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Orchestra Hall: The Challenges Are Monumental
November 30, 1986
By Thomas Hine, Inquirer Architecture Critic
It seemed as if it would never happen, but it has. The Philadelphia Orchestra board of directors has voted to move the ensemble from the Academy of Music at Broad and Locust to a new concert hall, yet undesigned, at the southwest corner of Broad and Spruce Streets. Opening night is planned for September 1991, which means it is probably a bit early to start shopping for a new dress. Even though the idea has been discussed for years, this actual commitment by the Philadelphia Orchestra Association board will have implications that have scarcely been considered.
Over The Rainbow Despite Disc Rage, Decade Awaits Opening Of New Orchestra Hall
January 2, 1990
By Tom Di Nardo, Daily News Classical Music Writer
For the music lover, the upcoming decade marks the end of the rainbow with the opening of a new Orchestra Hall. And, if the architects and acoustical wizards are successful, the Philadelphia Orchestra, led by Riccardo Muti, will not only have an audio recording venue, but a location capable of live audio and video broadcasting via satellite. European orchestras have been performing live on cable for years, and our great orchestra will be able to jump into the global market along with the wealth of concerts available to us. The new site at Broad and Spruce streets will also attract more opera and ballet to a renovated Academy of Music stage.
Unveiling The Orchestra Hall The First Sketches Are Out. Though Changes Are Inevitable, The Drawings Promise Comfort And Convenience For Concertgoers. And Incomparably Better Facilities For The Musicians.
July 2, 1989
By Thomas Hine, Inquirer Architecture Critic
The idea of a new hall for the Philadelphia Orchestra is not something that people here have taken much to heart, and it is not difficult to understand why. The Academy of Music, where the orchestra has played since it was founded, is one of the most beautiful theaters anywhere. The music and the place have become so thoroughly identified with each other that many loyal concertgoers would not wish to have to choose one or the other. Until last week, the apparent choice was between a familiar, beloved place and setting off for something unknown.
Neil Courtney, prominent bassist, dead at 82
June 20, 2015
By Peter Dobrin, Inquirer Music Critic
Neil Courtney, 82, of Center City, a double bass player with the Philadelphia Orchestra for 48 years and the "king of the double bass in Philadelphia," died Wednesday, June 17, at home after many years of declining health from heart disease. He joined the orchestra as a section player in 1962, and served as assistant principal double bassist from 1988 until his retirement in 2010. Mr. Courtney liked to compare the double bass' range to that of a baritone singer, but bemoaned its limited repertoire and listening public.
Curtis musicians bring the sound of renewal to Verizon
October 25, 2011
By Peter Dobrin, Inquirer Music Critic
With its recent tumult of labor strife and money woes, the Kimmel Center seems an unlikely site to stage a musical spring. Yet there it was last weekend, the irrepressible stirring of renewal. At Saturday morning's first Philadelphia Orchestra family concert this year, cellist John-Henry Crawford, 18, a Curtis student and winner in the orchestra's Albert M. Greenfield Student Competition, projected polished charisma and a singing sound in the first movement of Prokofiev's Symphony-Concerto . His was only one voice among a hundred the next afternoon at the season's first outing of the Curtis Institute of Music orchestra beyond its luxurious new tailor-built rehearsal room.
Time To Move The Orchestra Needs A New Concert Hall
December 15, 1986
By Dan Rottenberg
When Philadelphia's Academy of Music was built in the 1850s, many of the city's movers and shakers opposed the project, partly because the dominant Quaker tradition disapproved of music altogether. It was supported only because of another Quaker tradition - tolerance. The result of that communal decision, of course, was a building that is today recognized as the oldest, handsomest and grandest concert hall in America - "this marvelous place to sing," as Luciano Pavarotti once described the academy.
And In The Seventh Year, They Played The Chicago Symphony's Home Is Reborn - Fast, And With Eager Public Support.
January 6, 1998
By Daniel Webster, INQUIRER MUSIC CRITIC
The Chicago Symphony enters the new year housed in a boldly expanded building that has been transformed in less than six years from creaky concert hall to expansive social center. Symphony officials call it a template for all orchestras trying to find their place in the new century. Musicians, accustomed to the old hall's vagaries and harshness, say it is letting Chicagoans hear their orchestra for the first time. The Symphony Center, built and renovated in a $110 million project, opened Oct. 4 at the end of a construction schedule that moved with the precision of clockwork, according to Henry Fogel, the symphony's president.
An Aural Challenge Takes This Editor To New York Which Sounds Better - The Academy Of Music Or Carnegie Hall? Can A Tin Ear Really Tell?
October 7, 1990
By DAVID R. BOLDT
There was a mood of at least light anxiety within the splendid red, gold and ivory confines of the Academy of Music as the Philadelphia Orchestra began its performance last Monday evening. The reason for the anxiety was simple. The composer of the first number on the program was - how can we say this nicely? - well, the composer was not yet dead. This is almost always a bad sign, and this particular composer, Richard Wernick, a professor of music at Penn, had put audiences at the academy through what some recalled as a particularly painful episode some years ago during the world premiere of a strikingly dissonant string sonata.
Phila. Orchestra Unveils New Hall More Practical, Less Plush
February 15, 1989
By Maria Gallagher, Daily News Staff Writer
The Philadelphia Orchestra's next home was unveiled today as being more practical but less plush than its current digs, the Academy of Music at Broad and Locust streets. Orchestra officials gave a "design-in-progress" view of the $95 million, five-story Orchestra Hall, scheduled to open in 1993 just south of the academy. The 2,700-seat hall will be compatible to the demands of digital technology, and its acoustics will provide a "warmer" sound than exists at the academy, said orchestra executive director Stephen Sell.
Are They Loved Only In Rio?
June 15, 1988
When the Chicago Symphony Orchestra completed its first European tour back in 1971, the city honored its members with a full-fledged parade from Orchestra Hall to City Hall, where the late Mayor Richard Daley presented the musicians with a huge trophy. In Philadelphia, where only athletes rate parades, the citizens have long taken their world-class symphony orchestra for granted. There was no cheering crowd at the airport when the orchestra returned earlier this month from its triumphant tour of South America, and none was required.
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Neil Courtney, prominent bassist, dead at 82
June 20, 2015
By Peter Dobrin, Inquirer Music Critic
Neil Courtney, 82, of Center City, a double bass player with the Philadelphia Orchestra for 48 years and the "king of the double bass in Philadelphia," died Wednesday, June 17, at home after many years of declining health from heart disease. He joined the orchestra as a section player in 1962, and served as assistant principal double bassist from 1988 until his retirement in 2010. Mr. Courtney liked to compare the double bass' range to that of a baritone singer, but bemoaned its limited repertoire and listening public.
Curtis musicians bring the sound of renewal to Verizon
October 25, 2011
By Peter Dobrin, Inquirer Music Critic
With its recent tumult of labor strife and money woes, the Kimmel Center seems an unlikely site to stage a musical spring. Yet there it was last weekend, the irrepressible stirring of renewal. At Saturday morning's first Philadelphia Orchestra family concert this year, cellist John-Henry Crawford, 18, a Curtis student and winner in the orchestra's Albert M. Greenfield Student Competition, projected polished charisma and a singing sound in the first movement of Prokofiev's Symphony-Concerto . His was only one voice among a hundred the next afternoon at the season's first outing of the Curtis Institute of Music orchestra beyond its luxurious new tailor-built rehearsal room.
A night of bold strokes with orchestra
October 30, 2003
By Peter Dobrin INQUIRER MUSIC CRITIC
Yakov Kreizberg is the kind of conductor you bring in when you want to hear music expressed in bold strokes. He's not exactly a detail man. And as for the ability to establish a rapport with an orchestra based on subtle gestures that get a nuanced response, well, Kreizberg is just not that kind of communicator. But for the program he put together Tuesday night in Verizon Hall with the Philadelphia Orchestra, Kreizberg was just fine. Dvorak's Carnival overture was propelled by animal energy, and quite exciting in its own way. The Ravel Bolero that ended the concert was like any other - that is, it ticked by with the inevitability of a time bomb, the ending assured to get a standing ovation pretty much regardless of who was on the podium.
A great orchestra hall? No. Verizon Hall isn't. But critics who savaged its sound when the Kimmel Center opened should give it another hearing.
September 22, 2002
By Peter Dobrin and David Patrick Stearns INQUIRER MUSIC CRITICS
So, how's the new hall? For even the casual eavesdropper on the orchestra scene, that question was the question last season. Nine months after the Kimmel Center's opening night, it's still the question. Does the Philadelphia Orchestra, which opened its first full season in Verizon Hall last week, finally play in a great orchestra hall? The answer, alas, is no. A "dry," "pale," "piercing," no. At least, that's what many critics from across the country so far have said.
Orchestra shows hall's potential with 'Leonore No. 3'
September 21, 2002
By Peter Dobrin INQUIRER MUSIC CRITIC
Sometimes things just click. There's a moment when various factors come together to telegraph the message that everything's going to be OK. For the Philadelphia Orchestra and its rocky move into a new home, such a moment arrived Thursday night - specifically, during Beethoven's Leonore Overture No. 3. That's really the first time it became apparent that Verizon Hall stands a good chance of being a truly worthy home to the orchestra....
Affection for Academy as listeners bid farewell The union of orchestra and hall was more than 100 years old.
December 13, 2001
By David Patrick Stearns and Peter Dobrin INQUIRER MUSIC CRITICS
The notion grew to become one of those incontrovertible laws of Philadelphia physics - this idea that the Philadelphia Orchestra and the Academy of Music were one and the same. But the cultural universe turned upside down last night as the orchestra performed its last concert in the Grand Old Lady of Locust Street, its home since the orchestra played its first Beethoven and Tchaikovsky on Nov. 16, 1900. Now, it will play in what retired concertmaster Norman Carol called, in a post-concert speech, "the cello-shaped young girl" down the street.
A new hall, just 93 years in the making
December 9, 2001
By Peter Dobrin INQUIRER MUSIC CRITIC
The Philadelphia Orchestra decided it had had enough of the Academy of Music. It needed a home built especially for its needs. A prominent Philadelphia architect was hired to design a 2,800-seat concert hall with a chamber-music room for 500 listeners. Could the orchestra afford it? Wouldn't it be better to raise money for an endowment? And what was wrong with the Academy of Music, anyway? The year was 1908. History does have a way of repeating itself, and looking back at the idea for a new home for the Philadelphia Orchestra, the same themes emerge, playing over and over with only a few variations: concert hall plus chamber-music hall.
Going Up . . . As The Philadelphia Orchestra's New Hall Rises, Ticket Prices Climb, Too - More Than Usual Next Season.
March 8, 2001
By Peter Dobrin INQUIRER MUSIC CRITIC
The cost of hearing the Philadelphia Orchestra will jump next season by an average of 16 percent - the biggest increase since 1987. In addition, the ticket surcharge will double to $2 per ticket. A small number of ticket prices will stay the same or even drop slightly. But most listeners will pay substantially more, depending on seat location, to experience the orchestra live in the future. The increase comes as the orchestra prepares to become a tenant in a new hall that will be both more expensive to operate and will offer fewer seats than the Academy of Music.
Closer To The Music A Year From Tomorrow Is Opening Night For The Kimmel Center For The Performing Arts. It's Rising On Time And On Budget, And Already The Orchestra Hall Feels Promisingly Intimate.
December 14, 2000
By Peter Dobrin, INQUIRER MUSIC CRITIC
Somewhere beneath the soaring steel beams going up at Broad and Spruce, down past the drying concrete and dangling wires and dead-end air vents, is a spot in the Philadelphia Orchestra's new concert hall so close to the stage that you feel you could reach out and tug at the maestro's long black tails. There's another seat just like it. And another. In fact, the new orchestra hall, a year away tomorrow from opening its doors to the public, contains 2,500 such listening perches - each promising to bring audiences closer to orchestral music than has ever before been possible in this town.
An Institution Designed To Draw Visitors The Academy Of Music Was Planned As An Opera House. The Orchestra Came Later.
October 28, 1999
By Inga Saffron, INQUIRER ARCHITECTURE CRITIC
At a time when the west side of Broad Street was still a marshy wilderness, when City Hall was a mere gleam in the eye of politicians, when the Union League was still homeless, city leaders built the Academy of Music at Broad and Locust Streets to assert and assure Philadelphia's position as a major American city. Broad Street was very much the outskirts of Philadelphia in 1853, when the corner site was acquired for the new opera house, yet few doubted that the city would eventually fulfill William Penn's original plan and stretch from river to river.
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Reviewed By Karl G (Okatie, SC) Reviewed for a 2016 Volvo S60 —9/25/2016 5:29 AM
The rack system is truly matched to this vehicle, utilizing manufacture installed post holes to properly align racks on vehicle ! Solid construction
Reviewed By Donald S (ATKINSON, NH) Reviewed for a 2010 Scion xB —9/22/2016 3:29 AM
I took my time during installation. After all, being male, I tend to assume things and check t he instructions if something goes wrong. But the quality of the parts and constructions impressed me and it looks great. They are silent when I am driving with nothing else on the roof. I plan to carry my 18' canoe on my Scion xB from New England to Florida.

subset: commoncrawl


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US: Textile enforcements up in many categories in 2013
By Leonie Barrie | 21 March 2014
The number of textile and apparel enforcements made by US Customs and Border Protection (CBP) edged up year-on-year in several categories during 2013, including seizures, commercial fraud penalties and examinations.
During 2013 there were 9,300 intellectual property rights-related seizures valued at $15.7m. This works out at a rise of 29.6% in volume terms compared with the prior year's 7,174 intellectual property seizures - but an increase of just 8.7% in value over the $14.44m recorded in 2012.
Quarterly figures ranged from a high of 3,246 seizures in the second quarter to a low of 1,085 in the third quarter.
In contrast, non-IPR seizures, including smuggling, fell to 67 valued at $5.79m, down from the 95 seizures valued at US$7.48m booked in 2012.
Meanwhile, some 23 commercial fraud penalties were imposed, totalling $22.01m, compared to 21 penalties totalling $27.32m in the prior year. This remains well below the 48 penalties worth $27.32m recorded in 2011.
There were 968 liquidated damages claims associated with textiles during 2013, with 908 related to entry, 44 related to temporary importations under bond, and 16 related to redelivery.
CBP officials visited eight countries and 143 factories over the year for illegal transshipment, finding some 14.7% discrepant. This was down on last year, when nine countries and 172 factories were visited and 26% were found discrepant.
The results continue to come in well below the high of 12 countries and 712 factories visited during the 2004 financial year, when some 65% of factories were found discrepant.
143 factories in eight countries were also visited for trade preference claims in 2013, with 35.7% found to be discrepant. This fell from 174 factories in nine countries in 2012, when 39% were discrepant.
The number of examinations rose to 11,279 last year, up 12.2% on the 10,055 carried out in 2012. But while 1155 or 10% were found discrepant, this is marginally down on the 1,108 or 11% a year earlier.
Some 33 audits were initiated and 43 completed in 2013, with $7.16m in recommended recoveries. In contrast, there were 39 audits initiated and 40 completed the year before, with recommended recoveries of $1.36m.
Meanwhile the number of laboratory analyses rose significantly, with CBP laboratories testing 1170 samples, of which 614 or 52% were found discrepant. In 2012, 572 out of 1,014 samples were found discrepant.
CBP also initiated seven special enforcement operations over the course of the year and completed nine.
Sectors: Apparel, Fibres & fabrics, Sourcing
An interactive databank with intelligence on the major apparel sourcing countries
Most Popular
- Under Armour on track with new UAS sportswear line
- Myanmar garment exports surged 20% in 2015
- Unravelling cotton's supply and demand challenges
- Why synthetic fibres are a safe bet for the future
- Better factory conditions boost the bottom line
- US retailers urge action on Hanjin Shipping crisis
- Brexit may hit suppliers with UK duty-free access
- Zara launches eco-friendly Join Life collection
- Adidas unveils first Speedfactory running shoe
- New US tariff classifications impact woven apparel
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The pogo stick is one of those toys that nearly all kids try out at least and quickly quit after failing a couple times. It's like the unicycle, you really have to commit to get the hang of it. But once you do, you're in for a crazy ride.
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Unemployment in large metropolitan areas, September 2009
October 29, 2009
Of the 49 metropolitan areas with a Census 2000 population of 1 million or more, Detroit-Warren-Livonia, Michigan, reported the highest unemployment rate in September, 17.3 percent. The large area with the lowest rate was Oklahoma City, Oklahoma.
The large areas with the next highest rates were Riverside-San Bernardino-Ontario, California, 14.2 percent, and Las Vegas-Paradise, Nevada, 13.9 percent. Sixteen additional large areas posted rates of 10.0 percent or more.
The large areas with the lowest jobless rates in September were Oklahoma City, Oklahoma, 5.9 percent; Washington-Arlington-Alexandria, D.C.-Virginia-Maryland-West Virginia, 6.2 percent; and Virginia Beach-Norfolk-Newport News, Virginia-North Carolina, 6.7 percent.
All 49 large areas registered over-the-year unemployment rate increases of at least 1.6 percentage points. Detroit-Warren-Livonia, Mich., had the largest jobless rate increase from a year earlier (+8.4 percentage points). The next largest rate increase occurred in Las Vegas-Paradise, Nev. (+6.2 percentage points). Five other large areas recorded over-the-year rate increases of 5.0 percentage points or more.
These data are from the Local Area Unemployment Statistics program and are not seasonally adjusted. The most recent metropolitan area unemployment rates are preliminary and subject to revision. For more information, see "Metropolitan Area Employment and Unemployment: September 2009" (HTML) (PDF), news release USDL 09-1301.
Bureau of Labor Statistics, U.S. Department of Labor, The Economics Daily, Unemployment in large metropolitan areas, September 2009 on the Internet at http://www.bls.gov/opub/ted/2009/ted_20091029.htm (visited September 29, 2016).
Recent editions of Spotlight on Statistics
A look at healthcare spending, employment, pay, benefits, and prices
As one of the largest U.S. industries, healthcare is steadily growing to meet the needs of an increasing population with an increasing life expectancy. This Spotlight looks at how much people spend on healthcare, current and projected employment in the industry, employer-provided healthcare benefits, healthcare prices, and pay for workers in healthcare occupations.
Employment and Wages in Healthcare Occupations
Healthcare occupations are a significant percentage of U.S. employment. Some of the largest and highest paying occupations are in healthcare. This Spotlight examines employment and wages for healthcare occupations.
Fifty years of looking at changes in peoples lives
Longitudinal surveys help us understand long-term changes, such as how events that happened when a person was in high school affect labor market success as an adult.


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Set up for display. Hardly used. Only see 1 stain on hello kitty's face. Comes with ottoman also. $70 OBO
This ad was posted with the eBay Classifieds mobile app.
Aug 20 -
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Antelope - Baby & kid stuff
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Great Room in ManhattanStati UnitiNew YorkNew York
Su questo annuncio
This is a fully furnished apartment with 2 private bedrooms, 1 bathroom, living room, dinning room and 1 kitchen. The private room is furnished with a bed, a desk, an office chair, and a closet.
Uno spazio in cui gli ospiti possono cucinare
Asciugamani, lenzuola, sapone e carta igienica
This is a fully furnished apartment with 2 private bedrooms, 1 bathroom, living room, dinning room and 1 kitchen. The private room is furnished with a bed, a desk, an office chair, and a closet.
This is a fully furnished apartment with 2 bedrooms, 1 bathroom and 1 kitchen. This apartment is to share with students, tourists and/or young professionals. You enter the premises through the hallway. The living room is furnished with a sofa, a side table, a dinning table and a TV. The bedroom has two windows, two closets and a radiator. It is furnished with a full size bed/futon, a desk, a lamp and side table. There is cookware, dinning ware and other kitchen utensils available for you to use. The full tiled bathroom is equipped with a toilet, a shower in tub, a sink and a cabinet with a mirror.
The building is located in a safe neighborhood. Supermarket, McDonalds, Subway, French-Bistro, Popeyes, Dominos, iHop, Make my Cake Bakery, pharmacy, fish Market, bank, laundromat are nearby.
Couples are welcomed, rate for couple is $85/night.
- Living Room
- Bathroom
- Private room
- Kitchen
Residential neighborhood.
Transportation is available 24/7:
- Trains B and C run at 135th Street Station (Entrance on 137th Street), three (3) blocks from the building.
- 2 and 3 trains also run at 135th Street Station 4 blocks away from the building
- Trains A and D run at 145 Street Station, five blocks away from the building.
- There are two bus Stops located one (1) block away from the apartment each.
- No extra guests are allowed in the room. If a visitor wants to visit you at the apartment please discuss it first with the owner.
- Parties are strictly prohibited.
- Keys of the apartment and room must be given back to the owner upon departure.
- Key of the apartment is electronic. If lost a fee of $150 USD must be paid to the owner.
- Smoking in the room is strictly prohibited.
90 Recensioni
Il tuo Host
I am Software Engineer living in NYC. I've been an AIRBNB host for almost 6 years already. I enjoy meeting new people, good food, soccer (futbol), adventure.


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gets a new look !
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A Feature film by Agnès Varda
Release in France : 11/04/1962
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While waiting for the result of a biopsy, the French singer Cléo, aka Florence, visits a fortune teller; drinks coffee and buys a new hat with her housekeeper; is visited by her lover and her composers; visits her model friend; and meets and has a brief affair with a military man. Finally, she meets her doctor who gives her his diagnosis.
Source : IMDb
Marin Karmitz, Bernard Toublanc-Michel
Georges de Beauregard, Carlo Ponti
Paul Bonis, Liliane de Kermadec, Agnès Varda, Raymond Cauchetier
Julien Coutellier, Jean Labussière


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Hi Christos
Thanks so much!
Warm greetings from Australia, Paul
another beautiful picture under the sign of Paul Strasser! what can i do than give it a favorite?! :)
have a nice weekend, greetings from Romania
Hi, Paul. Beautiful picture. LIKE. I added you to my Favorite Photographer. Best regards, Sergey
I don't know what happened to my response Elena, but I thank you very much for your wonderful compliment!
Warm greetings, Paul
That's a great compliment Sergey! I'm truly honoured. Thank you very much!
Kind regards, Paul
Photo taken in Docklands VIC 3008, Australia


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Eagles quarterback Michael Vick said he had "nothing to do" with a shooting incident at his 30th birthday party and that he has been "completely truthful and fully cooperative from the very beginning" with law enforcement and NFL investigators, in a statement released last night through attorney Billy Martin.
Vick had not previously commented on the incident that happened early Friday morning outside the Guadalajara in Virginia Beach, Va.
"After I left the event, I learned that a man was shot outside the restaurant," Vick said in the statement. "I want to assure everyone that I had nothing to do with that incident. I left the restaurant prior to it occurring and did not witness what happened."


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Product Photo Editing
This project was successfully completed by Shimauli for $15 USD in 2 days.Get free quotes for a project like this
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Skills Required
Project Budget$10 - $40 USD
Completed In2 days
Total Bids84
Project Description
Hello Freelancers,
I have some 50-60 images of products like necklace, rings, earring, bracelets, scarfs, etc.
Your job will be:
1. To remove the background of the product and make the background plane white
2. Add some shadow of the product which make the product more pleasant
3. Also you will have to convert all the images to 1000 x 1000 px. (This should not affect the quality of the images, you can use sharpen tool option in PhotoShop)
You can message me your per image editing cost if you want OR total project cost. This is an on going project.
Freelancer must have account in DropBox.
Lowest bid with good reputation wins the job.
Happy Bidding.
Looking to make some money?
- Set your budget and the timeframe
- Outline your proposal
- Get paid for your work
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- Forbes
- The New York Times
- Time
- Wall Street Journal
- Times Online


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- Overview
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- Reviews
Spin Doctor Bike Wash 22ozGive your bike a bath and let it shine! Spin Doctor Bike Wash is a bio-friendly cleaner that easily washes away dirt and road grime to keep your bike looking its best and feeling loved.
- Clean and protect your entire bike
- Safe on all surfaces including carbon fiber, titanium, aluminum, steel, chrome, rubber, plastic, vinyl and leather
- Biodegradable, non-flammable formula is non-corrosive
- Contains no damaging chlorinated solvents, phosphates, benzenes or naptha
- Convenient spray bottle for easy application
Spin Doctor Bike Wash 22oz
- use:
- Cleaner
- weight:
- 22oz
- rating:
- 5
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Extra 20% Off: valid 9/26/16 online and by phone only. No coupon code is required to receive offer online or by phone; discount is reflected in cart. Extra 20% off is not valid on bikes, Team Performance memberships or renewals, gift cards, Spin Doctor Services or Service Plans, previous purchases, shipping or sales tax. Some brand and/or item exclusions may apply to this promotion – visit Terms and Conditions for details. Offer cannot be combined with any other coupon.


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Bar owners scramble to keep up with fake ID technology
The arms race between bar owners and college students with increasingly sophisticated fake IDs is heating up.
Students today can spend $100 to $150 on fake identification through a number of websites that claim superior quality down to the holograms and bar codes. There's an underground review that rates the quality of fake IDs from different sites. Students can even watch YouTube videos on how to make IDs showing they're 21, the legal drinking age. »Read Full Article(30)
Chieftains keep it simple and fun at Pabst Theater
After 52 years, you might expect the Chieftains to give a phoned-in performance.
You'd be wrong. »Read Full Article(1)
Theatrical Tendencies' 'Temperamentals': Being gay in '50s
Late in playwright Jon Marans' "The Temperamentals," the lead character addresses the audience, challenging the notion that the gay liberation movement began with those now-legendary 1969 riots outside a Greenwich Village bar.
"Before Stonewall," gay activist Harry Hay (Mark R. Neufang) tells us, "an even braver bunch of us stood up to the plate — before there even was a plate!" Led by Hay and his lover in Los Angeles, these brave pioneers called themselves the Mattachine Society. »Read Full Article
6 chefs, 5 courses, 5 beers as dinner series kicks off at Hinterland
The first in a series of beer dinners that bring together some of the city's top chefs will be March 25 at Hinterland Erie Street Gastropub.
Chefs cooking for the Best of Milwaukee beer dinner are Justin Aprahamian of Sanford, Daniel Jacobs of Odd Duck, Paul Zerkel and Lisa Kirkpatrick of Goodkind (due to open in spring in Bay View), Dan Van Rite of Hinterland and Matt Kerley of Blue Jacket. »Read Full Blog Post
'Cesar Chavez,' the movie and the book
"Cesar Chavez" a new feature film that tells the story of the famed farm worker organizer and civil rights leader, opens soon in theaters across the country.
The movie bio-pic stars Michael Peña, and Rosario Dawson. »Read Full Blog Post
Brewers still working out details on Hank the dog's new home
Phoenix — The question persists: Where will home be for Hank, the Brewers dog?
For the answer, apparently, we'll have to wait a little longer. »Read Full Article(18)


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|12 Reviews
|Separate WC's
|Property type
|Minimum Stay
|7 nights
Your booking will be backed by our Book with Confidence Guarantee when you complete your reservation online and finalise payment on HomeAway.Learn more
A spacious 200 sq. met Independent 3 double bedroom 2 bathroom villa set in beautiful walled gardens of 500 sq. met. Approached through electric gates with video screening inside the villa, situated at the end of a road containing only two other villas. It is very secluded allowing a high level of privacy.
Al fresco living is really the Puglese way of life especially in the summer months. The villa is covered by large verandas on 3 sides, one part with blinds to shade from the sun, there are very comfortable seating and dining arrangements here. A covered outside kitchen has a wood burning pizza oven and an open bar-b-que along with a preparation area.
The mosaic tiled infinity pool is 6 x 12 met and entered by built in steps which are also great for sitting/lying on. There is a low diving board, depth varies from 1.5-3 metres.Sun beds are dotted around on the paved patio.The pool and surrounding area is lit for evening swimming.
A large wood and sail pergola sits at one side of the pool for when you wish to escape the sun rays.The garden is mostly lawn with an irrigation system, the more formal areas have pebbled pathways to stroll around consisting of various plants and trees including Palms,Olives,Figs,Nespole,Almond,Pomegranate,Mandarin and Feyoia. There are 5 fountains around the property. Close to the pool there is an outdoor shower and cloakroom facilities.
Roof chill lounge area complete with lounging bean bags is an ideal place for enjoying pre and post dinner drinks while star gazing and wishing on the falling stars.
The living area of the villa is open plan. All rooms have air conditioning with remote controls. The kitchen is very well laid out with filtered drinking water on tap. Fridge/freezer, dishwasher,oven,5 ring gas hob, washing machine .Extending dining table, closed, seats 6 open, seats 12 with additional chairs in the garage along with a larger fridge/freezer.
The lounge area has 2 x 3 seat sofas and an armchair. An open fire, Unlimited broadband, 48'' plasma TV, Blue ray video player. Sky, including movie channels, most can be viewed in English. CD player and many DVDS and books.
Master bedroom has a King size bed, bedside drawers, lamps, two wardrobes and en-suite facilities with large walk in shower.
Bedroom 2 Has a queen size double bed, bedside drawers, lamps, double wardrobe.
Bedroom 3 has two 3' Bali style beds, shelving and drawer units, lamp and a double wardrobe.
The family bathroom has a large bath, sink, toilet, bidet and large independent shower.
In the bedroom wing corridor there is a tumble dryer.
There are hair dryers.
All windows in the villa are double glazed, have mosquito nets and steel shutters along with rolled metal blinds.
There is also an alarm system which is connected to the vigilanza office, should you want to use it.
The property is very well maintained, painted annually, weekly gardeners, it is a home.
Life is London has always been very fast paced with retail showrooms, travelling to design fares and all the daily hassel of running a business. Puglia gave us the opportunity to re-claim ourselves, find tranquility, beauty in nature and to understand and live 'La Dolce Vita'.
Annette Chaplin purchased this villa in 2004
The relaxed life style we could create here made it the villa for us.
Puglia is steeped in History and traditions of a past time, It fills, for many, something that is missing with the pace of life today. it allows you to kick back and chill, the life is simple, the food fabulous and the local wines......... It has the finest sandy beaches in Italy with the Ionian Sea being clear with hues of blue and green. It has many coves which ensure in the summer months that the sea is always warm. The Adriatic is cooler and the beaches are a mixture of sand and pebble.
The light here is incredible, so bright it naturally gives an endorphin kick when you wake.
The stylish villa with delightful, mature garden and super pool was enjoyed by our party of six to sixty-six year olds. The local water park was sometimes a bit noisy although I expect that is only during August. Maintenance problems were quickly sorted by the management team who were also happy to make reservations for us in local restaurants. Whilst Puglia is of course unpretentious it has some beautiful old towns that are still great value for money. Our six year old palaeontologist was in dinosaur heaven when we found the dinosaur footprints in Altamua. All in all one of the best holiday homes we have stayed in.
A wonderful 2 week vacation in the very Rustic Puglia giving us the chance to experience a very real part of Italy. With easy access to the coast below, or wonderful trips to the North to some wonderful Masseria and the unique Trulli - for us one of the wonders of the world, our trip was a foody, winey and visual heaven.
The team supporting the villa accommodated our every whim and even organised a memorable meal with 2 brilliant and humble chefs for our Mum's 70th Birthday. The villa is great and the pool tremendous. The local swim/funpark was useful for the kids and the local town had supermarkets, delis, bakeries, a pharmacy and very helpful Italians. Memorable.
The villa is beautifully designed and equipped. It is set in a large well laid out garden with a sheltered swimming pool. The villa is about 15 minutes drive from Francavilla town and around 40 minutes from the best beaches.
A great for a quiet relaxing break.
Lovely villa fully equipped with everything you could need for your holiday. Great beds and air con. Very helpful and thoughtful owner and manager. Yummy 'welcome to your holiday' provisions. Amazing pool which kept the kids entertained for 7 full days!
We loved it and happily return!
From start to finish this was just what the doctor ordered. When we arrived at the Villa, we were greeted by Zohar and were totally blown away by the attention to detail. This included a great little welcome pack made up of local wines and cheese plus the obligatory milk for the first tea of the day. The villa is set in beautiful gardens but the pool takes centre stage and is just perfect for the early morning swim or for the less active, a leisurely day of sunbathing and a quick dip to cool down. As for the Villa, it is clearly well cared for and we felt very comfortable (almost home from home) and the photos on the Web site don't fully convey just how good it is. Personally my favourite activity was making our own Pizza. Lighting the fire was a challenge at first (build the fire at the front of the oven until its well alight and then slide it to the rear and add more logs) Make your own base and buy the fresh toppings and salads from the nearby Masseria. Bliss!! When we did manage to drag our selves away from the Villa, the local towns and villages are idyllic and great for people watching or a coffee and pastry, not good for the waist line! We went looking for a week of total relaxation and were not disappointed (our expectations were totally exceeded) and I would recommend this to any one in need of real down time in a part of Italy that ticks all the boxes. We will definitely be back next year.
I recently spent a week at this tranquil villa. I feel rejuvenated and full of life after a relaxing stay. I highly recommend using the pizza oven and also the outdoor bbq area, such fun making the fire and creating our own pizzas, so easy too!
The local masseria's provide food that heaven sent from fresh cheeses to delicious wines. The local town, Francavilla Fontana, has an easy chilled vibe about it with very welcoming locals and countless coffee bars to gorge yourself on freshly made local pastries.
We barely ventured out to the beach as life by the pool became a welcome routine that I will certainly miss.
Thank you for a beautiful stay x
In the summer months there is nightly entertainment in both the baroque town of Francavilla Fontana (4.5 k) and the medieval town of Oria (8k). Entertainment takes the various forms of music, dance, the local Pizzica is a dance that tells the story of the journey between dreams and hopes,an ancient tradition. Also there is theatre.and open air cinema in the piazzas, summer 2013 saw Skyfall amongst others to watch whilst enjoying the local Ice cream.There are also the famous Medieval games where all contestents are dressed to do battle in costume to honour their quarter in Oria in August.There are always fireworks to celebrate celebration! Being nestled between the Ionian and Adriatic seas, allows you to choose depending on the breeze, just a glance at the trees to see, which beach to visit, both a 25 minute drive from the villa.Further afield you have beautiful Byzantine city of Leece(53k) from which you see the influences that have made Puglia so unique. A good drive to observe how Puglia changes from North heading South, enjoying a super lunch whilst gazing at where the 2 seas meet is Santa Maria de Leucca (104k). Heading north you have the Zoo at Fasano (50k) and the remarkable caves of Grotte di Cattellana (53k).
My indulgence: laying by the pool watching the swallows dive for water whilst chilling.
My treat: a 45 minute flight to Rome leaving in the morning from Brindisi airport for shopping, lunch and people watching and being back at the villa by 18.00 for a chilled Prosecco.
|Rental Period
|Minimum Price
|Additional Nights
|Weekend Night
|Event Price
3 Sep 2016 - 30 Sep 2016
Changeover Day: Saturday
7 night minimum stay
for 7 nights
1 Oct 2016 - 28 Oct 2016
7 night minimum stay
for 7 nights
May 2017
6 May 2017 - 26 May 2017
7 night minimum stay
for 7 nights
27 May 2017 - 30 Jun 2017
7 night minimum stay
for 7 nights
July/August 2017
1 Jul 2017 - 1 Sep 2017
7 night minimum stay
for 7 nights
September 2017
2 Sep 2017 - 29 Sep 2017
7 night minimum stay
for 7 nights
October 2017
30 Sep 2017 - 28 Oct 2017
7 night minimum stay
for 7 nights
|No additional mandatory fees
|Refundable Damage Deposit
A security deposit of £300 will be required with balance payment and refunded within 10days after vacating the villa subject to damage.
Rates inclusive of one weekly clean prior to arrival.
Mid week cleaning can be arranged and paid for locally.
Check in Saturday after 16.00 pm
Check our Saturday by 10.00 am
A fair share of electricity is included but there may be a charge for excessive use,


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The annual Ohio State football spring game went down in Cincinnati's Paul Brown Stadium Saturday afternoon, where quarterback Braxton Miller led the Scarlet team to a 31-14 victory over the Gray team.
Urban Meyer and the coaching staff split Ohio State's roster in two Friday morning, and the Scarlet team featured much of the first-team offense while the Gray team received most of the defensive starters.
Miller and the Scarlet team carved up the Gray team through the air, as the trio of Devin Smith, Evan Spencer and Bri'onte Dunn hauled in a combined 13 passes for 213 yards.
The Gray team, led by Kenny Guiton for much of the first half and Cardale Jones for most of the second, struggled to move the ball against what amounted to Ohio State's second-team defense.
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Fixed PriceBudget: $120
Start DateDecember 7, 2012
I wish to have new website built in Wordpress.
My existing website is www.vaccinationscheduler.com and has built in Unbounce as I can not code. So I want a new sexy effective website in wordpress
My Target Market:
99.9% Mothers. Specifically mothers who have a child 0-4 years old
My Objective:
Sell my iPhone app to these parents - Vaccination Scheduler.
Some design considerations.
1. I like the use of clean lines, Very much Apple look and feel, as the product is medical and clean.
2. The image of the baby in green is the face of the product, so have used hte Green of the baby's blanket throughout. This also matches the colours of the app itself. We can also use more baby/parent images.
3. Scrolling Down is Good. But the Links to other Pages need to be better done - Links include: Media Release, Support, List of Countries, Vaccination Report
4. Note. Social Proof is very important which is why I have Facebook insert at top and Media just below. This app needs social proof and media proof to help it sell
Basically I am happy with my layout and design but know it can be improved and help conversion.
Can you please provide estimate cost and timeframe to take my existing website and rebuild in WordPress
Please submit your BEST 5 WordPress designs so I can see your work style.
Skills: design
About the Client
Bondi 06:55 PM
Jobs Posted
53% Hire Rate, 2 Open Jobs
Over $50,000
Total Spent
146 Hires, 3 Active
Avg Hourly Rate Paid
6,865 Hours


text:
|Publication number
|Publication type
|Application number
|Publication date
|Jun 9, 1998
|Filing date
|Oct 6, 1995
|Priority date
|Jan 19, 1993
|Fee status
|Also published as
|Publication number
|Bruce Allan Harrington, Patrick Brant, Anthony Jay Dias
|Original Assignee
|Exxon Chemical Patents, Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (27), Referenced by (24), Classifications (24), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
This is a continuation of application Ser. No. 08/234,287, filed Oct. 14, 1994, now abandoned, which is a CIP of application Ser. No. 08/005,676, filed Jan. 19, 1993.
This invention relates to blends of crystalline or semi-crystalline polymers, such as polypropylene, with predominantly amorphous, elastomeric copolymers that have a packing length greater than that of the host polymer. These copolymers, when blended with semi-crystalline homopolymers such as polypropylene act to toughen the homopolymer without detrimentally affecting the surface properties of the semi-crystalline homopolymer.
Semi-crystalline polymers such as polypropylene are versatile polymers useful in many applications since their crystallinity imparts desirable mechanical properties such as stiffness. They suffer however from brittleness in certain applications. One of the methods used to reduce the brittleness of semi-crystalline polymers is to blend them with low glass transition temperature (Tg) elastomers such as ethylene-propylene rubber or ethylene-propylene-diene modified terpolymers (EPRs and EPDMS). These blends are less brittle and provide an improved impact resistance, however they often suffer from reduced gloss, haze, and poor tactile quality, as well as decreased flexural modulus when these properties are compared to the original semi-crystalline homopolymer. One reason for this loss of surface properties has to do with chain flexibility. Both the semi-crystalline polymers and the rubber copolymers that are blended with them comprise very flexible chains. They have similar packing lengths as defined and disclosed in Fetters, L. J., Lohse, D. J., Richter, D., Witten, T. A., and Zirkel, A. Macromolecules, 1994, and Brant, P., Karim, A., Sikka, M., and Bates, F. S., J. Poly. Sci., Poly. Phys. Ed. 1994, incorporated by reference herein. Because of their similar flexibility and packing lengths, both polymers can reside at interfaces and surfaces with similar ease, i.e. when the chains come to an interface or surface, they can fold themselves to fit along the surface, or fold themselves to return to the bulk of the polymer without much trouble. Hence, there exists a roughly equal probability that both the rubber polymer (rubber phase) and the semi-crystalline polymer (continuous phase) of the blend can reside at the surface. In turn, two phases on the surface of a polymer contributes to a decrease in gloss and an increase in haze. Therefore, there exists a need in the art to provide blends of semi-crystalline polymers with impact modifying rubbers that achieve a balance of useful mechanical properties and desirable surface properties.
In accordance with the present invention, blends comprising a semi-crystalline polymer and a rubbery thermoplastic copolymer having good strength and surface properties without significant loss of optical or tensile properties are provided.
FIG. 1 is a plot of 1% Secant Flexural Modulus vs. 23� C. Garner Impact for neat polypropylene and blends P, Q, R and S.
The present invention relates to blends of a semi-crystalline polymer, such as polypropylene, with a rubbery copolymer with a significantly different surface tension, preferably a difference of 3 dynes per centimeter or more. In a preferred embodiment the rubbery thermoplastic copolymer has a surface tension 3 or more dynes/cm greater than the surface tension of the semi-crystalline polymer, even more preferably 5 dynes/cm greater, even more preferably 8 dynes/cm greater, even more preferably 10 dynes/cm greater. These blends have superior strength, haze and gloss properties, among others. In particular these blends have increased impact resistance without a significant reduction in flexural modulus and gloss.
Hereinafter the use of the term polypropylene is merely exemplary, and is not intended to limit the scope of the invention in any way. Those of ordinary skill in the art will recognize that other semi-crystalline polymers comprising C2 to C40 α-olefins would be used in a similar fashion.
In one set of embodiments the rubbery thermoplastic copolymer is typically present in the blend in amounts of up to about 90 weight %, preferably up to about 70 weight %, even more preferably up to about 50 weight % with the balance being made up of the semi-crystalline polymer. (wt % is based upon the weight of the blend) In an alternate set of preferred embodiments the rubbery thermoplastic copolymer is present at about 0.5 to about 45 wt %, even more preferably 1 to about 30 wt %, even more preferably about 10 to about 25 wt %, with the balance being made up by the semi-crystalline polymer.
Preferred semi-crystalline polymers that may be blended or combined with the rubbery copolymers include propylene homopolymers and copolymers. The homopolymers preferably have about 95% or more heptane insolubles, more preferably about 97% or more heptane insolubles (Insolubles measured on bulk polymer samples dried at 100� C. in a vacuum oven prior to boiling in n-heptane for 1.5 hours. Thereafter samples are vacuum dried, rinsed with acetone, dried further in a vacuum oven at 100� C. and thereafter heated in a muffle furnace for 8 hours at 1100� F. (593� C.). Heptane insolubles=100�(weight of sample after heating in muffle furnace divided by weight of the sample prior to combining with n-heptane).) The copolymers may be copolymers of propylene with any aliphatic or aromatic cyclic or branched olefin, preferably ethylene or any C4 to C100 α-olefin, preferably ethylene or any C4 to C20 α-olefin. For the purposes of this invention ethylene is considered an α-olefin. Such propylene copolymers and homopolymers are well known in the art and are commercially available under many trade names.
Rubbery copolymers with lower flexibility can be made by incorporating rigid or bulky comonomers into the polymer chains. For example the rubbery copolymer can be an alpha-olefin, preferably ethylene or propylene, with a cyclic olefin, preferably norbornene and the like, or styrene or the like. Preferred rubbery thermoplastic copolymers and methods to make them are disclosed and claimed in U.S. patent application Ser. No. 08/005,676, filed Jan. 19, 1993 (now published as WO 9417113, pub. Aug. 11, 1994), which is incorporated by reference herein. Preferred rubbery thermoplastic copolymers of an α-olefin and a cyclic olefin which are blended with the polypropylene described above are preferably copolymers which can be made, for example, by polymerizing cyclic olefin comonomers with one or more α-olefins in the presence of a coordination catalyst, preferably a single site catalyst. Preferred rubbery thermoplastic copolymers generally comprise from about 5 to about 30 mole percent of the cyclic comonomer, preferably from about 10 to about 20 mole percent of the cyclic comonomer. Preferred rubbery thermoplastic copolymers have a high molecular weight up to 2,000,000 or more, preferably from about 30,000 to about 1,000,000, even more preferably from about 50,000 to about 500,000, even more preferably 80,000 to about 250,000. (As used herein, molecular weight refers to the weight average molecular weight (Mw) unless otherwise indicated.) In preferred embodiments the rubbery thermoplastic copolymers may have a relatively narrow molecular weight distribution (MWD), i.e. (Mw /Mn) of less than about 4, preferably less than about 2. The rubbery thermoplastic copolymers generally have a glass transition temperature(Tg) in the range of -50� C. to 50� C., preferably -15� C. to about 25� C. As used herein, Tg is determined by differential scanning calorimetry (DSC) under ASTM E 1356.
The rubbery copolymers also have a number of unusual properties which make them rather desirable for blends with polypropylene and other semi-crystalline copolymer, such as toughness and optical clarity combined with elasticity and good recovery after elongation. (As used herein, ultimate tensile strength, elongation at break, and recovery are determined at 25� C. using procedures in accordance with ASTM D-412, unless otherwise noted.)
In addition to having a long statistical chain segment length, the preferred rubbery thermoplastic copolymers have:
1) an elongation at break of 300% or more and especially of 400% or more;
2) a tensile strength at 150% elongation of at least 800 psi (5.5 MPa), preferably at about 1000 psi (6.8 MPa);
3) an elastic recovery of at least 70% after 10 minutes relaxation from 150% elongation, more preferably recovery of at least 80%;
4) an ultimate tensile strength of at least 2500 psi (17.2 MPa), more preferably above 3500 psi (24.1 MPa)and/or
5) a surface tension of about 33 dynes/cm or more, preferably about 37 dynes/cm or more.
The rubbery copolymers described above are also unique in that they remain elastic well above their glass transition temperatures and remain ductile well below their Tg. In general, the copolymer remains rubbery at temperatures above the approximate Tg (as measured by DSC) of the copolymer, for example, from the Tg (-50� C. to 50� C.) to above 100� C., preferably above 150� C. In another preferred embodiment the rubbery copolymer is elastic over the temperature range of from its Tg to 100� C. above its Tg, preferably over the range of from its Tg to 150� C. above its Tg. This unusual elasticity may also be reflected by a rubbery storage modulus over this temperature range. The rubbery storage modulus of the copolymers is readily observed as a plateau between about 1 and about 100 MPa by dynamic mechanical thermal analysis (DMTA) at a frequency of 1 or 10 Hz with a 2� C./min temperature ramp using commercially available DMTA equipment, for example, from Polymer Laboratories, Inc. The ductile-brittle transition can be measured by ASTM D-746 and although the rubbery thermoplastic copolymers may have a Tg of -5� C. to 5� C. as measured by DSC, they remain ductile to temperature below -20� C., and even to temperatures below -30� C.
If desired, the rubbery modulus can be extended to higher or lower temperatures by the optional use of crosslinking, plasticizing additives, or a combination of crosslinking and plasticizers. In general, plasticizers tend to lower the temperature at which the copolymer becomes brittle, while crosslinking raises the temperature at which the copolymer will flow or otherwise suffer a significant reduction in strength.
Surface tension is measured by using standard treat solutions well known in the art (ASTM D2578-94). ASTM D2578-94 is hereby incorporated by reference. A typical Ethylene-norbornene copolymer having about 10 mol % norbornene has a surface tension of about 41 dynes/cm and typical polypropylene has a surface tension of about 30 or 31 dynes/cm.
The α-olefin(s) which are copolymerized with the cyclic olefin(s) to make the rubbery thermoplastic copolymer can be any unsaturated, copolymerizable monomer having at least 2 carbon atoms, or mixture or combination thereof. Typically, the α-olefin is a substituted or unsubstituted C2 -C20 α-olefin, such as, for example, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-pentene-1, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3,5,5-trimethylhexene-1, allyltrimethyl silane, and the like; or vinyl aromatic and alicyclic monomers, such as, for example, styrene, alkyl-substituted styrene, vinyl cyclohexene, and the like. The α-olefin can also be (or include) a longer α-olefin (having 10 or more carbon atoms), a branched α-olefin or a polyene, or a combination thereof; either alone as the sole α-olefin comonomer(s), or more preferably as a termonomer in combination with a C2 -C20 α-olefin, particularly a C2 -C8 α-olefin, especially ethylene, propylene or a mixture of ethylene and propylene. (As used herein the term "α-olefin" or "alpha-olefin" is intended to refer generically to longer α-olefins, branched α-olefins, and polyenes, as well as the more usual C2 -C20 α-olefins. Also as used herein the term copolymer is intended to refer to polymers of two or more different monomers.)
In general, any cyclic olefin can be copolymerized with the α-olefin to produce the rubbery copolymer provided the cyclic olefin includes cyclized ethylenic or acetylenic unsaturation or ethylenic or acetylenic unsaturation pendant to the cyclic structure as in styrene or vinylcyclohexane, said unsaturation which undergoes addition polymerization in the presence of the catalyst (substantially without ring opening) so that the ring structure in which the unsaturation is present is incorporated into the polymer backbone. A method to prepare the rubbery copolymers and lengthy list of preferred cyclic monomers is disclosed in PCT publication WO/9417113, published Aug. 11, 1994, and incorporated by reference herein.
Especially preferred cyclic olefins include cyclobutene, cyclopentene, deltacyclene, norbornene, methylnorbornene, tetracyclododecene, methyltetracyclododecene, dimethyltetracyclododecene, tricyclo(126.96.36.199,5)-3-decene, and pentacyclo(22.214.171.124,5.08,13.19,12). Of these, norbornene is preferred for its ready commercial availability and effectiveness.
Polyenes having two or more double bonds can optionally be used in a relatively minor proportion to impart higher molecular weight to the copolymer and/or provide residual pendant side chain unsaturation for functionalization or crosslinking. Where the polyenes can participate in polymerization at two (or more) sites, these monomers tend to promote chain extension which can double or quadruple the molecular weight at low incorporation rates, and also raise the upper temperature at which the rubbery storage modulus plateau is present. Ideally the polyene is not present in such high amounts which might result in excessive crosslinking and produce insoluble gel formation. Preferably, the molecular weight is suitably increased by including the optional polyene in the copolymer at from 0.5 to 3 mole percent.
Suitable polyenes include, for example, α,ω-dienes having from 5 to 18 carbon atoms, such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, 1,14-pentadecadiene, 1,15-hexadecadiene, 1,16-heptadecadiene, 1,17-octadecadiene, or the like.
When two (or more) of the double bonds are sufficiently reactive under the particular reaction conditions to participate in the polymerization reaction, suitable optional polyenes generally also include other linear or branched aliphatic dienes and trienes, monocyclic dienes and trienes, bicyclic dienes and trienes, polycyclic dienes, aromatic dienes, and the like. Specific representative examples of non-conjugated polyenes include 1,4-hexadiene, 6-methyl-1,4-heptadiene, 4-isopropyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 4-isopropyl-1,4-hexadiene, 6-phenyl-4-propyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 6-phenyl-1,4-hexadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 6-methyl-1,5-heptadiene, 5,7-dimethyl-1,5-octadiene, 4,5-dipropyl-1,4-octadiene, 5-propyl-6-methyl-1,5-heptadiene, 5-ethyl-7-methyl-1,6-octadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,8-decadiene, 1,9-decadiene, and 1,10-undecadiene; dicyclopentadiene, tricylopentadiene, 1-vinyl-4-(1-propenyl)-cyclohexane, 4-methylcyclo-1,4-octadiene, 4-methyl-5-propylcyclo-1,4-octadiene, 5-methylcyclopentadiene, 4-methyl-5-ethyldicyclopentadiene, 5-isopropyldicyclopentadiene, 1,5,9-cyclododecatriene, 4-(1-butenyl-2)-styrene, 4-2-butene-2-yl)-styrene and trans-1,2-divinylcyclobutane, 5-ethylidenenorbornene-2, 5-propylidenenorbornene-2, 5-butylidenenorbornene-2, 5-isopropylidene-norbornene-2, 2-methyl-2,5-norbornadiene, 5-methyl-2,5-norbornadiene, 2-propyl-2,5-norbornadiene, 5-methylene-2-norbornene, 5-(2-butenyl)-2-norbornene, 3-heptyl-2,5-norbornadiene, 2-ethyl-3-propyl-2,5-norbornadiene, 2-(1',5'-dimethylhexene-4-yl)-2,5-norbornadiene, dicyclopentadiene, 5-isopropyldicyclopentadiene, 5-isopropylidenebicyclo (2.2.2)octene-2, 5-ethylidenebicyclo(2.2.2)octene-2, 5-butylidenebicyclo (2.2.2)octene-2, 2-ethylbicyclo (2.2.2)octadiene-2,5, 2-methyl-3-ethylbicyclo (2.2.2)octadiene-2,5, 2-hexylbicyclo (2.2.2)octadiene-2,5, 2-(1',5'-dimethylhexenyl-4) bicyclo(2.2.2)octadiene-2,5, 1-isopropylidenebicyclo (4.4.0)decadiene-2,6, 2-isopropylidenebicyclo (4.4.0)decene-6, 2-ethylidenebicyclo (4.4.0)decene-6, 3-ethylidenebicyclo (3.2.0)heptadiene-2,6, 3-methylbicyclo (3.3.0)octadiene-2,6, 3-methyltetrahydroindene, 6-methyltrahydroindene, 2-propyltetrahydroindene, 1-isopropylidenetetrahydroindene, 1-(1'-phenyl)-ethylidenetetrahydroindene and the like.
In a preferred embodiment, the polymerization methodology is practiced in the manner and with the catalyst systems referred to, disclosed, and described in the following references: U.S. Pat. No. 5,055,438; U.S. Pat. No. 5,507,475; 5,096,867; WO 92 00333; U.S. Pat. No. 5,264,405; U.S. Pat. No. 5,324,800; CA 1,268,753; U.S. Pat. No. 5,017,714; 5,240,894; U.S. Pat. No. 5,198,401; U.S. Pat. No. 5,153,157; WO 94 03506; EPA 520,732, pub Dec. 30, 1992; EPA 129,368, pub. Dec. 27, 1984; and EPA 277,003 & 277,004, pub. Jun. 3, 1988, which are hereby incorporated herein by reference.
Generally, the preferred catalyst systems employed in preparing the copolymer of the invention can comprise a complex formed upon admixture of a Group 4 transition metal component with an activating component. The catalyst system can be prepared by addition of the requisite transition metal and alumoxane components, or a previously cationically activated transition metal component, to an inert solvent in which olefin polymerization can be carried out by a solution, slurry or bulk phase polymerization procedure.
Optimum results are generally obtained when the Group 4 transition metal compound is present in the polymerization diluent, in a concentration of preferably from about 0.00001 to about 10.0 millimoles/liter of diluent and the activating component is present in an amount to provide a molar activating component to transition metal ratio of from about 0.5:1 to about 2:1 or more, and in the case of alumoxane, the molar alumoxane to transition metal can be as high as 20,000:1. Sufficient solvent is normally used so as to provide adequate heat transfer away from the catalyst components during reaction and to permit good mixing.
The catalyst system ingredients, that is, the transition metal, the alumoxane and/or ionic activators, and polymerization diluent can be added to the reaction vessel rapidly or slowly. The temperature maintained during the contact of the catalyst components can vary widely, such as, for example, from -100� C. to 300� C. Greater or lesser temperatures can also be employed. Preferably, during formation of the catalyst system, the reaction is maintained within a temperature of from about 25� C. to 100� C., most preferably about 25� C.
In a preferred embodiment, the catalyst system is utilized in the liquid phase (slurry, solution, suspension or bulk phase or combination thereof), high pressure fluid phase or gas phase (where the α-olefin and cyclic olefin are sufficiently volatile, e.g. up to C8) for copolymerization of α-olefin and cyclic olefin. These processes may be employed singularly or in series. The liquid phase process comprises the steps of contacting α-olefin and cyclic olefin with the catalyst system in a suitable polymerization diluent and reacting said monomers in the presence of said catalyst system for a time and at a temperature sufficient to produce a copolymer of high molecular weight. Conditions most preferred for the copolymerization of α-olefin are those wherein α-olefin is submitted to the reaction zone at pressures of from about 0.019 psi (0.1 KPa) to about 50,000 psi (345 MPa) and the reaction temperature is maintained at from about -100� C. to about 300� C. The reaction time is preferably from about 10 seconds to about 4 hours.
One example of polymerization for production of the α-olefin/cyclic olefin copolymer is as follows: in a clean, dry and purged stirred-tank reactor containing solvent and optional scavenger, liquid comonomer is introduced, such as 2-norbornene. The catalyst system is introduced via nozzles in either the vapor or liquid phase. Feed ethylene (or other olefin) gas is introduced either into the vapor phase of the reactor, or sparged into the liquid phase as is well known in the art. The reactor contains a liquid phase composed substantially of solvent, liquid comonomer, together with dissolved ethylene gas, and a vapor phase containing vapors of all monomers. The reactor temperature and pressure may be controlled via reflux of vaporizing comonomer (autorefrigeration), as well as by cooling coils, jackets etc. The polymerization rate is generally controlled by the concentration of catalyst. The ethylene and comonomer contents of the polymer product are determined by NMR and manipulating the ratio of ethylene to comonomer in the reactor.
Alternatively, the α-olefin/cyclic olefin copolymer can be prepared by a high pressure process. The high pressure polymerization is completed at a temperature from about 105� C. to about 350� C., preferably from about 120� C. to about 250� C., and at a pressure of from about 100 bar to about 3200 bar, preferably from about 200 bar (20 MPa) to about 1300 bar (130 MPa), in a tubular or stirred autoclave reactor. After polymerization and catalyst deactivation, the product copolymer can be recovered using conventional equipment for polymer recovery, such as, for example, a series of high and low pressure separators wherein unreacted α-olefin, and unreacted cyclic olefin in some instances, particularly when the comonomer is relatively volatile, can be flashed off for recycle to the reactor and the polymer obtained extruded in an underwater pelletizer. An advantage of the high pressure process is that the flashing off of the cyclic olefin is relatively effective, particularly at the ratio of cyclic olefin: α-olefin used in the copolymerization to obtain the desired comonomer incorporation in the copolymer. Pigments, antioxidants and other known additives and fillers, as are known in the art, can be added to the polymer.
The copolymerization process can be a continuous or batch reaction. Typically, the continuous process, where reactants are continuously fed to the reactor and product continuously withdrawn, is preferred in commercial production facilities for economic reasons. The continuous process also has the advantage of promoting more uniform comonomer incorporation into the polymer.
As before noted, any suitable coordination catalyst system can be used. Preferably, however, the catalyst system has the ability to incorporate a relatively high content of the comonomer. The catalyst preferably has a relatively low α-olefin:cyclic olefin reactivity ratio less than about 300, more preferably less than 100, and especially from about 25 to about 75. Accordingly, the selection of the transition metal component, and other catalyst system components, is another parameter which may be utilized as a control over the α-olefin content of a copolymer with a reasonable ratio of α-olefin to cyclic olefin feed rates.
Preferred catalyst systems include:
Cp2 ZrMe2 combined with DMAH B(pfp4);
Cp2 ZrCl2 combined with MAO;
Cp2 HfMe2 combined with DMAH B(pfp4);
Cp2 HfCl2 combined with MAO;
Me2 Si bis(Ind)HfMe2 combined with DMAH B(pfp4);
Me2 Si bis(Ind)HfCl2 combined with MAO;
Dimethylsilyl(tetramethyl-cyclopentadienyl) (amidocyclododecyl) titanium dichloride combined with MAO;
Dimethylsilyl(tetramethyl-cyclopentadienyl) (amidocyclododecyl) titanium dichloride combined with DMAH B(pfp4);
Me2 Si(H4 Ind)ZrCl2 combined with MAO; and
Me2 Si(H4 Ind)ZrMe2 combined with DMAH B(pfp4).
Abbreviations: Cp=cyclopentadienyl, Me=methyl, DMAH B(pfp4)=dimethylanilinium tetra(perfluorophenyl) borate, MAO=methylalumoxane, and Ind=indenyl.
In a preferred embodiment rubbery α-olefin/cyclic olefin copolymer (preferably an ethylene/norbornene copolymer) would be polymerized by the following procedure: A 1-liter or 2-liter autoclave reactor equipped with a paddle stirrer, an external water or steam jacket for temperature control, a regulated supply of dry nitrogen, ethylene, propylene, toluene and hexane, and a septum inlet for introduction of comonomer, transition metal compound, co-catalyst and scavenger solutions would be dried and purged thoroughly prior to use. Optionally solvent, if used, would be introduced to the reactor (typically toluene or hex). A quantity of cyclic olefin (typically in toluene or a hexanes solvent), optionally a scavenger would be added by cannula (typically an AlR3, preferably TEAL or TIBA, most preferably TIBA) and the ethylene or propylene monomer (as a liquid or gas) would be introduced into the reactor. The reactor would then heated to between 30� C.-80� C. and a toluene solution of the transition metal compound, previously activated by the co-catalyst, will be introduced into the system by cannula using high pressure nitrogen or solvent. The polymerization reaction would be generally conducted for 10 to 120 minutes. The reaction will be halted by rapidly cooling and venting the system. The resulting polymer would be recovered by precipitation in methanol and/or isopropanol, filtration and drying the polymer in vacuo for about 12-48 hours at ambient temperature up to 100� C.
Scavengers, when used, would be 2.0 molar solutions of triisobutyl aluminum (TIBA), trimethyl aluminum (TMA), diisobutyl aluminum (DiBAL) or triethyl aluminum (TEA). Possible transition metal compounds include dimethylsilyl bis(indenyl) hafnium dimethyl, dimethylsilyl(tetramethyl-cyclopentadienyl) (amidocyclododecyl) titanium dichloride, bis(cyclopentadienyl) zirconium dimethyl or dimethylsilyl bis(tetrahydroindenyl) zirconium dichloride.
The blends, including the cured blends discussed below, produced herein are useful in any application where rubber toughened polypropylene has been used in the past. For example the blend may be molded, blown, cast, extruded or otherwise formed into articles.
Examples include automotive trim, automotive bumpers, packages, containers, films, sheets, strips and the like.
Ethylene/norbornene copolymer (ENBl) was produced according to the following procedure:
About 15.5 g norbornene dissolved in 400 ml hexanes were added to a one liter Zipperclave reactor equipped with a paddle stirrer; an external water or steam jacket for temperature control; a regulated supply of dry nitrogen, ethylene, propylene, toluene and hexane; and a septum inlet for introduction of comonomer, transition metal compound, co-catalyst and scavenger solutions the reactor was dried and purged thoroughly prior to use. Ethylene was introduced at a pressure of 50.0 psig (345 kPa) and the reactor was heated (30� C.) and stirred. 23.0 mg of the bis(cyclopentadienyl) zirconium dimethyl (a molar excess) and 9.6 mg of dimethylanilinium tetra(perfluorophenyl)borate were mixed in toluene (2-3 ml) and left to activate for 10 minutes. This two-phase oil/toluene mixture was sealed in a vial with septa, the vial was connected to the reactor via cannula and then pressurized with N2 in the reactor. Thee polymerization reaction was conducted for 19 minutes, yielding 3.91 g of copolymer. ENB2 and ENB3, were made following the procedure above except for the differing conditions noted in Table 1 which reports the polymerization and some physical data.
TABLE 1______________________________________Rubbery Ethylene/Norbornene Copolymer Data ENB1 ENB2 ENB3 ENB4______________________________________Cp2 ZrMe2 (mg) 23 16 42 VDMAH B(pfp4) (mg) 9.6 20 48 VTemp (�C.) 40 50 40 40C= 2 (psi/kPa) 50/345 36/248 38.8/268 35/241Norbornene 15.5 g 38.8 g 38.8 g 40 gTime (hr) 0.33 0.33 0.25 VYield (g) 3.91 52.0 NA VAct. (g/g - h) 24,300 25,00 NA VMw 67,000 110,000 150,000 72,000Mol % NB* 11.9 11.7 8.7 14.0Stress@ (psi/MPa) 3140/22 NA NA 3840/26Elong.# (%) 535 NA NA 443______________________________________ Elong.# = elongation at break as measured by ASTM 412. Stress@ = stress at maximum load as measured by ASTM 412. Mol % NB = mole percent of norbornene in the polymer as measured by 13 CNMR and/or 1 HNMR. V Variable. ENB4 was a composite blend of many small batch runs. The values given are for the final blended material. ENB5 is ENB4 with a stabilizer package of IRGAPHOS 168 ™ (750 ppm) and IRGANOX 1076 ™ (1500 ppm) added. NA Data Not available.
Several polypropylenes were made or purchased. These were:
(1) PP1--high crystallinity, brittle, isotactic PP (98.7% heptane insolubles) made using a supported TiCl4 /MgCl catalyst activated with a methylcyclohexyldimethoxysilane donor in typical commercial slurry conditions.
(2) PP2--a commercially available isotactic PP homopolymer sold under the trade name ESCORENE PP1012™ by Exxon Chemical Company having a melt flow rate of 5.0 g/10 min (ASTM D 1238-65T condition L);
(3) PP3--a commercially available polypropylene homopolymer sold under the trade name Escorene PD 3345E from Exxon Chemical Company, having a melting point of 165� C. and a melt flow rate of 35 g/10 min (ASTM D 1238-65T condition L);
(4) PP4--a commercially available polypropylene homopolymer sold under the trade name Escorene PD 4193 from Exxon Chemical Company, having a melt flow rate of 7.3 g/10 min (ASTM D 1238-65T condition L); and
(5) PP5--a low melt flow rate (MFR) atactic PP made by polymerizing propylene in the presence of Me2 Si Me4 CpN(C12 H23)!TiCl2 and methylalumoxane in solution conditions.
Several blends, A-H, were physically mixed using a Brabender Counter rotating mixer using the small mixing head (45 ml). Mixing conditions were as follows:
The head was preheated to 190� C. for 5 minutes. A manually blended mixture was fed into the mixing chamber with screws rotating at 60 rpm. The mixture was blended for 5 minutes and then removed. The blends were then compression molded. The blends and the test data are reported in Table 2.
Several blends (M-T) were mixed and pelletized using two passes through a single screw extruder with a 200 mesh screen pack. The pellets were injection molded into test pieces.
TABLE 2______________________________________Blend PP (g) ENB (g) wt. % rubber______________________________________A PP5 (0.032) ENB1 (0.6) 95%B PP5 (0.07) ENB1 (0.6) 90%C PP5 (0.106) ENB1 (0.6) 85%D PP5 (0.4) ENB1 (0.6) 60%E PP5 (0.6) ENB1 (0.6) 50%F PP3 (36.31) ENB2 (90.4) 20%G PP3 (27.15) ENB2 (18.14) 40%H PP4 (34.92) ENB3 (11.64) 25%M* PP1 (10 lbs) none 4%N* PP1 (9.6 lbs) ENB5 (181.6 g) 4%O* PP1 (9.6 lbs) VISTALON457 ™ (181.6 g) 4%P PP2 (9.6 lbs) ENB5 (181.6 g) 4%Q PP2 (9.6 lbs) Vistalon719 ™ (181.6 g) 4%R PP2 (9.6 lbs) Vistalon404 .sup.™ (181.6 g) 4%S PP2 (9.6 lbs) Vistalon457 ™ (181.6 g) 4%T PP2 (10 lbs) none 4%______________________________________ * = 550 ppm of BHT and 800 ppm of calcium stearate were added as a stabilizing package.
The copolymers were selectively tested for norbornene content by carbon nuclear magnetic resonance (CNMR) and/or proton NMR (1 HNMR); molecular weight (Mw) and molecular weight distribution (Mw /Mn) by gel permeation chromatography; and glass transition temperature (Tg) by differential scanning calorimetry (DSC) using ASTM E 1356 . The DMTA was done on a Polymer Laboratories, Inc. DMTA apparatus using a single cantilever head and a 2� C./min. temperature ramp according to the manufacturer's recommended procedures at 1 Hz and 10 Hz from -120� C. to 150� C. Physical properties such as tensile strength at break; elongation at break; tensile strength at 150% strain; and recovery (100 minus tension set) were measured according to ASTM 638. Physical properties were measured on an Instron tensile testing apparatus at 4 in./min. (200%/min.), and the recovery data at 20 in./min. (1000%/min.). Testing was at ambient conditions unless otherwise indicated. Youngs modulus and yield stress were measured by a ASTM 638. Flexural strength was measured by ASTM 638. 1 % Secant flexural modulus was measured by ASTM D 790. Gardner impact was measured by ASTM D 5420. Tm was measured by DSC, second melt. Mold shrinkage is measured by ASTM D 955. 600 gloss is measured by ASTM 2457.
The blends were injection molded into plaques and tested for tensile at break, elongation at break, yield stress, Young's Modulus, flex strength, 1% Secant flexural modulus, Gardner Impact at 23� C., melting point(Tm), crystallization temperature(Tc), mold shrinkage and 60� gloss. The results are presented in Table 3a and 3b.
TABLE 3a______________________________________Tensile at Elong. Yieldbreak at break stress Young's modulus Flex strengthBlend(psi/MPa) (%) (psi/MPa) (psi/MPa) (psi/MPa)______________________________________M 3491/24.0 730 5189/35.7 109723/756.5 7164/49.3N 3193/22.0 656 5041/34.7 109889/757.6 6963/48.0O 3018/20.8 771 4758/32.8 98296/677.7 6409/44.1P 3233/22.2 889 4712/32.4 91651/631.9 5855/40.4Q 2759/19.0 817 4529/31.2 70965/489.3 5652/38.9R 3143/21.6 928 4437/30.5 83668/576.8 5383/37.1S 3093/21.3 950-NB 4404/30.3 71120/490.3 5476/37.7T 3337/23.0 950-NB 4794/33.0 88281/608.6 5883/40.5______________________________________ NB = no break
TABLE 3b______________________________________Secant 1 Gardner Mold 60�mod. impact Tm Tc shrinkage glossBlend(psi/MPa) (in/lbs) (�C.) (�C.) (%) (%)______________________________________M 252727/1743 8.2 Br 168/160 114 1.35 87.6N 247397/1706 61 BrSh 168/160 115 1.36 87.1O 230029/1586 197 DuSh 168/160 116 1.29 87.0P 200500/1382 167 DuSh 160 115 1.3 87.4Q 193079/1331 163 DuSh 161/144 113 1.3 86.9R 183279/1264 167 Du 166/155 112 1.25 86.7S 192026/1324 177 Du 166/155 113 1.22 86.8T 201100/1387 118 DuSh 161.4 120.2 1.21 87.4______________________________________ D = ductile, Sh = shatter, Br = brittle.
Izod tests were also conducted according to ASTM D-256. The results are reported in table 4.
TABLE 4______________________________________(Izod impact results in ft-lbs/in (J/cm)) Notched Unnotched Unnotched Unnotched UnnotchedBlend 23� C. 23� C. -18� C. -23� C. -40� C.______________________________________M 0.65/4.4 32.7/225.4 4.0/27.5 3.3/22.7 3.8/26.2N 0.68/4.6 30.4/209.6 4.5/31.0 3.6/24.8 2.8/19.3O 0.88/6.0 30.0/206.8 5.7/39.3 4.4/30.3 4.5/31.0P 0.47/3.2 22.5/155.1 3.1/21.3 2.8/19.3 2.8/19.3Q 0.60/4.1 30.3/208.9 3.2/22.0 2.7/18.6 3.1/21.3R 0.70/4.8 30.1/207.5 4.0/27.5 4.4/30.3 3.4/23.4S 0.74/5.1 30.2/208.2 3.8/26.2 4.2/28.9 3.9/26.8T 0.66/4.5 27.4/188.9 4.1/28.2 4.0/27.5 3.8/26.2______________________________________
Blends M through T compared the physical and mechanical properties of two polypropylenes blended with E/NB rubber and different commercial EP rubbers to the non-blended PP. Both rubbers provide significant impact resistance improvement, but the E/NB modified polymers show no loss of tensile strength or flex strength as the EP modified polymers do (Table 3 and 4). In addition there is no loss of surface gloss incurred by adding E/NB rubber as there is when adding EP rubber (Particularly evident with the commercial PP blends P through T). The mold shrinkage results were inconclusive at these rubber levels. The E/NB modified polymers retained low temperature impact properties as measure by the IZOD impact test (Table 4) down to somewhere between -18� and -29� C. but lost impact resistance at -40� C.
Typically there is an inverse relationship between strength and impact resistance in a blend of semi-crystalline polymer and rubbery copolymer. (As more rubber is added to the semi-crystalline polymer, its impact properties improve, but strength is lost.) This relationship may be represented by a line drawn between the Modulus and Gardner Impact values for homopolypropylene and the values of 160,000 psi Modulus and 320 ft-lbs Gardner Impact. Most of the commercial impact modified PP's have properties that fall on or close to this line. It is desirable to find impact modifying rubbers that result in values that are above and to the right of this line.
FIG. 1 plots 1% Secant flexural modulus (kpsi) vs. 23 � C. Gardner Impact (ft-lb) for five compositions.
______________________________________Symbol Description______________________________________▪ ESCORENE ™ 1012 polypropylene Blend P▴ Blend QX Blend RZ Blend S______________________________________
Blends Q, R, and S, all modified with commercially available elastomers, have properties that fall close to the line connecting the two squares in FIG. 1, which represents the expected behavior. Blend P, an example of the present invention, had the greatest impact improvement without a loss of strength, and as a result falls well above the expected behavior line. This is a significant improvement that will be magnified in blends with higher rubbery thermoplastic copolymer content.
In summary, the instant blends provide impact resistance to PP without loss of tensile strength, flex strength, or surface gloss as the commercial EP rubber blends do. The instant blends provide this impact resistance even at below ambient temperatures, in a temperature range that is commercially significant.
It is well known on the art that crosslinking of the rubber phase after it has been dispersed in the semi-crystalline polymer can improve the toughness of the blend. Crosslinking by peroxide cure treatment, E-beam treatment, or gamma irradiation treatment acts to increase the molecular weight of the rubber phase and prevent migration or aggregation of the rubber particles. In another embodiment of this invention the alpha-olefin/cyclic olefin rubber phase of the blend is crosslinked, preferably using a peroxide cure treatment to increase the molecular weight of the rubber phase, and thereby the overall toughness of the PP blend. Typical peroxides include di-cumyl peroxide and di-t-butyl peroxide.
11.6 g of PP4 was physically admixed with 11.6 g of ENB3 then poured into a preheated Brabender with 0.1201 g of di-t-butyl peroxide (98.5% pure). The components were blended for ten minutes at 190 C using a small 45 g mixing head. The cured blend was then tested for physical properties. The data for the cured blend, one uncured blend and neat polypropylene are summarized in Table 5.
TABLE 5______________________________________Strain Behavior of PP/Rubber Blends BeforeAnd After Peroxide Cure Approximate TensileHost Rubber ID Young's % Strain Energy- EnergyPolymer Weight % Modulus at Maxi- To-Break AbsorptionMFR Rubber (psi) mum Load (lb-in) (lbs/in)______________________________________PP3 None 12 20 100(35) 0%PP3 ENB2 78,600 9 5 31(35) 20%PP4* ENB3 71,700 404 132 802(7.5) 25%______________________________________ *di-t-butyl peroxide
The data show that the rubbery thermoplastic copolymer will crosslink to improve the toughness of the blends to such an extent that they are competitive in properties with commercial reactor thermoplastic olefins. The instant blends are different however because the rubbery thermoplastic copolymer has a higher packing length than the semi-crystalline polymer causing it to be excluded from the surface. Packing length is defined and measured or calculated in Fetters, L. J., Lohse, D. J., Richter, D., Witten, T. A., and Zirkel, A. Macromolecules, 1994, incorporated by reference herein. After crosslinking the rubber phase the rubber particles remain excluded from the surface causing no loss of surface properties while increasing the toughness significantly. Evidence that the rubbery copolymer is excluded from the surface is provided by X-ray photoelectron spectroscopy (XPS) which gave unperturbed, characteristic PP spectra before and after blending rubber, as well as before and after peroxide cure treatment.
As is apparent from the foregoing description, the materials prepared and the procedures followed relate to specific embodiments of the broad invention. It is apparent from the foregoing general description and the specific embodiments that, while certain forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of this invention. Accordingly, it is not intended that the invention be limited thereby.
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|International Classification
|Cooperative Classification
|European Classification
|Sep 28, 2001
|Fee payment
Year of fee payment: 4
|Nov 23, 2005
|Fee payment
Year of fee payment: 8
|Jan 11, 2010
|Maintenance fee reminder mailed
|Jun 9, 2010
|Lapse for failure to pay maintenance fees
|Jul 27, 2010
|Expired due to failure to pay maintenance fee
Effective date: 20100609


text:
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Another target of Marissa Mayer's Yahoo makeover may be the company's mobile apps, she said Tuesday while speaking at the Goldman Sachs Technology and Internet Conference, Business Insider reported. According to the report, Mayer said that Yahoo needs to cut down the number of apps from 60 to 12 to better focus on its users needs and "daily habits" of checking sports, news, stocks, and email. It's not the first time that Mayer has mentioned focusing on users' daily habits: During the fourth quarter earnings call she told investors that the company is focusing on about a dozen new products, which each focus on improving a different "digital daily habit."
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