text:
Hell I can make grocery shopping romantic fun and exciting...
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53 • Saint Paul, MN • Woman
I'm looking for
- Men
- Ages 47–65
- Near me
- Who are single
- For new friends, long-term dating
My details
- Last online
- Yesterday – 7:11pm
- Orientation
- Straight
- Ethnicity
- White
- Height
- 5′ 5″ (1.65m)
- Body Type
- A little extra
- Diet
- Anything
- Smokes
- No
- Drinks
- Rarely
- Drugs
- Never
- Religion
- Catholicism
- Sign
- Leo, but it doesn't matter
- Job
- Politics / Government
- Status
- Single
- Offspring
- Has a kid, but doesn't want more
- Pets
- Likes dogs
- Speaks
- English
My self-summary
Write a little about yourself. Just a paragraph will do.
I'm a gal that enjoys life to the fullest. No drama here...At my age, its all about enjoying life, smiling and laughing..oh...and shopping! Ha ha ha...Looking for someone else that doesn't take life so seriously, living each day to the fullest, that could share lots of laughs good conversation, and new adventure. I am very affectionate, love to kiss, cuddle and always PDAs...and a teaser, but well worth it...lol...
Hell I can make grocery shopping romantic fun and exciting...
Hell I can make grocery shopping romantic fun and exciting...
What I'm doing with my life
Don't overthink this one; tell us what you're doing day-to-day.
Living a carefree happy life, listen to a great band, some dancing. Always enjoy a good movie or play. Classic cars, shows, I like to do just about anything...like new adventures. Love meeting new people and making new friends
I'm really good at
Go on, brag a little (or a lot). We won't judge.
Being sincere and caring about my friends and family. Long walks with great music. Conversation and listening. Kissing, touching, cuddling, PDA......love to dance...if you can lead it I can follow it. Also, I love to shop..
The first things people usually notice about me
I'm an empty essay… fill me out!
Maybe my smile or laugh, or just maybe its my shoes...ha ha ha
Favorite books, movies, shows, music, and food
Help your potential matches find common interests.
Like to read Nora Roberts and Fern Michaels books. I read Fifty Shades of Grey....whew..oh lala....Love a great comedy movie. Or a great chick flick...love any kind of music, really enjoy watching a great band.
The six things I could never do without
Think outside the box. Sometimes the little things can say a lot.
Great health
Love of family and friends
curling iron
And purses
Great health
Love of family and friends
curling iron
And purses
I spend a lot of time thinking about
Global warming, lunch, or your next vacation… it's all fair game.
What a wonderful life I have, wonderful family, friends and good health,my comfy home and lucky to have my job.
On a typical Friday night I am
Netflix and takeout, or getting your party on — how do you let loose?
Usually out with friends enjoying a good band, dancing
They say ...."Dance like no one is watching"..
I did, and....... My Court Date is pending....lol
They say ...."Dance like no one is watching"..
I did, and....... My Court Date is pending....lol
The most private thing I'm willing to admit
I'm an empty essay… fill me out!
Can't admit it now...but maybe later, I'll whisper it in your ear....
oh la la..ha ha ha
oh la la..ha ha ha
You should message me if
Offer a few tips to help matches win you over.
You're a positive happy Guy, no drama, looking for adventure, good conversation, if you like to kiss and like to be touched...lots of laughs and a good friend...Good relationships begin as friends
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subset: commoncrawl


text:
Liberty: Settling questions it deems too big for the voters is not the Supreme Court's job. On delicate issues like race and family, the justices — liberal and conservative alike — are obliged to trust the people.
The mad rush to transform marriage, which has inevitably landed into the laps of the nation's nine highest-ranking arbiters, must be viewed in the context of cultural history.
In the last half-century American society has undergone nothing less than a social revolution.
The left would have us believe this upheaval bubbled up from the masses, but most of the radical change was handed down from on high by elites — in Hollywood, the press, academe, and, not least, the legal profession.
To take one area, censorship of word and image, the hard-charging attorney who in the '50s and '60s litigated smut into art, Charles Rembar, 45 years ago admitted that First Amendment protection of sexually explicit materials was something very new.
"In 1956 the concept did not exist at all," Rembar pointed out in his 1968 book "The End of Obscenity." But "in 1966 it was full grown and dominant, and turned a hard hand against censorship," he reported.
It was done by the courts, not by elected lawmakers. Just as there was no majority in America in the '60s demanding constitutional protection for pornography, and no majority in the '70s pining for abortion-on-demand, there was also no majority in 2003 demanding the right to marry for homosexuals. In that year, Massachusetts' highest court declared there was no rationale "for denying marriage to same-sex couples."
If, as some polls suggest, a majority now favors radically redefining humankind's most ancient social institution, it's the result of entertainment and news media saturation in favor of that position, at least partly spurred by the Massachusetts judicial diktat.
The Supreme Court is now scrutinizing both California's Proposition 8, enshrining traditional marriage in the state constitution, which passed with a healthy majority in 2008, and the Defense of Marriage Act, enacted with overwhelming majorities of 85—14 in the U.S. Senate and 342—67 in the House of Representatives in 1996, and signed into law by President Bill Clinton.
The U.S. Constitution says as much about marriage as it does about abortion: nothing. If Americans want to change that, there is the amendment process. But, as in Roe v. Wade, the Supremes seem to believe they have the power to knock down democratically passed laws.
"There are some 40,000 children in California ... with same-sex parents," said right-leaning swing Justice Anthony Kennedy last week, "and they want their parents to have full recognition and full status."
But consider the slippery slope of the logic here.
If same-sex couples are entitled to marriage rights, how about three or four people? What about polygamists? Or incestuous couples?
The wisdom of further revolutionary transformation of society and family is dubious at best.
But when a free people do embark on such a path, the change should be by them doing it themselves, after long, reasoned debate. Not by judicial elites.
Crisis: Tax evasion is Greece's national sport, some of the country's politicians say. There are reports that as much as 30 billion euros go uncollected each year. Is this a cultural problem? Or are Greece's tax rates just too high?Two out of every three Greeks practices tax evasion, according to ...
It used to be that budget cuts were the best way to kill a law you hated but lacked the votes to formally repeal. You know: If you can't beat 'em, defund 'em. Times have changed. Now the mantra is: If you can't beat 'em, out-God 'em. Don't like same-sex marriage, contraception, HIV testing or even ...
Markets: After a selloff in which shares lost nearly a quarter of their value, China's government has stepped in to lend money to those who want to buy stocks. Gee, what can possibly go wrong with that?Leftist governments always suffer from the delusion that they can manipulate markets to do ...
Regulation: If you run a bank and your board is all or mostly white men, plan on having to justify the makeup at your next federal bank examination. Diversifying Wall Street is part of Dodd-Frank financial "reforms."According to Democrats, who authored the massive regulation and are now ...
The House of Representatives is scheduled this week to consider the 21st Century Cures Act (H.R. 6), a health policy bill designed to improve the economic incentives and streamline the process for inventing new medicines. We applaud the act. It will go a long way to solving the crisis in ...
Investor's Business Daily provides exclusive stock lists, investing data, stock market research, education and the latest financial and business news to help investors make more money in the stock market. All of IBD's products and features are based on the CAN SLIM® Investing System developed by IBD's Founder William J. O'Neil, who identified the seven common characteristics that winning stocks display before making huge price gains. Each letter of CAN SLIM represents one of those traits.


text:
The Karma Test
Their result for The Karma Test ...
The 3-toed sloth
Congratulations! You scored ###!
Their Analysis (Vertical line = Average)
They scored 25% on karmapoints, higher than 48% of your peers.
All possible test results
The banana slug
Unfortunately you have some work to do to reach enlightenment. But then we all do, don't we? If you start now, you may not be reincarnated as a banana slug but it will take some doing. Read more
The wood-rat
You have made contributions towards your karmic load but you still have a ways to go. At least you won't come back as a banana slug. Read more
The lemur
Ah, you have walked this world with compassion and joy and your karma will aid you. With work, you could become enlightened this lifetime. With a lot of work. On the other hand, scampering through the... Read more
The vulture
You are a compassionate human who works to better the world around you. Material objects are not important to you and you share with others. Enlightenment is not far away! In your next life you will g... Read more
The 3-toed sloth
Greetings master, I bid you welcome as you walk among the unenlightened of us. Your presence brightens the sangha and makes the dharma clearer. You will move with peace and tranquility in your next li... Read more
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text:
As June rolls on, many Americans are waiting for the U.S. Supreme Court to deliver a landmark decision on whether or not states can ban gay marriage.
Many legal experts believe the court will strike down the bans, thus declaring gay marriage a constitutional right.
Although it's a landmark decision and while many might see it as the end of the debate, a quick survey of American history shows that landmark Supreme Court decisions can be a little overrated on the landmark part. more >>
In his remarks regarding Wednesday night's massacre inside the historic Emanuel African Methodist Episcopal Church in Charleston, South Carolina, President Barack Obama outlined how the congregation has a 200-year history of dealing with persecution brought on by racism and hatred.
After a white gunmen, identified as 21-year-old Dylann Roof, shot and killed a pastor and eight other worshipers attending a Bible study at Emanuel AME Church, Obama issued a spoken statement on Thursday condemning the attack and added that he was personally angered by it.
"Any death of this sort is a tragedy," Obama stated. "There is something particularly heartbreaking about the death happening in a place in which we seek solace and we seek peace, in a place of worship." more >>
Several evangelical groups have praised Pope Francis' major encyclical on the environment released on Thursday, which warns that climate change is real and is impacting all of God's creation, including impoverished people in different corners of the world. Francis said that it's wrong to treat nature and other living creatures as "mere objects" for "human domination."
"We are grateful that the pope has joined with over 300 Evangelicals like Rick Warren, Rich Stearns, and Bill Hybels, and other Christian leaders who understand climate change is the greatest moral challenge of our time and the greatest opportunity for hope. It's time to make hope happen by fueling the unstoppable clean energy transition, stopping the ideological battles, and working together," said in a statement Rev. Mitch Hescox, president & CEO, Evangelical Environmental Network.
"Creating a new energy economy that benefits all and addresses climate change is not about a political party but living as a disciple of Jesus Christ. We urge all people of good will, especially fellow Christian conservatives, to read and study these timely words from Pope Francis." more >>
A time of worship and prayer came to a horrific end Wednesday night, as a white gunman, identified as Dylann Roof, 21, opened fire during a Bible study in a historic black church in Charleston, South Carolina, slaying nine people, including the church's pastor, in what the police have called a "hate crime" and the city's mayor has labeled an act of "pure hatred."
The suspect began firing at the Emanuel African Methodist Episcopal Church on Calhoun Street, one of the oldest black churches in the South with roots dating back to 1816, around 9 p.m. Wednesday night. Eight people were killed on the scene, while two others were transported to a nearby hospital, one of whom died along the way.
The gunman, believed to be Roof, successfully fled the church as remains at-large as of Thursday morning. more >>
As Pakistani lawmakers consider legislation to reform the nation's corrupt blasphemy laws, Islamic clerics are bashing the government for even considering such an option, and are calling for the release of the murderer of the Punjab governor who advocated for blasphemy reform in 2011.
Asia News reports that 10 Muslim scholars and a former Pakistani judge gathered recently at a "seminar for protection of the prophet's dignity" and expressed their concern over the proposed legislation that is attempting to add the word "intention" to the nation's blasphemy law.
Speaking at the seminar was former Pakistani justice Mian Nazir Akhtar, who represents Mumtaz Qadri, the bodyguard who killed Punjab Governor Salman Taseer for referring to Pakistan's blasphemy law as a "black law." Akhtar bashed the proposed legislation and asserted that those who insult the Muslim prophet Muhammad deserve to be killed and "sent to hell." more >>
Jewish author Avi Lipkin claimed Monday that "all" churches in America have been infiltrated by Muslim spies who frequently pretend to have found Christ but are really looking to provide intelligence to radical Muslims who will try to kill all Jews and Christians when jihad is ordered upon the U.S.
Lipkin, who has authored a number of books critical of radical Islam, frequently speaks at Christian churches around the U.S. to emphasize the importance of unity between the Jewish and Christian communities in standing against the advance of radical Islam. Lipkin, who immigrated from New York to Israel in 1968, spoke at this week's Future Conference held at Skyline Church in San Diego where he proclaimed that the world is facing the "most interesting" biblical period since the days of Jesus Christ and contended that the coming of the Messiah is just around the corner.
"We are realizing with our own very eyes fulfillment of more Bible prophecy than in any other generation in 2,000 years," Lipkin asserted. "I believe the Messiah is in our time and I believe Israel will realize its borders." more >>


text:
Welcome to the very first edition of Swell-o-vision vs. Hell-o-vision of 2012! We're here! The world still exists and thus, so does the world of television! So, now we present you with what we loved and hated on TV this week.
Breaking Bad's blue "meth" is available on Etsy
Night Blade, starring Todd from Community!
Funny or Die went bonkers this week with fake shows from 1986, but this one, starring weirdo Todd from Community, Robert Davi, and Ray Wise, features
inline skates roller blades and lasers, thus cementing it as our favorite.
Bob Greenblatt's honesty about NBC
The new boss of the network isn't resorting to spin, opening his executive session at the Television Critics Press Tour with: "We had a really bad fall. Worse than I'd hoped for but about what I expected." Shazam! Unlike previous heads of NBC *cough* Ben Silverman *cough*, we're rooting for this guy.
Tyler's psycho freak-out on Revenge
And his brother's mediocre acting!
Alana, Honey Boo Boo Child
You thought you'd seen it all on Toddlers and Tiaras. You were wrong. This is a Vesuvian meme-splosion waiting to happen.
A lady pretends she's Rudy Huxtable to avoid arrest
To get out of a shoplifting charge, a woman in Iowa told police she'd played Rudy (Keisha Knight Pulliam) on The Cosby Show to get out of a shoplifting charge. Cliff would send her to bed with no Puddin' Pops.
Project Runway without Tim Gunn and Heidi Klum
The two mainstays of the popular reality competition are nowhere to be found on Project Runway All Stars. We found ourselves whispering to the contestants (and to ourselves), "Make it work, people."
Showtime's less-than-classy subscriber bait
The cable network is currently previewing the first episode of many of its shows for FREE on its web site, which is swell (go watch Homeland... NOW!). But during a viewing of House of Lies, a gray box covering nudity featured a pop-up that read, "See what you're missing, order Showtime now!" What are we, 13 years old?
Erika the Law Student on The Bachelor
Bachelor Ben's dating pool is a hodgepodge of stiletto'd wackos. "The verdict is in, and you are *clickclick* guilty… of being sexy." Great line! We'll have to try that one out.
Work It
What made your list of TV loves and hates this week?


text:
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[February 06, 2014]
Oracle and Pluribus Networks Collaborate on OpenStack Plug-Ins for Software Defined Networking Products
(Marketwire Via Acquire Media NewsEdge) REDWOOD SHORES, CA -- (Marketwired) -- 02/06/14 -- Oracle (NYSE: ORCL) News SummaryThe cooperation between Oracle and Pluribus Networks is designed to help create unique customer value by offering customers the ability to use OpenStack� plug-ins to manage their cloud environments based on Oracle Solaris and Pluribus Networks' Netvisor. This builds on the newly completed certification of Oracle Solaris 11 on Pluribus Networks' Freedom series Server-Switch platform, which is already allowing customers to take advantage of the unique performance, scalability, efficiency and security advantages of Oracle Solaris in their network infrastructure.
News Facts Oracle has entered into a technology access agreement with Pluribus Networks, a pioneer in open, bare-metal SDN/NFV application infrastructure, enabling Pluribus Networks to conduct development and testing on a number of different software-defined networking (SDN) technologies that will be managed by OpenStack technologies, such as a distributed virtual switch. Pluribus Networks is a Gold level member of Oracle PartnerNetwork (OPN). Oracle and Pluribus Networks will be collaborating to enable customers to manage Oracle Solaris 11 compute nodes via the OpenStack Nova plug-in, as well as Pluribus Networks switches via the OpenStack Neutron plug-in and Oracle Solaris-based ZS3 Series storage via Oracle ZFS Storage Appliance Cinder Driver, taking full advantage of the stability, efficiency, performance, scalability and security of Oracle Solaris. Pluribus Networks has recently certified Oracle Solaris 11 on their Freedom series Server-Switch platform running the Netvisor bare-metal network hypervisor hosted on the Oracle Solaris 11 operating system. Running Oracle Solaris 11 on Pluribus Networks' switches means that virtual networking services can be dynamically re-provisioned from compute nodes to networking to help maximize throughput performance, while minimizing latency. This will provide an ideal platform for the SDN features that are scheduled to be available in the next update of Oracle Solaris 11. Oracle announced last month that it plans to integrate OpenStack capabilities into Oracle Solaris. When the Pluribus Networks development and testing work is completed, customers will be able to take full advantage of the enterprise class innovations in Oracle Solaris 11 including scalability, high availability, high performance file systems, Oracle Solaris Zones virtualization and network services in a converged OpenStack orchestrated and managed Compute, Network and Storage environment. Since the release of Oracle Solaris 11 over 4,000 customers have gone into production and many of them are deploying applications in Oracle Solaris-based clouds. With the integration of OpenStack components in Oracle Solaris, customers will be able to expand their usage of Oracle Solaris in new cloud deployments. OpenStack also provides an ideal platform for OPN members like Pluribus Networks who are interested in providing a seamless management experience between Oracle Solaris and their products.Supporting Quotes "With the release of Oracle Solaris 11, as well as Oracle's SPARC T5, M5 and M6 servers, we are now seeing the Oracle Solaris/SPARC ecosystem expanding rapidly. OpenStack is providing us with the ideal platform to expand our relationships with companies like Pluribus Networks and I'm very excited to see Oracle Solaris 11 now running on Pluribus Networks' Freedom Server-Switches. This means customers can now take full advantage of the unique performance, scalability, efficiency and security features of Oracle Solaris in their network infrastructure," said Markus Flierl, vice president, Oracle Solaris. "Running Oracle Solaris on compute, network and storage infrastructures means we can provide fine-grain end-to-end observability, which is unprecedented in the industry, and also offer customers the ability to enforce end-to-end SLAs. Combined with the deep integration between the Oracle Database and Oracle Solaris we can solve the most complex problems that customers are facing today." "We are very excited about expanding our relationship with Oracle," said Kumar Srikantan, Chief Executive Officer, Pluribus Networks. "Oracle Solaris 11 is providing us with unique performance, scalability, efficiency and security features that help us differentiate our products. For instance, we can now take advantage of Oracle Solaris 11 security features like the immutable root file systems and ZFS encryption."Supporting Resources Oracle Solaris Blog Connect with Oracle Solaris via Facebook, Twitter and LinkedIn Oracle Hardware on Facebook, TwitterAbout OracleOracle engineers hardware and software to work together in the cloud and in your data center. For more information about Oracle (NYSE: ORCL), visit www.oracle.com.
TrademarksOracle and Java are registered trademarks of Oracle and/or its affiliates. Other names may be trademarks of their respective owners.
Contact Info Jacki DeCoster Oracle +1.650.633.7788 Email Contact Drew Smith Blanc & Otus +1.415.856.5127 Email Contact Source: Oracle Corporation
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text:
not bad
- Member for
- 3 years 15 weeks
Recent Comments
|26 weeks 1 day ago
|5th by win percentage, not number of wins.
5th by win percentage, not number of wins.
|27 weeks 2 days ago
|Nobody believes that...
Nobody believes that... Except Wayne Gretzky himself. " I am on record as saying that you're the greatest hockey player of all time, and some other pretty good players, including Bobby Orr, have said the same thing," said Wayne Gretzky to Gordie in an interview.
|27 weeks 5 days ago
|How is it "holding out" when
How is it "holding out" when he is still in the middle of his season? If this were happening two weeks from now, then it would seem like he was using Michigan.
|27 weeks 5 days ago
|If sometime over the next two
If sometime over the next two days the NFL guys turn it to 50/50, then we will know this has to be the case.
|27 weeks 6 days ago
|I would have just called it
I would have just called it general douchery, but I guess your way is a little more explicit if he somehow didn't realize it. I'm
|28 weeks 2 days ago
|Reading comprehension.
Reading comprehension. Clearly the title is implying that he accepts the Youngstown State head coaching job exists; just like he accepts UFOs and pixie dust.
|30 weeks 6 days ago
|I thought maybe he was an
I thought maybe he was an Apple device that hates Michigan, but the h would be capitalized.
|35 weeks 3 days ago
|Oh boy
Oh boy.
|42 weeks 18 hours ago
|Not sure if serious...
So you're saying he only did something worth being fired over the courts say he is guilty of a crime? You need a conviction to tell you that beating a woman is wrong and a crime? This is NOT a case of guilty in the court of public opinion, there is a video of him knocking her unconscious.
A guy beats the crap out of his fiancée, in public, and the thing "wrong" with our society is that he lost his job. Seems a little backwards to me.
Also, staying that the victim forgave him so everybody else should as well is completely ignoring how domestic abuse works. Domestic abuse is often a cycle of abuse and forgiveness that is much more complex than you are making it.
|47 weeks 1 day ago
Rumors like this are how feelings get hurt.
|1 year 3 weeks ago
|Run means nothing
That runner doesn't mean anything, there is no double play in order and he will not tie the game. If you think the shift is the best way to get the batter out, you shift. If you want to argue the merits of the defensive shift, great, but it would take an equal number of hits to tie/win even if you allow that guy to steal home.
|1 year 7 weeks ago
|You are a true fan
Double posting definitely makes me a bad fan.
|1 year 7 weeks ago
|You are a true fan
You are right, everybody that did not renew is a BAD fan because the price has not changed. You must know the finacial sacrifices that they made last year, and must know that attending football games is still more important. You are a true fan, because you kept your tickets. Since you are the expert, please give a list of other things that would make me a bad fan. Am I allowed to wear a green shirt to work? Can I miss a game to go to a wedding? Can I yell at my tv when a player drops a ball, or is that overly critical? I would really like to be like you and feel like I have the right to look down on everybody else's fandom, so please let me know what I am doing wrong.
|1 year 10 weeks ago
|Woooo Knights!
Woooo Knights!
|1 year 12 weeks ago
|Sounds like
Sounds like you did not appreciate people criticizing what you thought to be a topic worthy of discussion. If you do not like "that guy," then don't be "that guy."
|1 year 21 weeks ago
|"Damn my hair looks good
"Damn my hair looks good today."
|1 year 45 weeks ago
|It does happen.
The article provides no evidence that it does not happen, it says that there is not an unwritten "in the vicinity" rule to call the runner out. There is a big difference. If you look at how often the call is missed based on the rule, it is pretty clear that MLB is perfectly fine with the fielder being given the benefit of the doubt.
|1 year 45 weeks ago
|Thought to ponder...
Would the conferences sue EA for using their likeness?
|3 years 14 weeks ago
|It's an issue of consistency.
It's an issue of consistency. Hoke would have done the same no matter who the recruit was and would not wait until the 4th visit. I have no clue if Meyer told other recruits the same thing.
|3 years 15 weeks ago
|Not race, not academics; just spoiled brats
Grand Blanc would do the same thing to my high school, which was about 90% white and they were not that much better academically. It boiled down to their students thinking they were better than us because their families had money, and they couldn't handle losing to a school of "inferior" students. It's a stereotype that isn't true for a lot of their students, but they just had a lot of kids that felt entitled.


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2013-14 SophomoreSeason:Placed 28th in the 200 backstroke (1:59.94). placed 7th in the 200 free (1:46.76), and placed 9th in the 500 free (4:45.07) at the Big Ten Conference Championships (02/20-02/22) Placed 1st in the 100 backstroke (57.88) and 3rd in the 100 fly (57.37) at the Minnesota Challenge (02/08) Placed 5th in the 200 backstroke (2:02.98) and 4th in the 200 free (1:50.53) vs. Purdue (01/31-02/01) Placed 3rd in the 400 medley ( 4:26.38) and 2nd in the 200 free (1:50.26) vs. NC State (01/24) Placed 7th in the 100 butterfly (58.68) and 1st in the 100 free (53.10) at the Jean Freeman Invitational (12/07) Placed 6th in the 200 backstroke (2:00.86), finished the 200 free with a time of 1:48.87), placed 4th in the 100 backstroke (55.99), and placed 7th in the 200 free (1:47.77) at the Minnesota Grand Prix (11/14-11/16) Placed 7th in the 100 backstroke (58.46) and placed 2nd in the 200 free (1:51.24) vs. Wisconsin (10/18) Placed 4th in the 200 backstroke (2:03.73) vs Michigan (10/11)
Personal: Born May 22, 1995 daughter of Margot and Jeffrey Hoch has one older sister, Roxanne plans to major in Industrial Engineering favorite swimming memory was competing in her first YMCA Nationals and being a part of the team's 800 free relay team enjoys cooking.
Hoch's Top Times:
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6/22/2015Weekend Roundup: June 22
6/12/2015Future Freshman: Maggie Werba
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05/29/2015Future Freshman: Erin Emery
05/15/2015Future Freshman: Kaia Grobe
05/14/2015Plant Earns Academic All-District Honors
05/14/2015Harding Named to Canadian National Team
05/13/2015Register for Minnesota Swim Camps
05/02/2015Gophers Host Badgers in LC Competition


text:
Hi all,
I am looking to buy a fire pager, but I don't feel like going through the trouble of buying a used pager and having to have it reprogrammed myself. Are there anywhere that I can buy one and they will reprogram it for me before I get it?
Thanks in advance,
Know how to save a wet phone?
It's not with a dryer and it's not with rice. CNET shows you the secret to saving your phone.


text:
KNOXVILLE — A.W. Davis, an All-America guard at Tennessee who later worked as an assistant coach and broadcaster for his alma mater, has died. He was 71.Comments
KNOXVILLE — Tennessee has dismissed running back Treyvon Paulk from the team following a police report that he hit a woman in the mouth at a party.Comments
The SEC on Monday announced a noon start time for the Gators-Vols game at Neyland Stadium on Oct. 4.Comments
Tennessee coach Butch Jones said he made a point after last week's 34-10 loss at No. 4 Oklahoma to see how each of his players was reacting to it. This was one instance in which he appreciated all the looks of disappointment.Comments
Tennessee (2-1) already has allowed nine sacks through the first three games of the season. Only nine of the 128 Football Bowl Subdivision teams have yielded more sacks.Comments
Tennessee wide receiver Josh Smith has a high ankle sprain, leaving his status uncertain for the Volunteers' next game Sept. 27 at No. 13 Georgia.Comments
NORMAN, Okla. — Trevor Knight passed for 308 yards and a touchdown and ran for another score to help No. 4 Oklahoma defeat Tennessee 34-10 on Saturday night.Comments
When Tennessee visits No. 4 Oklahoma on Saturday, the Volunteers will be carrying a 2-0 record into a road game with a top-five team for the second straight season. Last year, the Volunteers got trounced 59-14 at No. 2 OregonComments
The countdown to the Battle at Bristol has officially begun, although for some Virginia Tech fans the game can't come soon enough.Comments
Tennessee opponents have converted just seven of their 31 third-down situations through the first two weeks of the season, a remarkable turnaround for a defense that struggled in those scenarios the last few years.Comments


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43 year old man | Sedco Hills, CA, USA | Seeking women 27-50 in California, United States
I've been looking for you baby..all night long
I am a caring, loving,affectionate, giving,good father, honest and a total goofball and say it how it is kinda guy thats just looking for the same in a woman.Sounds easy right? Well its not so all i ask if you contact me is to just be real!! I cook,clean and take care of myself and like a woman to be the same about her looks and her home.Not looking for a clean freak..just someone who picks up after herself.My parents have been married for almost 52 years next month.My parents never gave up and im just looking for someone who is a motovated person when it comes to relationships.Shes got to be giving,loving and a goofball like me.Ok so i am a huge chargers fan and yes they suck soooo this year bad but its in the blood forever..Im also a motocross fan and love going to all the west coast races.Love country music,going out shooting and hunting and wine tasting.I goto church as much as i can and im not a bible thumper but im a believer and have faith and i hope my girl would be the same..and be by me to go to church at times.Ok so if you wanna know more ..please ask..have a great day!!! xo
Cooking , Dining out , Fishing/Hunting , Music and concerts , Playing sports , Watching sports , Wine tasting
Auto racing / Motorcross, Baseball, Basketball, Football, Running, Weights / Machines
I exercise 1-2 times per week.
I like Dogs
Middle of the Road
I enjoy old town temecula for dinner and the night life there.Love to goto vegas from time to time and going out shooting.Glamis is my sandbox and goto the river as much as i can.I grew up in s.d. and enjoy hitting all the hot spots down there
Palomar College, San Marcos, CA
I like fuel and speed tv because i like extreme sports especially motocross.Two and half men is funny great show,sons of anarchy.Love country music and mexican and italian food
I Like going out riding my bike, going to country concerts having lunch and ejoying a beer people watching.Going to charger games and motocross,supercross events.River and desert are must each year..Love sunday fundays watching my bolts loose :(
Well the last magazine i read was a guns and ammo mag..haha
Z{{Cta}} {{#if HasMoreInfo}} ?{{CtaSecondary}} {{/if}}
|What he is looking for
|6'2" (187cms)
|5'0" (152cms) to 6'0" (182cms)
|Body type:
|Athletic and toned
|Slender, About average, Athletic and toned, A few extra pounds
|Blue, Brown, Grey, Green
|Auburn / Red, Black, Light brown, Dark brown, Blonde, Dark blonde, Platinum
|No Way
|No Way, Occasionally, Yes, but trying to quit
|Social Drinker
|Social Drinker, Moderately
|Labor / Construction
|Administrative / Secretarial, Executive / Management, Financial / Accounting / Real Estate, Legal, Medical / Dental / Veterinary / Fitness, Political / Govt / Civil Service / Military, Sales / Marketing, Self-Employed / Entrepreneur, Education / Teacher / Professor, Fashion / Model / Beauty, Architecture / Interior design
I work alot 50 to 60 hrs a week.But will make time for you.Sometimes i wont come home for a week but will be home on weekends.Does'nt happen all the time but a understanding partner will always be there nomatter what.
|$100,001 to $150,000
|$35,001 to $50,000, $50,001 to $75,000, $75,001 to $100,000, $100,001 to $150,000, $150,001+
|Never Married, Widow / Widower, Currently Separated, Divorced
|Have kids:
|Yes, and they sometimes live at home (1)
|Yes, and they sometimes live at home, Yes, and they live away from home, Yes, and they live at home
|Wants kids:
|Not sure
|Someday, Not sure, Probably not, No, No, but it's OK if my partner has kids
|White / Caucasian
|Latino / Hispanic, Middle Eastern, Native American, Pacific Islander, White / Caucasian
|Christian / Catholic
|Christian / Catholic, Christian / LDS, Spiritual but not religious, Christian / Other
|Some college
|High school


text:
Tel: (606)475-1919
Carter Christian Academy (CCA) is an Evangelical Christian School that seeks to wed academic excellence with joyous and life-changing faith in Jesus Christ as Savior and Lord of the world.
We believe that God created this world in all its wonder, order and complexity.
As parents and teachers, we also take seriously the responsibility we have to educate our children about the laws God has given to govern the universe.
Our faith and academic studies inform each other to make both strong and vibrant.
This combination produces students with outstanding Christian character that impacts the world for good.
At CCA, we are convinced that everyone in the world believes in something.
Some believe in themselves.
CCA provides a wonderful opportunity for your child to explore and gain understanding of the most profound questions of life, while preparing him or her with academic excellence for the rigors of life in the twenty-first century.
School Overview
|School Membership(s)School Assoc.
|Association of Christian Schools International (ACSI)
|Religious Affiliation
|Grades Offered
|Grades Prekindergarten - 9
Student Body
|Total Students
|49 students
|Student Body Type
|Students by Grade
Academics and Faculty
|Total Classroom Teachers
|5 teachers
|Student : Teacher Ratio
National avg.: 13:1
Nearby Schools:
All Schools | High Schools | Elementary Schools | Preschools | Public Schools
Show me:
- School Location Miles Students Grades
CatlettsburgCalvary Christian School
17839 Bear Creek Rd
Catlettsburg, KY 41129
(606)929-5599(Christian)14.6 mi | 47 students | Gr. PK-11
AshlandRose Hill Christian School
1001 Winslow Rd
Ashland, KY 41102
(606)329-1957(Baptist)15.7 mi | 215 students | Gr. PK-12
AshlandHoly Family School
932 Winchester Ave
Ashland, KY 41101
(606)324-7040(Roman Catholic)18 mi | 148 students | Gr. PK-8
Franklin FurnaceFranklin Furnace Christian Academy
Po Box 239
Franklin Furnace, OH 45629
(740)354-9301(Baptist)18.2 mi | 21 students | Gr. 1-12
IrontonSt Joseph Central High School
912 S 6th St
Ironton, OH 45638
(740)532-0485(Roman Catholic)18.3 mi | 150 students | Gr. 7-12
School Reviews
Area Statistics
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Recent Articles
Updated June 28, 2015
When it comes to choosing a private school, there are so many choices to consider that the project can be a huge challenge to most of us. We offer some help and advice to help you get started.
Sending your child to a foreign language school makes good sense when you have been posted to this country from abroad and in other circumstances as well.
Do you need financial aid? Not sure? Confused by how financial aid works? Here are some answers.


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Monday, 6 July 2015
Last updated 8 hours ago
May 29 2013 | 12:03pm ET
Odey Asset Management has returned as much in four-and-a-half months this year as it returned all of last year.
The London-based hedge fund's performance is made all the more impressive as its European Fund rose 24.1% in 2012. But it's done even better through May 14 of this year, returning 25% over the period, ValueWalk reports.
The first half of this month has been particularly strong, as Odey European was up just 16.5% at the end of April. Among the firm's best bets on the year have been shorts against mining companies and a lack of enthusiasm about gold.
Firm founder Crispin Odey told investors on a conference call that he was bullish on the U.S. housing market, and criticized German shareholder policies.
Jun 26 2015 | 6:47am ET
If you want to set up an offshore hedge fund, like any great team, you're only...
Jun 8 2015 | 12:37am ET
The Wall Street Decathlon — a 10-event physical challenge that will crown "Wall...
Jun 26 2015 | 10:07am ET
In this article, financial expert Greg Silberman explores how to hedge a private...
May 27 2015 | 2:15pm ET
Support Hedge Funds Care, also known as Help For Children (HFC), by participating in this year's raffle. All proceeds go to support HFC's mission of preventing and treating child abuse. Read more…


text: Money MoneyScience Sarah Wolfe on Mar 19, 2014 @ 3:13 PMMar 19, 2014 @ 3:13 PM PublishedNASA spent four years stitching more than 10,000 images to map the north pole of the moonNASA has released this interactive map of the moon's north pole. It's the largest high-resolution map of our moon ever made.The folks at NASA have stitched together four years of images to create an amazing new interactive map of the moon.At nearly 867 billion pixels, it's the largest high-resolution lunar map ever made, covering an area equal to more than a fourth of the United States.More from GlobalPost: Brightest moon explosion ever recorded announced by NASA (VIDEO)Users can get super up close and personal, too.Comprised of 10,581 pictures, the mosaic provides enough detail of the moon's north pole that you can see subtle shading on the lunar terrain."This unique image is a tremendous resource for scientists and the public alike," said John Keller, LRO project scientist at NASA's Goddard Space Flight Center. "It's the latest example of the exciting insights and data products LRO has been providing for nearly five years."The images were taken over a four-year period by NASA's Lunar Reconnaissance Orbiter.More from GlobalPost: NASA probe crashes into the moon; crash site named after Sally Ride (VIDEO)Launched in 2009, the orbiter's sole purpose is to map the entire lunar surface.Scientists are using the images to help determine where future missions should land, and even where a lunar outpost might be built.So far, we'd say the orbiter is doing a bang-up job.Access the interactive map here.


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NINETY-SIX BROKER-DEALERS SUED FOR COMMISSIONS GENERATED FROM TENANT-IN-COMMON PONZI SCHEME 0 commentsJan 18, 2013 12:46 PM
Mr. James Zazzali, trustee for the DBSI Inc. bankruptcy, is suing ninety-six broker-dealers to recover $49 million in commissions for securities fraud related to tenant-in-common investments (TICs). In the complaint, Mr. Zazzali alleged that DBSI's TIC deals were part of a $600 million Ponzi scheme. Mr. Zazzali contends that the broker-dealers should return investors' payments and commissions, which should be distributed to DBSI creditors.
TICs are investment vehicles that allow individual investors to buy shares of real estate interests directly, rather than shares of stock, bond certificates, or other forms ownership. Properties can include a high-rise office building, a retail center, a triple-net lease from a national drugstore chain, oil or gas wells, or any other type of investment property. Investors are attracted to TICs because they can purchase an interest in expensive properties - typically $30 million or more in value.
DBSI was one of the largest creators and distributors of TICs until it defaulted on investor payments and filed for Chapter 11 bankruptcy protection. Of the ninety-six broker-dealers that actively sold DBSI TICs, twenty-two are now defunct. The broker-dealers that made most of the commissions from selling to DBSI include Berthel Fisher & Company Financial Services Inc., QA3 Financial Corp., DeWaay Financial Network LLC, The Private Consulting Group, and Questar Capital Corp. Mr. Zazzali alleged that the commissions were fraudulent transfers by DBSI and that earlier investors benefited from funds invested by latter investors.
Due diligence requires a reasonable investigation of all material facts before entering into an agreement or transaction with another person or entity. It is a measure taken to prevent unnecessary harm to an innocent party. In many instances, broker-dealers do not perform sufficient due diligence prior to offering products such as tenant-in-common investments. If broker-dealers do not perform their due diligence, they risk misrepresenting the true nature of the product and placing clients in an unsuitable investment. As a result, an investor can claim damages against the entity that sold the investment for not performing its due diligence prior to the offer and sale.
Have you suffered a loss in a tenant-in-common investment? If so, call Robert Pearce at the Law Offices of Robert Wayne Pearce, P.A. for a free consultation.
The most important of investors' rights is the right to be informed! This Investors' Rights blog post is by the Law Offices of Robert Wayne Pearce, P.A., located in Boca Raton, Florida. For over 30 years, Attorney Pearce has tried, arbitrated, and mediated hundreds of disputes involving complex securities, commodities and investment law issues. The lawyers at our law firm are devoted to protecting investors' rights throughout the United States and internationally! Please visit our website, www.secatty.com, post a comment, call (800) 732-2889, or email Mr. Pearce firstname.lastname@example.com for answers to any of your questions about this blog post and/or any related matter.Themes: Berthel Fisher, Berthel Fisher DBSI Losses, DBSI Fraud Attorney, DBSI Fraud Lawyer, DeWaay Financial, Florida TIC Attorney, Florida TIC Lawyer, Florida Tenant-in-Common Attorney, Florida Tenant-in-Common Lawyer, Tenant-in-Common InterestsBack To Robert W Pearce's Instablog HomePage »
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text: Baltimore Ravens linebacker Ray Lewis speaks at a news conference in New Orleans on Monday. The Ravens face the San Francisco 49ers in Super Bowl XLVII on Sunday. It will be Lewis' last game. Patrick Semansky/AP hide caption itoggle caption Patrick Semansky/AP Sweetness And Light History Joins The 49ers In Opposing Ray Lewis January 30, 2013 It's rare in sport for someone to declare that this will be the finale and then go out a winner, says commentator Frank Deford. But, on Sunday, Baltimore Ravens linebacker Ray Lewis hopes to do just that. Listen Loading… 3:51 Playlist Download Embed Embed Close embed modal <iframe src="http://www.npr.org/player/embed/170567081/170630557" width="100%" height="290" frameborder="0" scrolling="no">


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Kroll Bond Rating Agency (KBRA) downgraded the Financial Strength Rating (FSR) of Banco Espirito Santo SA (BES) from "D" to "E" last week. BES is a Portuguese bank with $114.1 billion in assets and $9.7 billion in capital as of March 31, 2014. Shares of BES and its holding company, Espirito Santo Financial Group SA (ESFG), have been suspended from trading since Thursday July 10, 2014, due to delayed coupon payments on some commercial papers by Espirito Santo International SA, the Bank's Luxembourg-based holding company, which sought protection from creditors on Friday.
As of June 30, 2014, BES' exposures to the Espirito Group companies was estimated at €1.2 billion ($1.6 billion) of loans, securities, and other items. BES stated that its retail clients hold approximately €853 million of commercial paper and bonds issued by Espirito Santo International, Rioforte and its subsidiaries, and Espirito Santo Financial and its subsidiaries. Additionally, the Bank's institutional clients held €511 million of debt securities issued by Espirito Santo International and €1.5 billion of debt securities issued by Rioforte and its subsidiaries. The government of Portugal made it clear that there would be no state support for BES.
The downgrade of BES' financial strength rating to "E" from "D" reflects the increased risks for the Bank's stakeholders, given the troubles at the Espirito Santo Group and its affiliates. ESFG owns 25% of BES. According to a June 2014 presentation by BES, other shareholders of the bank include French banking group Credit Agricole (14.6%) the Brazilian banking group Bradesco (3.9%), BlackRock (5.1%), Capital Research and Management (4.2%), and UK investment fund Silchester (4.7%).
About Kroll Bond Ratings' Financial Strength Ratings:
A financial strength rating (FSR) is an issuer-level assessment intended to represent the stand-alone, intrinsic risk of a commercial bank. KBRA's FSRs are expressed via 11 rating categories, with the symbol "A+" issued to institutions with the strongest financial health and "E" reserved for those with the weakest financial health. It captures the financial and operating risk of a bank and, ultimately, is an indication of the likelihood that the bank will either fail or need to be rescued. In many ways, it is similar to the CAMELS rating used by U.S. bank regulators to assess the viability of a bank. The FSR does not reflect the likelihood that a bank will be rescued, nor does it reflect currency-transfer risk. KBRA's Subscription Rating Service (SRS) provides FSRs for nearly all U.S.-based deposit taking institutions, including commercial banks, savings and loans, and credit unions. KBRA also provides FSR coverage for several hundred non-U.S. banks. The FSRs for U.S.-based banks are updated quarterly and rely on federal regulatory filings as data inputs. The ratings are generated from an algorithmically based approach, using factors found to be highly predictive of bank failures. KBRA's FSRs for non-U.S. banks are derived from an analysis of published financial data, which may vary depending on the jurisdiction.
About Kroll Bond Rating Agency
KBRA is registered with the U.S. Securities and Exchange Commission as a Nationally Recognized Statistical Rating Organization (NRSRO). In addition, KBRA is recognized by the National Association of Insurance Commissioners (NAIC) as a Credit Rating Provider (CRP).
- Finance
- Investment & Company Information
- Banco Espirito Santo
- Espirito Santo
Marjan Riggi, 646-731-2354
Managing Director
Christopher Whalen, 646-731-2366
Senior Managing Director
Isabelle Nana, 240-394-4153


text:
Hip Hop - Jazz Camps
Hip Hop and Jazz Camps
Now enrolling!
Join us for super fun jazz and hip hop camps! Campers should bring a lunch for daily picnics. A performance will be held on the last day showing off all the fun moves we learned!
Disney Channel Rocks
A fun week of rocking out to all the best of Disney Channel
Liv and Maddie, Shake it Up, Austin and Aly and MORE!!
Dates August 3-7 Hours are 10:30 to 2:30PM in Fair Haven Monday to Friday for ages 5 to 9
Cost is $275 including all supplies and a snack daily.
Superhero in Training Boys Hip Hop Camp! – An exciting week of Hip Hop dance, games, and hero training just for the boys!
Dates July 27-31 Hours are 9AM -12 pm in Rumson Cost is $240
American Girl Adventures! Travel back in time and learn about both the historical dolls and the dolls of today!!
July 20-24 Rumson Cost is $240


text: Home eMed Chris Seper : Article 27 results found Filter Options Items/Page --select -- 10 25 50 123Next Type Articles Audio Blog Book File Links Videos Title Author Date Five questions entrepreneurs must answer to get an investment from West Health Seper Chris 12/6/2011 Blog Resource Summary: How do medical device startups and other new healthcare businesses get investments? They need to know how to answer some key questions, according to the manager of the West Health Investment Fund. Read More Why should some medical cities be happy about Occupy Wall Street? Seper Chris 12/19/2011 Blog Resource Summary: New healthcare businesses in some medical cities may benefit from the Occupy Wall Street movement. Read more about how cities in areas without state incentives for investment could be better off in the near future. Read More Life Science Ventures Summit packed with advice for entrepreneurs Seper Chris 6/21/2012 Blog Resource Summary: Life science entrepreneurs at the Life Science Ventures Summit are set to gain valuable knowledge this weekend from those in the know. Read more about this event for life science entrepreneurs. Read More Healthy above all: Genomic Health CEO's guide to starting a great business Seper Chris 6/22/2012 Blog Resource Summary: Hiring smart people for a new company is not enough, says Kim Popovits of Genomic Health. Read more about what she thinks is important when growing a company. Read More Revisiting the Kauffman Life Science Ventures Summit via Storify Seper Chris 6/24/2012 Blog Resource Summary: Thoughts on entrepreneurship in the life sciences and digital health from the Kauffman Life Science Ventures Summit are the featured topic of this Storify piece. Read More Video: Help along the way for life science entrepreneurs Seper Chris 6/24/2012 Blog Resource Summary: Advice for life science entrepreneurs goes beyond the dollar value that could be placed on it. Watch this collection of videos with insights on a variety of topics of interest to life science entrepreneurs. Read More Digital health companies getting larger investment deals this year Seper Chris 6/26/2012 Blog Resource Summary: Investments in digital health are on the rise this year, both in terms of the amount of dollars invested and the number of companies getting investment deals. Read more about this trend. Read More eMed's 6 to follow in entrepreneurship Chris Seper 3/29/2013 Blog Resource Summary: Read about the six lifescience and healthcare entrepreneurs we'll be following this week on twitter. Read More eMed's 6 to follow in entrepreneurship Chris Seper 4/5/2013 Blog Resource Summary: Here's the next in our series of people for entrepreneurs to follow on twitter. Join the conversation. Read More eMed's 6 to follow in entrepreneurship Chris Seper 4/12/2013 Blog Resource Summary: Join the conversation this week with eMed's entrepreneurs to follow on twitter. Read More 123Next


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No. 2 Notre Dame beats No. 10 Louisville 93-64
"I thought we attacked and went hard to the basket," he said. "Somehow they got to the line 26 times. Stuff happens, I guess."
Walz was visibly unhappy about the officiating at times, complaining when a foul against Achonwa was overturned and changed into a traveling call and again when Jude Schimmel was called for a foul with 0.1 seconds left in the first half when Diggins attempted a 25-foot running shot as she tried to beat the buzzer. "Danielle, welcome to Notre Dame," a frustrated Walz yelled toward Big East associate commissioner Danielle Donehew at the end of the court.
Kayla McBride added 15 points, Jewell Loyd 12 points and nine rebounds, and Ariel Braker scored 10 for the Irish. Antonita Slaughter had 16 points and Shoni Schimmel had 13.
Although the game wasn't as exciting as the men's game, the crowd of 8,368 still got into the game, letting out a loud cheer when Loyd scored on a fastbreak layup to give the Irish an 85-60 lead and again when Madison Cable hit a 3-pointer to give the Irish a 90-62 advantage.
The win marked just the fourth time in 10 tries the home team has won in the series.
"That's a great win for us, to come in and play that well against a really good team," McGraw said.


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A class of hydrolytically stable bis(aralkylphenyl)pentaerythritol diphosphites is disclosed, which is suitable as an antioxidant additives in polyolefins, particularly, in polypropylene. The diphosphites are of low volatility, have a high thermal decomposition temperature and resist yellowing when blended into a polyolefin base. A preferred diphosphite is bis(2,4-dicumylphenyl)pentaerythritol diphosphite.
1. A diphosphite of formula (IV) with improved resistance to hydrolysis and increased thermal stability comprising: ##STR7## and wherein R1, R2, R4, R5, R7, R8, R10 and R11 are selected independently from the group consisting of hydrogen and alkyl radicals of generic formula Cm H2m+1 wherein m ranges from 1 to 4 and R3, R6, R9 and R12 are selected independently from the group consisting of hydrogen and alkyl radicals of generic formula Cm H2m+1 wherein m ranges from 1 to 4, and further wherein n ranges from 0 to 3.
2. The diphosphite of claim 1 wherein R1, R2, R4, R5, R6, R7, R8, R10, and R11 are methyl radicals, and where n is 0 in Rn 3, Rn 6, Rn 9, and Rn 12 thereby forming a diphosphite of formula (V) ##STR8##
3. The diphosphite of claim 2 having an acid number of 6.13 or less after exposure to 85% relative humidity at 25� C. for 163 hours.
4. A polymer composition comprising
(a) a polyolefin; and
(b) a diphosphite sufficient to stabilize the polyolefin, the diphosphite of formula (IV) ##STR9## and wherein R1, R2, R4, R5, R7, R8, R10 and R11 are selected independently from the group consisting of hydrogen and alkyl radicals of generic formula Cm H2m+1 wherein m ranges from 1 to 4 and R3, R6, R9 and R12 are selected independently from the group consisting of hydrogen and alkyl radicals of generic formula Cm H2m+1 wherein m ranges from 1 to 4, and further wherein n ranges from 0 to 3.
5. The composition of claim 4 wherein R1, R2, R4, R5, R6, R7, R8, R10, and R11 are methyl radicals, and where n is 0 in Rn 3, Rn 6, Rn 9, and Rn 12 thereby forming a diphosphite of formula (V) ##STR10##
6. The polymer of claim 4 wherein the polyolefin is polypropylene.
7. A polymer composition comprising
(a) a polyolefin;
(b) a diphosphite sufficient to stabilize the polyolefin, the diphosphite of formula (IV) ##STR11## and wherein R1, R2, R4, R5, R7, R8, R10 and R11 are selected independently from the group consisting of hydrogen and alkyl radicals of generic formula Cm H2m+1 wherein m ranges from 1 to 4 and R3, R6, R9 and R12 are selected independently from the group consisting of hydrogen and alkyl radicals of generic formula Cm H2m+1 wherein m ranges from 1 to 4, and further wherein n ranges from 0 to 3; and
(c) a hindered phenol.
8. The composition of claim 7 wherein R1, R2, R4, R5, R6, R7, R8, R10, and R11 are methyl radicals, and where n is 0 in Rn 6, Rn 6, Rn 9, and Rn 12 thereby forming a diphosphite of formula (V) ##STR12##
9. The polymer of claim 7 wherein the polyolefin is polypropylene.
10. The polymer of claim 7 wherein the hindered phenol is selected from the group consisting of 4,4'-isopropylidene-diphenol, butylated hydroxyanisole, 1,3,5-trimethyl-2,4,6-tris(3,5-di-di-tert-butyl-4-hydroxybenzyl)benzene, 4,4'-methylene-bis(2,6-di-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 2,6-di-tert-butyl-4-ethylphenol, bis-[3,3-bis-(4'-hydroxy-3'-tert-butyl-phenyl-butanoic acid]-glycol ester, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl-phenyl)butane, 4,4'-thio-bis(6-tert-butyl-m-cresol), 4,4-thio-bis(2-tert-butyl-m-cresol), 4,4'-butylidene-bis(2-tert-butyl-m-cresol), 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-sec-butylphenol, 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), 1,3,5-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5G)-trione, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 1,6-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), tetrakis{methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}methane, octadecyl-3-(3'5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid triester with 1,3,5-tris(2-hydroxyethyl)-s-triazine-2,4,6-(1H,3H,5H)trione.
11. The polymer of claim 10 wherein the hindered phenol is selected from the group consisting of tetrakis{methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}methane, octadecyl-3-(3'5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid triester with 1,3,5-tris(2-hydroxyethyl)-s-triazine-2,4,6-(1H,3H,5H)trione, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl-phenyl)butane, and 1,3,5-trimethyl-2,4,6-tris-(3,5-di-di-tert-butyl-4-hydroxybenzyl) benzene.
12. The polymer of claim 6 having an acid number of 6.13 or less after exposure to 85% relative humidity at 25� C. for 163 hours.
13. The polymer of claim 9 having an acid number of 6.13 or less after exposure to 85% relative humidity at 25� C. for 163 hours.
The invention described herein pertains generally to a new class of phosphites, i.e., a bis(aralkylphenyl)pentaerythritol diphosphites, and their ability to be used as a stabilizer for several polymers, particularly, polypropylene.
Plastics are used in a myriad of widely diverse applications, in automobile parts, in components for houses and buildings, and in packaging from food to electronic parts. Plastics would not be able to perform such diverse functions without the assistance of a very broad range of plastics additives. Without them, some plastics would degrade during processing and, over time, the polymers would lose impact strength, discolor, and become statically charged, to list just a few problems. Additives not only overcome these and other limitations, but also can impart improved performance properties to the final product.
Formulating with plastics additives has always been a tricky business. Incorporating additives into a polymer requires a fine balance between the properties of the polymer and the additive. Formulating a plastic for enhanced ultraviolet light resistance, for example, can have an impact on the polymer's color stability and retention of its functional characteristics. Formulators need to choose additives carefully, so that the additive not only possesses a specific functionality, but that it also minimizes the effect on other additives and the formulated plastic.
Antioxidants are but one class of additives applicable in polyolefin and other polymer resins. These additives retard the oxidative degradation of a plastic. Degradation is initiated when free radicals, (highly reactive species with an unpaired electron), are created in the polymer by heat, ultraviolet radiation, mechanical shear, or metallic impurities. Without the protection of antioxidants, loss of molecular weight, brittleness, discoloration, crosslinking, and deterioration of other polymer properties will occur.
When a free radical is formed, a chain reaction begins that initiates polymeric oxidation. Subsequent reaction of the radical with an oxygen molecule yields a peroxy radical, which then reacts with an available hydrogen atom to form an unstable hydroperoxide and another free radical. In the absence of an antioxidant, these reactions become self-propagating, and lead to polymer degradation.
There are two basic types of antioxidants, primary and secondary. Primary antioxidants intercept and stabilize free radicals by donating active hydrogen atoms. Hindered phenols and aromatic amines represent the two main types of primary antioxidants. Secondary antioxidants prevent formatin of additional free radicals by decomposing the unstable hydroperoxides into a stable product. Phosphites and thioesters are secondary antioxidants that function by decomposing hydroperoxides, thus preventing free-radical formation. Secondary antioxidants are often used along with primary antioxidants, but can be used alone, especially if they contain a hindered phenolic group within their structure. Together they decrease the discoloration of the polymer and may also regenerate the primary antioxidant.
There are several commercially available phosphites that are used to stabilize polymer materials against color degradation and melt flow degradation. One product which has been found to be especially useful is a bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite as shown by formula (I) described in U.S. Pat. No. 4,305,866 to York. ##STR1## Another product which has been mentioned in the literature is bis(2-t-butyl-4-{alpha,alpha'-dimethylbenzyl})pentaerythritol diphosphite as shown by formula (II), described in U.S. Pat. No. 4,983,657 to Humplik. ##STR2## Both phosphites of formulas (I) and (II) have problems in that they are hygroscopic, and are not hydrolytically stable. On exposure to moisture for a period of time, they have a tendency to lump and become a sticky mass.
Additionally, symmetrical triarylphosphite stabilization systems have been described for polyolefins in U.S. Pat. No. 4,187,212 to Zinke et al., as shown for example in formula (III) ##STR3##
While this phosphite does possess good hydrolytic stability, it is not as effective as desired for color stability and melt-flow stabilization. Pentaerythritol diphosphites such as shown in formulas (I) and (II) are more effective in maintaining color stability.
To date, there still exists a need to provide a phosphite product, based on pentaerythritol, which is slower to absorb moisture, thereby maintaining its effectiveness for longer periods of time in humid conditions.
In accordance with the present invention, there is provided more hydrolytically stable bis(aralkylphenyl)pentaerythritol diphosphites, which are suitable as an antioxidant additive in polyolefins, particularly, in polypropylene.
It is an object of this invention to provide a thermally stable polymer additive of low volatility, which possesses a high thermal decomposition temperature.
It is another object of this invention to provide a polymer additive which is resistant to phosphite hydrolysis upon exposure to moisture for an extended period of time, thereby remaining granular and free-flowing.
It is still another object of this invention to maintain the Hunter yellowness color index number as low as possible thereby indicating that the additive has limited the amount of degradation of the polymer under processing conditions.
It is yet another object of this invention to maintain the melt-flow index of the polymer thereby indicating that the additive has limited the amount of degradation of the polymer under processing conditions.
It is a further object of this invention to provide a method for synthesizing a bis(aralkylphenyl)pentaerythritol diphosphite in improved yield.
It is yet a further object of this invention to demonstrate that a bis(aralkylphenyl)pentaerythritol diphosphite can be used in combination with a class of hindered phenols to maintain both color and minimize melt-degradation of the polymer in a synergistic manner.
These and other objects of this invention will be evident when viewed in light of the detailed description and appended claims.
Polymer degradation is the deterioration in the physical properties of a polymer caused by chemical reactions involving the backbone of the polymer chain. Symptoms of degradation are yellowing, loss of tensile strength, loss of impact strength, changes in melt-flow, and poor processability. This degradation can be caused by contamination in the polymer, residual catalyst (potentially causing depolymerization), temperature, and light. Degradation tends to occur under the following conditions: polymer drying; polymer pelletizing and compounding; polymer storage and shipment; polymer fabrication processing; and during recycling.
One technique which ameliorates some of the above problems is through the use of an additive, in particular, a phosphite additive. One of the problems with the addition of pentaerythritol phosphite stabilizers has been their tendancy to absorb moisture, thereby decreasing the product's ability to flow freely. It has been found, that pentaerythritol-based diphosphites of the invention, shown in generic form as formula (IV), are more hydrolytically stable than prior art pentaerythritol diphosphites, and therefore require less precautions to be taken in their handling, and are more desirable as additives. ##STR4## Specifically, within the pentaerythritol-based diphosphite of formula (IV), Rl, R2, R3, R4`, R5, R7, R8, R10 and R11 are selected independently from the group consisting of hydrogen, alkyl radicals of generic formula Cm H2m+1 wherein m ranges from 1 to 4 and substituted derivatives thereof; Rn 3, Rn 6, Rn 9, and Rn 12 are selected independently from the group consisting of hydrogen, alkyl radicals of generic formula Cm H2m+1 wherein m ranges from 1 to 4, aryl radicals, and further wherein n ranges from 0 to 3, and the substituent is located at a position ortho, meta or para to the bridging methylene radical.
In particular, a preferred embodiment of the invention, is a diphosphite of formula (V), a bis(2,4-dicumylphenyl)pentaerythritol diphosphite. ##STR5##
Cost and time prohibit real-life testing of stabilizer systems, therefore laboratory tests have been developed to simulate conditions under which degradation occurs. Thermal gravimetric analysis (TGA) is a sensitive technique used to follow the weight change of a sample as a function of temperature, thereby providing information about the thermal stability, volatiity and decomposition temperature temperature of the material studied. The test simulates conditions which the polymer would experience during manufacturing and compounding.
As shown in Table I, TGA scans were used to measure the thermal stability of a series of phosphite stabilizers shown previously by formulas (I), (II), (III) and (V). The percentage weight loss of the starting phosphite was determined as a function of temperature.
TABLE I______________________________________TGA.sup.(1) Comparison temperature at % of weight loss T(�C.) T(�C.) T(�C.) T(�C.)Percent Phosphiteweight loss (I) (III) (V) (II)______________________________________ 5 250 258 250 31410 275 265 275 33220 300 282 300 34330 315 293 318 35040 320 297 329 35450 327 303 336 36580 345 318 364 375______________________________________ .sup.(1) DuPont 2000 TGA using a heating rate of 10� C. from room temperature to 800� C. under nitrogen
As shown in Table I, the bis(2,4-dicumylphenyl)pentaerythritol diphosphite (V) exhibited good high temperature stability and low volatility in comparison to the bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite of formula (I) and the trisubstituted symmetrical triphenylphosphite of formula (III) and similar characteristics to the bis(2-t-butyl-4-{α,α'-dimethylbenzyl})pentaerythritol diphosphite of formula (II).
All phosphites will eventually react with water and hydrolyze. As this reaction occurs, an acidic species is produced which is titratable. In the first stage of hydrolysis, the phosphite reacts with a molecule of water to form an alcohol or substituted phenol and dialkyl or dialkylaryl phosphite. The dialkyl or dialkylaryl phosphite once again reacts with water to form a monoester and once more with water to yield the dibasic phosphorous acid. By monitoring a phosphite for the alcohol or phenol and acid content, the extent of hydrolysis can be determined and thereby gauge the product's fitness for use.
The acid number was determined by weighing out a one gram phosphite sample. Approximately 75 ml of methylchloride was neutralized with 0.02N sodium butylate to a blue-green endpoint using about 4-6 drops of a 0.1% bromothymol blue indicator solution. The neutralized methylene chloride was added to the phosphite sample and dissolved. The solution was immediately titrated with 0.02N sodium butylate to a blue-green endpoint.
A hydrolytic stability comparison was made between the prior art products, formulas (I) and (II) in comparison to new formula (V), by exposing the 5 g samples of the phosphites to 85% relative humidity at about 25� C. for various periods of time, and noting when the powder changed its physical characteristics to either non-powdery or became sticky and lumpy. Without being held to any particular theory, it is proposed that the hydrolytical stability of formula (V) is due to the large bulky groups adjacent to the phosphorus. This provides a good deal of steric hindrance to hydrolysis.
TABLE II______________________________________Phosphite Hydrolysis.sup.(1)Hours 0 67 163 consistencyPhosphite acid number.sup.(2) after 163 hrs______________________________________(I) 0.06 0.01 21.9 sticky(II) 0.08 0.12 10.1 sticky(V) 0.67 2.36 6.13 granular & free flowing______________________________________ .sup.(1) exposure phosphites to 85% relative humidity at 25� C. .sup.(2) acid number (mg KOH/g) as a function of time (hours)
As can be seen in Table II, diphosphites of formulas (II) and (V) exhibit a lower acid number for longer periods of time, and additionally, for the case of formula (V), the diphosphite remains granular and free-flowing even after exposure to extremely elevated moisture levels for more than 163 hours.
Tests which simulate compounding and fabrication include measurements of the polymers' torque rheometry using a Brabender and multiple pass extrusions. These tests subject the molten polymer to heat and shear for extended periods of time. After the test exposure, the polymer is prepared into samples which can be used for physical property, color, and viscosity testing. A Brabender plasticorder PL2000, multipurpose instrument was used to study the viscosity or flow properties of polymer materials under various temperatures and shear rates. For testing, samples were prepared by accurately weighing additives to be added to the polymer (e.g., polypropylene). They were dry blended in a plastic 1000 ml beaker by shaking for approximately 5 minutes.
The Brabender consisted essentially of a measuring head with roller blades, drive control and measuring unit. For the series of tests performed, the temperature was set at 200� C. and the speed was 100 rpm. The sample weight was 39 g. The length of the time of the test was approximately 12-40 minutes. The sample to be evaluated was charged to the mixer head by means of a loading chute ram on a 5 kg weight. The Brabender then continuously recorded torque, which is a measure of viscosity at a constant temperature of 200� C. over a time period varying from 0-40 minutes. Torque and temperature were continuously monitored. Torque gives an indication of the viscosity of the polymer. For polypropylene, as the polymer degrades, the viscosity decreases and the torque decreases. Immediately upon conclusion of the test, the measuring head was removed. Using a brass knife, a sample was quickly removed to be used for color determination from the mixing head and placed on a clean stainless steel plate. The sample was measured for color determination. When cool, the sample was placed between two polished plates and inserted in a Carver press for 6 minutes at 5 metric tons of pressure and a temperature of about 150� C. After pressing the plates containing the samples, they were cooled for 6 minutes, the sample removed and the color read on a Hunter Colorimeter. The Brabender also computed the specific energy imparted to the sample over the period of time the evaluation was carried out. The higher the specific energy for a given period of time, the less the polymer degraded.
Melt indexes were measured in accordance with the requirements of Condition L of ASTM D1238. The test method covers measurement of the rate of exudation of molten resin through a die of a specified length and diameter under prescribed conditions of temperature and load. The results of this test give some indication of the molecular weight of the polymer. For polypropylene, as the polymer is degraded and the molecular weight decreases, the melt index or flow through the orifice increases. For Condition L, the temperature is 230� C. with a load of 2.16 kg. Melt index or melt flow is given in numbers of g/10 minutes.
Color measurements were determined using a Hunter Lab D25-PC2 Delta Processor. This processor calculates the yellowness index per ASTM D1925 and ASTM E313. The industrial standard for measuring color for polymer such as polyethylene and polypropylene is the yellowness index. Visually, yellowness can be associated with scorching, soiling and general product degradation by light, chemical exposure or processing variables. Yellowness Index, ASTM D1925 is used to measure these types of degradation for plastics and paint industries. The test is carried out by comparing the yellowing of the sample to a white standard the lower the number YI, the whiter the sample and the less degradation. The higher the YI, the yellower the sample and indicates more degradation.
Typically polymers such as polypropylene, polystyrene, polyethylene terephthalates (PET), polyalkylene terephthates, and polycarbonates will tend to break down or chain scission as they are processed at higher temperatures for a period of time. This will result in an increase in melt index. Polyethylene on the other hand, can increase in molecular weight due to crosslinking and oxidation. When evaluating polyethylene by melt index, and basically for all polymers, it is desirable that the melt index not change from the beginning to the end.
In regard to the yellowness index, the more the polymer is processed, the higher the yellowness index or the darker the material becomes. Again, it is desirable that there be minimal change in this index during processing.
TABLE III______________________________________Evaluation of Phosphites in Polypropylene Torque.sup.(3) Hunter YIPolymer (meter-grams) yellowishcomposition 12 min 24 min 36 min color index______________________________________base.sup.(1) 875 550 375 40.8base + (I).sup.(1) 1075 720 395 17.5base + (II).sup.(2) 1025 700 375 17.6base + (V).sup.(2) 1075 725 375 15.5base + (III).sup.(2) 1000 685 375 44.3______________________________________ .sup.(1) base formulation (a) 100 parts polypropylene, Profax ™ 6501 produced by Himont, an isotactic homopolymer with a meltindex of 4, a density of 0.9 g/cm3, a tensile strength of 5,000 psi, and elongation at yield of 12%. (b) 0.10 parts Irganox 1076 (octadecyl 3(3',5 di-t-butyl-4hydroxyphenyl)propionate, formula (VI) ##STR6## .sup.(2) 0.2% phosphites added to the base .sup.(3) Brabender temperature 200� C. 100 rpm
As shown in Table III, without the addition of any phosphite additive, the torque, which is a measure of the polymer degradation, measured at 12 min. was significantly lower than the torque measured for samples to which 0.2% phosphites had been added. Additionally, the unstabilized polypropylene exhibited significant discoloration as indicated by the high yellowish color index number. The diphosphite (V) performed equally effectively to that of a known state-of-the-art products, formulas (I) and (III), and significantly better than formula (III) in discoloration.
The improvement resides therefore, in the ability to outperform phosphites, such as formula (I) and (II) in its resistance to hydrolysis, as indicated in Table (II) and additionally, in its inherent thermal stability as indicated in Table (I).
A multi-extrusion study was performed using phosphite (V), a bis-2,4-dicumylpentaerythritol diphosphite, with several other phosphites using polypropylene in accordance with the amounts shown in Table IV. The samples were blended and extruded at 210� C. through a twin-screw extruder. The extruded material was pelletized and a small sample was retained for melt-flow and color resting. The remaining pellets were extruded again, up to a total of five extrusions.
TABLE IV__________________________________________________________________________Multi-Pass Extrusion Studybase.sup.(1)Additives melt flow.sup.(5) melt flow.sup.(5) YI.sup.(6) YI.sup.(6)polymerCa.sup.(2) phenol.sup.(3) phosphite.sup.(4) 1st pass 5th pass 1st pass 5th pass__________________________________________________________________________#1 PP0.05% 0% 0% 26.9 208.3 4.6 6.7#2 PP 0.1% 0% 7.0 12.2 4.5 6.3#3 PP 0.1% (V) 0.05% 5.9 7.8 4.5 5.4#4 PP 0.1% (I) 0.05% 3.9 4.8 4.0 6.1#5 PP 0.1% (II) 0.05% 3.5 4.8 4.0 6.1#6 PP 0.1% (III) 0.05% 6.0 54.6 4.3 5.4#7 PP 0.1% (V) 0.05% 4.0 5.1 4.0 4.6#8 PP 0.05% (V) 0.10% 3.9 15.0 4.1 4.4__________________________________________________________________________ .sup.(1) polypropylene (PP) .sup.(2) calcium stearate .sup.(3) hindered phenol (I1076 of formula (VI)) .sup.(4) amount of added phosphite of appropriate formula .sup.(5) melt flow (grams/10 minutes) .sup.(6) Hunter Yellowness Color Index
The data clearly shows that the phosphite of formula (V) does improve the stability over the base polymer. Additionally, as shown in run #8, it is also indicated that doubling the level of phosphite (V), does indicate that less of the polymer is degraded. The amount of phosphite added is well-known by those skilled in the art, but in general is guided by cost considerations and FDA approval. Typical amounts added however, will generally range from 0.01% to about 0.5%.
While only one hindered phenol is shown in Table IV, there are many different phenolic compounds which are equally suitable for use in the invention, and well-known to those skilled in the art. A non-inclusive list of examples of such suitable phenolic-based compounds would be: Bisphenol™ A (Dow Chemical Co., 4,4-isopropylidene-diphenol); TENOX™ BHA (Eastman Chemical, butylated hydroxyanisole); ETHANOX™ 330 (Ethyl Corp., 1,3,5-trimethyl-2,4,6-tris(3,5-di-di-tert-butyl-4-hydroxybenzyl)benzene); ETHANOX™ 702 (Ethyl Corp., 4,4-methylene-bis(2,6-di-tert-butylphenol)); MIXXIM™ AO-30 (Fairmount Chemical Co., 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane); ANULLEX™ BHEB, (Hodgson Chemicals Ltd., 2,6-di-tert-butyl-4-ethylphenol); HOSTANOX™ 03 (Hoechst Celanese Corp., bis-[3,3-bis-(4'-hydroxy-3-tert-butyl-phenyl-butanoic acid]-glycol ester)); TOPANOL™ CA (ICI Americas Inc., 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl-phenyl)butane); SANTONOX™ R (Monsanto Co., 4,4-thio-bis(6-tert-butyl-m-cresol)); SANTONOX™ (Monsanto Co., 4,4-thio-bis(2-tert-butyl-m-cresol)); SANTOWHITE (Monsanto Co., 4,4'-butylidene-bis(2-tert-butyl-m-cresol)); SUSTANE BHT (UOP Biological & Food Products, 2,6-di-tert-butyl-p-cresol); VANOX™ 1320 (R.T. Vanderbilt Co., Inc., 2,6-di-tert-butyl-4-sec-butylphenol); CYANOX™ 425 (American Cyanamid Co., 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol)); CYANOX 1790 (American Cyanamid Co., 1,3,5-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5G)-trione); CYANOX™ 2246 (American Cyanamid Co., 2,2-methylene-bis(4-methyl-6-tert-butylphenol)); IRGANOX™ 245 (Ciba-Geigy Corp., 1,6-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)); IRGANOX™ 1010 (Ciba-Geigy Corp., tetrakis{methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}methane); IRGANOX™ 1076 (Ciba-Geigy Corp., octadecyl-3-(3'5-di-tert-butyl-4-hydroxyphenyl)propionate); IRGANOX 3114 (Ciba-Geigy Corp., 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate); and IRGANOX™ 3125 (Ciba-Giegy Corp., 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid triester with 1,3,5-tris(2-hydroxyethyl)-s-triazine-2,4,6-(1H,3H,5H)trione).
The best mode for carrying out the invention will now be described for the purposes of illustrating the best mode known to the applicant at the time. The examples are illustrative only and not meant to limit the invention, as measured by the scope and spirit of the claims.
A glass reactor was fitted with an agitator, reflux condenser, and a gas outlet. The reactor was charged with 150 g of 2,4-dicumylphenol, 100 g heptane and 100 g toluene and heated to 35� C. After sufficient mixing, 62.6 g of PCl3 were added and the reaction mixture heated to 90� C. After 0.5 hours at 90�-95� C., HCl was still evolving. The reaction is allowed to proceed for approximately 1.25 hours at 90�-95� C., followed by cooling to 45� C. with the addition of 31.4 g of pentaerythritol under vigorous agitation. The reaction is allowed to proceed with agitation for about 3 hours at 50� C. A nitrogen purge was initiated over the reaction and 120 g of additional heptane was added to the batch with heating to 100� C. for 8 hours. The product is a milky-white suspension. After cooling, filtering and drying, 129 g of bis(2,4-dicumylphenyl)pentaerythritol diphosphite was recovered (66% yield). The acid number varied from 2 to 6. The mother liquor can be recycled into another batch to produce additional product if desired.
A glass reactor was fitted with an agitator, reflux condenser, and a gas outlet. The reactor was charged with 150 g of 2,4-dicumylphenol, 0.22 g of triethanolamine, 100 g heptane and 100 g toluene and heated to 35� C. After sufficient mixing, 62.6 g of PCl3 were added and the reaction mixture heated to 90� C. After 0.5 hours at 90�-95� C., HCl was still evolving. The reaction is allowed to proceed for approximately 1.25 hours at 90�-95� C., followed by cooling to 45� C. with the addition of 31.4 g of pentaerythritol under vigorous agitation. The reaction is allowed to proceed with agitation for about 3 hours at 50� C. A nitrogen purge was initiated over the reaction and 120 g of additional heptane was added to the batch with heating to 100� C. for 8 hours. The product is a milky-white suspension. After cooling, filtering and drying, 147 g of bis(2,4-dicumylphenyl)pentaerythritol diphosphite was recovered (75.4% yield). The acid number varied from 2 to 6. The mother liquor can be recycled into another batch to produce additional product if desired.
The addition of a trialkanol amine increasing the yield of bis(2,4-dicumylphenyl)pentaerythritol diphosphite from 66% to more than 75%.
The invention has been described with reference to preferred and alternate embodiments. Obviously, modifications and alterations will occur to others upon the reading and understanding of the specification. It is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
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