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Das Kleine Stapelhauschen
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Getting' ready to cruise
Brought brekky this morning at the Cologne railway station because we discovered they have lovely yogurt and muesli. Then we went shopping. I bought a pair of German shoes, made in Hamburg, for $52! Rosanne bought a very comfortable pair of new season shoes for a little more. While we were in the hotel lounge this morning we overheard a group of Brits on a coach tour being corralled into where they needed to go by their super efficient tour guide and made a ...
Fun day in Cologne
... the past as well as the modern. It was probably all the rage back in the day. It was nice weather, the best we've had so far so we walked along the esplanade. The Rhine is a lovely river and we saw boats like the one we are about to board tomorrow for our cruise. In the afternoon we watched a film about the Cologne cathedral and then walked around the cathedral. It is simply huge and we could easily have spent a day exploring it. We discovered one stained glass ...
Super-sized barges
Found unbelievable bargain at a 5* Hotel. & couldn't resist. To put it into context the breakfast cost 50% of the room rate! We didn't have breakfast! Even better, parking was also extra but as GG was too tall for their underground car park, we had to park with the smart cars in front of the Hotel at no charge. Hilarious!
sun shining again, so ...
Day 13 Cologne - Germany.
... This city didn't impress me at all. I thought it was dirty and just like many big cities. As Robyn, my sister, pointed out, it is possibly better known for it galleries, which is something you would struggle with in the time frame, if that is what took your interest. After lunch we had a presentation from the Tour Director, Mark, on the difference between Holland and The Netherlands. As he was born and bred in Amsterdam, he was very passionate about it ...
... say this is the more well known of the two. Moving right along, we wandered around viewing some old buildings, but mostly new(er) ones because Cologne was pretty much flattened during WW2. The 'city' was first established by the Romans in about 50AD, so nearly 2000 years old. Pretty much none of the original stuff left, however as new buildings are constructed around the city, besides still commonly finding unexploded ordnance, many roman ruins are found and of course have to ...


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Front of House Catering Assistants
YSP is strengthening its Front of House catering team to help deliver a first class visitor experience. As a member of the catering Front of House team, you will play an important part in maintaining our high standards of visitor service. Successful applicants will have previous front of house experience, excellent presentation, communication skills and a warm and approachable manner. Shifts are on a rota over seven days and successful candidates must be available to work on Saturdays and Sundays. For more information, download the job description
To apply, please send a completed application form and equal opportunities monitoring form to firstname.lastname@example.com
Closing date midday 12 October 2015
Fixed term ending 31 January 2016
Our Cleaning team provides a professional, efficient and effective cleaning service that enhances the appearance of the Yorkshire Sculpture Park and supports a healthy environment. Hours vary each week however, you must be available to work weekends. For more information, download the job description
To apply for the role, please send a completed application form and equal opportunities monitoring form to email@example.com
Closing date is midday Monday 5 October 2015
Early Years Artist Researcher
This is an exciting opportunity to work with the Learning Team at YSP – an extraordinary place that sets out to challenge, inspire, inform and delight. As one of Britain's leading contemporary art organisations, it has an internationally renowned exhibition and engagement programme. The multi-award winning Learning Programme underpins all YSP activity, aiming to make art, landscape and heritage accessible to the whole community, and to offer opportunities for people to engage with the arts in a creative and meaningful way.
The successful candidate will have a passion for making art accessible to all, a deep understanding of the creative process, and an interest in the multitude of ways people learn and enjoy the world around them. This must sit alongside a motivation to open doors for those who may need a helping hand, and a willingness to investigate the many layers of society that shape how people live around the world.
Total Fee: £7,520
We invite an application from an artist who has a considerable understanding of working with Early Years and family learning. The artist will work with families who have children that attend Wakefield Early Years Services. This forms part of Learning Together, a fascinating three year action research programme funded by the Paul Hamlyn Foundation, which aims to enrich, inform and help develop the existing YSP family programme.
The successful applicant will assist the Head of Learning and Family Learning Coordinator in developing and delivering a programme of activities and resources to engage Early Years family audiences.
This is an exciting opportunity for a committed and experienced artist to help investigate and build relationships with intergenerational participants at YSP.
For more information download the job description and artist brief or contact Emma Spencer, Family Learning Coordinator on +44 (0)1924 832535 or firstname.lastname@example.com
To apply: please send a copy of your CV, covering letter, application form and equal opportunities monitoring form to firstname.lastname@example.com
Closing date for applications is 19 October at 9am. Interviews take place on 3 November.
Yorkshire Sculpture Park values a diverse workforce and welcomes applications from all sections of the community.

subset: commoncrawl


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Nov 10,2013
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Way to Live: Christian Practices for Teens
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This book will start you upon the spiritual journey of a lifetime. You can find even more stories and conversations about Christian practices as well as a helpful Leaders Guide at www.waytolive.org, a web site for youth and youth leaders.
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|Format: Paperback
Number of Pages: 304
Vendor: Upper Room
Publication Date: 2002
|Dimensions: 9 X 6 (inches)
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Through teen-friendly language and relevant examples, Way to Live uses stories and ideas that make Christian practice come alive. Practices such as forgiveness, work, play, stuff, justice, prayer, food, and time are discussed as ways to nourish a more meaningful life offered by Jesus Christ.
18 teens and 18 adults joined together to write Way to Live. Their collective wisdom and experience offers things that readers can do -- rather than things not to do. It also presents each practice as a gift and not a task that engages readers in the real world.
Great for youth ministry and small group study, Way to Live is perfect for individual use too.


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News Digest: Honors: Christopher Adolph and Ruth Johnston
Posted under: , , , ,
UW political scientist Adolph wins book prize
The International Political Science Association, sponsor of the journal Governance, has awarded its 2014 Levine Prize to the book "Bankers, Bureaucrats and Central Bank Politics." by Christopher Adolph, University of Washington associate professor of political science.
The Levine Prize is given annually to a book that, according to the association, "makes a contribution of considerable theoretical or practical significance in the field of public policy and administration, takes an explicitly comparative perspective, and is written in an accessible style."
Adolph's "interesting and innovative" book, the association states, "raises important questions about the assumed all-importance of central bank independence and provides a fascinating insight into the ways the professional background of key officials shapes monetary policy."
Business officers recognize Ruth Johnston's professional development activities
Ruth Johnston, UW associate vice president with finance and facilities and an associate vice provost, has received the 2014 Professional Development Award from the National Association of College and University Business Officers. The association representes chief business and financial officers at more than 2,500 colleges, universities and other higher education providers around the world.
Johnston received the award foroutstanding individual contributions to the association's professional development activities as well as the association's publication programs, according to a news release. She received her award this month at the association's annual meeting in Seattle.
At the UW, Johnston oversees the Environmental Stewardship & Sustainability Office and the Business Diversity Program. In her role as associate vice provost, she directs the university's Organizational Excellence program by leading and facilitating strategic planning, process improvements developing leaders and staff, creating metrics and measuring performance and helping to manage change.
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StartUpHire is the place to find Strategic Alliances, Senior Manager - SE jobs. Review the list of Strategic Alliances, Senior Manager - SE career opportunities to the left. These Strategic Alliances, Senior Manager - SE jobs represent some of the most rewarding careers available.
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Location:Renton, WA Job Code:320 # of openings:1 Description Job Description Seeking new career opportunities? Consider taking on an exciting and challenging role at Parallels. We are a private, profitable and rapidly growing global software company with offices in 168/25/2015 Renton, WA Save This Job
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Job ID 2015-1727 Job Location US-GA-Atlanta Type Regular Full-Time Posted Date 7/30/2015 Targeted Job Start Date .. # of Openings 1 More information about this job: POSITION SUMMARY & RESPONSIBILITIES: Virtustream (www.virtustream.com) is the enterprise-class cloud software8/15/2015 Atlanta, GA Save This Job
Department: Clinical Development Location: Emeryville, CA Position Summary Zogenix is currently seeking a senior Project Management Professional experienced in Pharmaceutical Drug Product Development, to lead the project management function at Zogenix including direct8/22/2015 Emeryville, CA Save This Job


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A Canadian official acknowledged that his country held onto samples from a cow infected with mad cow disease for four months, possibly allowing potentially sick cows into the food chain.
Dr. Claude Lavigne, a top official at Canada's animal products directorate, said officials are searching for other cows infected with the disease, also known as bovine spongiform encephalopathy.
"At this point, it's a precautionary measure," he said Wednesday in a teleconference with U.S. and Canadian reporters.
On Tuesday, Canada said it found a cow had been sick with mad cow disease, a brain-wasting illness. Officials got the test results four months after taking samples from the cow at a rendering plant.
U.S. and Canadian officials have said none of the infected animal went into the food supply.
Canada still is looking for where the 8-year-old cow was born and other cattle, including newborn calves, with which it may have been in contact. The disease can incubate in a cow for up to eight years.
Sen. Byron Dorgan of North Dakota said Canadian officials should have promptly checked samples and released the results.
"Somehow it took four months to have it tested and to tell the people in this country, and also in Canada there was a cow with mad cow disease killed in January," said Dorgan. "That's absurd."
Although Canadian and U.S. officials have declared that the food supply is safe, Consumers Union said the two governments cannot guarantee that.
"That's exactly what they said in Britain, and now nobody trusts the government there," said Mike Hansen, a senior research associate at the U.S. consumers group.
Mad cow disease sickened herds in Britain in 1986, killing more than 2 million cows. It also was linked to 130 human cases of Creutzfeldt-Jakob disease, the human form which causes paralysis and death. Scientists believe humans get it by eating meat from infected cattle.
Canadian veterinarians took samples of the infected brood cow on Jan. 31 at a rendering plant. They suspected the cow had pneumonia
a belief that led to the long delay in discovering that the animal had mad cow disease, said Dr. Gerald Ollis, Canada's chief provincial veterinarian.
Samples were sent to the Edmonton laboratory on Feb. 8.
"They sat there until we had time to process them," Ollis said.
The lab checks samples from livestock destined to be made into food and then tests those taken from euthanized and downed animals.
Canadian officials do not know how the cow got sick with the fatal disease. Cattle can get mad cow by eating feed that contains infected animal protein products, such as bone meal. Both Canada and the United States outlawed such feed for cattle, sheep and goats in 1997 to guard against the disease.
The discovery led to bans on Canadian beef in the United States, Australia, South Korea, Singapore, New Zealand and Japan, which had an outbreak last year.
The United States imported nearly 1 billion pounds of Canadian beef and 1 million head of cattle last year, according to the National Cattlemen's Beef Association.
The group's chief executive, Terry Stokes, said he believed American consumers should be confident that their food is safe because of the ban and because the U.S. government routinely tests for the disease.
By Dan Collins AP May 27, 2003, 7:11 AM
Canadians Sat On Mad Cow Sample
© 2003 The Associated Press. All Rights Reserved. This material may not be published, broadcast, rewritten, or redistributed.


text:
Bell+Howell® Solar Spotlight
Item # WX2-105733
- Google+
- Details & Specs
Showcase outdoor areas for safety and effect with this Bell+Howell® Solar Spotlight.
Safely and beautifully spotlight or backlight your garden, driveway, landscaping, patio and MORE! Each Bell+Howell® Solar Spotlight provides up to 8 hours of solar-powered lighting, and you can group several together to set off larger areas.
No electricity or wiring... just stake them into the ground or mount them on a wall or other hard surface. Built-in solar panel partially rotates so you can aim it to absorb max. sunlight and charge batteries; lights power up automatically in the dark.
- 4 bright LED lights
- Rechargeable NiCd batteries included
- Durable, weatherproof plastic
- Mounting hardware included
- 6 1/2 x 3 3/4 x 15"h. (with 7 1/4"h. ground stake), 7 3/4"h. with deck mount.
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Bell+Howell Solar Spotlight is rated out of 5 by 32.Rated 4 out of 5 by EDWARD from goodDate published: 2014-08-05Rated 4 out of 5 by DANIEL from Bought Light For Flag On porch to light it at night and it's doing a good job of lighting up flag. ThanksDate published: 2014-05-20Rated 1 out of 5 by JOHN E from The lights are more of a beacon. I planned on using them to illuminate an archery target, so I could shoot a night. Since they don't emit a beam of light, they're useless. I did allow them to fully charge in unobstructive sunlight.Date published: 2013-08-07Rated 1 out of 5 by MARK from Thought the Bell + Howell name would mean a more sturdy spotlight, but this has the same flimsy plastic pivot for the collector that will soon see it detached and hanging by the wires--just like the ones I bought these to replace.Date published: 2013-08-07Rated 2 out of 5 by RICHARD J from The lighting is minimal and if they don't receive direct sunlight for at least 8 hours in a day they don't light up. Under perfect charging conditions they only stay lit for maybe 6 hours. Very disappointed.Date published: 2013-07-22Rated 1 out of 5 by ROBERT L from You consider not selling this product. It's by far the worst product I've ever received from SG. Poorly constructed and doesn't put out enough light to get a person out of a dard bathroom. If it didn't cost more than it's worth to send it back I would. I'll just take my lumps on this purchase, but I certainly hope I don't have another bad experience with a product from SG or I might have to go back to BassPro, Cabela's or....Date published: 2013-02-17Rated 3 out of 5 by DENNIS/SUE from I would not recommend these spotlights to other shoppers. They produce very little light.Date published: 2012-06-27Rated 5 out of 5 by RANDALL from very satisfied excellant price as usual.Date published: 2012-03-16

 It's unclear to me. How many units are there? Then how many LEDs in each unit?

Asked by: Mr Dave

 Thank you for your question.This is one spotlight and it has 4 LED bulbs,
Answered by: Customer Service

Date published: 2015-10-04

2015-10-05T11:29CST

bvseo_cps, prod_bvqa, vn_cps_3.1.6

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Worst Voyager race: Farengi
View Single Post
January 6 2013, 05:59 PM
Location: Delta Quadrant Borg Queen appartement 8472
Re: Worst Voyager race: Farengi
SonicRanger wrote:
False Profits
, the director Cliff Bole gave some insights in interviews that are quoted over at Memory Alpha:
Director Cliff Bole explained, "This was the producers' attempt to get some of the little, evil Ferengi into the series because they're so well-liked and accepted by the fans. We call them the 'Peter Lorres of space,' you know? The producers wanted some lightness, some comedy." (The Official Star Trek: Voyager Magazine, issue #15)
After having directed this episode, Cliff Bole came to the opinion that he had made the installment somewhat too silly. "That one is 'Cliff's Folly,'" he said of the episode. "In fact, everyone should join in on that." Moments later, Bole remarked that this episode's level of comedy "went overboard." He continued by saying of the installment, "I don't think the studio was too happy with it, but they did get a lot of positive mail on it. It's not one of my favorites [....] It just got a little bit too silly. I'll take the hit for it, because I let everyone go a little too far. We were all enjoying the fact that it wasn't another new villainous character. And those damn Ferengi are so much fun to work with." (The Official Star Trek: Voyager Magazine, issue #15)
There's one other interesting bit of information at Memory Alpha: the writer Joe Menosky hadn't even set foot in the writers' room when he wrote the script:
This was the first episode that returning Star Trek staff writer Joe Menosky was involved in writing after a four-year stint of working and living in France, he having previously served as a staff writer on Star Trek: The Next Generation. (Star Trek Monthly issue 20) In fact, this Star Trek episode was one of several that Menosky wrote while still in Europe, prior to him joining the writing staff of Voyager for its third season. (Cinefantastique, Vol. 29, No. 6/7, p. 90)
Thank you for the Information very nice
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updated 12/10/2013 AT 1:00 AM ET
•originally published 12/10/2013 AT 8:50 AM ET
Blame it on the heat.
The Real Housewives of Beverly Hills headed to the desert on Monday's episode for some sun and fun, but ended up burning each other instead.
Joyce Giraud organized a girls weekend to Palm Springs, and the wives arrived at the sprawling mountainside compound ready to relax.
But a lazy afternoon by the pool dampened their spirits before the vacation had even begun.
"Please get in the water," Brandi Glanville, 40, begged host Giraud, 38, after stripping down to her bikini and jumping in the pool.
"I really don't want to get in the pool," said Giraud, who remained in her chaise, later admitting, "I can't swim."
"You're a black person," Glanville said with a laugh, immediately offending Giraud and shocking the group. "It was a joke, and my black friends would have laughed crazy because they don't go in the pool because they will [mess up] their weaves All my black friends can't swim."
"Yes, I'm black. What's your problem?" asked the former Miss Puerto Rico. "Puerto Ricans are black, they're Indian and they're Spanish, so I am a mix of three cultures, and I am very proud to represent all three."


text:
Hotel Speraesole, Olbia
- Free buffet breakfast, free WiFi, and free parking
Main amenities
- 57 guestrooms
- Restaurant and bar/lounge
- Outdoor pool
- Airport shuttle
- 24-hour front desk
- Air conditioning
- Garden
- Laundry service
- Meeting room
- Multilingual staff
- Wedding services
What's around
- In Murta Maria
- Porto Istana Beach (1.6 mi / 2.6 km)
- Le Saline Beach (2.3 mi / 3.8 km)
- Marina Maria Beach (2.7 mi / 4.3 km)
- National Archaeological Museum of Olbia (5.9 mi / 9.6 km)
- Basilica of San Simplicio (8.3 mi / 13.4 km)
Functional comfortable, very affordable hotel after long drive from caligari. Nice pool.…
Very nice hotel, but I have never before had a minibar, where the hotel had a label on…
Enter dates to check prices
Hotel Info: 866-539-8117from $45
- Triple Room
- Double Room Single Use
- Family Room
- Standard Room
Also popular with travelers from the USA
At a glance
Key facts
Hotel size
- This hotel has 57 rooms
- This hotel is arranged over 3 floors
- Check-in time starts at 2 PM
- Check-out time is 10:30 AM
Required at check in
- Credit card or cash deposit required
- Government-issued photo ID required
Travelling with others
- Pets not allowed
- Free WiFi in public areas
- Free WiFi in rooms
- Airport shuttle *
- Free self parking
- Accessible parking
- Beach shuttle *
Nearby Four Star Olbia hotels
In the hotel
- Free buffet breakfast
- Restaurant
- Bar/lounge
- Poolside bar
- Room service
- Beach shuttle (surcharge)
- Outdoor seasonal pool
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Global Regulatory Issues for the Cosmetics Industry
- Karl Lintner
This volume examines regulatory issues of ingredients, manufacturing, and finished products, as well as claim substantiation, packaging, and advertising. A chapter on Chinese regulations will be one of the first about this country to be published in book form.• Includes a regulatory map of India and China • Global IP protection strategies • REACH and European Regulatory standards • "Green chemistry" in relation to cosmetics and regulationView full description
Policy makers, lawyers – anyone working in the formulation, marketing, packaging, and exporting of cosmetic products.
Book information
- Published: January 2009
- Imprint: WILLIAM ANDREW


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Posted 10/08/2015 04:26:46 EDT
Adding to kwalkes comment above if you look at the point re the last 7 WS winners only CC and Carpenter weren't home grown...and one can make the point that both those signings really didn't pay in th more »
Posted 10/08/2015 07:27:35 EDT
Ball players have the right to a free market just like anyone else... nFL players have never been able to fight the system to earn guaranteed contracts as they have in other sports. more »
Posted 10/08/2015 06:05:50 EDT
Arrieta is 29 .... had a pretty decent year in 2014 ... but prior to that -- at least based on stats -- he was AWFUL in the AL. So ... late bloomer? or different league? Whichever the answer, it just more »
Posted 10/07/2015 07:12:51 EDT
He's still a bargain compared to Hanley or Pablo.... more »
Posted 10/07/2015 07:10:52 EDT
yeah...awful contract for Ells ...so why don't the Sox do a Castillo and Hanley plus 20 mil going to the Yanks for Ells. more »
Posted 10/06/2015 09:34:15 EDT
Yankees did all they could to dump, void, alienate....just get rid of Arod this past off season. Sox will likely do the same with Hanley.... Thinking they'll have the same result....so here's to hopin more »
Posted 10/04/2015 07:49:46 EDT
Not too many years ago the Henry ownership group ... I think it was actually LL ..sarcastically wondered why some New Englanders still referred to them as the "new" owners..... Well guys, its because more »
Posted 10/02/2015 04:24:55 EDT
Yes... Nice article... Just too bad this paper can't show a little love for all the New England kids that get to college ball without tie ins more »
Posted 10/01/2015 07:30:24 EDT
Yeah....only 2 of the ox starting 9 played the majority of the year in the Majors.....but hey Yanks lineup doesn't look to great either more »
Posted 10/01/2015 06:46:26 EDT
with Dave O'Brien? That's kind of interesting..... more »
Posted 10/01/2015 04:48:50 EDT
Really hoping that Farrell will choose to transition into a development role with the club on his own. Just cant imagine all the second guessing if he comes back..... Especially when they hit a skid. more »
Posted 10/01/2015 04:44:26 EDT
Not sure you can call "everyone is being evaluated for next year" as playing without any pressure. more »
Posted 10/01/2015 04:28:27 EDT
Serious get away day lineups here! more »
Posted 09/30/2015 06:29:29 EDT
On The O'Brien for Orsillo thing .... John Henry loves O'Brien from his days with the Marlins.... nuff said. more »
Posted 09/30/2015 06:27:52 EDT
Any Chance the Nats would take Allen Craig for Pap? more »
Posted 09/28/2015 07:04:24 EDT
29 - 22 since the trade deadline ..... and of the 22 losses what would you say ...at least ...and I mean at LEAST 4 would have been wins with even an average pen .....not bad. more »
Posted 09/28/2015 05:30:13 EDT
You got it Hadger...... Eat some money and trade Hanley for Paps more »
Posted 09/28/2015 05:28:01 EDT
The 3 out of 4 last place finishes line assumes they finish last this year..... more »
Posted 09/28/2015 07:16:08 EDT
Watching the disinterested O's simply emphasizes why fans should be excited about this team moving forward. The young Sox will end the season having played almost two months straight of exciting baseb more »
Posted 09/26/2015 06:37:00 EDT
Yeah....assume they want to give Leon some exposure and given he caught Hill in Pawtucket and during the early Spring with the Nats it provides the best fit more »
Posted 09/24/2015 08:07:31 EDT
Alex, Alex, Alex ..... since when does highlighting 10 examples of something lead to any kind of responsible conclusion? Data needs sample size! more »
Posted 09/24/2015 08:03:48 EDT
sorry ...re-read and you didn't say Hate .... only "I can't Stand" .... but point still applies more »
Posted 09/24/2015 08:02:53 EDT
Check the list of GM's above .... only 2 have won WS titles ... thinking"Hate" is a bit strong a word. more »
Posted 09/24/2015 07:27:16 EDT
agreed.... I would think a few games at first might help ... then again ... if he stinks! more »
Posted 09/23/2015 01:37:21 EDT
26 year old lefty that throws 94-95 .... yeah, he won't be the clsoer enxt year.... but probably worth showing a little patience with him ... especially given the rest of the bullpen crew more »
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Don Saul at the time, represented by 'EASY RIDER' to 'KING' was the pinnacle of football shoes upper that combines "Avanti". In fact appeared in \33, 000 higher in 1998 JIL SANDER became explosive now, despite the model faithfully reproduces as a puma shoes. Side gold seal was changed at PUMA from JIL SANDER, is marvelously played reprint in same livery.
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|Publication number
|Publication type
|Publication date
|Jul 15, 1952
|Filing date
|Aug 30, 1946
|Priority date
|Aug 30, 1946
|Publication number
|Edwin O Hook, Elmer W Cook
|Original Assignee
|American Cyanamid Co
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (3), Referenced by (2), Classifications (12)
|External Links: USPTO, USPTO Assignment, Espacenet
Patented July 15, 1952 PLAsTIoIzING NATURAL AND SYNTHETIC ELASTOMERS BY INCORPORATION or N-ISOPROPYL THIOSALICYLAMIDE Edwin 0. Hook, Old Greenwich, Conn, and Elmer W. Cook, New York, N. Y., assignors to Ameri- I can Cyanamid Company, New York, N. Y., a
corporation of Maine No Drawing. Application August 30,1946,
c Serial No. 694,163
This invention relates to a new plasticize-r for elastomeric compositions, to. methods of plasticizing ela'stomer compositions and'to compositions so 'produced. 1 1
One such procedure is the'plasticizingof rubher or synthetic rubbers by the action of' hot air or oxygen under suitable conditions. Others are based on the fact that small amounts of chemicals, for example some of the aromatic mercaptans and certain nitroso compounds, can be utilized under various conditions to produce :the desired effect. 7 While the exact nature of their action is not completely understood, the use of these chemical plasticizers or peptizers has become well known. It is with their manufacture and use that the present invention is concerned.-
In the past, the available plasticizers have been objectionable from one or more of several reasons. Some are not suitably compatible with various elastomers. Some are toxic. Many operate either as skin irritants or skin sensitizers, resulting in objections from those who are obliged tov handle the material. Others are characterized by very disagreeable odors which are'oiten imparted to the finished articles. Manyfof the commonly used'materials are subject to several such objections. As a result of these objectionable features, the use of plasticizers has tended to be limited in spite-of the wide demand for materials for the purpose.
When the necessity arose for handling synthetic, rubber-like polymers, such, for example, as copolymers of butadiene and styrene or butadiene and acrylonitrile, operational difficulties became much more pronounced. These synthetic rubbers were found to be much more difficult to process than natural rubber. Therefore, the demand for effective plasticizers or peptizers which are not subject to the objectionable properties of materials previously used was markedly increased. 7
In accordance with the present invention new and novel plasticizable and plastioized elastomeric compositions are provided. The plasticizer used is thiosalicylisopropyl amide of the formula H I coir-50 mm)? I Preparation of typical'members of thisseries of compounds may be illustrated. by the followin examples which are intended as illustrative only and not by way of limitation. Allparts are byweight unless otherwise noted.
.3. Claims. (01. 2e0-aos EXAMPLE: 1 Preparation of dithiosalicyl chloride solution I About 6.0 parts of dithiosalicyclic acid are re.-
acted in 175 parts of toluene with 84 parts oi P015. On. concipletionof reaction the resultant P0013v andsolvent are removed under reduced pressure, the residue taken up in'boiling toluene andfiltered. Where in the succeeding examples a toluene solution of dithios'alicylyl chloride is required, this solution is used. .The chloride if desired is isolated by solvent removal.
, A solution of .dithiosalicyl chloride, .obtaine as in Example 1; fromparts. of dithiosalicylic acid, wasslowly added, withnooling and stirrin to 35. parts of.,isopro.pylaminein' 1751 parts of toluene, a condenser being used to prevent escape of the isopropylamine. stirring being continued some time after the exothermic reaction subsided. The product, dithiosalicylisopropylamide, was separated and onrecrystallization appeared as white needles melting at 233-236 C. (uncorrected) 20 parts of this product was reduced with zinc in glacial acetic acid andtheproduct, thiosalicylisopropylamide-of theapparent, formula was separated. On recrystallization from 50% aqueous ethanol the product melted at 97- 101 -C., and exhibited a nitrogen content of 7.10% as against calculated 7.18%.
As was noted above this compoundvpossesses a marked utility as a plasticizer for natural and synthetic elastomers. Its effective use may be obtained through any conventional procedure at temperatures above about C. whether using open mills, a Banbury mixer or the like or in oven treating. In milling operations the plasticizer maybe directly incorporated at mill temperatures. For oven plasticizing itis usually best to incorporate the plasticizer-at temperatures somewhat below 10,0 C. and plasticize subsequently at somewhat higher temperatures.
EXAMPLE 3 we I Natural Rubber Thiosalicylisopropylamide Plasticity Tests:
Williams 3 Min. Y at 100 C.l\ I1ls 130 1 Minute Recovery at 100 C.--M1ls... 16 11 That the thiosalicylisopropylamides should have this markedly useful plasticizing property is highly surprising. The relative inactivity of thiosalieylic acid is well known as shown in U. S. Patent 2,064,580. It was this inactivity whichled to the defining of the aromatic mercaptans which are preferable for use as plasticizers as those of the type R-SH in which R represents an aryl radical such as phenyl, tolyl, biphenyl, naphthyl, methylnaphthyl, or a'higher aromatic nucleus in which the sole substituents consist of carbon and hydrogen. such as valkyl and aralkyl radicals.-
Such adefinition, which hasbeen widely accepted, clearly excludes the thiosalicylamides' of the present invention. Obviously thelatter contain a substituent which is not solely carbon and hydrogen. g r
Further, those aromatic mercaptans which in accordance with the above noted prior art definition constitute preferred plasticizers are physiologically objectionable. Not only are they more toxic and irritating than is desirable in a commercial plasticizer, they are further objectionable in the odor'jthey possess or impart to the finished rubber goods. The. thiosalicylisopropyl amide of the present invention is only free from thisobjection but is equally or more efiective as a plasticizer than the better offthe aromatic mercaptans of the priorart. This iswell illustrated in the following example in which thiobetanaphthol, one of the best of such, mercaptans, is directly compared'with the present invention.
EXAMPLE 4 An additional sample of naturalrubber was again divided into 300 gm. samples and milled for eight minutes at 100-110C. in a 6' x12" mill with the plasticizers shown in the following Table II. The plasticity measurements are also shown.
Table II Natural Rubber- 100 100 100 ThiobetanaphthoL 0833 Thiosaliizcy lso gropylamide .0833 Plastici es s:
1 Williams 3 Min. Y at 100 C.Mils 135 111 100 1 Min. Recovery at 100 C.Mils 14 8 9 EXAMPLE 5 Samples of GR-I, an isobutylene-diolefin (isoprene) copolymer type of synthetic elastomer composition were treated for ten minutes at 115 0. on a 6x12"' mill, with and without plasticizer. "Illustrative results are shown in the following Table III. p
Table IV ggf -r 10s cy sopropy am1 e Plasticity Tests:
Williams 3 Min. Y at 100 O.-Mils 1 Min. Recovery at 100 O.Mi1s 46 In general in using the plastioizer of the present invention the amount required will vary somewhat with the elastomer to be treated. It also depends on whether or not the thiosalicylisopropylamide is used per se or as one of its salts. A number of the latter are-readily used aseflectively as the free amide. These include,- for-example, both organic amine saltsand salts of bimetallic metals, the zincsalts being particularly useful with a number of synthetic elastomer compositions.
On the other hand, these variations are relatively small as compared with the amount required for different types of; rubber.: Natural rubber compositions, for example, oftenmay be satisfactorily treated with as little as 0.0l-0.03% by Weight and seldom require more than about 2.0%. By comparison, synthetic elastomers of the butadiene-acrylonitrile type may require from about 1.0150 5.0% or more whereas in elastomers of the GR-S 'type usually from about 0.05 to .5 is effective and more than about 3.0 is seldom required. V 1
Effective plasticizing action is found with substantially any of the elastoprenes such, for example, as natural rubber; polymers of butadiene and substituted butadienes; copolymers of these and other conjugated diolefines such as isobutylene with materials copolymerizable therewith having a single olefinic linkage such as styrene, substituted styrenes, isoprene and acrylonitrile; and ohloroprene polymers.
Weclaim: 1. A method of increasing the plasticity of elastomeric compositions which'comprises disseminating in a vulcanizable elastoprene selected from the group consisting of natural rubber, rubber-like polymers of conjugated diolefines and copolymers of a conjugated dioleflne and a compound copolymerizable therewith containing a single olefinic linkage containing 0.01-5.0% by Weight of the elastoprene of a plasticizing agent comprising a compound selected from the group consisting of N-isopropyl thiosalicylamide and the organic amine and zinc salts thereof, and subjecting the mixture to a temperature above 70 C. for asuflicient time to produce the-desired plasticity. 1 Q I 2. A composition comprising sulfur, a vulcanizable elastoprene selected from the group consisting of natural rubber, rubber-like polymers of conjugated diolefines and copolymers of a conjugated diolefine and a compound copolymerizable therewith containing a single olefinic linkage, having uniformly disseminated therein 0.01-5 .O% by weight of the elastoprene of a plasticizing agent comprising a.compound selected from the group] consisting of N-isopropyl 5 thiosalicylamide and the organic amine and zinc salts thereof.
3. A vulcanizate obtained by vulcanizing a composition comprising sulfur, an elastoprene selected from the group consisting of natural 5 rubber, rubber-like polymers of diolefine and conjugated copolymers of a conjugated diolefine and a compound copolymerizable therewith containing a single olefinic linkage, having uniformly disseminated therein 0.015.0% by weight of the elastoprene of a plasticizing agent comprising a compound selected from the group consisting of N-isopropyl thiosalicylamide and the organic amine and zinc salts thereof.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,389,489 Dean et a1 NOV. 20, 1945 2,460,580 Huber Feb. 1, 1949 FOREIGN PATENTS 10 Number Country Date 542,645 Great Britain Jan. 21, 1942 OTHER REFERENCES Ind. and Eng. Chem, vol. 39, pp. 94 and 9'7, January 1947.
|Cited Patent
|Filing date
|Publication date
|Oct 15, 1942
|Nov 20, 1945
|American Cyanamid Co
|Plasticized compositions
|Mar 18, 1943
|Feb 1, 1949
|Sulzer Ag
|Method and device for fixing and sealing tubes in a partition wall by use of fluid pressure
|Title not available
|Citing Patent
|Filing date
|Publication date
|Apr 22, 1953
|Oct 16, 1956
|Schenley Ind Inc
|Bactericidal and fungicidal compounds
|Dec 22, 1980
|Apr 3, 1984
|Usv Pharmaceutical Corporation
|Aroyl-aminoacids, amides and esters thereof
|U.S. Classification
|524/225, 564/162, 524/925, 556/135, 562/838
|International Classification
|Cooperative Classification
|European Classification


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