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Gluten Free Phyllo Dough
Total Time
Prep 15 mins
Cook 0 mins
I have not tried this yet, but have been searching long and hard for such a recipe. From message board poster jenvan at celiac.com. Time and yield are estimates. Update 1/2/07: I finally tried this recipe! It was delicious and fairly easy to work with, but I was not able to roll it as thinly as I would have liked. I thought it tasted more like pie crust than phyllo dough, but everyone loved the flavor! This may become my new GF pie crust recipe! If anyone figures out how to roll it really thin I'd love to hear how you accomplished it!
Ingredients Nutrition
- Mix together rice flour, sweet rice flour, xanthan gum and gelatin.
- Make a well in dry ingredients large enough to hold the liquids.
- Lightly beat egg with ¼ C milk, butter and honey.
- Pour this into well in dry ingredients.
- Mix everything together until you have a soft dough. (Depending on brand of rice flour, you may want to stir in more milk).
- Wrap dough in plastic wrap until ready to use for your favorite holiday pastry.
- Store in refrigerator if not using immediately.
- *Use margarine or oil to make dairy-free dough.
Most Helpful
We used the dough for fried spring rolls, and we really enjoyed the taste. However, we has a tough time rolling out the dough since it's sticky. After trying wax paper, flour, and oil, we got lucky with plastic wrap. We placed plastic wrap between the dough and the counter top, as well as on top of the dough before using the rolling pin. That process was rather easy. We will be using this recipe again!
I have been looking for a GF pie crust recipe now for a long time. Thank you so much!!

subset: commoncrawl


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Changing the Perception of Aging
Click Here to listen to founder of Second Wind Dreams, P.K. Beville provide insight on this international nonprofit and its flagship programs on eCareDiary's radio show.
Making a Difference with Dreams
More than 10,000 dreams have been fulfilled nationwide since Second Wind Dream's founding in 1997. Join us in our mission.
Older Americans Month!
This month we celebrate older americans nationwide. Click Here to learn how you can get involved!
Join the ranks of the more than one million people in 17 countries who have experienced the Virtual Dementia Tour.
Second Wind Dreams is an international, nonprofit organization dedicated to changing the perception of aging through the fulfillment of dreams and the offering of educational programs including its flagship, sensitivity training, the Virtual Dementia Tour®.
The Virtual Dementia Tour® (VDT®) is a scientifically proven method that builds sensitivity and awareness in individuals caring for those with dementia by temporarily altering participants' physical and sensory abilities. This evidenced-based program simulates changes associated with cognitive decline. Geriatric specialist, P.K. Beville authored and invented the VDT as her post-graduate work. This patented program offers hope by providing practical ways to create an environment that supports the disease and increases understanding. More than one million people in 17 different countries have experienced the Virtual Dementia Tour.
The Virtual Dementia Tour is available in different formats to cater to every walk of life and provide ways to identify and better understand the behaviors and needs of those living with dementia. Proceeds of the VDT helps to fund elders' dreams through the Dreams Program of Second Wind Dreams.
The VDT® Comprehensive Program includes:
Click here to review the Terms & Conditions of Use/License Agreement.
For all international orders, please contact Second Wind Dreams directly.
The VDT is a unique, interactive program proven to improve communication and care. This easy to follow experiential training is designed for care giving facilities and community organizations to help identify with and understand patients' behaviors and needs. This Comprehensive Program has been used for new employees, hospitals, colleges and universities, and other caregivers. Upon the completion of VDT training, caregivers were able to identify with and better understand the behaviors and needs of those in their care.
When dementia strikes, it strikes the whole community, not just the individual. In addition to caregivers and staff, appropriate participants include:
Second Wind Dreams is committed to restoring faith and respect in our elders by engaging them, helping them achieve their dreams, and giving them a sense of self-worth. The dreams fulfilled by your donations range from the simple to the sublime - from having a Skype call with a daughter, to meeting the President. Help make a dream come true today.
Second Wind Dreams is a 501(c)3 non-profit organization and your donations are tax-deductible. Please help fulfill a dream here.
Watch our video to see how your donation is making a difference in the lives of our elders!Donate Today »
Join Second Wind Dreams and our award-winning Dreams Program as we shed light on the positive aspects of aging. And remember, you're never too old to dream!
Click here to learn more about the steps to fulfilling a dream.
Donations of time, talents, resources and monetary value are greatly appreciated in support of making dreams come true. There are so many ways to help!Dream Gallery »
Thank you for your interest in volunteering with Second Wind Dreams. We are excited to hear from people with a heart to help. To be added to our volunteer list and receive updates, please contact: mailto: email@example.com.
Explore the various volunteer opportunities at Second Wind Dreams.Find Out How »
Join more than 500 Second Wind Dreams members as we change the perception of aging through dream fulfillment for those living in eldercare communities nationwide. The Second Wind Dreams program is an opportunity to expose society to the truth that age does not erase hopes and dreams. We believe dreams can satisfy the most basic and pure part of us as humans, and would be honored to have you join our mission!
Learn more about the membership benefits with Second Wind Dreams.Become A Member »
At Second Wind Dreams, we are committed to ensuring our corporate partners are given the opportunity to have a significant role in their local communities, thereby becoming active participants in our global mission. Our programs give organizationsa unique and exciting way to engage its employees through community action and effect real change for an underserved, marginalized group of people. We do this by making dreams come true for our elders and creating more sensitive care for those with dementia.
Joining Second Wind Dreams mission will position your organization with nearly 45 million family members, friends and caregivers in the US alone who work diligently to serve this precious resource. We are confident that our programs will give your organization the opportunity to demonstrate its moral fortitude in a society where capitalism prevails.Become A Sponsor »
"My mom struggled with dementia for 12 years, but it wasn't until I spent 8 minutes inside the Virtual Dementia Tour that I truly understood what her world was like."
–Leeza Gibbons, Leeza's Care Connection
The Virtual Dementia Tour accurately simulates what it is like to live with dementia and common physical impairments that come with age. Watch this video to witness the profound effects.
Call us today: 678-624-0500 to learn more about the Family Edition of the Virtual Dementia Tour.
Fundamentals, Facilitator and Certified Training programs are important for the professional use of the VDT.
The Comprehensive Program is for eldercare communities, healthcare professionals and educators.
The sun shining above, the smell of the salty sea, the breeze blowing softly in your face, and the feeling of pure exhilaration while sailing out on the ocean. This is the dream of Ted Coronel. Ted is 93 years old and has always wanted to own a small sailboat and sail along the coast. Although we cannot help him to buy a boat, we would love to give him the opportunity to sail along the coast and experience something that he has only been able to dream about. Ted lives in our senior living community and has a knack for playing cards. He is always smiling. We want to put the biggest smile ever on his face. We want to get him out on the water sailing. Sail San Diego has a 3 hour sailing tour that allows someone like Ted to get out and sail the San Diego coast. He will need some assistance that we will be glad to give, but we need help to get him on the sailing tour. Will you help us to get him there?Donate to This Dream »
Rosemary is unique - and very, very busy! She is constantly on the go - and loves, loves, loves being outside. Her communication is really expressed through her sparkling eyes & laughter.
Rosemary's family recalls how happy she was at home, always working in the garden. She loves getting her hands in the dirt - and doing everything!
A raised bed, complete with cover, would be perfect for Rosemary. She would raise veggies and herbs - constantly being able to "get her hands right in there!"
Randy Coles, Maintenance Director here at Elmcroft of Arlington has contacted our lawn service, Green Briar, who has agreed to furnish the potting soil & plants. They will also install a watering line to the raised bed!
We still need funding for the raised bed itself - which will cost $371.96. We have a Commitment from Allstar Home Health for $100.00.Donate to This Dream »
At Azura Memory Care we know that there is no such thing as a dream too big or too small, and we are delighted to do whatever it takes for our residents to experience their best day. For Carlton in Kenosha, Wisconsin, it is to attend a baseball game one last time.
With your donation, you would not only help Carlton relive some of his best memories on a baseball diamond, but also provide him with the chance to once again experience a pastime he used to frequently enjoy prior to moving into his Azura home.
We strive to offer a unique model of memory care services and a program for those suffering with dementia and Alzheimer's disease, and it is through generous individuals like yourself that help make this possible. From everyone at Azura, we thank you for the continuous support as you help us achieve more dreams for our residents!
Donate to This Dream »
At Azura Memory Care we know that there is no such thing as a dream too big or too small, and we are delighted to do whatever it takes for our residents to experience their best day. For Darlene in Sheboygan, Wisconsin, it is to take care for animals and a garden. Our Azura Team has made plans for Darlene to visit a farm to visit with a few animals, and to go shopping for flowers to tend at our Azura Memory Garden.
With your donation, you would not only help Darlene experience a day that would bring joy to her life, but also provide her with the chance to enjoy the simple pleasures in life she used to frequently enjoy prior to moving to her Azura home.
We strive to offer a unique model of memory care services and a program for those suffering with dementia and Alzheimer's disease, and it is through generous individuals like yourself that help make this possible. From everyone at Azura, we thank you for the continuous support as you help us achieve more dreams for our residents!
Donate to This Dream »
We did a special Second Wind Dream today.
We have a very special lady Ms. Ella Owen Reed that turned 103 today. We had a birthday blowout. We had many friends, family and special dignitaries from the community here to honor Ms. Reed.
She had special visits from Wilson County Mayor Hutto, State Representative Mark Pody, Ms. Donna Wright from Wilson County Schools, and Mr. Scott Benson from Lebanon Special School District (LSSD).
Ms. Ella is a retired school teacher from LSSD. She taught for over 35 years and never missed a day. She started teaching in the Wilson County Schools in a one room school house with eight grades all together. When she retired, she was a teacher at Byers Dowdy for the 4th grade.
Also she had surprise visits from 4 of her former students and Mr. Winfrey that was the Superintendent of the school district when she retired.
We had a wonderful gathering and shared lots of memories. Also she had several friends from her church that attended that party.View This Dream »
Sue Hagewood is an 82 year old lady that resides at Elmcroft of Hendersonville. She has always loved children, and what better way to make her day but to take her to a day care facility and let her interact with the kids. She was ready for her little journey on June 29, complete with doughnuts to hand out to the children. First we watched the little ones on the playground, and then we went inside where all the children gathered around her while she told her stories of when she would sneak off to her grandmother's house. She handed out her doughnuts, smiling all the while. One young lady just couldn't get enough of Sue, and hung on to her and told her that she had a great grandmother, too. Sue was surprised that none of the children were bashful or afraid of her. (Maybe it was the doughnuts!!) Sue had a wonderful time being "grandma" again to all the children. One little girl asked her when she would be back, and Sue smiled so big and said "whenever they will bring me". It brought back a lot of memories of the days when Sue watched children in her home and taking care of her own grandkids.View This Dream »
At Azura Memory Care we know that there is no such thing as a dream too big or too small, and we are delighted to do whatever it takes for our residents to experience their best day. For Elsie in Kenosha, Wisconsin, it is to play a few games of Bingo at a local Moose Lounge with her family on Wednesday, July 8th.
With your donation, you would not only help Elsie relive some of her best days, but also provide her with the chance to once again experience a pastime she used to frequently enjoy prior to her moving into her Azura home.
We strive to offer a unique model of memory care services and a program for those suffering with dementia and Alzheimer's disease, and it is through generous individuals like yourself that help make this possible.
Your donation would provide Elsie with transportation, more Bingo cards than she can count, and food to enjoy while she once again delights in an old hobby with her family. From everyone at Azura, we thank you for the continuous support as you help us achieve more dreams for our residents!
View This Dream »
Nothing brings joy to Helen like a big bowl of her favorite ice cream. After discussing options for our dreamer with her family, we decided that an ice cream party with her as the guest of honor would bring her joy and give her a second wind at life.View This Dream »
When Marion, a resident at Azura Memory Care, was asked what her greatest day would be, she expressed her dream of attending a Broadway show and enjoy a little date with her daughters. This was something she had done numerous times prior to being diagnosed and thoroughly enjoyed. Hearing this, plans began immediately to help Marion relive one of her best days.
The local community was contacted in hopes of finding a theater company that would be able to provide accommodations for Marion's dream. Sure enough, it was discovered that the Overture Center in Madison, WI would soon be hosting the production Momma Mia!, and that Nick's Restaurant would be a perfect spot for her and her daughters to grab a bite to eat before the show, all while enjoying a mother-daughter date.
Unfortunately between with the limited available tickets at the Overture Center and Marion's fading eyesight due to the disease process, she wouldn't be able to properly view or enjoy the show. However, upon hearing this, the staff at the Overture Center quickly came to the rescue and found closer seats for Marion, her daughters, and a few caregivers completely free of charge. In addition, the Overture Center reached out to their partner, Broadway Across America, who contacted a few cast members. Upon hearing Marion's dream and story, nine of the cast members took time to meet with Marion after the show.
A special thank you to those who helped Marion relive one of her best day with her daughters. Without the support of community members and organizations, Azura would not be able to continue creating and executing magical MOSAIC moments!
View This Dream »
Mary Ruth never imagined she would ever find love again at age 82. Neither did Dick Schack. They met in the elevator of The Lafayette & then seated at the same table in the dining room. Sparks flew! Dick finally asked her out & after a short time they knew they wanted to marry! They wanted to keep it simple so only 2 staff were invited to their new apartment to witness the ceremony which was performed by a friend. It was wonderful. They then eloped for the weekend on their honeymoon. Upon their return they informed family & friends who were delighted for them.
A wedding reception will be Saturday June 13th at The Lafayette. Everyone is invited!View This Dream »
Victoria just loves animals! Her daughter lives in New York and will be visiting near her birthday. We have planned a day just for her. To start the dream off we will begin June 1st doing a month long donation for food for animals here at Elmcroft to be able to present in Victoria's honor to the shelter we visit. First she will have breakfast with her guests in the Ambassador Room that will be decorated for a true animal lover. Then we will head out to a shelter that she and her daughter have an association with. We will have a set up where she can visit with as many animals as time allows and photograph her with each animal. From there we will have Calendars printed for the family for the 2016 year.....View This Dream »
Lois & Wilma wanted to learn how to Line Dance so we contacted a local dance group "The Energizers" to inquire about their interest in teaching classes at The Lafayette Country Place Retirement Community. One of their members, Debi Binford, was happy to get involved. Lois & Wilma are dedicated students & they recently performed at our 30 year anniversary party to the delight of the crowd!
View This Dream »


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Select Local Merchants
South Carolina State Museum FoundationRead MoreThough built in 1893 to manufacture textiles, the Columbia Mills' storied stone halls now weave tapestries of knowledge with exhibits on everything from lasers and space travel to South Carolina's role in the Civil War. Boasting accolades by Columbia Metropolitan magazine and the Smithsonian, South Carolina State Museum devotes each of its four floors and part of its fourth dimension to art, cultural history, natural history, and science and technology represented by more than 70,000 artifacts. Through a series of permanent exhibits, curators lead visitors on a cultural and geological voyage. Guests stroll through years of traditional and contemporary art by state artists, marvel at a 43-foot white shark display and full dinosaur skeletons, or cast imaginations back in exhibits on turn-of-the-century transportation, laser technology, and aviation. The museum also excavates the surrounding landscape to present 14,000 years of local culture in Native American tools and colonial-era lifestyle items. Five galleries also house changing exhibits featuring assemblages of artifacts from Civil War–era Charleston or 300 years of American-made telescopes, each carefully monitored to ensure they contain just the right amount of science. While museum staffers frequently rotate their exhibits, they also host traveling displays and send others on the road through the Traveling Exhibits Program. Various education displays such as interactive children's labs, living-history reenactments, and lectures from visiting scholars further enrich all-ages visitors.301 Gervais St.Columbia, SC US
Charleston Pirate ToursRead MoreEric Lavender is one of very few men in the world who can show up for work each day in a pirate costume and expect to keep his job. The licensed guide and professional storyteller, who has been featured on networks such as the Travel Channel and SCETV, also has an unconventional coworker—Captain Bob, a chatty blue and gold macaw who perches on his arm. Sometimes aided by other guides in pirate and colonial garb, he introduces visitors to lesser-known aspects of Charleston's more than 300-year history on walking tours to National Historic Landmark buildings. During his signature pirate tour, Eric divulges stories of buccaneer revelry and crimes, such as Blackbeard's harbor blockade, or unveils local spooky legends and pieces of Gullah lore on his ghost and pirate tour. Eric also leads custom walking tours and teaches children about pirate lore and city history through his educational programs. Sabrina Lavender and companion Doozer, a yellow-naped Amazon, are also on hand to guide travellers around Charleston, learning about local landmarks and history.79 Cumberland St.Charleston, SC US
H. L. HunleyRead MoreIt was February 17, 1864. The USS Housatonic floated in Charleston Harbor atop calm, cold waters. Below the surface, a group of Confederate soldiers sweated bullets as they cranked the propellers of the H. L. Hunley, speeding toward the Union's Housatonic on a historic mission: they would become the first submarine crew ever to sink an enemy ship. A 135-pound torpedo struck the Housatonic's stern, detonating a fiery explosion that sank the vessel within minutes. The Hunley then surfaced just long enough for the crew to flash a blue magnesium light, signaling to fellow forces on the shore that the mission succeeded and the submarine would return. And it did—but not until almost 140 years later, when it was raised from the harbor's sandy bottom on August 8, 2000, after author Clive Cussler discovered the wreck intact. Today, the leaders of the nonprofit H. L. Hunley Submarine seek to conserve, restore, and ultimately exhibit this historic vessel, as well as solve the mystery of how it completed its mission only to vanish moments later. They welcome visitors to see the submarine in its current condition—within a 90,000-gallon conservation tank—and educate guests on the vessel's many details. Guides walk guests through features such as the manual-propulsion system and automatic moon roof, and illuminate exhibits such as a lifesize model from the TNT movie The Hunley.1250 Supply St.North Charleston, SC US
Wine and Design CharlestonRead MoreThe faculty of local artists at Wine and Design in West Ashley and Mt. Pleasant helps students create works of art in a social, supportive setting with lessons designed for people with no artistic experience. After uncorking bottles of wine and kegs of paint, budding artists spend two hours imitating pros stroke for stroke as they transform canvases into paintings of colorful landscapes and vibrant still lifes. Guests of any experience level are welcome and Wine and Design provides all necessary materials, including paint, brushes, and corkscrews. In addition to regular classes, Wine and Design offers private parties and Art Buzz summer camp for kids at both Mt. Pleasant and West Ashley. In an effort to paint it forward (Mt. Pleasant and West Ashley), they also donate funds to causes, such as Relay For Life and the MUSC Children's Hospital.424 Broadway StMount Pleasant, SC US
Culture and Heritage MuseumsRead MoreCulture & Heritage Museums safeguard the Carolina Piedmont's historical treasures and educate residents and visitors about the region's unique past. Instituted in the 1950's, York County's group of affiliated museums and attractions forms a multi-campus network encompassing a wealth of educational opportunities across various disciplines. Each year, museumgoers view antique documents and photographs at the Historical Center located inside the McCelvey Center. They can get to know more than 1,500 natural specimens at the hands-on Naturalist Center inside the Museum of York County, and march through Historic Brattonsville's 775-acre Revolutionary War site. Locals can volunteer at the museums in fascinating roles, such as specimen preparers, who beautify avian exhibits by helping with taxidermy and surgical beak-lifts.4621 Mount Gallant RdRock Hill, SC US
Bju Museum & Gallery IncRead MoreWhat began as fewer than 30 paintings hanging in two rooms has since grown into the Bob Jones University Museum & Gallery, a collection of more than 400 baroque paintings displayed in 30 galleries. The paintings—works by Rubens, van Dyck, and Murillo that date from the 14th through 19th centuries—are thoughtfully displayed in context, surrounded by furniture, sculptures, tapestries, and popular emoticons from their respective time periods. Architectural elements also add texture to the various galleries, flooding them in colorful light from stained-glass windows or framing their walls with the carved corners of fireplace mantels. At Heritage Green, a satellite location boasts special exhibits of works pulled from the main galleries or on loan from private and public collections. Up on the second floor, interactive exhibits educate visitors of all ages on works by the old masters.1700 Wade Hampton BoulevardGreenville, SC US


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VIEWS: 9 PAGES: 1 POSTED ON: 10/3/2012 Public Domain
Attachment B, DJJ 11.1 GEORGIA DEPARTMENT OF JUVENILE JUSTICE Office of Health Services Youth Medical Services Orientation Form During the first week you are admitted to , the medical staff will ask you about your health history, you will be given immunizations that are needed and blood work will be done, if needed. You will have a physical examination done by the doctor, nurse practitioner or physician assistant. Cooperate fully with the medical staff by giving honest information. They are here to help you. All medical information that you give the medical staff will be kept confidential in most cases. If you become sick and want to be seen by the Medical Department, Dental Clinic or Mental Health Department, you should do the following: 1. Get a Help Request Form from any of the designated areas in the facility. 2. FILL OUT THE TOP of the form (be sure to be specific as to what your needs are). 3. Put your completed Help Request form in the locked Help Request box. The medical staff will collect all Help Request forms daily. A nurse will review your Help Request and you will be scheduled to see a staff member from the service you requested according to your medical, dental, mental health, or counseling needs. DO NOT pretend to be sick or injured when you are not. If you have a chronic medical problem, you will be monitored as needed by the medical staff. A chronic condition can be asthma, high blood pressure, diabetes, seizures, heart problems or others. If you have a medical problem, the nurse will call and verify this problem with your parent/guardian. If you need medication or bring medication with you, the doctor must approve these medications before they are given to you. If the doctor approves the medication, it will be given to you as prescribed. Take all medications given to you according to directions. DO NOT try to hide or save medications, and DO NOT give your medications to someone else. If you are found to be doing this, your medications will be crushed or given to you in liquid form. You have the right to refuse medical treatment. You must sign a refusal form each time when refusing to follow the doctor's orders for medications, treatments, procedures or test. Your counselor, parent/guardian, JPPS and the doctor will be notified when non-compliant with medical treatment and medications. Feel free to speak with the medical staff about problems or questions with treatments or medications before refusing to see if they can be corrected. I have read or have had read to me, the information above and understand its content. _________________________________________ ________________________________ Print Youth Name Date of Birth (DOB) ___________________________________________ ________________________________ Student Signature Date/Time ___________________________________________ ________________________________ Medical Staff Signature/Title Date/Time Rev. 08/12
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List all words starting with cental
2 words found.
List all words starting with cental sorted by length or by how common the words are.
Some random words: tuatara vocable sky takin wrack odd rijsttafel
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Town Square
Epicure: A year of recession cooking
Original post made on Jan 6, 2009
Read the full story here Web Link posted Thursday, January 1, 2009, 12:48 PM
Comments (1)
a resident of San Ramon
on Jan 6, 2009 at 12:50 pm
I appreciate this column, especially this week's. I am having a tough time and cooking for pennies is tough. Also, thanks for the websites too.
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Results 1 to 6 of 6
Thread: Nightcity Concept sketch...
July 4th, 2006 #1
Nightcity Concept sketch...
My first conceptual artwork. This should be a sort of metro entrance or something... I'm not to happy with the perspective.
Photoshop: in about an hour...
I'm working on a more detailed version...
Hope you like it...
Hide this ad by registering as a memberJuly 4th, 2006 #2
your first? I find that hard to believe, wonderful color and feel.
July 4th, 2006 #3
Thx... It is, though... I never painted something architectual... I'll be doing more of this stuff, I hope.
July 4th, 2006 #4
I just went to your site, very nice work.
Architectural and design steeped and bound by the constructs of perspective are very difficult for many artists steeped in character design background, it uses a different part of the brain, so if this is your first thumbnail, then well done.
July 4th, 2006 #5
That's great to hear... I'll try to rework that pic with some more definition on it...
July 4th, 2006 #6
Yeah, I don't think the perspective is quite right either. The entrance to the tunnel and the tunnel itself doesn't line up with the rest of the structures. So far, the lighting effect looks great, any plans to take this farther?


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Chinese lesbian couple snubbed by registry official
February 13, 2013
"Mayu Yu, a 27-year old social worker from Beijing, said a male official at the registry told her and her partner that they could not be registered because the law did not recognise a marriage between two women. The couple decided to challenge the marriage law because they had been emboldened by a growing number of countries embracing gay marriage.
The video below shows the couple talking to Pu Cunxin, a Chinese actor and a member of Chinese People's Political Consultative Conference."
Other China Video
South Koreans dead in China bus crash
3 Jul 2015
China stocks slide despite easing boost
30 Jun 2015
Japan surveillance plane flies over South China Sea
24 Jun 2015
Dog meat festival draws fans and opponents
23 Jun 2015
Chinese tourists saying 'nihao' to America
21 Jun 2015
Hollywood looks to China to help boost their film industry
18 Jun 2015


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Getting into Heaven, its 1 in 1000, take it serious - Ministry Videos
Fighting on the 7 Mountains, Seven Mountain Mandate / Cultural War - @robertbrownell
00:36:59 336 views
3 Days to Victory, The Amazing story of what Jesus did during those 3 days in the grave. - @robertbrownell
00:21:09 282 views
Embed robertbrownell 3017 views 2012-10-10T04:34:05 During a tragic Near Death Experience, A conservative Presbyterian Pastor named Yong Park was taken to Heaven and Hell. He was shown why some saints are richly rewarded in Heaven, while others have no reward; why some saints have magnificent Mansions in Heavens, while others live in small Community homes. He was shown why, after serving the Lord his whole life, his house was still small and unfinished. He also witnessed how gruesome Hell was, and why so many Christians wound up there; and what sins we must repent of. Pastor Park's testimony is a wake up call to the Church, it will encourage those who are serving Jesus faithfully, it will strengthen your resolve for Jesus, and will bring the Fear of God to those who are not living Holy.
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Jesus Of Nazareth Book "Zealot" To Be Adapted Into Feature Film
Reza Aslan's Zealot: The Life and Times of Jesus of Nazareth, the subject of a rather infamous FoxNews.com interview, was picked up by Lionsgate.
Zealot: The Life and Times of Jesus of Nazareth, the somewhat controversial historical book about Jesus by Dr. Reza Aslan, will be adapted by Lionsgate into a feature film, the studio announced late Wednesday.
"I am thrilled to have the opportunity to work with Lionsgate," Aslan said in a statement. "Their vision for Zealot: The Life and Times of Jesus of Nazareth is aligned with my objective in writing the book, which was to illuminate the life of Jesus in a humanistic, as opposed to religious, context."
There are no other filmmakers attached to the project.
Aslan's book came under scrutiny less for its historically based assertions — for one, Aslan contended that Jesus' mother Mary was likely not a virgin when Jesus was born — than for Aslan's Muslim heritage. Aslan was born in Iran to a secular Muslim family, and after moving to America, converted as a teenager to Christianity before leaving the faith and returning to Islam.
He also spent 20 years working as a religious scholar, earning a Ph.D. in the sociology of religions from the University of California, with a speciality in the New Testament. Those extensive credentials especially became a focal point during a contentious interview on FoxNews.com's Spirited Debate, in which the host of the show kept asking Aslan about his qualifications to write a book about Jesus.
- Police in Athens used pepper spray on protesters two days ahead of Greece's major bailout vote.
- A medical helicopter crashed in Colorado. The crash killed the pilot and injured two crew members.
- Serena Williams survived an upset at Wimbledon and defeated current Britain's Heather Watson. She'll play her older sister Venus in the next round of the tournament ?


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Prop. 8 ruling
Evidently the judge is out of it a bit. To clarify, let's state it clearly so he can understand life, along with the people that are seeking marriage.
Let's see, God created Adam & Eve; it worked.
(Then God thought: maybe create two Adams on one side of the world and two Eve's on the other side of the world? Hmmm ... if they do not meet each other, I would not have a human generation to populate this world I created.)
Good thinking. That's why we call him God, not senator, congressman, lawyer or judge.
- Russell E. Spencer Sr.,
Simi Valley
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Netflix Renews ORANGE IS THE NEW BLACK for Third Season
Lock up your screwdrivers and hide the pie!
Ahead of its second season premiere, Netflix has renewed its hit series Orange is the New Black for a third season.
Laura Prepon broke the news on her Instagram account today, posting, along with the photo to the left: "It's official!! Season 3!! #oitnb #alexvause#backtothebighouse"
The second season of ORANGE IS THE NEW BLACK, consisting of 13 episodes, debuts next month, on June 6, 2014.
The highly-anticipated second season of Netflix's Orange is the New Black goes back behind bars for another sentence with the fearless, funny and unforgettable inmates of Litchfield prison. The series' ensemble includes Taylor Schilling, Jason Biggs, Prepon, Kate Mugrew, Danielle Brooks, Uzo Aduba, Natasha Lyonne, Taryn Manning, Laverne Cox, Michael Harney, Samira Wiley, Yael Stone and more. Lorraine Toussaint joins the cast in season two as Yvonne "Vee" Parker.
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The invention provides for highly crystalline syndiotactic polypropylene comprising a high percentage of racemic (r) dyads. The high crystallinity may be due to the polymerization mechanism of metallocene catalysts of a particular structure which appear to produce syndiotactic polypropylene of a new microstructure.
1. Syndiotactic polypropylene having a value greater than or equal to 0.83.
2. Syndiotactic polypropylene as in claim 1 having a value greater than or equal to 0.89.
3. Syndiotactic polypropylene having a value from about 0.75 to 0.95.
4. Syndiotactic polypropylene as in claim 3 having a value from 0.757 to 0.88.
This is a continuation-in-part of application Ser. No. 07/220,006 filed on Jul. 15, 1988, now abandoned.
1. Field of the Invention
The invention relates to highly crystalline syndiotactic polypropylene and, particularly, to syndiotactic polypropylene having a syndiotactic index of greater than 75%.
2. Description of the Prior Art
As known in the art, syndiotactic polymers have a unique stereochemical structure in which monomeric units having enantiomorphic configuration of the asymmetrical carbon atoms follow each other alternately and regularly in the macromolecular main chain. Syndiotactic polypropylene was first disclosed by Natta et al, in U.S. Pat. No. 3,258,455. The Natta group obtained syndiotactic polypropylene by using a catalyst prepared from titanium trichloride and diethyl aluminum monochloride. A later patent to Natta et al, U.S. Pat. No. 3,305,538, discloses the use of vanadium triacetylacetonate or halogenated vanadium compounds in combination with organic aluminum compounds for producing syndiotactic polypropylene. U.S. Pat. No. 3,364,190 to Emrick discloses a catalyst system composed of finely divided titanium or vanadium trichloride, aluminum chloride, a trialkyl aluminum and a phosphorus-containing Lewis base as producing syndiotactic polypropylene.
As disclosed in these patent references and as known in the art, the structure and properties of syndiotactic polypropylene differ significantly from those of isotactic polypropylene. The isotactic structure is typically described as having long sequences of monomer units with the same relative configuration of the tertiary carbon atoms. Using the Fischer projection formula, the stereochemical sequence of isotactic polypropylene is described as follows: ##STR1## The methyl groups attached to the tertiary carbon atoms of successive monomeric units on the same side of a hypothetical plane through the main chain of the polymer, e.g., the methyl groups are all above or below the plane.
Another way of describing the structure is through the use of NMR. Bovey's NMR nomenclature for an isotactic pentad is . . . mmmm . . . with each "m" representing a "meso" dyad or successive methyl groups on the same side in the plane. As known in the art, any deviation or inversion in the structure of the chain lowers the degree of isotacticity and crystallinity of the polymer.
In contrast to the isotactic structure, syndiotactic polymers are those in which long sequences of monomer units have an alternating relative configuration of the tertiary carbon atoms. Using the Fischer projection formula, the structure of a syndiotactic polymer is designated as: ##STR2## The methyl groups attached to the tertiary carbon atoms of successive monomeric units in the chain lie on alternate sides of the plane of the polymer.
In NMR nomenclature, this pentad is described as . . . rrrr . . . in which each "r" represents a "racemic" dyad, i.e., successive methyl groups on alternate side of the plane. The percentage of r dyads in the chain determines the degree of syndiotacticity of the polymer. Syndiotactic polymers are crystalline and like the isotactic polymers are insoluble in xylene. This crystallinity distinguishes both syndiotactic and isotactic polymers from atactic polymer that is soluble in xylene. Atactic polymer exhibits no regular order of repeating unit configurations in the polymer chain and forms essentially a waxy product.
While it is possible for a catalyst to produce all three types of polymer, it is desirable to produce predominantly isotactic or syndiotactic polymer with very little atactic formed. Catalysts that produce isotactic polyolefins are disclosed in European Patent Application No. 87870132.5 (Publication No. 0 284 308) published Oct. 5, 1988 and U.S. Pat. Nos. 4,794,096 issued Dec. 27, 1988 and 4,975,405 issued Dec. 4, 1990. These applications disclosed chiral, stereorigid metallocene catalysts that polymerize olefins to form isotactic polymers and are especially useful in the polymerization of a highly isotactic polypropylene. The present invention, however, utilize a different class of metallocene catalyst that are useful in the polymerization of syndiotactic polyolefins, and more particularly syndiotactic polypropylene.
The present invention provides highly crystalline syndiotactic polypropylene. It was discovered that the catalyst structure affected the formation of a syndiotactic polymer as opposed to an isotactic polymer. One theory, without limiting the scope of the claims of the present invention, is that the catalyst structure appears to affect the type and number of deviations in the chain from the principally repeating units in the polymer. Previously, the catalyst used to produce syndiotactic polypropylene were believed to exercise chain-end control over the polymerization mechanism. These previously known catalysts, such as the ones disclosed by Natta et al in the references cited above, produce syndiotactic polymers which primarily have the following structure: ##STR3## or in NMR nomenclature . . . rrrmrrr . . . The NMR analysis for this structure of syndiotactic polypropylene is shown in Zambelli, et al., Macromolecules, Vol. 13, pp 267-270 (1980). Zambelli's analysis shows the predominance of the single meso dyad over any other deviations in the chain.
The present invention provides syndiotactic polypropylene having a high syndiotactic index. The highly crystalline syndiotactic polypropylene is obtained through use of a stereorigid metallocene compound described by the formula
R"(C5 R4)(C4 R'4 C5 C4 R'4)MeQp
wherein (C5 R4) is a cyclopentadienyl ring or substituted cyclopentadienyl ring; (C4 R'm C5 C4 R'n) is a substituted cyclopentadienyl ring, preferably a fluorenyl radical; each R and R' is hydrogen or hydrocarbyl radical having from 1-20 carbon atoms, a halogen, an alkoxy, and alkoxy alkyl or an alkylamino radical, each R and R' may be the same or different; (C5 R4) has bi-lateral or pseudo bi-lateral symmetry for the proximal carbon atoms and bi-lateral symmetry only for the distal carbon atoms, "proximal" referring to position 2 or 5 of the cyclopentadienyl rings and "distal" referring to position 3 or 4 of the cyclopentadienyl ring relative to the carbon attached to R" (position 1), i.e., proximal being near the bridgehead carbon and distal being away from the bridgehead carbon; R" is a structural bridge between the (C5 R4) and (C4 R'4 C5 C4 R'4) rings to impart stereorigidity and, preferably, is a hydrocarbyl radical having 1-4 carbon atoms, a silicon hydrocarbyl compound, agermanium hydrocarbyl compound, an alkyl phosphine, an alkyl amine, a boron compound or an aluminum compound and may be unsubstituted or substituted with hydrocarbyl groups, such as an alkyl, aryl, alkylaryl or arylalkyl radical, to form the bridge; Q is a hydrocarbyl radical, such as an alkyl, aryl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a Group IIIB, IVB, VB, or VIB metal as positioned in the Periodic Table of Elements; and p is the valence of Me minus 2. It was discovered that the use of a metallocene catalyst as described above product highly crystalline syndiotactic polypropylene.
The highly crystalline syndiotactic polypropylene is obtained by introducing at least one of the compounds described by the above formula with a cocatalyst or ionizing agent, such as alumoxane, into a polymerization reaction zone containing propylene monomer. In addition, an electron donor compound, such as an organosilicon compound and/or a scavenging agent, such as an aluminum alkyl, may be introduced into the reaction zone. Further, the catalyst may also be pre-polymerized prior to introducing it into the reaction zone and/or prior to the stabilization of reaction conditions in the reactor. The prepolymerization of the catalyst system can occur by contacting the metallocene compound with a small amount of the cocatalyst or ionizing agent and an olefin monomer at a temperature below that at which polymerization occurs in the reaction zone.
FIG. 1 is an illustration of the structure of a catalyst useful in producing highly crystalline syndiotactic polyolefins. FIG. 1 specifically shows isopropyl(cyclopentadienyl)(fluorenyl) hafnium dichloride.
FIG. 2 is an illustration of the structure of the preferred catalyst useful in producing highly crystalline syndiotactic polyolefins. FIG. 2 specifically shows isopropyl (cyclopentadienyl)(fluorenyl)zirconium dichloride.
FIG. 3 is an NMR spectra for the polymer produced in Example 1 with the polymer being recrystallized once from xylene.
FIGS. 4 and 5 are IR spectra for the polymers produced in Examples 7 and 8 respectively with the polymer being recrystallized three times from xylene.
The present invention provides highly crystalline polypropylene. The polymer consists of a high percentage of racemic dyads, i.e., greater than 75%.
When propylene or other alpha-olefins are polymerized using a catalyst consisting of a transition metal compound, the polymer product typically comprises a mixture of amorphous atactic and crystalline xylene insoluble fractions. The crystalline fraction may contain either isotactic or syndiotactic polymer, or a mixture of both. Highly iso-specific metallocene catalysts are disclosed in European Patent Application No. 87870132.5 (Publication No. 0 284 708) published Oct. 5, 1988 and U.S. Pat. Nos. 4,794,096 issued Dec. 27, 1988, and 4,975,405 issued Dec. 4, 1990. In contrast to the catalysts disclosed in those applications, the catalysts useful in producing the polymers of the present invention are syndio-specific and produce a polymer with a high syndiotactic index. Some of these catalyst are disclosed in U.S. Pat. No. 4,892,451. It was discovered that syndiotactic polypropylene has lower heats of crystallization than the corresponding isotactic polymers. It has been discovered that the catalysts disclosed in U.S. Pat. No. 4,892,451 appear to produce a polymer with a different microstructure than that previously known. These new catalysts produce syndiotactic polymers which are believed to primarily have the following structure: ##STR4## or in NMR nomenclature . . . rrrmmrrr . . .
The polymerization mechanism of these catalysts produces polymer having a high percentage of racemic dyads in the structure and is known to be an enantiomorphic site control mechanism, different from the previously known chain-end control mechanism.
In the prior art, Lotz et al, (Macromol, 2378 (1988)) obtained polymer with a syndiotactic dyad fraction of [r]=0.769, which was produced in heptane solvent and precipitated in methanol. Doi et al (Macromol, 12, 248 (1979)) obtained a polymer whose [rr]-value was as high as 0.76, which was produced in heptane solvent and repeatedly washed by ethyl alcohol. The highest [r]-value by Doi was reported as 0.81 (Makromol. Chem., 186, 2529 (1985). Zambelli et al., (Macromolecules, 7, 750 (1974)) reported [rrrr]-value as high as 0.51, which was produced in toluene, had syrupy consistency, coagulated and precipitated with excess methanol [J. Polymer Sci.(pt-C 4, 411 (1963))].
As for the solubility of syndiotactic polypropylene in hydrocarbons, Natta succeeded in separating syndiotactic polypropylene from the mixture consisting of amorphous, isotactic and syndiotactic portions by solution chromatography, adopting highly crystalline and high molecular weight isotactic polypropylene as absorbent, and then eluting with isoPr2 O, n-hexane and n-heptane, successively, under somewhat below boiling temperature (Atti accad. Nazl. lincei Rend, class Sci. Fis.Mat.Nat., 28, 539 (1960)). Marchetti et al., obtained solution-grown single crystals of syndiotactic polypropylene from a dilute solution of hydrocarbons. (J. Polymer Sci., Polymer Physics ed., 12, 1649 (1974). Dissolution temperature of syndiotactic polypropylene are reported 36.5� C. for n-hexane, 38.5�-46� C. for n-heptane, and crystallization temperature is 0� C. for hexane and heptane. (No data are reported as to the result from n-dodecene grown crystals). There is no disclosure in the prior art that syndiotactic polypropylene is soluble in cold (0� C.) xylene.
The metallocene catalyst of the present invention may be described by the formula:
R"(C5 R4)(C4 R'4 C5 C4 R'4)MeQp
wherein (C5 R4) is a substituted or unsubstituted cyclopentadienyl ring; (C4 R'm C5 C4 R'n) is a substituted cyclopentadienyl ring preferably a fluorenyl radical; each R and R' is hydrogen or hydrocarbyl radical having from 1-20 carbon atoms, a halogen, an alkoxy, and alkoxy alkyl or an alkylamino radical, each R and R' may be the same or different; (C5 R4) has bi-lateral or pseudo bi-lateral symmetry for the proximal carbon atoms and bi-lateral symmetry only for the distal carbon atoms, "proximal" referring to position 2 or 5 of the cyclopentadienyl rings and "distal" referring to position 3 or 4 of the cyclopentadienyl ring relative to the carbon attached to R" (position 1), i.e., proximal being near the bridgehead carbon and distal being away from the bridgehead carbon; R" is structural bridge between the (C5 R4) and (C4 R'4 C5 C4 R'4) rings to impart stereorigidity and, preferably is a hydrocarbyl radical having 1-4 carbon atoms, a silicon hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, an alkyl amine, a boron compound or an aluminum compound and may be unsubstituted or substituted with hydrocarbyl groups, such as an alkyl, aryl, alkylaryl or arylalkyl radical, to form the bridge, e.g., R" may be n-propyl or isopropyl in that it can be three linear carbon atoms or one branched carbon atom with methyl groups attached; Q is a hydrocarbyl radical such as an alkyl, aryl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a Group IIIB, IVB, VB, or VIB metal as positioned in the Periodic Table of Elements; and p is the valence of Me minus 2. The structure of the metallocene compound is given below: ##STR5##
In order to be syndio-specific, it was discovered that the C5 R4 ring in the metallocene compound must have bi-lateral or pseudo bi-lateral symmetry for the proximal carbon atoms and bi-lateral symmetry only for the distal carbon atoms. Proximal refers to position 2 or 5 of the cyclopentadienyl rings and distal refers to position 3 or 4 of the cyclopentadienyl ring relative to the carbon attached to R" as shown below. ##STR6## Proximal carbon atoms are those near the bridgehead carbon and distal carbon atoms are those away from the bridgehead carbon.
Bilateral symmetry is defined as the condition in which there is no substituents or one or moire substituents on one side and no substituents or one or more substituents on the other side in the same relative position such that a mirror image is formed from one side to another. One example of such a compound is isopropyl (cyclopentadienyl-1-fluorenyl)zirconium dichloride, abbreviated iPr[Cp(Flu)]ZrCl2. An illustration of the ligands of this compound are shown below: ##STR7## Bilateral symmetry is illustrated by the ligands having their right side being a mirror image of their left side.
Pseudobilateral symmetry is defined as symmetry such that a mirror image exists from one side to the other in regard to the existence and position of substitutents but the substitutents themselves are not identical. This is illustrated below: ##STR8## Pseudobilateral symmetry is illustrated by the substituents being in the same relative position, i.e., forming a mirror image as to location of substituents on the cyclopentadienyl ring, but the substituents are not the same.
In a preferred catalyst useful in producing polymers of the present invention (C5 R4) is preferably cyclopentadienyl (C5 H4), (C4 R'4 C5 C4 R'4) is preferably fluorenyl (C4 H4 C5 C4 H4), Me is preferably titanium, zirconium or hafnium; R" is preferably isopropyl; Q is preferably a halogen, and, most preferably, chlorine; and p is preferably 2. FIG. 1 shows the structure of a iso-propyl (fluorenyl)(cyclopentadienyl)hafnium dichloride. The zirconium analogue of the catalyst shown in FIG. 2 is preferred.
The catalyst may be prepared by any method known in the art. U.S. Pat. No. 4,892,451, hereby incorporated by reference, discloses two methods of preparing the catalyst with the second method being preferred as it produces a more stable and active catalyst. It is important that the catalyst complex be "clean" as the purity will affect the molecular weight and structure of the polymer produced. Generally, the preparation of the catalyst complex consists of forming and isolating the Cp or substituted Cp ligands which are then reacted with a halogenated metal to form the complex.
The metallocene catalysts of the present invention are useful in many of the polymerization processes known in the art including many of those disclosed for the preparation of isotactic polypropylene. When the catalyst of the present invention are used in these types of processes, syndiotactic polymers are produced rather than isotactic polymers. Further examples of polymerization processes useful in the preparation of polymers described by the present invention include those disclosed in U.S. Pat. Nos. 4,767,735 issued on Aug. 20, 1988, and 4,975,403 issued Dec. 4, 1990, the disclosures of which are hereby incorporated by reference. These preferred polymerization procedures include the step of prepolymerizing the catalyst.
Consistent with the prior disclosures of metallocene catalysts for the production of isotactic polymers, the catalysts of the present invention are particularly useful in combination with an aluminum cocatalyst, preferably an alumoxane, an alkyl aluminum, or a mixture thereof. In addition, a complex may be isolated between a metallocene catalyst as described herein and an excess amount of aluminum cocatalyst in accordance with the teachings of European Patent Publication No. 226,463 published on Jun. 24, 1987 assigned to Exxon Chemical Patent Inc. with Howard Turner listed as the inventor. The alumoxanes useful in combination with the catalysts of the present invention may be represented by the general formula (R--Al--O--) in the cyclic form and R(R--Al--O)n --ALR2 in the linear form wherein R is an alkyl group with one to five carbon atoms and n is an integer from 1 to about 20. Most preferably, R is a methyl group.
The Examples given below illustrate the present invention and its various advantages and benefits in more detail. The catalyst is iso-propyl(fluorenyl) (cyclopentadienyl) zirconium dichloride or iso-propyl(fluorenyl) (cyclopentadienyl) hafnium dichloride depending on the example. FIG. 1 shows the structure of the hafnium catalyst. The zirconium catalyst shown in FIG. 2 has essentially the same structure with Zr positioned in the place of the Hf atom.
The Examples below illustrate the preparation of the polymers of the present invention and its various advantages in more detail. The results of the polymerization process and the analysis of the polymer are shown in Table 1 for Examples 1-17 and Table 2 for Examples 18-33.
The polymerization of propylene was carried out using 0.16 mg of isopropyl(cyclopentadienyl)(fluorenyl) zirconium dichloride produced in accordance with Method A us U.S. Pat. No. 4,892,451. The catalyst was purified using fractional recrystallization. The catalyst was precontacted for 20 minutes with a toluene solution containing 10.7% by weight of methylalumoxane (MAO) with an average molecular weight of about 1300. The alumoxane serves as a co-catalyst in the polymerization reaction. Ten cc of the MAO solution was used in the polymerization. The catalyst and cocatalyst solution was then added to a Zipperclave reactor at room temperature followed by the addition of 1.2 liters of liquid propylene. The reactor contents were then heated to the polymerization temperature, T as shown in Tables 1 and 2, of 20� C. in less than about 5 minutes. During this time, prepolymerization reaction was allowed to run for 60 minutes during which time the reactor was maintained at the polymerization temperature. The polymerization was terminated by rapidly venting the monomer. The reactor contents were washed with 50% methanol in dilute HCl solution and dried in vacuo. The polymerization yielded 14 gms of polypropylene "as polymerized" i e. without any further isolations or purification.
The polymer was analyzed to determine the melting point Tm, the heat of crystallization Hc, the molecular weights (Mp, Mw, and Mn) and the syndiotactic index. Unless otherwise noted, the analyses were performed on the xylene insoluble fraction of the polymer which includes the syndiotactic fraction and any isotactic polymer produced. The atactic polymer was removed by dissolving the polymer product in hot xylene, cooling the solution to 0� C. and precipitating out the xylene insoluble fraction. Successive recrystallization performed in this manner result in removing essentially all atactic polymer from the xylene insoluble fraction.
The melting points, Tm, were derived using Differential Scanning Calorimetry (DSC) data as known in the art. The melting points, Tm1 and Tm2 listed in Tables 1 and 2 are not true equilibrium melting points but are DCS peak temperatures. In syndiotactic polypropylene, it is not unusual to get an upper and a lower peak temperature, i.e., two peaks, and both melting points are reported in Tables 1 and 2 with the lower melting point reported as Tm1 and the higher point as Tm2. True equilibrium melting points obtained over a period of several hours would most likely be several degrees higher than the DSC lower peak melting points. As is known in the art, the melting points for polypropylene are determined by the crystallinity of the xylene insoluble fraction of the polymer. This has been shown to be true by running the DSC melting points before and after removal of the xylene soluble or atactic form of the polymer. The results showed only a difference of 1�-2� C. in the melting points after most of the atactic polymer was removed. As shown in Table 1, the melting points were determined to be 145� C. and 150� C. for the polymer produced in Example 1. DSC data was also used to determine the heat of crystallization, --Hc as shown in Tables 1 and 2 measured in J/g. The melting points and --Hc were determined on the "as polymerized" sample before the atactic polymer was removed.
The molecular weights of the polymer were calculated using Gel Permeation Chromatography (GPC) analysis done on a Waters 150C instrument with a column of Jordi gel and an ultra-high molecular weight mixed bed. The solvent was trichlorobenzene and the operating temperature was 140� C. From GPC, Mp which is the peak molecular weight, Mn which is the number average molecular weight, and Mw which is the weight average molecular weight were derived for the xylene insoluble fraction of the polymer produced. The molecular weight distribution, MWD, is commonly measured as Mw divided by Mn. The values determined for this sample are shown in Table 1.
The syndiotactic index can be determined from GPC, IR or NMR data. The syndiotactic index is calculated from NMR data according to the following equation:
Syndiotactic index=rrrr+mrrr+mrrm+1/2(mrmr+mmrm+rrmr+mmrr)
The syndiotactic index obtained from NMR data is the most accurate indication of the degree of syndiotacticity. The syndiotactic index based on IR data is calculated by dividing the area of the IR peak at 11.53 microns by half of the area of the peaks at 2.32 and 2.35 microns represented by the following formula:
Syndiotactic indes=A11.53 /1/2(A2.32 +A2.35)
The syndiotactic index calculated from GPC data requires that the syndiotacticity of the syndiotacticity of the polymer be known beforehand. Unlike NMR and IR data, GPC data cannot show the tacticity of the polymer, i.e., whether a polymer is isotactic, or syndiotactic. The tacticity must be determined by other methods, such as IR or NMR, before the syndiotactic index (or isotactic index) of the polymer can be calculated from GPC data. The syndiotactic index is calculated as the area of the GPC peak related to the crystalline polymer divided by the total GPC peak area for the polymer "as polymerized" represented by the following formula:
Syndiotactic index=Acrystalline /ATotal �100
The syndiotactic index shown in Table 1 was determined from the GPC data. The syndiotactic index shown in Table 2 was determined from NMR data on samples which were recrystallized from xylene.
NMR analysis was used to determine the microstructure of the polymer. A sample of the polymer produced above was dissolved in a 20% solution os 1,2,4-trichlorobenzene/d6 -benzene and run on a Bruker AM 300 WB spectrometer using the inverse gate broad band decoupling method. The experimental conditions were: transmitter frequency 75.47 Mhz; decoupler frequency 300.3 Mhz; pulse repetition time 12 seconds; acquisition time 1.38 seconds; pulse angle 90� (11.5 microseconds pulse width); memory size 75K points; spectral window, 12195 Hz. Seven thousand transients were accumulated, and the probe temperature was set at 133� C. The NMR spectrum for the polymer produced and recrystallized from xylene one time is shown in FIG. 3. The calculated and observed values for the spectrum are shown in Table 3 with Example 1 representing the data for the sample recrystallized once from xylene and Example 1-A representing the data for the sample recrystallized three times from xylene. The calculated values were derived using the Bernouillian probability equations as disclosed in Inoue Y., et al, Polymer, Vol. 25, page 1640 (1984) and as known in the art.
The results show that in the sample recrystallized once from xylene the percentage of racemic dyads (r) is 95%. For the sample recrystallized three times from xylene the percentage of r dyads is 98% indicating a polymer that consists of 2% or less of the meso (m) dyad. Further, the NMR spectrum shows that the meso dyads occur predominately in pairs, i.e., mm triads, as opposed to the previously known single m dyad structure in the chain. The data in Table 3 establishes that the polymer does have a novel micro-structure.
The procedures of Example 1 were repeated except that 500 ml of toluene was used as a co-solvent in the polymerization reaction. Further, one gram of MAO was used in the polymerization, and the reaction temperature was 50� C. Fifteen grams of oil were obtained along with the polymer product. The polymer was analyzed in accordance with the procedures given above and the results are shown in Table 1.
The procedures of Example 2 were repeated except that hafnium was used as the transition metal in the catalyst. The other reaction conditions were as shown in Table 1, and the analyzed properties of the resulting polymer are also shown in Table 1.
The procedures of Example 1 were repeated except for the differing reaction conditions as shown in Table 1. In addition, Example 4 used chromatography as the purification procedure and Example 5 utilized no purification procedure. The results of the polymerization and the analysis of the polymer are shown in Table 1.
FIGS. 4 and 5 show the IR spectra for the polisher produced in Examples 7 and 8 respectively. The characteristic bands at 977 and 962 cm-1 for syndiotactic polypropylene are readily visible. The presence of these bands reaffirm the syndiotactic structure of the polymer. The corresponding bands for isotactic polypropylene are 995 and 974 respectively.
The procedures of Example 1 were repeated except for the changes in the amounts of catalyst and co-catalyst as indicated in Table 1. Further, the catalysts in Examples 9-13 and 15 were purified using both extraction with pentane and fractional recrystallization. Example 14 used extraction with pentane and chromatography as the purification procedures. Example 16 did not use any purification procedure.
The procedures of Example 1 were repeated except that hafnium was used as the transition metal for the catalyst. The other reaction conditions were as shown in Table 1. The catalyst was purified using extraction with pentane and fractional recrystallization. The results of the polymerization are shown in Table 1.
A hafnium metallocene catalyst was synthesized using Method B of U.S. Pat. No. 4,892,451 and using the 95% pure HfCl4 that contained about 4% ZrCl4. The polymerization was carried out using the polymerization procedures of Example 1 under the conditions shown in Table 2. The polymers were analyzed in accordance with the procedures set forth in Example 1 and the results are shown in Table 2.
A zirconium metallocene catalyst was prepared using the synthesis procedures of Method B of U.S. Pat. No. 4,892,451 and the polymerization of propylene was carried out under the conditions shown for each Example in Table 2. The polymer products were analyzed in accordance with the procedures of Example 1 and the results are given in Table 2. It should be noted that for Examples 20-22, the syndiotactic index was determined for the xylene insoluble fraction. The syndiotactic index for these fractions were nearly 100%. The observed (obsd.) NMR spectra data for Examples 20 and 22 are shown in Table 4. The data given for Examples 20 and 22 was collected from the polymers produced in Examples 20 and 22 respectively and recrystallized once from xylene. Example 22-A is the polymer of Example 22 that is recrystallized three times from xylene.
A hafnium metallocene catalyst was prepared using the synthesis procedure of Method B of U.S. Pat. No. 4,892,851. The catalyst for Example 32 was prepared using the 99% pure. HfCl4 while the catalyst in Example 33 was prepared from the 95% pure HfCl4 that contained about 4% ZrCl4. The polymerization was carried out in accordance with the procedures of Example 1 under the conditions shown for Examples 32 and 33 in Table 2. The results of the analysis of the polymer produced in these Examples are also shown in Table 2. The NMR data for Example 33 is shown in Table 4 with the sample as recrystallized once from xylene (Ex. 33) and three times from xylene (Ex. 33A).
TABLE 1__________________________________________________________________________Method A Catalyst MAO Yield -HcExampleMetal (mg) (cc) T (�C.) (g) Tm1� (C.) Tm2 (�C.) J/g Mp /1000 Mw /Mn S.I. %__________________________________________________________________________ 1 Zr 10.0 10.0 20 14 145 150 43 118 2.5 62 2 Zr 10.3 1 g 50 26 129 137 45 57 1.9 68 3 Hf 10.3 1 g 50 12 104 17 1222 46 4 Zr 5.0 10.0 50 130 132 138 37 61 87 5 Zr 5.1 10.0 50 83 131 138 38 62 84 6 Zr 5.0 0.3 g 70 22 115 127 34 71 83 7 Zr 5.1 5.0 50 68 131 140 37 60 38 8 Zr 5.1 10.0 50 110 132 140 38 60 42 9 Zr 5.1 1.0 50 14 114 126 21 58 2410 Zr 5.0 2.5 50 34 111 122 14 60 2311 Zr 5.1 5.0 50 68 119 130 21 60 3812 Zr 5.0 10.0 50 78 128 137 32 64 6513 Zr 5.0 1.0 50 83 121 132 22 59 4214 Zr 2.6 10.0 50 85 134 140 40 62 8915 Zr 5.1 10.0 50 110 125 134 29 60 4216 Zr 5.1 10.0 50 115 131 138 38 62 8417 Hf 10.3 1 g 80 55 89 108 223 52__________________________________________________________________________
TABLE 2__________________________________________________________________________Method B Catalyst MAO Yield -HcExampleMetal (mg) (cc) T (�C.) (g) Tm1� (C.) Tm2 (�C.) J/g Mp /1000 Mw /Mn S.I. %__________________________________________________________________________18 Hf 10.0 10 50 58 116 125 24 644 5.419 Hf 5.0 10 50 60 117 124 24 774 4.820 Zr 0.6 10 50 162 134 140 40 69 1.8 9521 Zr 1.5 10 29 49 142 146 45 106 1.9 9522 Zr 0.6 10 70 119 134 39 54 2.0 9523 Zr 0.2 10 50 27 135 140 39 69 1.924 Zr 0.6 10 50 162 134 140 40 69 1.825 Zr 0.6 10 25 26 145 44 133 1.926 Zr 0.6 10 70 119 134 39 54 2.027 Zr 1.5 10 29 49 142 146 45 106 1.928 Zr 2.5 10 50 141 135 141 40 70 1.929 Zr 5.0 10 28 152 128 137 43 88 2.130 Zr 0.5 10 60 185 128 137 37 52 1.831 Zr 0.5 5 70 158 120 134 36 55 2.432 Hf 2.5 10 70 96 103 19 474 2.633 Hf 10.0 10 50 27 114 26 777 5.3__________________________________________________________________________
TABLE 3______________________________________ Ex. 1 Ex. 1A obsd. % calc % obsd. % calc %______________________________________% r 95 95 98 98mmmm 0.3 0.2 0 0mmmr 0.3 0.6 0 0rmmr 1.5 1.4 1.3 1.0mmrr 2.4 2.9 1.9 2.1rrmr +mmrm 1.5 1.6 0 0mrmr 1.6 0.8 0 0rrrr 88.0 89.1 94.7 94.7mrrr 3.9 3.1 2.2 2.1mrrm 0.4 0.4 0 0dev. 0.2 0.1______________________________________
TABLE 4______________________________________EX. 20 EX. 22 EX. 22-A EX. 33 EX. 33-Aobsd. % obsd. % obsd. % obsd. % obsd. %______________________________________mmmm 0 0.77 0.51 2.34 2.04mmmr 0.23 0.45 0.31 0.73 0.76rmmr 1.67 1.82 1.81 2.72 2.96mmrr 3.58 4.25 4.06 5.72 6.44mrmm +rmrr 2.27 3.23 3.57 2.87 3.12mrmr 1.51 2.06 1.70 1.37 1.53rrrr 82.71 77.58 78.12 75.7 74.55mrrr 6.45 7.75 9.02 7.4 8.01mrrm 0.68 0.73 0.93 1.08 0.55______________________________________
The data shown in Tables 1-4 and in FIGS. 3, 4 and 5 show that the polymers of the present invention are predominantly syndiotactic polypropylene that has high crystallinity. Particularly, the NMR data shown in Tables 3 and 4 establish that the xylene insoluble fraction consists of a very high percentage of syndiotactic polymer with very little, if any, isotactic polymer being produced. Further, the syndiotactic polymer contains a high percentage of "r" groups and "rrrr" pentads indicating that there is only a small percentage of deviations from the ". . . rrrr . . . " structure in the polymer chain. The deviations that do exist are predominantly of the "mm" type. Indeed, the results for Ex. 1-A in Table 3 show that the only deviation in the chain is of the "mm" type. The other NMR samples show the predominance of the "mm" deviation over the "m" deviation. Thus, a novel microstructure for syndiotactic polypropylene has been discovered.
The data in Tables 1-4 and Examples 1-33 show the high crystallinity of the polymer product. The relatively high melting points, TM1 and TM2, and the relatively high heats of crystallization, --Hc, indicate that the polymers are highly crystalline. This high crystallinity is demonstrated by the syndiotactic index, ([r] value) which is a measure of the per cent of racemic (r) dyads in the polymer. In Tables 1 and 2 the syndiotactic index is shown to be above 50% ([r] 0.50) in twelve of the twenty examples in which results for the syndiotactic index is recorded, eight of the twelve are 83% or above ([r]≧0.83) and four of the eight are 89% or above ([r]≧0.89). As shown in Table 3, the syndiotactic index increases upon recrystallization. The sample from Example 1 has a syndiotactic index of 62% on the polymer "as polymerized" (see Table 1). After one recrystallization, the [r] value increased to 95% and after three crystallizations the [r] value increased to 98% (see Table 3). The syndiotactic index for Examples 20-22 for the Xylene insoluble fraction from a single recrystallization from xytene were "nearly 100%" where [r] would be 1.0. Recorded values are up to 0.95. Therefore, the syndiotactic index or [r] value of the present invention ranges from about 0.50 to about 1.0, preferably from about 0.83 to about 1.0 and, most preferably, from about 0.89 to about 0.95.
Tables 3 and 4 show that there is a high percentage of [rrrr] pentads. The values ranges from 74.55 to 94.79. Therefore, the [rrrr] pentads of the present invention range from about 0.75 to about 0.95. The median is about 0.85 and the mean average is about 81.6 with a standard deviation of 6.83.
The data further indicates a correlation between the polymerization reaction temperature, T, and the melting points, molecular weights and the heats of crystallization of the polymer. As the reaction temperature increases, all three of these properties decrease. There also seems to be a range of temperature within which the yield of polymer is maximized. This reaction temperature range will vary with the type of catalyst used but is typically 50�-70� C. The concentration of methylalumoxane (MAO) also appears to affect the polymer yield. The data indicates that to a point, the greater the concentration of MAO, the higher the yield of polymer. The concentration of MAO also seem to have some effect on the amount of atactic polymer produced. MAO appears to act like a scavenger for impurities and tends to reduce the amount of atactic polymer produced.
The data further indicates a difference between the zirconium catalyst and the hafnium catalyst of the present invention. The polymers produced with the hafnium catalysts tend to be less crystalline and have lower melting points than the polymers produced with the zirconium catalysts. The data in Table 4 also shows that the hafnium catalyst produces a higher percentage of isotactic blocks in the polymer chain as reflected by the presence of the isotactic pentad mmmm.
Examples 18, 19 and 33 show the ability to achieve a broader molecular weight distribution, MWD=Mw /Mn, by use of a mixture of the catalysts described by the present invention. The catalysts in these Examples were prepared using HfCl4 that contained about 4% ZrCl4. Therefore, both isopropyl (fluorenyl)(cyclopentadienyl) hafnium dichloride and isopropyl (fluorenyl)(cyclopentadienyl) zirconium dichloride were produced. The MWD of the polymer in these Examples with a mixture of two catalysts is significantly higher than the MWD of the polymer produced by an essentially pure hafnium catalyst--see Example 32. Thus, a mixture of two different catalysts can be used to produce a polymer with a broad MWD.
It should be further understood that the syndio-specific catalyst of the present invention are not limited to the specific structures recited in the Examples, but rather, include catalysts described by the general formula given herein in which C5 R4 is substituted in such a manner as to have bi-lateral or pseudo bi-lateral symmetry as described above.
From the detailed description of the invention just given, it is apparent that the invention provides a novel structure of syndiotactic polypropylene. Having described but a few embodiments, it will be apparent to one skilled in the art that various modifications and adaptations may be made to the polymers as described without departing from the scope of the present invention.
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: Larry Brooks:
Today could be Gaborik's last game as a Ranger
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Originally Posted by
yeah. Something like this.
I was going to say that it is not Gaborik who stinks. This smell is all around. Sorry...
I understand what you're saying and I somewhat agree with you (of course). We all know what kind of player Gaborik was, is and probably always will be. This is simply put not his game. He's a counterattacker.
We need to change our offensive game, period, and that has nothing to do with Gaborik. Preferably, measures must be taken to improve the ice conditions in the Garden, because the terrible ice isn't helping and our records speak for it.
We need to move the puck away from the boards and get it in front of the net, with 1-2 of our own players in the slot, willing to screen, willing to deflect, hungry for the rebound. That is the only way a blue collar team can be successful. To win the battle in front of the net. That, and learning how to connect two frigging passes within the team in a row without losing the puck. And starting to make the rushes count.
A puck in front of the net should be enough to make Gaborik's goal scoring ability count. He's scored his fair share of "dirty goals" around the crease and he's good at it, when the rush opportunity is gone.
That might also have to do with Drury falling off the earth offensively. No puck in front of the net, no opportunistic offensive contribution from Drury, period.
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Oklahoma State basketball notebook: Injuries create some caution
Up next: Hush, hush
Officially, OSU's next game is the regular season opener Nov. 9 against UC Davis at Gallagher-Iba Arena.
Tip time for that game is 8 p.m., the back half of a doubleheader with the OSU women, who play Cal Poly at 5:30 p.m.
Before then, however, the Cowboys are scheduled for a scrimmage — Sunday against North Texas if Twitter banter among players is accurate — which is allowed by the NCAA, but can't be publicized, reported on or open to the public or the media.
Lob Stilly still thriving
The Cowboys' "LobStilly" movement, a take off on the Los Angeles Clippers "Lob City" moniker attached to their highflying dunks, was back on display Thursday night.
Also familiar was Brown leading the way with several jams, including a breakaway, one-handed 360-degree spin dunk that wowed the crowd.


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Narrow your search
When you play the entire "Star Wars" film saga all at once in the same frame, the results make for a surreal sci-fi experience.
Mobile World Congress 2015
Apple's offering some free downloads of new shows like "Scream" and "Zoo." Meanwhile, HBO is streaming some new shows for free on Facebook.
Apple CEO Tim Cook and VP Phil Schiller unveiled the iPad Air 2 at an event on their Cupertino campus. Not only does Apple say it's thinner than any other tablet on the market, but it features an improved camera and a built-in fingerprint sensor.
This kid is amazingly fast. He sets a new world record by solving a Rubik's Cube in just over 5 seconds, besting the previous record by an impressive three-tenths of a second.
We popped along to Apple stores and other retailers around the world to see how fans are getting to grips with the new wearable device -- and how Apple is selling it.
The new sequel to Steven Spielberg's beloved blockbuster is all-out dinosaur war. Read on for our thoughts.
Steel-plated sub-zero freezer? Check. Soundproofing? Check. Foil-coated furniture? Check. Crickets, mealworms and live rats? Er, um ...
When all hell breaks loose at Jurassic World, NFL star cornerback Richard Sherman must run for his life or face a certain death by dinosaur.
The Brotherhood Workshop releases a "Jurassic World" short showing Lego raptors unenthusiastic about a new mission from Owen Grady.
Want to make live music better or block engine noise? Here Active Listening buds are like equalizers for real life.


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Did Mariah Carey Lip Sync The BET Awards [VIDEO]
Mariah Carey is on blast for her performance at this weekend's 2013 BET Awards. Don't misunderstand, the performance was flawless, mainly because she's accused of lip syncing.
Mariah Carey is on blast for her performance at this weekend's 2013 BET Awards. Don't misunderstand, the performance was flawless, mainly because she's accused of lip syncing.
In case anyone had any doubts, both Mariah Carey and Nicki Minaj confirmed their exits from 'American Idol' last night (May 30).
There have been rumors that producers planned for one diva (Jennifer Lopez) to oust another (Mariah Carey) on the 'American Idol' judging panel mid-season in a desperate attempt to boost sagging ratings. However, the latest consensus is that it was J. Lo who contacted Fox, and not the other way around. That's a pretty (J) lo(w) blow and an affront to Mimi, no?
Nicki Minaj stopped by 'The Tonight Show With Jay Leno' on Monday (Jan. 14), where she dished on her feud with 'American Idol' co-judge Mariah Carey.
Seems that feud (or publicity stunt, depending on your level of cynicism) between Mariah Carey and Nicki Minaj isn't over just yet, because during a 'Nightline' interview with Barbara Walters, Mariah threw major shade at her fellow 'American Idol' judge.
Meow, indeed.
Every time I watch "Late Night With Jimmy Fallon" I always say how much I love the house band "The Roots." This band is pure awesome. I keep meaning to pick up a few songs to use during my show. I mean these guys have a tuba in the band! How awesome is that? Well, it's pretty awesome
Remember those rumors of a feud between Nicki Minaj and Mariah Carey on the 'American Idol' judging panel? Both ladies denied any drama, but it looks like they may have been lying. New video has emerged of Minaj flipping out at Mimi, and though both the women are gorgeous, this footage ain't pretty.
Good news for 'American Idol' fans! The official list of judges has finally been released. Who will grace the stage?
Technically, Jennifer Lopez said this before Mariah Carey was announced as being a judge. But still, let's pretend that J.Lo was speaking directly to Mimi.
I remember a few days ago that Nick Cannon was asked about the possibility of Mariah Carey going over to American Idol. He pretty much said it would cost twice what Jennifer Lopez was making. So now it seems that Fox has ponied up the money.
'American Idol' sure is looking to fill the heels, er, judging spot, vacated by Jennifer Lopez, with someone bigger and better! The show is reportedly thisclose to replacing one diva with another in the form of Mariah Carey. O to the M to the F to the G. The five octave Carey as an 'Idol' judge? So much for those rumors that 'Idol' was planning to downsize for Season 12. Producers are shooting for the stratosphere if they close this deal.
As Nick Cannon continues to recover from mild kidney failure, Mariah Carey is passing along good news about her husband's progress. "Nick is in stable condition with a good prognosis, hopefully he'll be discharged within 2 days," she tweeted today. "As always he's laughing and in good spirits."


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A beautiful reminder of what's important, and an eloquent witness to others, this wall art features the word "Faith" amid feathery scrollwork. Lightweight polyurethane is easy to hang. 39" w x 12 3/4" h.
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found a new home!
Plenty of my friends are looking
for one too. Find a pet to adopt.
I am already spayed, housetrained, up to date with shots, good with kids, good with dogs, and not good with cats.
Velvet is a wonderful girl that was on the euthanasia list. She was tied to the front of the shelter and left there over night in the cold- she was so scared. She just huddled in the corner of her kennel not knowing what to think as to why she was there. We rescued her and she is thriving now.
We believe Velvet to be approximately two years old. She is a total love bug who just wants to be by your side, to be petted, and give you love in return! She is very playful, her favorite game being tug of war. She loves to play in the water and knows some basic commands. She loves her stuffed animals and will play with them for hours in her crate. When she is out of her crate she will go in and grab them all at once and bring them out- very funny to see her with five furry babies in her mouth! In general she is a total hoot, running around in the yard flipping her toys in the air twisting and turning- she is very bouncy and runs and hops a lot, so funny to watch. Besides being crate trained Velvet is completely housed trained. She likes other dogs when given the time to warm up to them but will need someone committed to help her through the process of being introduced to a new dog. She absolutely loves children- I have two nephews ages four and three, and two nieces ages sixteen and two. The only issue being because she is so crazy in the yard she may knock the little ones down, then she goes crazy kissing their tears away. Velvet is not good with cats and should not be considered for a home with them. She is spayed and heartworm negative.
Her adoption fee is $200.00 and that covers her spay cost and all vaccines. If you are interested in Velvet please call 925-337-6377
Velvet URGENT FOSTER NEEDED, a Livermore Pit Bull Terrier/Labrador Retriever dog was adopted! Here's how you can benefit by looking at adoption as an option to buying a Pit Bull Terrier/Labrador Retriever for sale in Livermore, or seeking a Pit Bull Terrier/Labrador Retriever dog from a breeder in Livermore.


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Marketing Technology Blog
By DK New Media
Open iTunes to buy and download apps.
The Marketing Technology is a must have app for any marketing professional or team. The app discusses the latest news, best practices, products and services for online marketing, inbound marketing, content marketing, search engine marketing, mobile marketing, social media marketing and more.
Download the app and you will have the latest guides and how-tos on how to leverage the latest technologies to improve your marketing efforts at your fingertips.
What's New in Version 3.0.1
- Stability fixes
- Fixed a crash that would occur for some users when opening a push notification
- Performance Enhancements
iPhone Screenshot
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- Category: Business
- Updated: 13 May 2013
- Version: 3.0.1
- Size: 8.5 MB
- Language: English
- Developer: Douglas Karr
- © Copyright 2012 DK New Media LLC
Compatibility: Requires iOS 5.0 or later. Compatible with iPhone, iPad, and iPod touch. This app is optimised for iPhone 5.