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As a Senior Solution Architect for the VMware TAM Program, I'm always looking for new ways to deliver best-in-industry services to you, our customer. So, I'm thrilled to let you know about a new process we've put in place to help us keep doing just that.
VMware Customer Intelligence.Next (CI.Next) enables and builds a new level of partnership between VMware, VMware TAMs, and our valued customers. We just started it this quarter, so if you're a VMware TAM customer and haven't heard about it from your TAM yet, you likely will hear it very soon.
In the meantime, here's what you need to know:
TAM Data Manager 2.0
First, we've completely reworked our TAM Data Manager (TDM) tool. It is now redesigned and re-released as TDM 2.0. Accessed either as an appliance or a Java application, TDM 2.0 works within your environment and collects telemetry information (configuration details) for vSphere core and Horizon View environments.
Crucially, TDM 2.0 also gathers and reports out information about the business drivers and strategic intent behind these telemetries and configurations—a combination that makes TDM 2.0 distinct from any other tool.
We take both sets of information, synthesize them, and generate reports that help you link specific builds, configurations, deployment locations, hardware profiles, and more to your business goals. This means you will understand your environment better and work within your environment to ensure consistency, which in turn helps mitigate risk. And as you receive more of these reports over time, you can observe how the business and technical environments develop relative to each other.
CI.Next: A richer, more strategically sophisticated TAM Service
But that's just the start. On our end, we also take that data and compare it with what we're seeing across the TAM program in similar industries or geographies. We then report it back, anonymously, so customers can see how others in similar environments are using VMware technologies. Soon, we'll also include benchmark results that are filterable in the same way, letting you determine whether you're on the cutting or the trailing edge of what's happening in your industry, helping you understand what kind of growth and development is possible in your field.
More immediately, you'll be able to leverage these benchmarks and analytics to strategically justify and drive new IT projects, or simply adjust and right size your existing deployments. Meanwhile, your TAMs will have access to similar information from other VMware deployments; therefore, they can alert you to situations where other customers have walked down a similar path, helping you overcome hurdles faster or even avoid them entirely.
Your advocate within VMware
This information (anonymized where appropriate, keeping in line with our NDA and licensing agreements) also allows us to work internally in VMware to advocate for you and drive change within our own organization on your behalf.
For example, it lets us say to specific VMware business units and product managers, "Listen, our customers are experiencing X" or "This important VMware customer needs additional assistance and support with Y."
When customers are using a newer VMware technology or if they're pushing a technology in a new way, their TAMs are now better placed to help them influence what's happening within VMware. This can mean that:
- Supportability is maintained.
- VMware can develop specific types of technical, design, or R&D elements to meet customer needs as closely as possible.
- Customers can have open access to alpha or beta programs.
- Customers can participate in events that are otherwise closed.
It's an exciting time!
I'm excited about the new CI.Next process because it helps us accomplish two goals.
First, TAMs now have a better understanding of their customers' environment than ever before. This means we can help in an even more strategic and proactive way.
Second, CI.Next helps our customers understand how their TAMs might be able to help them. With the shared information, we'll stay in closer touch as our customers adjust in response to the information we're reporting—and we'll be ready to supply the next level of feedback and inside access that our customers determine they need.
Here's the bottom line: While TAMs have always been trusted and valued partners for VMware customers, with CI.Next we're in a better position than ever before to help you thrive.
If you have any questions about CI.Next, don't hesitate to reach out to your TAM, or contact me directly.
If you aren't a TAM customer yet but would like to know more, drop me a line or check out the VMware Technical Account Manager Services website.
Eric Crossley is a senior solutions architect for VMware's Global Technical Services Professional Services Engineering group. For the last 8+ years, Eric has served as a partner and trusted adviser to VMware's customers and internal teams around the world. Eric works closely with VMware PS Management to ensure that VMware's future TAM program innovations align with essential market needs. Connect with Eric on LinkedIn!


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Engine Mechanical problem
2000 Ford F-450 V8 Four Wheel Drive
my hubby ran my f450 deisel out of fuel now it won't stay running. Got fuel to the sperartor and can get it to start using starter fluid but it dies after it. What can I do and how do I do it
Tuesday, January 5th, 2010 AT 4:15 PM

subset: commoncrawl


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Villa Erna
No prices found through our partners. Please contact the business directly or check some of our recommended alternatives.
How has this hotel rated in the past?
- Swimming pool
- Free parking
Travelers also recommend:
TripAdvisor Reviews Villa Erna Dubrovnik
Travel Blogs from Dubrovnik
Dubrovnik, als we later aan onze stop in Dubrovnik zullen denken, denken we vooral aan trappen, trappen en nog eens trappen. Je kan geen 100m wandelen zonder dat je moet klimmen of dalen.
Aangezien we 4 nachten ter plaatse zijn, hebben we het tempo laag gehouden. Bij aankomst, inchecken in ons appartement en een plons doen in het zwembad (die …
When the sun sets
... reliquaries. One room has a floor consisting of a dozen or so large tombstones, possibly hundreds of important monks and other dignitaries were buried in the monastery. And the church itself is relatively simple with new stained glass, very striking. I marvelled at the vellum books in display cases, the oldest was a huge 11th century bible and one smaller one from the 13th century was annotated in tiny writing all around the edges ...
Our Furtherest point South
Today we are leaving for Dubrovnik, which is known as the Pearl of the Adriatic. A rich and powerful city state until 1806, the proud city once known as Ragusa has a population of over 120,000. Structural damage suffered during the siege of 1991 and 1992, at the hands of the Yugoslav People's Army, has been repaired and visitors once again flock to this tranquil place.
The trip was expected to be around 6 1/2 hours so we needed to be gone by about 8.30. I slept ...
Somethin' quick from Dubrovnik
It's funny how difficult it is to find the appropriate vocabulary for conveying a sense of how comparatively developed a country is. First-world and third-world are out with the old millennia if I'm not mistaken; "Western Civilization" is a euphemistic misnomer that doesn't apply to the countries it geographically should, and "lesser-developed-" vs. "more-developed-countries" is so vague and ...
Olives, Oranges, Pomegranates, Pines and Palms
... little ginger kitten (still in the cute fluffy stage) and did the 'puss puss puss' call and it was like the zombie scene from Thriller… kittens flocked out of every nook and cranny. Needless to say the next 3 days involved lots of cat play, adding kitten food to our shopping lists and name selection. We had a big Golden retriever attack and try to kill one (little black one that was Tallis' favourite) but ...


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This story appeared in the Greater Pittsburgh edition of the December ESPN RISE Magazine.
There hasn't been a whole lot of downtime the past few summers for Tom Droney. But every few weeks during those warm months, when he can get away, he grabs his fishing rod and hits the Youghiogheny River, often from creeks around Seven Springs. But unlike some fishing enthusiasts, the quiet 18-year-old from Green Tree likes to "ease into it."
Calmness runs in his blood. His biggest catch, during a venture to Montana with his cousins last summer, was an exercise in that kind of patience. Droney, using fly-fishing methods for the first time, took to the water at 7 a.m. and waited -- and waited. Some eight hours after he got on the boat, he finally felt a tug: a 26-inch brown trout.
He's brought that same virtue to the hardwood at Sewickley (Sewickley, Pa.).
"The first two quarters, you don't want to rush," Droney says. "You want to see how things are going. Then in the third quarter, fourth quarter, you strike. You start attacking. That's how it is with fishing: You wait around to find a good hole. There are some parallels."
The 6-foot-6, Davidson-bound senior point guard has an arsenal of moves at his disposal -- crossovers, step-backs, pull-ups, and a vicious spin move. But he's at his most dangerous when passing up the rock in the early going of games and then taking over late. Last year, Droney averaged 23.7 points, 6.6 assists and 6.1 rebounds and dropped 40 in the championship as Sewickley won the WPIAL Class A title. And he did it by being patient and getting his teammates involved.
"He's great about supporting those guys," head coach Win Palmer says.
"We kind of rally off his big plays," adds teammate and close friend David Bonomo. "He just makes us all want to be better."
When the time comes, Droney has no reservations about turning it up and going for the kill. And can he ever turn it up -- especially at home, when the gym at his small school of roughly 300 is rocking.
"He really just lives and dies off the energy," Bonomo says. "He knows personally everyone in the crowd who's there. He definitely averages more points at home."
"He's a clutch type of player. He goes hard all the time," adds former Sewickley assistant Daryn Freedman, now the head coach at Kiski Prep. "When he gets in the zone, it's pretty awesome. You can see it on his face. He clenches both his fists, says 'Let's go' and then he goes out and makes eight shots in a row."
There were plenty of those kill-shot moments in the Panthers' run to the WPIAL title last season. Like his 47-point output in a 92-85 win over Our Lady of Sacred Heart last February, where he not only scored from everywhere on the floor -- pulling up, off the dribble, and even from 32 feet out -- but created open, high-percentage shots for his teammates.
Or the game against Clairton when, down by one with two minutes to go, Droney broke down his man and -- according to multiple witnesses -- dunked on four defenders. Or there's the performance most people talk about, his record-tying 40-point outburst in the Panthers' championship win over Serra.
Sure, everyone knew the talent was there from early on. That's why Palmer approached his seniors before the start of the 2006-07 season, telling them their leading scorer would be a 6-foot-4 freshman -- after which the team vowed to look after him in the hallways. Droney went on to average 15 points a game that season.
But Droney will tell you a different story, about how before he was the hot-handed playmaker lighting up Western Pennsylvania, he was a lanky 5-foot-10 eighth-grader with great handle, no shot, and no defense. He'll tell you he's lucky he got his growth spurt.
But there's nothing lucky about the work he's put in. In May of 2007, Palmer and assistant Alan Bauman sat down with Droney and set out a goal: 10,000 shots made by September.
Remarkably, Droney hit the mark by July.
"I've never done the math on how many shots that is in a day," Palmer says. (For those keeping score at home, it's more than 100.) "But the thing about it is these were 3-point shots. For someone as a freshman who probably made five 3-point shots on the year, to as a sophomore now averaging two a game, that's just a drastic difference. He completely changed his mindset."
The scouts began to take notice that summer, too. Droney got his first scholarship offer after impressing the coaching staff at Duquesne's camp. At the time that included Freedman, who left the Dukes that August, hopped on at Sewickley as a volunteer assistant and formed the Basketball Stars of America AAU program with Droney as one of its key players.
By then, word was already out on Droney. Big-name coaches like Mike Brey (Notre Dame), Jamie Dixon (Pitt) and Bob McKillop (Davidson) were spotted at Sewickley games. The next summer, he torched the Five-Star Basketball Camp and ended up on its all-star roster alongside some of the nation's top recruits.
Former Florida star Nick Calathes is a frequent comparison that comes up, but Freedman goes further back: "A bigger version of Chris Herren without the baggage," he says, referring to the brilliant but troubled former Fresno State point guard.
Droney ultimately picked Davidson this past July and can't wait to enroll. Though he's never bumped into former Davidson star and current Golden State Warriors rookie Stephen Curry during visits -- "We always miss each other by a few days," he says -- there is buzz about him being able to carry on the tradition Curry established.
There's work to be done before then, though. At the next level, he'll have to tighten up his one-on-one defense, particularly against speedy waterbug types. His lateral quickness will have to get better.
Nothing a little patience can't improve.


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Top Definition
The meager little bowel movement one has before dropping the mother load.
I was late for work because I had a false alarm. Total preview poop. After I got to work I practically gave birth!
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Related quotes
"The putts break toward the diamond lane on the freeway here. I had a putt break toward a call box, so I know it depends on what lane. I missed a two-footer because a guy was changing his tire in my line."
"I just could not make a putt. Either I hit good putts that didn't go in, or I hit atrocious putts that weren't even close. It was frustrating."
"He looks comfortable over putts and to me, he doesn't take as long to putt as he does full shots. His routine is consistent. He's got a simple-looking stroke, with nice pace and flow, a blend of mechanics and pace. But I always think guys who putt well are more fearless. They don't worry about the three-putt or the bad putt. They don't take that with them."
"No matter how you putt, these are tough greens. You almost have to say, 'I'm going to miss some putts."


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Jul 10
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To Listen log onto http://www.blogtalkradio.com/iconici_weekly_radio_show/2013/06/15/soulful-singer-songwriter-jennifer-lang-1
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Tonight's American Athletic Conference showdown features two All-American candidates.
No. 22 UConn (17-4, 5-3) leans on senior Shabazz Napier.
No. 7 Cincinnati (21-2, 10-0) relies on senior Sean Kilpatrick.
Let's take a closer look at the two star players:
Napier ranks first in AAC games in scoring at 21.5 points per game while Kilpatrick is first in scoring in overall games at 19.4 points.
Both players are riding hot streaks, as Napier is averaging 25.5 points in the last four games and Kilpatrick 22.5 points in the last six games.
They are nearly automatic from the free throw line -- Napier sinks 86.6 percent and Kilpatrick converts 86.8 percent.
They also are deep threats, as Napier ranks sixth in the conference in 3-point shooting percentage at 43.5 percent and Kilpatrick is second in 3-pointers made at 2.6.
They both play the role of Mr. Big Shot.
Here's UConn coach Kevin Ollie on Kilpatrick: "Kilpatrick is their finisher for them. The USF game, he scored the last 10 points. I think the Louisvillegame he scored 12 of the last 14, or something like that. When it gets down when they need a bucket, he's going to get the ball. He's a great player."
Cincinnati coach Mick Cronin on Napier: "Shabazz is one of the best players, if not the best guard, that we'll play against all year."
Kilpatrick needs just 109 points to become only the second player in the program's history to score 2,000 career points. He's third on the school's all-time scoring list.
Napier is climbing UConn's scoring charts, ranking 14th with 1,614 points. He needs 17 points to pass Jerome Dyson (2006-10). He's also fourth in career assists with 571. He's the only player in school history with 1,600 points and 550 assists.
Enjoy what should be a great game.
Game time is 7 p.m. at Fifth Third Arena inCincinnati. It will be televised by ESPN.
Junior DeAndre Daniels (high right ankle sprain) will not be in the lineup tonight after missing last Thursday's game against Houston.
UConn can make a huge statement by beating Cincinnati, which has won 14 straight and gone undefeated at home (15-0) this season.
"Cincinnati is playing at a high level," Ollie said. "They haven't lost in our conference. We want to go in there and hopefully give them their first loss."
The rematch is March 1 in Hartford.
Brothers arrested on drug charges after police pursuit, search
Lyme man killed in East Haddam crash was to begin serving 10-year prison sentence
Police: New London man forcibly kept woman in car during chase
State panel hears more about the pros, cons of L+M Hospital affiliating with Yale
Casey and The Sports Doctor with Jim Buonocore on schools of choice
Waterford fabricator, national barbecue champion team up to design and manufacture pits


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Shop Shindigz for all your school spirit supplies! We have a full selection of items that you can personalize and sell to raise money for your sports programs. Consider our car flags and magnets, or license plate frames. Or order bulk candy through Shindigz to stock your concession stand - pay less up front so you make more profit!


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Cath Bonnes from the Broken Hill Hearing and Resource Centre is looking forward to better facilities at the recently acquired new premises....Wednesday 11 February 2009
Explore by Topic
Latest Hearing stories on ABC Broken Hill
Latest Hearing stories on ABC Online
- In the wake of AM's story on Tuesday of a woman unable to pay for new hearing aids, representatives of peak audiology bodies have called for the Government to regulate the hearing industry sector, saying that industry self-regulation allows 'rogue traders' to overcharge for hearing aids with ...Thursday 30 June 2016
- Australia's Consumer watchdog has confirmed it's looking into claims of rorting in the unregulated audiology industry. Disability advocates have raised concerns that some businesses are taking advantage of those who need hearing aids. Some are even turning to crowd funding as a last resort, ...Tuesday 28 June 2016
- The first week of Jai Beasley's life was a busy one. A series of hearing tests diagnosed the newborn with profound deafness. But up until very recently, it might have taken years, not weeks to reach this diagnosis. Professor Melissa Wake of the Murdoch Childrens Research Institute and Royal ...Monday 8 February 2016
- Imagine playing a sport, but not being able to call out to your team mates or hear the referee's whistle. That's the reality for hundreds of athletes competing in the Australian Deaf Games in Adelaide this week. Last night some athletes who can hear put in ear plugs to experience the world of a deaf ...Wednesday 13 January 2016
- I am finally proud to have robot ears...Monday 14 December 2015


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Wise Quotes, Wisdom Sayings
A wise man talks less and says more.
Those who say it can't be done, shouldn't get in the way of those who are doing it.
Money is not everything but everything needs money.
I'm only responsible for what I say, not responsible for what you hear.
The only true wisdom is in knowing you know nothing.
– Socrates
He who loses his bed sheet feels the cold on his feet.
(Indian saying. When someone is going through difficulties in life only they truly feel the pain and anxiety and people never fully relate.)
Those that talk down to you are just trying to walk tall by making you feel small. Rise above.
Self-restraint is wisdom. Impulsiveness is foolishness.
– Dr T.P.Chia
Don't listen to people who tell you what to do. Listen to people who encourage you to do what you know in your heart in right.
Life can be miserable if you are possessed by and obsessed with immediate gratification.
– Dr T.P.Chia
Do not save what is left after spending, but spend what is left after saving.
Thought is the sleeping giant of the mind. The world belongs to those who wake up this sleeping giant.
– Dr T.P.Chia
Believe all but don't trust. Listen all but don't act without your own observation. Be careful from the people who always use, simply to convince for something, for someone with remarks. After God trust on self and act with common sense to avoid frustration in future.
Sanjiv Dogra – Toronto 28th September, 2011.
You can make money, you can lose it all, you can get it all back, but you can never get back time
He is no fool who gives what he cannot keep to gain what he cannot loose.
– Jim Elliot


text:
Email this article from PlasticsNews.com
Nestlé reports on efforts to reduce packaging
AMSTERDAM — Swiss giant Nestlé SA reduced the weight of its packaging by 601,147 tons over the 1991-2010 period. Out of this total saving, 34 percent was plastics and laminates.
More Events > Upcoming Events
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NEWS Thursday, July 28


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Best Video Arcade
Whether you're partial to that sweet young thing from the '80s, Ms. Pac-Man, or you need to burn up a little testosterone with Virtua Cop 2, you can conquer the universe of your choice at Video Roundup, an independently owned video arcade that's been around for more than a decade. Novice players will appreciate the back room full of old-school games, while serious gamers will find the most current recreational technology. Non-video-game heads can play at the Tetris or Solitaire stations; pinball wizards can get a finger-flipping workout on an impressive array of machines; and for a more aerobic experience, there's air hockey, foosball or billiards at one of 27 pool tables. We dare you to have more fun for so little money.
Get the Things to Do Newsletter
Sign up for our weekly guide to events in Phoenix, and never be bored again. With suggestions for every day of the week, our recommendations will keep you busy on any budget.
Upcoming Events
Modest Mouse & Brand New
TicketsMon., Jul. 25, 7:30pm
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Tue., Jul. 26, 9:30am
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Sponsor Content


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Helping You Cope With Treatment
Please contact your nearest CANSA Care Centre for support and find additional information regarding cancer treatment and coping with cancer…
Specialist care offered at our CANSA Care Centres and Clinics involves treatment of complications resulting from cancer treatment – specifically Lymphoedema, Stoma and treatment of acute and chronic hard-to-heal wounds.
Acute and Chronic Wound Care
The body heals wounds through a natural process. At times, however, some wounds – big and small – don't heal the way they should. Our certified Wound Care Therapists offer advice and basic wound-care.
Stoma Care
We offer pre- and post-operative counselling. Incontinence advice and coping skills are given to patients and families. We also offer the sale of cost effective stoma products. Read more about our stoma support service…
Lymphoedema Treatment
Our specially trained Lymphoedema Therapists offer Complete Decongestive Therapy (CDT) to manage the symptoms of patients affected by Lymphoedema.
CDT treatment includes manual lymph drainage, compression bandaging, special exercise, as well as skin and nail care.
Home-based Care
Home-based care is a collaboration between professional CANSA staff members and the community, aimed at empowering communities to take ownership of their own health and care for their patients.
Through the mobilisation of role players, resources and volunteers, patients receive cost-effective, quality home-based care including therapeutic and rehabilitative care, long-term maintenance and palliative care.
This service focuses on appropriate care and comfort, access to health and support facilities, volunteers and the participation of family members.
Assistive Devices & Medical Loan Equipment
CANSA supports patients by lending or helping them to obtain assistive devices & equipment to help them cope with cancer treatment and after surgery. This includes:
- wigs – if you wish to donate your hair to make a wig, read more…
- breast prostheses (sold at some Care Centres)
- wheelchairs
- commodes
- egg-shell mattresses
- other aids
- colorectal cancer patients can purchase stoma bags, linen savers and supplements at reduced prices
Has Cancer Touched Your Life?
Cancer affects one in four South Africans, through diagnosis of family, friends, colleagues or self.
We want you to know that you are not alone and that we would like to support you and your loved ones, regardless of how cancer has touched your life.
Find info & online resources to help you fight cancer and please read more about CANSA's Holistic Care & Support which is offered at our CANSA Care Centres countrywide.


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Book your room at Quality Hotel and Conference Center
Get an overview of this hotel3-star hotel with free breakfast and restaurant
Situated in a rural location, this hotel is within 9 mi (15 km) of Mercer Mall, Bluefield College, and Bluefield State College. Fincastle Country Club and Princeton Railroad Museum are also within 12 mi (20 km).
Hotel Features
Along with a restaurant, this hotel has an outdoor pool and a 24-hour fitness center. Free buffet breakfast, free WiFi in public areas, and free self parking are also provided. Other amenities include a sauna, a 24-hour business center, and coffee/tea in a common area.
Room Amenities
All 118 rooms offer free WiFi, coffee makers, and flat-screen TVs with cable channels. Free newspapers, free local calls, and hair dryers are among the other amenities that guests will find.Would you like to give us feedback? Share it! Opens in a new window
Quality Hotel and Conference Center3350 Big Laurel Hwy Bluefield WV 24701
Hotel Amenities
Hotel Amenities
In addition to an outdoor pool, Quality Hotel and Conference Center provides a sauna and a 24-hour fitness center. The hotel offers a restaurant. A complimentary breakfast is offered each morning. Public areas are equipped with complimentary high-speed wireless Internet access.
This 3-star property offers access to a 24-hour business center and meeting rooms. Event facilities measuring 3948 square feet (355 square meters) include conference space. This business-friendly hotel also offers coffee/tea in a common area, complimentary newspapers in the lobby, and dry cleaning/laundry services. Complimentary self parking is available on site.
- 24-hour business center
- 24-hour fitness facilities
- 24-hour front desk
- ATM/banking
- Coffee/tea in common areas
- Free newspapers in lobby
- Conference space
- Conference space size (feet) - 3948
- Conference space size (meters) - 355
- Dry cleaning/laundry service
- Free breakfast
- Free self parking
- Free WiFi
- Meeting rooms 3
- Number of buildings/towers - 1
- Number of floors - 2
- Number of meeting rooms - 3
- Outdoor pool
- Outdoor seasonal pool
- Restaurant
- RV, bus, truck parking
- Safe-deposit box at front desk
- Sauna
- Total number of rooms - 118
Family Friendly Amenities
- Cribs/infant beds (complimentary)
- Free Wi-Fi
- Outdoor pool
- Rollaway/extra beds available
Available in all rooms: Free WiFi
Available in some public areas: Free WiFi
Free self parking, RV, bus, truck parking
Room Amenities
- Air conditioning
- Cable TV service
- In-room climate control (air conditioning)
- Coffee/tea maker
- Free newspaper
- Free toiletries
- Connecting/adjoining rooms available
- Free cribs/infant beds
- Daily housekeeping
- Desk
- Flat-panel TV
- Free local calls
- Free WiFi
- Hair dryer
- Iron/ironing board
- Pay movies
- Phone
- Private bathroom
- Rollaway/extra beds available
- Shower/tub combination
Where to Eat
Guests are offered a complimentary buffet breakfast each morning.
Center Cafe - This restaurant specializes in American cuisine and serves dinner only. Guests can enjoy drinks at the bar. Open select days.
Nearby Things to Do
Recreational amenities at the hotel include an outdoor pool, a sauna, and a 24-hour fitness center.
To make requests for specific accessibility needs, complete the "Special or Accessibility Requests" section of "Trip Preferences" when you book your hotel.
- Accessible bathroom
- In-room accessibility
Hotel Policies
Check-in time starts at 4 PM
Check-out time is 11 AM
Payment types
- Pets allowed for an extra charge of USD 10 per pet, per night, plus a deposit of USD 50 per stay
- 2 per room (up to 50 lb)
You need to know
Extra-person charges may apply and vary depending on hotel policy.
Government-issued photo identification and a credit card or cash deposit are required at check-in for incidental charges.
Special requests are subject to availability upon check-in and may incur additional charges. Special requests cannot be guaranteed.
Optional extras
- Pet deposit: USD 50 per stay
- Pet fee: USD 10 per pet, per night
- Rollaway beds are available for an additional fee
Hotel Name
- Quality Bluefield
- Quality Hotel Bluefield
We should mention
Children 18 years old and younger stay free when occupying the parent or guardian's room, using existing bedding. The property has connecting/adjoining rooms, which are subject to availability and can be requested by contacting the property using the number on the booking confirmation.


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By: Harpoon Promotions Team Published:
As you know, we love running here at Harpoon. That's why we've partnered with our good friends at New Balance again this year to celebrate all things running in Boston this month! In case you missed it, last year we brewed a limited edition small batch beer with running in mind. It was called Harpoon 1906 (the year New Balance was founded) and was a thirst quenching Saison. Well, we are back at it again!
New Balance's "Nobody Runs #likeboston" campaign was the inspiration behind this year's collaboration beer. Our brewers landed on an easy-drinking and approachable Session IPA with runners in mind – because to us, no run is complete without a celebratory beer post-run! We're excited to introduce Harpoon After Boylston! This beer features wheat malt and flaked barley to give the beer a slight haze, a smooth mouthfeel, and a nice frothy head. A generous dose of orange peel was added to the boil to help bring out some of the citrus fruit characters in the hops. Harpoon After Boylston comes in at 4.8% ABV and is perfect to enjoy after you cross the finish-line and are ready to relax (or if you're just watching the finish line)!
Harpoon After Boylston is available in limited quantities at the Harpoon Beer Hall in Boston starting Wednesday, April 13th! Can't make it to the brewery? It will also be on tap at Solas at the Lenox Hotel on Boylston Street from Friday, April 15th until Race Day, April 18th.
Need another reason to stop by and enjoy it? In true Harpoon Helps fashion, we are donating $1 per pint sold to the Gillian Reny Stepping Strong Fund, which funds innovative research and clinical programs in trauma healing and limb reconstruction at the Brigham and Women's Hospital. Stepping Strong was established by the family of the very inspiring Gillian Reny—a young, pre-professional dancer who was critically injured in the 2013 Boston Marathon bombings.
Harpoon After Boylston won't be around long so make sure you grab a pint while you can. And remember the wise words of New Balance: "Nobody Runs #likeBoston!"
By: Paul Minore, Brewery Representative, New Jersey Published:
We are the proud sponsor of 11 Rugged Maniac races this year! To celebrate, we're giving away a chance to win an all-expenses-paid trip for 4 to a 2016 Harpoon-sponsored Rugged Maniac of your choice (11 cities to choose from!). You enter a team of four, and the team with the most votes by April 15th wins!
To help make your decision a little easier for which Rugged to go to, we want to highlight the Rugged host cities to callout our favorite hangout spots - from bars, to restaurants, to local activities.
Rugged Maniac is headed to Englishtown, New Jersey on 7/9 & 7/10. To find out a little more about all the awesomeness that the area has to offer, we asked our New Jersey Brewery Representative, Paul Minore, for tips on where to drink Harpoon, where to eat, and what to do…
"There are many unique spots to grab a cold Harpoon around Englishtown when you arrive in town for Rugged Maniac. If you're able to make a weekend out of it, be sure to check out these fun activities as well!"
Moores Tavern - a large sports bar in nearby Freehold. The original Moores was built in the Revolutionary War era by an aide to General Washington. It has since expanded and become one of the largest bars in the area with Harpoon IPA always on tap. A great place to watch the game!
Federicis- a renowned Italian restaurant in downtown Freehold, just down the street from Moores. They boast a full bar and the best pizza around.
A Little Bit of Cuba Dos - a fantastic Cuban restaurant in downtown Freehold. Try the empanadas or the ropa vieja! It is a BYOB restaurant so pick up your favorite Harpoon beer to enjoy with your meal.
Fireside Grill – a great bar with beer specials Monday through Friday and Harpoon IPA always on tap! What more could you ask for?
Local activities:
Freehold Raceway Mall – What's a trip to NJ without going to a mall? Freehold Raceway Mall (named after the nearby horse racetrack) is a large, modern mall with over 225 stores. You can find just about anything you are looking for here!
Freehold Raceway – Right next to the mall you will find Freehold Raceway, the oldest harness racing track in the United States. You can bet on the horses with hopes to win it big!
Forsgate Country Club – If you have the time to spare, try out Forsgate Country Club in nearby Jamesburg. Grab a day pass and try one of the two 18-hole courses!
Englishtown Auction – Founded in 1929 the Englishtown Auction is one of the largest flea markets in the state. It is open on weekends with free admission as well as free parking! Couldn't find what you were looking for at the mall? You're bound to find it here!
Now who's in for a trip to New Jersey?! Head to ufobeer.com and enter for a chance to win a trip!
Beers Spotlight
Subtly spicy and slightly fruityFind in stores and on tap


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Sounds like silonoid on starter not engaging. Intermediately. A lot of loud clicking from silonoid. If u stay on it it will eventually kick in, sound normal and turn over motor and start. Replaced starter. Still did it. Now the check engine light comes on. Autozone said the code reads AB1 cylinder? In the tranny? Related?
Tuesday, April 3rd, 2012 AT 2:44 AM


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All existing tables are with prefix dbo.TableNames
When I create a new table, it creates as login.MyTable instead of dbo.MyTable.
The screenshot is Security > Properties of my login.
Could you please show me step by step (I am not familiar with SQL securites) how to solve this problem?
Thanks in advance!


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The mother fawker is WORST than a spammer. All he spews is the same #$%$ drivel post after post. ALL GARBAGE, just like chen and his phoney company.
Tru Dat!
Done. I seldom post, but I find that guy to be the most annoying individual I've ever encountered. I've already placed so many on this board on ignore: Tipper, lobster, mfel, and now helmdeb.
How did so many freaks congregate into this stock?
Is there anyway to Ignore all aliases at once ? From the writing style it appears to me that these are uneducated Chinese speculators. Must put in a suggestion to Yahoo to be able to Ignore all aliases/identities associated with a poster.


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Jump to navigation
The Asia-Pacific Migration Report 2015: Migrants' Contributions to Development, produced by the Asia-Pacific Regional Thematic Working Group on International Migration, including Human Trafficking, provides an insight into how labour migration, the dominant migration trend in the Asia-Pacific region, can contribute to development in countries of origin and destination in the Asia-Pacific region.
This paper examines the skill needs of the Russian Federation and Kazakhstan, and the potential for these needs to be filled by migrant workers. It assesses the institutional structures with regards to skill development in countries of origin and destination and potential areas for future reform to bring needs and capacities into line.
The United Nations Building
Rajadamnern Nok Avenue
Bangkok 10200
(66-2) 288-1234
(66-2) 288-1000


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I just saw this meta tag in the wild and was wondering it does and why it's used?
<meta http-equiv="X-UA-Compatible" content="IE=edge,chrome=1" />
Reading the documentation on About.com, it says:
"IE=edge" tells Internet Explorer to use the highest mode available to that version of IE. Internet Explorer 8 can support up to IE8 modes, IE9 can support IE9 modes and so on.
But what about the
chrome=1 tag?


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2 results for el paso
Meet people with common interests and collaborate.
El Paso Etsy
For Etsians in the greater El Paso region.
West Texas Etsy
Handmade Artisans from the West Texas Area
Sign up for the Etsy Success Newsletter
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GreatNonprofits is the best way to find great local nonprofits.
Volunteers and donors use GreatNonprofits to search for ratings and reviews of nonprofits in their town.
Featured Review
Reel Grrls is such an innovative non-profit, teaching young people to create media that influences how we see the world- with a "feminist lens". I love that phrase and I believe that in our media flooded... more
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Stories About Giving Create High Online Engagement: Learnings from the #MyGivingStory Contest
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10 Ways You Can Actually Help Syrian Refugees
Smithtown Nonprofits and Charities
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I am a volunteer weekend puppy raiser in Massachusetts and have found my time volunteering with America's Vetdogs to be one of... more »
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5 stars 22 reviews
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Established in 1971, RSVP has given adults over 55 a chance to "give back" with more than 150k of volunteer hours in 2012. The... more »
Human Services
Guide Dog Foundation For The Blind, Inc.
5 stars 1 reviews
brokensailor wrote:
I am a 100% disabled veteran who can no longer work due to my service connected injuries. I am missing part of my right leg, my... more »
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paul28 wrote:
The Long Island Feline Adoption Center is truly unique among cat shelters. It is Cage-Free, with an environment filled with stimulus... more »
Civil Service Employees Association
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Shana Kay Memorial Foundation Inc
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Wildfire has a gluten free dinner scheduled for Wednesday April 13th. You can view the menu for the event here. Gluten free dishes will be paired with Omission Pale Ale and Lager, Bard's Gold, and Angry Orchard "Crisp Apple" Hard Cider. With the gluten free dinner quickly approaching, I decided to take a gluten free diner (let's call her "GFJ") to Wildfire to try their gluten free brunch. GFJ is very into the GF food and product scene.
We ordered the gluten free Banana Chocolate Pancakes, Chicken Moreno with Artichokes, a Bard's Gold (gluten free beer), and a side of green beans. We were served gluten free bread. GFJ said that the pancakes, chicken, and bread all "passed the test." She would have liked to try more than one gluten free beer (but the two Omissions from the upcoming dinner weren't available to us). It is nice that I – someone who doesn't require a special diet – could eat gluten free and not miss the gluten. It's a shame we aren't available for the gluten free dinner, because Wildfire knows how to handle gluten free dishes.


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Date: late 15th–16th century
Culture: Japanese
Medium: Iron, lacquer, copper, gold, silk
Classification: Helmets
Credit Line: Rogers Fund, 1913
Accession Number: 13.112.10
The helmet bowl is constructed of fifty-two ridged plates and is shaped like a melon (akodanari), with a pronounced rise at the back. It dates from the fifteenth century but was remounted for use in the late seventeenth or early eighteenth century. The bowl is inscribed with the character Kami (or Tatematsuru), used by the Haruta school of armorers in Nara. The badge on the turnbacks of the neck guard is that of the Sanada family, daimyo of Ueda.


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Homestead Studio Suites Mount Juliet hotels are listed below. Search for cheap and discount Homestead Studio Suites hotel rates in Mount Juliet, TN for your upcoming individual or group travel. We list the best Homestead Studio Suites Mount Juliet lodging properties so you can review the Mount Juliet Homestead Studio Suites hotel list below to find the perfect place.
Our page will list Mount Juliet, TN hotels/motels that have similar star rating to Homestead Studio Suites.Booking a group or meeting? Set up a group hotel block in Mount Juliet TN
Enter your stay dates and any discounts you qualify for to see Mount Juliet, TN rates found only on HotelPlanner!


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|Publication number
|Publication type
|Application number
|Publication date
|Apr 2, 2002
|Filing date
|May 23, 2000
|Priority date
|May 24, 1999
|Fee status
|Also published as
|Publication number
|Gerald Adams, Ezat Khoshdel, Anthony Moretta, Yvonne Christine Plant, Euan Stuart Reid
|Original Assignee
|Unilever Home & Personal Care Usa, Division Of Conopco, Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (10), Non-Patent Citations (3), Referenced by (6), Classifications (28), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
The present invention relates to polysiloxane block copolymers suitable for use in cosmetic and personal care compositions, their preparation, and to cosmetic and personal care compositions, such as hair styling compositions, containing the polysiloxane block copolymers.
Cosmetic and personal care compositions such as hair styling sprays, mousses, gels and shampoos, frequently contain resins, gums and adhesive polymers to provide a variety of benefits, for example, film-forming ability, thickening, sensory properties and hair shaping and setting.
Polymers for use in such compositions include organic or silicone-containing linear or graft copolymers which contain various monomers in an alternating, random, block or homopolymer configuration.
Graft copolymers are known for use as film-forming polymers in hair care and other personal care compositions. These graft copolymers typically comprise a polymeric backbone and one or more macromonomers grafted to the backbone, in which the physical and chemical attributes such as glass transition temperature and water solubility can be selected independently for the polymeric backbone and macromonomer grafts in order to provide the desired overall polymer properties.
For example, WO95/01383 and WO95/01384 describe the use of water or alcohol soluble or dispersible graft copolymers in hair and skin care compositions, in which the copolymer has a backbone and two or more polymeric side chains, and is formed by copolymerisation of randomly repeating monomer units A and B. Monomer A is selected to have a hydrophobic character and macromonomer B comprises a long hydrophilic part. EP 412,704, EP 408,313 and EP 412,707 have suggested the use of silicone grafted acrylate copolymers in hair care applications. U.S. Pat. No. 4,988,506 describes the use of non-pressure sensitive polysiloxane-grafted copolymers in hair care compositions.
Block copolymers have an advantage over graft copolymers in that the polymer architecture can be controlled more closely. This is particularly important when designing polymers with segments of distinct physical and chemical properties for particular applications, e.g. alternating "hard" and "soft" segments in a hairspray polymer for improved hold and feel.
U.S. Pat. No. 5,468,477 describes cosmetics and personal care compositions containing a vinyl-silicone graft or block copolymer comprising a silicone polymer segment and a vinyl polymer segment. This block or graft copolymer is prepared by the free radical polymerisation of a mercapto functional silicone chain transfer agent and vinyl monomers. Copolymers prepared by this method generally have a low molecular weight and a low silicone content due to premature chain termination. Also, intramolecular cross-linking reactions lead to polymer build up in an uncontrolled manner, and hence polydisperse systems with a mixture of chain lengths and molecular architectures. Furthermore, the presence of mercapto groups is a disadvantage in personal care applications since they tend to decompose to give odour problems.
Another approach to the synthesis of block copolymers is to use organopolysiloxane macroinitiators, which are organopolysiloxanes which contain groups which form radicals. These are described in U.S. Pat. No. 5,523,365 and used in WO98/48771, where a polydimethylsiloxane macroinitiator with azo groups is used to synthesise a block copolymer. Problems include the expense and safety hazards associated with the radical macroinitiator, which has to present in significant quantities, otherwise there will be insufficient siloxane content in the final product. Furthermore, the size of the polydimethylsiloxane macroinitiator means that the reaction is inefficient, and large quantities of unreacted silicone have to be removed in a time-consuming extraction process that would be extremely difficult to scale up.
A need exists for conveniently prepared and cost-effective polysiloxane block copolymers for use in cosmetics and personal care compositions.
The present invention provides an improved process for making polysiloxane block copolymers in which end-functionalised polymers are prepared using atom transfer radical polymerisation and then reacted with organopolysiloxanes using a simple nucleophilic displacement reaction, to prepare polysiloxane block copolymers of controlled architecture. Atom transfer radical polymerisation is described in general in Polymer Vol 39, No.21, pp 5163-5170 (Nakagawa et al) and used in WO98/51261 to make graft copolymers.
In a first aspect, the present invention provides a process for making a polysiloxane block copolymer which is built up from units of the formula [A] [B], in which A is a polymeric block built up from radically polymerisable monomer, and B is a polysiloxane block, the process comprising the steps of polymerising a radically polymerisable monomer in the presence of an atom transfer radical initiator to form an polymer which is end-functionalised with a leaving group capable of nucleophilic substitution by nucleophilic end-groups on a polysiloxane, and reacting the polymer with a polysiloxane having nucleophilic end-groups so that a polysiloxane block copolymer is formed via a nucleophilic displacement reaction between the end-groups on the polysiloxane and leaving groups on the polymer respectively.
In a second aspect, the invention provides a polysiloxane block copolymer which is obtainable by the process described above.
The invention also provides a cosmetic and personal care composition, such as a hair styling composition, comprising the polysiloxane block copolymer as described above.
The process of the present invention comprises two key reaction steps:
First Reaction Step
The first reaction step involves polymerising a radically polymerisable monomer in the presence of an atom transfer radical initiator to form an polymer which is end-functionalised with a leaving group capable of nucleophilic substitution by nucleophilic end-groups on a polysiloxane. By "end-functionalised" and "end-group" is meant that the group is at or near a terminal position of the polymer and polysiloxane respectively.
Typically, the atom transfer radical initiator comprises at least one —C(O)X group, in which X is a leaving group capable of substitution by a nucleophilic O, N or S atom on the polysiloxane in the second reaction step, and at least one organic halide group capable of generating a radical in the presence of a transition metal catalyst.
Examples of preferred atom transfer radical initiators have the formula:
where R1 is the organic halide group and X is the leaving group. Preferably X is a halogen atom (F, Cl, Br or I). By "organic halide group" is meant any linear, branched or cyclic (aromatic or otherwise) carbon structure, whether substituted or unsubstituted,, which also contains a halogen atom (F, Cl, Br or I).
Preferred radical initiators have the general formula:
where Hal′ and Hal independently denote halogen atoms, R2 and R3 are independently selected from hydrogen or a monovalent, optionally substituted, linear or branched C1-18 hydrocarbon radical, r is an integer having a value of 0 or 1, and R4 is selected from divalent, optionally substituted, linear or branched C1-C18 hydrocarbon radicals.
Examples of monovalent, unsubstituted radicals are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radical; alkoxy radicals, such as the methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy and tert-pentoxy radical; hexyl radicals, such as the n-hexyl radical; alkenyl radicals, such as the vinyl, allyl, 5-hexenyl, 4-vinylcyclohexyl and the 3-norbornenyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl, 4-ethylcyclohexyl and cycloheptyl radical; norbornyl radicals and methylcyclohexyl radicals; aryl radicals, such as the phenyl, biphenylyl, napthyl, anthryl and phenanthryl radical; alkaryl radicals, such as o-, m- and p-tolyl radical, xylyl radicals and ethylphenyl radical; and aralkyl radicals, such as the benzyl, styryl, and phenylethyl radicals.
Examples of monovalent, substituted radicals are halogenated hydrocarbon radicals, such as the chloromethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl and 5,5,5,4,4,3,3-heptafluoropentyl radical and the chlorophenyl, dichlorophenyl and trifluorotolyl radical; mercaptoalkyl radicals, such as the 2-mercaptoethyl and 3-mercaptopropyl radical; cyanoalkyl radicals, such as the 2-cyanoethyl and 3-cyanopropyl radical; aminoalkyl radicals, such as the 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl and N-(2-aminoethyl)-3-amino-(2-methyl)propyl radical; aminoaryl radicals, such as the aminophenyl radical; acyloxyalkyl radicals, such as the 3-acryloxypropyl and 3-methacryloxypropyl radical; and hydroxyalkyl radicals, such as the hydroxypropyl radical.
Preferred monovalent radicals are independently selected from C1 to C6 alkyl radicals or the phenyl radical, in particular the methyl, ethyl, propyl or phenyl radical.
Examples of divalent hydrocarbon radicals are linear or branched saturated alkylene radicals, such as the methylene and ethylene radical, as well as propylene, butylene, pentylene, hexylene, cyclohexylene and octadecylene radicals; alkoxyalkylene radicals such as the methoxyethylene and ethoxyethylene radical; unsaturated alkylene or arylene radicals, such as the hexenylene radical and phenylene radicals; alkarylene radicals such as the methylphenylene and ethylphenylene radical, and alkoxyarylene radicals such as the methoxyphenylene and ethoxyphenylene radical. The divalent hydrocarbon radical can be interrupted by divalent radicals, bonded to carbon atoms on both sides, such as —O—, —C(O)O—, —O(O)C—, —CONR5—, —NR5C(O)— and —C(O)—, where R5 is hydrogen or a monovalent, optionally substituted, linear or branched C1-18 hydrocarbon radical as described above.
A particularly preferred radical initiator corresponding to the above general formula has:
Hal and Hal′=Br, R2 and R3=methyl and r=0.
The first reaction step involves polymerising a radically polymerisable monomer in the presence of the atom transfer radical initiator. The reaction is catalysed by a Cu(I) salt or other transitional metal species. In this reaction step, the organic halide groups act as initiators in the presence of the radically polymerisable monomers and the catalyst, resulting in the linking of a block of radically polymerisable monomers onto the atom transfer radical initiator by atom transfer radical polymerisation. This block of radically polymerisable monomers constitutes the polymeric block (denoted A) of the polysiloxane block copolymer as described above. The product of the first reaction step is thus a polymer which is end-functionalised with a leaving group capable of nucleophilic substitution by nucleophilic end-groups on a polysiloxane.
The catalyst for the first reaction step is a transition metal salt, preferably a Cu(I) salt such as Cu(I) halide salts (Cl, F, Br, I) and which is preferably complexed to a ligand which is suitable for solubilising the Cu(I) salt in the reaction mixture. WO98/51261 describes preferred ligands for use in solubilising the Cu(I) salt in the reaction mixture (aprotic bidentates such as diphosphates, 2,2′ bipyridyl, C1-C20 alkyl substituted bipyridyl and combinations thereof, most preferably 2,2′ bipyridyl complexed to a Cu(I) halide salt, in particular CuCl). WO98/51262 also refers to several journal articles which describe examples of the polymerisation process (atom transfer radical polymerisation) used in the second reaction step of the process of the present invention. Further examples of such descriptions can be found in Polymer Vol 39, No.21, pp 5163-5170 (Nakagawa et al) and Macromolecules 1997, 30, 2190-2193 (Haddleton et al). Those skilled in the art would understand that a variety of other ligands can also be employed.
The polymerisation process of the first reaction step can be furnished in bulk, solution, emulsion and suspension, as would be understood by those skilled in the art.
Radically polymerisable monomers suitable for use in the first reaction step of the process of the present invention are preferably ethylenically unsaturated monomers.
By "polymerisable" is meant monomers that can be polymerised in accordance with the second reaction step of the process of the present invention using atom transfer radical polymerisation, more preferably "living" atom transfer radical polymerisation, in which polymer chain length and architecture can be controlled via stability of the radical, thus leading to improved monodispersity.
By "ethylenically unsaturated" is meant monomers that contain at least one polymerisable carbon-carbon double bond (which can be mono-, di-, tri- or tetra-substituted). Either a single monomer or a combination of two or more monomers can be utilised. In either case, the monomers are selected to meet the physical and chemical requirements of the final polysiloxane block copolymer.
Suitable ethylenically unsaturated monomers have the following general formula:
in which
R6 and R7 are independently selected from hydrogen, C1-C10 straight or branched chain alkyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethyl and 2-ethoxyethyl groups;
G is selected from hydroxyl, —O(M)2/V, —OR8,13 NH2, —NHR8 and —N(R8)(R9);
where M is a counter-ion of valency v selected from metal ions such as alkali metal ions and alkaline earth metal ions, ammonium ions and substituted ammonium ions such as mono-, di-, tri- and tetraalkylammonium ions, and each R8 and R9 is independently selected from hydrogen, C1-C8 straight or branched chain alkyl, N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl. Representative non-limiting examples of monomers useful herein include protected or non-protected acrylic acid and methacrylic acid and salts, esters and amides thereof.
The salts can be derived from any of the common non-toxic metal, ammonium, or substituted ammonium counter ions. The esters can be derived from C1-40 straight chain, C3-40 branched chain, or C3-40 carbocyclic alcohols, from polyhydric alcohols having from about 2 to about 8 carbon atoms and from about 2 to about 8 hydroxyl groups (non-limiting examples of which include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerol, and 1,2,6-hexanetriol); from amino alcohols (non-limiting examples of which include aminoethanol, dimethylaminoethanol and diethylaminoethanol and their qauaternised derivatives); or from alcohol ethers (non-limiting examples of which include methoxyethanol and ethoxyethanol).
The amides can be unsubstituted, N-alkyl or N-alkylamino mono-substituted, or N,N-dialkyl, or N,N-dialkylamino disubstituted, wherein the alkyl or alkylamino groups can be derived from C1-40 straight chain, C3-40 branched chain, or C3-40 carbocyclic moieties. In addition, the alkylamino groups can be quaternised. Also useful as monomers are protected and unprotected acrylic or/and methacrylic acids, salts, esters and amides thereof, wherein the substituents are on the two and three carbon position of the acrylic and/or methacrylic acids, and are independently selected from C1-4 alkyl, hydroxyl, halide (—Cl,—Br,—F,—I), —CN, and —CO2H, for example methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid and 3-cyano acrylic acid. The salts, esters, and amides of these substituted acrylic and methacrylic acids can be defined as described above for the acrylic/methacrylic acid salts, esters and amides. Other useful monomers include vinyl and allyl esters of C1-40 straight chain, C3-40 branched chain, or C3-40 carbocyclic carboxylic acids, vinyl and allyl halides (e.g. vinyl chloride, allyl chloride), (e.g. vinyl pyridine, allyl pyridine); vinylidene chloride; and hydrocarbons having at least one unsaturated carbon-carbon double bond (e.g. styrene, alpha-methylstyrene, t-butylstyrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutylene, p-methylstyrene); and mixtures thereof.
Preferred monomers useful herein include those selected from protected and unprotected acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methyl ethacrylate, ethyl ethacrylate, n-butyl ethacrylate, iso-butyl ethacrylate, t-butyl ethacrylate, 2-ethylhexyl ethacrylate, decyl ethacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxypropyl methacrylate, glyceryl monoacrylate, glyceryl monoethacrylate, glycidyl methacrylate, glycidyl acrylate, acrylamide, methacrylamide, ethacrylamide, N-methyl acrylamide, N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, N-butyl acrylamide, N-t-butyl acrylamide, N,N-di-n-butyl acrylamide, N,N-diethylacrylamide, N-octyl acrylamide, N-octadecyl acrylamide, N,N-diethylacrylamide, N-phenyl acrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-dodecyl methacrylamide, N,N-dimethylaminoethyl acrylamide, quaternised N,N-dimethylaminoethyl acrylamide, N,N-dimethylaminoethyl methacrylamide, quaternised N,N-dimethylaminoethyl methacrylamide N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, quaternised N,N-dimethylaminoethyl acrylate, quaternised N,N-dimethylaminoethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, glyceryl acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl ethacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-ethoxyethyl ethacrylate, maleic acid, maleic anhydride and its half esters, fumaric acid, itaconic acid, itaconic anhydride and its half esters, crotonic acid, angelic acid, diallyldimethyl ammonium chloride, vinyl pyrrolidone vinyl imidazole, methyl vinyl ether, methyl vinyl ketone, maleimide, vinyl pyridine, vinyl furan, styrene sulphonate, allyl alcohol, allyl citrate, allyl tartrate, vinyl acetate, vinyl alcohol, vinyl caprolactam and mixtures thereof.
More preferred monomers are those selected from methyl acrylate, methyl methacrylate, methyl ethacrylate, ethyl acrylate, ethyl methacrylate, ethyl ethacrylate, n-butyl acrylate, n-butyl methacrylate, n-butyl ethacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl ethacrylate, N-octyl acrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and mixtures thereof.
Most preferred monomers are those selected from N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, 2-ethylhexyl acrylate, hydroxyethyl methacrylate, N-octyl acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and mixtures thereof.
Second Reaction Step
The second reaction step involves reacting the polymer obtained from the first reaction step with a polysiloxane having nucleophilic end-groups.
The polysiloxane having nucleophilic end-groups may be linear, branched or hyperbranched, provided it has at least one nucleophilic end-group as described above. Typically such an end-group is one capable of nucleophilic attack via its O, N or S atom.
Examples of preferred polysiloxanes have the formula:
in which
n is an integer of 5 to 1,000,000;
R10 and R11 are independently selected from monovalent, optionally substituted, linear or branched C1-18 hydrocarbon radicals as described above,
R12 and R13 are independently selected from divalent, optionally substituted, linear or branched C1-C18 hydrocarbon radicals as described above;
p and q are integers having a value of 0 or 1, and
Y and Z are independently selected from hydroxyl, —NH2 and —NHR14 where R14 is a monovalent, optionally substituted, linear or branched C1-18 hydrocarbon radical as described above. Either, but not both, of Y and Z may also be hydrogen or a monovalent, optionally substituted, linear or branched C1-18 hydrocarbon radical as described above, thereby giving a mono-end-capped polysiloxane.
Particularly preferred polysiloxanes corresponding to the above general formula have:
n=5 to 1,000,000, preferably 5 to 500;
R10 and R11=methyl,
p and q=0 and Y and Z=hydroxyl; or p and q=1, R12 and
R13=(CH2)3 and Y and Z=N2.
In the second reaction step, a polysiloxane block copolymer is formed via a nucleophilic displacement reaction between the end-groups on the polysiloxane and leaving groups on the polymer respectively.
The nucleophilic displacement reaction of the second reaction step may be carried out under conventional reaction conditions.
Polysiloxane Block Copolymers
A typical polysiloxane block copolymer obtainable by the process described above is built up from units of the general formula [A]L[B], in which A is a polymeric block built up from radically polymerisable monomer, B is a polysiloxane block and L is a divalent linker group which links the A and B blocks via O—Si, N—Si or S—Si bonds to the B block. Preferably L is selected from:
in which
R15 is a divalent, optionally substituted, linear or branched C1-C18 hydrocarbon radical as described above, and
R16 and R17 are independently selected from monovalent, optionally substituted, linear or branched C1-18 hydrocarbon radicals as described above.
The overall molecular architecture of the silicone block copolymers of the invention can be described by the formulas A—L—B, A—L—B—L—A, —(A—L—B)n—, wherein n is an integer of 2 or greater, or [A—L—][A—L—]B[—L—A][—L—A], wherein A—L—B represents a diblock structure, A—L—B—L—A represents a triblock structure, —(A—L—B)n— represents a multiblock structure, and [A—L—][A—L—]B[—L—A][—L—A] represents a dendritic structure.
Cosmetic and Personal Care Compositions
The polysiloxane block copolymers of the present invention are preferably formulated into hair care compositions, especially hairspray compositions, but can also be formulated into a wide variety of product types, including mousses, gels, lotions, tonics, sprays, shampoos, conditioners, rinses, hand and body lotions, facial moisturisers, sunscreens, anti-acne preparations, topical analgesics, mascaras, and the like. The carriers and additional components required to formulate such products vary with product type and can be routinely chosen by one skilled in the art. The following is a description of some of these carriers and additional components.
Hair care compositions of the present invention can comprise a carrier, or a mixture of such carriers, which are suitable for application to the hair. The carriers are present at from about 0.5% to about 99.5%, preferably from about 5.0% to about 99.5%, more preferably from about 10.0% to about 98.0%, of the composition. As used herein, the phrase "suitable for application to hair" means that the carrier does not damage or negatively affect the aesthetics of hair or cause irritation to the underlying skin. Carriers suitable for use with hair care compositions of the present invention include, for example, those used in the formulation of hair sprays, mousses, tonics, gels, shampoos, conditioners, and rinses. The choice of appropriate carrier will also depend on the particular copolymer to be used, and whether the product formulated is meant to be left on the surface to which it is applied (e.g., hair spray, mousse, tonic, or gel) or rinsed off after use (e.g., shampoo, conditioner, rinse).
The carriers used herein can include a wide range of components conventionally used in hair care compositions. The carriers can contain a solvent to dissolve or disperse the particular copolymer being used, with water, the C1-C6 alcohols, lower alkyl acetate and mixtures thereof being preferred. The carriers can also contain a wide variety of additional materials such as acetone, hydrocarbons (such as isobutane, hexane, decene), halogenated hydrocarbons (such as Freons) and volatile silicon derivatives such as cyclomethicone. When the hair care composition is a hair spray, tonic, gel, or mousse the preferred solvents include water, ethanol, volatile silicone derivatives, and mixtures thereof. The solvents used in such mixtures may be miscible or immiscible with each other. Mousses and aerosol hair sprays can also utilise any of the conventional propellants to deliver the material as a foam (in the case of a mousse) or as a fine, uniform spray (in the case of an aerosol hair spray). Examples of suitable propellants include materials such as trichlorofluoromethane, dichlorodifluoromethane, difluoroethane, dimethylether, propane, n-butane or isobutane. A tonic or hair spray product having a low viscosity may also utilise an emulsifying agent. Examples of suitable emulsifying agents include nonionic, cationic, anionic surfactants, or mixtures thereof. If such an emulsifying agent is used, it is preferably present at a level of from about 0.01% to about 7.5% of the composition. The level of propellant can be adjusted as desired but is generally from about 3% to about 30% of mousse compositions and from about 15% to about 50% of the aerosol hair spray compositions.
Suitable spray containers are well known in the art and include conventional, non-aerosol pump sprays i.e., "atomisers," aerosol containers or cans having propellant, as described above, and also pump aerosol containers utilising compressed air as the propellant.
Where the hair care compositions are conditioners and rinses the carrier can include a wide variety of conditioning materials. Where the hair care compositions are shampoos, the carrier can include, for example, surfactants, suspending agents, and thickeners.
The carrier can be in a wide variety of forms. For example, emulsion carriers, including oil-in-water, water-in-oil, water-in-oil-in-water, and oil-in-water-in-silicone emulsions, are useful herein. These emulsions can cover a broad range of viscosities, e.g., from about 100 cps to about 200,000 cps. These emulsions can also be delivered in the form of sprays using either mechanical pump containers or pressurised aerosol containers using conventional propellants. These carriers can also be delivered in the form of a mousse. Other suitable topical carriers include anhydrous liquid solvents such as oils, alcohols, and silicones (e.g., mineral oil, ethanol, isopropanol, dimethicone, cyclomethicone, and the like); aqueous-based single phase liquid solvents (e.g., hydro-alcoholic solvent systems); and thickened versions of these anhydrous and aqueous-based single phase solvents (e.g., where the viscosity of the solvent has been increased to form a solid or semi-solid by the addition of appropriate gums, resins, waxes, polymers, salts, and the like).
Additional Components
A wide variety of additional components can be employed in cosmetic and personal care compositions according to the present invention. Examples include the following:
sunscreening agents such as 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl N,N-dimethyl-p-aminobenzoate, p-aminobenzoic acid, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4′-methoxy-t-butyldibenzoylmethane, 4-isopropyl dibenzoylmethane, 3-benzylidene camphor, 3-(4-methylbenzylidene) camphor, titanium dioxide, zinc oxide, silica, iron oxide, and mixtures thereof.
anti-dandruff actives such as zinc pyrithione, piroctone olamine, selenium disulphide, sulphur, coal tar, and the like.
conditioning agents for hair care compositions such as hydrocarbons, silicone fluids, and cationic materials. The hydrocarbons can be either straight or branched chain and can contain from about 10 to about 16, preferably from about 12 to about 16 carbon atoms. Examples of suitable hydrocarbons are decane, dodecane, tetradecane, tridecane, and mixtures thereof. Examples of suitable silicone conditioning agents useful herein can include either cyclic or linear polydimethylsiloxanes, phenyl and alkyl phenyl silicones, and silicone copolyols. Cationic conditioning agents useful herein can include quaternary ammonium salts or the salts of fatty amines.
surfactants for hair shampoo and conditioner compositions. For a shampoo, the level is preferably from about 10% to about 30%, preferably from 12% to about 25%, of the composition. For conditioners, the preferred level of surfactant is from about 0.2% to about 3%. Surfactants useful in compositions of the present invention include anionic, nonionic, cationic, zwitterionic and amphoteric surfactants.
carboxylic acid polymer thickeners. These crosslinked polymers contain one or more monomers derived from acrylic acid, substituted acrylic acids, and salts and esters of these acrylic acids and the substituted acrylic acids, wherein the crosslinking agent contains two or more carbon-carbon double bonds and derived from a polyhydric alcohol. Examples of carboxylic acid polymer thickeners useful herein are those selected from the group consisting of carbomers, acrylates/C10-C30 alkyl acrylate crosspolymers, and mixtures thereof. Compositions of the present invention can comprise from about 0.025% to about 1%, more preferably from about 0.05% to about 0.75% and most preferably from about 0.10% to about 0.50% of the carboxylic acid polymer thickeners.
emulsifiers for emulsifying the various carrier components of the compositions of the invention. Suitable emulsifier types include polyethylene glycol 20 sorbitan monolaurate (Polysorbate 20), polyethylene glycol 5 soya sterol, Steareth-20, Ceteareth-20, PPG-2 methyl glucose ether distearate, Ceteth-10, Polysorbate 80, cetyl phosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate,Polysorbate 60, glyceryl stearate, PEG-100 stearate, and mixtures thereof. The emulsifiers can be used individually or as a mixture of two or more and can comprise from about 0.1% to about 10%, more preferably from about 1% to about 7%, and most preferably from about 1% to about 5% of the compositions of the present invention.
vitamins and derivatives thereof (e.g., ascorbic acid, vitamin E, tocopheryl acetate, retinoic acid, retinol, retinoids, and the like.
cationic polymers (e.g., cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride, available as the Jaguar C series from Rhone-Poulenc).
preservatives, antioxidants, chelators and sequestrants; and aesthetic components such as fragrances, colourings, hair nutrients and essential oils.
The invention will now be illustrated by the following non-limiting Examples:
A silicone block copolymer was prepared by the following process:
Step 1
CuIBr (0.0852 g, 0.594 mmol) along with a magnetic stirrer bar was placed in a dry Schlenk flask which was then evacuated and flushed with nitrogen three times. 2-dimethylaminoethyl methacrylate (DMAEMA) (5.0 mL, 0.030 moles), toluene (7.2 mL) and 2-bromoisobutyryl bromide (0.15 mL, 1.19 mmol) were added to the Schlenk using degassed syringes.* The solution was then deoxygenated by three freeze-pump-thaw cycles. Finally, once the flask had reached the desired reaction temperature of 90� C. the npropyl-2-pyridinalmethanimine ligand (1) (0.20 mL, 1.19 mmol) was added with stirring. The reaction mixture immediately turned dark brown in colour on addition of the ligand. The polymerisation reaction was carried out for eight hours.
The monomer was purified by passing down a basic alumina column prior to use and purged with nitrogen for at least one hour. Toluene, which was used as a solvent for all polymerisations, was also degassed in this manner. CuIBr was purified before use according to a published procedure.1
1) Keller, R. N.; Wycoff, H. D. Inorganic Synthesis, 1947, 2, 1.
The product was purified by a conventional dissolution and precipitation method (three times). It had GPC molecular weight of Mn 4,300, Mw 5,200, D 1.18.
Step 2
Poly(dimethyl siloxane) containing hydroxyl groups at both ends (5.6 g, molecular weight 15,000) was dissolved in toluene (100 mL). To this solution, 4-dimethylaminopropylpyridine (0.26 mmol, 0.031 g) was added. Then a solution of the product prepared in Step 1 (3.2 g, Mw 5,200) in toluene (100 ml) was added dropwise over one hour. The reaction was left overnight at room temperature. The reaction mixture was warmed to 50� C. for two more hours to drive the esterification reaction to completion. The solvent was removed under vacuum to yield the block copolymer.
The resultant block copolymer (ABA triblock structure) had a controlled molecular weight and narrow polydispersity.
Tests showed that the copolymer had excellent film-forming, bond strength and sensory properties when formulated into a hairspray.
|Cited Patent
|Filing date
|Publication date
|Aug 3, 1993
|Nov 21, 1995
|Minnesota Mining And Manufacturing Company
|Vinyl-silicone polymers in cosmetics and personal care products
|Oct 14, 1997
|Nov 24, 1998
|Mandom Corporation
|Base material for hair cosmetics
|Nov 5, 1997
|Oct 12, 1999
|The Procter & Gamble Company
|Personal care compositions
|May 16, 1997
|Nov 16, 1999
|The Procter & Gamble Company
|Method of making graft polymers
|Nov 5, 1997
|Jul 25, 2000
|The Procter & Gamble Company
|Personal care compositions
|Apr 28, 1999
|Apr 12, 2000
|Kaneka Corporation
|Block copolymer
|Jul 9, 1997
|Jan 15, 1998
|Carnegie Mellon University
|Preparation of novel homo- and copolymers using atom transfer radical polymerization
|Mar 11, 1998
|Sep 17, 1998
|Carnegie Mellon University
|Improvements in atom or group transfer radical polymerization
|Apr 24, 1998
|Nov 5, 1998
|The Procter & Gamble Company
|Hair spray compositions
|May 18, 1998
|Nov 19, 1998
|The Procter & Gamble Company
|Personal care compositions containing graft polymers
|International Search Report Application No. PCT/EP 00/04429 mailed Oct. 4, 2000.
|Nakagawa Y. et al. "Development of a Novel Attachable Initiators for Atom Transfer Radical Polymerization. Synthesis of Block and Graft Copolymers from Poly(dimethylsiloxane) Macroinitiators" Polymer, GB, Elsevier Science Publishers B.V. vol. 39. No. 21.
|Search Report under Section 17, Application No. GB 99/12073.5 dated September 3, 1999.
|Citing Patent
|Filing date
|Publication date
|Feb 15, 2006
|Sep 8, 2009
|L'oreal, S.A.
|Polymer particle dispersion, cosmetic compositions comprising it and cosmetic process using it
|Oct 19, 2010
|L'oreal, S.A.
|Polymer particle dispersion, cosmetic composition comprising it and cosmetic process using it
|Feb 15, 2006
|Aug 31, 2006
|Celine Farcet
|Polymer particle dispersion, cosmetic compositions comprising it and cosmetic process using it
|Mar 18, 2004
|Nov 23, 2006
|Gerald Adams
|Aba block copolymers for hair styling composition
|Apr 22, 2009
|Jun 3, 2010
|Dueva-Koganov Olga V
|Delivery of hydrophobic benefit agents from bodywashes and the like onto a keratinous substrate
|Apr 23, 2010
|Oct 28, 2010
|Atrp Solutions Inc
|Well defined stars with segmented arms
|U.S. Classification
|525/101, 525/102, 424/70.12, 424/70.1, 525/106, 514/63, 525/100, 424/401, 424/70.122
|International Classification
|Cooperative Classification
|European Classification
|Oct 4, 2000
Owner name: UNILEVER HOME & PERSONAL CARE USA, DIVISION OF CON
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Effective date: 20140402


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- The Medical Minute: When to get a second opinion Getting a second opinion for a medical condition isn't quite the same as cheating on your hairstylist. In fact, when it comes to complex or serious, life-threatening conditions, most doctors encourage second opinions.More...
- Broach receives lifetime achievement award James Broach, distinguished professor and chair of the Department of Biochemistry and Molecular Biology at Penn State College of Medicine, has received a Yeast Genetics Meeting Lifetime Achievement Award for his contributions in the field of yeast genetics and outstanding community service.More...
- Zebrafish help researchers study human genes While a popular fixture of home aquariums, zebrafish have become a popular and important tool for studying human disease. The fish have more in common with humans than meets the eye, and provide an effective and efficient way to study genes. Perhaps nowhere in central Pennsylvania is that more apparent than at Penn State College of Medicine's newly constructed Zebrafish Functional Genomics Core.More...


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I'm Laine and I'm Alcoholic/Addict - page 2
I grew up in a working class family. Our family was mosty close knit until the late elementary years. I had a younger brother born in 1990. Two summers later in 1992 he died by drowing in a pool... Read More
0Jul 7, '08 by SerenityloveHi
I made through my birthday and I have 8 days clean and sober. I have been to a meeting everyday and have started writing step 1 with the guidance of a sponsor. I am feeling so much stuff.
0Jul 8, '08 by ms. papa RN AGAINCongrats on 8 days!!! It gets easier. Hang in there!
0Jul 11, '08 by Sugargirl66Thank you Laine