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October 31st, 2014 by Libera Boys
Now that the hard work was over, we drove out of Central Washington and made our way to our next hotel; a lovely ski-resort hotel, which was cosy and the best way to end the amazing tour. We didn't do any ski-ing, however.
We decided to visit one of the most interesting science museums we had ever been too; the Da Vinci Centre of science. Inside, the boys had all sorts of fun sorting puzzles, discovering that a snowboard is not the best object to pack on a space trip, spinning around on a gyrosphere, admiring bees, floating foam balls in air, and even building large skyscrapers out of Jenga-like blocks.It was a truly amazing experience, and dare I say it, better than most science museums in South London. The range of activities, along with the compact area, made it a hive of learning without the boring stuff.
After invading an EPIC local playground with soft cushioned floor and mad climbing structures, we returned to our luxury hotel.
The science museum did sound like fun to you, I'm sure. But what would rest and relaxation be to a group of young boys from a thrill-seeking performance based life, than thrill-seeking unlike no other. Oh yes, a trip to a theme park was in play. Not just any theme park, but a water park and theme park packed into one bedazzling dizzy-making day. Dorney Park.
Visiting a theme park such as this was rare indeed for us. None of us were expecting a spectacle and sight such as a waterslide being so close to a twirling roller coaster, and the element of surprise was the perfect way to end the tour. Many of the boys had immense fun on the roller coasters, and with the shows done, we could essentially scream our heads off. We didn't, but that's only because it's hard to scream spinning upside down at 60 miles per hour.
The weather was kind to us, and our days relaxing were becoming our last days in America. Soon, it was time to drive back to Washington and catch a plane back home.
Before we leave though, we took the time to say that this trip was something special, and it was sad to leave. We packed our toy mooses (or moosen, I'm not sure which plural to use) and made our way to the airport – and said good-bye to our wonderful washington driver, Sean. It was time to tell our parents all the stories from the trip, or maybe they will read this!
See you next tour, unless the mooses steal the music to start their own choir.
October 31st, 2014
Now that the hard work was over, we drove out of Central Washington and made our way to our next...read more »
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Connie Beach in Davidson wants the recipe for Bettys Pimento Cheese from Harpers.
My entire family thinks its the best pimento cheese we have ever tasted. It has just the right amount of thickness, and some special flavor we have never been able to identify. We even took a professional chef with us one night to see if she could figure it out, but she could not. We live about 30 minutes from the restaurant, so we are not able to indulge very often, and it would be wonderful to surprise my family with the recipe!
It is the season for surprises, not to mention holiday gatherings. This pimento cheese, named for Betty Sasser, the mother of Harpers founder Tom Sasser, is versatile enough to bring to party after party and serve it a different way every time.
You could go old school and serve it chilled with crackers, potato chips or crudités. You could serve it warm, perhaps with some pita chips. For a heavy hors doeuvre, you could serve burger sliders dolloped with warm pimento cheese.
If you have pimento cheese left after the party, you could enjoy it the way Sasser did as a kid in a sandwich served with a bowl of tomato soup. It doesnt get much better than that. Unless, of course, you slather it between two slices of white bread and make a grilled pimento cheese.
Robin Domeier is owner of Nibbles Personal Chef.
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Situated on Orpington High Street, Café Medi is typical of Italian restaurants in its focus on good food and great, warm service. It's a modern dining spot, the glass frontage flanked by a row of
trimmed box trees, guiding you in to a spacious, calmly decorated room in light but cosy tones and with contemporary furnishings. From start to finish, guests will enjoy attentive, friendly but
understated service with a smile, an Italian trademark that has survived the journey to Kent in tact. Serving breakfast, lunch, dinner and a Sunday lunch too, as well as celebration banquets, Café
Medi is a restaurant for all occasions, the menus strong on Italian flavour and the food homemade by the kitchen team using authentic ingredients and favourite recipes both old and new. As well as
a wide range of pasta and risotto dishes, Café Medi serves real Italian pizzas, tempting meat and fish dishes and – be sure to leave room – delectable desserts too.
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Fort Standard
Fort Standard is a contemporary design studio founded in 2011 by Gregory Buntain and Ian Collings. Having studied Industrial Design together at New York's Pratt Institute and The Bauhaus University in Weimar, Germany, their work is a fusion of craft-based backgrounds and timeless materials paired with progressive design prowess and emerging technologies. Focusing on domestic products and furniture, their attention to detail, materials, and connections generate value through design executed in a refreshing and warm contemporary aesthetic.
From the Store
White Marble Platter$130.00
Crest 1 Bottle Opener$60.00
White Marble Trivet$88.00
Dry Good Vessels$84.00


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* Please scroll down for latest updates.
* Please scroll down for latest updates.
Two men arrested as part of the investigation into the abduction and murder of Jean McConville have been released unconditionally.
Sami Hyypia has resigned as manager of Brighton and Hove Albion just six months into his tenure at the Amex Stadium.
One man regrets returning from a comfortable life abroad to a life of poverty in Ireland, writes Noel Baker
In the inky trade, 'man bites dog' might be the gold standard for what qualifies as a legitimate news story but, in the case of Roy Keane, 'man rings doorbell' appears to be more than enough to merit the full shock 'n awe treatment.
A 'time of great interior crisis' early in his career turned Pope Francis into a family man and one who is determined that the Church puts the care of individuals above doctrine, writes Paul Valley
ON the face of it, I'm all set for Christmas. But not really.More
THE letterbox clanks. As is always the case, I gallop downstairs to see what the post brings. This, I think, is a feature of the self-employed. The lack of a buzzing office atmosphere means that the postman's arrival is a big deal. What will today bring? Maybe I've finally won the million euro in the Prize Bonds?More
The number of supermarket chickens infected with campylobacter has risen sharply this year, but what exactly is compylobacter and should you let it affect your Christmas dinner?
A phone app featuring a character called Nicholas Fromage kicking immigrants off the White Cliffs of Dover has been criticised by Ukip leader Nigel Farage.
Elton John and David Furnish have officially got married — exactly nine years after they tied the knot in a civil partnership ceremony.
This year has proved to be another bonanza one for receivers to the National Assets Management Agency debtors with the firms picking up €18.27m to date in receivership fees.
Fresh from the jungle Irish model Nadia Forde will be a guest presenter on TV3's Xposé today.
Hideaways for after Santa's visit and before the new year resolutions kick inBy Tony Clayton-Lea


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America's Road to Financial Ruin: Opinion
NEW YORK ( TheStreet) -- Pundits, economists and politicians love to use the phrases "black swan" or "nobody could have seen it coming" when describing events that have brought the United States of America to the brink of insolvency. Such statements are ridiculous -- much of the excesses and malfeasance committed by our leaders came in plain sight.
Alas, America's corporate and political leaders have had the luxury of "failing upwards." They were awarded more power and responsibility after making disastrous mistakes, and the public has largely turned a blind eye.
Today, our country faces record deficits, a national debt accelerating at the fastest pace in history and nearly 45 million Americans relying on food stamps for subsistence.
Executive compensation is nearly six times higher than it was in 1980; presidential campaign spending has increased more than threefold in little more than a decade; labor force participation is at a 25-year low; and the unfunded liabilities of America's social programs equate to more than $1 million per taxpayer.As a government shutdown looms, one may wonder how we got here. To answer that question, TheStreet has turned to its archives for articles, interviews and commentary that document how America went off the rails and into a ditch of financial fright. The timeline below is not comprehensive and must be considered in light of numerous other economic events, but it nonetheless provides a sobering look at how we got where we are today. TheStreet will continue to update this timeline as we uncover additional articles whose lessons withstand the tests of time:
November 11, 2000The Rise and Fall of Long Term Capital Management
Roger Lowenstein, author of When Genius Failed, offers insight into America's first derivative-based crisis: The spectacular collapse of Long Term Capital Management. Lowenstein also highlights the Federal Reserve's curious decision to lessen derivative regulation in the aftermath of the disaster.
July 25, 2001Understanding the Lunacy of the Dot-Com Bubble
Because of a technicality, Staples (SPLS) management is forced to explain to shareholders how they arrived at a valuation for (the not-yet-launched) Staples.com -- providing a window into the madness that inflated the dot-com bubble.
October 10, 2001Economist Argues Against Federal Bailouts in the Wake of Sept. 11
Economist David Henderson warns that federal bailouts, in response to 9/11/01, will deplete the budget surplus, lead to future borrowing and increase the role of federal government.
October 1, 2002Fannie Keeps the Profits, Taxpayers Take the Risk
Ken Wolff exposes the uncomfortable relationship between Fannie Mae (FNMA), Freddie Mac (FRE), the U.S. Treasury and the Federal Reserve; and highlights Congressman Ron Paul's efforts to regulate the government-sponsored mortgage industry.
April 23, 2003Fleckenstein: All Roads Lead to Inflation
Hedge fund manager Bill Fleckenstein slams the policies of the Federal Reserve, predicts a U.S. housing bubble and calls for a bull market in precious metals.
September 21, 2007The Credit Crisis Could Be Just Beginning
Satyajit Das, a leading expert in credit derivatives, predicts the subprime crisis in an account so accurate, it could have been written after the fact.
December 15, 2010Chart: U.S. GDP vs. Spending vs. Revenue
A 20-year snapshot of America's economic growth, spending and revenue (tax receipts) reveals that far-left and far-right political ideologies deserve equal blame for our financial woes. -- Written by John DeFeo in New York City Follow @johndefeo
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The Knicks had won their previous games in San Antonio entering the night, meaning that they were only due to regress to the mean. They did, and now that their losing streak has hit double digits and the team is reportedly turning on itself, panic has officially taken over New York.
Articles tagged with: San Antonio Spurs
Last year, the Texas Triangle trip was supposed to turn the season around. Now, the Knicks have a new triangle to show off to their Southwestern foes, but how will they fare against the likes of the Spurs, Rockets, and Mavericks?
Every now and then, the Turn On The Knicks staff will debate an issue surrounding the team here in Roundtable Format. Make sure to give everybody a follow on Twitter, and follow the site right here. Let us know if you agree/disagree. What are your first round playoff predictions?
Ok then! The Knicks started off the 2014 calendar year with their banner win of the season (if there can be such a thing when you're 10-21) by knocking off the San Antonio Spurs in the first game of a three-game Texas swing. There were some excellent performances throughout for the Knicks, which is a …
With tonight's Knicks-Spurs matchup in mind, I think a visit back to the 1999 NBA Finals is in order.
The New York Knicks are headed down south this week for three unfavorable matchups in the dreaded Texas triangle. Read on to see what else they have on their plate for the upcoming week.
That was about as bad as it can get. Had the Knicks played the way they did on Sunday against a middling team, they still would have lost. But when you play with such malaise and ineptitude, especially on defense, against a team like the Spurs, things get ugly and out of control. Some thoughts:
The New York Knicks have three games this upcoming week, including a home-and-home series with the Charlotte Bobcats. Read on to see what else is happening in New York.
Since staring at the schedule isn't making the 2013-14 season get any closer, TOK is going to break down the New York Knicks games by division over the next couple weeks. We start with the Southwest Division.
Chris DiGioia dismisses the argument that the New York Knicks have a small championship window


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Power (Watt) = Current (A) × Voltage (V). Apple does tell what the power rating for the iPad battery is: "Built-in 25-watt-hour rechargeable lithium-polymer battery" (http://www.apple.com/ipad/specs/). Assuming nominal 3.7V voltage for a lithium-ion battery, we find this: 25W / 3.7V = 6.75675... ≈ 6.76A. In other words, something in the 6700mAh range.
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Windows Help
It's free to register, to post a question or to start / join a discussion
Which of these 3 to get rid of metro
« previous 1 2
Likes # 0
Posted January 19, 2013 at 12:49PM
Classis Shell....StartbuttonX....Startmenu8
are any better than the other any comennts anyone compared them to each other.
[not got w8 yet still genning up for new laptop]
- Tags:
- metro
Likes # 0
Posted January 20, 2013 at 3:39PM
can i delete about 80% of the tiles? not into social media stuff and make new squares from shotcuts to programes,docs and favorites?
Likes # 0
Posted January 20, 2013 at 4:36PM
yes of course you can, just right click the tile and you'll see a menu open up at the bottom. Select unpin from start. Tile gone
If you want to put a tile on the start screen simply right click the file / folder and select pin to start.
Have a look here for loads of info about Win8 and the customising the start screen. http://www.eightforums.com/tutorials/ http://www.eightforums.com/software-apps/ http://www.eightforums.com/tutorials/?filter1=Taskbar%20Start%20Screen
Those should keep you occupied for a while. As I said the start screen is much more useful than it 1st looks. The other important thing to remember with win8 is the keyboard shortcuts using the windows key. Have a look here http://www.eightforums.com/tutorials/2355-windows-8-keyboard-shortcut-keys-list.html
Regards Aquatarkus PS presume your in Staines because of your user name?
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"Ditch Your New 12 months's Resolutions Day," is an trustworthy to goodness holiday. It s a day the place you can guilt-free depart the resolutions you made less than three weeks before, behind. Polls show most individuals declare they have dropped their resolutions by the tip of January, so this date is calculated as the average date most individuals give up their resolutions. Most individuals fail because they don't make a targeted lifelike goal that has a workable motion plan hooked up to it. You'll think that individuals who selected to train extra, be part of a gymnasium or purchase something like a treadmill or a Schwinn recumbent bike would follow it, merely as a result of financial funding!
Over all this is a horrible holiday for many who actually wish to make a change of their life by exercising. In 2010 Michelle Obama determined to focus on the child obesity downside that has been documented in information studies time and again. People of all ages need encouraged to maintain at it, and create an motion plan that will profit their health. They should not be given a built in excuse to drop it!
Listed here are a number of issues that will assist create a reachable train goals.
The primary is evaluating whether or not to purchase home train equipment or to affix a gym. There are professionals and cons for each, and the underside line is it doesn't matter, as long as there's a dedication to whichever path is chosen. It's silly to resolve to affix a gymnasium if you don't get home till seven o'clock, your family won't ever see you. In the identical vein it could be silly to purchase a chunk of kit if the one spot you'll find means everybody will trip throughout it.
In the event you select to purchase something on your home, take time to look at the totally different prices, types and brands of train equipment. Sticking to a budget is vital, so you aren't swayed by fashions you can't afford. Train bikes are often chosen as a result of extra cheap cost. The Schwinn recumbent bike has turn out to be a popular selection not solely because they offer a number of entry stage value fashions, but the ergonomic design lets you get the most productive exercise with the least muscle fatigue.
All that's left is to create a sensible schedule, aiming for three times every week for a minimum half hour at first, could make this look doable. Schedule it round a tv show, save a magazine, listen to your favourite music and you can make the purchase of you Schwinn recumbent bike a decision you're grateful for. Once you get started it should turn out to be routine, and easier to maintain going.
Next yr on January 17 you can proudly show the "Ditch Your New 12 months's Resolution Day" crowd that they're flawed while you notice how a lot weight you lost, you don't run out of breath while you choose up the Holiday containers to pack away and keep in mind how low your depth and resistance levels have been compared to the place you at the moment are!
As soon as your resolution is made to purchase a Schwinn Recumbent Bike the next factor that has to happen is select which model and value range you can afford. Article Source and associated Links: Pearl iZUMi Barrier MTB Mountain Bike Shoe Cover , Reusable Neoprene Commuter Pollution Mask and Crash Pads Upper Body Armor .


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Sep 20, 2013
Bid On Chris' Romero Britto Collaboration
The collaboration is an initiative of Chris' Symphonic Love Foundation to raise funds and awareness for Best Buddies International. Breezy and Britto are long-standing supporters of the cause, whose mission is to establish a global volunteer movement that creates opportunities for friendship, employment and leadership training for people with intellectual and developmental disabilities.
Click here to bid on this one-of-a-kind piece now through October 10.


text: There is a consensus concerning the likelihood of 2010 being an uncapped year, with all the Free Agency/financial implications that brings. What impact does an uncapped year have on contract length for draft picks? Would NE be more likely to draft at 22 or trade up a couple places if they can now squeeze a prospect for a six year contract? Could they force a second rounder to sign a five year deal? Is Cody at #22 a more attractive option than keeping Wilfork long term if he can be signed to a six...or even a seven year deal? Does BB now find an OLB conversion more attractive in round one if he can lock him into a six+ year deal to get a better return on the development time he'd need?


text:
Comments about 'Matthew Sanders: Unwieldy bureaucracy is crippling the economy'
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"f the old adage holds true, that "time is money" then when
regulations cost time, they cost jobs."
would love to see this economic model where capitalist driven businesses would take their windfall and automatically transfer that lower cost of doing business into more jobs. This completely ignores the demand side. For many to most products, demand is finite. Less regulation on the production side does not equate to increased demand.
Most industries, given the constraints of demand, would not turn a profits windfall into jobs - that money would flow to the bottom line. This notion that less regulation equates to a higher demand curve is a fiction of neoconservatives minds. There are many other constraints on demand. Deregulation does not, even in most cases, drive demand.
The idea that bureaucracy is crippling the economy is a popular neocon idea. ANd yet there are models that show that consumer confidence in products also drives demand - vis a vie - epa and fda reeducation. A perceived "safe" product has a much higher demand curve. Take cars as an example - the corollary is clear.
The notion the deregulated products have a higher demand curves - therefor driving jobs - is pure fiction.
- 6:08 a.m. Feb. 1, 2013
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@ DesNews: Really? You're running the same story from yesterday with a
different headline - do you not have anything else for the opinion section?
As for regulations - there is a reason we have them. Namely, some businesses cannot be trusted to do the right thing. Regulation protect both consumers and good businesses from the bad businesses.
- 6:21 a.m. Feb. 1, 2013
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Please refer to comments under "Matthew Sanders: Six things you should know
about the costs of federal regulation" as it is the identical printed
printed a day earlier.
The points made in this story are all valid but there are salient counterpoints that should also be considered as well.
- 7:25 a.m. Feb. 1, 2013
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I'm surprised that there wasn't a word in this piece about the reason
for the regulations. Might it be to ensure that the food we're eating and
the water we're drinking are clean and healthy? Could it be that the
financial services industry nearly brought this country--indeed the world--to
its knees because of complex and largely unregulated financial products like
derivatives, labeled "financial weapons of mass destruction" by Warren
Buffett back in 2003? Could it be that predatory lenders managed to convince
naive and unsophisticated home buyers to take on loans they wouldn't be
able to pay for when interest rates reset?
Sure, there is a cost to regulations. But there is an enormous cost to society when we let capitalism go unchecked.
Next time, it might be nice if the Deseret News tried to show both sides of the story.
- 7:36 a.m. Feb. 1, 2013
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I don't trust business or the people who run it to let it function without bureaucracy.
- 8:50 a.m. Feb. 1, 2013
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Let's hear from Matt about what happens (or HAS happened) when there is inadequate regulation. Our food, water, pensions, mortgages, working conditions, traveling safety, and general product quality all come into play here. It's not just jobs.
- 9:37 a.m. Feb. 1, 2013
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The notion that the government itself is a greedy, profit seeking, organization
that puts itself above the general welfare of it's citizens, is a phony
propaganda tool of those who want freedom to act in unfair and criminal ways.
The proper reason for government regulations is the protection of the little people from their internal enemies who would take their wealth without providing the proper goods and services. It is our Constitution that brought that reason to the fore.
Another reason is that given the power to control our government, business and it's greedy parents use government regulations in the competition with competing business operations. Because of the great financial power of business, this reason sometimes overshadows the proper reason.
So to avoid an all-out war with other corporations, the strategy is to remove all the regulations using the false notion that regulations are bad. The real loser from this strategy is the general welfare of people.
- 10:03 a.m. Feb. 1, 2013
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There used to be an insulation company that ran ads saying you pay for
insulation whether you have it or not. The same could be said for regulations.
You pay if you don't have them in the form of diminished health, injuries,
and other ways. A certain amount of regulation is necessary to maintain quality
of life-- even Mitt Romney acknowledged this in the second presidential debate.
While there can be regulatory overreach, it seems many conservative commentators
tend to lump all regulations together as bad, regardless of merit.
The alternative to having regulations is to handle all damages through the tort system. This might be doable for something like E. coli contamination from tainted spinach, where a specific harm (illness or death) could be traced back to a particular supplier, but it becomes vastly less tenable as the linkage between source and effect becomes more diffuse, say, a death from smog from SLC's inversions. Who are you going to sue, every car owner in the valley? If critics of regulations want to eliminate them and turn to torts, then all they are doing is shifting the costs from the executive branch to the judicial branch.
- 10:39 a.m. Feb. 1, 2013
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There are regulations, and then there are regulations. Typically, liberals tend
to frame the argument in terms of "lots of regulations" versus "no
regulations." The sensible middle ground -- just the right amount of
regulation -- gets ignored.
The problem is that there is no serious effort by government to ensure that a regulation yields more public benefit than it costs those on whom it is imposed. That asymmetry is irrational, and results in society as a whole being less well off.
We require there to be an environmental impact analysis done before certain projects are undertaken, to make sure that a project with a private benefit, doesn't impose greater costs on everyone else. This should also be done with regulations: There should be an Economic Impact Analysis requirement, to make sure that we aren't imposing $100 of costs on the regulated, in order to obtain $10 of public benefit.
- 2:30 p.m. Feb. 1, 2013
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Lagomorph, one problem is that the United States -- unlike virtually all of its
international competitors, including the supposedly "socialist"
Scandinavian countries (which are actually more free-market than *we* are, now
that they've liberalized and we've bureaucratized) -- has a horribly
unwieldy and irrational regulatory regime, layered *on top of* the world's
costliest and most plaintiff-friendly tort system. We have two redundant layers
of protection against harm, either of which alone is more cumbersome than it
needs to be.
Ironically, "regulation" can lead to a false sense of security. The financial industry, for instance, is one of the most strictly regulated industries in the universe. It *still* blew up -- because in the race between underpaid G-10s writing regulations versus the $800/hour corporate lawyers structuring transactions around them, who do you think's going to win?
And so we had idiot borrowers thinking "duh, they wouldn't loan me this money if they didn't think I could pay it back," when they should have been asking *themselves* if they could pay it back. The loan terms really weren't that obscure; any fool should have known them.
- 2:34 p.m. Feb. 1, 2013
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text:
Sept. 28 (Bloomberg) -- Lithuania said it may borrow 9.5 billion litai ($3.8 billion) a year in 2012 and 2013 to finance its budget deficit and refinance maturing debt.
Borrowing may fall to 6 billion litai in 2014, the government, based in the capital, Vilnius, said today on its website. State debt is projected to narrow to 35.4 percent of gross domestic product by 2014 from an estimated 38.1 percent this year, it said.
--Editors: Andrew Langley, Douglas Lytle
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text:
A collection of news and information related to Bars and Clubs published by this site and its partners.
Top Bars and Clubs Articles
Displaying items 121-132
Dining review: Pasadena's StillRoom Seafood
Dining review: Burbank's Prizzi's is food with a mom-and-pop heart
Small Wonders: Friendliness and a good haircutStory | Jul 8, 2011 | 12:28 PMWhat's that saying about lipstick on a pig? Or a new dress on an old… Well, you get the idea. Not exactly the phrase I'm looking for; neither makeup nor evening wear, pigs nor prostitutes are on my mind. But in hopes of adding to our lexicon,...
Craft beer is hopping
Jazz scene hits all the right notes
Note to self: tackle life boldly, and buy a guitarStory | Aug 26, 2011 | 1:03 PMSo I turned 44 last week. Not old. But certainly not young. I'm tempted to ride my kids' skateboard, confident I could still show them a thing or two. But I know if I do, I'll be that guy on "America's Funniest Home Videos&...
Money raised for domestic violence outreachStory | Aug 30, 2011 | 2:28 PMThe Armenian Relief Society of Western USA held a fundraising event at its regional headquarters in Glendale on Aug. 14 in which the organization raised more than $15,000 for domestic violence outreach objectives. It was the first such fundraising event...
Hot summer, cool musicStory | Aug 31, 2011 | 4:16 PMThe 2011 Summer Music in the Park concert series drew to a close Sunday evening with the performance of Soca & Reggae Music Upstream in La Cañada's Memorial Park. Despite the heat of the day, where temperatures hovered in the upper 90s to low 100s,...
On the Radar: More booze for Californians, music tonight and metro safetyStory | Sep 22, 2011 | 11:05 AMBooze conosuers are putting forth their best efforts to get Gov. Jerry Brown to sign bill into law that would overturn a ban on serving cocktails made with infused alcohol in the state, Laist.com reported. For almost the past 100 years it has been...
On the Radar: Protesters visit CFO's home and L.A. Beer Week comes to BurbankStory | Oct 7, 2011 | 9:14 AMSan Marino Police Department apologized to residents in a statement Thursday for not doing more to stop a protest outside Wells Fargo CFO Tim Sloan's San Marino home Wednesday night, accodring to San Marino Patch. About one hundred protesters...
On the Radar: Local honey and college getting costlier?Story | Sep 15, 2011 | 12:33 PMAmid increasing enrollment and state budget cuts, UC tuition hikes are on the table, ABC7 reported. UC undergraduate students currently pay approximately $12,000 for basic tuition. Beginning in the 2015-2016 academic year, tuition under the proposed plan...
In good spirits


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'Munchkin makes the world a better place for babies and mums.'
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+ - 100,000+ Have Signed Up For Stanford's Class on AI-> 2
Link to Original Source
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I've signed up, and I'm going to pass.
I've already got the textbook, but I'll be good and wait before reading too far ahead... I could probably have completed my A-Level Computing (IRL, btw) in 6 months (or less, trying not to be cocky!) if not for the "lowest common denominator" attitude here in the UK. It took 2 years instead, and was modular (AS Level 1st year and A2 Level 2nd year, you know the drill).
Come on Slashdot, get this on the front page, now. This is news for nerds, stuff that matters.
The solution of problems is the most characteristic and peculiar sort of voluntary thinking. -- William James


text:
Organopolysiloxane compositions curable into elastomeric state, whether in single- or two-component form, comprise an α, ω-dihydroxypolydiorganopolysiloxane oil, a crosslinking agent therefor, optionally, inorganic fillers and an adhesion promoter, and a catalytically effective amount of a pentacoordinated tin monochelate produced by reacting a tin bischelate with an organic carboxylic acid.
1. An organopolysiloxane composition of matter curable into elastomeric state, comprising (1) a curable organopolysiloxane base which is an organopolysiloxane polymer and a crosslinking agent therefor, and (2) a catalytically effective amount of the product of reaction between (a) a diorganotin bischelate of the formula: ##STR7## in which: the symbols R1 and R2, which may be identical or different, are each an optionally substituted, monovalent C1 -C18 hydrocarbon radical;
the symbols R3 and R5, which may be identical or different, are each one of the radicals R1 or R2, a hydrogen atom, C1 -C5 alkoxy radical or an Si(R1)3 silyl radical; and
the symbol R4 is a hydrogen atom, or an optionally halogenated C1 -C8 hydrocarbon radical, with the proviso that R4 and R5 may together form, with the carbon atoms from which they depend, a divalent C5 -C12 cyclic hydrocarbon radical, or an optionally substituted such cyclic radical bearing at least one chloro, nitro and/or cyano substituent, with (b) an organic acid of the formula:
in which X is a radical of the formula R6 COO wherein R6 has the same definition as R1, in a molar ratio (1)/(2) ranging from 0.01 to 100 said product of reaction being a monochelate of pentacoordinated tin of valency IV.
2. The organopolysiloxane as defined by claim 1, said molar ratio ranging from 0.5 to 3.
3. The organopolysiloxane composition as defined by claim 1 wherein said curable organopolysiloxane base comprises:
(A) 100 parts by weight of an α,ω-dihydroxypolydiorganosiloxane polymer having a viscosity of 500 to 1,000,000 mPa.s at 25� C. and which comprises recurring units of the formula (R2)SiO where the symbols R, which may be identical or different, are hydrocarbon radicals containing from 1 to 10 carbon atoms, optionally substituted by at least one halogen atom or cyano radical;
(B) 0.5 to 20 parts by weight of an organosilicon compound crosslinking agent containing more than two hydrolyzable groups bonded to silicon atoms, per molecule;
(C) 0 to 250 parts by weight of inorganic filler material; and
(D) 0 to 20 parts by weight of an adhesion promoter.
4. The organopolysiloxane composition as defined by claim 3, comprising a silane crosslinking agent B of the formula:
Ra Si(Z)4-a ( 4)
in which R is a hydrocarbon radical containing from 1 to 10 carbon atoms and Z is N-substituted amino, N-substituted amido, N,N-disubstituted aminoxy, ketiminoxy, alkoxy, alkoxyalkyleneoxy, enoxy or acyloxy, and a is 0 or 1.
5. The organopolysiloxane composition as defined by claim 1, formulated in single-component form.
6. The organopolysiloxane composition as defined by claim 1, formulated in two-component form.
1. Field of the Invention:
The present invention relates to novel curable polyorganosiloxane compositions and, more especially, to such novel polyorganosiloxane compositions containing a catalytically effective amount of a tin monochelate crosslinking catalyst produced by reacting a tin bischelate with an organic carboxylic acid.
2. Description of the Prior Art:
Many tin compounds have heretofore been proposed to this art as a catalyst for crosslinking polyorganosiloxane compositions and, in particular, RTV compositions (room temperature vulcanizable compositions), whether in a single pack of in two packs, otherwise known as single- or two-component compositions.
The most widely used compounds are tin carboxylates such as tributyltin monooleate, tin 2-ethylhexanoate or dialkyltin dicarboxylates such as dibutyltin dilaurate and dibutyltin diacetate (see Noll, Chemistry and Technology of Silicones, page 337, Academic Press, 1968--2nd edition).
In U.S. Pat. No. 3,186,963, such a tin catalyst is described which is the reaction product of a dialkyldialkoxysilane with a tin carboxylate.
In Belgian Patent No. 842,305, the catalyst is the reaction product of an alkyl silicate or of an alkyltrialkoxysilane with dibutyltin diacetate.
And in U.S. Pat. No. 3,708,467, a catalyst system is described which is a mixture of certain tin salts with a specific titanium chelate, in a single-component composition.
Lastly, in U.S. Pat. Nos. 4,517,337 and 4,554,310 the use of diorganotin bis(β-diketone) is described for the crosslinking of neutral single-component compositions (U.S. Pat. Nos. 4,517,337 and 4,554,310) or for single- and two-component compositions (EP-A-147,323).
Although EP-A-147,323 represents a significant advance in the quest for a tin catalyst useful for both single- and two-component compositions, it has become apparent that diorganotin bis(β-diketonates) exhibit a core setting time which is a little too slow, particularly in the case of the two-component compositions.
The problem which typically arises in the case of the single-component compositions is essentially that of storage stability and of the retention of physicochemical properties (extrudability, pourability, setting time) of the composition and maintaining these properties by the reticulate (mechanical properties, hardness, elongation, tear strength, adhesiveness, and the like).
Thus, need exists in this art for a catalyst which crosslinks very rapidly on exposure to atmospheric moisture, not only on the surface thereof, but which at the same time provides a thorough crosslinking uniformly therethrough which is as complete as possible, and which is also active in minor amounts, while reducing to the minimum the reticulate degradation reactions which are inherent in the presence of tin.
With regard to the three-dimensional shaped article or reticulate thus obtained, the same problems as exist in the case of the single-component compositions also exist in the case of the two-component compositions, but, in addition, the exposure or open time (that is to say, the time during which the composition may be employed after mixing without hardening) must be sufficiently long to permit its effective use, but sufficiently short to produce a molded object capable of being handled not later than 24 hours after the production thereof.
This catalyst must therefore provide a good compromise between the open time of the catalyzed mixture and the time after which the molded object can be handled. In addition, the catalyst must impart to the catalyzed mixture a spreading time which does not vary as a function of the storage period.
Accordingly, a major object of the present invention is the provision of an improved catalyst system adapted for the crosslinking of both the single- and two-component elastomer compositions.
Another object of the present invention is the provision of an improved catalyst system which simultaneously meets the storage, use and crosslinking constraints common to both types of elastomer compositions, while addressing the specific problems presented by each, without, however, initiating detrimental secondary effects in either case.
Briefly, the present invention features improved organopolysiloxane compositions comprising, on the one hand, a silicone base polymer capable of being cured into an elastomer by a polycondensation reaction beginning at ambient temperature and, on the other hand, a catalytically effective amount of the product of reaction between (a) a diorganotin bischelate of the formula: ##STR1## in which: the symbols R1 and R2, which may be identical or different, are each an optionally substituted, monovalent C1 -C18 hydrocarbon radical;
the symbols R3 and R5, which may be identical or different, are each one of the radicals R1 or R2, a hydrogen atom, a C1 -C5 alkoxy radical or an Si(R1)3 silyl radical;
the symbol R4 is a hydrogen atom, or an optionally halogenated C1 -C8 hydrocarbon radical, with the proviso that R4 and R5 may together form, with the carbon atoms from which they depend, a divalent C5 -C12 cyclic hydrocarbon radical, or an optionally substituted such cyclic radical bearing at least one chloro, nitro and/or cyano substituent, with (b) an organic acid of the formula:
in which X is a radical of the formula R6 COO wherein R6 has the same definition as R1.
More particularly according to the present invention, the diorganotin bischelates of the formula (1) are known to this art and are described in the chemical literature.
Various methods for the preparation thereof are described, in particular, in U.S. Pat. Nos. 3,055,845 and 4,517,337 and in European Patent Application EP-A-147,323, in the publication, Metal β-diketonates and Allied Derivatives, by R. C. Mehrotra, R. Bohra and D. P. Gaur, published in 1978 by Academic Press, and in the publication, The Chemistry of Organotin Compounds, by R. C. Poller, published in 1970, also by Academic Press.
Exemplary such derivatives are those of the formulae: ##STR2##
Exemplary of the carboxylic acids of formula (2), representative are:
(i) saturated carboxylic acids such as formic, acetic, propionic, butyric, isobutyric, valeric, isovaleric, pivalic, lauric, 2-ethylhexanoic, myristic, palmitic and stearic acids and versatic� acids which are mixtures of saturated tertiary monocarboxylic acids containing, overall, the same number of carbon atoms, which generally ranges from 8 to 12;
(ii) unsaturated carboxylic acids such as acrylic, propiolic (CH.tbd.C-COOH), methacrylic, crotonic, isocrotonic, oleic and maleic acids;
(iii) aromatic carboxylic acids such as benzoic, phthalic, isophthalic and terephthalic acids;
(iv) organic dicarboxylic acids.
The reaction of the bischelate of formula (1), which may be designated by the simplified formula R1 R2 SnC2 (CH being the simplified formula of the organic chelating ligand), with the acid XH of formula (2), may be carried out in bulk, beginning at ambient temperature, by merely incorporating (mixing) one of the compounds in the other. The mixture is stirred for at least a few minutes in order to homogenize the liquid mass. Slight heating (for example up to 80� C.) may be applied to accelerate the reaction. The above process is used when both starting materials are liquid.
In the case of two starting materials, one of which is solid and the other liquid, it may be necessary to heat slightly to about 40�-80� C. to dissolve the solid material.
In the case of two solid materials, the mixture must be heated at least to the melting temperature of one of the two starting materials.
The reaction may also be carried out in an inert organic solvent.
The starting materials are preferably employed in a molar ratio (1)/(2) equal or close to 1, preferably ranging from 0.5 to 3. Molar ratios ranging from 0.01 to 100 can, nevertheless, also be employed.
It has been demonstrated that the reaction described above results in the formation of a monochelate of pentacoordinated tin of valency IV, referred to hereinafter as the tin monochelate, having the formula: ##STR3## or, more simply, having the abbreviated formula R1 R2 SnCX, in which the symbols X, R1, R2, R3, R4 and R5 are as defined above.
The monochelates of the above formula (3) may be identified by the analytical techniques of NMR spectroscopy (119 Sn, 13 C and 1 H nuclear magnetic resonance), by mass spectroscopy, and by measurement of the Mossbauer effect.
It has been found, however, that in the present state of the art of analytical techniques, the 119 Sn NMR analytical method such as described, in particular, in the article by Peter J. Smith, Chemical Shifts of 119 Sn Nuclei in Organotin Compounds, page 291 et seq, published in the Annual Reports on NMR Spectroscopy, volume 8, 1978, Academic Press, is a method which is by itself sufficiently accurate to characterize the various tin compounds present within a mixture, particularly within a reaction mixture, and to make it possible to determine the chemical formulae of most of these compounds.
The fundamental parameter evaluated by 119 Sn NMR is the value of the chemical shift, expressed in parts per million (ppm) relative to a reference (generally tetramethyltin).
The value of the chemical shift is particularly sensitive to the electronegativity of the groups carried by the tin and to the change in the coordination number of the tin atom. Specific studies of characterization of organostannic derivatives using 119 Sn NMR are described in particular by A. G. Davies and P. J. Smith, Comprehensive Organo-metallic Chemistry, 11 Tin, pages 523 to 529 and by J. Otera, J. of Organomet. Chem., 221, pages 57-61 (1981).
Analysis of the reaction mixtures obtained according to the process of the present invention has made it possible to demonstrate the production of the monochelate product R1 R2 SnCX of formula (3) within a reaction mixture free from the tin oxide of the formula R1 R2 SnO, of the bischelate R1 R2 SnC2 of the formula (1) and, in most cases, of the distannoxane XR1 R2 SnOSnR1 R2 X.
The tin compound other than the product of formula (3) present in the equilibrium reaction mixture is principally the diorganotin dicarboxylate of the formula R1 R2 SnX2 and, sometimes, the distannoxane of formula R1 R2 SnOSnR1 R2 X.
When a molar ratio of starting materials (1)/(2) which is higher than approximately 1.5 is employed, the concentrations of the constituents of the reaction mixture in molar %, calculated in gram-atoms of tin metal are, in principle,
______________________________________ R1 R2 SnCX 15 to 90 R1 R2 SnX2 85 to 5 XR1 R2 SnOSnR1 R2 X 0 to 5.______________________________________
When a molar ratio of starting materials (1)/(2) equal to or lower than approximately 1 is employed, then significant quantities (up to approximately 60 mol %) of R1 R2 SnX2 appear, at the expense of R1 R2 SnCX and R1 R2 SnC2.
In the above formulae, the symbols R1 and R2, which may be identical or different, denote optionally substituted monovalent C1 -C18 hydrocarbon radicals.
More especially, these organic radicals include:
(i) C1 -C18 alkyl radicals, halogenated or otherwise, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, decyl, dodecyl, octadecyl, chloromethyl and 2,5-dichloroethyl radicals;
(ii) C2 -C18 alkenyl radicals, halogenated or otherwise, such as vinyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 3-octenyl, 5-fluoro-2-pentenyl and pentadecenyl radicals;
(iii) C4 -C10 cycloalkyl radicals, halogenated or otherwise, such as cyclopentyl, cyclohexyl, methylcyclohexyl, cyclooctyl, 3,4-dichlorocyclohexyl and 2,6-dibromocycloheptyl radicals;
(iv) C6 -C15 mononuclear aryl radicals, halogenated or otherwise, such as phenyl, tolyl, xylyl, cumenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl and trifluoromethylphenyl radicals;
(v) C7 -C15 mononuclear arylalkyl radicals, halogenated or otherwise, such as phenylmethyl, phenylethyl, phenylpropyl and trifluoromethylphenylethyl radicals.
The symbols R3 and R5, which may be identical or different, have the same definitions as R1 and R2, namely, optionally substituted, monovalent C1 -C18 hydrocarbon radicals, and may additionally denote hydrogen atoms, cyanoalkyl radicals containing a C2 -C4 alkyl moiety, C1 -C5 alkoxy radicals or --Si(R13 silyl) radicals.
Cyanoethyl, cyanopropyl and cyanobutyl radicals are exemplary of the cyanoalkyl radicals, and ethoxy and propoxy radicals are exemplary of the alkoxy radicals.
The symbols R4 denotes the hydrogen atom, or an optionally halogenated C1 -C8 hydrocarbon radical.
More especially, this radical includes alkyl radicals, halogenated or otherwise, such as methyl, ethyl, propyl, butyl, hexyl and octyl radicals and mononuclear aryl radicals, halogenated or otherwise, such as phenyl, tolyl, chlorophenyl and dichlorophenyl radicals.
In addition, on coupling with R5, R4 forms with R5 a divalent cyclic C5 -C12 hydrocarbon radical, substituted or otherwise by chloro, nitro or cyano groups.
Representative such ring members are those of the formulae: ##STR4##
The symbol X is a halogen (chlorine, bromine, iodine, fluorine) atom or a monocarboxylate radical of the formula R6 COO in which the symbol R6 has the same definition as the symbol R1 above, and preferably denotes a linear or branched chain C1 -C18 alkyl radical.
Unless otherwise indicated, all percentages and parts given herein are by weight.
The monochelate of formula (3) or the equilibrium reaction mixture, referred to hereinafter as the tin catalyst according to the invention, is stable in storage in a closed container, at ambient temperature.
It is used to permit or facilitate the curing of the organopolysiloxane base to a silicone elastomer, beginning at ambient temperature.
These bases, which cure (crosslink) by polycondensation reactions, are well known to this art. After having been catalyzed, in most cases by means of a metallic derivative of a carboxylic acid, they are utilized for the manufacture of seals, of water-repellent coatings, of molds, of coating materials, for the adhesive bonding and the assembly of the widest variety of materials, for coating organic and inorganic fibers, and the like.
These bases are described in detail, in particular, in many patents and they are available commercially.
These silicone bases may be single-component, that is to say, packaged in a single pack that is stable in storage in the absence of moisture and capable of being cured in the presence of moisture, in particular of moisture contributed by the surrounding air or by the water generated within the base when it is used.
These single-component bases are generally of three types, as described in further detail below, and are catalyzed by the incorporation of a catalytically effective amount of the monochelate of formula (3) or of the equilibrium reaction mixture. This catalytically effective amount is on the order of 0.0001 to 5 parts, preferably from 0.01 to 3 parts per 100 parts of the single-component base.
Other than the single-component bases, it is also possible to employ two-component bases, that is to say, those packaged in two packs, which cure as soon as the tin catalyst is incorporated. They are packaged in two separate fractions, it being possible for one of the fractions, for example, to contain only the tin catalyst or the mixture of the catalyst with the crosslinking agent.
The catalytically effective amount of tin catalyst is on the order of 0.01 to 10 parts, preferably from 0.1 to 5 parts per 100 parts of the two-component base.
As already indicated above, single-component and two-component silicone bases which cure (crosslink) via polycondensation reactions are described in detail in the literature and are available commercially.
These bases are generally prepared from the following constituents:
(A) 100 parts of an α, ω-dihydroxypolydiorganosiloxane polymer, having a viscosity of 500 to 1,000,000 mPa.s at 25� C., comprising recurring units of the formula (R2)SiO where the symbols R, which may be identical or different, are hydrocarbon radicals containing from 1 to 10 carbon atoms, optionally substituted by halogen atoms or cyano groups;
(B) 0.5 to 20 parts of a crosslinking agent selected from among organosilicon compounds containing more than two hydrolyzable groups bonded to silicon atoms, per molecule;
(C) 0 to 250 parts of inorganic fillers; and
(D) 0 to 20 parts of an adhesion promoter.
The radical R is typically methyl, ethyl, propyl, phenyl, vinyl or a 3,3,3-trifluoropropyl radical, at least 80% of the groups R being methyl.
A first type of single-component formula results from mixing the polymer A with a crosslinking agent B, which is advantageously a silane of the formula:
Ra Si(Z)4-a (4)
in which R is as defined above for the polymer A, and Z is a hydrolyzable group advantageously selected from among N-substituted amino, N-substituted amido, N,N-disubstituted aminoxy, ketiminoxy, aldiminoxy, alkoxy, alkoxyalkyleneoxy, enoxy and acyloxy groups, and a denotes 0 or 1.
Single-component bases of this type are described in detail, particularly in European Patent Applications EP-A-141,685 and EP-A-147,323, hereby incorporated by reference.
The most widely used compositions are those in which Z is an acyloxy and ketiminoxy group, which are described in greater detail in European Patent Application EP-A-102,268, also hereby incorporated by reference.
Two-component flowing compositions, in which Z is an acyloxy group, and whose crosslinking is accelerated by the addition of an alkaline earth metal hydroxide or phosphate are described in European Patent Applications EP-A-118,325 and EP-A-117,772, also hereby incorporated by reference.
In a second type of single-component base, the starting point is not a mixture of A and B but the product A1 of reaction of A with B. In general, the hydrolyzable group is an alkoxy group and the composition additionally contains from 0 to 15 parts of crosslinking agent B per 100 parts of functionalized polymer A1.
The reaction of A with B can be carried out in the presence of various catalysts such as an organic amine (U.S. Pat. No. 3,542,901), an organic titanium derivative (U.S. Pat. No. 4,111,890), a carbamate (European Patent Application EP-A-210,402) and an N,N-disubstituted hydroxylamine (European Patent Application EP-A-70,786).
To these single-component bases there may be added adhesion promoters D, selected from among organosilicon compounds simultaneously bearing, on the one hand, organic groups substituted by radicals selected from among amino, ureido, isocyanate, epoxy, alkenyl, isocyanurate, hydantoyl, guanidino and mercaptoester radicals and, on the other hand, hydrolyzable groups, generally alkoxy groups, bonded to the silicon atoms. Examples of such adhesion promoters are described in U.S. Pat. Nos. 3,517,001, 4,115,356, 4,180,642, 4,273,698 and 4,356,116 and in European Patent Applications EP-A-31,996 and EP-A-74-001.
A third type of single-component bases are those prepared by mixing 100 parts of polymer A, from 0.5 to 20 parts of crosslinking agent B which is a polyalkoxysilane (formula 4), Z=alkoxy or alkoxyalkyleneoxy, from 0 to 250 parts of inorganic fillers and from 0.5 to 15 parts of a compound D1 selected from among:
(i) D1-a : a primary organic amine having a pKb of less than 5 in aqueous medium, an aminoorganosilane and an aminoorganopolysiloxane bearing at least one C1 -C15 organic group linked by a Si--C bond to the silicon atom per molecule, and substituted by at least one amino radical at least one C1 -C5 alkoxy or C3 -C6 alkoxyalkyleneoxy radical; and
(ii) D1-b : an organic titanium or zirconium derivative bearing an organoxy and/or β-diketonato group.
Single-component bases comprising D1-a are described in European Patent Application EP-A-21,859, and those comprising D1-b are described in French Patents Nos. FR-A-2,121,289 and FR-A-2,121,631, also hereby incorporated by reference.
The two-component bases are formed by mixing:
(a) 100 parts of polymer (A);
(b) 1 to 20 parts of a crosslinking agent selected from among a silane of formula (4) above, and the products of partial hydrolysis of the silane of formula (4);
(c) 0 to 150 parts of inorganic fillers; and
(d) 0 to 20 parts of an adhesion promoter.
These compositions are well known to this art; in particular, they are described in European Patent Applications EP-A-10,478, EP-A-50,358 and EP-A-184,966 and in U.S. Pat. Nos. 3,801,572 and 3,888,815.
The adhesion promoter employed may be the silanes D employed in the case of the single-component bases and silanes bearing a morpholino group (EP-A-184,966) or an organic radical comprising a tertiary nitrogen atom (U.S. Pat. Nos. 3,801,572 and 3,888,815).
The products of partial hydrolysis of the alkoxysilanes of formula (4), which are usually referred to as alkyl polysilicates, are well-known products which exhibit the property of dissolving in the usual hydrocarbon solvents such as toluene, xylene, cyclohexane and methylcyclohexane; the most widely used material is ethyl polysilicate 40� with a silica content of 40%, a value obtained after total hydrolysis of the ethoxy radicals.
The inorganic fillers (c) employed in the case of the single- and two-component bases are very finely divided materials whose mean particle diameter is below 0.1 micrometer. These fillers include pyrogenic silicas and precipitated silicas; their BET specific surface area is generally greater than 40 m2 /g.
These fillers may also be in the form of more coarsely divided materials, with a mean particle diameter greater than 0.1 micrometer. Examples of such fillers which are representative are ground quartz, diatomaceous silicas, calcium carbonate, calcined clay, rutile-type titanium dioxide, iron, zinc, chromium, zirconium and magnesium oxides, the various forms of alumina (hydrated or otherwise), boron nitride, lithopone, barium metaborate, barium sulfate and ballotini; their specific surface area is generally below 30 m2 /g.
These fillers may have been surface-modified by treatment with the various organosilicon compounds usually employed for this purpose. Thus, these organosilicon compounds may be organochlorosilanes, diorganocyclopolysiloxanes, hexaorganodisiloxanes, hexaorganodisilazanes or diorganocyclopolysilazanes (French Patents Nos. FR-A-1,126,884, FR-A-1,136,885 and FR-A-1,236,505, British Patent No. GB-A-1,024,234). In most cases, the treated fillers contain from 3 to 30% of their weight of organosilicon compounds.
The fillers may be a mixture of a number of types of fillers of different particle size distribution; thus, for example, they may comprise 30 to 70% of finely divided silicas with a BET specific surface area greater than 40 m2 /g and of 70 to 30% of more coarsely divided silicas with a specific surface area below 30 m2 /g.
The tin catalyst according to the invention is more particularly effective in the case of the single- and two-component silicone bases where the crosslinking agent (B) of formula (4) contains radicals Z which are identical or different, selected from among alkoxy and alkoxyalkyleneoxy radicals of formulae R7 O and R7 OTO in which R7 is a C1 -C4 alkyl radical and T denotes a C2 -C4 alkylene group.
In addition, in the case where the silicone base has two components, it is possible to use the product of partial hydrolysis of the crosslinking agent (B).
These ingredients include organosilicon compounds, chiefly polymers, which are capable of affecting the physical characteristics of the compositions according to the invention (formed by mixing the bases with the tin catalyst) and/or the mechanical properties of the silicone elastomers obtained using these compositions.
These compounds are well known; for example, they include:
(i) α, ω-bis(triorganosiloxy)diorganopolysiloxane polymers having a viscosity of at least 10 mPa.s at 25� C. in which the organic radicals bonded to the silicon atoms are methyl, vinyl and phenyl radicals, preferably at least 80% of the radicals are methyl radicals and not more than 3% are vinyl radicals; α,ω-bis(trimethylsiloxy)dimethylpolysiloxane oils having a viscosity of 10 mPa.s at 25� C., to 1,500 mPa.s at 25� C. are preferably employed;
(ii) liquid, branched methylpolysiloxane polymers containing from 0.1 to 8% of hydroxyl groups bonded to the silicon atoms, comprising (CH3)3 SiO0.5, (CH3)2 SiO and CH3 SiO1.5 recurring units distributed such as to provide a (CH3)3 SiO0.5 /(CH3)2 SiO ratio of 0.01 to 0.15 and a CH3 SiO1.5 /(CH3)2 SiO ratio of 0.1 to 1.5;
(iii) α,ω-di(hydroxy)dimethylpolysiloxane oils having a viscosity of 10 to 300 mPa.s at 25� C. and α,ω-di(hydroxy)methylphenylpolysiloxane oils having a viscosity of 200 to 5,000 mPa.s at 25� C.; and
(iv) diphenylsilanediol and 1,1,3,3,-tetramethyldisiloxanediol.
The above α,ω-bis(triorganosiloxy)diorganopolysiloxane polymers may be completely or partly replaced by organic compounds which are inert towards the various constituents of the bases and which are miscible at least with the diorganopolysiloxane polymers (A) or (A1). Specific examples of such organic compounds are mineral oils, petroleum cuts and polyalkylbenzenes obtained by the alkylation of benzene with long-chain olefins, particularly olefins containing 12 carbon atoms obtained by propylene polymerization. Organic compounds of this type appear, for example, in French Patents Nos. FR-A-2,392,476 and FR-A-2,446,849.
Each of the above organosilicon compounds may be employed in a proportion of 1 to 150 parts, preferably 3 to 75 parts, per 100 parts of diorganopolysiloxanes (A) or (A1).
Non-organosilicon ingredients may also be introduced, for example heat stabilizers. These compounds improve the heat resistance of the silicone elastomers. They may be carboxylic acid salts, rare-earth oxides and hydroxides, as well as from combustion titanium dioxide and various iron oxides. From 0.1 to 15 parts, preferably from 0.15 to 12 parts, of heat stabilizers are advantageously employed per 100 parts of the diorganopolysiloxanes (A) or (A1).
In the case of the single-component compositions, to produce the compositions according to the invention it is necessary to employ apparatus which enables the various fundamental constituents, to which the above-mentioned adjuvants and additives are added if desired, to be intimately mixed in the absence of moisture, with and without application of heat.
All these ingredients may be charged into the apparatus in any order of addition. Thus, the diorganopolysiloxane polymers (A) or (A1) and the fillers (C) can first be mixed, and the crosslinkers (B), the compounds (D) and the tin monochelate can then be added to resulting paste.
It is also possible to mix the polymers (A) or (A1), the crosslinkers (B) and the compounds (D) and subsequently to add the fillers (C) and the tin monochelate. The mixtures may be heated during these operations to a temperature in the range 50�-180� C. at atmospheric pressure or at a reduced pressure in order to promote the elimination of volatile materials such as water and polymers of low molecular weight.
The compositions prepared in this manner may be employed as such or in the form of a dispersion in organic diluents. These diluents are preferably conventional commercial products selected from among:
(i) aliphatic, cycloaliphatic or aromatic hydrocarbons, halogenated or otherwise, such as n-heptane, n-octane, cyclohexane, methylcyclohexane, toluene, xylene, mesitylene, cumene, tetralin, decalin, perchloroethylene, trichloroethane, tetrachloroethane, chlorobenzene and orthodichlorobenzene;
(ii) aliphatic and cycloaliphatic ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone; and
(iii) esters such as ethyl acetate, butyl acetate and ethylglycol acetate.
The quantities of diluents introduced must be sufficient to produce stable dispersions which spread easily on the substrates. These quantities depend essentially on the nature and on the viscosity of the initial organopolysiloxane compositions. They may consequently vary within wide proportions; nevertheless, formulation of dispersions containing from 15 to 85% by weight of diluents is recommended.
The single-component compositions according to the invention, which are used as such, that is to say, undiluted, or in the form of dispersions in diluents, are stable in storage in the absence of water and cure beginning at ambient temperature (after removal of the solvents in the case of dispersions) to form elastomers, in the presence of water.
After the compositions as such have been deposited onto solid substrates, in a moist atmosphere, it is found that a process of curing to elastomers takes place, proceeding from the outside towards the inside of the deposited mass. A surface skin forms first and then the crosslinking continues into the depth of the mass.
The complete formation of the skin, which manifests itself as a non-sticky surface feel, requires a period of time which can be in the range from 1 minute to 55 minutes; this time period depends on the relative humidity of the atmosphere surrounding the compositions and on the ease of crosslinking of the latter.
Furthermore, the cure throughout the deposited layers, which would be sufficient to allow the elastomers formed to be demolded and handled, requires a longer period of time. This period depends, in fact, not only on the factors mentioned above in the case of the formation of a non-sticky feel, but also on the thickness of the deposited layers, which thickness generally ranges from 0.5 mm to several centimeters. This longer period of time may range from 10 minutes to 20 hours.
The single-component compositions may be employed for many applications, such as sealing in the building industry, the assembly of a very wide variety of materials (metal, plastics, natural and synthetic rubbers, wood, cardboard, earthenware, brick, ceramic, glass, stone, concrete, masonry components), the insulation of electrical conductors, coating of electronic circuits, and the production of molds used for the manufacture of shaped articles made of synthetic resins or foams.
The above-mentioned dispersions of these compositions in the diluents can be employed for thin-layer impregnation of inorganic, synthetic, organic, metallic, woven or non-woven products and articles, and coating of metal, plastic or cellulosic sheets. The deposition can be produced, for example, by dipping or by spraying; in the latter case, a spray gun is used which permits uniform coatings with a thickness of 5 to 300 μm to be obtained. After the dispersions have been sprayed, the diluents evaporate off and the compositions released cure to a rubbery film.
The production of two-component compositions according to the invention is also carried out by mixing the various constituents in suitable apparatus. To obtain homogeneous compositions it is preferable to mix the polymers (A) with the fillers (C) first; the combination may be heated for at least 30 minutes to a temperature above 80� C. such as to complete the wetting of the fillers by the oils. The other constituents, namely, the crosslinking agents (B), the organic tin derivative and, if desired, various additives and adjuvants, and even water, can be added to the mixture obtained, which is preferably heated to a temperature below 80� C., for example on the order of ambient temperature.
Such compositions are not stable in storage and must therefore be used quickly, for example within a time interval of 40 minutes.
The various additives and adjuvants are the same as those introduced into the single-component compositions. In particular, the α,ω-bis(triorganosiloxy)diorganopolysiloxane polymers having a viscosity of at least 10 mPa.s at 25� C., in which the organic radicals bonded to the silicon atoms are methyl, vinyl and phenyl radicals, are representative. α,ω-(Trimethylsiloxy)dimethylpolysiloxane oils having a viscosity of preferably 20 mPa.s at 25� C. to 1,000 mPa.s at 25� C., are generally employed in a proportion not exceeding 150 parts per 100 parts of polymer (A).
The introduction of water in a proportion not exceeding 1 part per 100 parts of polymers (A) is recommended to promote the curing of the two-component compositions which are employed in thick layers whose thickness is, for example, greater than 2 cm.
This water addition is unnecessary if the fillers (C) contain enough of it. To facilitate its incorporation, water is preferably added in the form of a dispersion in a paste comprising, for example, the above-mentioned α,ω-bis(triorganosiloxy)diorganopolysiloxane oils and the fillers (C).
For packaging and storage, the two-component compositions cannot, therefore, contain all the fundamental constituents, namely, the polymers (A), the crosslinker (B), the fillers (C) and the tin catalyst (E). On an industrial scale, they must be formulated in the form of two components, each being stable in storage.
A first, storage-stable, component may, for example, comprise the constituents (A), (B) and (C); it is preferably prepared by introducing the crosslinking agents (B) into the homogeneous mixture produced by compounding the polymers (A) with the fillers (C).
The second component then comprises the tin catalyst.
Other ways of presenting the two-component compositions may be selected; for example, a first component containing the polymers (A) and the fillers (C) and a second component containing the crosslinking agents (B) and the tin catalyst.
In many applications it is preferable that each of the two components be sufficiently fluid such as to easily form compositions whose viscosity ranges, for example, from 10,000 to 800,000 mPa.s at 25� C.
These compositions, which remain sufficiently fluid for at least 40 minutes, preferably for at least 80 minutes, after the mixing of the two components, can be employed more especially for the manufacture of silicone elastomer molds. They may, however, be employed for other applications such as coating electronic equipment and coating metallic surfaces or textile or cellulosic substances.
The molds which are manufactured are intended to reproduce articles made of cellular or non-cellular materials formed from organic polymers. Among such materials, exemplary are polyurethanes, polyesters, polyamides and polyvinyl chloride. The use of these molds for the reproduction of polyurethane articles is, however, recommended, since they withstand quite well attack by constituents of the mixtures used to produce polyurethanes (in particular polyisocyanates).
The introduction of the tin catalyst according to the invention, at least partly comprising the tin monochelate, makes it possible to attain the best conditions of use in the case of the single- and two-component compositions. It makes it possible to subsequently produce elastomers having stable properties upon use thereof and which are independent of the age and of the storage conditions of the compositions.
In order to further illustrate the present invention and the advantages thereof, the following specific examples are given, it being understood that same are intended only as illustrative and in nowise limitative.
1 mole of a di-n-octyltin bischelate in which the chelating ligand was 1-benzoyl-4-methyl-2-pentanone, and one mole of 2-ethylhexanoic acid, were introduced under a nitrogen atmosphere into a 1-liter three-necked round-bottomed flask fitted with a central stirrer, a condenser and a thermometer. Stirring was continued for one hour at 50� C.
The reaction mixture obtained was analyzed in the absence of atmospheric moisture using 119 Sn NMR.
The results obtained are reported in Table I below, where t denotes the reaction temperature.
The operating procedure of Example 1 was repeated, except that the reactants and/or the quantities introduced, and the reaction temperature, were changed.
The results obtained are reported in Table I below.
The reaction may be expressed schematically as follows: ##STR5## with a and b representing the molar quantities which were introduced, of R1 R2 SnC2 and of XH.
XH1 is 2-ethylhexanoic acid
XH2 is lauric acid
The columns PR1, PR2, PR3 and PR4 report the mol % calculated in gram-atoms of tin metal for the products present in the reaction mixture:
PR1: R1 R2 Sn CX
PR2: R1 R2 Sn X2
PR3: R1 R2 Sn C2
PR4: X R1 R2 SnO Sn R1 R2 X
TABLE I______________________________________Ex-ample R1 and R2 a XH b t PR1 PR2 PR3 PR4______________________________________1 n-octyl 1 XH1 1 50 45.6 22.8 22.8 7.02 n-octyl 1 XH1 2 50 31.4 68.6 0 03 n-octyl 1 XH1 3 50 17.6 82.4 0 04 n-octyl 1 XH2 1 80 55.4 15.7 19.3 4.8______________________________________
A composition P1 was prepared by mixing:
(i) 100 parts of an α,ω-dihydroxydimethylpolysiloxane oil having a viscosity of 10,000 mPa.s at 25� C.;
(ii) 70 parts of an α,ω-bis(trimethylsiloxy)dimethylpolysiloxane oil having a viscosity of 800 mPa.s at 25� C.;
(iii) 55 parts of a pyrogenic silica having a specific surface area of 300 m2 /g, treated with hexamethyldisilazane;
(iv) 50 parts of ground quartz having a mean particle diameter of 5 micrometers; and
(v) 10 parts of a paste made up of 90 parts of the above-mentioned α,ω-dihydroxydimethylpolysiloxane oil, having a viscosity of 10,000 mPa.s at 25� C., 5 parts of a pyrogenic silica having a specific surface area of 150 m2 /g and 5 parts of water.
The composition P1 was catalyzed with a cross-linking system containing the catalysts (C) forming the subject of Examples 1 to 3, and partially hydrolyzed ethyl silicate.
The composition P1 was catalyzed by mixing 100 parts of this composition with two parts of the crosslinking system containing 17.5 by weight and 82.5% by weight of partially hydrolyzed ethyl silicate. This crosslinking system catalyst (C) was employed as such, freshly prepared (Δt=0) or after having been subjected to aging at 70� C. for a period Δt of 72, 148 and 336 hours.
The spreading time (st) of the catalyzed composition was then determined by noting the time for which this composition remained in a sufficiently fluid state to spread under its own weight and thus to adopt the configuration of the internal volume of the receptacles into which it was poured.
The test employed for assessing the spreadability was as follows:
The freshly catalyzed composition (15 grams) was poured into an aluminum capsule of cylindrical shape with a diameter of 4 cm; after a time not exceeding 5 minutes its surface must be perfectly horizontal.
The catalyzed composition was converted into a silicone elastomer after several hours at ambient temperature; 24 hours after the preparation of this catalyzed composition, the Shore A hardness of the elastomer formed was measured. The results relating to the spreading time (st) in minutes and the Shore A hardness values (SAH) are reported in Table II below.
The catalyst in the comparative example was the bischelate of formula R2 Sn(C)2 with R=n-octyl and C denotes: ##STR6## whose CH precursor was 1-benzoyl-4-methyl-2-pentanone.
The results are reported in Table II below, where C example n (c ex n) shows that the tin catalyst employed was that obtained in Example n.
It was found that the catalysts according to the invention, in contrast to the control catalyst, endow the silicone elastomer with satisfactory hardness and spreading time values even after prolonged aging of the crosslinking system.
TABLE II______________________________________EXAMPLE 5 6 7 8CATALYSTCONTROL C ex 1 C ex 2 C ex 3st SAH st SAH st SAH st SAH______________________________________ 0 140 5 100 12 95 8 70 6Δt 72 145 3 110 15 125 10 120 7 168 180 1 140 10 150 4 135 0 336 450 1 277 11 280 8 280 4______________________________________
While the invention has been described in terms of various preferred embodiments, the skilled artisan will appreciate that various modifications, substitutions, omissions, and changes may be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention be limited solely by the scope of the following claims, including equivalents thereof.
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You won't need these - the EC is hoping to offer wireless broadband to all European citizens.
Originally Posted by Jamie
Where does the upstream come from?
Originally Posted by Jamie
Where does the upstream come from?
It wouldn't be open - the EC is planning to offer access to the wireless broadband system, in the same way as you have access to a GPRS wireless system - you still need to pay for a contract (or PAYG SIM, pedants) and hardware in order to actually use it and can thus be tracked.Originally Posted by Sleepstreamer
And how would their antipiracy-suing-scheme work if everyone use a single open network? I must be missing something...
This is part of the reason why it needs to go through the EC - licensing. Your 802.11 cards are tightly restricted to two 'ISL' bands that are unlicensed, and in sort-of the same fashion, mobile handsets are limited to specific frequency bands by license. So yes, the upstream frequency would certainly require its own radio in your CPE but it would of course be tightly locked to the frequencies allowed by the license given to your service provider.Originally Posted by BlademrkQuote:Originally Posted by Jamie
Where does the upstream come from?
Was wondering that myself, would everyone need to have their own RF transmitter?
Originally Posted by Timmy_the_tortoise
When it comes to internet connection.. I just think that wireless is too unreliable.
I'd much rather they improved the hard-wired infrastructure to improve ADSL speeds.
Originally Posted by CardJoe
The European Commission has unveiled plans to use the freed up analogue TV spectrum to offer high-speed wireless broadband to all citizens.
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