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HR Advisor/Administrator/Support-CIPD-North East Salary 32-36k plus benefits A fantastic opportunity has arisen for an experienced HR Advisor to join my client based in the North East. Reporting to the Head of HR for the site and working within a...
Read more about HR Advisor/Administrator/Support-CIPD-North East
03/07/15 |
Full-time |
£32k-£36k |
An exciting, lucrative, field sales executive opportunity has arisen with my market leading client for top performers with recent experience of selling copiers, document management solutions, MFD's and MPS On offer is an achievable, excellent...
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03/07/15 |
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We need: A Qualysguard Threat and Vulnerability Specialist to be in a team of 4 located at our head offices in Swindon Salary from £34,613 - £44,228 based on skills and experience plus excellent benefits. We are expanding our Threats and...
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03/07/15 |
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Sales Representative - Medical/Healthcare I am currently looking for a new Territory Business Manager to join our Critical and Chronic Care Solutions division. This position is field based on territory, covering Berkshire, Oxfordshire, Bedfordshire,...
Read more about Business Territory Manager - Chronic Care
03/07/15 |
Full-time |
£30k-£35k |
West Midlands
Junior Java Developer (m/f) - Hamburg Take your future into your own hands and bring your career in motion, with an entry into a successfully operating group of companies in the areas of consulting and development. With us you are developing...
Read more about Junior Java developer
03/07/15 |
Full-time |
£35k-£50k |
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Apartments 40 meters from the sea
From $333 / week
Description from the owner
Description from the owner
Bedrooms: 1/
Bathrooms: 1/
Sleeps: 2/
Type: Apt. / Condo
Located just 40 metres from the sea, Bleus Apartments is set in a quiet fishermen's village of Brna. It features air-conditioned apartments with free Wi-Fi and satellite TV. The lush garden is full of Mediterranean vegetation, and features a barbecue and a furnished terrace.
All apartments feature a seating area, a desk and a fully equipped kitchenette. Private bathroom provides a shower, free toiletries and a hairdryer. The balcony overlooks the sea.
The village of Smokvica, where guests can sample local wines, can be reached in 3.5 km. Cafes and bars can be reached in a couple of steps, while a fish restaurant and a fresh food market can be ...Read more
About the owner
About the owner
- Response rate: 0%
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- Calendar updated: 7 months ago
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JM Richards Twitter Stats
@Hamilton_EMS - Tracking since March 17, 2014
Fun/Parody Account NOT affiliated with Hamilton Emergency Services, ------- Listen to Pages - https://t.co/FJENAntt71?
Hamilton Ontario Canada
JM Richards Tweets
@Hamilton_EMS has posted 1,570 tweets in the last 30 days, which translates to an average of 52.3 tweets per day.
JM Richards Followers
@Hamilton_EMS has 108 followers.
This account is #49,637,255 in the worldwide rank of the most popular Twitter users.
JM Richards Following
@Hamilton_EMS is following 388 Twitter accounts.
Last month this account followed 2 users.
JM Richards Predictions & Milestones
@Hamilton_EMS will hit 110 followers in the next 3 months, and 114 in one year.
You are on JM Richards 's Twitter stats page
We track these Twitter stats since March 17, 2014 . You can see how many followers JM Richards lost or gained and what the prediction is for tomorrow or the next 15 days, together with all kinds of other stats like rank compared to all Twitter users, tweets etc.
Why don't you give it a try and compare JM Richards to yourself ? Or if you are JM Richards get even more feature rich & up-to-date stats with Premium & Pro Twitter Stats.
Twitter Counter is the #1 Twitter stats site powered by Twitter. It all started in June 12, 2008 and we grew rather rapidly because of our Twitter Counter badge. The button is a nice small image that shows your visitors how many followers you have on Twitter. Within a year the button was on many many blogs around the world and we displayed more than 100 million buttons in one month. We track follower stats for over 180 million users now.


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- Food & Drink
- 495 Peachtree St., Atlanta, GA, 30308
Web Analytics Basics: How to Demystify Your Nonprofit's Website
HandsOn Tech Atlanta
Tuesday, December 3, 2013 from 10:00 AM to 11:30 AM (EST)
Your nonprofit's website is up and running, but have you ever wondered:
How many visitors are coming to your website?
How did they get there?
What actions do they take once they arrive?
Web analytics can answer these and many other questions, and this FREE training will show you how. During this training, you will learn how your nonprofit can utilize web analytics to collect, analyze, and act on valuable information and data about your website. The information collected through web analytics provides valuable insight into what PR efforts drive most traffic, how visitors use your website, and whether your website is meeting organizational goals. In addition, you will discover free web analytics tools and useful key performance indicators to track progress, so your nonprofit can easily put web analytics into action.
Presenter Bio: Tamara Meier is a partner at CliXelerate LLC, an online marketing and eCommerce consulting company in Woodstock, GA. She helps businesses and nonprofits achieve online success through online marketing, SEO, and website architecture improvements. Meier also has enterprise-level experience working for companies like eBay and Exodus Communications.
You won't want to miss this practical and informative training with this experienced and knowledgeable instructor.
If you have any further questions, please contact us at email@example.com or visit www.handsontechatlanta.org. Don't forget to like us on Facebook and follow us on Twitter.
What are my transport/parking options getting to the event?
Parking Info: Hands On Atlanta has a gated parking lot for our guests. Please park there, walk around the gate up to the front door that is off the main street. The training room will be all the way to the right.
Public Transportation: You can take the #1 bus to the Marietta St/Boss St. stop. Our office is located right behind Marietta Street.
HandsOn Tech Atlanta strives to increase nonprofit capacity in the greater Atlanta area through free technology trainings and in-depth tech consulting.
Join millions of people on Eventbrite.
In order to purchase these tickets in installments, you'll need an Eventbrite account. Log in or sign up for a free account to continue.


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'Extreme climatic disaster possible in coastal Nigeria'
Extreme climatic and physical events of the Hurricane Katrina proportion are possible in coastal Nigeria,a geograp her, Professor Akin Mabogunje has said.
The Professor of Geography spoke yesterday at the opening of the second joint international conference of the University of Ilorin(UNILORIN), and University of CapeCoast,Ghana, in Ilorin, Kwara State. The conference was entitled: "Climate change and sustainable development."
Mabogunje predicted that the surges in Lagos could have unimaginable consequences, adding: "For West Africa in particular, the significance of this exigency is the fact that our colonial masters in the past deemed it fit to locate most of our capital cities in the coastal areas."
He said: "It could be claimed that Africa and, in particular, West Africa, has been providentially protected from all these extreme events and, therefore, need not be overly bothered about the probability of their occurrence. They should be ready to deal with the consequences of their incidence. No scientist can subscribe to such position.
"The well-known School of Sceptics about the urgency of the phenomenon has been silenced by the extreme climatic andphysical events, such as Hurricane Katrina in the United States,the Tsunamis in South-East Asia and Japan, the Tornadoes in the United States and the flooding in many countries.
"Climate Change has assumed a global status, not only as a very privileged problem of scientific enquiries, but also as a practical challenge of policy making by governments. Indeed, no scientist can ignore the reality of global causation of climate change or deny the reality of greenhouse emissions and of global warming.
"This is particularly so when some of the resultant effects such as thawing away and disappearance of the polar ice-caps and glaciers are patently visible that their consequences with respect to rising sea-levels cannot be wished away."
Prof Mabogunje, who chaired the ceremony, urged scientists to monitor these climatic and physical occurrences so as to determine the probabilities of their occurrences in West Africa.
"Rigorous, persistent and multivariate measurements are, of course, the bedrock of such capacity. In West Africa, we have always been presented with climatic phenomena whose bases are still a matter of enlightened rationalisation.
"Features of changes in these and other climatic parameters are bound to have significant effects on sustainable development in our region. "Some of these changes may be gradual and widespread in their incidence such as reduced total precipitation or drought, undermining the livelihoods and welfare of a large section of the population. "Others such as floods and ocean surges and even Tsunamis may be sudden and catastrophic, destroying properties and lives and posing serious challenges to the insurance industry and to government's capacity for disaster management."
Chairman, Local Organising Committee,Prof Kayode Ayorinde said the climate change phenomenon had brought about diverse ecological, health, economic, agricultural, production, and genetic problems.
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What Boko Haram and NADECO have in common
As we watched troubled President Goodluck Ebele Jonathan in his black kaftan with black cap behind the distraught emir of Kano last week, it was ... Full story


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Just this morning Srila Prabhupada's disciple, Kurma Rupa prabhu, passed away in Sri Vrindavan dhama due to cancer. He took care of Krsna's cows in Vraja for many, many years. Below BB Govinda Maharaja recounts his visit to Kurma Rupa prabhu a few days back. Thank you Kurma Rupa prabhu for showing us how to [...]
On The Road
The Positive Alternative
"Here in France … they are chanting Hare Krsna also village to village in buses, so the propaganda work is going on nicely." [ Srila Prabhupada letter to Bon Maharaja, August 11, 1975 ] Srila Prabhupada, I was heading up one of those buses in France ( actually large vans ) that you refer to [...]
Lord Caitanya's Sankirtan Festival In Moldova
Today I begin my journey to Moldova, a landlocked country between Romania and Ukraine in Eastern Europe. Moldova is the poorest country in Europe. Sixty devotees [ from 8 countries ] are coming by bus from Poland, where they have been rehearsing, and will meet me in the capital Chisinau, where we will hold a [...]
Lamenting The Departure Of Brahmananda Prabhu
I am lamenting the departure of Brahmananda prabhu as he was instrumental in bringing me to Krsna consciousness and the lotus feet of Srila Prabhupada. In the autumn of 1970 I met him, Visnujana Swami, Gargamuni prabhu and Subal dasa on the lawn of the campus of the University of Michigan in America. Along with [...]
Srila Bhaktivinoda Thakura's Signature
A precious jewel: Srila Bhaktivinoda Thakura's signature in his autobiography entitled, "Svalikhita Jivani."
Merit Of Chanting The Holy Names Of Krishna
"All rituals and fasts associated with Vedic sacrifice, all bathing in holy places around the world, all penances and fasts within this world, thousands of recitals of Vedic literature, and hundreds of circumambulations of the entire surface of the earth cannot match even a sixteenth portion of the merit acquired by chanting the holy name [...]
Our Main Business
"If you have got some time, the best thing would be to chant Hare Krishna more and more. Because our life is very short we have to finish our Krishna Consciousness in this life very quickly. We do not know when we shall meet our next death, our next exit from this platform. But before [...]
The Highest Award For Bravery
This is a photo of Vladimir, a highly decorated Russian soldier, who by chance walked into our hall program in Yekaterinburg. He fought for years with Russian special forces in both Afghanistan and Chechnya. After listening to my lecture he approached me and said, "Thank you for coming to our country. Yours is a message [...]
A rare gem
A page from Srila Bhaktivinode Thakur's personal handwritten song book. A rare gem! How fortunate we are to see it.
The Final Moments Of Hiranyakashipu
The Final Moments of Hiranyakashipu From the Subhasita-ratna-bhandagara [When Hiranyakashipu saw his servant running towards him in fear, he spoke as follows:] Hiranyakashipu: "What is it? What is it?" Servant: "O Lord! It is a lion!" Hiranyakashipu: "So what?" Servant: "O Lord! He has a human body! I have never seen such a strange creature." [...]


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MTV Movie Awards: See The List Of Nominees!
The 2015 MTV Movie Awards will be hosted by Amy Schumer, you'll be able to see who wins on April 12th, here's most of the nominees…. MOVIE OF THE YEAR PRESENTED BY GEICO American Sniper […]
Best and worst Oscars moments Of All Time
Remember Ellen's selfie with the A-Listers? It made the cut, but did the Naked Streaker behind Sir David Niven? Peter O'Tolle mistakingly thinking he won or Marlon Brando's strage stand in accepting his Oscar in protest? […]
5 Crazy Moments in Oscar History
The Oscars are often a den of crazy, from rambling speeches and mangled names to some truly terrible host routines. But do you remember Sacheen Littlefeather? Or the streaker?
Teens Flash Mob Mall After Denied Entrance To 'Fifty Shades of Grey'
A mall in Florida has enacted strict new rules for teenagers after a scary incident! 100 teens rushed a movie theater Saturday night after they were denied tickets to see "Fifty Shades of Grey," which […]
19 Great Valentine's Day Movies — Romance You Can Stream Online
From 'Casablanca' to 'Crazy Stupid Love', we've got 19 films about romance and love you can stream at home…alone, with friends or with your special sweetie.
Spider-Man in the Marvel Cinematic Universe: 5 Things to Avoid
Marvel announced yesterday that everyone's favorite web slinger, Spider-Man, is going to appear in the Marvel Cinematic Universe.
The 27 Sexiest Movies Of All Time
Fifty Shades Of Grey comes out this weekend, have you seen these other sexy titles?
Marvel And Sony Team Up To Bring Spider-Man Into Marvel's Cinematic Universe
Comic book movie fans everywhere are rejoicing this morning as Marvel Studios and Sony Pictures Entertainment have announced that Spider-Man is coming to the Marvel Universe.
Before 'Ted': Hollywood's History of Talking Animal Movies
Mark Wahlberg isn't the only Hollywood star who can talk to the animals. See our top 10 films featuring Hollywood's chattiest critters.
Watch the 'Fantastic Four' Trailer
The latest reboot of the classic Marvel team comes out August 7.


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By Catholic Online (NEWS CONSORTIUM)
11/5/2013 (1 year ago)
Catholic Online (www.catholic.org)
Pope Francis is calling world attention to modern forms of slavery including human trafficking, forced labor, and prostitution. A meeting was held at the Vatican to discuss the issue.
By Catholic Online (NEWS CONSORTIUM)
Catholic Online (www.catholic.org)
11/5/2013 (1 year ago)
Published in Living Faith
Keywords: human trafficking, slavery, Vatican, Pope Francis, conference, solutions, issue
ROME, ITALY (Catholic Online) - A group of 100 international experts including doctors, clergy, and academics, met at the Vatican on Monday to discuss topics associated with modern slavery and human trafficking. It is a startling fact that there are now more slaves in the world today than at any other time in history.
The Vatican reported the topics are very important to Pope Francis who is concerned that human trafficking will become increasingly lucrative and the world's largest criminal activity. The Pope himself has explained that human trafficking is an issue in his home country, Argentina, and reportedly two experts from Buenos Aries were invited to attend the conference.
The Pope plans additional meetings over the next two years.
The Holy Father was also gravely concerned that children were being used in trafficking schemes, deployed to transport and sell drugs and in some cases even to commit murder.
The issue of prostitution was also discussed. Although many social libertarians argue that prostitution should be legal, despite the obvious moral reasons to condemn the practice, the practice is often linked to illicit trade and other schemes. Organized crime engages in forced prostitution, and it is commonly related to drugs and various forms of violence.
The meeting led to a list of 50 recommendations, although that list has not yet been made public. Bishop Marcelo Sanchez Sorondo, the head of the Pontifical Academy of Sciences said about the list in an interview, "The idea is that it should be something along the lines of European courts that go beyond borders."
About 30 million people live as slaves around the world, and although slavery is technically outlawed, several nations disregard the practice. In some places, such as Mauritania, slavery is ingrained into the local culture.
Slavery even occurs in places where it isn't expected. Large portions of the marijuana crop grown in the UK use child labor, and child sexual slavery in the United States in on the rise as criminal street gangs find the practice even more lucrative than selling guns or drugs.
A birth foretold: click here to learn more!
St. Christopher
St. Francis of Assisi
St. Joseph
St. Mark
St. Florian
St. George
St. Joseph of Cupertino
St. Brigid of Ireland
St. John the Baptist
St. Matthew
St. Anthony
St. Ann
St. Isidore the Farmer
St. Gerard
St. Barbara
St. Benedict
By Tony Magliano
While Pope Francis' new encyclical Laudato, Si' is enjoying wide publicity, few people are aware this year marks the 20th anniversary of another powerfully prophetic social justice and peace encyclical: Evangelium Vitae ("The Gospel of Life"). Trying to awaken the ... continue reading
By Linky C. (NEWS CONSORTIUM)
Several incorruptible bodies of saints remain to displayed to be honored around several churches in Italy. These haunting images bring a different kind of eerie to the tourist and locals who are visiting these churches. Some of these saints are in a fragmented state, ... continue reading
By Atarah Haely (NEWS CONSORTIUM)
Archaeologists have discovered an ancient decorated mosaic floor of an ancient church, underneath its modern incarnation, during an excavation. The Christian mosaic is believed to be about 1,700-years-old and part of the old Byzantine church of the fourth century. ... continue reading
By Linky C. (NEWS CONSORTIUM)
Former Auschwitz guard, Oscar Groening has asked for God's forgiveness after serving Austchwitz during his testimony in court, last Wednesday. The 94-year-old worked for Austchwitz when he was just 13 and later became the "Accountant of Auschwitz." MUNTINLUPA, ... continue reading
By Matt Hadro (CNA/EWTN News)
Looking forward to Pope Francis' September visit to the U.S., the nation's bishops were exuberant on Tuesday, as the itinerary for the apostolic voyage was released. Washington D.C. (CNA/EWTN News) - Fewer than three months before the scheduled visit, Archbishop ... continue reading
By Catholic Online (NEWS CONSORTIUM)
Pope Francis' visit to both the United States and Cuba will be hectic. In addition to meeting with political officials in both countries, the Pontiff will meet with prisoners at the Curran-Fromhold Correctional Facility in Philadelphia and the homeless at the ... continue reading
By Deacon Keith Fournier
There are lessons that can only be learned under the broom tree. The lesson St Paul gave to the early Christians in Greece about the reality of being shipwrecked and experiencing daily struggles in life is critical in our age. God is searching for men and ... continue reading
By Catholic Online (NEWS CONSORTIUM)
It is definitely going to happen -- but where and when has yet to be decided. The head of the Russian Orthodox Church and Pope Francis have agreed to meet in an attempt to repair the major rift between the Eastern and Western branches of Christianity. LOS ... continue reading
By CNA/EWTN News
The Pope focused on the virtue of faith during his Sunday Angelus address, saying the whole gospel is written in its light. VATICAN CITY (CNA/EWTN News) - "Faith is this: to touch Jesus and to draw from him the grace which saves," Pope Francis explained June 28 at ... continue reading
By CNA/EWTN News
During his Mass for the feast of Saints Peter and Paul on Monday, Pope Francis called on the Church's new archbishops to be courageous witnesses who are not ashamed of Christ, and who are convinced by what they themselves teach. VATICAN CITY (CNA/EWTN News) - ... continue reading


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For full effect: http://tunapkatz.ytmnd.com
This is part of an in-browser music video I'm working on. I have it storyboarded. Now I'm just producing each asset for assemblage. This is my first ever walkcycle. What do you think? Is it me, or is his head weird?
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Cheers offers MLB Extra Innings by DirectTV with access to 80 baseball games every week including ALL Indians games!
PLUS...Cheers now has NHL Center Ice! Watch all your favorite teams compete for the Stanley Cup!
Cheers Sports Bar and Grill is conveniently located near Cedar Point, the Lake Erie Islands and lots of other local attactions.
Click here to get a list of many of the great things to see and do during your visit to Sandusky, Ohio!
The midwest's largest motorcycle rally,
Ohio Bike Week, takes place
May 29th through June 7th, 2015 right here
in Sankdusky, Ohio! Stop by Cheers Sports Bar & Grill to cool off in our A/C,
enjoy some great food and drink and watch the big game!
Each month we feature a new brew at a special price to entice you to try something
new and different. This month we are featuring the oh so tasty Not Your Father's Root Beer from Small Town Brewery. Even if you don't like beer, you should give it a try!
Head to Cheers on Thursday evenings STARTING MAY 28TH for "Pick your Cut, Pick Your Size" Steak Night.
Check out the selection of tasty beef, choose what you like best and how much you would
like. We cut your steak fresh right there, weigh it and then grill it up for you. Super fresh, super tasty!
Fishing or boating and need a change of scenery? Cheers Sports Bar & Grill welcomes all
our marina neighbors! Order a cold one, enjoy some delicous food and watch your favorite team!
And if the weather has you stuck at the dock, we're here from 11am 'til the wee hours, so stop on by!
Open Daily 11am-2am
Kitchen til 12am Sun-Thu & 1am Fri-Sat


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Primary Care Doctor, Family Practitioner
27 years of experience
Accepting new patients
27 years of experience
Accepting new patients
16180 SE Sunnyside Rd
Ste 102
Clackamas, OR 97015 Phone number & directions
Ste 102
Clackamas, OR 97015 Phone number & directions
License & Identifications
A medical license is required for a doctor to practice medicine in a particular state. Requirements vary by state but most require, at a minimum, post-graduate training in the doctor's specific specialty. An NPI number is a national identifier unique to an individual health care provider and is managed by the Center for Medicare & Medicaid Services (CMS).
Learn more about Dr. Elaine Marcus:
View the full profile to get information on:
- Qualifications
- What's important to you
View full profile
Patient Reviews
Patient comments (1)
The overall average patient rating of Dr. Elaine Marcus is Excellent.
|Patient Ratings
|Accurate Diagnosis
Specialties & Research
Dr. Elaine Marcus, MD is board certified in Family Medicine.
Education & Awards
Dr. Marcus graduated from New York University.
Home > Find a Primary Care Doctor > OR > Clackamas Primary Care Doctors > Dr. Elaine Marcus, MD
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- Additional Information
- Dr. Elaine R Marcus MD is a female Family Practitioner, has 27 years of experience and practices in Family Medicine.
- Where does Dr. Elaine R. Marcus practice?
- Dr. Elaine Marcus has 8 office locations.
Dr. Elaine Marcus practices Family Medicine near Clackamas, OR.
Additional practice locations include: Portland, OR and Canby, OR.
See Clackamas Primary Care Doctors.


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My LO is alittle over 4 months old and it didn't occur to me until we were at his 4 month well check that he doesn't "babble" as much as he used to. When he was 2 1/2 - 3 months old he would "talk" our ears off.
When his Dr ask me if he's "babbling" I kind of taken aback when I thought, "No, not really any more". It's almost as if he's moved on from saying Ooooo, Ahhhh and Yaaaa and Raaaa. Also he has his fingers in his mouth most of the time, so even if he's saying anything it just sounds like mush, lol. He's got himself a new bag a tricks though. He's gone from cooing to squealing at everything and blowing razzies and humming and a lot more whining, lol. I believe his hearing to be fine, because he'll wake up from loud noises, like dogs barking, etc. And he'll look over at someone (for the most part as long as he's not distracted by something else) if some calls him.
But I kind of think that he's so interested in everything that's going on around him that he is getting distracted, like he's noticing more of the world around him.
So my question is, how is your LO doing in the "language" department? Are you having similar experiences? Or not?
I think if this pattern continues up to his 6 month well check I'm going to bring it up to his Dr. Thanks!


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Imperial War MuseumMarch 5Museum • Duxford, United Kingdom
Brilliant place to visit great information for kids
David Duncan helps business owners utilise search and social media to market their business online,for more visit - http://davidduncan.brandyourself.com
Brilliant place to visit great information for kids
Healthy food at a reasonable price, great for a quick stop over
Live music and great whiskey selection. Party
Wonderful home made scones
Watch the parking prices it was £6 for two hours and five minutes. Outrageous
Great balcony with views of the Eifel Tower from 7th floor
Book in advance on Friday or Saturday evenings


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Mango-Jalapeño-Chicken Salad in Cumin Tortilla Bowls
Grilled Teriyaki Chicken Sandwiches
Grilled Chicken Breasts with Mandarin Orange Salsa
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Teriyaki Chicken and Pasta
Caribbean Salsa Chicken
Dinner ready in 25 minutes! Enjoy this sweet and tangy chicken cooked with vegetables, served over rice – a hearty skillet meal.
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Recent News
"Laudato Si" and the Society of the Sacred Heart
The much-anticipated papal encyclical 'Laudato Si' is now public.
What can we learn about our relationship with creation from the insights of Laudato Si and the wisdom of our own Society writings? What might this tell us about the emerging future?
Chile: Colegio del Sagrado Corazón de Jesús in Concepción
The Religious of the Sacred Heart in the community of Michaihue, Chile, has had a memorable week as part of this yearlong celebration of 150 years of our school in Concepción.
I have arrived today. I am faceless.
20 June - World Refugee Day:
"Perhaps you can can look me in the eyes, open the door, give me a hand, help me to walk. Perhaps, if we each give something of ourselves, we might even become friends." ~Tere Iribarren rscj (ESP)
2015 Feast of the Sacred Heart
"On this Feast of the Sacred Heart we turn our gaze to the God of deep compassion, to the God of love and mercy...."
~ Message of the General Council
A Letter to Pope Francis
"I do not wish to be the voice of the voiceless, as the "people of Paraguayan land" have their own voice, their own words. But I assure you that, when you listen to them, you will find yourself at the "heart" of the Paraguayan people."
Margot Bremer rscj
Celebrating 200 years of the writing of the first Constitutions of the Society of the Sacred Heart – 1815-2015
This year we also celebrate the 200th anniversary of the 1815 Constitutions of the Society of the Sacred Heart.
Dear Saint Madeleine Sophie
This is the prize-winning entry in a competition among all the 50 Sacred Heart Schools in Spain, commemorating the 150th anniversary of Sophie's death.
Commemorating 150 years of the death of St. Madeleine Sophie with a "new" portrait
This portrait of St. Madeleine Sophie Barat is located in the General Archives of the Society in Rome. Its origin is unknown, though there are indications that it may have been sent to the Mother House in Paris from Italy in 1879.
Sophie: 150 Years
The Centre Sophie Barat in Joigny, France invites us to an "interior pilgrimage" ....
Living Our Charism Today
"Like the Samaritan woman we are invited to deep engagement with Jesus as we welcome new life for the emerging future.... We are called to be evangelizers who preach the gospel with joy...."
Sol Navidad rscj (PHI)
Celebrating Sophie's Feast
St. Madeleine Sophie's feast on May 25 is fast approaching. Here are some resources for prayer or reflection that are available on websites of some Provinces.
Brothers and Sisters: Missionaries of Joy!
A gathering of young religious was held on May 2-3, 2015 in Paris, as part of the Year of Consecrated Life.


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Experience the world of puppetry in Brookline Village.
Summer Puppet Adventures this July!
Join us for the kick-off of our 41st Season →
Puppetry Summer Camps
Register now for our exciting summer enrichment programs for ages 5-7 and 7-12
NEW Adult Classes Announced!
Learn diverse puppetry styles from master artists in these exciting summer intensives →
Puppets at Night for Adult Audiences
Boston's only puppetry cabaret returns July 18 →
Upcoming Mainstage Puppet Shows
Help Save the Monkey
by Liz Hara and Marta Mozelle Macrostie
Wednesday July 1 - Friday July 3
Wed-Fri at 10:30am & 1pm
FREE Summer Kick-Off event: Fri July 3 from 11:30am to 3pm
by National Marionette Theatre
Wednesday July 8 - Saturday July 11
Wed-Sat at 10:30am & 1pm
Friday Night Adventures: July 10 at 7pm
View More Upcoming Mainstage Puppet Shows →
Upcoming Puppets at Night Events
Puppet Showplace Slam
July 18, 2015
Connect with Us
Who is this stranger in the box office??!! Our disguises are inspired by "Help Save the Monkey" this… https://t.co/tQK0LPCrVn
RT @hillhouseboston: SO MUCH FUN for Kiddie Kamp this week, including a visit from @PuppetShowplace today! #HHCamp2015 http://t.co/jbGoHLdBO4
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Lakeshore Technical College is governed by a nine-member District Board of Trustees appointed by the County Board Chairs of those counties making up the Lakeshore district–Calumet, Manitowoc, Ozaukee, and Sheboygan. Pursuant to Wisconsin Statute, the Board consists of two employer members, two employee members, three additional members, one elected official member who holds a state or local office, and one school district administrator. Board members serve staggered three-year terms and meet once a month.
Nancy Crowley,
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Christine Adleman
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Roy Kluss
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43 year old man | Stafford, VA, USA | Seeking women 29-42 within 20 miles
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I currently work for a defense contractor as a Network Engineer here in Stafford. I have two wonderful sons who are a very important part of my life. In my free time I enjoy concert photography as a side hobby. In the summers I like to go out on the river with my jet ski or just hang out on the water. I enjoy traveling and seeing new places, I really dont have a favorite place to go I pretty much enjoy everything from the beach to the mountains from the city to the country. I am looking for someone to balance my life out with, someone who is honest, caring, and knows how to laugh. I'm looking for a lasting relationship, and have reached a point where I'm not interested in games.
Camping , Dining out , Fishing/Hunting , Movies/Videos , Music and concerts , Exploring new areas , Playing cards , Playing sports , Travel/Sightseeing , Watching sports
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I like pretty much all types of music, I enjoy live concerts. Lets see as far as T.V shows I like Family Guy,Sopranos, Criminal Minds, and some of the newer shows on TBS mostly I just channel surf.
In my spare time I try to spend as much time with my two sons as possible. Taking them to parks or anywhere else around the area. As far as when I have time to myself I like to attend a concert, I enjoy all types of music. I like to travel as well.
I mostly read books for my job, so not much excitement on that front. I also like to read books about ghosts and haunted places.
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Plan on going back and finishing up some college classes, then maybe transfer to a 4yr school. I have spent the last 10yrs concentrating on studying things for my job so now I want to learn other things.


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28 Passage Cardinet, Paris, Paris, 75017, France, 1-844-302-2242
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Situated in 17th Arrondissement within a 15-minute walk of Square des Batignolles and Parc Monceau, Hotel Prince Albert Wagram offers 3-star Paris hotel accommodations. Arc de Triomphe and Moulin Rouge are also within 2 mi (3 km).
This hotel offers free WiFi, an elevator (lift) and concierge services. Multilingual staff are available at the front desk 24 hours-a-day and can provide tour/ticket assistance and express check-in.
This hotel offers free WiFi, an elevator (lift) and concierge services. Multilingual staff are available at the front desk 24 hours-a-day and can provide tour/ticket assistance and express check-in.
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Abstract available in
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Description (OCR text may contain errors)
May 6, 1969 KAZUO QGATA ET AL 3,442,868
NOVEL PROCESS FOR THE PREPARATION OF POLYESTER Filed July 15. 1966 United States Patent US. Cl. 260-75 4 Claims ABSTRACT OF THE DISCLOSURE A process for producing fiber forming polyesters, e.g., polyethylene terephthalate without direct contact of the acid and glycol components comprising (1) as the first step reacting terephthalic acid or a mixture of dibasic acids containing at least 85% of the same with an oligomer (A) comprising the reaction product of such terephthalic acid or mixed acid component and a glycol, oligomer (A) having a degree of polymerization of one or more but less than 3 and having termini hydroxyl groups, to form an oligomer (B) having a higher degree of polymerization, i.e., 3 to and hydroxyl groups substantially at the termini; (2) as a second step,
reacting at least a portion of oligomer (B) with the glycol to depolymerize (B) to form oligomer (A') having a degree of polymerization of one or more but less than 3; and
(3) as a third step,
forming the fiber forming polyester by polycondensing a material comprising any remaining portion of oligomer (B), a portion of oligomer (A') or mixtures thereof while recycling the remaining portion of oligomer (A') for use as oligomer (A) in the first step.
This invention relates to a novel process for the preparation of polyester from aromatic dibasic acid and glycol.
The invention particularly relates to an improved proc- (3) oligomer of higher degree of polymerization glycol ess for the preparation of polyethylene terephthalate from terephthalic acid and ethylene glycol.
It is well known that highly polymerized polyester can be prepared from aromatic dibasic acid and glycol, inter alia, excellent polyester having fiberand film-forming ability can be prepared from terephthalic acid and ethylene glycol. And, such polyester is prepared by a two-stage process, viz., the first stage of preparing monomeric bisglycol ester of aromatic dibasic acid or its oligomer from the aromatic dibasic acid or its lower aliphatic ester and glycol, and the second stage of subjecting the product to further polycondensation. Whereas, it is self-evident that, in the above process, direct reaction of aromatic dibasic acid with glycol without the intervening conversion of the acid to its lower aliphatic ester is the more economical. However in case of directly reacting a difficultly soluble aromatic dibasic acid such as terephthalic acid with glycol without first converting it to its lower aliphatic ester, normally a great excess of glycol must be used and the esterification reaction is extremely time-consuming. During the reaction, furthermore, impurities such as diethylene glycol are by-produced due to the interreaction of glycol and introduced into the main chain of the polyester to de- 3,442,868 Patented May 6, 1969 grade the quality of the product, as known among the experts.
For example, when a glycol condensate such as diethylene glycol is introduced into main chain of polyester, the resultant polyester has its softening point lowered, and its properties such as heat resistance, light resistance and oxidation resistance are all degraded. The degradation of such properties becomes still more distinct when the polyester is shaped into, for example, fiber or film. Particularly for the production of such articles as industrial fiber, film and the like which are frequently exposed to severe conditions, aforesaid degradation in the polyester properties prove to be fatal. Therefore it is a matter of extreme importance to devise a way of directly producing from terephthalic acid and glycol such polyester having minimum possible content of glycol condensate such as diethylene glycol, with a reaction rate industrially acceptable.
As an improvement in the production process of such high quality polyester by means of the direct method, it has been proposed to use as the reaction medium bisw-hydroxy alkyl terephthalate (hereinafter abbreviated as BHET) which is a reaction product, with the view to accelerate the reaction rate of terephthalic acid wth glycol or to inhibit the side reaction (cf. British Patent No. 776,282, German Patent No. 1,024,713).
However such improvement process is still incapable of inhibiting the objectionable side reaction to a satisfactory degree because in which free glycol is likewise present in the reaction system. Accordingly, as a further improvement of the said process, a proposal was made to control the mol ratio of terephthalic acid component to glycol component in the reaction system to no greater than 1:2 (cf. French Patent No. 1,327,594 and French Patent No. 1,368,576).
In such processes, however, evidently the following three types of reactions concurrently take place in the reaction system, viz.,
olig- BHET or its oligomer.
In the above, the reaction 1) is the main course of the esterification, and the reaction (2) is also an esterification reaction in which the terminal hydroxyl groups of the oligomer are bonded with terephthalic acid. The reaction (3) is the glycolysis (depolymerization) of the oligomer having a greater degree of polymerization formed in the reaction (2). In contrast to the process of the said British Patent No. 776,282 in which the reaction (1) is the dominant reaction, that of the latter French patents is the preferable, in the point that in the later the hydroxyl group concentration per unit volume of the reaction system is still lessened, but the two are essentially the same in that glycol is always present in the esterification reaction system Therefore in neither of the two, occurrence of etherification which is a side reaction, can be avoided.
Accordingly, the present invention relates to a process for the preparation of high quality polyester from aromatic dibasic acid and glycol with high efliciency, in which the deficiencies inherent in the conventional processes are eliminated.
More particularly, the invention relates to a process for the preparation of fiber-forming polyester comprising the below-specified three steps, viz.
1) As the first step, reacting terephthalic acid with an oligomer (A) of terephthalic acid and a glycol of an average degree of polymerization 1 or more but less than 3 having terminal hydroxyl groups [hereinafter to be referred to merely as oligomer (A) at the ratio of more than 1 mol of the latter per mol of the former at the temperature range of 220280 C., preferably 230260 C., thereby preparing an oligomer (B) having an average degree of polymerization ranging 3-l0 and hydroxyl groups substantially at the termini [hereinafter to be referred to merely as oligomer (3)];
(2) As the second step reacting the said oligomer (B) with the glycol at the temperature range of 200-250 C., preferably 220230 C., to depolymerize the oligomer (B), thereby preparing an oligomer (A') of an average degree of polymerization 1 or more but less than 3; and
(3) As the third step, heating and condensing a part of the said oligomer (B) and/or the oligomer (A') to form polyester, while recycling the all or the rest of the oligomer (A') to use the same as the oligomer (A) of the first step.
In this invention, it is permissible to use any dibasic acid mixture containing no less than 85 mol percent of terephthalic acid in the first step, in place of the aforesaid terephthalic acid. In such a case, the oligomer (A) to be reacted with the mixture should consist of the same acid component and glycol component as of the dibasic acid mixture and the glycol, at substantially the same ratio.
According to the novel preparation process of polyester of the present invention, characteristically the aforesaid reaction (esterification) (1) terephthalic acid glycol BHEI or its oligomer does not take place at any stage of the polyester formation, and furthermore the aforesaid reaction is concurrently present. This means an increase in solubility of terephthalic acid into the reaction system, and the consequential increase in carboxyl radical concentration per unit volume makes up for the low hydroxy radical concentration caused by the absence of free glycol, and this, together with the high temperature of the reaction system, contribute to maintain the high rate of esterification. On the other hand, for the depolymerization step, viz., the second step, no consideration needs be given to the esterification reaction, but it is possible to choose the optimum depolymerization conditions such as relatively low temperature, considering only of the etherification reaction. As the result, according to the process of the invention high quality polyester having an extremely low glycol condensate content is formed.
The amount of the terephthalic acid to be added to the oligomer (A) of terephthalic acid and glycol in the first step of the present invention should be such as will make the esterified product trimer to decamer, particularly trimer to heptamer. An amount less than the above lower limit is of little practical value from the stand point of productivity, and with the use of a greater amount than the upper limit not only a large quantity of unreacted carboxyl radical is found in the esterification reaction product, but also, due to the addition of a large quantity of terephthalic acid to the oligomer (A) at the initial stage of the reaction, viscosity of the slurry rises to lower the agitation efiiciency and heat-conductivity, thereby preventing the smooth progress of the esterification reaction.
Further, the addition of terephthalic acid in this step may be elfected at a single time or done at several times dividedly.
As the oligomer (A) of terephthalic acid and glycol employed in the esterification reaction according to the invention, mainly those of degree of polymerization 1 to (depolymerization) (3) oligomer oi higher degree of polymerization glycol BIIET or its oligomer is performed in the substantial absence of free dibasic acid.
Consequently, according to the present invention substantially the reaction below (2) terephthalic acid BHET (or its oligomer having a degree of poly- (esterification) merization less than 3) an oligomer of a higher degree of polymerization (degree of polymerization 3 10) alone participates in the polyester formation an as esterification reaction.
Again in the British Patent No. 776,282 and German Patent No. 1,024,713, the above reaction (3) is performed in the presence of free acid (e.g. terephthalic acid). When the reaction (3) is so performed in the presence of free acid, dehydration reaction between the hydroxyl radicals of glycol is promoted to result in mixing of glycol condensate such as diethylene glycol in the reaction product, causing lowering of the quality of the polyester formed, as shown in a later appearing comparative example. Whereas, according to the present invention at no stage of the polyester-forming reaction the reaction (3) taking place in the presence of free acid, the possibility of such glycol condensates being co-polycondensed is minimized.
Furthermore, in accordance with the invention the reaction (2) and reaction (3) being conducted separately, optimum temperature conditions for each can be set up independently of the other. Thus, for example, the reaction (3) can be conducted at relatively lower temperature condition than that of the reaction (2), such as ZOO-250 C., preferably 220-230" C. For this reason also it is made possible in this invention to minimize the formation of glycol condensate.
In the present invention thus the esterification step, viz., the first step, being performed in the substantial absence of free glycol, not only the rate of etherification can be reduced but also the temperature of the reaction system can be raised, comparing the case in which free glycol less than 3 are intended, but the presence of a minor amount of tetramer or oligomer of higher order is permissible, since in the invention isolation of such an oligomer of one and certain degree of polymerization as the starting material is not practiced.
Upon addition of the above specified amount of terephthalic acid to such a oligomer (A) in the first step of the invention, the reaction starts from at about 220 C., and the boiling point gradually rises with the increase in the average degree of polymerization of the liquid phase reaction system. The esterification in accordance with the invention is not necessarily conducted always at the boiling point of the reaction system, but it better meets the purpose to raise the reaction temperature with the rise in the boiling point as the reaction progresses. The inside temperature, however, should preferably be controlled so that the highest temperature should not exceed 280 C. to prevent coloration of the product.
With the progress of the esterification reaction the un-dissolved terephthalic acid disappears, and when the liquid reaction phase becomes substantially transparent, the esterification step comes to the termination.
The depolymerization reaction which is the second step of the invention is performed with addition of glycol to the reaction system containing the above esterified product [oligomer (B )1, a small amount at a time.
In that case, the total amount of the glycol to be added should preferably be no greater than that sufficient to convert the oligomer (B) to bisglycol ester, at the most.
Thus a bisglycol ester of terephthalic acid of a low side product content, and its lower oligomer having a degree of polymerization less than 3 are obtained. If an excess of glycol should be used in this stage, when the product is recycled to participate in the first step reaction, the boiling point of the reaction system is lowered to undesirably retard the rate of the esterification reaction and also the etherification reaction takes place. Consequently the object high quality polyester of the invention cannot be obtained. For this reason the use of glycol within the above-specified quantity range is perfcrred.
In the second step of the invention, with the view to accelerate the rate of depolymerization with glycol, known and suitable ester-interchange catalyst or polycondensation catalyst may be present with advantage. Also the reaction may be optionally performed at an elevated pressure.
. In the recirculation step, viz., the third step of the invention, the esterification reaction product [oligomer (B)] of the first step and/or the depolymerization product [oligomer (A)] of the second step are withdrawn as the starting material for the subsequent polycondensation step.
The polycondensation step is performed in themanner known per se, in the presence of known catalyst and suitable additives.
The process of the present invention is practicable either batchwise or continuously, but is particularly adapted for continuous method.
Thus in accordance with the invention, the oligomer (B) or the oligomer (A) are withdrawn from the reaction system in an amount corresponding to that of the terephthalic acid added in the first step and that of the glycol added in the second step, and subjected to polycondensation, while the remaining oligomer (A) is recycled to be used an the starting oligomer (A) of the first step, and accordingly it is made possible to continuously produce high quality polyethylene terephthalate of extremely low glycol condensate content, using merely terephthalic acid and glycol as the starting materials to be freshly supplied.
Furthermore, with the practice as above in accordance with the subject invention, high quality polyethylene terephthalate of the level hardly attainable by conventional direct method can be obtained at high efliciency and continuously.
Again the terephthalic acid may be replaced by a mixture of terephthalic acid with other dibasic acid or acids, of which terephthalic acid content is at least 85 mol percent, as aforesaid. In that case, modified polyester is likewise obtained. As the dibasic acids useful for the invention other than terephthalic acid, the following may be named, for example: aromatic dibasic acids such as isophthalic, phthalic, homoterephthalic, 4,4 diphenyldicarboxylic, naphthalenedicarboxylic and tetrachloroterephthalic acids as well as 1,2-bis(4-carboxyphenyl) ethane and 1,2-bis(pcarboxyphenoxy) ethane; alicyclic dibasic acids such as hexahydroterephthalic and 2,6 decahydronapththalenedicarboxylic acids; and aliphatic dibasic acids such as succinic, glutaric, adipic, sebacic, and w,w'-diethyletherdicarboxylic acids, etc.
As the useful glycols, besides those represented by the formula (in which n is a positive integer of 2-10), aliphatic glycols having side chains such as isobutylene glycol, neopentylene glycol and the like; alicyclic glycols such as 1,4- cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutanediol and the like. 2,2-bis(4-hydroxyphenyl) propane, hydroquinone, 2,5- or 2,6-dihydroxynaphthalene, p-( 18-hydroxyethoxy) phenol and the like may also be named.
A polyfunctional compound may be added to an extent such that it may keep the polymer substantially linear and may not lead to the loss of its fiberand film-forming ability. Addition of monofunctional compound neither interferes with the achievement of the invention. Inorganic compounds such as titanium oxide and carbon black may also be added for the purpose of delustering, coloring, and the like. Addition of known catalysts is not detrimental to the process of this invention.
Hereinafter an explanation will be made with reference to the attached drawing.
The drawing is for still detailed explanation of the subject process, showing one embodiment of esterification reaction in continuous manner. In figure, terephthalic acid stored in the tank 1 is continuously fed to the esterification tank 3 via the screw-type conveyor 2. The esterification tank 3 is of horizontal type, inside of which is divided into plural chambers with partitions. In every chamber, agitation is performed with the stirrer blade attached to one common rotation shaft. Also the chambers are heated by a common heating medium. With the progress of the reaction, each of the chambers is given a temperature higher than the one preceding, and the content of each of the chambers overflows into the next chamber in sequence. From the reaction product which becomes substantially transparent in the last chamber, the oligomer (B) in an amount corresponding to the terephthalic acid added per unit time is sent to the polycondensation apparaus (not shown) by an oligomer (B) measuring pump 10, and the remnant is fed into a pressurized depolymerization tower 9 provided with a heating jacket, through a measuring pump 6. Into the tower ethylene glycol is continuously fed through a measuring pump 7 and a preheater 8, to perform the depolymerization reaction therein. The reaction product [oligomer (A)] is recycled into the first chamber of the esterification tank 3, through a measuring pump 11. The steam formed in the esterification tank 3 is separated by means of a distillation column 4 and removed from the system through a condenser 5.
In another embodiment of the invention, the oligomer (B) formed by esterification reaction is entirely depolymerized without being discharged from the measuring pump 10. In this case the reaction product [oligomer (A)] in an amount corresponding to that of terephthalic acid fed per unit time is delivered through the measuring pump 10 to the polycondensing apparatus, and the remainder is returned to the first chamber of the esterifying tank 3.
Hereinafter the invention will be explained in further detail with reference to working examples, in which in trinsic viscosity is that measured in o-monochlorophenol at 35 C., and softening point is the softening temperature measured with penetrometer. Esterification ratio refers to the reaction ratio of the terephthalic acid supplied, and degrees of polymerization, to the apparent degree of polymerization obtained when all of the acid component and the glycol component reacted. Unless otherwise indicated, part is by weight. The measurement of diethylene glycol content is done in accordance with the process of R. Janssen, H. Ruysschaert & R. Vroom described in Makromol. Chem., vol. 77, -p. 153 (1964), and the content is expressed in mol percent to the acid component.
Example 1 A one-liter flask heated with a mantle heater was equipped with a distillation column having a packed portion of 10 cm., a thermometer, a stirrer and a device for addition of ethylene glycol.
To the same, 102.2 g. of a melt of a low polymer containing terephthalic acid and glycol at the molar ratio of 1:1.2 (number average degree of polymerization=5, melting point=249 C., antimony trioxide content=0.025 mol percent to the terephthalic acid) was added. When the inside temperature reached 250 C., 18.6 g. of ethylene glycol was added to the system by the adding device, for over 3 minutes.
The inside temperature fell to 205 C. with the addition of glycol, and then gradually rose to 225 C. During that time, no distillation of ethylene glycol was observed. To the system then 41.5 g. of nitrogen-substituted terephthalic acid and 0.02 g. of antimony trioxide were added. Thereupon the inside temperature fell to 217 C., but as soon as it rose to 218 C., distillation of water started. The inside temperature gradually rose to 255 C. after 52 minutes, when the content became transparent. The distillation of water stopped at that point, and thereafter the inside temperature rapidly rose to 267 C. within the subsequent minutes.
Thereupon 27.9 g. of ethylene glycol was added for over 7 minutes, during which the inside temperature fell to 220 C., which again rose to 227 C. after additional 10 minutes. The resultant reaction mixture was a white solid weighing 182 g. and having a melting point of 189 C. The same solid was polycondensed in a heated bath of 285 C. with stirring, for the initial minutes under the pressure gradually decreasing from 760 mm. Hg to 1 mm. Hg, and for the subsequent 50 minutes, under the pressure of 0.3 mm. Hg. Then the reaction was suspended.
A water-white polyester having an intrinsic viscosity of 0.703, a softening point of 263.6 C., and a carboxy radical content of 11.0 millieq./kg. was obtained.
Example 2 To a molten esterified product (temperature=265 C.) obtained in the manner as described in Example 1, 27.9 g. of ethylene glycol containing 0.03 g. of antimony trioxide was added for over 7 minutes. During the addition the inside temperature fell to 220 C., and 13 minutes thereafter rose to 230 C. when 62.2 g. of terephthalic acid was added to the system. The inside temperature rose from 224 C., at gradually accelerated rate and reached 255 C. after 88 minutes, whereupon the reaction system becoming transparent. Throughout the operation the temperature at the top of the column was 102 C. and constant, and from the top water formed was continuously withdrawn. The reaction product was a transparent melt (total amount=231 g.) slightly tinged with yellow, having a melting point of 249.5 C. A part of the same was taken and polycondensed in a heated bath of 285 C. in the similar manner as in Example 1, to form a white polyester having an intrinsic viscosity of 0.722, a softening point of 263.2 C. and a carboxyl radical content of 10.5 millieq./kg.
Example 3 In a continuous plant constructed as shown in the flow sheet of figure, from the continuous powder supplying device 2, 36 kg. of terephthalic acid per hour, and from the recirculation pump 11, 111 kg. of a low polymer having a degree of polymerization of 1.25 per hour, were supplied continuously into the first chamber of the esterification tank 3. The inside of the tank 3 was maintained at the temperature level averaging 235 C. by means of a heating jacket. The terephthalic acid and the oligomer (A) moved from the first chamber ultimately to the fourth chamber in sequence by means of overflow, while homogeneously stirred. The steam formed by the reaction was separated from the vapor of ethylene glycol by the rectification column 4, and removed from the system through the condenser 5. After the average staying time of about 4 hours, the oligomer (B) having a degree of polymerization of 4.6 was taken out with the pump 6, which was transparent and had an esterification ratio of 96%. Ethylene glycol containing as dissolved therein 0.025 mol percent to the terephthalic acid supplied of antimony trioxide was sent from the pump 7 to the preheater 8 to be preheated to 225 C., and then was mixed with the above intermediate polymer. The mixture was fed into the depolymerization tower 9, inside of which was maintained at a pressure of 3 kg./cm. and at a temperature of average 225 C. by means of a jacket. After about 40 minutes reaction, the product withdrawn had a melting point of no higher than 160 C., and thus was converted to an oligmer (A) having a degree of polymerization of 1.25 and an esterification ratio of 97%, due to the thorough depolymerization. Among the low polymer, 111 kg./ hour was recycled to the esterification tank 3, and the rest was taken out the pump 10 at a rate of 53 kg./hour, which was sent to continuous polymerization step after addition thereto of the necessary catalyst, stabilizer and delusterant. Thus a polymer having an intrinsic viscosity of 0.65 was continuously produced, which had a softening point of 261.5 C., a diethylene glycol content of 1.5 mol percent .and a very satisfactory color tone.
Example 4 Using the same apparatus as in Example 3, experiments were run with varied reaction conditions, with the results as shown in Table 1.
Degree of polymerization of reaction product [oligomer (13)] 3 5 5 8 Esterification degree of reaction product [oligomer (13)] (percent) 96 97 04 DEG content of the reaction product [oligomer (13)] (mol percent) 1. 95 1. 78 l. 70 l. 50
run SECOND s'rnr Amount of ethylene glycol (kg./hr.) 24.2 27 19 19 Type of depolymerization catalyst Mn-acetate SbzO: Amount of depolymerization catalyst (mol percent) O. 015 0.015 0. 015 0. 015 Average reaction temperature 0.). 225 230 230 230 Average staying time (hr.) 0. 5 O. 9 0.7 0.8 Degree of polymerization of reaction product [oligomer (A)] 1. 25 1.0 1. 7 1. 7 Esterification degree of reaction product [oligomer (A)] (percent) 97 98 96 95 DEG content of reaction product (oligomer (A)] (mol percent) Example 5 Using the same apparatus as used in Example 3, the operation was run under the same reaction conditions employed in Example 3 except that in place of the terephthalic acid, terephthalic acid containing 10 mol percent of isophthalic acid was used. The oligomer (B) taken out by the pump 6 was a transparent liquid having a degree of polymerization of 4.6 and an esterification ratio of 97%. The reaction product [oligomer (A)] at the exit of the depolymerization tower, i.e., the low polymer, had a degree of polymerization of 1.25 and an esterification ratio of 98%. The same was sent to the continuous polymerization step to produce a polymer of excellent color tone, having an intrinsic viscosity of 0.65, a softening point of 236 C., and a diethylene glycol content of 1.5 mol percent.
Example 6 In a polymerization autoclave, 151 g. of the oligomer (A) having an average degree of polymerization of 1.25 obtained in Example 3 was heated to 200 C. and melted. To the melt 41.5 g. of terephthalic acid was added, and the system was made into a homogeneous solution under a temperature level maintained at 240 C. The inside tem perature of the autoclave was raised to 270 C. and, after removal of the ethylene glycol subsequently distilled, further raised to 285 C. while the pressure was gradually reduced to 0.1 mm. Hg for over 30 minutes. Sixty minutes thereafter, a polymer of excellent color tone having an intrinsic viscosity of 0.65 and a softening point of 262.3 C. was obtained.
Example 7 This example is to show the difference between below specified reactions (A) and (B) for synthesizing the same amount of bis(B-hydroxyethyl) terephthalate (BHET), as illustrated by the amount of diethylene glycol (DEG) byproduced.
TPA+2EG BHET+2H O /z Dimer-l- /zEG-eBHET Reaction (A) and 124 parts of ethylene glycol (EG), and its inside air was replaced by nitrogen gas. Then the inside pressure was raised to 2.5 kg./cm. (gauge). The autoclave was then immersed in a bath of 265 C. while subjected to an agitation of 60 r.p.m. The inside temperature rose substantially proportionally for minutes, during which the pressure was controlled to 2.5 kg./cm. (gauge) by means of a needle valve provided on the apparatus. When the inside temperature reached 220 C. after 30 minutes heating, distillation off of water started, and the temperature reached to a substantially constant level at 230 C. Two hours after the starting of the distillation, the temperature at the top of the column started falling, and when it reached 90 C. after subsequent 30 minutes, the reaction was suspended. The reaction time totalled .180 minutes. The reaction product was a white solid containing 4.60 mol percent of diethylene glycol.
Reaction (B) Bis (ii-hydroxyethyl) terephthalate synthesized by esterinterchange reaction of 97 parts of dimethyl terephthalate, 62.0 parts of ethylene glycol and 0.015 mol percent of manganese acetate was placed in a flask provided with a short packed tower, and made into a melt of 240 C. Upon addition thereto of 27.6 g. of terephthalic acid, the inside temperature of the system fell to 220 C., and so the system was heated with a mantle heater with an agitation at the rate of 60 rpm. With the progress of the reaction the inside temperature gradually rose, and when it reached 242 C. the terephthalic acid disappeared. This product was of dimeric composition of bis(p-hydroxyethyl) terephthalate, and its diethylene glycol content was 1.07 mol percent. To the same dimer 0.03% of antimony trioxide and 20.7 parts of ethylene glycol were added, causing a temporary temperature fall of the system to 200 C. The inside temperature again gradually rose as the heating was continued, and when it reached 230 C., the depolymerization reaction terminated. The reaction time required was 40 minutes. Thus obtained reaction product had a composition of bis([3-hydroxyethyl) terephthalate, and of which diethylene glycol content was 1.17 mol percent. Accordingly, under the above reaction condtions, the increase in diethylene glycol content was no more than 0.1 mol percent.
Example 8 This example is to show the influence of the presence of carboxyl radical of terephthalic acid upon the reaction rate of etherification at the same temperature level and same hydroxyl radical concentration.
2.50 grams of pure bis(B-hydroxyethyl) terephthalate (melting range=l08.5109.0 C.) was sealed in a glass tube of 8 mm. inner diameter of which inside air was substituted with nitrogne. Five of such sealed tubes were prepared and which are made the group A. Separately, five sealed tubes were prepared in which 1.66 g. of terephthalic acid and 1.24 g. of ethylene glycol were similarly sealed. These were made the group B tubes. The tubes of the both groups were immersed in a constant temperature oil bath of 240 C. and after 150 minutes the terephthalic acid in the tubes B dissolved to make a homogeneous solution. There after each one of the group A tubes and group B tubes were withdrawn from the bath at every 2 hours and quenched. The results of measuring the diethylene glycol (DEG) content and carboxyl radical (COOH) content in the contents of the tubes are as shown in Table 2.
In the group A tubes, 7.68 eq./kg. of hydroxyl radical participated in the ether formation in the presence of 0.20 eq./kg. of carboxyl radical formed by the hydrolysis caused by the water present in bisQS-hydroxyethyl) terephthalate. Again in the group B tubes, 8.65 eq./kg. of hydroxyl radical participated in the ether formation in the presence of 1.75 eq./kg. of carboxyl radical (accor-dingly, with the reaction ratio of 74.6%). The rate of ether formation being proportional to the square of hydroxyl radical concentration, when proton in the reaction system does not promote etherification, the ratio of diethylene glycol formation rate between the group B and group A is assumably (8.65/7.68) =1.27. However, as shown in Table 2, the ratio of diethylene glycol formation rate empirically obtained was 3.50, which is 2.76 times the calculated value. This is due to the presence of a large quantity of carboxyl radical which accelerates the etherification reaction.
Control This control is to show, in esterification of terephthalic acid with ethylene glycol, how the presence of oligomer influences the softening point of the ultimately produced polyester.
To 127 parts of bis( 3-hydroxyethyl) terephthalate obtained in the reaction (A) of Example 7, 0.03 mol percent of antimony trioxide was added, and the mixture was placed in a polymerization autoclave and heated to 285 C. First ethylene glycol distilled oil under atmos pheric pressure was removed, and thereafter the pressure was gradually reduced to 0.2 mm. Hg for over 30 minutes. Fifty minutes later, a polymer having an intrinsic viscosity of 0.67, a softening point of 257.6 C. and a diethylene glycol content of 2.90 mol percent was obtained.
Again when an experiment was run in the manner of reaction (A) of Example 7 using 127 parts of bis( 3- hydroxyethyl) terephthalate obtained in Example 7, 83 parts of terephthalic acid and 62 parts of ethylene glycol, 70 minutes after the distillation of water started, the temperature at the top of the column started to fall, and the reaction terminated within the total reaction time of 130 minutes. The reaction product was polycondensed in the similar manner as above, with 0.03 mol percent of antimony trioxide added thereto, to produce a polymer having an intrinsic viscosity of 0.66, a softening point of 258.4 C., and a diethylene glycol content of 2.57 mol percent.
We claim:
1. A process for the preparation of fiber-forming polyesters wherein the direct reaction of an acid component and a glycol is avoided, such process comprising:
(1) as a first step,
reacting (i) an acid component selected from the group consisting of terephthalic acid and dibasic acid mixtures containing at least mole percent of terephthalic acid with (ii) an oligomer (A) comprising the reaction product of (x) an acid component of the same composition as said acid component and (y) a glycol, said oligomer (A) having an average degree of polymerization of 1 or more but less than 3 and having hydroxyl radicals at the termini, at the ratio of more than 1 mol of (ii) per mol of (i) and within the temperature range of 220-280 C. to form an oligomer (B) having an average degree of polymerization of 3-10 and having hydroxyl radicals substantially at the termini;
(2) as a second step,
reacting at least a portion of said oligomer (B) with a glycol of the same composition as said glycol (y), within the temperature range of ZOO-250 C. to d e polymerize said oligomer (B) to produce an oligomer (A) having an average degree of polymerization of 1 or more but less than 3 and (3) as a third step,
polymerization of less than 3 and hydroxyl radicals at the termini, and
(3) as a third step,
preparing said polyethylene terephthalate by polycondensing, with heating, a material selected from the group consisting of (a) any remaining portion of said oligomer (B), (b) bis(;8-hydroxyethyl)-terephthalate, (c) a portion of said oligomer (A) and ((1) mixtures thereof, with the provision that at least some of (a), (b), or c) must be polycon- (A) of the first step. 2. The process of claim 1 wherein the reaction of step (1) is conducted at a temperature of 230-260" C.
3. The process of claim 1 wherein the reaction of step (2) is conducted at a temperature of ZOO-220 C.
4. Process for the preparation of polyethylene terephthalate wherein the direct reaction of terephthalic acid and ethylene glycol is avoided, such process comprising densed to form said polyethylene terephthalate, while recycling any remaining portion of said bis(B-hydrox yethyl)-terephthalate or the oligomer (A) to use it respectively as the bis([3-hydroxyethyl)-terephthalate or the oligomer (A) of the first step.
References Cited UNITED STATES PATENTS 2 799 664 7/1957 Drewitt et a1. (1) as a first step,
reacting (i) terephthalic acid with (ii) bis(/3-hydrox- 2 3$; 260 475 yethy1)-terephthalate or an oligomer (A) of bis(13- 3174830 3/1965 W t i hydroxyethyl)-terephthalate, said oligomer having an average degree of polymerization of less than 3 FOREIGN PATENTS and having hydroxyl radicals at the termini, in a 1,368,576 @1964 France ratio more than 1 mol of (ii) per mol of (i) at :1 1,065,608 9/1959 Germany temperature in the range of 230-260 C., to form 676,372 7/1952 Great Britain an oligomer (B) having an averagedegree of polym- 775,030 9/1957 Great Britain erlzatlon of 3 10 and hydroxyl radicals substantially 1,001,787 8/1965 Great Britain the term, 292,981 7/1965 Netherlands.
(2) as a second step,
reacting at least a portion of said oligomer (B) with ethylene glycol at a temperature in the range of 200250 C. to depolymerize the said oligomer (B), thus producing bis(fi-hydroxyethyl)-terephthalate or an oligomer (A) of bis(fi-hydroxyethyl)-terephthalate, said oligomer having an average degree of WILLIAM H. SHORT, Primary Examiner.
LOUISE P. QUAST, Assistant Examiner.
US. Cl. X.R.
Patent Citations
Referenced by
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Nuke 5 Essential Training was created and produced by Steve Wright. We are honored to host his material in the lynda.com Online Training Library®.
Nuke 5 Essential Training is designed for digital artists already familiar with compositing visual effects using programs like Adobe After Effects or Shake. This course provides a solid foundation in operating Nuke, using the core functions of keying, motion tracking, and color correcting, as well as Nuke's key strength, 3D compositing. Tour the Nuke user interface, its unique color management system, and overviews of HDR images, masking, keyframe animation, and 2D and 3D motion blur. Exercise files accompany the course.
The Auto Levels is designed to cope with very saturated colors. We didn't have any in our current composite, so I have prepared this test pattern, so you can see the effect. When supersaturated colors like these are keyed and composited, results tend to give you dark edges or colored fringes. The autolevels toggle is designed to cope with this. It trims the matte to shrink it down to get rid of these artificial edges. The autolevels toggle is over here, and it enables all the other three.
So, with it turned off, none of these have any effect at all. I turn the autolevels on, and you could see it got rid of the dark edges, but it has also introduced some discolorations in the Cyans and the Yellows. There you go! Also, if we look at the Alpha Channel, when I turn on the autolevels, I lose Opacity in the same Yellows and Cyans in the Alpha Channel. So, to guard against that, you turn on the autolevels, and if you want to protect the Yellows, you click the Yellow button.
So, that protects the Yellows from the autolevels setting. If you want to protect the Cyans, you turn on the Cyan button. With both of these toggles turned on, you have completely disabled the whole autolevels algorithm. It's the same as having it turned off entirely. So, in a composite, if you have those dark or colored fringes, try the autolevels button to see if it helps. More than likely, it'll help one part of the picture but ruin the rest of the composite. So, what you'll have to do is isolate the area that it helps and composite that separately from the rest of the picture.
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Waterloo house
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Starting on Wednesday 29th, 8pm to 9pm
Aikido is a Martial Art based on the principle of not interfering with the opponent. This means that no strength is required and it is suitable for everyone.
We follow the teachings of Alan Ruddock and Henry Kono (see picture below). Both studied Aikido with Morihei Ueshiba , the founder of Aikido.Both travel several times per year to Ireland to give seminars well worth attending.


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College of Complexes, Weekly Free Speech Forum Message Board › SEO,SMM and Web-Development Service
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Apartment Fire
Three-Alarm Fire Destroys 4 Units At Apartment Complex
Firefighters battled a three alarm fire at an apartment complex in Fort Collins early Wednesday morning.
Lightning Strikes, Starts Fire At Apartment Building
Lightning is believed to have started a fire at a condominium complex in Denver on Friday afternoon.
Fire At Denver High Rise Displaces 2
Two adults are out of their apartment after an early morning fire in Denver.
Community Rallies After High School Football Coach Loses Everything In Fire
A fire at the Verona Apartments in Littleton last week destroyed several apartments, including one belonging to a high school football coach.
Neighbors Bang On Apartment Doors To Warn Residents Of Fire
People in Littleton helped make sure everyone escaped an apartment fire by going door to door, banging on them, warning residents to get out.
Coroner's Office IDs Woman Killed In Aurora Apartment Fire
Authorities have released the name of a woman who was killed in a fire at an apartment complex in Aurora.
1 Killed In Apartment Fire In Aurora
Emergency crews rushed one person to the hospital after responding to an apartment fire in Aurora Monday morning.
Crews Douse Apartment Fire In South Denver, Children Among The Displaced
Firefighters responded to a two alarm fire at an apartment building in South Denver that left three adults and five children displaced.
1 Injured In Apartment Complex Fire In Fort Collins
One person has been injured in a three-alarm fire at a Fort Collins apartment complex
Denver Firefighters Find Man Dead After Responding To High Rise Fire Alarm
A man was found dead in an apartment fire at a Denver high rise Monday afternoon.


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Tavis Smiley | Nancy Brinker - 10/1/10 | PBS
Duration: 13:05
Program: Tavis Smiley #2100
Broadcast Date: Oct. 1, 2010
The "Susan G. Komen for the Cure" founder talks about breast cancer issues.Tags:
TAVIS SMILEY | Nancy Brinker | PBS (#2100)
Founder-CEO of Susan G. Komen for the Cure shares how breast cancer used to be an unattractive topic. 02:00
Tavis Smiley | Michael Hirsh -... (#2100)
Hirsh explains how the president's attention is needed for the state of the economy. 01:13
Tavis Smiley | Michael Hirsh -... (#2100)
Hirsh explains why President Obama must be taken to task for the state of the economy. 10:53
Tavis Smiley | The Supremes'... (#2755)
Full Program: The Supremes co-founder reflects on the 50th anniversary of the group's first album. 26:42
TAVIS SMILEY | Kristen Stewart... (#2751)
Actress Kristen Stewart tells Tavis how she handles the enormous media attention. For more information visit www.pbs.org 02:57
Tavis Smiley | Singer-songwriter... (#2745)
Full Program: The Grammy winner talks about her new project, 'Charmer'—her first CD in four years. 26:42
Tavis Smiley | Filmmaker Eugene...
Full Program: The filmmaker unpacks his documentary on America's war on drugs, 'The House I Live In.' 26:42
Tavis Smiley | Adam Nagourney | PBS (#2716)
The "NY Times" LA bureau chief explains why California's controversial Prop 32 ballot measure matters to the nation. 02:21
TAVIS SMILEY | Ethan Hawke | PBS (#2710)
The two-time Oscar nominee and "Sinister" star shares why he believes audiences appreciate horror films. To see this... 02:22
TAVIS SMILEY | Arianna... (#862)
From the DNC in Charlotte, Huffington discusses the power of social media over the conversations circling around... 01:34
TAVIS SMILEY | Kyra Sedgwick | PBS (#2680)
"The Closer" star reflects on the show's seven-year run and shares why she feels the program resonated with its... 01:52
TAVIS SMILEY | Ben Stein | PBS (#2679)
The economist and award-winning writer explains why he would never vote for a Democrat in an election. To see this... 02:44
TAVIS SMILEY | Daniel Wolff | PBS (#2677)
The author-filmmaker discusses sustaining the conversation about the Hurricane Katrina tragedy and the myth of... 02:58
TAVIS SMILEY | Newt Gingrich | PBS (#716)
The former GOP presidential candidate sheds light on what he believes Mitt Romney needs to do to connect with... 02:39
TAVIS SMILEY | Brian Castner | PBS (#2675)
The Iraq war veteran opens up about his experiences on the battlefield and how they've impacted his daily life,... 03:02
TAVIS SMILEY | Ralph Nader | PBS
The consumer advocate weighs in on the 2012 presidential race and on how voters should push politicians into action.... 02:32
TAVIS SMILEY | Jeff Foxworthy | PBS (#2672)
The comedian discusses the balance of teaching lessons about Christian ethics while avoiding proselytizing and why he... 02:42
TAVIS SMILEY | Erin Brockovich... (#2640)
The famed environmentalist discusses the documentary, "Last Call at the Oasis," and the challenge of spreading the... 03:46
TAVIS SMILEY | Eddie Levert | PBS (#2639)
The O'Jays frontman shares why, after all these years, he's decided to release his debut solo album, "I Still Got... 03:37
- Watch more video from this program
Post Date: October 4, 2010


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Who Is the Better Cook: You or Your Significant Other? [Poll]
I just read a national statistic on cooking. I'm curious how this plays out locally.
I just read a national statistic on cooking. I'm curious how this plays out locally.
We found a new cooking trick for you to learn this weekend.
Someone from Japan figured out how to create a reverse hard-boiled egg.
The video explains the key is to move the yolk while it's still inside the shell
Peeling carrots always seems to take forever but chef and food stylist Kara Michelson has come to the rescue!
She recently shared a technique she uses that is much faster
"As a chef, when we're cooking a lot of product, we might want to do a whole bag or a couple bags of carrots
You don't need a celebrity chef or your mom's homemade recipe to tell you how to cook a Thanksgiving turkey.
How about a simple shrimp alfredo recipe that almost everyone will love?
The decadently creamy Knorr Pasta Sides Alfredo becomes a delicious meal for four when you add juicy shrimp, plump cherry tomatoes and fresh spinach.
It's probably just easier to hit the drive-thru, but the nerdy cook in all of us really wants to know what is in the secret sauce.
Okay, mixing the word 'hack' with 'breakfast' does not sound good. How about easy ways to make a healthy breakfast? Nope, I'm a millennial - these are hacks!
News is a bit slow tonight, BUT it is still Fat Tuesday AND National Pancake day! That gives us plenty to discuss!
While surfing the world wide web of misunderstandings, I found a book that has to be the most depressing cookbook of all time. No joke.
Thanksgiving is just days away. It's time to get your turkey and all of the ingredients for the side dishes.
Then there's a big decision to be made...how to cook your turkey.
What is the tastiest way to cook a turkey?
If you're serious about combating childhood obesity and raising healthy children, here's one easy tip: teach your kids to cook.
I could eat!
Especially after seeing what the aspiring chef's of Top Chef Masters prepared for Maroon 5 during last night's episode!
The cooking competition is on Bravo every Wednesday at 11 p.m. -- my bedtime, thank goodness. Otherwise, I'd be in my kitchen preparing a late night snack and I need to stay away from the extra calories!


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In addition to their unquestionable value in environmental terms, Portugal's forests and the companies operating in the forestry sector are extremely important in the Portuguese economy - contributing about 10% of the country's exports, with Gross Value Added (GVA) equivalent to 1.2% of GDP and investment of about €2.4 million between 2000 and 2014.
The President of the Portuguese Republic and the Minister of Agriculture and Sea visited Corticeira Amorim on a day dedicated to Portuguese Forests
Hydrocork, The first low thickness, water resistant cork floating floor
Comprising a reduced thickness core of agglomerated cork composite, this new solution maintains all the characteristics of natural cork, with the added advantage of being water resistant, i.e. without the risk of possible swelling of the flooring.
Américo Amorim, a man with history, a living company
Américo Amorim's career path, at 80 years of age, remains a living example of the power of work and individual determination, inspiring multiple generations all over the world. A real story that is reaffirmed every personal and professional birthday of the Chairman of the Amorim Group.
Amorim invests 1 million euros in new projects of innovative applications for cork
The mission of Amorim Cork Ventures (a business incubator set up by Corticeira Amorim) is to promote entrepreneurship in order to enhance research and innovation activities in the cork industry. The newest Corticeira Amorim company was established with the purpose of fostering the creation/design of new cork products and cork-related businesses, mainly targeted at foreign markets.
Cork synonymous with quality wine
Consumer suerveys show that consistently and in different markets - USA, Australia, Germany and China - the cork stopper is a powerful selling point. In general - and in some countries unexpectedly - the natural closure is regarded as the preferred option for quality wines.
The Metamorphosis of cork
"This exhibition, with works by renowned architects and designers highlights the enormous potential of a product for which Portugal is the world leader. It clearly shows how innovation, creativity, the liaison between companies and research centres can add value to cork and promote it in a different manner, even in those sectors which are considered traditional in Portugal."
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At V inexpo, the two global leaders, Corticeira Amorim and O-I, unveiled "HELIX", an innovativecork-glass wine packaging solution for the fast turnaround wine segment.
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Located in the centre of Napa Valley, the project, with a total area of over 13,500 m² and a built area of 5,000 m², is the most innovative in the world.