text:
JFK Website (0)
Digital Archives (109)
Person: O'Donnell, Kenneth (Kenneth P.), 1924-1977
Oral history(4)
Sound recording(2)
Textual folder(3)
White House Photographs(95)
Papers of John F. Kennedy. Presidential Papers. Miscellaneous Presidential Files. White House Telephone Memorandums and Toll Tickets(3)
John F. Kennedy Oral History Collection(2)
Robert F. Kennedy Oral History Collection(2)
Papers of John F. Kennedy. Presidential Papers. President's Office Files.(2)
Margaret Ronayne Hahn Personal Papers(1)
Voyages and travels(51)
International relations(32)
News media(8)
Kennedy, John F. (John Fitzgerald), 1917-1963(85)
Salinger, Pierre (Pierre Emil George), 1925-2004(24)
Behn, Gerald A., 1916-1983(20)
Powers, Dave (David Francis), 1912-1998(16)
Onassis, Jacqueline Kennedy, 1929-1994(15)
New York (State)(13)
Mexico City (Mexico)(11)
New York (N.Y.)(7)
Aeropuerto Internacional Benito Juárez(8)
Basílica de Nuestra Señora de Guadalupe (Gustavo A. Madero, Mexico)(3)
Department of Defense. Department of the Navy. Naval Air Station, Alameda, California. (09/18/1947 - 04/25/1997)(3)
United States. Army. Military Academy(8)
United States. Navy(3)
Kennedy, John F. (John Fitzgerald), 1917-1963(2)
Knudsen, Robert L. (Robert LeRoy), 1929-1989(43)
Rowe, Abbie, 1905-1967(9)
Sellers, Harold L.(3)
Stoughton, Cecil W. (Cecil William), 1920-2008(40)
White House Staff Files 1961-1964. Staff Assistant, Office of Personnel and Miscellaneous Staff Services. Correspondence, memorandums, files relating to recruitment of Presidential and non-Presidential appointees.
Photographs, 1957–1970. Black-and-white prints of images made by New York Times photographers featuring John F. Kennedy and administration officials during the Kennedy Presidency; Robert F. Kennedy as Senate counsel, United States Attorney General, U. S. Senate candidate, United States Senator for New York, and 1968 Presidential candidate; and the ...
Papers 1924-1977. Assistant and friend to Robert and John F. Kennedy, government official, politician, author, businessman. Assistant Counsel, Select Committee to Investigate Improper Activities in Labor-Management Relations in the Senate (1957-59), Campaign Director, Kennedy for President (1960), Appointment secretary to the President (1961-1963)...
White House Staff Files 1962 - 1963. Assistant to the President (1961-65); Appointment secretary to the President (1961-63); Special Assistant to the President (1961-65). Correspondence [fragment].
In this interview they discuss their article in Look magazine; personal recollections of President John F. Kennedy's [JFK] assassination; working on JFK's 1960 presidential campaign; JFK's campaigning style; JFK's relationship with the press, White House staff, and his family; and JFK's trips to Nassau, Europe, and Vice President Lyndon B. Johnson'...
In this interview Dutton discusses his personal and working relationships with Robert F. Kennedy [RFK]; his role in Lyndon B. Johnson's 1964 presidential campaign; RFK's staff from 1964 to 1968; and RFK's 1968 presidential campaign, among other issues.
In this interview Hackett discusses meeting Robert F. Kennedy [RFK] for the first time at Milton Academy and their continued friendship; working on John F. Kennedy's 1960 presidential campaign, including observations of other members of the campaign staff; the lead up to and working on RFK's 1968 presidential campaign, including tensions between th...
In this interview Halaby discusses different civil rights issues throughout John F. Kennedy's [JFK] Administration, including the process of and problems with desegregating airport terminals in accordance with Boynton v. Virginia (1960); the 1961 hijacking of a plane, referred to as the El Paso incident; constructing and dedicating the new John Fos...
President John F. Kennedy poses with his staff in the Oval Office, White House, Washington, D.C. (L-R) Front Row: Assistant Special Counsel to the President Richard Goodwin; Secretary to Pierre Salinger Sue Mortensen Vogelsinger; Staff Assistant Dorothy McCann; Personal Secretary to the President Evelyn Lincoln; two unidentified; President Kennedy;...
Special Assistant to the President Kenneth P. O'Donnell. White House, Washington, D.C.
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JOHN F. KENNEDY PRESIDENTIAL LIBRARY AND MUSEUMColumbia Point, Boston MA 02125 (617) 514-1600


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subset: commoncrawl


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COLLIER COUNTY, Fla.- The Florida Highway Patrol says one person has died after a 3-car crash on St. Road 82 and Corkscrew Rd. in Collier County. All lanes of 82 are back open this morning.
It happened around 7:30 Friday night. FHP says a driver heading east on SR 82 tried to pass traffic, and hit a car heading west.
That car overturned and the driver, 74-year-old Medardo Garcia of Miami, died on scene.
Five other people went to the hospital with injuries.


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Findern Footpaths Group was formed in 1998 when Findern Parish Council wished to set up a working party to care for our countryside. We are all volunteers and we work to maintain, improve and promote the ten kilometres of public rights of way we have here in Findern. These rights of way follow a wide variety of routes alongside streams, ponds and the Trent and Mersey Canal and through flower-rich meadows, historical sites and woodland. Some routes offer stunning views over the countryside towards Repton or Derby
Have you ever seen down to the bottom of a...Read More
Are you interested in mammals? Are you the...Read More
Group members were out recently with members from...Read More
We have been working in partnership with to...Read More
There were lots of things to do and see at our on...Read More
A programme of improvements have succeeded in making the routes more accessible to everyone particularly the less able and those with young children. Additionally, a regular programme of events has dramatically increased the number of people using the routes for walking, horse riding or cycling. On land leased by Findern Parish Council, the group have created diverse habitats to encourage wildlife, including the creation of woodland, managed scrubland, hedgerow, wetland, wildflower meadow and the restoration of two ponds.


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There's no such thing as showing too much Kevin Harvick pride on a race weekend, so walk proudly boasting your pride for the #29 in this Vintage Stripe tee. The front features racing team-colored stripes on the left side overlayed by a large printed sponsor logo on the top. As you race around the crowd trying to find your seats, everyone will still know that you root on the #29 as Harvick's number is printed on the back with a Richard Childress Racing logo. Your loyalty to one of the greatest racers today will never be questioned again.
- 100% Cotton fabric
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Special event items are produced by manufacturers only after the outcome of a game or event. These are advanced sale items and will ship immediately after they are received in our warehouse.
Manufacturer direct items are shipped directly from the manufacturer. These items are not available for international or expedited shipping.
Customized items can be personalized with options such as your name, your favorite number, and/or designs. Some options may be limited by league rules.


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Paramount (T.PZG) intercepts 3.79 g/t Au and 184 g/t Ag over 5.4 metres on newly discovered Dana structure
101,thanks for the post. As I read it, the Don Ese zone could be really important for the project economics. What's your point of view...
Paramount Gold and Silver Reports Positive New Resource Estimate for Its San Miguel Project, Mexico WINNEMUCCA, NEVADA--(Marketwired -...
Paramount Gold and Silver Reports Excellent Recoveries From Leaching of San Miguel Project Open Pit Material WINNEMUCCA, NEVADA...
May 13, Jeb wrote > Keep a close eye on Paramount Gold and Silver (PZG) as there is a large short on it that may soon run for cover.
Entry into a Material Definitive Agreement, Financial Statements an Item 1.01. Entry into a Material Definitive Agreement...


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Department: Technology Location: Providence, RI Type: Full time, Salaried, Exempt Web Developers at ShapeUp build and maintain the web platform that drives better health and fitness for hundreds of thousands of people throughout the world. ShapeUp is on a mission to create a11/25/2014 Providence, RI Save This Job
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Zipper Front Denim Sheath Dress
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Most Popular "Concert" Titles
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1. Old School (2003)
R | 91 min | Comedy
Three friends attempt to recapture their glory days by opening up a fraternity near their alma mater.
Writers: Court Crandall, Todd Phillips, Scot Armstrong | Director: Todd Phillips | Stars: Luke Wilson, Vince Vaughn, Will Ferrell, Jeremy Piven
2. Taken (I) (2008)
PG-13 | 93 min | Action, Crime, Thriller
A retired CIA agent travels across Europe and relies on his old skills to save his estranged daughter, who has been kidnapped while on a trip to Paris.
Writers: Luc Besson, Robert Mark Kamen | Director: Pierre Morel | Stars: Liam Neeson, Maggie Grace, Famke Janssen, Jon Gries
3. Ted (2012)
R | 106 min | Comedy, Fantasy
As the result of a childhood wish, John Bennett's teddy bear, Ted, came to life and has been by John's side ever since - a friendship that's tested when Lori, John's girlfriend of four years, wants more from their relationship.
Writers: Seth MacFarlane, Alec Sulkin, Wellesley Wild | Director: Seth MacFarlane | Stars: Mark Wahlberg, Mila Kunis, Seth MacFarlane, Joel McHale
4. Hot Tub Time Machine (2010)
R | 101 min | Adventure, Comedy, Sci-Fi
A malfunctioning time machine at a ski resort takes a man back to 1986 with his two friends and nephew, where they must relive a fateful night and not change anything to make sure the nephew is born.
Writers: Josh Heald, Sean Anders, John Morris | Director: Steve Pink | Stars: John Cusack, Rob Corddry, Craig Robinson, Clark Duke
5. Almost Famous (2000)
R | 122 min | Drama, Music, Romance
A high-school boy is given the chance to write a story for Rolling Stone Magazine about an up-and-coming rock band as he accompanies it on their concert tour.
Writer: Cameron Crowe | Director: Cameron Crowe | Stars: Billy Crudup, Patrick Fugit, Kate Hudson, Frances McDormand
6. Fracture (2007)
R | 113 min | Crime, Drama, Mystery
An attorney, intent on climbing the career ladder toward success, finds an unlikely opponent in a manipulative criminal he is trying to prosecute.
Writers: Daniel Pyne, Glenn Gers | Director: Gregory Hoblit | Stars: Anthony Hopkins, Ryan Gosling, David Strathairn, Rosamund Pike
7. God's Not Dead (2014)
PG | 113 min | Drama
College philosophy professor Mr. Radisson's curriculum is challenged by his new student, Josh, who believes God exists.
Writers: Hunter Dennis, Chuck Konzelman, Cary Solomon | Director: Harold Cronk | Stars: Shane Harper, Kevin Sorbo, David A.R. White, Dean Cain
8. Clouds of Sils Maria (2014)
124 min | Drama
At the peak of her international career, Maria Enders is asked to perform in a revival of the play that made her famous twenty years ago. But back then she played the role of Sigrid, an ... See full summary »
Writer: Olivier Assayas | Director: Olivier Assayas | Stars: Juliette Binoche, Kristen Stewart, Chloë Grace Moretz, Lars Eidinger
9. The Pianist (2002)
R | 150 min | Biography, Drama, War
A Polish Jewish musician struggles to survive the destruction of the Warsaw ghetto of World War II.
Writers: Ronald Harwood, Wladyslaw Szpilman | Director: Roman Polanski | Stars: Adrien Brody, Thomas Kretschmann, Frank Finlay, Emilia Fox
10. Get on Up (2014)
PG-13 | 139 min | Biography, Drama, Music
A chronicle of James Brown's rise from extreme poverty to become one of the most influential musicians in history.
Writers: Jez Butterworth, John-Henry Butterworth, Steven Baigelman | Director: Tate Taylor | Stars: Chadwick Boseman, Nelsan Ellis, Dan Aykroyd, Viola Davis
11. Gattaca (1997)
PG-13 | 106 min | Drama, Romance, Sci-Fi
A genetically inferior man assumes the identity of a superior one in order to pursue his lifelong dream of space travel.
Writer: Andrew Niccol | Director: Andrew Niccol | Stars: Ethan Hawke, Uma Thurman, Jude Law, Gore Vidal
12. Inside Llewyn Davis (2013)
R | 104 min | Drama, Music
A week in the life of a young singer as he navigates the Greenwich Village folk scene of 1961.
Writers: Joel Coen, Ethan Coen | Directors: Ethan Coen, Joel Coen | Stars: Oscar Isaac, Carey Mulligan, John Goodman, Garrett Hedlund
13. The Lost Boys (1987)
R | 97 min | Comedy, Horror
After moving to a new town, two brothers are convinced that the area is frequented by vampires.
Writers: Jan Fischer, James Jeremias, Jeffrey Boam | Director: Joel Schumacher | Stars: Jason Patric, Corey Haim, Dianne Wiest, Barnard Hughes
14. The Crow (1994)
R | 102 min | Action, Fantasy
A man brutally murdered comes back to life as an undead avenger of his and his fiancée's murder.
Writers: James O'Barr, David J. Schow, John Shirley | Director: Alex Proyas | Stars: Brandon Lee, Michael Wincott, Rochelle Davis, Ernie Hudson
15. Walk the Line (2005)
PG-13 | 136 min | Biography, Drama, Music
A chronicle of country music legend Johnny Cash's life, from his early days on an Arkansas cotton farm to his rise to fame with Sun Records in Memphis, where he recorded alongside Elvis Presley, Jerry Lee Lewis and Carl Perkins.
Writers: Johnny Cash, Gill Dennis, James Mangold | Director: James Mangold | Stars: Joaquin Phoenix, Reese Witherspoon, Ginnifer Goodwin, Robert Patrick
16. The Blues Brothers (1980)
R | 133 min | Action, Comedy, Crime
Jake Blues, just out from prison, puts together his old band to save the Catholic home where he and brother Elwood were raised.
Writers: Dan Aykroyd, John Landis | Director: John Landis | Stars: John Belushi, Dan Aykroyd, Cab Calloway, John Candy
17. Rock of Ages (2012)
PG-13 | 123 min | Comedy, Drama, Musical
A small town girl and a city boy meet on the Sunset Strip, while pursuing their Hollywood dreams.
Writers: Justin Theroux, Chris D'Arienzo, Allan Loeb | Director: Adam Shankman | Stars: Julianne Hough, Diego Boneta, Tom Cruise, Alec Baldwin
18. Home Alone 2: Lost in New York (1992)
PG | 120 min | Adventure, Comedy, Family
One year after Kevin was left home alone and had to defeat a pair of bumbling burglars, he accidentally finds himself in New York City, and the same criminals are not far behind.
Writer: John Hughes | Director: Chris Columbus | Stars: Macaulay Culkin, Joe Pesci, Daniel Stern, Catherine O'Hara
19. Red Dragon (2002)
R | 124 min | Crime, Thriller
A retired FBI agent with psychological gifts is assigned to help track down "The Tooth Fairy", a mysterious serial killer; aiding him is imprisoned criminal genius Hannibal "The Cannibal" Lecter.
Writers: Thomas Harris, Ted Tally | Director: Brett Ratner | Stars: Anthony Hopkins, Edward Norton, Ralph Fiennes, Harvey Keitel
20. Across the Universe (2007)
PG-13 | 133 min | Drama, Fantasy, Musical
The music of the Beatles and the Vietnam War form the backdrop for the romance between an upper-class American girl and a poor Liverpudlian artist.
Writers: Dick Clement, Ian La Frenais, Julie Taymor | Director: Julie Taymor | Stars: Evan Rachel Wood, Jim Sturgess, Joe Anderson, Dana Fuchs
21. Inspector Morse (1987–2000)
100 min | Crime, Drama, Mystery
Inspector Morse has an ear for music, a taste for beer and a nose for crime. He sets out with Sergeant Lewis to solve each intriguing case.
Stars: John Thaw, Kevin Whately, James Grout, Peter Woodthorpe
22. Wayne's World (1992)
PG-13 | 94 min | Comedy, Music
Two slacker friends try to promote their public-access cable show.
Writers: Mike Myers, Bonnie Turner, Terry Turner | Director: Penelope Spheeris | Stars: Mike Myers, Dana Carvey, Rob Lowe, Tia Carrere
23. Animal House (1978)
R | 109 min | Comedy
At a 1962 College, Dean Vernon Wormer is determined to expel the entire Delta Tau Chi Fraternity, but those trouble-makers have other plans for him.
Writers: Harold Ramis, Douglas Kenney, Chris Miller | Director: John Landis | Stars: John Belushi, Karen Allen, Tom Hulce, Stephen Furst
24. Hard Candy (2005)
R | 104 min | Crime, Drama, Thriller
A teenage girl raids a man's home, suspecting he is a pedophile, in order to expose him.
Writer: Brian Nelson | Director: David Slade | Stars: Patrick Wilson, Ellen Page, Sandra Oh, Odessa Rae
25. Chloe (2009)
R | 96 min | Drama, Mystery, Thriller
A doctor hires an escort to seduce her husband, whom she suspects of cheating, though unforeseen events put the family in danger.
Writers: Erin Cressida Wilson, Anne Fontaine | Director: Atom Egoyan | Stars: Julianne Moore, Amanda Seyfried, Liam Neeson, Max Thieriot
26. White Christmas (1954)
Approved | 120 min | Comedy, Musical, Romance
A successful song-and-dance team become romantically involved with a sister act and team up to save the failing Vermont inn of their former commanding general.
Writers: Norman Krasna, Norman Panama, Melvin Frank | Director: Michael Curtiz | Stars: Bing Crosby, Danny Kaye, Rosemary Clooney, Vera-Ellen
27. The Adventures of Tintin (2011)
PG | 107 min | Animation, Action, Adventure
Intrepid reporter Tintin and Captain Haddock set off on a treasure hunt for a sunken ship commanded by Haddock's ancestor.
Writers: Steven Moffat, Edgar Wright, Joe Cornish, Hergé | Director: Steven Spielberg | Stars: Jamie Bell, Andy Serkis, Daniel Craig, Simon Pegg
28. Road House (1989)
R | 114 min | Action, Thriller
A tough bouncer is hired to tame a dirty bar.
Writers: David Lee Henry, Hilary Henkin | Director: Rowdy Herrington | Stars: Patrick Swayze, Kelly Lynch, Sam Elliott, Ben Gazzara
29. August Rush (2007)
PG | 114 min | Drama, Music
A drama with fairy tale elements, where an orphaned musical prodigy uses his gift as a clue to finding his birth parents.
Writers: Nick Castle, James V. Hart, Paul Castro | Director: Kirsten Sheridan | Stars: Freddie Highmore, Keri Russell, Jonathan Rhys Meyers, Terrence Howard
30. The Broken Circle Breakdown (2012)
Not Rated | 111 min | Drama, Music, Romance
Elise and Didier fall in love at first sight, in spite of their differences. He talks, she listens. He's a romantic atheist, she's a religious realist. When their daughter becomes seriously ill, their love is put on trial.
Writers: Johan Heldenbergh, Mieke Dobbels, Carl Joos, Felix van Groeningen, Charlotte Vandermeersch | Director: Felix van Groeningen | Stars: Veerle Baetens, Johan Heldenbergh, Nell Cattrysse, Geert Van Rampelberg
31. Queen of the Damned (2002)
R | 101 min | Fantasy, Horror, Music
The vampire Lestat becomes a rock star whose music wakes up the queen of all vampires.
Writers: Anne Rice, Scott Abbott, Michael Petroni | Director: Michael Rymer | Stars: Aaliyah, Stuart Townsend, Marguerite Moreau, Vincent Perez
32. Jodorowsky's Dune (2013)
PG-13 | 90 min | Documentary
The story of cult film director Alejandro Jodorowsky's ambitious but ultimately doomed film adaptation of the seminal science fiction novel.
Director: Frank Pavich | Stars: Alejandro Jodorowsky, Michel Seydoux, H.R. Giger, Chris Foss
33. I Love You, Man (2009)
R | 105 min | Comedy
Friendless Peter Klaven goes on a series of man-dates to find a Best Man for his wedding. But when his insta-bond with his new B.F.F. puts a strain on his relationship with his fiancée, can the trio learn to live happily ever after?
Writers: John Hamburg, Larry Levin | Director: John Hamburg | Stars: Paul Rudd, Jason Segel, Rashida Jones, Sarah Burns
34. An Education (2009)
PG-13 | 100 min | Drama
A coming-of-age story about a teenage girl in 1960s suburban London, and how her life changes with the arrival of a playboy nearly twice her age.
Writers: Lynn Barber, Nick Hornby | Director: Lone Scherfig | Stars: Carey Mulligan, Peter Sarsgaard, Alfred Molina, Olivia Williams
35. Music and Lyrics (2007)
PG-13 | 96 min | Comedy, Music, Romance
A washed up singer is given a couple days to compose a chart-topping hit for an aspiring teen sensation. Though he's never written a decent lyric in his life, he sparks with an offbeat younger woman with a flair for words.
Writer: Marc Lawrence | Director: Marc Lawrence | Stars: Hugh Grant, Drew Barrymore, Scott Porter, Nick Bacon
36. Get Him to the Greek (2010)
R | 109 min | Comedy, Music
A record company intern is hired to accompany out-of-control British rock star Aldous Snow to a concert at L.A.'s Greek Theater.
Writers: Nicholas Stoller, Jason Segel | Director: Nicholas Stoller | Stars: Jonah Hill, Russell Brand, Elisabeth Moss, Rose Byrne
37. The Runaways (2010)
R | 106 min | Biography, Drama, Music
A coming-of-age biographical film about the 1970s teenage all-girl rock band The Runaways. This film also explores the relationship between band members Joan Jett and Cherie Currie.
Writers: Floria Sigismondi, Cherie Currie | Director: Floria Sigismondi | Stars: Kristen Stewart, Dakota Fanning, Michael Shannon, Stella Maeve
38. Black Snake Moan (2006)
R | 116 min | Drama
A God-fearing bluesman takes to a wild young woman who, as a victim of childhood sexual abuse, looks everywhere for love, never quite finding it.
Writer: Craig Brewer | Director: Craig Brewer | Stars: Christina Ricci, Samuel L. Jackson, Justin Timberlake, S. Epatha Merkerson
39. Walk Hard: The Dewey Cox Story (2007)
R | 96 min | Comedy, Music
Singer Dewey Cox overcomes adversity to become a musical legend.
Writers: Judd Apatow, Jake Kasdan | Director: Jake Kasdan | Stars: John C. Reilly, Jenna Fischer, David Krumholtz, Nat Faxon
40. Prom (2011)
PG | 104 min | Comedy, Drama
A group of teenagers get ready for their high school prom.
Writer: Katie Wech | Director: Joe Nussbaum | Stars: Aimee Teegarden, Thomas McDonell, DeVaughn Nixon, Danielle Campbell
41. Doctor Zhivago (1965)
PG-13 | 197 min | Drama, Romance, War
The life of a Russian physician and poet who, although married to another, falls in love with a political activist's wife and experiences hardship during the First World War and then the October Revolution.
Writers: Boris Pasternak, Robert Bolt | Director: David Lean | Stars: Omar Sharif, Julie Christie, Geraldine Chaplin, Rod Steiger
42. Just My Luck (2006)
PG-13 | Comedy, Fantasy, Romance
Manhattanite Ashley is known to many as the luckiest woman around. After a chance encounter with a down-and-out young man, however, she realizes that she's swapped her fortune for his.
Writers: I. Marlene King, Amy Harris, Jonathan Bernstein, Mark Blackwell, James Greer | Director: Donald Petrie | Stars: Lindsay Lohan, Chris Pine, Samaire Armstrong, Bree Turner
43. I'm Not There. (2007)
R | 135 min | Biography, Drama, Music
Ruminations on the life of Bob Dylan, where six characters embody a different aspect of the musician's life and work.
Writers: Todd Haynes, Oren Moverman | Director: Todd Haynes | Stars: Christian Bale, Cate Blanchett, Heath Ledger, Ben Whishaw
44. 9 Songs (2004)
Not Rated | 71 min | Drama, Music, Romance
In London, England, love blooms between an American college student, named Lisa, and a British glaciologist, named Matt, where over the next few months in between attending rock concerts, the two lovers have intense sexual encounters.
Writer: Michael Winterbottom | Director: Michael Winterbottom | Stars: Kieran O'Brien, Margo Stilley, Huw Bunford, Cian Ciaran
45. The Living Daylights (1987)
PG | 130 min | Action, Adventure, Romance
James Bond is living on the edge to stop an evil arms dealer from starting another world war. Bond crosses all seven continents in order to stop the evil Whitaker and General Koskov.
Writers: Richard Maibaum, Michael G. Wilson | Director: John Glen | Stars: Timothy Dalton, Maryam d'Abo, Jeroen Krabbé, Joe Don Baker
46. Howard the Duck (1986)
PG | 110 min | Action, Adventure, Comedy
A sarcastic humanoid duck is pulled from his homeworld to Earth where he must stop an alien invader.
Writers: Steve Gerber, Willard Huyck, Gloria Katz | Director: Willard Huyck | Stars: Lea Thompson, Jeffrey Jones, Tim Robbins, Ed Gale
47. The Simpsons Movie (2007)
PG-13 | 87 min | Animation, Adventure, Comedy
After Homer accidentally pollutes the town's water supply, Springfield is encased in a gigantic dome by the EPA and the Simpson family are declared fugitives.
Writers: James L. Brooks, Matt Groening, Al Jean, Ian Maxtone-Graham, George Meyer, David Mirkin, Mike Reiss, Mike Scully, Matt Selman, John Swartzwelder, Jon Vitti, Joel H. Cohen, John Frink, Tim Long, Michael Price | Director: David Silverman | Stars: Dan Castellaneta, Julie Kavner, Nancy Cartwright, Yeardley Smith
48. Ray (I) (2004)
PG-13 | 152 min | Biography, Drama, Music
The story of the life and career of the legendary rhythm and blues musician Ray Charles, from his humble beginnings in the South, where he went blind at age seven, to his meteoric rise to stardom during the 1950s and 1960s.
Writers: Taylor Hackford, James L. White | Director: Taylor Hackford | Stars: Jamie Foxx, Regina King, Kerry Washington, Clifton Powell
49. The Lizzie McGuire Movie (2003)
PG | 94 min | Adventure, Comedy, Family
Lizzie McGuire has graduated from middle school and takes a trip to Rome, Italy with her class. And what was supposed to be only a normal trip, becomes a teenager's dream come true.
Writers: Susan Estelle Jansen, Ed Decter, John J. Strauss, Terri Minsky | Director: Jim Fall | Stars: Hilary Duff, Adam Lamberg, Clayton Snyder, Hallie Todd
50. Dreamgirls (2006)
PG-13 | 130 min | Drama, Music, Musical
A trio of black female soul singers cross over to the pop charts in the early 1960s, facing their own personal struggles along the way.
Writers: Bill Condon, Tom Eyen | Director: Bill Condon | Stars: Beyoncé Knowles, Jamie Foxx, Eddie Murphy, Danny Glover


text:
The Sabres Observer
Report: Regier Interested In Kings' Toffoli
by @DaveDavisHockey on 03/26/13 at 02:12 PM ET
Comments (3)
We've been seeing plenty of names on Buffalo's roster reported in trade talks, but not much has been mentioned in the way of whom they'd like to get back.
An aritcle this morning did indeed bring up the name of a promising young prospect attracting interest from the Sabres.
According to a report from The Fourth Period, Sabres GM Darcy Regier is making an effort to land Los Angeles Kings youngster Tyler Toffoli.
The 20-year-old center from Scarborough, Ontario is considered by many to be the top prospect in L.A.'s system. Although Robyn Regehr & Drew Stafford have been mentioned in talks between the Sabres and Kings, I'd be very surprised if those players were enough to land Toffoli. Scouts see him as having a great skill set and terrific upside. Check out his impressive goal against Chicago last night:
Filed in: | The Sabres Observer | Permalink
Tags: "tyler+toffoli"
Its also rumored that people in hell want ice water
Posted by Hootinani on 03/26/13 at 02:33 PM ET
As a Sens fan, I would hate for Buffalo to get Tyler. Having watched him play junior with the 67's, he's a helluva player.
Posted by Chris M on 03/26/13 at 02:43 PM ET
The ice water in hell comment was funny last year when Regier wanted Cody Hodgson.
Posted by @DaveDavisHockey from Buffalo, NY on 03/26/13 at 02:47 PM ET
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text:
Various phenol-free phosphites for use in PVC as an alternative to the conventional phenol-containing products phenyl diisodecyl phosphite and diphenyl isodecyl phosphite were tested. These phosphites utilize para-cumyl phenol-based derivatives in order to provide a phenol free derivative of the above mentioned conventional phosphites.
1. A process for reducing phenol emissions from a polymer resin comprising the step of adding at least one phosphite additive of formula (I) to said resin, wherein said formula (I) comprises:
R1 is
R2 is selected from the group consisting of C8-16 alkyls;
R3 is selected from the group consisting of C1-4 alkylenes;
m is 1;
a is an integral value ranging from 1 to 4 inclusive;
b is an integral value ranging from 1 to 2 inclusive; and
R4 and R5 are independently selected from the group consisting of C1-3 alkyls;
R6 is selected from the group consisting of C8-12 alkyls and C8-12 alkoxy compounds;
c is an integral value ranging from 0 to 4 inclusive; and
d is equal to m.
2. The process of
R2 is C10H21;
R3 is selected from the group consisting of ethylene and propylene;
a is 1;
R4 and R5 are methyl;
c is 0; and
d is 1.
4. The process of
5. The process of
6. The process of
7. A process for reducing phenol emissions from a polymer resin comprising the step of adding at least one phosphite additive of formula (II) to said resin, wherein said formula (II) comprises:
8. The process of
R2 is C10H21; and
a is 1.
9. The process of
10. The process of
11. The process of
12. A process for reducing phenol emissions from a polymer resin comprising the step of adding at least one phosphite additive to said resin, said at least one phosphite selected from the group consisting of formulas (I) and (II)
R1 is
R2 is selected from the group consisting of C8-16 alkyls;
R3 is selected from the group consisting of C1-4 alkylenes;
m is 1;
a is an integral value ranging from 1 to 4 inclusive;
b is an integral value ranging from 1 to 2 inclusive;
R4 and R5 are independently selected from the group consisting of C1-3 alkyls;
R6 is selected from the group consisting of C8-12 alkyls and C8-12 alkoxy compounds;
c is an integral value ranging from 0 to 4 inclusive; and
d is equal to m.
13. The process of
R2 is C10H21;
R3 is selected from the group consisting of ethylene and propylene;
a is 1;
R4 and R5 are methyl;
c is 0; and
d is 1.
15. The process of
16. The process of
17. The process of
18. A process for reducing the emission of phenol from a polymer resin which comprises replacing at least a portion of a phosphite additive which emits phenol from said resin with a phosphite composition selected from the group consisting of
R1 is
R2 is selected from the group consisting of C8-16 alkyls;
R3 is selected from the group consisting of C1-4 alkylenes;
m is 1;
a is an integral value ranging from 1 to 4 inclusive;
b is an integral value ranging from 1 to 2 inclusive;
R4 and R5 are independently selected from the group consisting of C1-3 alkyls;
R6 is selected from the group consisting of C8-12 alkyls and C8-12 alkoxy compounds;
c is an integral value ranging from 0 to 4 inclusive; and
d is equal to m.
19. The process of
R2 is C10H21;
R3 is selected from the group consisting of ethylene and propylene;
a is 1;
R4 and R5 are methyl;
c is 0; and
d is 1.
21. The process of
22. The process of
23. The process of
This invention claims priority to U.S. patent application Ser. No. 10/709,510, filed May 11, 2004, now U.S. Pat. No. 7,320,764 which is a continuation-in-part of U.S. patent application Ser. No. 10/086,619, filed Mar. 1, 2002, now U.S. Pat. No. 6,824,711 which is a non-provisional patent application of U.S. Provisional Patent Application Ser. No. 60/315,746 filed on Aug. 29, 2001 and United States Provisional Patent Application Ser. No. 60/314,181 filed on Aug. 16, 2001 and U.S. Provisional Patent Application Ser. No. 60/273,303 filed on Mar. 2, 2001.
The invention relates to phenol-free phosphites, which can be used to stabilize organic polymers, especially polyvinyl chloride (�PVC�).
Liquid organic phosphites have been used for many years alone and in combination with mixed metal stabilizers for the stabilization of vinyl halide polymers, especially PVC. The Encyclopedia of PVC, Volume 1, L. Nass, Ed., Marcel Dekker Inc., New York, 1977. The phosphite esters employed may be trialkyl, triaryl, mixed alkyl/aryl, and even polymeric.
The problem of imparting polyvinyl chloride with sufficient heat processing stability at temperatures at which the polymer becomes sufficiently fluid or softened to permit shaping is of course of long standing, and has been satisfactorily resolved by the addition to the polymer of various combinations of known heat stabilizers. At processing temperatures, the PVC resin can degrade, liberating hydrogen chloride, discolor, become brittle, and stick to the processing equipment. These problems are overcome by combining with the polymer before heat processing or during heat processing, one or more of the well established and conventional heat stabilizers, such as, for example, alkyl tin mercaptides or barium/cadmium or barium/zinc or calcium/zinc salt mixed metal stabilizers, aryl, alkyl and mixed aryl/alkyl phosphites, or combinations of the above.
These stabilizers, in preventing the deterioration of the polymers during processing at high temperatures, also permit manufacture of products with increased intrinsic quality because of the enhancement of their resistance to thermal and light degradation during use. In addition, because of the ability of these products to withstand more rigorous conditions, their versatility is increased and new areas of application are thereby opened. Without going into details or theory, it has been found that mixed alkyl/aryl phosphites such as diphenylisodecyl phosphite and phosphites based on pentaerythritol give the best overall performance in combination with mixed metal stabilizer systems for the stabilization of PVC.
In recent years there has been much concern with exposure to volatiles from the processing of PVC resin, and the exposure to volatiles from articles shaped from stabilized PVC resin exposed to elevated use temperatures. The volatilization of one or more components, or of the decomposition products therefrom, cause the condensation of these volatile components as �fog� on surfaces adjacent to the PVC articles. It has been found that one of the volatiles from the processing of PVC containing certain stabilizers is phenol. The phenol comes from the phosphite used in combination with the mixed metal stabilizer. There is a great need to eliminate or at least minimize the phenol content of phosphite stabilizers and still have a stabilizer which gives good color and processing stability and is relatively inexpensive.
One important objection to the contamination of PVC resins with phenol is based on the use of vinyl chloride polymers in food applications, e.g. in the manufacture of food containers. The use of phenol-free stabilizers prevents the transfer of objectionable odors or materials to food. Another consideration is the fact that for other applications, phenol has been identified as the source of the cause of premature discoloration, and is a water-soluble component.
A preferred phosphite for use with mixed metal stabilizers is diphenyl isodecyl phosphite, but this stabilizer contains about 50% of total phenol. Other phosphite stabilizers based on dialkyl pentaerythritol diphosphites have been known for some time as effective stabilizers for vinyl polymers. Despite wide usage as stabilizers for vinyl chloride polymers, polyolefins, polyurethanes, styrene polymers, and ABS, this type of phosphite has not been entirely satisfactory. The reason for this is the fact that, because of the method of preparation, namely by transesterification from triphenyl phosphite, the dialkyl pentaerythritol diphosphite is contaminated with phenol. Also, pentaerythritol phosphites are prone to hydrolysis that liberate solid pentaerythritol. In addition, it is advantageous to use mixed metal/phosphite stabilizer combinations as a single liquid component added to the PVC resin during processing. The dialkyl pentaerythritol diphosphites mentioned above are not easily combined with the liquid mixed metal stabilizers, and on standing, a mixture of the liquid mixed metal stabilizer and the dialkyl or diaryl pentaerythritol diphosphite separate into a lighter liquid layer and a more solid layer of heavy sludge. The dialkyl or diaryl pentaerythritol diphosphite also has a tendency to separate from the PVC matrix on compounding, causing a phenomenon known as plate-out. This lack of package stability and formation of plate-out greatly reduces the usefulness of this type of phosphite.
It is also known that trialkyl phosphites, while providing good early stability and color as well as good initial ultraviolet stability, suffer from poor long-term stability. Triaryl phosphites by contrast, provide good long-term stability, but suffer from early color and ultraviolet stability. Bis-phenol A diphosphites are recognized to provide excellent performance, but at a cost which is higher than commercially viable for many applications.
Pentaerythritol type phosphites and vinyl resins stabilized with such phosphites are disclosed in U.S. Pat. No. 3,281,381 by I. Hechenbleikner and F. C. Lanoue. These pentaerythritol phosphites are prepared by the transesterification of triphenyl phosphite with pentaerythritol to give, depending on the molar ratio of the triphenyl phosphite and pentaerythritol, a variety of possible structures. Tetra-phosphites are made by using four (4) moles of the tri(aromatic phosphite), such as triphenyl phosphite for each mole of the pentaerythritol. �Spiro� products, which are diphosphites, are made from the reaction of two moles of the triaryl phosphite with one mole of pentaerythritol. Mixed cyclic and non-cyclic esters are made by the reaction of three moles of the starting phosphite with each mole of pentaerythritol. Although the phenol formed in the transesterification reaction used to produce these materials from triphenylphosphite is removed by distillation during the preparation, the products still contain small quantities of free phenol, and phenol bound as a phosphite ester may be liberated during compounding or mixing.
Hechenbleikner, in U.S. Pat. No. 3,205,250 suggests the use of dialkylpentaerythritol diphosphites as stabilizers for polyvinyl chloride. Such dialkyl pentaerythritol diphosphites are prepared according to U.S. Pat. No. 4,206,103 by the reaction of two moles of an alkyl alcohol with a diphenyl- or dichloropentaerythritol diphosphite, made by the reaction of two moles of triphenylphosphite or phosphorous trichloride with one mole of pentaerythritol. When diphenyl pentaerythritol diphosphite is the reactant, the spiro isomer comprises about half the combined total of spiro and caged isomers in the product. When dichloropentaerythritol diphosphite is substituted for the diphenyl pentaerythritol diphosphite, the product which results is the relatively pure spiro isomer, which is generally a solid.
The preparation of dialkylpentaerythritol diphosphites which are not contaminated by the presence of phenol is disclosed in U.S. Pat. No. 4,290,976. The process disclosed utilizes the dichloropentaerythritol diphosphite made from phosphorous trichloride and pentaerythritol as a starting material since it does not contain a phenyl group and there is no possibility of phenol being formed as a contaminant. The products of the process described are characterized by higher set points and as a result do not form stable one-phase mixtures with liquid mixed metal stabilizers.
U.S. Pat. No. 3,047,608 describes the preparation of trialkyl phosphites and dialkyl pentaerythritol diphosphites by transesterification from triphenyl phosphite using a dialkyl or diphenyl phosphite as catalyst. The completeness of the transesterification and the removal of the byproduct phenol is controlled by the addition of an excess of the higher aliphatic alcohol, and removal of that excess along with the residual phenol by slow co-distillation under vacuum. The use of the diphenyl phosphites as catalysts, however, is not efficient, and the product from reaction of pentaerythritol with two moles of triphenyl phosphite and four moles of the higher aliphatic alcohol is mostly in the spiro form, and is incompatible with liquid mixed metal stabilizers.
U.S. Pat. No. 6,362,260 describes liquid organic phosphites of low volatility, based on pentaerythritol, alkyl alcohols and alkyl phenols, which are essentially phenol-free, but which require a pentaerythritol core structure.
Accordingly, there remains a need for essentially phenol free phosphites (as used in this application to mean less than or equal to 0.5%) which have good compatibility, performance, low volatility, package stability with mixed metal stabilizers and good performance, eliminating the drawbacks typically associated with current state-of-the-art phenol-based phopshites such as didecyl phenyl phosphite or diphenyl decyl phosphite.
One aspect of the present invention is a phosphite useful as a thermal stabilizer in vinyl polymers, especially polyvinyl chloride resin, of very low or nil phenol content (less than 0.5%) which is compatible with liquid mixed metal stabilizers.
It is another aspect of the present invention to provide essentially phenol-free phosphites for use in PVC as an alternative to the conventional phenol-containing products such as phenyl diisodecyl phosphite and diphenyl isodecyl phosphite. It is easily recognized that phenol with a boiling point of 182� C., will be liberated significantly more quickly than either nonylphenol with a boiling point of 295� C. or para-cumylphenol with a boiling point of 335� C. both nonylphenol and para-cumyl phenol are insoluble in water, whereas phenol is moderately soluble.
It is a further aspect of the present invention to provide phosphite which use para-cumyl phenol in order to provide an essentially phenol-free derivative of the above mentioned conventional phosphites, yet provide equivalent or better performance to more traditional phosphite stabilizers used presently.
These and other objects of this invention will be evident when viewed in light of the drawings, detailed description and the pending claims.
The invention may take physical form in certain parts and arrangements of parts, a preferred embodiment of which will be described in detail in the specification and illustrated in the accompanying drawings which form a part hereof, and wherein:
Various phenol-free phosphites for use in PVC as an alternative to the conventional phenol-containing products phenyl diisodecyl phosphite and diphenyl isodecyl phosphite were tested. The bulk of these phosphites utilize either nonylphenol or para-cumyl phenol in order to provide a phenol free derivative of the above mentioned conventional phosphites.
All phosphites were rated based on the stability performance they provide for PVC when used in the presence of a zinc compound. Testing parameters were thermal stability at 185� C. and 70� C., and weathering performance in a QUV weatherometer at 65� C.
The below listed phosphites were synthesized from triphenyl phosphite (TPP), alcohol, and the indicated functionality to produce a �phenol-free� phosphite. In this application, the following abbreviations will be employed:
All compounds listed above were compared to the following phenol-containing phosphites for performance.
Tables I and II compare the volatilities of the various phosphites.
Table I shows that phosphites based on para-cumyl phenol, rather than phenol, require much higher temperatures for 10% and 25% weight loss than the corresponding phosphites based on phenol. Compare for example DPDP (Doverphos�8) to its para-cumyl phenol analog DPCPDP.
A temperature of 232� C. vs. 276� C. for 10% weight loss and 259� C. vs. 322� C. for a 25% weight loss. Also compare PDDP (Doverphos 7) to its para-cumyl phenol analog PCPDDP.
A temperature of 242� C. vs. 259� C. for 10% weight loss and 269� C. vs. 300� C. for a 25% weight loss. Lower volatility will result in less undesirable �fogging.� Table II shows isothermal volatility at 185� C. (typical processing temperature) after 15 and 30 minutes.
The use of the above identified phosphites to serve as essentially phenol-free alternatives in zinc based stabilizer packages was studied using the chemical formulation listed below in Table III.
All samples were compounded on a 2-roll mill at approximately 180� C. for 5 minutes. Compounded samples were tested for Mathis oven thermal stability at 185� C. for a 2 hour period.
Derivative phosphites of DoverPhos�8 (DP-8) performed exceptionally well in thermal stability evaluations.
The data above indicates both the para-cumylphenyl derivative (DPCPDP) and bis nonylphenyl isodecyl phosphite (DNPDP) derivatives offer improved performance compared to diphenyl isodecyl phosphite (DPDP). However, the performance of bis (dinonylphenyl)isodecyl phosphite (DDNPDP) did not perform as well although it did show that phenol-free derivatives can offer similar performance. The DoverPhos� 7 based derivatives (PDDP) also exhibited the comparable trends of improved performance in PVC systems. The paracumyl phenol version of the phenyl diisodecyl phosphite (PCPDDP) and the nonylphenyl version (NPDDP) both performed exceptionally well (especially PCPDDP), while the dinonylphenyl derivative offers equivalent performance to the DoverPhos�7 phosphite (PDDP) as illustrated in
The tensile strength (in psi) of the resultant molded PVC compounds all appeared to be relatively equivalent showing no significant changes in the overall mechanical properties, as would be expected and as illustrated in
QUV analysis at 65� C. shows relatively equivalent performance for a filled PVC formulation as shown in
This applies to both the DoverPhos�7 and DoverPhos� 8 based derivatives. The exception in QUV performance appears to be di-nonylphenol diisodecyl phoshite, which did show some increased initial discoloration.
Additional work was then done on examining possible variations of a phenol free phosphite. In particular we examined the paracumylphenyl diisodecyl phosphite. Two more products were made to evaluate in zinc based stabilizer systems, namely ethoxy-paracumylphenyl diisodecyl phosphite (EPCPDDP) and propoxy-paracumylphenyl diisodecyl phosphite (PPCPDDP) wherein m=2 and 3 respectively, but can be any integral value from 1 to 4.
The performances of these two phosphites were compared to various other phosphites, as well as the PCPDDP product. Thermal stabilities for these phosphites closely matched the PCPDDP phosphite which, offered slightly improved long term stability compared to the PDDP product. This performance was a little worse than the typical DoverPhos� 675 (C10 bisphenol-A phosphite) but significantly better in long term performance than the DoverPhos� 6 phosphite (triisodecyl phosphite) as illustrated in
In more generic form, what has been illustrated is an essentially phenol-free forming phosphite additive having the following Markush formulation:
In an alternative generic form, what has been illustrated is an essentially phenol-free forming phosphite additive having the following Markush formulation
While halogenated polymer resins, particularly PVC are believed to be one of the preferred embodiments of this invention, the teachings and claims are not so limited. In fact, the compositions and the methods of the current invention may be used to stabilize any of the polymers known in the art, such as polyolefins, polyesters, polyurethanes, polyalkylene terephthalates, polysulfones, polyimides, polyphenylene ethers, styrenic polymers, polycarbonates, acrylic polymers, polyamides, polyacetals, halide containing polymers and polyolefin homopolymers and copolymers. Additionally included would be mixtures of different polymers, such as polyphenylene ether/styrenic resin blends, polyvinylchloride/ABS or other impact modified polymers, such as methacrylonitrile containing ABS, and polyester/ABS or polyester plus some other impact modifier may also be used. Such polymers are available commercially or may be made by means well known in the art. However, the diphosphites of the invention are particularly useful in thermoplastic polymers, such as polyolefins, polycarbonates, polyesters, polyphenylene ethers thermoplastic polymers, such as polyolefins, polycarbonates, polyesters, polyphenylene ethers and styrenic polymers, due to the extreme temperatures at which the thermoplastic polymers are often processed and/or used.
Polymers of monoolefins and diolefins, for example would include polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) may be used. Mixtures of these polymers, for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE), may also be used. Also useful are copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as, for example, ethylene/propylene, LLDPE and its mixtures with LDPE, propylene/butene-1, ethylene/hexene, ethylene/ethyl pentene, ethylene/heptene, ethylene/octene, propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates, ethylene/alkyl methacrylates, ethylene/vinyl acetate (EVA) or ethylene/acrylic acid copolymers (EAA) and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene-norbornene; as well as mixtures of such copolymers and their mixtures with polymers mentioned above, for example polypropylene/ethylene-propylene copolymers, LDPE/EVA, LDPE/EAA, LLDPE/EVA and LLDPE/EAA.
Thermoplastic polymers may also include styrenic polymers, such as polystyrene, poly-(p-methylstyrene), poly-(α-methylstyrene), copolymers of styrene, p-methylstyrene or alpha-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/maleic anhydride, styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methacrylate; mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene, such as, for example, styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene. Styrenic polymers may additionally or alternatively include graft copolymers of styrene or alpha-methylstyrene such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylonitrile on polyacrylates or polymethacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures of the styrenic copolymers indicated above.
Nitrile polymers are also useful. These include homopolymers and copolymers of acrylonitrile and its analogs such as methacrylonitrile, such as polyacrylonitrile, acrylonitrile/butadiene polymers, acrylonitrile/alkyl acrylate polymers, acrylonitrile/alkyl methacrylate/butadiene polymers, acrylonitrile/butadiene/styrene (ABS), and ABS which includes methacrylonitrile.
Polymers based on acrylic acids, such as acrylic acid, methacrylic acid, methyl methacrylate acid and ethacrylic acid and esters thereof may also be used. Such polymers include polymethylmethacrylate, and ABS-type graft copolymers wherein all or part of the acrylonitrile-type monomer has been replaced by an acrylic acid ester or an acrylic acid amide. Polymers including other acrylic-type monomers, such as acrolein, methacrolein, acrylamide and methacrylamide may also be used.
Halogen-containing polymers are particularly preferred. These include resins such as polychloroprene, epichlorohydrin homopolymers and copolymers, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, fluorinated polyvinylidene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinylacetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride tercopolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate tercopolymer, vinyl chloride-acrylic acid ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymer and internally plasticized polyvinyl chloride.
Other useful thermoplastic polymers include homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ethers; polyacetals, such as polyoxymethylene and those polyoxymethylene which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or methacrylonitrile containing ABS; polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with polystyrene or polyamides; polycarbonates and polyester-carbonates; polysulfones, polyethersulfones and polyetherketones; and polyesters which are derived from dicarboxylic acid and diols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethyliol-cyclohexane terephthalate, poly-[2,2,4-(4-hydroxyphenyl)-propane] terephthalate and polyhydroxybenzoates as well as block copolyetheresters derived from polyethers having hydroxyl end groups.
Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide-4, polyamide-6, polyamide-6/6, polyamide-6/10, polyamide-6/9, polyamide-6/12, polyamide-4/6, polyamide-11, polyamide-12, aromatic polyamides obtained by condensation of m-xylene, diamine and adipic acid; polyamides prepared from hexamethylene diamine and isophthalic and/or terephthalic acid and optionally an elastomer as modifier, for example, poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide may be useful. Further copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as for instance, with polyethylene glycol, polypropylene glycol or polytetramethylene glycols, and polyamides or copolyamides modified with EPDM or ABS may be used.
The resulting stabilized polymer compositions comprising the phosphites made by the process of this invention may optionally also contain various conventional additives, such as the following:
(1) Antioxidants
(1.1) Alkylated monophenols, for example
(1.2) Alkylated hydroquinones, for example
(1.3) Hydroxylated thiodiphenyl ethers, for example
(1.4) Alkylidene bislphenols, for example
(1.5) Benzyl compounds, for example
(1.6) Acylaminophenols, for example
(1.7) Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid, with monohydric or polyhydric alcohols, for example methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentacrythritol, tris-(hydroxyethyl)isocyanurate and N,N′-bis-(hydroxyethyl)oxamide.
(1.8) Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols, for example methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)isocyanurate and N,N′-bis-(hydroxyethyl)oxamide.
(1.9) Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols, for example methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)isocyanurate and N,N′-bis-(hydroxyethyl)oxamide.
(1.10) Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid, for example
(2) UV Absorbers and Light Stabilizers.
(2.1) 2-(2′-hydroxyphenyl)-benzotriazoles, for example the 5′-methyl-, 3′,5′-di-tert-butyl-, 5′-tert-butyl-,
(2.2) 2-Hydroxybenzophenones, for example the
(2.3) Esters of unsubstituted or substituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol,
(2.4) Acrylates, for example ethyl or isooctyl α-(cyano-β,β-diphenylacrylate, methyl α-(carbomethoxycinnamate, methyl or butyl α-(cyano-β-methyl-p-methoxycinnamate, methyl α-(carbomethoxy-p-methoxycinnamate or N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.
(2.5) Nickel compounds, for example nickel complexes of 2,2′-thiobis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 complex or the 1:2 complex, if appropriate with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonates, such as the methyl or ethyl ester, nickel complexes of ketoximes, such as 2-hydroxy-4-methylphenyl undecyl ketoxime, or nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, if appropriate with additional ligands.
(2.6) Oxamides, for example 4,4′-di-octyloxyoxanilide,
(3) Metal deactivators, for example, N,N′-diphenyloxamide,
(4) Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis-(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl) 4,4′-biphenylene diphosphonite and
(5) Peroxide scavengers, for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide and pentaerythritol tetrakis-(β-dodecylmercapto)propionate.
(6) Polyamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
(7) Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, barium stearate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatecholate and zinc pyrocatecholate.
(8) Nucleating agents, for example, 4-t-butyl-benzoic acid, adipic acid, diphenylacetic acid.
(9) Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
(10) Aminoxypropanoate derivatives such as methyl-3-[N,N-dibenzylaminoxy]propanoate; ethyl-3-[N,N-dibenzylaminoxy]propanoate; 1,6-hexamethylene-bis[3-(N,N-dibenzylaminoxy)propanoate]; methyl-[2-(methyl)-3(N,N-dibenzylaminoxy)propanoate]; octadecyl-3-[N,N-dibenzyl-aminoxy]propanoic acid;
(11) Other additives, for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame-proofing agents, anti-static agents, blowing agents and thiosynergists such as dilaurylthiodipropionate or distearylthiodipropionate.
Hindered phenolic antioxidants may also be present in the polymer composition. Use of bis(alkylpheny)l pentaerythritol diphosphites of the present invention may result in enhanced polymer protection by reducing the formation of color resulting from the presence of the phenols. Such phenolic antioxidants include in addition to those specifically mentioned previously, n-octadecyl-3,5-di-t-butyl-4-hydroxyhydrocinnamate, neopentaneterayl tetrakis-(3,5-di-t-butyl-4-hydroxyl-hydrocinnamate), din-octadecyl-3,5-di-t-butyl-4-hydroxybenzyl-phosphonate,
(12) Lactones, for example, 5,7-di-t-butyl-3-phenyl-3H-benzofuran-2-one;
Other additives, such as oxazaphospholidines, may additionally or alternatively be present. Likewise, the instant compounds prevent color formation when hindered amine light stabilizers are present, such hindered amines including-bis(1,2,2,6,6-pentamethyl-4-piperidyl)2-n-butyl-2-(3,5-di-t-butyl-4-hydroxy-benzyl) malonate; bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate; dimethyl-succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol; and polymers of 2,4-dichloro-6-octylamino-s-triazine with N′-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine.
Thus, what has been shown is that one way to reduce the formation of volatile phenol is to substitute at least a portion of the phosphite additive with a phosphite which does not break down into a phenolic unit or minimally breaks down into phenolic units. Preferred examples of this type of phosphite include ethoxy-paracumylphenyl diisodecyl phosphite, propoxy-paracumylphenyl diisodecyl phosphite, para-cumyl phenyl diisodecyl phosphite and bis para-cumyl isodecyl phosphite as well as more generically, formulas (I) and (II).
More generally disclosed is a process for reducing the emission of phenol in a polymer resin which comprises replacing at least a portion of a phosphite additive which releases phenol upon exposure to heat with a phosphite composition selected from the group consisting of formula (I)
This invention has been described in detail with reference to specific embodiments thereof, including the respective best modes for carrying out each embodiment. It shall be understood that these illustrations are by way of example and not by way of limitation.
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MVC Widget Error
7 Tips to Prepare for Your Appointment
The key to a successful appointment is communication. To get the most out of your visit, prepare ahead of time so you can lead the conversation with your doctor. These 7 tips will get you ready
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Dana A Burrello
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Basic information on Dana A Burrello, Cleveland OH. Find Dana A Burrello's age, gender, possible aliases, relationship status and professional status.
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Dana A Burrello Has Attended 1 School
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2009 - 2013
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Waterproof cot mattress 10.00
The matress has a breathable side and a waterproof side. From mothercare
The matress has a breathable side and a waterproof side. From mothercare
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Cot bed with matching wardrobe and chest of drawers for sale. Mattress not included. The wardrobe and drawers are in excellent condition. The cot bed is in very good condition but has a few marks.
I am selling a pink cot bedding set from Mothercare's My Little World Of Dreams co-ordinated matching range. Included is a cot bumper, 2 flat sheets with embroidered design, 2 fitted bottom sheets with hearts and spots, and a warm fleece-backed cover
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Mamas and Papas Summerhouse cot top changer, demerera colour, in good condition.
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URGENT SALE: DRESSING FOR COT BED (WHICH IS ALSO FOR SALE) SPINNING MOBILE BLANKET TINY TEDDY AND CUSHION BORDER FOR RACKS ON COT BED. bundle all together as mat hinge set. Was expensive. Bargin now!!!! Neutral colours. Washed and ready for collecti
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here welcome to: forums > music > lyrics > where have you been rihanna
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Post the best lyrics from your favorite songs and find other music lyrics that are similar. Keep it clean!
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Virginia coach Mike London occasionally has to remind himself that the veteran in his defensive secondary is only entering his second season.
"He's playing with some young safeties," London said Thursday, referring to sophomore corner back Demetrious Nicholson, before cracking a smile.
"I say young safeties," London said. "Here he is, just a sophomore himself."
Nicholson started all 13 games for the Cavaliers in 2011, becoming the program's first true freshman to start the season opener at Virginia since 2005. He finished the season fourth on the team with 60 tackles, intercepted a pair of passes, and tied Chase Minnifield for the team lead with eight pass break-ups.
This summer, Nicholson is the only starter back in the secondary for the Cavaliers.
"It definitely has put a lot of pressure on me to be the guy," he said Thursday. "To be a leader; to be the guy we look at on film and be like, "He's doing it right," for the younger guys to follow.
"And I'm still young myself. I'm still learning," Nicholson admitted. "But I'm going to use the experiences that I got, and try to lead those guys."
London thinks Nicholson has greatly benefited by getting the opportunity to play a season with Minnifield, an All-ACC performer in 2011 who is now on the Redskins' Injured Reserve list.
"Having a guy like Chase Minnifield with him has rubbed off on him, in terms of his preparation. He comes out here and he works everyday," London said.
"I took a whole lot from him. He's a great guy, a great leader. He was the definition of a leader," said Nicholson. "He prepared hard. He worked hard everyday in practice, never took a rep off. And being around a guy like that, you can't do nothing else but follow in those footsteps. Bring along things that you already have for yourself, and just put it all together."
Nicholson admitted on Thursday that even though he was a freshman, he wasn't satisfied with his performance in 2011. But he hopes to use his experiences to help the new faces filling the holes around him in the secondary.
"Mistakes I made last year, I can tell the young guys about it. And I can also better myself by not making the same mistakes this year," Nicholson said. "I'm more comfortable. Things are becoming more noticeable. I'm starting to recognize things, and just learn the overall game."
"He's a special player. He's a special person," said London. "In the classroom, in the community, on the field. We're glad we have him."


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In short: Best value ever, friendly and fantastic organisation - Run was ok too!Date of review: June 16, 2005
In short: A good race after a day at workIn full: A good race if not the most exciting course (two laps around a park) but cheap and cheerful.Date of review: June 16, 2005
In short: A good effortIn full: The 40th anniversay race mug made my day.Lack of parking around Willen Lake was a bit of an issue; there aren't many ways to get to places in a town built for the motor car (Milton Keynes). A course I run around regularly - very flat and fast. Suits beginners but this type of race will always appeal more to serious and semi-serious runners.Date of review: June 16, 2005
In short: Crowded streetsIn full: The BUPA-branded races are slickly organised. However, the narrow streets of the city centre combined with 15,000 runners don't make for PBs. There was also an odd split of runners - the mass start went off in three waves but there were plenty of slow runners in the first wave and they held others up. I can only imagine this arrangement was for the TV cameras' benefit. The bulk of the race was up a rather dull highway looping round Old Trafford. I love Manchester but there could have been better use of its many famous and beautiful landmarks.Date of review: June 16, 2005
In short: A regular favouriteIn full: Always enjoy this event, great venue, relaxed atmosphere, bit like a very big club run. Date of review: June 16, 2005
In short: Biggest and bestIn full: ...unless you're a good runner looking for a PB - the sheer number of runners will put paid to that. The organisation is superb and the atmosphere unsurpassed. Extremely beginner-friendly. Once bitten, forever smitten.Date of review: June 16, 2005
In short: WorthwhileIn full: In parts very stunning with a good atmosphere and the full range of weather conditions for those bored of the London Marathon's full-time sunshine this year! It was also good to start and finish at Holyrood Park. Not as hilly as feared but there are some cobbled sections.On the minus side, there were too few portaloos at the race start and the course had too many hoops. However, it's a young event and will only get better.Date of review: June 16, 2005
In short: Partner did not get a medal until we complained by e mail after the evnt - the marshalls were brusque and the whole thing left a bit of a sour taste. The end of the race was clogged with people standing about so was a bit disorganised.Date of review: June 16, 2005
In short: Great setting and a great downhill fast finish, which I certainly needed after that hill at the 3 mile mark!!!Date of review: June 16, 2005
In short: Marvelous!Date of review: June 16, 2005
In short: very enjoyable and friendlyDate of review: June 16, 2005
In short: the best event of the year - ideal for your first Ultra - but beware YOU WILL GET SERIOUSLY HIGHIn full: OPEN LETTER TO PHIL HAMPTON - RACE DIRECTORDear PhilThankyou once again for a wonderful race! It was only really when I got back home that it hit me how well the Discovery is doing. After the cancellation of the 2001 event (extreme circumstances – Foot & Mouth!), the 2002 DD had the lowest number of finishers (69 including just 6 ladies) – this was surely partly due to the World Cup that was on at the same time – remember? the England v Germany match on the same day.When I got online at www.runnersworld.co.uk early in 2003 I was determined to start a thread on the Discovery to try and boost numbers. Then SHADES & others got involved. We had started the ball rolling! Then Thanks to forumite RichK, and his excellent website www.richk.co.uk I was able to find a home online for my photos of the 2003 event. It was the first time I had really seen the moor, and I was so glad I had a camera with me! (91 finished including 15 ladies – the female finishers had more than doubled!) So then it was apparently thanks to my photos that persuaded Rich to take up the challenge in 2004 and ofcourse along with him came quite a few others, with travelling distance no impediment! (welcome the macs!!) If 2003 gave a boost to the female percentage, then 2004 was even better (100 finished including 24 ladies).Having had the "best year yet" in 2004 – what then? AN EVEN BETTER EVENT IN 2005!! (123 finished including 27 ladies) CONGRATULATIONS!!The Discovery's excellent reputation will carry it onwards (see the Runners World homepage!)Please thank all the people involved – at HQ, feed stations, the marshals, the time-keepers, the back-up vehicles, the lead car & radio car, the ambulance, the masseurs, catering helpers and the "all year" work involved; all those "small" gestures that mean such a lot, especially later on when you're tired and a bit spaced out, eg. when the guy in the back-up vehicle went ahead, parked beyond one of the cattle grids, leapt out and ran back to open the gate for me – and closed it behind me! Everyone was friendly, encouraging, stoical, witty, marvelous! We've now had the gamut of weather changes – 1999 was very wet, with several flash floods to wade through; 2000 was dull & misty; 2002 was chilly & windy, but warm & muggy in Ashburton, then windy & raining back on the moor; 2003 was the first year of "better" weather, it was WARM; 2004 was actually HOT & sunny; this year, 2005, was almost perfect weather for runners – cool, breezy – but with just a little too much of a headwind in the last 5 miles!It's difficult for others to appreciate how different an Ultra Marathon is until you've done one – how special you are made to feel; but not only that, in this Ultra – how exceptional it is to be running a "road race" through a protected National Park which is home to many different animals that roam freely (mainly sheep, wild ponies and cattle) and who WILL eat gel wrappers, lucozade packs, plastic bottles & plastic tops, sponges and paper cups. The Rules for Human Behaviour on Dartmoor are simple, but essential: 1. TAKE YOUR LITTER AWAY2. DO NOT FEED THE ANIMALS – VIEW FROM A DISTANCE3 IF YOU OPEN A GATE – ALWAYS CLOSE IT BEHIND YOU4 DO NOT CROSS CATTLE GRIDS (GO THROUGH THE GATES)It is remarkable that we are able to enjoy being in the wild spaces on the Moor, there is an atmosphere unique to this place that I tried to get my head round in the 2002 event when I was at my slowest. ("gentle ruggedness"; "magic and mystery of the moor"; "sheer serenity" - might sound a bit over the top – so don't take my word for it - just come and find out for yourselves!) It is truly running in the wild places, often alone, but with the knowledge that every few miles there will be friendly & helpful folk manning water stations, marshalling junctions, driving back-up vehicles, others waving as they pass, cheering you on in your solitary quest – it's always a privilege to participate.I very nearly didn't come this year, but no sooner had that thought occurred, I knew I would regret it rather badly. "OK, I'll definitely go, but maybe I should not run." How about going round on the bike? Well I reckon that would be just as hard as going round on foot – if not harder. The severe downhill sections would scare the shorts off me – and I'd be pushing the bike up most of the hills!When you next go to Princetown, make sure you find time to go to the High Moorland Visitor Centre. (Tel: 01822 890414 for the excellent free information newspaper "Dartmoor Visitor") This rather grand looking building is an information centre which includes exhibitions of paintings & photography, a "History from Neolithic times" with displays of landscape, wildlife and Dartmoor's ancient woodlands. There is also film footage, with separate seating, and a range of books, postcards, clothing, maps & gadgets to help you safely explore the moor. I came away with a few souvenirs and one remarkable poster which you have to see to believe – when I took it to the local printers here in Penzance to get it mounted – they all wanted one!The poster is a map of Dartmoor, which has been enhanced to show the relief in 3-D (you can easily follow the race route, recognizing all the varied scenery on the way). It's almost an aerial view but from a southerly angle. It's an artwork in itself and confirms what I have been suspecting since 2002 – that the moor itself is an ancient slumbering creature; and if you respect it, you will have a positive, maybe even a mystical, experience; but if you mistreat it – watch out!Kind Regards,Lize (aka Paskha)PS. There is just one further challenge which still has me beaten – and that is getting the Race Director (you!) on to the dance floor at the disco!Date of review: June 16, 2005
In short: First marathon so on a high for the whole race. There could be more toilets with better location.Date of review: June 16, 2005
In short: Very friendly race in lovely setting, will return next yearDate of review: June 16, 2005
In short: A bit of fine tuning required but funIn full: The entry fee was expensive, the Expo laughable and the toilets and baggage at the beginning a riot. The course was hilly but not too much but I did struggle over the cobbles towards the end. However, the marshalls were good and the atmosphere fab and I managed a PB so I am happy. The scenery along the promenade kept me going when my legs were tired. Nice unexpected goody bag at the end.Date of review: June 16, 2005
In short: very pleasant running on a summer evening in the forest.Date of review: June 16, 2005
In short: Great Local race, very well organised.Date of review: June 16, 2005
In short: Super race, well organised.In full: A very minor crit, but the start would benefit from a loud speaker/pa system ,people at the back couldn't hear the starters dedication speech.Date of review: June 16, 2005
In short: Worth combating rush hour traffic for!In full: Absolutely loved this! First time and didn't know what to expect. First 3 miles undulating and loved the downward feel for the last couple of miles! You sped up, whether you wanted to or not! Loved the mug and Mars bar! Very friendly and people from all over! Can't wait for 2006!Date of review: June 16, 2005
In short: Excellent race - will be back again.Date of review: June 16, 2005
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