text:
|Days Inn Allendale properties are listed below. Search for cheap and discount Days Inn hotel rates in Allendale, SC for your upcoming meeting or individual travels. We list the best Days Inn Allendale hotels so you can review the Allendale Days Inn hotel list below to find the perfect place.
This service will also list discounted Allendale, SC properties that have a comparable rating of a Days Inn.
Booking a group or meeting? Get bids from hotels in Allendale SC
All Days Inn in or near Allendale
More Days Inn properties for Allendale
Next: Show All Available Comparable Hotels with Pricing >


text:
Our Bare Escentuals® product range is so pure you can sleep in it, allowing excellent coverage even after waxing. Its SPF qualities protect against sun damage. Bare Escentuals® is a classic range which will make you look radiant.
Day Spa
Online bookings let you pick date/time for your visit.
If you purchase an eVoucher you will need to book with the venue directly.
Our old Wahanda Gift Vouchers can still be redeemed at over 3,000 locations. Use them to pay as you would with cash. Please note, the Wahanda Gift Voucher's successor – the Wahanda Gift Card – can only be used for online purchases.

subset: commoncrawl


text:
Wanna Bees to play at 'Song of Toledo' acoustic concert May 20Written by Julie Ryan | | firstname.lastname@example.com
Note: Toledo Free Press and FOX Toledo are profiling, in random order, the top five vote-getters in the "Song of Toledo" contest. The winner will be revealed May 20.
Songwriter Chuck Riepenhoff heard about the Song of Toledo contest when FOX Toledo and Toledo Free Press announced it in March. He was already a part of The Wanna Bees, a children's entertainment music group, and thought the Song of Toledo contest sounded too fun to pass up.
"I thought, 'Hey, let's give this a shot,' " he said. "I have a group of guys with this Wanna Bees project, and we were getting together every couple of weeks to write songs and record songs for that project."
The band will join the other top five contestents — Empire Drift, Kyle White, Purpose and Highbinders, plus People's Choice Award winner Buck 69 — at an acoustic concert, 3 p.m. May 20 at the Downtown Main Branch of the Toledo-Lucas County Public Library. The bands will play their contest entries, and the contest winner will be revealed.
The four members of The Wanna Bees, Mike Hayden, Brad Bury, Tom Pokornik and Riepenhoff, meet every other Thursday in Toledo to record music. Kurt Hattendorf helped with their contest entry, "You're In Toledo, Baby!"
"I literally wrote down and made a list of all the Toledo landmarks off the top of my head and crossed them off until I incorporated them into the song," Riepenhoff said. The list included more than 20 landmarks.
"I have a 2-year-old daughter, so the zoo is big for me," Hayden said. "We try to go to the art museum and we try to go there — it's one of the jewels of the city."
Riepenhoff said he began writing, "You're In Toledo, Baby!" with the chorus first, focusing on making it catchy and energetic — since The Wanna Bees, after all, is a project for kids.
"Typically, there's not a lot of people who talk upbeat about the city," Hayden said. "So we wanted to make it upbeat and not a ballad or something slow."
Riepenhoff said the song came together during their second recording session.
"When you have the four guys hovering around the microphone and yelling 'Oh your in Toledo Baby,' it was a lot of fun and we were all laughing and having fun with that," Riepenhoff said. "And then when you hear that on tape, you realize 'Oh, this is pretty cool.' By the end of the night, we were pretty proud of the song and felt that we had a chance in this contest."
However, their recording process hit a minor hitch when Riepenhoff went to the studio to record the second verse.
"I didn't realize I hadn't written full lyrics for the second verse yet," he said. "It was just like, 'Oops.' I started singing and I didn't quite write that yet, just a piece of paper with 'Jeep' here and 'Jamie Farr' there. So, that was a group effort. We all had our list of Toledo trademarks that worked to incorporate into the song, so together we worked to write the second song."
After 10 hours of recording, Hayden said he mastered and produced the song in his home studio. Riepenhoff turned in the contest entry just before deadline.
"Our intent was to write a commercial for the city of Toledo," Riepenhoff said. "We wanted to write a song that you could listen to but at the same time visualize all the cool things that Toledo has to offer. I could totally see a video going right behind the song with The Wanna Bees hopping on a TARTA bus on a quest to get to a Mud Hens game Downtown."
The Wanna Bees plan to release a CD, "Work Together," this year. Follow the band at www.myspace.com/whatuwannabee.


text:
For a collection of all our previous recipes, check out our blog here
Tricolore Rice (Sanshoku Donburi)
Ingredients (1 Serving)
- 1 portion cooked rice
- 100g minced beef or pork
- 1 tbsp. shoyu soy sauce
- 1 tbsp. mirin
- A 1/2 tbsp. sugar
- 3-4 runner beans, finely sliced
- 1 egg, lightly beaten
- 2 tbsp. dashi (or water with a pinch of dashi powder)
- 1 tsp. sugar
- Tare sauce (2 tbsp. shoyu soy sauce and 2 tbsp. mirin)
- 1 tbsp. pickled ginger
- Place the minced beef/pork in a saucepan together with shoyu, mirin and sugar and cook very gently over a low heat for 5 minutes. Set aside.
- Cook the runner beans in salted boiling water for 3-4 minutes. Drain and set aside.
- Scramble the eggs with dashi and ginger. Set aside.
- Take the same pan you used for either the beef or scrambled egg (as it will save on washing!) and add the shoyu and mirin together to make the tare sauce and bring to the boil. Pour the sauce into the bottom of a large rice bowl.
- Place the cooked rice on top of the sauce and then arrange the beef/pork, beans and egg into three equal sections on top of the rice. Place the ginger in the middle.
Egg, Asparagus & White Miso Bake
Ingredients (1 Serving)
- 2 eggs
- 1 bunch green asparagus
- 1 tbsp. butter
- 100ml single cream
- 1 tbsp. white miso
- 2 tsps. shoyu Japanese soy sauce
- 1 tsp. chives, finely chopped (optional)
- Pre-heat the oven to 200°C.
- Wash the asparagus and discard the 'woody' ends.
- Lay the asparagus on a baking dish and dot with butter. Then drizzle 1 tsp. of shoyu soy sauce over the asparagus and place in the oven for 5-8 minutes. The timing will depend on the thickness of the spears.
- Mix the cream, miso and the rest of the shoyu in a bowl. Take the asparagus out of the oven and pour this sauce over.
- Crack eggs onto the asparagus. Cover the dish with foil and bake for a further 6-7 minutes. Sprinkle chives if desired.
Turkish Delight Ice Cream
Ingredients (4 Servings)
- 500ml vanilla ice cream
- 3 pcs. rose Turkish delight
- 3 pcs. lemon Turkish delight (or use 6 pcs. rose Turkish delight instead)
- 1 tsp. rose water
- 1 tbsp. brandy (optional but very nice)
- Take the vanilla ice cream out of the freezer and leave at room tempurature for 10 minutes to soften.
- Cut the Turkish delight into small cubes.
- Fold the Turkish delight, rose water and brandy (if using) into the ice cream. Mix thoroughly.
- Put the ice cream back into the freezer and leave it for at least 2 hours.
Delicious served with spicy ginger biscuits, fruit compote or steamed pudding of your choice.
Duck Salad with Hoisin Dressing
Ingredients (2 Serving)
- 150-200g coocked duck
- 6 lettuce leaves
- 4 spring onion
- 2 tbsp. hoisin sauce
- 2 tbsp. lemon juice
- 2 tbsp. soy sauce
- Shred the duck meat, lettuce leaves, spring onion respectably.
- Mix the hoisin sauce, lemon juice and soy sauce in a saucepan, heat gently and add the duck and spring onion.
- Place the lettuce leaves in a bowl and add the duck and the sauce whilst warm.
This salad also makes a great filling for wraps/sandwiches.
Bulgogi Steak
Ingredients (1 Serving)
- 150g steak (rump, rib-eye, sirloin etc.)
- 1 tsp. butter
- 1 tsp. oil
Ingredients for bulgogi sauce
- 2 tbsp. shoyu Japanese soy sauce
- 1 tbsp. toasted sesame oil
- 1 tbsp. white sesame seeds
- 1 tbsp. onion, very finely sliced
- 1 tsp. sugar
- 1 clove garlic, grated
- Toast the white sesame seeds in a dry frying pan for 15 seconds.
- Mix all the ingredients for the bulgogi sauce together with the toasted sesame seeds and marinade the steak for 20 minutes.
- Heat a frying pan and add the butter and oil, then cook the steak adding all the sauce as well for 3 minutes each side.
Delicious served with rice/potatoes, green vegetables and Korean kimchi pickle if you can get hold of some. You can also use a bottle of ready made bulgogi sauce if you're in a rush!
Recipe of the month
Tricolore Rice (Sanshoku Donburi)


text:
Welcome to WebmasterWorld Guest from 126.96.36.199
Moderators: phranque
I really am confused and need help from you guys :(
Actually, I have a portal in which I am using some BANNERS, to navigate to other sites.
What I want is to validate if the link is working or not. Can you plz tell me about a site or tool that will help me solve this problem?
If I am using: <FORM action ="www.Somedomain.com/foldername/filename.Ext">
Will XENU check if the url "www.Somedomain.com/foldername/filename.Ext" exists or not?
I don't know of any program that fills out forms...
Is there something else to solve the problem.
I think this problem should be taken seriously and requires solution as soon as possible.
Till then I will validate the form by submitting it manually
Las VegasOctober 6-8, 2015


text:
The Dorothy Marron University Community Chapel at Georgian Court is a lovely, faith-filled place for a wedding. The chapel holds 150 people.
Weddings may be scheduled:
In order for a wedding to take place, the following requirements must be met:
If the bride and/or groom meet the above requirements and have a verbal confirmation of a date and time from their officiant, Campus Ministry will be happy to hold a reservation for the chapel.
For more information or to reserve the chapel, please contact Mrs. Kathleen Brum in the Office of Campus Ministry at 732-987-2691.
Tuesday, Aug 4Graduate Information Sessions
Wednesday, Aug 12Summer Visit Days
Monday – Friday and selected Saturdays throughout the year
Campus Tours


text: Dementia is a loss of mental ability memory, judgment, and ability to think. While there are numerous causes of dementia, Alzheimer's disease is the most common. For someone with dementia, life is confusing; it's difficult to remember so many things; personality may change. Medication can help control behavior problems, and some drugs can slow the rate of decline.


text:
Miami preseason outlook
Coach: Al Golden
2013 record: 9-4 overall, 5-3 in ACC (Tied for Second in Coastal Division)
Overview: Al Golden's fourth season at Miami is already different than any of his first three — since the NCAA probe revolving around the actions of a former booster is finally a thing of the past. With star running back Duke Johnson healthy again after his 2013 season ended early because of a broken ankle, and plenty of playmakers on both sides of the football, the Hurricanes are expected to be in the mix for the Atlantic Coast Conference's Coastal Division title. But there is a major question still to be answered, that being who will be the starting quarterback when the season begins at Louisville on Sept. 1. Ryan Williams would have been the presumed starter but is still recovering from a torn knee ligament, though is expected back at some point this season. Transfer Jake Heaps and true freshman Brad Kaaya seem like the top contenders for the job, and neither has thrown a pass at Miami. The winner of the quarterback job will get plenty of help from Johnson, not to mention a talented crop of receivers. Miami had 10 receivers with catches of 25 or more yards last season. If defenses are going to be kept honest and not able to stack the box against Johnson, finding a way to keep the deep ball in the repertoire would seem crucial. The Hurricanes' defense has been on the field an average of 34 minutes per game over the last two seasons, the second-highest total among all major college teams.
Player to watch: Duke Johnson, RB – The junior rushed for 115 yards per game, which would have ranked second in the ACC, and averaged 6.3 yards per carry before suffering a season-ending ankle injury in the eighth game. Expect eight-man fronts until Miami's passing game proves itself.
Game to watch: Miami at Lousiville, Sept. 1. Miami's 2013 season ended with a one-sided loss to Louisville in the Russell Athletic Bowl, and the Hurricanes open this season as the Cardinals' opponent for their ACC debut.


text:
Rick Ricketts
2009 (Junior) - Played and started in all 13 games ... led all defensive linemen and was fourth on the team overall in tackles with 57, including 23 unassisted ... had 6.5 tackles for loss for 39 yards ... second on the team in quarterback sacks with 4.0 for 28 yards ... had one forced fumble and one recovery ... had a career-best nine tackles vs. Navy ... six tackles vs. TCU, Utah and Houston ... had five tackles, two tackles for loss and a sack vs. Wyoming.
2008 (Sophomore) - Played in every game as a backup defensive lineman ... led all reserve defensive linemen with 28 total tackles ... had 13 unassisted stops ... had 2.5 tackles for loss and a sack ... also had a forced fumble and fumble recovery ... blocked an extra point vs. TCU to record his first-career blocked kick and the first block for the Falcons during the season ... two tackles, a tackle for loss and a forced fumble vs. Utah ... season high in tackles with five vs. Navy and Army.
2007 (Freshman) - Played in 11 games ... did not play against Utah and TCU ... recorded 15 total tackles, including five unassisted ... had a half tackle for loss and a pass breakup ... season-best four tackles, including three unassisted, vs. Navy ... three tackles and a half tackle for loss vs. Army ... one tackle and a pass breakup vs. San Diego State.
High School - Lettered three years in football, two in basketball and one in track ... West County Athletic League defensive lineman of the year ... two-time first-team all-WCAL ... second-team all-section ... second team all-Metro in San Francisco Bay Area ... on the honor roll ... high school football coach was Matt Haniger.
Personal - Son of Jeff and Carol Ricketts ... member of cadet squadron 12 ... major is management ... completed the powered flight program, worked Basic Cadet Training and took a course in astronautical engineering this past summer ... has three sisters, Samantha, Keilani and Stephanie ... Samantha was an All-American softball player at Oklahoma and Keilani currently plays at Oklahoma, Stephanie currently plays at Hawaii ... favorite book is Rich Dad/Poor Dad ... favorite movie is Rudy ... favorite class is investments ... listens to Linkin Park before games ... person in history he would most like to meet is Vince Lombardi ... something most people don't know about him is that he is part-Samoan ... father is a police sergeant ... credits his father as having the greatest influence on his sports career because "he preached the value of commitment" ... hobbies are playing basketball, golfing, reading, skiing, and working out ... favorite NFL team is the San Francisco 49ers ... favorite player is Minnesota Viking Jared Allen ... favorite non-traditional sport to watch on TV is the running of the bulls.
Ricketts Career Defensive Statistics


text:
The Momofuku Cookbook's Kimchi Stew with Rice Cakes
This recipe for Kimchi Stew with Rice Cakes from the Momofuku cookbook is addictively good. David Chang uses two-week old kimchi (fresh and crisp with a not-too-sour taste), any type of broth (he suggests pork; no big surprise given Momofuku's obsession with pork), and rice cakes made with glutinous rice. More


text:
SIDE STREETS EXTRA: Armstrong jersey a symbol of sport's worst cheat
You've reached your 4 FREE premium stories for this 30 day period*
Register for 4 more free articles.
Are you a subscriber and having trouble viewing stories?
You must be logged in to post a comment.
If you already have an account, login here: Login
New user? Register Now


text:
RUSH TOWNSHIP– Daniel Dissinger, 13, was curious, talkative, and smart.
His Brother Gavin, 7, was active, friendly and loved to be outdoors,
The boys and their brother Arthur, 2, were killed when flames consumed their house on South Smith Road near Danville Friday morning.
A sister and brother escaped and tried to get help, but it was too late.
A day later, flowers began to cover the scorched foundation of the home, brought by people paying tribute.
One of them was Mary Weikel, a Sunbury firefighter.
"I would not have wanted to be the firefighter that brought them out."
Friends and relatives also visited Danville Middle School where Daniel Dissenger was a student. His locker transformed into a memorial covered by cards inscribed with messages from classmates. One reads,"Daniel I love like a brother."
On Saturday, the school served as a refuge for staff and students, offering grief counseling and more informal support.
In the following days, Daniel and Gavin will be remembered in a number of ways.
"Letting the kids talk through what they are dealing with, understand the stages of grief, some of them are going to be impacted for quite some time," said middle school principal Charles Smargiassi.
Administrators have planned activities to help the district's youngest kids cope.
"We have stories prepared, we have books that talk about loss and grief, activities as simple as making a poster, making a banner, writing a message to the students, so they have a way of feeling connected," said primary school principal John Bickhart.
On Tuesday at the Danville Mennonite Church, a visitation will take place at 12:30 p.m., a funeral at 1:30 p.m.
Several fundraisers are in the works including one at the school on Monday.
A fund to help the Dissinger family has been set up at M-C Federal Credit Union. If you'd like to help, stop by any branch of the M-C Federal Credit Union or send a check to:
"Dissinger Family, Loss Donation Fund"
230 Walnut St, Danville, PA 17821
The credit union is also collecting supplies including bedding and toiletries.
More information about branch locations and how to help can be found here.


text:
Marvin T Brown PhD has been teaching and consulting in business
and organizational ethics for over 30 years. His work first focused
on the challenges that workers and managers face in dealing with
differences and disagreement. As his work developed, he shifted to
a civic perspective for analyzing organizational relationships.
More recently, he applied a civic perspective to the economy, which
offers an alternative to both capitalism and socialism by basing
the economy not on property ownership or social classes, but on
civic membership in a global civil society.
He continues to teach business ethics in the Philosophy
Department at the University of San Francisco. He has previously
taught organizational ethics at Saybrook University, Alliant
International University and JFK University, all in the San
Francisco Bay Area. Along side his teaching, Marvin has served as
an ethics consultant for such companies as Levi Strauss and Company
and Northern California Automobile Association. He has also given
presentations at the Society of Business Ethics, the Association
for Professional and Practical Ethics, and the Association for
Social Economics in the USA; at the ISSBE meeting in Sao Paulo,
Brazil; the European Business Ethics Network in Bonn, Germany and
Dublin, Ireland, The Academy of Social Sciences in Warsaw, Poland;
the International Center for Education and Development in Caracas,
Venezuela; the University of Argentina, in Buenos Aires, Argentina;
and the Shanghai Academy of Social Sciences in Shanghai, China.
Dr. Brown's academic degrees are from Nebraska Wesleyan
University (BA), Union Theological Union (MD), and Graduate
Theological Union (Ph.D.). He is the author of Working Ethics
(1990), The Ethical Process (1993), Corporate Integrity (2005), a
Choice selection for Outstanding Academic book in 2006, and
Civilizing the Economy (2010), which was selected by the PtoP
Foundation as 2010 Book of the Year. His books have been translated
into Spanish, Portuguese, German, Polish, Italian, Chinese and
Korean. He has recently received a Faculty Service Award from the
University of San Francisco, and an Alumni Achievement Award from
Nebraska Wesleyan University. He is now a regular blogger on the
web site: civilizingtheeconomy.com
List of publications (pdf)
University of San Francisco
College of Arts and Sciences
2130 Fulton Street
San Francisco, CA 94117


text:
Resumen disponible en
Reclamaciones disponible en
Descripción (El texto procesado por OCR puede contener errores)
United States Patent 3,404,109 PRODUCTION OF POLYETHER DIOLS USING WATER AS A TELOGEN Jack Milgrom, Akron, Ohio, assignor to The General Tire & Rubber Company, a corporation of Ohio No Drawing. Continuatiou-in-part of application Ser. No. 258,530, Feb. 14, 1963. This application Oct. 15, 1965, Ser. No. 4%,721
11 @laims. (Cl. 260-611) ABSTRACT OF THE DHSCLOSURE Low molecular weight hydroxy-terminated polyoxyalkylene diols having a hydroxyl functionality of approximately 2 are prepared by polymerization in the presence of a small amount of water of epoxide and/or oxetane monomers using certain double metal cyanide complexes, e.g., zinc cobalticyanide acyclic polyether complex, as polymerization catalysts. The resulting telomers may vary from light oils to greases and solids are useful in making polyurethane foams and elastomers by reaction with polyisocyanates.
Cross reference to related application Reference is made under the provisions of 35 USC 120 to copending application Ser. No. 258,530, filed Feb. 14, 1963, now US. Patent No. 3,278,457 of which the pres ent application is a continuation in part.
It is an object of the present invention to provide a method for producing substantially hydroxy-terminated polyoxyalkylene diols.
It is another object of this invention to provide a process for producing relatively low molecular weight liquid polyoxyalkylene diols having a hydroxyl functionality of approximately 2.
These and other objects and advantages of the present invention will become more apparent to those skilled in the art from the following detailed description and examples.
According to the present invention it has been discovered that substantially hydroxy-terminated polyoxyalkylene diols can be produced by the polymerization of (1) epoxide and/or oxetane monomers with (2) water (3) in the presence of certain double metal cyanide complexes which have been treated with organic materials such as alcohols, ethers, esters and the like. Depending upon the amount of water employed, the resulting polymers (hereinafter referred to as telomers) can vary from light oils to greases and solids having a hydroxyl functionality of about 2.
The organic cyclic oxides which can be telomerized in accordance with the process of this invention include any cyclic oxides, such as the 1,2-epoxides, oxetanes, 3- substituted oxetanes or 3,3-disubstituted oxetanes, having an oxygen-carbon ring in which an oxygen atom is joined to 2 or 3 carbon atoms in the ring which will open and telomerize with the same or other cyclic oxide monomers in the presence of the double metal cyanide complex catalyst and which have up to a total of 18 carbon atoms. That is, to say, 3 carbon atoms in the ring and up to 15 carbon atoms in the side chains. These cyclic oxide monomers may also contain 1, 2 or more aliphatic double bonds. Preferably, the cyclic oxides contain only 1 aliphatic carbon-to-carbon double bond. The alkenyl, ether and halogen substituted derivatives (except easily ionized halogen) of these cyclic oxides also can be employed.
Examples of useful cyclic oxides which can be employed in the process of the present invention are ethylene oxide (1,2-epoxy ethane), 1,2-propylene oxide, 1,2-butene oxide, 1,2-hexene oxide, 1,2-dodecane monoxide, isobutylene oxide, styrene oxide, 1,2-pentene oxide, isopentene 3,404,109 Patented Oct. 1, 1968 oxide, 1,2-heptene oxide, allyl glycidyl ether, isoheptene oxide, 1,2-octene oxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, butadiene monoxide, isoprene monoxide, oxetane (1,3-propylene oxide), tolyl glycidyl ether, 3,3-dimethyl oxetene, 3-allyl-3-methyl oxetane, 3-vinyl-3-methyl oxetane, 1,2-pentadecene oxide, 3- butyl-3-decyl oxetane, 3-chloromethylene oxetane, 3-chloromethyl-3-methyl oxetane and the like.
It is preferred to employ the lower molecular weight oxides such as ethylene oxides, propylene oxides, butylene oxides and the like containing from 2 to 12 carbon atoms.
The double metal cyanide complex catalysts which are useful in the process of this invention are prepared by reacting a transition metal cyanide complex with a metal salt in aqueous media. Removal of substantially all of the water present in the catalyst is desirable to enhance the activity of the catalyst although it would appear that removal of all the water is not practicable and may not be desirable. It has been found that most of the water can be removed and the activity of the catalyst further enhanced by treating the catalyst with a complexing or c0- ordinating material such as an alcohol, ether, ester, sulfide, ketone or aldehyde.
In general, the double metal cyanide catalysts employed in the present invention have the following rational formulas:
wherein M is a metal ion which forms a metal-oxygen bond that is relatively more stable than the co-ordinate bond between the metal and nitrogen atoms of the cyano, CN, group. On the other hand, M is a transition metal ion that has more than 1 stable valence form and forms a relatively strong covalent bond with the carbon atom of the cyano group. An individual catalyst can contain more than 1 type of the M or M metal ion in its structure. The grouping of these metals, with the cyanide ion sharing electrons with the 2 metal ions, usually exists in polymeric form as follows: (M-CN---M---NCM) wherein n is an integer of at least 1, and super threedimensional polymers can be formed depending upon the co-ordination numbers of M and M. Moreover, those metal ions, which produce active cyanide catalysts can all co-ordinate with 6 groups (such as hexacyanoferrate (111)). Most of the hexacyanoferrates(III), including zinc hexacyanoferrate(III), have a cubic face-centered lattice.
The CN- group in the catalyst molecule is the bridging group. However, other bridging groups can be present in the catalyst molecule so long as the catalyst molecule contains at least a majority of CN- bridging groups. Thus, r and t are numbers and r is greater than t. t is 0 only when the CN group is the bridging group. For example, X in the formula above, which can be present with the CN" group, can be F-, Cl, Br, 1-, OH, NO, 0'1 CO, H O, N0 1 C 04- or other acid radicals, SO; '3 CNS, CNO NCO", NCS and the like.
In the above formulas M is preferably a metal selected from the group consisting of Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Mo(IV), Mo(VI), Al(III), V(IV), V(V), Sr(ll), W(IV), W(VI), Mn(II), and Cr(III). On the other hand, M is preferably a metal selected from the group consisting of Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), V(IV), and V(V). Also a, b and c are integers whose values are functions of the valences and co-ordination numbers of M and M, and the total net positive charge on M multiplied by a should be essentially equal to the total net negative charge on M[(CN) or [M'[(CN) (X) multiplied by c. In most instances b corresponds to the co-ordination number of M and is usually 6.
Examples of catalysts which fall Within the above description and which may be employed in the process of the present invention are zinc hexacyanoferrate (III) zinc hexacyanoferrate (II) nickel (II) hexacyanoferrate (II) nickel II) hexacyanoferrate (III) zinc hexacyanoferrate (III hydrate,
cob alt(II hexacyanoferrate II) nickel (II) hexacyanoferrate III hydrate, ferrous hexacyanoferrate (III) cob alt (II hexacyanocobaltate (III) zinc hexacyanocobaltate (II) zinc hexacyanomanganate (II) zinc hexacyanochromate (III) zinc iodopentacyanoferrate (III) cobalt (II chloropentacyanoferrate (II) cob alt (II) bromopentacyanoferrate (II) iron (II) fluoropentacyanoferrate(III) zinc chlorobromotetracyanoferrate (III) iron (III) hexacyanoferrate (III) aluminum dichlorotetracyanoferrate (III) molybdenum (IV) bromopentacyanoferrate (III) molybdenum (VI) chloropentacyanoferrate (II) vanadium (IV) hexacyanochromate (II) vanadiurn(V) hexacyanoferrate III) strontium (II) hexacyanoman'ganate (III) tungsten (IV) hexacyanovanadate (I aluminum chloropentacyanovanadate (V) tungsten (VI hexacyanoferrate (III) manganese (II) hexacyanoferrate II) chromium (III) hexacyanoferrate (III) and the like.
Other cyanide complexes which can be employed are those such as and the like. Mixtures of the above compounds can also be employed.
In general, the complex catalysts of this invention are prepared by reacting aqueous solutions of salts which give a precipitate of a metal salt of a transition metal complex anion. For example,
wherein M is a metal ion which precipitates complex anion salts, for example, Zn+ a, b and c in the above equation are integers but do not necessarily have the same values on both sides of the equation since their values are functions of the valences and co-ordination numbers of M, M, M" and possibly Y and Z. Z is a halide or other anion, for example, Cl. M" is a hydrogen ion or a metal ion whose complex anion salts are soluble in water or other solvent, for example K Ca++ and the like. M is a complexing transition metal ion, for example, Fe+++. Y is a complexing anion, for example, CN. In producing the complex cyanide catalyst useful in the present inven tion, an excess of M Z is usually desired.
Apparently extraneous ions in the solution used to form the precipitate are easily occluded with the complex. Anions (Cl, etc.) co-ordinate to the positively charged metallic ions in the lattice, and cations (K co-ordinate to the negatively charged nitrogen atoms of the cyanide bridging groups. These ions, especially those anions co-ordinating to or associated with the M atom, inhibit catalytic activity or prevent the complex from causing appreciable polymerization. Additionally, these ions, for example, easily ionizable Cl, may terminate the polymer chain.
To obtain a catalyst having the highest activity for the telomerization, an organic complexing agent is added to the catalyst precipitate preferably before it is centrifuged or filtered. This complexing agent can be mixed with the water during washing of the precipitate. It can be employed alone as the Washing media provided the complexing agent is able to replace or dissolve the occluded ions, or it can be employed to treat or Wash the precipitate after the precipitate has been washed with water, to replace at least a portion of the water. Sufficient complexing agent is employed to affect these results in order to enhance the activity of the catalyst. Such complexing agent should desirably co-ordinate with the M element or ion and should be a relatively low molecular weight organic complexing agent. The complexing agent should preferably be water miscible or soluble or substantially so, have a substantially strai ht chain and may contain up to 18 carbon atoms. Preferably, the complexing agent contains only up to 10 carbon atoms and is a liquid at room temperature.
Examples of complexing agents which can be employed in the double metal cyanide catalysts are alcohols, aldehydes, ketones, monoethers, diethers, polyethers and acyclic aliphatic polyethers. The alcohols are, for example, alkanols, such as methanol, ethanol, propanol, isopropanol, butanol, octanol, octadecanol and the like. The aldehydes are, for example, formaldehyde, acetaldehyde, butyraldehyde, valeric aldehyde, glyoxal, benzaldehyde, toluic aldehyde and the like. The ketones are, for example, alkanones, such as acetone, methyl ethyl ketone, 3-pentanone, Z-hexanone and the like. Examples of the cyclic ethers are dioxane, trioxymethylene and paraldehyde. Aliphatic saturated monoethers, diethers, polyethers and acyclic aliphatic polyethers are also useful as treating agents, such ethers are, for example, diethyl ether, l-ethoxy pentane, bis-(beta-chloro ethyl) ether, butyl ether, ethyl propyl ether, bis-(beta-methoxy ethyl) ether, dialkyl ethers of alkylene glycols such as ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dimethoxy methane, acetal, methyl propyl ether, diethoxy methane, octaethylene glycol, dimethyl ether, and the like. The acyclic polyethers are preferred. Still other complexing agents which can be employed are, for example, amides, esters, nitriles, and sulfides, of which the following are examples: formamide, acetamide, propionamide, butyramide, valerarnide, amyl formate, ethyl formate, hexyl formate, propyl formate, ethyl acetate, methyl acetate, triethylene glycol diacetate and the like; acetonitrile, propionitrile and the like; dimethyl sulfide, diethyl sulfide, dibutyl sulfide, diamyl sulfide and the like. Ethers having more than 1 oxygen atom and which form a chelate with respect to the metal M are preferred. Mixtures of these organic complexing agents can also be employed. Where there is an excess of that required to complex with the metal catalyst, the excess can be removed by extraction with a hydrocarbon solvent, such as pentane, hexane, and the like.
After treatment With the organic complexing agent, the catalysts have the following rational formulas:
wherein d is an integer or a fraction and c is a number which may be an integer or a fraction, since the catalyst is a nonstoichiometric complex in which various amounts of Water and the R groups may be bonded to the various metals. e is 0 when the catalyst is not treated with the complexing agent. R is One or more of the complexing agents such as the organic amides, alcohols, aldehydes, esters, ethers and the like, as herein above set forth. M, M, CN, X, a, b. c, r and t have the same meaning as herein above set forth. In general, d and e will have values corresponding in part to the co-ordination number of M. The sum of the oxygen and nitrogen co-ordinating atoms from water, the organic complexing agent is from about 0.1 up to about 5.0 gr.-atoms per g.-atom of the metal M. As the catalyst is subsequently heated and dried to remove all of the water and/ or organic complexing agents, the resulting product exhibits a loss or a substantial decrease in its catalytic activity.
As shown in the above formulas if the organic complexing material is not used, R will not be present and thus e will equal 0. Thus, the same formulas for these catalysts is M (Z) -(H O) -(R) where M, H O, R, c, d and e have the above-identified meanings where d and e can also be or approach 0, wherein Z is selected from groups consisting of M'(CN) and M'[(CN) .(X) and where M, CN, X, b, r, and t have the above-identified meanings. In the above formulas, the subscripts represent whole numbers as well as fractional numbers.
In the preparation of the catalyst it is to be noted that Where the catalyst is filtered or centrifuged from the solution in which it was prepared and then washed with one of the polymerizable cyclic oxides such as propylene oxide, it contains little or no catalytic activity. For the subsequent polymerization of such monomers in order to obtain a storage stable catalyst for the polymerization of the cyclic oxide, the catalyst should be filtered or centri- 'fuged from the solution in which it was prepared and then Washed with water and an ether or other organic complexing compound as hereinabove described and subsequently with 1 of the polymerization cyclic oxide monomers. This results in a very active catalyst species.
After the washing steps, the catalyst can be employed per se. However, it is preferred to dry the catalyst to remove excess treating agent and any remaining easily removable water and to provide for a more easily handled material. Such drying is accomplished by subjecting the catalyst'to a vacuum or by heating the catalyst in air or in an inert atmosphere at a temperature up to about 100 C. It is preferred to dry the catalyst under a vacuum at low temperature (for example, 25 C. at 0.5 to 1 mm. Hg), or in a stream of air, nitrogen, or inert gas at from 5 to 25 C. A heat-treated catalyst shows lesser activity and thus must be employed in higher concentration than the vacuum treated catalyst. High temperatures are to be avoided since the catalytic activity of the catalyst is decreased as the temperature of drying is increased. It is believed that, at the high temperatures, some of the oxygenated or other organic complexing agents which are weakly co-ordinated to the metal M may be lost thereby leaving voids in the crystal lattice, and the atoms in the crystal lattice may rearrange to satisfy co-ordination requirements of the metals. Heating may also remove the cyanide ions, and reduce the metal M. It is also possible that the molecular weight of the catalyst can increase thereby reducing the number of exposed metal ions on the surface of the catalyst and/or active sites. It is preferred to employ freshly prepared catalysts since the catalysts slowly decompose upon storage and thus reduce the catalytic activity. Where the catalyst is to be stored for long periods of time, it is preferred that they be stored at reduced temperatures to decrease the amount of decomposition.
While it is not precisely known what occurs to make the double metal cyanide complexes so useful in this polymerization, it is believed that the following takes place. While the following discussion relates to the treatment of the double metal cyanide catalyst with ethers, it will be appreciated that it is generally also applicable to the treatment with other organic complexing agents hereinabove set forth. It has been shown that, for example, with respect to zinc hexacyano-ferrate, as an illustration, when the precipitate is washed with dioxane, a more effective catalyst is produced. During this treatment with dioxane it is believed that a number of reactions take place: (1) some of the chloride ions in the lattice are oxidized, resulting in the reduction of Fe(III) to Fe(II); (2) the chlorine from reaction (1) reacts with the water and ether present during the wash-treatment to give Cl, and chlorinated ether; (3) the successive washes remove some of the products of reaction (2); and (4) the oxygen atoms of the ether apparently co-ordinate to the zinc ions in the lattice, rearranging the lattice structure by inserting dioxane groups between the zinc ions as follows:
Fe-CN Zn CHzCHz-O Zn NC-Fe- Thus, in the case of some of the dioxane-zinc hexacyanoferrate complexes, elemental analyses revealed that they were apparently nonstoichiometric complexes having the formula Zn [Fe(CN) (C H O (H O) Where 3 :1 to 2 and x=2.5 to 3.1. According to infrared and elemental analyses some of the dioxane in the complex may be chlorinated and some of the H 0 may be in the form of --OH or -O- groups. As ordinarily prepared, these complexes generally contained from about 4% to 5% of Cl and a smaller amount of K If the catalyst is prepared with Zn(NO instead of ZnCl approximately 50% of the normal amount of dioxane is incorporated in the catalyst. This catalyst is not as effective as the one prepared from the chloride.
Although a great part of the iron in the ether (or other organic complexing moiety)zinc hexacyanoferrate complex is believed to be Fe(II), as a result of the oxidationreduction reaction that occurs during preparation, the dioxane complex prepared from ZnCl and K,,Fe(CN) is not as active even at polymerization temperatures of C. Analyses showed that a reduced amount of dioxane was incorporated in such complexes and the chlorine content was high.
The reduced catalytic effect when using Zn(NO or K Fe(CN) in the preparation of the catalyst complex is apparently related to the mechanism of the etherhexacyanoferrate reaction. This mechanism may be viewed as follows. As the chloride ions of the surface zinc ions in the crystal lattice transfer electrons into the 'Zn NC-Fe grouping, ether molecules can displace the resulting chlorine atoms and form ether-zinc coordinate bonds. For example,
(Note: 1 in the above equation is a number and may not be the same as in the preceding formulas.) The driving force for this reaction is the removal of C1 by solution of the gas in the water and ether and the reaction of C1 with ether.
This oxidation-reduction reaction and displacement of the chlorine by ether is accompanied by a change in the crystal lattice. According to elemental and infrared analyses, most of the zinc ions in the lattice appear to form coordination bonds with from 1 to 2 oxygen atoms. The oxygen atoms of both the water and the ether are involved in this coordination. X-ray analysis and density measurements appeared to confirm this lattice change. Thus, the oxygen atoms of the ether compete with the CN groups of the Fe(CN) anion to produce a polymeric structure with more exposed zinc ions as shown below:
This process of opening up the lattice is aided by the presence of water during the ether treatment. Apparently, the Water dissolves the Fe(CN) anion sections in the lattice that are coordinated with K+ ions and more of the lattice thereby becomes exposed to the ether during the hexacyanoferrate-ether reaction.
Th experiments have indicated that chloride ions can inhibit the polymerization of the cyclic oxide employed in the double metal cyanide complex catalyst. Thus, it is desirable to reduce the amount of ionizable chlorine or other ionizable anions in the catalysts. For example, the catalyst can be washed with an ether-water solution whereby the soluble chloride salt can be removed. In another method the zinc hexacyanoferrate is prepared by reacting compounds such as calcium ferricyanide, aluminum ferricyanide or lithium ferricyanide with zinc chloride and the chloride salt which forms can be removed by the ether during the washing operation. It has also been found that when ions such as Cl are covalently bonded to the complexing catalyst, they apparently do not adversely affect the polymerization of the epoxides and oxetanes. In fact, chlorinated ethers have been found to improve the efiiciency of the catalyst since it is believed that the halogenated ethers are more readily displaced by the epoxidcs and oxetanes to initiate polymerization.
It is preferred to employ the polyethylene glycol ethe'rs to treat the double metal cyanide since a very active catalyst is thereby obtained. Apparently a chelate bond is formed with the zinc ion thereby increasing the driving force of the hexacyanoferrate-ether reaction, whereby a very open lattice is produced since polymeric coordination through the oxygen atom is prevented. The use of the dimethyl or diethyl ethers of diethylene glycol was found to increase the efficiency of the catalyst. It thus appears that the most active catalysts for the cyclic oxide polymerization are those which contain the greatest amount of Zincoxygen-ether bonds rather than zinc-oxygen-water bonds and the least amount of ionizable chlorine.
The amount of catalyst employed can range from about 0.001 to 15% by weight of the total weight of the telomerizable cyclic oxide monomers employed during telomerization. It is preferred to employ from about 0.01 to 1.0% by Weight of the catalyst based on the total weight of the monomers.
The amount of water employed as a telogen in the process of this invention is dependent upon the molecular weight of the polyoxyalkylene diol desired. The amount of water can vary from as low as .000l% by weight to as high as 5.0% by weight based on the polymerizable oxide. Where molecular weights below 5,000 are desired, the amount of water should be about .4% and higher. This water is added in the propylene oxide and does not include any water that may be occluded in the catalyst The cyclic oxide may be telomerized in bulk or in a solvent. The cyclic oxide should be telomerized under inert or non-oxidizing conditions, for example, under a nitrogen, argon, neon, helium, krypton, or other inert gas. The cyclic oxide can also be telomerized under pressure of the vaporized cyclic oxide.
When large amounts of water are employed to yield low molecular weight telomers, it is preferred to add the water incrementally because large amounts of water decrease the rate of telomerization. Thus, in order to obtain practical rates of reaction, the water is added incrementally. The incremental addition of water can also be employed to give telomers of a broader molecular weight distribution than those possible where all of the water is added at the beginning of the reaction.
The telomerization is preferably conducted in a closed container at atmospheric pressure or at pressure slightly greater than atmospheric. The pressure should be sufficient to maintain a liquid state for dispersion of the catalyst and heat transfer, although it is also possible to bubble gaseous cyclic oxide monomers into the solution for the telomerization.
The temperature at which the process of this invention is conducted is not critical and can vary from about C. to 125 C. or somewhat higher, preferably the temperatures from about C. to 80 C. are employed. In some instances an induction period may be observed with the less active catalyst species.
The telomerized product in accordance with the process of this invention can generally be extended by employing the organic diisocyanates such as toluene diisocyanate, p-phenylene diisocyanate, ethylene diisocyanatc, trimethylene diisocyanate, dodecamethylene diisocyanate, butylene 1,2 diisocyanate, m-phenylene diisocyanate, benzene 1,2,4-triisocyanate, polymethylene polyphenyl isocyanate and the like to yield polyurethane foams and elastomers. The polyurethane elastomers are useful as gaskets, foot mats, shoe heels, engine mountings and the like. The polyurethane foams are useful as insulation and the like.
The following examples serve to further illustrate the invention and are not to be construed as limitations thereon. In the examples all parts are by weight unless otherwise specifically stated.
Example I A zinc-hexacyanoferrate-dioxane complex catalyst (essentially Zn (Fe(CN) -3.1C H O -1.6H O) was prepared as follows: An aqueous solution (200 ml.) of K Fe(CN) [0.430 molar] was added slowly to 75 ml. of an aqueous solution of zinc chloride (1.89 molar). This is equivalent to a 10 mol percent excess of zinc chloride. The precipitated zinc hexacyanoferrate was separated by centrifugation (2,000 rpm. for 30 min.) and washed four times with ZOO-ml. portions of anhydrous, peroxidefree dioxane and dried at 25 C. at less than 1 mm. Hg overnight. It was employed to catalyze the polymerization of propylene oxide and allyl glycidyl ether in the presence and in the absence of water. 0.1 gram of the zinc hexacyanoferrate dioxane complex and 0.1 gram of phenyl-beta-naphthylamine and air was charged into a a dry, crown-capped, beverage bottle, containing a magnetic stirring bar. The bottle was flushed with nitrogen, capped and propylene oxide (47.1 grams, 0.81 mole) and allyl glycidyl ether (2.88 grams, 0.25 mole) was added by means of a hypodermic syringe. In the first instancethe propylene oxide contained no water and in the second, the propylene oxide contained .00023 weight percent water. The polymers obtained at the same conversion (93%) had intrinsic viscosities in isopropanol at C. of 4.9 and 2.8 respectively. This shows the effect of water in reducing the molecular weight.
Example II In this example a zinc-hexacyanocobaltate-acetone complex prepared as follows was employed as the catalyst. A solution containing 694 g. Ca [Co(CN) and 505 g. water was added dropwise to a solution of ZnCl (55.5 g.) in 63.2 g. water. Acetone (1895 g.) was then added to the slurry of the precipitate in water and the mixture was stirred for 15 minutes. The precipitate was separated by centrifugation (7000 rpm, 40 min.) and then washed ten times with volume percent acetone in water. Approximately 2000 ml. of solution was used for each wash. After two additional washes with 2000 ml. of pure acetone, the solid cake was dried at 25 C. at less than 20 mm. Hg for 9-1O hours.
Then general procedure for the telomerization reaction is as follows. The catalyst was charged into a dry beverage bottle, the bottle capped, evacuated and filled with nitrogen. A propylene oxide-water mixture (25 grams) was added by means of a hypodermic syringe. The bottle was then placed in a constant-temperature bath maintained at C. and agitated in an end-over-end rotating assembly. The product was recovered by evaporating the propylene oxide. The pertinent data are summarized in Table I. The molecular weight was determined by vapor phase osmometry. The hydroxyl content was determined and the functionality was calculated by dividing the number of moles of the hydroxyl group by the number of moles of the telomer.
Example III The catalyst employed in this example was prepared as follows:
A glyme-zinc hexacyanocobaltate complex (essentially Zn [Co(CN) -l.7 glyme-1.2H O-L2ZnCl was prepared as follows. An aqueous solution (100 ml.) of K Co(CN) [0.296 M] was passed through a bed containing the acid form of Amberlyst 15. In this process H+ was exchanged for K+. The acid solution was then evaporated at room temperature to a volume of 80 ml. resulting in a 0.370 M solution of H Co(CN) and the solution was then rapidly mixed with 10 ml. of an aqueous solution of ZnCl [4.87 M]. This is equivalent to using a 10 mol percent excess of ZnCl After the precipitation of Zn [Co (CN) was complete, 60 g. of glyme was added slowly to the aqueous slurry and stirred for 15 minutes. The precipitate was separated by centrifugation (7000 r.p.m., 40 min.) and then washed twice with glyme (total volume: 188 ml.). The precipitate was finally recovered and dried at 25 C. at less than 1 mm. Hg overnight. Glyme is the dimethylether of ethylene glycol.
The catalyst Zn [Co(CN) -glyme (.08 g.) was weighed out and placed in a 12 ounce Pyrex bottle. All bottles were washed and rinsed in deionized water and dried at 200 C. overnight. After charging the catalyst, the bottles were immediately capped and evacuated at less than 22 mm. Hg pressure for 15 minutes. Propylene oxide (60 ml., 50 g.) was then added and deionized water then added by means of a syringe. The sample bottles were immediately placed into the safety can and placed in an 80 C. tumble action bath. The pertinent data in this example is summarized in the following chart.
TABLE II A B C D Catalyst, gm 08 08 08 08 Propylene oxide, g-m 50 50 50 50 Water, ml:
1st addition 1. 35 .20 20 2nd addition".-- 65 .80 80 Total 1. 00 1.00 1. 00 1.00 Time between 1st and 2nd addition of water (min.) 218 100 68 Reaction times, hrs... 24 24 24 24 Temperature, 0..-- 80 80 80 80 Percent conversion. 6. 3 22. 6 52. 40. 8 Hydroxyl number 261 58.1 76. 9
From the above data, it is evident that the incremental addition of water greatly improves the yield of the telomer.
What is claimed is:
1. A process for the preparation of polyoxyalkylene ether diols wherein the hydroxyl groups are substantially terminal hydroxyl groups which comprises admixing at least one polymerizable 1,2-epoxide, oxetane, 3-substituted oxetane or 3,3-disubstituted oxetane monomer selected from the group hereinafter defined with water in an amount from about 0.0001 to 5.0% by weight based upon said monomer in the presence of a catalyst in an amount of from about 0.001 to by weight of said monomer, said catalyst comprising a double metal cyanide complex compound which in its generic form has the general formula M (Z) wherein Z is selected from the group consisting of M(CN) and M[(CN),(X) wherein M is at least one metal selected from the group consisting of Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Mo(IV),
10 Mo(VI), Al(III), V(IV), V(V), Sr(lI), W(IV), W(Vl), Mn(II) and Cr(III), M is a metal selected from the group consisting of Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), V(IV) and V(V), X is a member selected from the group consisting of F, Cl, Br, I-, OH*, NO: 0*, CO, H O, N0 1 C O 50,-, CNO-, CNS, NCO and NCS-, a, b and 0 being numbers whose values are functions of the valences and the coordination numbers of M and M, the total net positive charge on M times a being essentially equal to the total net negative charge on Z times 0, r being a number greater than the number 1, and maintaining said admixture at a temperature of from about 0 to 180 C. under an inert atmosphere wherein said water and said monomer react to produce polyoxyalkylene ether diols, said monomer being selected from the group consisting of ethylene oxide; 1,2-propy1ene oxide; 1,2-butene oxide; 1,2- hexene oxide; 1,2-dodecane monoxide; isobutylene oxide; styrene oxide; 1,2-pentene oxide; isopentene oxide; 1,2- heptane oxide; allyl glycidyl ether; isoheptene oxide; 1,2- octene oxide; methyl glycidyl ether; ethyl glycidyl ether; phenyl glycidyl ether; butadiene monoxide; isoprene monoxide; oxetane; tolyl glycidyl ether; 3,3-dimethyl oxetane; 3-allyl-3-methyl oxetane; 3-vinyl-3-methyl oxetane;
1,2-pentadecene oxide; 3-butyl-3-decyl oxetane; 3-ch1oro- I methylene oxetane and 3-chloromethyl-3-methyl oxetane.
2. A process as claimed in claim 1 wherein said catalyst contains Water as a component.
3. A process as claimed in claim 1 wherein said catalyst contains an alkanol of having 1 to 18 carbon atoms as a component.
4. A process as claimed in claim 1 wherein said catalyst contains as a component an aldehyde selected from the group consisting of formaldehyde, acetaldehyde, butyraldehyde, valeric aldehyde, glyoxal, benzaldehyde and toluic aldehyde.
5. A process as claimed in claim 1 wherein said catalyst contains as a component an alkanone having 2 to 6 carbon atoms.
6. A process as claimed in claim 1 wherein said catalyst contains as a component a cyclic ether selected from the group consisting of dioxane, trioxymethylene and paraldehyde.
7. A process as claimed in claim 1 wherein said catalyst cimtalins as a component a dialkyl ether of an alkylene g yco 8. A process as claimed in claim 7 wherein said dialkyl ether is selected from the group consisting of ethyl- C11; glycol dimethyl ether and triethylene glycol dimethyl et er.
9. A process as claimed in claim 1 wherein said temperature is between 15 to C.
10. A process as claimed in claim 1 wherein said catalyst is a zinc cobalticyanide complex.
11. A process as claimed in claim 1 wherein said catalyst is employed in an amount between 0.01 to 1% by weight and said water in an amount between 0.001 to 1% by weight.
References Cited York, 1963, pp. -476, 222-224.
LEON ZITVER, Primary Examiner.
I-LT. MARS, Assistant Examiner.
Citas de patentes
Citada por
Imagen original


text:
Bachelor Bitter Cured Corned Beef
Sub Title:
Corned Beef Recipe (not just for bachelors)
Recipe Type:
Pub Recipe
Ingredients12 oz of Bachelor Bitter (grab a growler at our Bend or Portland Pub)
3 C water
1/4 C kosher salt
1 8 lb beef brisket
2 peeled cloves of garlic
6 peppercorns
6 whole cloves
1 bay leaf
3 sprigs of thyme
1/2 chopped onion
2 chopped carrots
2 ribs chopped celery
DirectionsPlace beef brisket in a large, deep casserole dish. Combine remaining ingredients and pour over brisket to cover. You may need to weigh the meat down. Cover and refrigerate for 4 to 5 days. When brisket has finished curing, remove from brine and rinse well. Strain the brine and reserve for cooking.
Preheat oven to 350 degrees, place brisket and reserved ingredients in a large casserole dish. Cover with fresh water and cover with lid. Cook brisket for 3-4 hours or until tender. Let meat cool slightly before serving. Serve with boiled cabbage, potatoes & a pint of Bachelor Bitter of couse.
Serves 8


text:
Waynflete girls ride fast start past NYA
PORTLAND—After struggling through 90 frustrating minutes and settling for a 1-1 tie at North Yarmouth Academy just over two weeks ago, the Waynflete girls' soccer team decided to make life easier on itself in the rematch Friday afternoon at Fore River Fields.
In a game pivotal for Heal Points and playoff positioning, the Flyers came out and seized control in the first five minutes, courtesy a pair of goals from sophomore Esme Benson.
Then, just before halftime, the hosts ended all doubt, as senior Ella Millard and freshman Beata Vest tickled the twine for a commanding 4-0 advantage.
Any Panthers' comeback hopes were dashed by a second Millard goal, with just over 23 minutes to play, and after NYA got on the board, courtesy its clutch scorer, sophomore Alex Wahlstrom, Waynflete ended all doubt when sophomore Meddy Smith scored on a rebound with just over six minutes to go.
The Flyers went on to a surprisingly convincing 6-1 victory, improved to 10-1-2 and ended the Panthers' best regular season since 2009 at 7-5-2.
"I think we've improved a lot," said Millard. "We've come together as a team a lot since we played them last time. We came out a little flat the last time we played them and today we talked about coming out with urgency."
Rivalry renewed
While Waynflete, as the defending champion, was a proven commodity coming into the 2013 season, little was expected of NYA, which has returned to form.
The Panthers opened with a 2-0 home win over Traip. After falling by 3-2 scores to visiting Gray-New Gloucester and host Traip, NYA handled visiting Old Orchard Beach and Buckfield by 6-0 margins. After playing visiting Fryeburg to a scoreless tie, the Panthers beat visiting Sacopee Valley, 3-1. A 3-0 loss at Freeport followed, but on Oct. 2, NYA battled back to tie visiting Waynflete, 1-1, earning some confidence in the process. After a 3-1 loss at Poland, the legend of Alex Wahlstrom began, as she had overtime winners at Lake Region, Old Orchard Beach and Sacopee Valley to give her team 2-1 victories each time.
Waynflete has a lot of new faces this fall, but has remained impressive. After holding off visiting Traip in the opener, 5-3, the Flyers won at Fryeburg (2-0), tied host Lake Region (2-2), then beat visiting Gray-New Gloucester (3-0) and host Old Orchard Beach (5-0) before falling from the unbeaten ranks with a 2-1 home loss to Poland. A 3-1 home win over OOB followed, then Waynflete tied at NYA, 1-1. The Flyers bounced back to blank host Sacopee Valley and Freeport by 2-0 scores, then handled visiting Sacopee Valley (2-1) and host Traip (4-1).
For a stretch last decade, the NYA-Waynflete girls' soccer rivalry was as fierce as any. From 2005-2009, the teams met every year in the postseason, including three times in the regional final, with the winner going on to capture the Class C championship each team.
Entering Friday's game, since the start of the 2001 season, the Flyers had won 13 times, the Panthers 10 and four other games ended in draws (please see sidebar, below).
NYA came to Waynflete seeking its first win over the Flyers since a 4-0 home victory Oct. 3, 2009, but instead, Waynflete improved to 7-0-2 against the Panthers in the last nine meetings and it didn't take long for the Flyers to put this one away.
Millard almost broke the ice in the second minute, but her rush was broken up by NYA senior defender Lizzie Lewis.
The hosts kept the pressure on and sophomore Arianna Giguere played the ball down the right side before crossing it in front where Benson waited. Benson didn't get much on the ball, but still managed to steer it past diving Panthers junior goalkeeper Scout Fischman for a 1-0 lead.
"I barely got my foot on it," Benson said. "I guess it was enough."
After a long free kick from Flyers sophomore Marijke Rowse was deflected just wide of the mark, Benson made it 2-0.
Benson got a gift on her second goal, as a defender tried to clear the ball, but didn't get much on it and the ball came right to Benson who had a clean look and shot it past Fischman from the top of the box to give Waynflete some breathing room.
"We talked about finishing it early, so we could relax more in the second half and not have to stress," Benson said. "We did that. I just took a touch after the defender sent it to me."
"We came out ready to play," said Flyers coach Todd Dominski. "It showed from the beginning of the game. We haven't come out in all our games like that. When we come out to play we can really play. It was nice to see us ready to go. Esme did a nice job with her spacing. Finding her was the other piece. We haven't been able to get the ball to her all the time, but we found her today and she put them away."
NYA almost got back in the game in the seventh minute, but Wahlstrom shot just wide.
In the 10th minute, Wahlstrom lofted a shot from the left side with Waynflete junior goalkeeper Julianna Harwood out of the cage, but the ball just missed its mark.
Rowse then broke up a rush by Panthers junior Melanie Regan before the Flyers transitioned to offense.
In the 13th minute, the hosts almost went on top by three, but after senior Sofia Canning set up senior Leigh Fernandez with a pretty pass, Fernandez's shot was just high.
In the 15th minute, Benson looked to complete a hat trick as she bore down on a ball in the box at the same time Fischman and an NYA defender reached it. Benson managed to get her foot on the ball, but sent it just wide.
After Millard shot just high and had a rush broken up, Smith sent a one-timer just wide of the far post.
Then, with 5:33 remaining in the first half, Giguere got the ball after a turnover, passed to Millard, and Millard launched a shot from about 20-yards out which ticked the inside of the far post and bounced into the net to make it 3-0.
After Giguere's rush (set up by a picture perfect feed from Fernandez) was broken up by a sliding Fischman, who kicked the ball away, Waynflete struck once more before the break.
With just 17 seconds to go, Millard passed to Vest, who launched a shot just over Fischman from the top of the box and it was 4-0 Flyers at halftime.
Waynflete had a 13-4 shots advantage in the first 40 minutes.
The Flyers knew the game wasn't over and didn't sit on their lead.
NYA just missed getting on the board with 27:27 to play, but a shot from Regan hit the post, then was cleared by Waynflete senior Sophie Raffel.
Then, Millard struck again to extend the lead.
With 23:26 showing, Canning set up Millard for a 20-yard rocket, which again just slipped inside the far post for a 5-0 advantage.
"We weren't finding feet well in the first half, so we wanted to keep coming and have energy," Millard said.
"I thought Ella and Ari both worked well up top," said Dominski. "When they work hard up top, we're tough to defend."
A minute later, Harwood had to make a sprawling save on a deflected shot off the foot of NYA sophomore Anna Laprise.
The Panthers finally broke through with 17:54 left, as Wahlstrom got to a long lead pass and one-touched it past Harwood to make it 5-1.
Waynflete didn't let NYA get any momentum, however, as sophomore Christian Rowe had a timely block of a bid from sophomore Taylor Leach and senior Jillian Bjorn-Caron sent the rebound high. A minute later, Rowe broke up a Leach rush.
Then, with 6:12 to play, Smith was in the right place to bang home a rebound, making the score 6-1.
Down the stretch, Harwood denied Regan and Regan shot just wide and the Flyers were soon able to celebrate their impressive victory.
"It was a good result for us today," said Dominski. "Obviously, NYA's a rival. We wanted the game and we wanted the (Heal) Points. We want to seed ourselves as high as possible. We want to get rolling for the playoffs."
Waynflete finished with an 18-12 shots advantage (7-6 on frame), had a 3-1 edge in corner kicks and got four saves from Harwood (Rowe also had a defensive save).
Harwood missed the first half of the season recovering from a knee injury, but hasn't shown much rust.
"(Julianna's) come back to true form quickly," Dominski said. "It hasn't taken much for her to get there."
NYA was hoping for more.
"The game was disappointing for the girls because we gave up a lot of silly goals that we could have stopped," said Panthers first-year coach Josh Thornton. "The girls have been outstanding this season, however, they learned a tough lesson. We have won the last three games in overtime after not playing well. They had to learn that if they don't play well against good teams they will get punished. Wayneflete's good and moves the ball well. :
Even in the aftermath of the defeat, NYA was very pleased with what it's accomplished so far.
"The girls have won twice as many games this year as last year and are set for possibly playing a home game in playoffs," Thornton said. "We played four games in eight days and won three of them, so I'm delighted."
Time to get serious
NYA projects to finish eighth or ninth in the Western Class C Heal Points standings and will now prepare for its first playoff game since 2009.
Waynflete, meanwhile, still has a chance to move up when it hosts three-time defending Class B champion Falmouth Monday afternoon. The Flyers (fifth Western C) can make a quantum leap if they could find a way to knock off the Yachtsmen.
"If we come with the same intensity we had today, we'll be good," Benson said.
"We can always improve on things," said Millard. "We're really coming together and we're excited to play Falmouth. We're excited to see how it turns out."
"We're getting there," Dominski added. "It's effort and making sure we do the right things out there. We're no different than anyone else playing right now that's a little banged up. We'll go out and give Falmouth our best and see what we can get out of it. I think if we beat them, we'd get up there, but they'll want to finish high like we do. It's nice to play teams of high caliber. It pushes us to see what we have."
Sports Editor Michael Hoffer can be reached at firstname.lastname@example.com. Follow him on Twitter: @foresports.
Recent NYA-Waynflete results
@ NYA 1 Waynflete 1 (tie)
@ Waynflete 2 NYA 0
Waynflete 3 @ NYA 0
@ Waynflete 8 NYA 0
Waynflete 6 @ NYA 0
@ Waynflete 4 NYA 1
@ NYA 0 Waynflete 0 (tie)
@ Waynflete 1 NYA 0 (2 OT)
@ NYA 4 Waynflete 0
Western C quarterfinals
@ Waynflete 2 NYA 1
Waynflete 4 @ NYA 0
Western C Final
@ Waynflete 2 NYA 0
@ Waynflete 3 NYA 1
Western C Final
NYA 1 @ Waynflete 0 (OT)
NYA 4 @ Waynflete 0
@ NYA 5 Waynflete 2
Western C Final
@ NYA 1 Waynflete 0
Waynflete 2 @ NYA 1
NYA 2 @ Waynflete 1
Western C semifinals
NYA 3 @ Waynflete 1
@ Waynflete 1 NYA 1 (tie)
@ NYA 2 Waynflete 0
@ NYA 2 Waynflete 1
NYA 2 @ Waynflete 0
Waynflete 5 @ NYA 2
@ Waynflete 0 NYA 0 (tie)
Waynflete 2 @ NYA 0


text:
Valley Forest Wood Products
Live On-Site Auction with Online Bidding
Began: Tuesday, February 05, 2013 at 10:30 AM CST
Location: 48985 State Highway 38, Marcell, MN 56657
Began: Monday, February 04, 2013 at 1:00 PM CST
Ended: Monday, February 04, 2013 at 5:00 PM CST
Location: 48985 State Highway 38, Marcell, MN 56657
Complete liquidation of the Valley Forest Wood Products pellet mill facility. This auction includes the complete pellet mill line - mills, hogs, blower systems, pneumatic conveyor lines, bagging system, waste wood furnace system, stoarge bins, and more!
Truck Scale System
Dump Station
Pellet Mill
Pellet Mill Dust Collection System
Storage Bins
Bag House
Wheel Loader, Pickup, and Material Handling
Logs, Pallets, and Feedstock
Shop Tools/Miscellaneous
Large amount of scrap – including car bodies, hopper bins, electric motors, reservoir tanks, 55-gal steel drums, corrugated galvanized steel, and large assortment of additional scrap! Come prepared to purchase large quantities!
Auction Terms
Complete payment day of sale: Cash or certified funds. Checks must be accompanied by a current bank letter of guarantee. No property removed until fully settled for. After the auctioneer has sold a piece of equipment, it becomes the sole responsibility of the purchaser. All equipment is sold as-is and where-is. Any announcements made day of sale take precedence over printed material. Onsite: 15% buyers premium/fee in effect (3% discount for cash/guaranteed funds). Online (payment by credit card only): 18% buyer's premium/fee.
The information contained in this listing is subject to inspection and verification by all parties relying on it. No liability for its accuracy, errors, or omissions is assumed by the seller, the representative of the seller, Grafe Auction Company or their agents. In rare situations, pursuant to federal UCC regulations, the seller may retain one or more items that have been advertised for sale. Every effort is made to provide notice of retention as soon as Grafe Auction Company becomes aware.
Minnesota Licensed Auctioneer: Judd T Grafe 2310013
28 miles North of Grand Rapids, MN on MN-38 to facility on left (48985 State Highway 38, Marcell, MN).
We'll keep you in the loop for all future auctions!
What are you looking for? We'll help you find it!
What are you looking for? We'll help you find it!


text:
COLUMBIA CITY — There was no shortage of suggestions at last night's aquatics facility public forum.
Since the announcement of Burnworth Memorial Pool closing in 2014, a task force has been working on a replacement for the public pool option.
Kevin Post, of Counsilman-Hunsaker, led the forum with his expertise on facility design and execution.
"The typical pool has a life of 30 to 50 years. Burnworth Pool is out of that life expectancy. It is definitely time to look at another aquatics option," Post said. "But the idea of what a pool is has evolved over the years."
COLUMBIA CITY — Columbia City High School saluted its top students at its Honors Convocation Monday evening. Awards were handed out to students for academic achievements, scholarships, service work and excellence in athletics. CCHS Principal Jennifer Reiff praised the top Eagles of 2013, lauding their hard work in the classroom and the community.
Dennis Robert Firestone, 60, of South Whitley, died at 6:54 a.m. Sunday, May 19, 2013, at his home.
He was born December 31, 1952, in Whitley County, a son of Robert G. and Mildred A. (Schneider) Firestone.
Surviving include his two children, two grandchildren and his domestic partner, Sarah Mills, South Whitley.
A memorial gathering will be held Saturday at the VFW Hall, South Whitley, from 2 to 6 p.m. A memorial service will be held at a later date.
Condolences may be made at www.smithandsonsfuneralhome.com.
CHURUBUSCO — Churubusco's baseball team dropped an extra-inning NECC game Monday.
The Eagles fell to Lakeland, 6-5, in 10 innings.
Churubusco took a 5-0 lead after three innings. The Lakers slowly crawled back, chipping in a run in the fourth and four more in the top of the fifth.
Lakeland finally broke the scoreless struggle that went into extra innings by notching one run in the top of the 10th.
Columbia City's softball team suffered a season-ending loss to Carroll in the first round of sectionals Monday.
After taking a 1-0 lead, the Lady Eagles fell 11-1 to the Lady Chargers. Pictured above is Allie Vodde.
ANGOLA — Whatever momentum Columbia City's baseball team had built up heading towards sectionals was lost Monday night at Angola.
The Eagles were 10-runned by the Hornets by a final of 13-3 after five innings.
Columbia City was only down 5-3 in the middle of the fifth frame.
However, what started as a feasible deficit to overcome turned into an insurmountable one that ultimately ended the game without the Eagles getting another turn to bat. Angola scored eight runs in the bottom of the fifth to win the matchup, 13-3.
ANDREWS — Whitko's boys golf team picked up a win on the way to sectionals later this week.
The Wildcats beat Southwood Monday, 184-192 at Etna Acres Golf Club.
Whitko was paced by Danny Zawlocki, who shot 44, tying him with two Southwood golfers for the top score.
KENDALLVILLE — Churubusco sophomore linkster Beau Barkley made 1st-Team All-Northeast Corner Conference for the second time Saturday, placing eighth.
Barkley, along with junior Brad Martin, led the Eagles to a fifth-place finish at the NECC match at Noble Hawk Golf Links.
Martin was also named 1st-Team All-Conference, finishing 12th for the Eagles.
He dropped a 10-foot birdie put on the 18th hole that lifted him from 16th to 12 place. Martin missed all-conference by one stroke last season.
COLUMBIA CITY — Indian Springs Middle School's boys and girls track teams ended their season this month.
The boys 8th-grade squad took first place in the Northeast Lakes Middle School Conference meet, downing Whitko, Lakeview, Edgewood, Lincoln, Riverview and Crestview.
ISMS barely edged Lincoln, by five points, to earn the title.
Many tracksters placed higher in their events than they were seeded.
The girls took third in the NELMSC conference meet, and Whitko's girls won.
Results for Whitko's athletes were not available.
COLUMBIA CITY — Due to the Memorial Day holiday, there will be no collections Monday for trash and recycling.
Monday collections will be made on Tuesday. Tuesday collections will be on Wednesday. Wednesday collections will be made on Thursday. Thursday collections will be made on Friday.
Friday collections will be made on Saturday.
All trash and recycling collections the week of May 27 will be performed one day later than normally scheduled.


text:
Guns In Arizona: A Life-Or-Death Question
Professor John Donohue is quoted in this Arizona Republic article on the doubt he has over research done by economists at the University of Chicago that indicates allowing citizens to carry concealed weapons deters violent crimes. Donohue and Yale Professor Ian Ayres calls the evidence "sporadic and extraordinarily fragile."
Arizona has some of the least restrictive gun laws in the nation. It also has one of the highest rates of gun deaths in the country.
But how closely are guns and violence connected?
The answer, like much involving guns in America, is complicated.
Law professors Ian Ayres of Yale and John Donohue of Stanford are among those who have cast doubt on the rigor of the analysis.
In their 2003 paper, they acknowledged that Lott and Mustard had established that the predicted bloodbaths from more lenient concealed-weapons laws didn't happen. But Ayres and Donohue found "sporadic and extraordinarily fragile" evidence that the changes helped reduce crime. They said it appeared just as likely the gun laws increased crime.


text:
Carl Matthes: If Rick Santorum were Pope, nuns would would be given veils. If he was President, women would be brought into the bedroom only for procreation.
Bhutto:The Film — Heartbreaking, Thought-Provoking History Lesson
Georgianne Nienaber: Bhutto: The Film presents the story of a woman whose strength of personality and conviction totally dominates the constraints of a fundamentalist religious society where women had no intrinsic value. The voice over of Bhutto describing her birth is the ghost in the room. Her extended family was in mourning that Benazir entered the world in a society where the only desire is that the firstborn be a boy. "Dogs and cats were giving birth to boys," she narrates from the grave.


text:
Kick off the editing process with Adobe Prelude. Learn how to transfer, transcode, and log your media before you move to Premiere Pro.
Explore how to ingest and organize tapeless media for post-production using Adobe Prelude.
Use Prelude to organize, ingest, transcode, tag, comment, subclip, and build a rough cut before sending media on to Premiere Pro for editing.
"Thank you for the great teachers, training, wide subject matter, and affordable pricing." —Bud S.
more from our members »


text:
Connect with Us
Podcasts & RSS Feeds
|All Content
|View all podcasts & RSS feeds
Now Playing
Now Playing
Most Active Stories
Inside NPR.org
3:13 pm
Fri October 12, 2012
Want To Spend Election Night at NPR HQ?
Originally published on Sat October 13, 2012 12:42 pm
Have you ever wondered what it's like to be at NPR on election night? Here's your chance to find out.
On Tuesday, Nov. 6, NPR's social media desk will host around two dozen of you at NPR headquarters in Washington, D.C. We're looking for people from across the political spectrum — bloggers, Twitter users, Tumblrs, Redditors, etc. — who plan to cover election night on their own. It'll be a chance to hang out with fellow political geeks and NPR staff, as well as an opportunity to experience election night at NPR in person. We'll supply the food and the wifi, too.
If you're interested in applying, please fill out this form. We'll make our selections over the next couple of weeks on a rolling basis, so the sooner you apply, the better.


text:
Two weeks ago, I reported on a recent visit to Future World's Spaceship Earth, The Universe of Energy, and Test Track, looking at each attraction from a historical perspective as well as through the eyes of today's visitors. While I still contend that the original versions of these Imagineering classics far outshine anything that has come afterword, I admit that there is much to like about today's incarnations of these Epcot experiences.
Today, come along with me as we conclude our visit with a stop at the attractions located in Future World West, specifically The Living Seas, The Land, and Journey into Imagination.
The Living Seas/The Seas with Nemo and Friends
The original Living Seas, opened in 1986, strove for authenticity and realism. After viewing a short film simply entitled "The Sea," visitors to The Living Seas boarded an elevator called a "hydrolater" before sitting down in a Seacab that took them along an underwater tunnel through a huge aquarium. Guests disembarked at Sea Base Alpha, the central exhibit area to view sea creatures, interact with educational exhibits, and to listen to scientists and divers talk about the seas as well as the creatures that call the seas "home."
While the goal was realism, the original attraction fell short on several levels. For one thing, the opening film was not especially engaging. Eventually, Disney made the film optional, allowing guests to freely move on to the "ride" portion of the attraction. The hydrolater was another problem. While the concept of taking guests "below" was a good one, the execution was problematic. Hot, crowded, and not at all convincing, the hydrolaters were an unconvincing combination of the worst elements of 20,000 Leagues Under the Sea and Mission to Mars at the Magic Kingdom. The actual exhibit area was wonderful, clearly the highlight of the pavilion.
From 2003 to 2007, The Living Seas was transformed into its current incarnation as The Seas with Nemo and Friends. In many ways, this experience—while not as authentic or scientific as the original—is far more entertaining and eliminates those awkward "realistic" moments with pure fantasy in an educational and engaging way.
The main "ride" here is based on the Disney-Pixar film Finding Nemo, and follows the basic plotline of that well-known film. After journeying through a very long circuitous queue that gives the illusion of being underwater, guests board "Clamobiles" taking them through the Nemo story as well as the huge Disney created aquarium. Using a newly developed projection system, images from the animated film are seamlessly interwoven with the actual sea creatures living in the aquarium.
Sea Base Alpha is still home to a variety of exhibits, presentations, interactive stations, as well as human presenters and speakers. It is also home to world-class aquariums that give visitors an up-close-and–personal look at sea creatures and sometimes human divers interacting with them. It is also home to the immensely popular Turtle Talk with Crush, a show that is as appealing to adults as it is to children. While grownups sit on padded benches, children are invited to sit on the floor in front of a large movie screen. Crush, as well as a human Cast Member, interact with children—Crush answers questions, calls children by name, and responds "live" to the Cast Member and to audience members alike. It is a charming, memorable show.
The Seas with Nemo and Friends is the one update to a Future World classic that, in my humble opinion, outshines the original. It manages to entertain and educate, charm and inform, delight and challenge—the exact ideals that EPCOT Center originally fostered.
The Land
One of Future World's original pavilions when the park opened in 1982, The Land plays host to several attractions and several restaurants as well. The original design, from 1982 to 1992, was sponsored by Kraft and featured a boat ride, Listen to the Land, a film entitled "Symbiosis," a restaurant, and an audio-animatronic show called "Kitchen Kabaret."
The original film, "Symbiosis," looked at man's complex and interconnected relationship with the earth. This film was replaced in 1995 with The Circle of Life: An Environmental Fable, which kept the spirit of the original film and added characters from Disney's widely popular film, The Lion King.
This update, like the one at the Living Seas, irked many longtime Epcot fans. They felt that the integrity of the EPCOT vision was compromised with the inclusion of cartoon characters. While there is definably merit in that overall concern, The Circle of Life: An Environmental Fable adheres to the goal of educating while entertaining, even if it does so in a more user-friendly way.
The signature attraction, Listen to the Land, featured a boat ride through Disney created environments such as the rainforest, the Great Plains, and the American farm. It concluded with a visit to the immense greenhouses where actual research was conducted on plant and animal production. The original featured actual cast members on board as hosts, as well as a wonderful song entitled, appropriately enough, "Listen to the Land."
When The Land received its first makeover in the mid 1990s, this attraction was renamed "Living with the Land" and remained virtually unchanged (although, sadly, the song was removed). In 2009, an automated system was installed and the "live" cast members were unfortunately replaced with a pre-recorded audio track.
The Land's third original attraction, the clever audio-animatronic show called "Kitchen Kabaret," featured a cast of endearing members of the various food groups who provided a memorable and tuneful lesson in good nutrition. This show was updated to the very tacky Food Rocks in 1994. This regrettable attraction represents all that was terrible about that unfortunate era when Disney tried to be "hip" and "relevant"—ignoring the fact that timeless and classis are always relevant.
In 1995, Food Rocks made way for Soarin', one of present-day Epcot's most memorable and popular experiences. This award-winning attraction, originally conceived for Disney California Adventure park, gives riders a simulated experience of hang gliding over some of California's natural and artificial landmarks. It is truly one of Epcot's most stunning experiences.
In many ways, this spirit of this pavilion embodies Epcot's goals, original and present day. There are thrills in Soarin', educational elements in Living with the Land, serious conservation issues in The Circle of Life: An Environmental Fable, and good food at the Sunshine Seasons and the Garden Grille Restaurant. We enjoyed all of the attractions here and look forward to exploring them again soon.
Journey into Imagination
In a recent piece highlighting the announcement from Marvel and Disney Kingdoms that a new series featuring Figment and the Dreamfinder will premiere this June. In it, I provided a short history of this pavilion:
"When EPCOT Center opened its gates to the world in 1982, guests were greeted by boundless optimism and never-before-seen wonders. Two of Epcot's most famous characters, however, did not make their appearance until 1983. These beloved characters, created by Disney especially for Epcot, were an integral part of the EPCOT experience until 1998.
For 15 years, Dreamfinder, along with his dragon-like friend Figment, entertained guests in Audio-Animatronic form in the Journey into Imagination attraction housed in the two glass pyramids located near the Land pavilion in Future World and in person near the 'Jellyfish Fountains' located outside. After the debacle of the 1999 Journey into YOUR Imagination, a Figment-free renovation that generated mountains of guest complaints, the attraction reopened in 2002 as Journey into Imagination with Figment. While Dreamfinder is still absent (and replaced with a filmed host played by Eric Idle), Figment returned, as did the wonderful Richard and Robert Sherman song entitled "One Little Spark," complete with additional verses. While the current version is in no way shape or form as charming as the first, Figment's return was a welcome one indeed."
The current version is entertaining, albeit technically unspectacular. Figment's impish charm goes a long way in making this a fun attraction for small children, and while the activities featured after the ride are in no way as stunning as those found in the old Image Works, there are ample diversions to keep little explorers busy for an extended amount of time. The return of Captain EO, however, is less successful for a variety of reasons. Still, it was a nostalgic blast from the past and reminded me of EPCOT visits as a member of the Walt Disney World College Program back in the day. The kids liked the "creatures" and the last song, "We Are Here to Change the World."
At the end of the day, however, this entire attraction needs updating. The color scheme is chaotic, the ride unimaginative, the film, dated, and the experiences limited. This pavilion has so much potential—here's hoping the new Figment series is a hit and leads to a reimagined, reinvented imagination pavilion.
Final Thoughts
My family and I were able to create a few new "magic moments" in one of my favorite parks this past spring break. Our time spent in Future World's reimagined attractions was time well spent. While the awe and reverence we of the "EPCOT Generation" felt when first entering this Disney marvel of marvels may have been diminished over the years, the overall Epcot experience is still a very good one. Today's Epcot lives up to the promise pronounced on opening day:
To all who come to this Place of Joy, Hope and Friendship—WELCOME
Epcot is inspired by Walt Disney's creative vision. Here, human achievements are celebrated through imagination, wonders of enterprise and concepts of a future that promises new and exciting benefits for all.
May EPCOT Center entertain, inform and inspire and, above all, may it instill a new sense of belief and pride in man's ability to shape a world that offers hope to people everywhere.


text:
MEMPHIS, Tenn. — Sydney Bailey is celebrating life after homelessness.
"I love it y'all! I love it love it y'all!"
Bailey is one of the 100 homeless people who now have a home thanks to the Community Alliance for the Homeless and their partners.
They used to make homeless people go to counseling and sign up for treatment before providing housing, but very few made it, so they made a change.
Katie Kitchin said, "What we find is that they participate in services in a much higher rate once they have their housing addressed."
Kitchen says over the course of nearly two years, the Community Alliance for the Homeless talked to 800 homeless people in Shelby County. They identified the 100 most at risk of dying on the street, and prioritized them.
"There's a safety concern and a health concern that affects the entire community."
County Mayor Mark Luttrell says 100 people may not seem like a lot, but it's making a difference.
"Any time we can have a victory with removing someone from the homeless condition you're contributing to overall the communities environment."
The battle isn't over once they find them a house. The focus then becomes getting a job and treating the problems that led to homelessness, giving people like Bailey a second shot at victory.
Bailey said, "I'm striving now, more. I'm happier now, I'm cleaner now, I'm just, I'm so happy."
Click here for more information on Community Alliance for the Homeless.


text:
Grey's Anatomy
Your Ultimate Grey's Anatomy Season 8 Relationship Primer
The Grey's Anatomy Season 8 premiere is tonight! Doesn't last season's finale feels like forever ago? So don't even worry: you're totally excused for not remembering Season 7 and exactly who loved whom, who sexed up whom, and who hated on whom. Lucky for you, it's our job to keep track of the romantic trajectories, so we can give you some Grey's Cliff Notes.
Meredith & Derek
Between speeding tickets, Alzheimer's scares, and hostile uteri, Meredith and Derek had a lot to worry about in the beginning of the season but they soon got their groove back. The couple even made their Post-it marriage official in order to adopt little orphan Zola. But then Mer went behind Der's back and made sure Richard's wife Adele received the clinical drug and not the placebo, she violated the trial's ethics and Derek's trust. Last we saw, they weren't even under the same roof. Yowza.
Cristina & Owen
Shonda & Co. wasted no time binding Cristina and Owen in holy matrimony — they got married in the first episode of Season 7. But then Cristina's post-traumatic stress disorder makes her all kooky-crazy, and she even considered dumping Owen. (How whack was that?!) Luckily, she's soon back in the OR and back in love with Owen. That is until a helluva double-whammy comes along: First, Owen doesn't choose her as Chief Resident, and then he knocks her up and asks Cristina to consider what she considers inconsiderable, keeping the McKid. (Not McKidd, people. McKid.)
Alex & Lucy
After screwing up things up royally with Lexie and aborting a hook-up with April, Alex finally finds a new "special friend" in Lucy, the cutesy OB/GYN. But she scoops up the job in Africa that he passes up (in order to stay with her), and then brushes her off when she wants him to give her a reason to stay. (Just like what happened with Ava/Rebecca!)
Bailey & Nurse Eli
Bailey breaks up with anaesthesiologist as she reels from the trauma of the shooting. And what helps her in her recovery? Why, Nurse Eli, of course. They even serenaded each other. But we hear that Ben might not be too far away...
Callie & Arizona
Callie and Arizona easily had the most tumultuous relationship of Season 7! Arizona takes a job in Malawi, and Callie agrees to go with her, but Arizona realizes that Callie is less-than-enthused and chooses to go alone, effectively ending the relationship. Then, however, she cuts her time in Africa short to beg for Callie's forgiveness, and Callie eventually accepts her back so long as Arizona helps her with the child she conceived with (gasp!) Mark. One ill-timed marriage proposal and a nearly-fatal car crash later, Arizona and Callie are happily wed, and the two of them plus Mark and baby Sofia are one big happy family.
Mark & Lexie
Mark screws over Lexie twice—once by sleeping with Derek's sister Amelia and again by sleeping with Callie—and finds himself alone and still in love with that Little Grey but resigned to the life of bachelorhood.
Lexie & Jackson
Lexie and Jackson are a steamy couple having steamy sexy-times all over the place, even if Lexie still holds a significant torch for Mark.
Teddy & Andrew (& Henry)
Teddy has a brief relationship with Andrew Perkins, the grief counselor, which ends when he leaves town. She then marries patient Henry Thomas, but only so that he can use her medical insurance. Then the sham marriage starts feeling more and more real, so much so that even when Perkins comes back for her, Teddy commits to Henry.
Richard & Adele
Richard and Adele are totally in love again, but Adele is diagnosed with Alzheimer's, so we're already in mourning for this relationship. Listen: we've all seen The Notebook...
What twists and turns with Season 8 hold for these characters' love lifes? Only one way to find out (without spoilers): Tuning in to the big show on Thursday, September 22 at 9 pm ET/PT.


text:
Kate Fuller
April 14, 2014
ATHENS, Ga.—Georgia women's tennis senior Kate Fuller was named to the 2014 SEC Community Service Team, the league office announced Monday.
Fuller is one of 12 SEC women's tennis players to be named to the team, which highlights student-athletes from the conference who give back to their community through service. She is the team's first four-time honoree since the award expanded to include a team for each individual sport in 2003.
Fuller volunteers for UGA's Safe Route to School program, UGA Special Olympics and Relay for Life. She was a speaker for Girl Power Day, an event for underprivileged youth and girl scouts. She is also an active member of the Clarke County school mentor program, and has volunteered with Habitat for Humanity and Food Bank of Northeast Georgia.
Fuller, a senior from Suwanee majoring in marketing, is 20-7 this season in singles and is 24-4 in doubles with partner Silvia Garcia. The Bulldogs will begin play in the 2014 SEC Tournament on Friday in the quarterfinals at 11 a.m.