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"We can only hope for more help," said Sen. Joe Manchin, D-W.Va., who was re-elected in November. "Any time you have new members arriving you have that expectation of bringing fresh ideas and kind of a vitality that is needed. We hope that they're coming eager to work hard and make some difficult decisions and put the country first and not be bogged down ideologically."
The next two months will be crucial, with tough economic issues looming. Congress put off for just eight weeks automatic spending cuts to defense and domestic programs that were due to begin with the new year. The question of raising the nation's borrowing authority also must be decided. Another round of ugly negotiations between Obama and Congress is not far off.
There are 12 newly elected senators — eight Democrats, three Republicans and one independent, former Maine Gov. Angus King, who will caucus with the Democrats. They will be joined by Scott, the first black Republican in decades, who was tapped by South Carolina Gov. Nikki Haley to fill the remaining term of Sen. Jim DeMint. The conservative DeMint resigned to lead the Heritage Foundation think tank.
In a sign of some diversity for the venerable body, the Senate will have three Hispanics — Democratic Sen. Bob Menendez of New Jersey, Republican Sen. Marco Rubio of Florida and one of the new members, Republican Ted Cruz of Texas. There will be 20 women in the 100-member chamber, the highest number yet.
At least one longtime Democrat, Sen. John Kerry of Massachusetts, will be departing in a few weeks, nominated by Obama to be secretary of state. That opens the door to former Republican Sen. Scott Brown, the only incumbent senator to lose in November's elections, to possibly make a bid to return to Washington.
Eighty-two freshmen join the House — 47 Democrats and 35 Republicans. Women will total 81 in the 435-member body — 62 Democrats and 19 Republicans.
In the Senate, Reid and Republican leader Mitch McConnell are negotiating possible changes in the rules as lawmakers face a bitter partisan fight over filibusters, according to a Senate Democratic leadership aide who spoke on condition of anonymity because he was not authorized to speak publicly about private matters.
Reid has complained that Republicans filibuster too often and has threatened to impose strict limits with a simple majority vote. That step could set off retaliatory delays and other maneuvers by Republicans, who argue that they filibuster because Reid often blocks them from offering amendments.
The aide said Reid was preserving the option of making changes with a simple majority vote.
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Modesto Dr Cheryl Carmichael
1. Carmichael, Paul, MD
2121 Colorado AveTurlock, CA 95382
2. Horsley, Cheryl C, MD
600 Coffee RdModesto, CA 95355
3. Cheryl C Horsley MD
1015 E Main StTurlock, CA 95380
4. Horsley, Cheryl C, MD
1015 E Main StTurlock, CA 95380
5. Modesto Arts Medical Group Inc
The doctor's all seem friendly and knowledgeable. The rest of the staff however, rude. The receptionists and front desk people seem barely entry l…
6. First Choice Physician Partners
1541 Florida Ave Ste 200 ModestoModesto, CA 95350
From Business: First Choice Physician Partners (FCPP) is committed to enhancing and fostering the health care needs of the communities in which they operate through quality medica…
7. Golden Valley Health Centers
I'm so unhappy w/ the services of the doctors because i tried to reach my doctor and there was no response @ all. I ended up in the emergency room @…
8. Advanced Retina Institute
Wow. I just learned through my primary care you have a new office. I am very excited for you. I first met Dr. Chandran about 3 years ago when my d…
9. Modesto Vein Center
4101 Tully RdModesto, CA 95356
From Business: The Modesto Vein Center is a specialized, state-of-the-art medical clinic exclusively focused on the diagnosis and treatment of all venous problems. The Center is c…
10. Modesto Surgical Associates-A Medical Group
1401 Spanos CtModesto, CA 95355
11. Eggen Gib D O
112 E Fairmont AveModesto, CA 95354
12. Lasik Vision Institute
My experience there was all good. The actual procedure took about 5 minutes and by the next morning, everything was amazingly sharp and clear. Aft…
13. Hensley E Kip MD FACS
411 W 20th StMerced, CA 95340
14. Laser Spine Institute
This is the greatest, Had surgery July 2015. Haven't had any problems since, Enjoying life to the fullest.
15. Madayag-Capuno Elaine MD
232 W F StOakdale, CA 95361
16. Olson David A MD
232 W F StOakdale, CA 95361
17. Delta Eye Medical Group Inc
Serving the Modesto Area.
From Business: Delta Eye Medical Group is a full-service ophthalmology practice with three locations in Central California (Stockton, Lodi, and Tracy). The origins of the group go…
18. Tuolumne Foot Care
13975 Mono WaySonora, CA 95370
19. The Lasik Vision Institute, LLC
2868 Prospect Park Dr Suite 150Rancho Cordova, CA 95670
From Business: Contact The Lasik Vision Institute for a Free Evaluation to learn why so many people are choosing to get Lasik at LVI. In just minutes, the highly experienced indep…
20. SkinRenew Laser Medical CenterServices
1213 Coffee Rd Ste QModesto, CA 95355
From Business: Skinrenew Laser Medical Center is a facility that is a all in one skin care facility. Many different services are available to our clients that wish to rejuvinate t…
21. Wagner Gary MD MS FAADServices
1500 McHenry AveModesto, CA 95350
From Business: * Board Certified In Dermatology & Dermatopathology * Licensed Esthetician On Staff * DCL ANTI-AGING PRODUCTS * Demalogica Skin Cancer * Skin Care Programs Acne * P…
22. Allergy Medical GroupServices
935 Reserve DrRoseville, CA 95678
From Business: Our personalized treatment plans allows us to provide optimal therapy for adults and children with asthma, hay fever and other allergic disorders. We also offer com…
23. Express Lane Urgent CareServices
This place is great! Quick, quality care. Staff is friendly and helpful. I brought my friend in with her son, and we were in and out in less than …
24. Anderson Gordon D MDServices
1130 Coffee RdModesto, CA 95355
25. Dr. Fred Adams MD
1400 Florida Ave (Suite 205A)Modesto, CA 95350
26. SylvaneyesassocServices
Friendly Staff and Great Service! Yes, I would recommend Sylvan Eye to all of My Friends and Family
27. Modesto Urgent CareServices
1908 Coffee RdModesto, CA 95355
28. Valley Heart Associates
1540 Florida AveModesto, CA 95350
29. Ways Susan PHD MDServices
200 W Coolidge AveModesto, CA 95350
30. Valley Optometric GroupServices
i'm not a huge fan of the main physician, but the followup and the staff is amazing. not only is kathy nice, she really works for you and what fits …

subset: commoncrawl


text:
Welcome Back
148 Welcome Back Articles
Salman Khan and Anees Bazmee finally bury the hatchet!3 months ago 0
The actor and director had been on less than friendly terms for years Now it can be told. Salman Khan and Anees Bazmee have buried the hatchet… Read Article ▶
Housefull 2, Race 2, Welcome Back, Shootout At Wadala – The 7 BIGGEST hits of John Abraham!3 months ago 0
The star has always entertained us with his films... John Abraham is one of the most accomplished action heroes of Bollywood. The hunk made his… Read Article ▶
John Abraham – Shruti Haasan starrer Rocky Handsome gets delayed!9 months ago 0
The film's release has been postponed to February 5 next year... After a success in an ensemble cast in Anees Bazmee's Welcome Back, John wants to… Read Article ▶
Shruti Haasan crosses 3 million followers on Twitter!9 months ago 0
Other than successfully juggling films in three industries, Shruti Haasan is highly popular on Twitter Shruti Haasan is having a splendid 2015. Her… Read Article ▶
Rumour Has It: Shruti Haasan is Abhishek Bachchan's heroine in Hera Pheri 3?9 months ago 0
After being a part of a successful multi starrer comedy Welcome Back, Shruti Haasan may have bagged a role in yet another comic caper Tides are… Read Article ▶
Welcome Back box office collection: The John Abraham and Shruti Haasan starrer collects Rs. 94.87 crore in 17 days!9 months ago 0
The film continues its solid run at the box office... The John Abraham and Shruti Hassan starrer, Welcome Back continued its magical run at the box… Read Article ▶
Welcome Back box office collection: John Abraham – Anil Kapoor's comic caper inches towards Rs 100 crore mark!10 months ago 0
The Anees Bazmee directorial released on September 4 Anees Bazmee's latest offering, Welcome Back, might not have received great reviews from… Read Article ▶
After the success of Welcome Back, John Abraham to now focus on Rocky Handsome and Force 210 months ago 0
Rocky Handsome will release on February 5, 2016. After making the audience laugh with Welcome Back, actor John Abraham says his next film "Rocky… Read Article ▶
Here's why Shruti Haasan is the lucky charm for Vijay's Puli and Ajith's Thala 56!10 months ago 0
Bestowed with beauty in abundance and an enviable singing voice, Shruti Haasan seems to be riding on lady luck this year Being born to extremely… Read Article ▶
Anees Bazmee not yet paid for Welcome Back, have the producers duped the director?10 months ago 0
The director was supposed to get Rs 4.5 crore before the release of the film but is yet to be paid Director Anees Bazmee claims he is yet to receive… Read Article ▶
Welcome Back box office collection: John Abraham – Anil Kapoor starrer rakes in Rs 74.02 crore and becomes the second highest week 1 earner!10 months ago 0
The film released last Friday on September 4 Anees Bazmee's latest offering, Welcome Back which is a sequel to the hit 2009 Akshay Kumar - Katrina… Read Article ▶
Why has Shruti Haasan walked out of Ajay Devgn's Baadshaho?10 months ago 0
The Welcome Back actress had signed the Milan Luthria film a few days ago Shruti Haasan has been having a great run with her Hindi, Tamil and Telugu… Read Article ▶
Anil Kapoor to miss out on a few projects due to his TV series 2410 months ago 0
Kapoor will sport face fuzz for the second season of the desi version of 24; hasn't decided on style yet Anil Kapoor has already started prepping… Read Article ▶
Welcome Back box office collection: The John Abraham – Anil Kapoor starrer collects Rs 58.52 crore in 4 days!10 months ago 0
The film continues its steady run at the box office... Welcome Back starring John Abraham, Anil Kapoor, Nana Patekar and Shruti Haasan, opened… Read Article ▶
Welcome Back box office collection: John Abraham – Anil Kapoor's slapstick comedy mints Rs 51 crore over the weekend!10 months ago 0
Despite average reviews, the film is doing well at the box office Anees Bazmee's latest offering, Welcome Back starring John Abraham, Shruti Haasan… Read Article ▶


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Standing up for little kids
Does sitting down too much affect children's cognitive development?
Researchers from the University of Wollongong have found that kids in child care centres are spending considerable amounts of time being sedentary. So what can be done to get them moving?
- Professor Tony Okely
- Director, Interdisciplinary Educational Research Institute (IERI)
Director of Research, Early Start
University of Wollongong
- Linda Logue
- Director of the Keira View childcare centre
- Presenter
- Natasha MItchell
- Producer
- Ian Coombe
Comments (2)
Susan Ambler :
04 Feb 2014 9:59:18am
So, as many have been saying, some children that are being labelled as ADHD may be just normal children exercising their need to move?
That fun sounding pre-school seems similar to my memories of pre-school in the late sixties/early seventies. Am I just fantasising or are we re-learning something that early childhood educators were already doing back then?
Thanks for the interesting programmes, Susan, Katoomba.
Leanne :
04 Feb 2014 10:52:33am
What about playground design? Most new childcare centres in Sydney have small playgrounds covered in artificial turf. Opposite my house an expensive centre has has a playground about the size of a 1970's backyard only it's for 160 kids. Children need to be able to run around on real grass scrunch real leaves, dig in dirt etc. It doesn't get much better at school where portables are eating into playground space as the population expands.


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Native Plants
Q. Who is Mr. Smarty Plants?
A: There are those who suspect Wildflower Center volunteers are the culpable and capable culprits. Yet, others think staff members play some, albeit small, role. You can torture us with your plant questions, but we will never reveal the Green Guru's secret identity.
Did you know you can access the Native Plant Information Network with your web-enabled smartphone?
Ask Mr. Smarty Plants is a free service provided by the staff and volunteers at the Lady Bird Johnson Wildflower Center.
rate this answer
Wednesday - October 01, 2008
From: The Woodlands, TX
Region: Southwest
Topic: Turf
Title: Clover for possible lawn area in The Woodlands, TX
Answered by: Barbara Medford
QUESTION:I have two areas in my large lawn that grass refuses to grow. I am thinking of seeding with clover which old lawns used to always have. Which clover will grow in this area? Where do I find seeds and how do I plant?
Before we talk about clover or anything else in your lawn, we need to find out why grass will not grow in those spaces. Too much shade? Clovers, as well as grasses, need full sun; i.e., 6 or more hours a day. Tree roots beneath the soil blocking the grass roots and denying them access to the moisture and nutrients in the soil? Clover isn't going to like that, either. Rock-hard construction fill, without any organic matter available to plants? Ditto, ditto. So, before you go to the trouble and expense of planting clover or any other ground cover, find out why the grass is not flourishing there, and correct the problem.
Apparently, you're not the only one to consider this, as we found this website from Landscape.about called Clover Lawns vs. Lawn Grass. On the other hand, when you Google on "clover for lawns" you get a number of articles about how to kill off the clover in lawns. We do have several native clovers in our Native Plant Database; they have lovely flowers and attract bees and other pollinators. However, they also grow from 1 to 3 feet tall. We don't know where in The Woodlands you live, but we're betting it's not okay for you to have 3 foot flowering plants in the middle of your lawn. Of course, they can be mowed along with the grass, but then you've lost part of the point of having clover. The three native clovers that you can consider are:
Dalea purpurea var. purpurea (purple prairie clover) - could not find seed availability
Dalea multiflora (roundhead prairie clover) - Round Head Clover available at Native American Seed
Dalea candida var. candida (white prairie clover) - White Prairie Clover at Native American Seed
Seeds ordered from that supplier usually have planting instructions.
If that's not going to work for you, there are some other low-growing native plants. They're not grasses, and they are called "weeds" a lot of places, and might not take real close scrutiny from the Lawn Police in your neighborhood, but they are green, and will often grow where other things will not. They may already be growing in your lawn or flower beds.
Calyptocarpus vialis (straggler daisy) - perennial, shade tolerant, moderate foot traffic
Dichondra carolinensis (Carolina ponysfoot) - perennial, part shade to sun
Hydrocotyle bonariensis (largeleaf pennywort) - part shade to sun
If you can't find a start of one of these around, you can go back to Native American Seed and see if they sell seeds of these plants.
More Turf Questions
Need shade friendly native grass for lawn under pine trees in Carthage, TX.
September 07, 2010 - My home is situated on six acres of woods in the East Texas piney woods area. Other than a few beds I have tried to plant, the yard has not been landscaped. I am trying to cover dirt and weeds in a p...
view the full question and answer
How Can I Replace my Lawn with Natives in Houston, Texas
January 12, 2011 - I want to remove the turf grass from my lawn and put in gravel and sand. I want to put in native and adapted plants that will attract butterflies and I want different native and adapted ornamental g...
view the full question and answer
Native turf grasses for shady lawn
May 25, 2011 - I am interested in planting a native lawn using the grasses discussed on the website (2lb of buffalograss, 1� lb of bluegrama and at least 4 oz of curly mesquite). My front yard is relatively small w...
view the full question and answer
Habiturf installation after Take-All fungus
January 24, 2012 - Are other soil remedies needed (besides those listed in your Habiturf brochure) to install Habiturf on land which had a St. Augustine lawn which was decimated by take all patch.
view the full question and answer
Need help with an invasive ground cover type plant filling in damaged areas in lawn.
November 25, 2009 - Since the drought this summer, there is an invasive ground cover type plant filling in the damaged areas in my lawn . It is dark greenish/purplish very small clover type plant, difficult to pull up an...
view the full question and answer
|Support the Wildflower Center by Donating Online or Becoming a Member today.


text:
Originally posted on my personal website.
We started TrueAccord in 2013 because we wanted to crowd out the "bad guys" in the debt collection space. Every dollar that will be paid through our system, we figured, is a dollar not paid through them. We will get involved in the messy world of debt coll...(more)
TrueAccord is looking for a Lead UI/UX designer. We are a fast growing financial services company working with major financial institutions to change the way people in debt are treated. Come help us build an experience that impacts more than 77m Americans each year.(more)


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Shot and a beer by night, craft cocktail and chair massage by (Mon)day
Picture the Jackpot Saloon, and "relaxing" and "refreshing" probably aren't the first words that jump to mind. On a busy night the downtown bar best known for its eclectic mix of live music is dark, crowded, sweaty and loud, and its signature $5 specials are flowing — that would be a 16-ounce can of PBR with a shot of Jim Beam.
"At nighttime that pretty much explains this bar," bartender Mike Harmon said.
But have you been in on a Monday afternoon lately? Welcome to Jackpot's version of a spa day.
From 2 p.m. to 7 p.m., there's daytime-appropriate cocktails made with fresh fruits and a massage therapist on site giving chair massages, which are free but tips are encouraged. The bar's only-on-Monday drinks usually include a bloody mary made with fresh tomatoes instead of bottled juice, a fresh strawberry shandy (Boulevard Wheat beer, lemonade, sprite and muddled fresh strawberries) and a fresh raspberry Tom Collins (muddled raspberries, lime and gin). The licensed massage therapists are borrowed from Body Boutique. When I popped in this week, they had a game of Dr. Mario set up in the front booth, though that may or may not be a recurring feature.
Harmon said his teacher-friends inspired the idea, envisioned to help people relax and get ready to tackle the week. And the drinks are easygoing enough you could have one or two and still go about your day (however, that shot-and-a-beer special is always available if you're looking to take your Monday afternoon in a more traditional Jackpot-like direction).
D & D Tire Company 785-843-0191
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Home > All Cities > Braintree Real Estate Listings > luxury homes
luxury homes homes for sale in Braintree, MA
100 Hannah Niles Way, Braintree, MAList Price: $889,000 | Bed: 6 | Bath: 4.1
Custom 6 bed 5 bathroom colonial located in a premium cul-de-sac road location and sought after Liberty School District of Braintree. 5,600 + sq ft home on Hannah Niles Way. Too many details to list. Subzero frig, custom maple cabinets, hardwood floors throughout the 1st and 2nd floors. Formal and informal dining rooms. Large open kitchen that leads to a 3 tiered outside deck and Murphy brick patio. 7 heating zones. 2 brick wood burning fireplaces. 9 & 8 ft ceilings. Large master bath with a dua
Listing Office: Gibson Sotheby's International Realty | MLS ID#: 72006182
110 Quincy Ave, Braintree, MAList Price: $849,900 | Bed: 5 | Bath: 3.1
Seller Motivated... Looking for a Unique Home? Here it is!!! Fully re-modeled Victorian home situated on a beautiful professionally landscaped 20,786 sq ft lot. New thermopane windows, New roof, New Cement Fiber Board exterior siding. Modern State of the Art Kitchen with two level island with room for 6 stools, Quartz Counter tops. Pearl White Cabinets and Stainless Appliances. The foyer and formal Dining Room have the original oak woodwork with curved glass built in cabinets. Large Grand Ballro
Listing Office: Success! Real Estate | MLS ID#: 71969337
1259 Liberty Street, Braintree, MAList Price: $839,990 | Bed: 5 | Bath: 2.1
Beautiful new construction colonial located in the Braintree Highlands!! Amazing new construction with dark stained hardwood floors, tiled floors, quartz countertops, stainless steel appliances, stamped concrete. 5 bedrooms located in the most desirable area in Braintree. Located directly next to South Middle School and St.Claires Church. Everything is top notch from lighting fixtures to remote controlled gas fireplace. Must see!!!
Braintree Highlands
Listing Office: CLM MGMT | MLS ID#: 72030067
95 Harness Ln, Braintree, MAList Price: $809,900 | Bed: 5 | Bath: 2.1
NO SHOWINGS UNTIL OPEN HOUSE SUNDAY JUNE 26 2-330 pm. Location, Location, Location! This spacious beautiful home features an eat in kitchen with granite counters, stainless steel appliances and breakfast island that opens up to a dining area and large living room with fireplace and huge first floor family room. Spacious master suite with full bath and his and her closets. The three other bedrooms on second floor are very large. Finished basement with a great play room or man cave and a bedroom
Listing Office: Celebration Real Estate | MLS ID#: 72028798
9 Canavan Dr, Braintree, MAList Price: $799,900 | Bed: 3 | Bath: 2.2
This Home is located in one of Braintree's premier locations and sits back from the street on a private acre of land. The tree wide lined streets symbolize the Open Arms that welcome you to the Buckingham Place neighborhood. Whether you enter the home through the sun drenched family room or though the marbled front entryway you immediately appreciate the quality. The sky lit family room opens to the kitchen, the custom shelving and fireplace mantle warm the room and immediately bring a feeli
Listing Office: Keller Williams Realty | MLS ID#: 72004569
55 Harness Ln, Braintree, MAList Price: $799,000 | Bed: 6 | Bath: 3.0
Need a Bright, sun-filled home - look no further! Come and see this beautiful 1991 custom built home on cul du sac. This home is Spacious. Has 6 large bedrooms, Chef's kitchen with 2 ranges, 2 sinks ,impressive pantry and custom made cabinets, beautiful hardwood floors. This Home is conveniently located in the Highly desirable area of Braintree, just a short distance to the highways, shopping malls, restaurants, schools, parks, & much more!! Bonus : Beautifully finished
Listing Office: Century 21 Annex Realty | MLS ID#: 72028461
67 Francine Rd, Braintree, MAList Price: $739,000 | Bed: 3 | Bath: 3.0
"Quality, Condition and Location are what you will find at this Exquisite New Construction Custom built contemporary European inspired design. High end maple wood cabinets, with white quartz granite counter tops. Top of the line Stainless Steel Appliances, breakfast bar & dining area that opens to the family room with beautiful crown moldings. Quality solid wood door leads you to your private backyard. Upstairs you will find a spacious Spectacular master suite with walk in closet and luxury ba
Listing Office: Simaku Realty, LLC | MLS ID#: 72023160
25 Sheridan Rd, Braintree, MAList Price: $724,900 | Bed: 4 | Bath: 2.1
Cul-De-Sac Location Featuring; Hardwood Floors with Mahogany Inlay,Wainscoting, $30k Water Feature in Back Yard, Imported Italian Tiles in bathroom, Fireplace Living Room, Attached Garage is Plastered, Insulated and heated with its own Zone, Central Vac/Air, Wired for Central Sound inside/out, New Windows, Kitchen has New Granite Counters, New Dishwasher/Compactor & Jenn-Aire Range, 90% of lighting has been converted to energy efficient LED ( in/out), Stunning Finished Lower Level with Kitchenet
Listing Office: Century 21 Professionals | MLS ID#: 72029273
1727 Liberty Street, Braintree, MAList Price: $699,000 | Bed: 4 | Bath: 2.1
Brand new construction!! Harwood Floors throughout!! Convenience location, minutes away from shopping plaza. Featuring central air, granite counter-tops. recessed lighting, and forced hot air. Deck off kitchen. Beautiful staircase going up to cozy 2nd floor bedrooms with luxurious master bath. Huge walk up attic for lots of storage. Attached 2 car garage. Top Quality.***( On top of this, a barn at the back yard that comes along with it.)
Listing Office: Central Real Estate | MLS ID#: 71992341
894 Liberty St, Braintree, MAList Price: $650,000 | Bed: 2 | Bath: 2.1
THE LUXURY OF A SINGLE FAMILY WITH THE CONVENIENCE OF A CONDOMINIUM! This condominium in the Homes of Braintree Court offers all one floor living! Granite counters in state of the art kitchen and baths, cherry cabinetry, stainless steel appliances, jacuzzi tub. Cathedral ceilings, skylights, and sun porch. Extremely large master bedroom with HUGE walk in closet and master bath. Walkout lower level can be finished for added space or inlaw. Convenient to all transportation. Property consists of 1
Listing Office: Landmark Limited Partnership | MLS ID#: 72003167
116 Liberty St, Braintree, MAList Price: $614,000 | Bed: 4 | Bath: 3.0
A Polished Diamond. A prestige home with 4 bedrooms and 3 bathrooms and 2 attached garages. Right on Liberty St and minutes from the commuter rail/highway, this home is ideally situated. Amazing private driveway leads to 1 of the 2 attached car garages located on Lincoln Street. It's set on professionally landscaped fenced lot that boasts plenty of outdoor entertaining space. Cathedral ceilings, open floor concept, contemporary kitchen with cherry custom cabinets and granite counter tops, inc
Listing Office: Success! Real Estate | MLS ID#: 72028225
1208 Matthew Woods Dr, Braintree, MAList Price: $599,990 | Bed: 4 | Bath: 4.1
Commuters dream! Minutes to route 3, the Red Line, 20 min. to Boston, in a safe dead end street. Most desired Liberty Woods Condominium now available to you! Enjoy the privacy of a single family, w/ the convenience of a townhouse, don't worry about mowing the lawn, removing snow. The Master Suite is on the first floor with private bath w/ double sink vanity, separate shower and Jacuzzi tub. The living room has a combined dining area w/ soaring 18"cathedral ceilings, a gas fireplace, skylights, g
Listing Office: Marcia Marques Real Estate | MLS ID#: 72021121
21 Forest St, Braintree, MAList Price: $599,900 | Bed: 3 | Bath: 1.1
Classic Cape style home in desirable Braintree Highlands! Short drive to T station and highway. Walk to Liberty elementary and South Middle schools. Restaurants and shopping close by. The exterior has been recently painted and the half acre manicured lot is professionally maintained. This home has hardwood floors throughout including the new kitchen with stainless steel appliances, trash compactor, bosh dishwasher and granite counter top. Two fireplaces, one in the living room and one in the fi
Braintree Highlands
Listing Office: Molisse Realty Group | MLS ID#: 72003328
471 Elm Street, Braintree, MAList Price: $599,900 | Bed: 4 | Bath: 2.1
As you turn down the driveway flanked by a time honored New England stone wall, you will be eager to enter this outstanding classic colonial set on nearly a half-acre of matured manicured lawns. The home is ready for summer time entertaining at its best, with an above ground pool, and a walk out basement complete with a full in-law set up including a kitchen and bath. The impeccably landscaped, irrigated grounds are ready for an afternoon pickup game of football, or soccer underneath the crisp s
Listing Office: Cusack & Associates | MLS ID#: 72013039
30 Winter St, Braintree, MAList Price: $579,900 | Bed: 4 | Bath: 2.1
Welcome home to this charming sun drenched 4 bedroom 2.5 bath Braintree Highlands home that is made for entertaining. Just unpack and move right in. Home features a 1st floor master suite with hard wood floors. Great work space kitchen with dining area that flows nicely into 1st floor living room. Upstairs features 3 good sized bedrooms with one full bath. A great fire placed family room in the basement that is great for entertaining or just relaxing and watching TV. Check out the French do
Listing Office: Bird Dog Real Estate, LLC | MLS ID#: 72027147
1091 Liberty St, Braintree, MAList Price: $569,900 | Bed: 4 | Bath: 1.3
With possibility of a build-able lot. Long time family home well maintained bright 3 Season room looking over built in swimming pool, with new storm windows, new appliances, many updates and lots of space. A must see! No showing until open house June 4, 11-1
Braintree Highlands
Listing Office: Molisse Realty Group | MLS ID#: 72014288
190 Brewster Ave, Braintree, MAList Price: $559,900 | Bed: 4 | Bath: 3.0
This ranch is unique in that there are 4 bedrooms on the first floor with 2 full baths. The basement is finished with a full bath. The yard is fenced in and there is a two car garage. Short walk to elementary school. Bus stops on Washington street.
Listing Office: Lauria Real Estate | MLS ID#: 72019220
239 Pearl St, Braintree, MAList Price: $559,000 | Bed: 4 | Bath: 1.1
Newely remodled Home .Commuter's Dream! 4 bedroom 1.5 bath home walking distance from the TRAIN. Farmers porch .Hardwood floors throughout first and second floors.Open floor plan Kitchen With granite countes.Built in china cabinet in Dining room.Large deck of kitchen leading out to the large level yard.Off street parking .Corner lot .All new heating and electric.Roof siding.
South Braintree
Listing Office: Keller Williams Realty | MLS ID#: 71992965
24 Farm Rd, Braintree, MAList Price: $509,000 | Bed: 3 | Bath: 2.0
Wonderful multi level home with two full bathrooms, only minutes to highway, yet tucked away nicely on a cul-de-sac. Updated appliances and granite counter-top in kitchen. Lovely spacious living room with recessed lighting and welcoming fireplace. Totally renovated upstairs bathroom and many more updates. Sliders to deck off living room for your summer barbecues and relaxing. Great finished room in basement also.
Listing Office: Elite Realty Advisors | MLS ID#: 72007157
30 Alida Rd, Braintree, MAList Price: $464,000 | Bed: 3 | Bath: 1.1
Welcome home..Picture perfect 3 bedroom,1.5 bath ranch w/ OVER 1700 sq. ft. of living space &a 12k plus CORNER lot situated in sought after neighborhood nestled in the Highland's area between Liberty & South Middle Schools.The home, with a wide open floor plan, has been COMPLETELY remodeled & is impeccable! Custom kitchen w/granite, island, recessed lighting, under cabinet lighting,stainless appliances & tile flooring. Beautiful renovated bathrooms, three large bedrooms, living room with firep
Listing Office: Keller Williams Realty | MLS ID#: 72020079
11 Norfolk Rd, Braintree, MAList Price: $449,900 | Bed: 3 | Bath: 1.0
Location, location, location! Highly sought after Braintree neighborhood just a short drive to the highway, shopping and restaurants. Love the existing home or take advantage of the expansion potential to suit your needs. Just a short walk to the Morrisson Elementary School. Boiler only 8yrs old, GAS already in the house for easy conversion! Newer Anderson windows, dry basement, freshly refinished floors and painted walls throughout first floor. Great back porch and yard for summer entertai
Listing Office: Keller Williams Realty | MLS ID#: 72029335
34 Butler Rd, Braintree, MAList Price: $449,900 | Bed: 4 | Bath: 1.1
Welcome home to Braintree, a 4 bedroom Cape style home with over 1800sq/ft of living, located in the Highlands School district. This home offers, 1.5 baths, an eat-in kitchen with Stainless Steel Appliances with an open style floor plan to the living room, and a finished room in the basement with a Granite Top Bar. Other desirable features would include gas cooking, gas heating and the home is insulated with NEWER Vinyl Windows (2014) throughout. The gas heating system was installed in 2008 w
Listing Office: Century 21 Tullish & Clancy | MLS ID#: 72013887
55 Woodedge Avenue, Braintree, MAList Price: $439,900 | Bed: 3 | Bath: 2.0
This well-maintained home on a side street in the desirable Highlands school district is ready for new owners! The floor plan is fairly open with a spacious living room with Harvey picture window, open dining area, a first-floor sunken family room with a pellet stove and a deck off, white kitchen with a huge pantry closet in the hallway, a tiled bathroom with laundry hookups, and a first-floor master bedroom with an office/sitting area alcove. Upstairs has two more spacious bedrooms with great
Braintree Highlands
Listing Office: Keller Williams Realty | MLS ID#: 72024663
304 Pearl St, Braintree, MAList Price: $389,900 | Bed: 3 | Bath: 1.0
Fantastic, bright/cheery, updated & cozy - classic Cape style home with all the charm & history of yesteryear - married with the modern touches of today. In a town praised for its education, this was once a Braintree schoolhouse. Impressive, updated kitchen with new cabinets and granite counter tops - stainless appliances including dw/disposal and microwave. Large granite island ideal for extra seating/cabinets/counter space. Open layout into the bright dining room. Cozy, fireplaced living ro
Listing Office: Free & Clear Real Estate | MLS ID#: 72009932
7 Bellevue Ave, Braintree, MAList Price: $379,900 | Bed: 2 | Bath: 1.1
6 room bungalow located on a quiet dead end street in the Braintree Highlands with open floor plan from kitchen to dining room to living room. Hardwood floors in living and dining rooms. Kitchen includes gas stove, in-wall gas oven, and lots of counter top space. Spacious family room with high ceilings and wood burning stove. Attached heated 2 car garage with built in shelving, Harvey windows. Custom 3-season porch in back with electrical outlets and single ceiling fan. Large corner lot, across
Braintree Highlands
Listing Office: Thread Real Estate | MLS ID#: 72027841
Properties 1 to 25 of 26
Beacon Rock. The information above, though secured from sources believed to be reliable, cannot be guaranteed. The buyer should independently verify this information to his/her satisfaction. MLS Property Information Network, Inc.


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Cultural heritage project presented in Baku
10 July 2014 [10:56] -
Baku hosted a presentation of a project called "Support for conservation and development of the cultural heritage of Azerbaijan" by the Independent Research Center ELS.
The presentation was attended by prominent public figures and representatives of cultural and artistic fields.
The project, financed by the Council of State Support to NGOs under the president of Azerbaijan, presupposes publishing albums and compact disks of the winners of competition "New songs for children 2013", Head of the center Irada Yagubova said.
The collections will be distributed in kindergartens of Baku and Sumgayit.
The event also included discussions on preservation and promotion of cultural heritage, training of teachers and other issues.
During the discussions was raised the issues of provision of schools with musical instruments and other problems identified within the research.
In their speeches, Vice-Rector of the Baku Music Academy Gulnaz Abdullazade, Chairman of the Education Council Ajdar Agayev, composer, People's Artist of Azerbaijan Oktay Zulfuqarov, Representative of the Institute of Education's Problems Natig Akhundov spoke about the educational process, as well as inconsistencies in the textbooks.
Speakers noted that music lessons, shop classes and sports should not take the second place in schools' programs. Finally, some proposals were made to resolve the existing problems in this area.
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text:
|Publication number
|Publication type
|Application number
|Publication date
|Mar 27, 1984
|Filing date
|Jul 22, 1982
|Priority date
|Jul 22, 1982
|Fee status
|Also published as
|Publication number
|Balwant Singh, Laurence W. Chang, Peter S. Forgione
|Original Assignee
|American Cyanamid Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (5), Referenced by (40), Classifications (25), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
This invention relates to the manufacture of isocyanates and in particular provides a new route for the synthesis of tertiary aralkyl isocyanates and also provides a valuable class of urethanes useful in the production of tertiary aralkyl isocyanates.
Isocyanates having an isocyanato group attached to a tertiary aliphatic carbon atom also having aromatic substituents, for example, meta- and para- tetramethylxylylene diisocyanates, are particularly useful for reaction with a wide variety of polyols to give urethane polymers which can be either rigid or flexible and which can be endowed with a wide variety of properties. Such urethane polymers can be formed into rigid and flexible foamed articles, sheets, high density sheets and articles of various shapes. The light stability of these urethane polymers makes them extremely useful in surface coatings and other applications where light stability is desirable, e.g. light stable RIM elastomers.
Such tertiary aralkyl isocyanates have been prepared by a variety of different reactions, such as by the phosgenation of corresponding organic amines, by reaction of corresponding olefins with isocyanic acid (U.S. Pat. No. 3,290,350), by reaction of the corresponding halides with an alkali metal isocyanate (U.S. Pat. No. 4,130,577) and by reaction of the corresponding halide with isocyanic acid (copending applications Ser. No. 333,696, filed Dec. 17, 1981, U.S. Pat. No. 4,361,518 Ser. No. 335,945 filed Mar. 8, 1982).
These various processes are diadvantageous for one or more of a variety of reasons, such as that the materials are difficult to handle or are corrosive, the yields are poor, expensive reactants are required and the products are difficult to recover.
It is an important object of this invention to produce such tertiary aralkyl isocyanates utilizing non-corrosive, low-cost starting materials in a simple process yielding the desired isocyanates whereby they are readily recovered and purified. In accordance with this invention the manufacture of a tertiary aralkyl isocyanate is by the preparation of the corresponding tertiary aralkyl carbamic acid ester of a lower aliphatic alcohol followed by the thermal cracking of such urethane to form the isocyanate and the free alcohol.
Since the esters of carbamic acid, such as methyl carbamate, the esters of substituted carbamic acids, such as the dimethyl ester of α,α,α'α'-tetramethylxylylene dicarbamic acid, and the polymers of poly isocyanates with polyols are all properly called urethanes, for the sake of clarity, herein an unsubstituted carbamic acid ester will be called "carbamate" or "carbamic acid ester;" a substituted carbamic acid ester will be called "urethane," "monourethane," "diurethane," "polyurethane" or "urethane ester;" and the polymers will be called "urethane polymers."
Urethanes which are useful in forming tertiary aralkyl isocyanates by thermal cracking in accordance with this invention are generally designated by the formulae: ##STR1## wherein R is an alkyl radial having from 1 to 18 or more carbon atoms; R1 is an alkyl radical having from 1 to 3 carbon atoms; and R2 represents an aromatic hydrocarbon moiety such as phenyl, biphenyl and naphthalyl and such an aromatic hydrocarbon moiety having substituents including halogen atoms, methyl and methoxy groups and substituents such as: ##STR2## and wherein R3 is an alkylidene group having from one to three carbon atoms.
These urethanes, which themselves are an important part of this invention, are thus tertiary aralkyl urethanes in which R is a radical derived from an aliphatic alcohol, such as methanol, ethanol, isopropanol, 2-ethyl-hexanol-1 and n-octadecanol. Such alcohol is split off on thermal cracking of the urethane ester and can usually be recovered and recycled as discussed below.
The tertiary aralkyl urethane esters of this invention can be prepared, for example, by reaction of the carbamic acid ester of a lower aliphatic alcohol and an olefin, as for example, is disclosed in Belgian Pat. No. 625,748, granted Dec. 12, 1962. As set forth in that patent the reaction of the olefin and carbamate generally proceeds at moderate temperatures in the presence of an acid catalyst.
The urethane esters of this invention are converted to the corresponding tertiary aralkyl isocyanates by thermal cracking. Yields are good, and alcohol recovery and removal are particularly high where the aliphatic alcohol group of the initial carbamic acid ester is methanol or other lower, preferably normal alcohol.
In accordance with this invention the preparation of the tertiary aralkyl urethane ester takes place at temperatures from 40� C. up to 150� C. in the presence of an acid catalyst, such as sulfuric acid, toluene sulfonic acid, dodecyl benzene sulfonic acid, hydrocarbon sulfate esters, hydrochloric acid, boron trifluoride and other Lewis and Bronstead acids. The reaction can take place in the absence of solvent or in the presence of solvents, such as methylene dichloride, toluene, xylene, chlorobenzene, and so forth.
Generally, the proportion of carbamic acid ester to olefin is in excess of stoichiometric. Preferably the carbamate is in substantial excess and functions as solvent and catalyst moderator as well as reactant. It is preferred in accordance with this invention to use from 50% to 800% stoichiometric excess of carbamate.
The amount of catalyst required to promote the addition of tertiary aralkyl olefin and carbamic acid ester is not critical and can be varied widely. Where substantial excess of carbamic acid ester is utilized the amount of catalyst, based on the olefin, is typically 0.01 and 10 mole% and preferably about 2 mole %.
Preferably the carbamate is heated mildly to maintain it molten, from 40� to 150� C. being preferred. The catalyst is dissolved in the molten carbamate, and the olefin is then slowly added. When the reaction is complete, the mixture is treated to remove or neutralize the catalyst. Unreacted carbamate ester is then removed by distillation.
Tertiary aralkyl urethane esters in accordance with this invention form the corresponding isocyanate by thermal cracking while splitting off the alkanol. In many cases the alcohol can usefully be recycled by reaction with urea or isocyanic acid (HNCO) to form the starting carbamate ester. In addition to their utility in the formation of the corresponding isocyanates the tertiary aralkyl urethane esters of this invention may also be useful for other purposes. For example, some of these compounds are quite similar to known herbicides, and herbicidal activity is anticipated. The urethane esters of higher alkanols can also be used as blocked isocyanates in powder coatings and the like.
In cracking the urethane esters according to this invention to form the corresponding isocyanates the catalyst must be removed or neutralized for example, with calcium oxide, sodium carbonate, sodium hydroxide and the like, which is followed by cracking of the urethane ester either neat or in high boiling solvents, such as hexadecane, diphenyl ether, diisopropyl naphthalene and the like. Cracking takes place at temperatures on the order of 150� to 350� C. splitting off the alkanol to yield the corresponding isocyanate.
This invention has particular application in the production of tertiary aralkyl polyisocyanates from polyolefins and carbamic acid esters by addition of the reactants to form the corresponding polyurethane esters followed by thermal cracking of the polyurethane esters to the corresponding polyisocyanates. Polyolefin reactants which are contemplated include diisopropenyl benzenes (DIPEB), triisopropenylbenzene and diisopropenyl naphthalenes, all of which yield highly desirable polyisocyanates. The addition reaction can also be utilized with diolefins, such as a diisopropenylbenzene, to favor the production of a monourethane, such as isopropenyl-α,α-dimethylbenzyl urethane (TMU), which can be thermally cracked to the corresponding olefinic monoisocyanate, such as isopropenyl-α,α-dimethylbenzyl isocyanate (TMI).
The thermal cracking of tertiary aralkyl polyurethanes derived by an acid promoted addition reaction to form the corresponding isocyanates is particularly surprising in view of the instability of such urethanes in the presence of even a small amount of acid Polyurethanes, such as tetramethylxylylene diurethane (TMXDU) crack extensively in the presence of traces of acid to form monoisocyanates and other undesired products. It is, therefore, also a feature of the invention that the urethane esters are thermally cracked only after complete neutralization of the acid catalyst. By "complete neutralization" it should be understood that the amount of alkali or alkaline material, such as calcium oxide, sodium hydroxide, sodium carbonate or the like, is not just in excess of the stoichiometric quantity but is sufficient to bring the pH of the mixture substantially to 7 or higher. Neutralization should be carried out before recovery steps, such as removal of the excess carbamic acid ester after which the urethane ester can be cracked.
The following Examples illustrate the preparation of urethane esters in accordance with this invention and the utilization of such esters in the preparation of isocyanates useful in preparation of polyurethanes.
A mixture containing 28.76 g (383.10 mmoles) of methyl carbamate, 8.8 ml of 1.08 M p-toluenesulfonic acid (9.50 mmoles) in toluene solution and 40 ml of methylene chloride was stirred at 45� C. until all solid was dissolved. Meta-diisopropenyl benzene (m-DIPEB) (15.19 g, 96.1 mmoles) was then added dropwise into the solution. After stirring at 45� C. for 22 hours, the reaction mixture was cooled to room temperature, washed with 10% aqueous sodium carbonate solution, and the organic layer dried over sodium sulfate. Analysis by GLC (heneicosane, C21 H44, internal standard) indicates a 67% yield of α,α,α',α'-tetramethyl-meta-xylylene diurethane (m-TMXDU) and a 20% yield of the methyl ester of m-isopropenyl-α,α-dimethyl-benzyl urethane (TMU).
Concentration of the resulting methylene chloride reaction mixture was carried out at reduced pressure. An equal volume of hexane was then added to precipitate the dimethyl ester m-TMXDU, giving a white solid which was collected by filtration (mp 128�-130� C.; yield: 44% m-TMU). The remainder of the m-TMXDU in the methylene chloride-hexane solution could be isolated by further evaporation of methylene chloride solvent, followed by the addition of more hexane to the oily residue.
To a flask containing 59.30 g (789.92 mmoles) of molten methyl carbamate (85� C. oil bath) was added 260 mg (2.6 mmole) of conc.sulfuric acid. The temperature of the oil bath was then lowered to 60� C., and 14.79 g (93.61 mmoles) of m-DIPEB added dropwise to the reaction mixture. The reaction mixture was stirred 60� C. for 4.5 hours, and 500 mg of anhydrous sodium carbonate added to neutralize the acid catalyst. The mixture was stirred at 60� C. for another 30 minutes and then distilled under the vacuum 95�/30 mm Hg) to recover unreacted methyl carbamate (44.05 g; >90% recovery). GLC analyses of the white residue showed that m-TMXDU and m-TMU were formed in 65% and 24% yields, respectively. The solid was then mixed with 50 g of hexadecane and 1.66 g of heneicosane (GLC internal standard), and the mixture cracked at 265� C. for 4 hours. GLC analyses indicated that α,α,α',α'-tetramethyl meta-xylene diisocyanate (m-TMXDI) (45%), meta-isopropenyldimethylbenzene isocyanate (m-TMI) (10%) and α,α,α',α'-tetramethyl-meta-xylene monourethane monoisocyanate (m-TMXUI) (3%) were formed based on the m-DIPEB.
To a flask containing 59.30 g (787.92 mmoles) of molten methyl carbamate (85� C. oil bath) was added 260 mg (2.6 mmoles) of concentrated sulfuric acid. The temperature of the reaction mixture was then lowered to 60� C. and 14.79 g (93.61 mmoles) of p-DIPEB added dropwise to the reaction mixture. The reaction mixture was stirred for 4.5 hours at 60�, and 1 g CaO added to neutralize the acid catalyst. The reaction mixture was stirred for another 30 minutes at 60� C. and distilled under vacuum (95�/30 mm Hg) to recover unreacted methyl carbamate (45.0 g; >90% recovery). GLC analysis of the residue showed that 69% p-TMXDU and 21% p-TMU had formed.
The resultant mixture was then cracked by the treatment described for the corresponding meta-compounds in Example 2. GLC analysis gave 62% p-TMXDI and 16% p-TMI based on the p-DIPEB.
By way of further examples of the thermal cracking of diurethane, a mixture containing 25.15 g of p-TMXDU (81.6 mmoles), 100 g of hexadecane and 14.25 g of heneicosane (an inert internal standard) was heated with stirring in a 265� C. oil bath in a slow stream of nitrogen. Methanol evolved was collected in a dry-ice acetone cold trap. Heating continued for 4 hours, and the reaction mixture analyzed with GLC and IR after cooling to room temperature. Both GLC and IR analysis confirmed the formation of p-TMXDI, p-TMXUI (mono-urethane-monoisocyanate) and p-TMI (mono-isopropenyl-monoisocyanate). GLC (internal standard method) indicated yields were 68%, 20% and 6%, respectively. The liquid collected in the cold trap weighed 4.57 g, and was mostly methanol, as indicated by IR analyses.
Although the preceding examples have been confined to urethanes produced by reaction of tertiary aralkyl olefins with methyl carbamate, urethanes which are esters of other lower alkanols, particularly straight chain alkanols, are useful in preparing isocyanates by thermal cracking following the procedures generally outlined above. A number of such urethane esters have been prepared and are described in TABLE I.
TABLE I__________________________________________________________________________EX. NO.URETHANE ESTER ALKANOL RESIDUE APPEARANCE__________________________________________________________________________ ##STR3## methyl white solid6 " ethyl white fluffy needles7 " n-propyl white needles8 " iso-propyl white powder9 " n-butyl white powder10 " 2-ethylhexyl white powder11 " cyclohexyl white powder12 ##STR4## methyl white crystalline powder13 " ethyl white needles (fine)14 " n-propyl fine white needles15 " iso-propyl white powder16 " n-butyl white crystals solid17 " benzyl white solid18 " n-octadecyl white solid19 ##STR5## methyl white solid20 ##STR6## methyl oil21 " ethyl oil22 " m-propyl oil23 " iso-propyl oil24 " n-butyl oil25 " benzyl oil26 " n-octadecyl white solid27 ##STR7## methyl white solid__________________________________________________________________________EX. NO. M.P., �C. NMR δ-VALUE (CDCl3) (60-MHz)__________________________________________________________________________5 182-184 1.6(12H,S,CH3);3.5(6H,S,O--CH3);5.1(2H,bS,NH); 7.25(4H,S,aro)6 159-160 1.15(6H,t J = 7Hz);1.64(12H,S);3.98(4H,q J = 7Hz); 5.05(2H,bs);7.30(4H,S)7 170-173 0.83(6H,t J = 7Hz);1.2-1.8(4H,m J ≃ 7Hz);1.65 (12H,S); 3.88(4H,t J = 7Hz);5.03(2H,bS);7.25(4H,S)8 196-197 1.12(12H,d J = 6.5Hz);1.65(12H,S);4.77(2H,septet J = 6.5Hz);4.97(2H,bS);7.30(4H,S)9 132-133.5 0.86(6H,t J ≃ 6Hz);1.0-1.8(8H,m),1.65(12H,S); 3.91 (4H,t J ≃ 6Hz);5.00(2H,bS);7.22(4H,S)10 97-98 0.86-1.8(30H,m);1.63(12H,S);3.86(4H,d J ≃ 4.5Hz); 5.00(2H,bS);7.25(4H,S)11 202-204 1.0- 1.9(22H,m);1.63(12H,S);4.5(2H,m);4.93(2H,bS); 7.23(4H,S)12 130-132 1.66(12H,S);3.55(6H,S);5.10(2H,bS);7.20(3H,m)7.33 (1H,m)13 101-103 1.14(6H,t J = 7Hz);1.64(12H,S);3.97(4H,q J = 7Hz); 5.02(2H,bS);7.15(3H,S);7.30(1H,m)14 94-95.5 0.83(6H,t J ≃ 6.5Hz);1.2-1.8(4H,m);1.63(12H,S ); 3.85(4H,t J ≃ 6.5Hz);4.98(2H,bS);7.13(3H,m);7 .28(1H,m)15 105-107.5 1.12(12H,d J ≃ 6Hz);1.63(12H,S);4.73(2H,septe t); 4.93(2H,bS);7.12(3H,m);7.27(1H,m)16 64-66.5 0.86(6H,t J ≃ 6Hz);1.1-1.8(8H,m);1.64(12H,S); N 3.90(4H,t J ≃ 6Hz);4.98(2H,bS);7.17(3H,m);7.2 7(1H,m);17 82-8418 47-4919 56-57 1.65(6H,S);2.12(3H,dd J1 ≃ 1.6,J2 = .8Hz);3.53(3H,S); 4.97(IH,dq J1 ≃ J2 ≃ 1.6Hz);5.05(1H,bS);5.25(1H,dq J1 ≃ 1.6,J2 ≃ 0.8);7.25(4H,S)20 bp 115 at 1mm 1.55(6H,S);2.05(3H,dd);3.45(3H,S);4.95(1H,dq); 5.25(1H,bS);5.65(1H,dq);7.16(3H,m);7.40(1H,m)21 -- 1.13(3H,t J = 7z);1.64(6H,S);2.10(3H,dd);3.95 (2H,q J = 7Hz);4.97(1H,dq);5.03(1H,bS);5.20(1H,dq): 7.13(3H,m);7.32(1H,m)22 -- 0.82(3H,t J - 7z);1.2-1.8(2H,m);1.65(6H,S);2.10 (3H,dd);3.85(2H,t J = 7Hz);4.97(1H,dq);5.02(1H,bS); 5.20(1H,dq);7.14(3H,m);7.30(1H,m)23 -- 1.12(6H,d J ≃ 6Hz);1.63(6H,S);2.12(3H,dd J ≃ 1.6 J2 ≃ 0.8;4.74(1H,septet);4.98(1H,dq J1 ≃ J2 ≃ 1.6); 5.03(1H,bS);5.23(1H,dq J1 ≃ 1.6,J2 ≃ 0.8);7.17(3H,m); 7.35(1H,m)24 -- 0.85(3H,t);1.1-1.8(4H,m);1.65(6H,S);2.12(3H,dd); 3.90(2H,t);4.97(1H,dq);5.10(1H,bS);5.23(1H,dq); 7.17(3H,m);7.23(1H,m)25 --26 78-8127 177-178 7.50(bm,3,Ar),5.15(bs,1,NH),3.52(S,3,OCH3,1.70 (S,6,CH3)__________________________________________________________________________
In Table I the urethane esters of alkanols other than methanol were prepared by reaction of the alkanol and the corresponding isocyanate, rather than by the addition reaction of carbamate ester and olefin. The addition reaction can, however, be employed to prepare these urethanes also. Yields of diurethanes are not as good as yields of monourethanes. The yields also are reduced as higher alkanols are used. Yields are generally better with normal alkanol esters of carbamic acid.
In a commercial processing arrangement the olefinic monourethane product TMU can be recycled with DIPEB in addition reaction with methyl carbamate. The two urethanes TMXDU and TMU are difficult to separate, however; and recycle of the TMU is not practicable. The thermally cracked product of the monourethanes, the isopropenyl monoisocyanate TMI, moreover, can not be recycled directly as it will not react with methyl carbamate under the reaction conditions for DIPEB and carbamate ester. Nevertheless, where this product is not desired for other purposes it can be reacted with methanol to reform the isopropenylmonourethanne TMU for recycle with DIPEB. The monourethane-monoisocyanate product of the thermal cracking stage can, of course, be recycled for additional thermal cracking. The following are Examples:
m-DIPEB was slowly added to molten mixture of methyl carbamate (mc) and concentrated sulfuric acid maintained at 60� C. (mole ratio of m-DIPEB: MC: H2 SO4 =1:8:0.025, respectively) After the addition of DIPEB, the reaction mixture was stirred for 4-5 hours, and 300% mole excess solid sodium carbonate relative to sulfuric acid was added to basify the mixture. The mixture was stirred at 60� C. for a half hour more and the reaction mixture vacuum distilled (approx. 80�/20 mm.) to recover unreacted methyl carbamate (>90% recovered). To the distillate residue which contained m-TMU (24% yield) and m-TMXDU (65% yield) was added 10% by weight of finely divided CaO. The mixture was heated at 200� at 20 mmHg. for 90 minutes to crack the urethanes to m-TMXDI and m-TMI. At the end of the cracking cycle, the vacuum was decreased to 10 mm and m-TMXDI and m-TMI collected by fractional distillation.
The m-TMI collected was recycled as described above, by first converting it to m-TMU by reaction with methanol.
A solution containing 34.2 g (170 mmoles) of m-TMI, 100 ml of methanol and 50 mg of dibutyltin dilaurate was heated with stirring in a 70� C. oil bath for 3 hours. The reaction mixture was then cooled to room temperature, and the excess methanol was removed at reduced pressure. The residue, an oil, was distilled under vacuum to yield 34.2 grams of m-TMU (bp 115� C., 1 mm Hg).
m-TMU 5 g (22 mmoles) was slowly added to a molten mixture of methyl carbamate (13.2 g; 176 mmoles) containing 0.26 g (2.6 mmoles) of concentrated sulfuric acid at 70� C. The mixture was heated for three hours at 70�, and analyzed by GLC in the usual manner. Analysis showed an 84% yield of m-TMXDU with 15% m-TMU unreacted.
To a molten mixture of 20.0 g (266.4 mmoles) of methyl carbamate and 100 mg (1 mmole) of conc. sulfuric acid maintained at 65� C. (oil bath) was added 5.2 g (32.9 mmoles) of m-DIPEB and 2.4 g (10.3 mmoles) of m-TMU. After the addition was completed, the reaction was stirred at 65� C. for 3 hours. and analyzed by GLC. Analysis indicated that the area percent ratio of m-TMXDU to m-TMU was the same as that observed in the m-DIPEB-methyl carbamate reaction (4˜5:1). The yields of m-TMXDU and m-TMU were 72 and 18% respectively.
A processing arrangement for production of TMXDI based on the preceding examples, particularly 29-31, is illustrated in the accompanying drawing which is a flow diagram.
As shown in the drawing, there are four basic steps involved in the production of TMXDI from DIPEB and the methyl ester of carbamic acid. These are the addition reaction of the carbamate and diolefin, indicated by the reference numeral 10; neutralization of the acid catalyst with base, indicated by the reference numeral 20; stripping of the methyl carbamate, indicated by the reference numeral 30; and thermal cracking of the resultant urethanes to TMXDI and other products, indicated by the reference numeral 40.
In this process the two basic ingredients, DIPEB and methyl carbamate are introduced at addition step 10, as indicated by flow lines 11 and 12. Catalyst, such as sulfuric acid, is also introduced as indicated by the reference numeral 13. Recycled TMU subsequently formed during the process is, as shown by flow line 15, is also introduced at addition step 10.
The product of olefin addition step 10 is admixed with base, such as sodium carbonate in the neutralization step 20, as indicated by flow lines 21 and 22 respectively. The neutralized material, as indicated by flow line 31, is then stripped of methyl carbamate at step 30 to recover methyl carbamate which via line 14 is recycled to addition step 10 with make-up methyl carbamate indicated by line 16. After stripping the methyl carbamate, the product as indicated by flow line 41 consisting basically of TMXDU, TMU and polymerized material, is then treated at cracking step 40. TMI and methyl alcohol are recovered in cracking step 40 as indicated by the flow lines 51 and 52, respectively. The desired product TMXDI is recovered from cracking step 40 as indicated by flow line 43, and still bottoms from cracking step 40 are indicated by flow line 44.
To the extent by-product TMI can not be used as such it is reacted with the recovered methanol by a process 50 such as described in Example 29 to convert the olefinic TMI to TMU, which then is recycled to the addition step, as indicated by flow line 15, for further reaction with methyl carbamate.
An important aspect of the recycle of TMU is that the product distribution in olefin addition step 10 is not affected by the presence of the added olefinic TMU. Thus the recycle of TMI as TMU greatly improves the efficiency in conversion of DIPEB to TMXDI.
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|U.S. Classification
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|International Classification
|Cooperative Classification
|European Classification
|Jul 22, 1982
Owner name: AMERICAN CYANAMID COMPANY, 1937 W. MAIN ST., STAMF
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:SINGH, BALWANT;CHANG, LAURENCE WU-KWANG;FORGIONE, PETERSALVATORE;REEL/FRAME:004077/0093
Effective date: 19820720
|Apr 2, 1985
|Certificate of correction
|May 4, 1987
|Fee payment
Year of fee payment: 4
|Aug 28, 1991
|Fee payment
Year of fee payment: 8
|Aug 24, 1995
|Fee payment
Year of fee payment: 12


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From Comcast SportsNet DeSean Jackson got his wish after all. Jackson agreed to a five-year contract with the Philadelphia Eagles on Wednesday. The deal is worth 51 million, a person familiar with the negotiations told The Associated Press on condition of anonymity because terms weren't officially announced. The two-time Pro Bowl wide receiver already was tagged as the franchise player, meaning he would've earned at least 9.4 million next season. Now, he gets the long-term security he sought last year. Jackson held out last training camp because he wanted an extension and let the contract situation affect him. He was deactivated for a game for being late for a team meeting, dropped more passes than usual and his production dropped. But the Eagles are counting on Jackson to be the dynamic player he was in 2009-10. "We are thrilled to be able to keep one of the NFL's top playmakers in Philadelphia," Eagles coach Andy Reid said. "DeSean is a game breaker. He has the speed and ability to score from anywhere on the field, and he has proven himself to be a big threat for our offense." Philadelphia stumbled to an 8-8 season last year, but closed with four consecutive victories, building momentum for 2012. The Eagles finished, despite a 4-8 start, just one game behind the New York Giants, who not only won the NFC East, but also the Super Bowl. Jackson has career totals of 229 receptions, 4,085 yards and 21 touchdowns in four years as an Eagle after being drafted out of Cal. He also has three rushing scores and a franchise-record four punt return touchdowns, as well. "Signing our own players was a big priority for us this offseason," Reid said. "And DeSean was certainly high on our list. We are very excited about his future as an Eagle." Jackson, 25, was named to the Pro Bowl following the 2009 and 2010 seasons, and is one of five players in NFL history to at least 900 yards receiving in each of his four seasons. Earlier in the day, defensive end Trent Cole and the Eagles agreed on a four-year contract extension through 2017, and on Tuesday, offensive tackle Todd Herremans agreed to a three-year contract extension through 2016. The Eagles also made a couple of roster moves, trading offensive lineman Winston Justice to Indianapolis and releasing former starting center Jamaal Jackson. Cole is a two-time Pro Bowl selection who ranks third on the team's all-time list for sacks with 68. He had 11 sacks in 2011, his fourth season with a double-digit total. "Trent plays the game with a level of tenacity that's hard to replicate," Reid said. "He's one of the premier defensive ends in the league." While Jackson's contract situation was somewhat contentious, Cole and Herremans never said a word about it. "I think that with Todd and me, we conducted business professionally, the way it's supposed to be conducted," Cole said. "We never went out to the media and complained. We did what we had to do to keep moving and we didn't cause any problems with the team and this atmosphere." With the key returnees, there's a feeling -- inside the organization, at least -- that Philadelphia will return to its status as a perennial playoff team in the NFC. "As the season went on, we started coming together a lot more and it showed by us winning our (last four) games," Herremans said. "We really feel that we don't need any extra pieces brought to us in free agency. We feel that the team we have in the locker room can make a great run and go to the Super Bowl next year." The Eagles spent plenty of money in free agency last year, signing several players with high pedigrees. They were expected to contend for the Super Bowl, and had to play under the "Dream Team" label that was attached to them by backup quarterback Vince Young, one of those high-priced signings that didn't pan out.
Quotes, notes and stars: Wright "today was tough"
Quotes, notes and stars: Wright "today was tough"
Quotes, notes and stars from the Red Sox' 10-3 loss to the Rangers:
* "On a night when he didn't have the consistency to the knuckleball that we've seen from many of his starts, he went to his fastball a little bit more. [Against] a good fastball hitting team . . . He's typically made good adjustments staying over the rubber to get his release point out front -- that wasn't the case [tonight]." John Farrell said about Steven Wright struggling with his knuckleball in his 4.2 inning outing.
* "The ball was spinning a lot out of my hand. It was a little bit hard to grip the ball because the humidity. But it was the opposite -- it was real sticky. That's the first time I've had that ever. But I still felt like I should have figured that out. It was one of those things where I think I started trying to hard . . . I was trying to the throw the kitchen sink at them but it wasn't working." Steven Wright said about struggling to find his knuckleball in the 10-3 loss.
* "It's hard for me because you want to go out there and try and go as deep as you can to try to help the bullpen, but, you know, today was tough, a tough day for me." Wright said on his disappointment with only going 4.2 innings.
* Hanley Ramirez laced his fourth homerun in his last 11 games. In his nine career games at Texas, Ramirez has six homeruns.
* David Ortiz went hitless for the first time since June 12th. Boston's designated hitter also hasn't hit a home run since June 17th -- his third longest homerless spell of 2016.
* Xander Bogaerts scored his 57th run of the season, putting him one run behind Ian Kinsler -- the fourth highest total in the majors.
1) Adrian Beltre
The ex-Red Sox third baseman finished 2-for-4 with an RBI, a walk -- scoring the team high three runs.
2) Ian Desmond
Desmond laced his 13th homer of the season in his second at-bat of the game, sparking Texas' offense with its first run of the game.
3) Elvis Andrus
Andrus ended Steven Wright's day quickly with a three-run triple in the fifth inning, finishing 1-for-2 with two walks and a run.
First Impressions from Boston's 10-3 loss to Texas
First Impressions from Boston's 10-3 loss to Texas
First impressions of the Red Sox 10-3 loss to Texas:
Steven Wright can't be stellar every night.
Although it's seemed like it lately, it's just not possible -- especially with a knuckleball.
He wasn't even that bad Saturday night. He just didn't get any help from his defense in the fifth frame.
But there's no denying he didn't have his best stuff. But whatever the reason, he couldn't find consistent command or movement from his knuckler and he gave up some hard hits as a result.
Did he receive a fate worse than he pitched? Yes. But what Boston saw from Wright in his Saturday start is there will be times his go-to pitch is off -- and there's really no way to work around that.
Hanley Ramirez's "timing issue" seems to be coming around.
Although he hasn't necessarily caught fire, Ramirez hit another home run -- once again to right field.
He's shown more patience at the plate, and not trying to pull every ball out of the yard.
Ramirez doesn't have everything completely figured out, but his homeruns have been plenty valuable at this point.
Ian Desmond is no joke.
The newly converted centerfielder is 5-for-10 against Boston pitching this series with a run and two RBI.
The ex-Nationals shortstop has good pop and good speed still. He seems to be a lot more comfortable in his new home after hitting .233 for Washington last year with 19 homeruns -- hitting his 13th Saturday night.
For all the criticisms Boston's bullpen has received, the Rangers' is definitely worse.
Although there wasn't the same miraculous comeback witnessed Friday night -- and Boston's pen wasn't particularly stellar in the loss -- the Ranger relievers did not look good in the second game of the series.
They put themselves into deep counts right away -- and was lucky Boston's offense was off.
Boston's bullpen has its faults -- no question -- but it's not nearly as bad as the one in Texas.
The Red Sox unfortunately have to rely on Clay Buchholz Sunday.
The bullpen is beaten down once again. The righty is still fighting for his job, so this would be the best time for him to pitch competitively into the sixth inning -- and maybe even longer.
DC United tops Revolution 2-0
DC United tops Revolution 2-0
WASHINGTON -- Lamar Neagle had a goal and an assist to give D.C. United an early lead that stood up in a 2-0 victory over the New England Revolution on Saturday night.
D.C., after being shut out in its two previous games and four of six, opened the scoring in the 20th minute when Luciano Acosta chipped a perfect pass over the defense to the foot of Neagle, who volleyed it in from 10 yards out.
Sean Franklin scored the second goal, his first of the season, when he knocked in Neagle's cross. Albaro Saborio sent a long ball down the right sideline that Neagle ran down and crossed to Franklin for the easy counter.
D.C. (5-6-5) leapfrogged the Revolution (4-5-7) into fifth in the Eastern Conference with its fourth shutout in the last seven games and improved to 2-0-1 in the series this season.


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Matterhorn Boots: Waterproof Steel Toe Chainsaw Boots 12277
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Whether you're a First Responder at a tragic disaster site or a logger doing your Paul Bunyan thing, you'll appreciate the protection (and comfort) provided by these Matterhorn 12277 Chainsaw Boots. We can count at least six degrees of protection: 1) The biggi ... (see full details) (see specifications) #MTH12277.
Matterhorn Boots: Waterproof Steel Toe Chainsaw Boots 12277
Whether you're a First Responder at a tragic disaster site or a logger doing your Paul Bunyan thing, you'll appreciate the protection (and comfort) provided by these Matterhorn 12277 Chainsaw Boots. We can count at least six degrees of protection:
1) The biggie, of course, giving this boot its name, is provided by seven layers of Kevlar for cut-resistant saw jamming. Kevlar is flame-resistant (uh-oh, another protection slipped in there for free), and is 5 times stronger than steel on an equal weight basis.
2) The stainless steel bottom plate is not for sneaky second helpings at the buffet, but meets national standards for puncture resistance. This means you could step on a rusty nail and it wouldn't pierce through to your foot if you weigh 270 pounds or less.
3) The toe cap on this Matterhorn 12277 extravaganza also meets national ASTM standards for impact resistance, so a piece of lumber or concrete dropping on your foot doesn't mean certain injury.
4) The steel toe cap also provides resistance to compression, so your toes are protected from up to 2500 pounds of pressure. Crazed forklift drivers become less of a hazard.
The Goodyear Welt Construction and Vibram Kletterlift sole combine to protect you from falls. This type of construction give the best kind of lateral stability because the sole is slightly larger than the boot. The Vibram sole's center star lug pattern and perimeter lugs deliver a great all-around combination of traction and stability.
5) Rain and its consequence will not slow you down due to the water-resistant 10-inch full-grain uppers and the Gore-Tex bootie. This lining guarantees no water will get in to make you uncomfortable.
6) Sweaty, clammy feet are warded off by the abrasion-resistant Cambrelle lining that works like a blotter-it can absorb 350% of its weight in water without feeling damp!
A "Scuffy High Abrasion Tip" (hey, we didn't make up the name) helps prolong the life of these boots, a leather collar minimizes irritation on your calf (along with the possibility of debris falling into you boot), and a removable midsole helps avoid uncomfortable foot shock as you jump down from elevated areas.
If you've been following along, you may realize there are actually more than six types of protection in these Matterhorn 12277 Waterproof Steel Toe Chainsaw Boots. However, those will not be on the final exam The final test is really up to you. What do you want on your feet when you're in a hazardous environment? We're betting you've found the answer right here.
Sizes Manufactured: Medium/Wide 7-12,13,14,15 (This medium/wide width is designed to accomodate regular and wide width feet.)
Detailed Product Specifications
Additional Product Features
- Discontinued
- Puncture Resistant
Customer Reviews For Matterhorn Boots: Waterproof Steel Toe Chainsaw Boots 12277
John Joblin
RJ Cutter Tree Care
I just wanted to get back to you folks and tell you how pleased I was with the service (and respect) I recieved from the Customer Service Agent who took and placed my order. It is now the riding season and Engineer style MC's are becoming more and more difficult to come by. Your Customer Service Agent was patient and kind to me. She researched the actual boot itself and compaired it to another very similar model. She then researched warehouse inventory and availability, as well as investigating how the sizes worked for that particular boot manufacturer. The information she provided me helped me to make - what I now consider - to be a very sound size decision. Great job!!!!!!! I look forward to getting my new boots."
Kevin H. from Kent, Conneticut