndiotactic/atactic block polypropylene as a component in a waterproof membrane. There is further provided a waterproof membrane comprising a sheet of syndiotactic/atactic block polypropylene modified with carbon black and/or a UV absorber and/or an antioxidant, and/or a weather resistance improver. Preferably, the amount of carbon black in the waterproof membrane is in the range 0.5% to 50%, more preferably 3% to 30%, depending on the grade of carbon black. It is found that carbon black dramatically improves the weathering resistance of the membrane. It is possible to extrude a very large sheet of the syndiotactic/atactic block polypropylene. In this way, the use of syndiotactic/atactic block polypropylene is similar to that of EPDM. Such sheets are useful in roofing applications.
In a further aspect, the present invention provides use of a syndiotactic/atactic block polypropylene in the form of a packaging film or as a component thereof. There is further provided a packaging material comprising a blown film of polypropylene comprising a syndiotactic/atactic block polypropylene. The polypropylene may comprise a blend of the syndiotactic/atactic block polypropylene. In one embodiment, the blown film is shrinkable. Good bubble stability is achievable in the production of blown films, particularly with a high molecular weight such as one above 180 kD. Shrinkable blown films are useful in bottle packaging, palette packaging and �thrown-away� packaging (i.e. packaging for additives used in formulations in which the additives are added to the formulation together with the packaging itself so that the packaging forms part of the formulation).
In a further aspect, the present invention provides a drawn fibre, film or thread of syndiotactic/atactic block polypropylene. The fibre, film or thread may therefore comprise other polymers, usually blended with the syndiotactic/atactic block polypropylene, preferably a polyolefin such as isotactic polypropylene, copolymeric polypropylene, high density polyethylene and/or low density polyethylene.
In a further aspect, the present invention provides use of a syndiotactic/atactic block polypropylene as a continuous phase component in a shapable composition. There is further provided a shapable composition comprising a continuous phase of syndiotactic/atactic block polypropylene in which is dispersed isotactic polypropylene, copolymeric polypropylene or another polymer such as a polyolefin. Preferably, the shapable composition softens upon heating and becomes rigid upon subsequent cooling. The shapable composition is typically soft and may be gently warmed for shaping, for example by hand. The syndiotactic/atactic block polypropylene has a glass transition temperature close to 0� C. When subsequently cooled, the composition becomes rigid owing to the presence of the isotactic polypropylene. The rigidity is due to crystallisation, whose speed is controlled by the amount of isotactic polypropylene, which is typically in the range 5 to 30% by weight of the composition. The shapable composition may be used in the production of a plaster cast or by craftsmen or artists. In a further aspect, the present invention provides use of syndiotactic/atactic block polypropylene as a component in an acoustic absorbent material. There is further provided an acoustic absorbent material comprising a blend, laminate or coextrudate of syndiotactic/atactic block polypropylene with at least one of isotactic, syndiotactic or copolymeric polypropylene or another polymer such as a polyolefin. Each constituent of the acoustic absorbent material will absorb a part of the acoustic spectrum. The material may be useful in automobile interiors, for example.
In a further aspect the present invention provides a foam comprising syndiotactic/atactic block polypropylene.
The foam may be extruded, injection moulded or compressed. Long chain branching of the Syndiotactic/atactic block polypropylene affords a high melt strength which is required in the foam form, especially for a soft foam. The syndiotactic/atactic block polypropylene is preferably crosslinked, typically by addition of peroxide during foaming, or by curing with electron beam. Alternatively, the Syndiotactic/atactic block polypropylene may be blended with another compatible polymer such as a polyolefin so as to afford greater rigidity, depending on the respective amounts of the ingredients. Typically, the compatible polymer is present in an amount of from 0 to 99% preferably 5 to 30%. Such foams may be used, for example, as thermal or acoustic insulating material or as shock absorbers.
In a further aspect, the present invention provides use of syndiotactic/atactic block polypropylene in a composition for moulding into a footwear component, usually in the sole. The invention further provides a composition for moulding into a footwear component, which comprises a syndiotactic/atactic block polypropylene optionally in combination with one or more additives known for this purpose, including plasticizer, polymeric fillers, mineral fillers and protective agents. Among these additives may be selected general purpose polystyrene, high impact polystyrene and/or appropriate oils. An appropriate choice of amount of syndiotactic/atactic block polypropylene and/or the selection of other components allows adjustment of the surface finish of the footwear component. In this way a matt or gloss finish may be achieved according to end use.
In a further aspect, the present invention provides a composition comprising a syndiotactic/atactic block polypropylene and a mineral filler, such as talcum, carbonate, silica and/or ash. Such mineral fillers may be used to improve the properties, such as weathering resistance, or reduce the price of the syndiotactic/atactic block polypropylene. Articles which may be made from such compositions include outdoor furniture, toys and sporting goods.
In a further aspect, the present invention provides use of syndiotactic/atactic block polypropylene as a compatibilizer, an emulgator or an emulsifier. Such use is particularly advantageous in plastics recycling or upgrading. The syndiotactic/atactic block polypropylene may be blended or mixed with plastics to obtain a mono-or biphasic system in which the syndiotactic/atactic block polypropylene may induce or create a continuous or dispersed phase depending on the processing conditions and the chemical and physical characteristics of the plastics.
In a further aspect, the present invention provides a coextrudate of syndiotactic/atactic block polypropylene with polypropylene and another polyolefin such as another polypropylene, a polypropylene copolymer, low density polyethylene, high density polypropylene or linear low density polyethylene. This is another example of the use of the Syndiotactic/atactic block polypropylene as a compatibilizer. For example, the syndiotactic/atactic block polypropylene may comprise an intermediate layer between a layer of a first polyolefin and a layer of a second polyolefin, which layers may be incompatible with one another in the absence of the intermediate layer. For example, the first polyolefin may comprise syndiotactic polypropylene and the second polyolefin may comprise isotactic polypropylene.
The Syndiotactic/atactic block polypropylene may be present as a layer in a laminate between a layer of the polypropylene and the layer of the polyolefin.
In this embodiment, the syndiotactic polypropylene imparts dielectric properties, higher gloss and improved impact resistance whereas isotactic polypropylene imparts a higher crystallinity which gives the co-extrudate rigidity.
In a further aspect, the present invention provides use of syndiotactic/atactic block polypropylene as a viscosity improver, especially in a motor oil. There is further provided a motor oil which includes syndiotactic/atactic block polypropylene, typically in an amount of from 1 to 10 by weight of the material. Typically the viscosity index (VI) of the motor oil is in the range 100 to 150 (where VI=viscosity at 100� F./viscosity at 210� F.).
In a further aspect, the present invention provides use of cross-linked syndiotactic/atactic block polypropylene as a spilled oil absorber. In one embodiment there is provided a thermoplastic elastomer gel comprising cross-linked syndiotactic/atactic block polypropylene. There is further provided a spilled oil absorber comprising the thermoplastic elastomeric gel. A thermoplastic elastomeric gel has both hydrophobic and oleophilic properties. Syndiotactic/atactic block polypropylene is more soluble in solvent than either syndiotactic or isotactic polypropylene.
In a further aspect, the present invention provides a bitumen composition comprising a blend of bitumen with a syndiotactic/atactic block polypropylene, preferably wherein the amount of syndiotactic/atactic block polypropylene is less than 35% by weight of the composition, generally in the range 15 to 30% by weight.
The bitumen composition may be used in a waterproof membrane, a bridge membrane or in joints, for example, for buildings.
In a further aspect, the present invention provides use of syndiotactic/atactic block polypropylene in a composition or article substantially stable to gamma irradiation. There is further provided a composition or article substantially stable to gamma irradiation, which comprises syndiotactic/atactic block polypropylene optionally blended or co-extruded with a polyolef in such as polyethylene. Such compositions or articles include articles for sterilisation and medical articles such as blood pouches.
The catalyst useful in the production of the syndiotactic/atactic block polypropylene comprises a metallocene, i.e., a metal derivative of a cyclopentadiene, and an ionizing agent. The metallocene compound contains only one substituted cyclopentadienyl ring and is of the general formula:
The term �symmetrically� shall mean that the local bilateral symmetry of the active polymerization sites is essentially maintained.
The process for producing syndiotactic/atactic block polyolefins, particularly syndiotactic/atactic polypropylene comprises utilizing at least one of the catalysts described by the above formula and introducing the catalyst into a polymerization reaction zone containing an olefin monomer. In addition, a cocatalyst such as alumoxane may be introduced into the reaction zone. Further, the catalyst may also be pre-polymerized prior to introducing it into the reaction zone and/or prior to the stabilization of reaction conditions in the reactor.
Metallocene catalysts are single site catalyst which, generally, produce polymer having narrow molecular weight distribution.
While the process is mainly directed to a-olefin homopolymerization, copolymerization with other olefins can be obtained.
The polypropylene may comprise alternating blocks of syndiotactic and atactic sequences, preferably long syndiotactic and short atactic sequences, most preferably comprising a fraction of syndiotactic triads (rr) of at least 70%. The polypropylene preferably has a molecular weight of at least 120 kD, more preferably at least 180 kD.
A more complete appreciation of the invention and many of the attendant advantages thereof will be readily understood by reference to the following detailed description when considered in connection with the accompanying drawings wherein:
The syndiotactic/atactic block polypropylene comprises alternating blocks of syndiotactic and atactic sequences. The polymer possesses particularly long sequences of syndiotactic species and short sequences of atactic species. The syndio-/atactic ratio can easily be modified by changing the polymerization conditions and/or the catalyst structure within the invention. For example, as shown below, increasing the polymerization temperature for a given catalyst decreases the syndio-/atactic ratio. As also evidenced below, replacing a dimethylsilyl bridge by a diphenylsilyl bridge also decreases the syndio-/atactic ratio for identical polymerization conditions.
The Syndiotactic/atactic block polypropylene has elastomeric properties. Without being bound by the theory, it may be considered that these properties are deriving from the combination of the crystalline syndiotactic part and the amorphous atactic part.
The polymer obtained may have a molecular weight ranging from 100,000 to 1,000,000 depending on the polymerization conditions and on the catalyst used in the process. For example, as shown below, replacing a dimethylsilyl bridge by a diphenylsilyl bridge results in increased molecular weight under identical polymerization conditions.
It has been unexpectedly found that the present catalyst can be used for the production of high molecular weight polyalphaolefin with stereoregular/stereoirregular block micro-structure.
When propylene or other alpha-olefins are polymerized using a catalyst consisting of a transition metal compound, the polymer product typically comprises a random mixture (reactor blend) of amorphous atactic and crystalline xylene insoluble fractions. The crystalline fraction may contain either isotactic or syndiotactic polymer or a mixture of both. The present catalysts have syndio-/atactic specificity and produce polymeric chains with differing syndio-/atactic block ratios.
The metallocene catalysts of may be described by the formula
(C4R′mC5C4R′n) is a flucrenyl ring, preferably substituted symmetrically; each R′ is hydrogen or hydrocarbyl radical having from 1-20 carbon atoms, a halogen, an alkoxy, and alkoxy alkyl or an alkylamino or alkylsilylo radical, each R′ may be the same or different, m and n independently are 0, 1, 2, 3 or 4, and with the proviso that the bilateral symmetry is maintained; R′ is a structural bridge between the hetero atom X and (C4R′mC5C4R′n) ring to impart stereorigidity, and preferably is a silyl or hydrocarbyl biradical having at least one silicon or carbon atom to form the bridge; Q is a hydrocarbyl radical, such as an alkyl, aryl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a Group IIIB, IVB, VB, or VIB metal as positioned in the Periodic Table of Elements; the transion metal can adopt any of the possible oxidation states. Preferred metals for the catalysts of the invention are Ti, Zr, Hf. A particularly suitable metal is Ti. (C4R′4C5C4R′4) comprises hydrocarbyl biradicals bonded to two adjacent carbon atoms in a cyclopentadienyl ring to form a fused ring.
In order to obtain syndiospecificity the cyclopentadienyl or fluorenyl rings in the metallocene catalysts must be substituted in an essentially symmetric manner with respect to the active coordination positions so that the metallocene exibits bilateral symmetry at least around the active coordination site. It has been unexpectedly noted that if in the original syndiospecific catalysts described in U.S. Pat. No. 4,892,851 the non-substituted cyclopentadienyl is replaced by a heteroatom ligand with one or two lone pair electrons and selected from elements of Group V A or VI A, the stereospecificty of catalyst will be periodically changed from syndiospecificity to aspecificity during the polymerization giving rise to the formation of atactic blocks within the predominantly syndiotactic chain.
Bilateral symmetry is defined as the condition in which there is no substituents or one or more substituents on one side and no substituents or one or more substituents on the other side in the same relative position such that a mirror image is formed from one side to another. One preferred example of such a compound is 2,7 di-tert-butyl-9-fluorenyl dimethyl silyl, tert-butyl amido titanium dichloride.
Whilst not wishing to be bound by a theory and without intending to limit the scope of the present invention as indicated by the claims, it is believed that during the polymerization reaction the growing polymer chain migrates from one coordination position to the other after each monomer insertion as the catalyst simultaneously isomerizes and enchains sequences of polymer of the syndiotactic structure; occasionally this mechanism is disturbed by a haptocity change of the fluorenyl-transition metal bonding or through inversion of the chiral nitrogen center, leading to the loss of steric control and formation of short sequences of atactic blocks whithin a predominantly syndiotactic polymer chain. This mechanism differs from that put forward for syndiospecific catalysts such as the active species formed from isopropylidene [cyclopentadienyl-9-fluorenyl] zirconium dichloride as disclosed in U.S. Pat. No. 4,892,851 wherein the fluorenyl ring exhibits mainly pentahapto bonding, i.e., all five carbon atoms of the fluorenyl rings are coordinated with the zirconium atom.
It is believed that the present catalysts demonstrate a reversible transformation of syndiospecific sites to atactic specific sites through a haptocity change related stereoregulation/stereoderegulation mechanism.
In theory, the steric condition for a preferred orientation of the growing chain, adoption of one of the two possible conformation, intermittently disyndiotactic/atactic block polypropyleneears and the coordination and insertion of either of the propylene prochiral faces at both lateral coordination positions becomes accidental. This mechanism enchains atactic sequences in a predominantly syndiotactic polymer chain by a spontaneous change in haptocity of the bonding between the fluorenyl and the transition metal from pentahapto to tri- and possibly mono-hapto bonding which results in the loss of stereoregulating property of the sites.
This electro-dynamic behavior of the active species provides in effect a temporary transformation of enantiotopic, equivalent sites to non-enantiotopic, non-equivalent environment at the lateral coordination positions, atactic sequences being formed whenever this occurs. Theoretically, only when both events, i.e., periodic loss of stereoregularity and the stereospecific character of the catalyst occur simultaneously, is a syndiotactic/atactic block homopolymer formed.
When catalysts of the present invention are used in polymerization of olefins, the polymer which results is of a syndio-/atactic microstructure as illustrated below:
In a preferred embodiment of the catalyst (C4R′mC5C4R′n) is preferably a substituted cyclopentadienyl ring with bulky substituents in 2 and 7 or positions combined 1,8 or 3,6 or 4,5 positions are also envisageble) such as tert-butyl and trimethylsilyl;
(C4R′mC5C4R′n) is more preferably a substituted fluorenyl radical; Me is preferably titanium, zirconium or hafnium, more preferably zirconium or titanium and most preferably titanium; Q is preferably a halogen and is most preferably chlorine; and R″ is preferably a silyl or hydrocarbyl biradical of at least one silicon or carbon atom which is coordinated with the heteroatom ligand and with (C4R′mC5C4R′n), most preferably a silyl or hydrocarbyl biradical of at least one silicon or carbon atom being connected with heteroatom ligand and (C4R′mC5C4R′Rn) moiety.
Exemplary hydrocarbyl biradicals for the structural bridge include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and the like. Other hydrocarbyl radicals useful as the structural bridge in the present catalysts include linear alkyl radicals of 1-10 carbon atoms or branched alkyl radicals of 1-20 carbon atoms, preferably one carbon atom, which may be substituted or unsubstituted, preferably substituted.
Exemplary silyl biradicals for structural bridge include dimethylsilyl (which is preferred), diphenylsilyl of the general formula R2Si═, with each R independently being any C1-C20 hydrocarbyl or C1-C20, mono-, di- or trialkyl silyl radicals.
The catalyst may be prepared by any method known in the art. Generally, the preparation of the catalyst complex consists of forming and isolating the substituted cyclopentadienyl or fluorenyl ligands which are then reacted with a halogenated metal to form the complex. The preferred method is that disclosed in U.S. Pat. Nos. 4,892,851. The catalyst may further be supported on an organic or inorganic carrier. The synthesis process generally comprises the steps of (1) preparing the halogenated or alkylated metal compound, (2) preparing the ligand, (3) synthesizing the complex, and (4) purifying the complex.
The present metallocene catalysts are useful in many of the polymerization processes (solution, slurry or gas phase) known in the art including many of those disclosed for the preparation of crystalline or amorphous polypropylene. When the catalysts are used in these types of processes, the processes produce syndiotactic atactic block polymers.
Further examples of polymerization processes useful in the practice of the present invention include those disclosed in U.S. Pat. No. 4,767,735 and European Patent Application Publication No. 310,734, the disclosures of which are hereby incorporated herein by reference. These preferred polymerization procedures include the step of prepolymerizing the catalyst and/or precontacting the catalyst with a cocatalyst and an olefin monomer prior to introducing the catalyst into a reaction zone.
The ionizing agent is an alumoxane, an aluminum alkyl, other Lewis acid or a combination thereof which will ionize a neutral metallocene compound to form a cationic metallocene catalyst. Examples of such ionizing agents are methyl alumoxane (MAO), triethyl aluminum (TEAl) and tris(pentafluorophenyl)boron. Other ionizing agents are disclosed in European Patent Publication Nos. 277003 and 277004 which are hereby incorporated by reference.
The present syndio-/atactic-specific catalysts are particularly useful in combination with an aluminum alkyl cocatalyst or with an alumoxane, preferably with the latter.
In addition, a complex may be isolated between a metallocene catalyst as described herein and an aluminum cocatalyst in accordance with the teachings of European Patent Publication Number 226,463. As disclosed therein, a metallocene is reacted with an excess of alumoxane in the presence of a suitable solvent. A complex of the metallocene and alumoxane may be isolated and used as a catalyst in the present invention.
The alumoxanes useful in combination with the catalysts of the present invention, either in the polymerization reaction or in forming the complex disclosed above, may be represented by the general formula (R�Al�O�)n in the cyclic form and R (R�Al�O�)nALR2 in the linear form wherein R is an alkyl group with one to five carbon atoms and n is an integer from 1 to about 20. Most preferably, R is a methyl group and the preferred alumoxane is methylalumoxane (MAO). The alumoxanes can be represented structurally as follows:
The alumoxanes can be prepared by various methods known in the art. Preferably, they are prepared by contacting water with a solution of trialkyl aluminum, such as trimethyl aluminum, in a suitable solvent such as a benzene. Another preferred method includes the preparation of alumcxane in the presence of a hydrated copper sulfate as described in the U.S. Pat. No. 4,404,344 the disclosure of which is hereby incorporated by reference. This method comprises treating a dilute solution of trimethyl aluminum in toluene with copper sulfate. The preparation of other aluminum cocatalysts useful in the present process may be prepared by methods known to those skilled in the art.
The Examples given below illustrate the present invention and its various advantages and benefits in more detail.
The synthesis procedure was performed under an inert gas atmosphere using a Vacuum Atmospheres glovebox or Schlenk techniques.
Step 1
Preparation of the 2,7-di-tert-butylfluorenyl-dimethylsilyl-chloride (1)
a) Aromatization of the fluorene: In a one liter flask equipped with magnetic stirring bar, nitrogen inlet and reflux condenser, there was added a solution of 0.1 mol 2,7-di-tert-butylfluorene in 300 cc of diethyl ether. To this solution was added at room temperature dropwise 0.1 equimol of methyllithium in ether (1.6 molar). The reaction was completed after gas evolution stops. The orange solution was used in the next step.
b) Reaction with dimethyldichlorosilane: The orange solution prepared in step 1 a was added dropwise to a solution of 0.1 mol of dimethyldichlorosilane in 200 cc of ether. The mixture was stirred for several hours at room temperature until the reaction was completed.
Step 2
Preparation of tert-butyllithiumamide (2).
In a one liter flask equipped with magnetic stirring bar, nitrogen inlet and reflux condenser 0.1 mol of tert-butylamine was dissolved in 200 cc of diethyl ether. The solution was cooled to −78� C. One equimol of methyllithium in ether was added dropwise to the solution. The temperature was increased to room temperature slowly. The reaction mixture was stirred for several hours at room temperature until the formation of the title compound was complete.
Step 3
Preparation of 2,7-di-tert-butylfluorenyl-dimethylsilyl-tert-butylamine (3).
The reaction products prepared in step 2 and step 3 were added together and stirred for several hours at room temperature. The LiCl formed as byproduct was filtered off and the ether filterate was subjected to evaporation. The title compound was obtained as a yellow oil.
Step 4
Preparation of 2,7-di-tert-butyl-dimethyl-tert-butylamido titanium dichloride (4).
a) Formation of dianion: 0.25 mol of 3 was dissolved in 200 cc of diethylether. To this solution was added dropwise 0.5 mol of methyllithium in ether. The solution became red. The reaction was stopped after gas evolution had stopped
b) Reaction of the dianion with TiCl4
The red powder obtained after evaporation of the ether from the solution resulting from step 4 b was washed several times with pentane and then reacted with 0.25 mol of TiCl4 in 200 cc pentane. The mixture was stirred for several hours at room temperature and filtered to separate the LiCl. Evaporation of the solvent led to the isolation of a brown powder. Recrystalization of the product from dichloromethane provided spectroscopically pure product �4� (Cf
2,7-di-tert-butyl-fluorenyl-dimethylsilyl-tert-butylamido-zirc onium dichloride (�5�) and the corresponding hafnium derivative (�6�) were formed by repeating example 1 while in step 4 b respectively ZrCl4 or HfCl4 were used instead of TiCl4.
Examples 1 to 3 were repeated while using diphenyldichlorosilane instead of dimethyldichlorosilane in step 1 b. The following metallocenes were formed:
2, 7-di tert-butylfluorenyldiphenylsilyl tertbutylamido titaniumdichloride (�7�).
2, 7-ditert-butylfluorenyldiphenylsilyl tertbutylamido zirconiumdichloride (�8�).
2,7-ditert-butylfluorenyldiphenylsilyl tertbutylamido hafniumdichloride (�9�).
Propylene was polymerized using the metallocenes produced by examples 1 to 6. Two liters of liquid propylene were introduced into a 4 liter bench reactor at room temperature. The metallocene was placed in three milliliters of a 11% solution of MAO in toluene to form a solution which was added to the reactor and the temperature increased to 40� C. The polymerization reaction was allowed to run for 60 minutes during which time the reactor was maintained at the temperature indicated in Tab. 1 for each individual run. The reaction was terminated by venting the reactor of monomer. The catalyst activity in grams of polypropylene per grams of catalyst per hour was calculated. The molecular weight, molecular weight distrubution and 13C NMR analysis of the polymer were determined. The results are shown in Table 1.
polymerization of propylene with �4� at 60� C.
polymerization of propylene with �4� at 40� C.
polymerization of Propylene with �4� at 40� C.
polymerization of propylene with �4� at 60� C. in 1 liter of cyclohexane
copolymerization of propylene and ethylene with �4� at 60� C.
polymerization of propylene with �5� at 60� C.
polymerization of propylene with �6� at 60� C.
polymerization of propylene with �7� at 60� C.
The polymerization conditions and results are summarized in Table 1.
6 batches of syndiotactic/atactic polypropylene (batches A to F) were prepared on pilot plant scale using a 120l reactor using catalyst 4. In this Example, the reaction was performed in the presence of cyclohexane as a solvent (the reaction could be performed in the presence or absence of solvent) at a starting temperature of 40� C. (starting temperatures of 35� C. to 60� C. can be used). Temperature and pressure were monitored during the reaction. The reaction is exothermic and the temperature was allowed to increase. The end of the reaction was determined when the temperature stopped increasing. The pressure during the reaction was maintained at 12 bar by addition of monomer. Consumption of monomer would tend to reduce the pressure otherwise. At the end of the reaction, conventional polypropylene antioxidants were added to the material. Polymer was recovered by steam stripping to remove solvent and produce white polymer crumbs in water, which were then further processed.
Various properties of the polymer product are set out in Table 2 and compared against Finaprene type pilot plant products F401 and F414. Finaprene is a commercially available elastomer produced by solution polymerisation using anionic-type initiators and is based on butadiene and styrene monomers.
It will be apparent from Table 2 that batches A to F increase in molecular weight and this increase in molecular weight tends to give rise to advantageous properties. In particular, elongation increases, and tensile strength and tensile modulus both decrease with increasing molecular weight. This suggests that the higher molecular weight material may be softer, which could partly result from an increased atactic content in the block copolymer. Depending on the end use of the syndiotactic/atactic block polypropylene, molecular weight and atactic/syndiotactic ratio may be optimised accordingly.
In this Example, batch E of syndiotactic/atactic polypropylene was subjected to different crystallisation times and compared again to the Finaprene F401 and F414 pilot plant materials. As set out in Table 3, the results indicate that adjustment of crystallisation time will affect the final properties of the polymer enabling it to be tailored for particular uses. Appropriate adjustment of the crystallisation time will affect the shapability and shrinkability of the polymer and can therefore be adjusted for use as a shapable composition or for use as a shrinkable packaging film. The final properties of drawn fibre can also be modulated in this way.
Table 4 sets out in further detail fusion and crystallisation parameters according to the indicated programme for a number of batches of the syndiotactic/atactic polypropylene according to the invention.
Footwear formulations were made as set out in Table 5 in which a blend of syndiotactic/atactic polypropylene with Finaprene F484 was compared with a standard Finaprene formulation. It was found that the melt flow index was higher when the syndiotactic/atactic polypropylene was used, enabling a higher output of material. However, the hardness of the material was very similar to the standard formulation. This suggests lower cost of production of material according to the present invention without loss of hardness, as compared with conventional formulations. Both rebound and elongation were lowered according to the invention suggesting better shock absorbance. The formulations according to the invention would therefore be excellent for use as soles in jogging shoes, for example.
The ability of syndiotactic/atactic to tolerate modification with mineral fillers was examined. Table 6 shows a comparison of various properties of blends of syndiotactic/atactic polypropylene with talc or carbon black as compared with pure syndiotactic/atactic polypropylene. It is apparent from the Table that hardness is only slightly altered through the addition of mineral fillers. This is unusual and is unexpected and represents a useful property because it is therefore possible to dilute the syndiotactic/atactic polypropylene without significant hardness variation. It is also found that the tensile strength at yield increases in spite of any large change in hardness. This is useful because the mineral fillers may be used to adjust the tensile strength without affecting the hardness thereby affording a degree of control over the final properties of the modified syndiotactic/atactic polypropylene depending on the use to which it is to be put. It will also be apparent from the Table that the rebound has been lowered upon modification with the mineral fillers. This property is useful in the production of shock absorbers.
The usefulness of syndiotactic/atactic polypropylene as a polymer modifier was investigated taking commercially-available polypropylene PP9060 as an example of a polymer to be modified. The results are set out in Table 7. It will be apparent from the Table that PP9060 modified with 5% syndiotactic/atactic polypropylene produces a material which, most strikingly, has an exceptional impact resistance when unnotched. This suggests that the syndiotactic/atactic polypropylene is highly useful as a polypropylene modifier and that the modified polypropylene would have utility as a shock absorber, a waterproof membrane, in packaging film, as a drawn film and in shapable compositions.
Bitumen was modified with syndiotactic/atactic polypropylene by mixing together 13% of syndiotactic/atactic polypropylene with 87% standard bitumen in a low speed blender. Various properties of the modified bitumen were assessed and the results presented in Table 8. It appears that the syndiotactic/atactic polypropylene forms a dispersed phase in a continuous phase of bitumen and that no significant swelling of the dispersed phase occurs. This is useful because it enables a degree of control over the modified bitumen product which is not readily available in the prior art. The modified bitumen may be used as a waterproof membrane or in the manufacture of joints where it is expected that application of syndiotactic/atactic polypropylene to a surface is easier to control.
Adhesive compositions were prepared using syndiotactic/atactic polypropylene in combination with various other standard adhesive components. The adhesive compositions are set out in Table 9, together with some of their properties. Adhesive formulations 2 and 3 in the Table are useful in bookbinding applications. This may be deduced from the so-called bookbinding �application window� in which the storage modulus G′ is in the range 3�106 to 5�107 and the glass transition temperature of the soft phase, Tg is in the range 5 to 30� C. Both formulations 2 and 3 fall within this range. The Theological behaviour of formulations 1, 2 and 3 are shown graphically in
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