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ebaying unopened christmas presents
(82 Posts)Message withdrawn at poster's request.
It's a scam
There won't be anything in the boxes
I saw some which were still wrapped so only a fool would pay for that!
really? as in still in the wrapping paper unopened? bizzare
Here's one. It's odd that they are all in the same paper, no?
See what else the seller has listed
It's a scam
Message withdrawn at poster's request.
This happens every year. Starts xmas day, with the story of my boyfriend finished with me so here are the presents he bought me blah blah.
Pile of shite in it I expect. And not one of them is unopened. They have beenopened and re-wrapped cos they are shite!
It would be quite exciting, if no one bought you anything it would be nice to have something to open that you had no idea what was in them!
Pound shop junk I'd guess
I've reported her. Hope other people do too
It's a scam and it goes;
Pop to the pound shop.
Buy tat.
Wrap in shiny paper.
Write vague listing making no promises of contents.
There can be no comebacks as there is no promise that the boxes contain anything, literally, they could be empty boxes and you couldn't complain as the seller has stated 'I don't think you'll be disappointed'
I doubt ebay will do anything about it. There are hundreds of these people doing exactly the same on there. And ebay wont care cos it's more money for them.
What sort of numpty bids £31 on this stuff?
Funny how the shapes of the boxes are the same in pictures 1 and 3. Pound shop special I think!
WTF? 30 odd quid and they are not even nicely wrapped ... shitty cheap looking paper too
Why are they Going for so much money though? £30 for what could be essentially empty boxes.
what utter madness!
You're wondering about £30?
Have a look in completed listings
A fool and his money...
There's one on there for £70, with a story about how generous her ex is and if he buys jewellery it will be white gold... why do I never think of these things?!
Shame you can't see the bidders like the old days because I can bet they are all bidding themselves up with other accounts, then some fool thinks it must be good, comes in with a generous bid and ends up with a load of shite through the post.
Surely that £1k+ bid is from someone taking the piss?!
Message withdrawn at poster's request.
Message withdrawn at poster's request.
1k one is probably someone
Who knows its a scam taking the piss
All those eBay presents where the same shape, obvious scam.
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Wednesday, September 09, 2015
Inside Crochet Issue 69
Hello, It has been awhile since I have updated my blog .Time seems to be flying by .I am knee deep in yarn. I am either designing or pattern writing, as well as sewing in all those pesky yarns ends .Its hard for us all trying to juggle all these hats we all have to have.
This months Inside crochet is out now. If you scroll down the link page you will see thumbnails of all this months patterns.
My Gaudi cowl is one of the published patterns. Inspired by my love of textured architecture. One of my favourite buildings is the stunning Sagrada Familia Cathedral - by Gaudi in Barcelona.
The cowl uses Sublime Yarns Baby Cashmere Merino Silk DK .
This wonderful Knight is by the wonderfully talented Annilies baes. I really want to make one for my little grandson. I have never in all the time I have been crocheting made a toy, but when I saw this I knew he simply must have one.
There are so many patterns I love in this months mag . this great slouchy hat by Simone Francis, is the perfect shape for me. I wear a lot of hats I find a slouchy hat perfect.
I adore crocheted socks and these welly socks by Vicky Brown are perfect for those colder months ahead. Do check out the magazine I am sure there will be something that tickles your fancy.
I am off to put my cooks hat on dinner needs to be made .
Have a lovely day whatever hat you put on.
All images are copyright by Lucy Williams
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Effects of Motivating People With Schizophrenia to Exercise
- Full Text View
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- Disclaimer
- How to Read a Study Record
Condition | Intervention |
Schizophrenia |
Behavioral: Motivational group sessions Other: Time and attention control group sessions |
Study Type: | Interventional |
Study Design: | Allocation: Randomized Intervention Model: Parallel Assignment Masking: Single Blind (Investigator) Primary Purpose: Treatment |
Official Title: | Motivating Persons With Schizophrenia to Exercise |
- Exercise group attendance [ Time Frame: Measured at Week 16 ]
- Exercise group persistence [ Time Frame: Measured at Weeks 4,8, 12 & 16 ]
- Exercise group compliance [ Time Frame: Measured at Weeks 4,8,12 & 16 ]
- Exercise attitude [ Time Frame: Measured at Weeks 4,8,12 and 16 ]
Enrollment: | 80 |
Study Start Date: | November 2007 |
Study Completion Date: | August 2009 |
Primary Completion Date: | August 2009 (Final data collection date for primary outcome measure) |
Arms | Assigned Interventions |
Experimental: 1
Exercise information group
Behavioral: Motivational group sessions
Motivational group sessions include 4 weeks of weekly 1-hour exercise information sessions.
Active Comparator: 2
General health information group
Other: Time and attention control group sessions
Time and attention control group sessions include 4 weeks of weekly 1-hour general health information sessions.
Detailed Description:
Schizophrenia is a chronic brain disorder that affects about 1% of Americans. People with schizophrenia experience extreme paranoia, often claiming that they hear voices not heard by others and that others are invading or controlling their minds with the intent to hurt them. More specific symptoms include hallucinations, delusional behaviors, disordered movements, and decreased ability to comprehend and apply information to everyday activities. The severity of these symptoms makes self-care and regular exercise difficult for people with schizophrenia. The fatality rate from diabetes, heart disease, and other obesity-related illnesses is significantly higher in people with schizophrenia. Exercise is known to reduce health problems associated with obesity, yet few studies have encouraged exercise as a treatment method for improving the health of those with schizophrenia. Furthermore, the long-term physical and mental effects of consistent exercise on people with schizophrenia are not well-known. This study will evaluate the impact of motivational guidance to exercise on people with schizophrenia, based on their attendance, persistence, and compliance to a walking program.
Participants in this study will be randomly assigned to one of two groups. Both groups will continue their regular medications and treatments throughout the study. Upon entry, members of both groups will complete the same two forms concerning attitudes toward exercise. Group 1 participants will attend weekly 1-hour exercise information sessions for 4 weeks. Group 2 participants will attend weekly 1-hour general health information sessions for the same 4 weeks. Participants of both groups will then take part in identical 16-week walking programs. The walking program will consist of three 30- to 50-minute walks per week, including 10 minutes of warm up and 10 minutes of cool down stretching. All participants will gradually increase their walking time from 5 minutes to 30 minutes during the program. At the completion of the walking programs, participants of both groups will complete repeat forms about their attitudes toward exercise. There will be no follow-up visits for the participants.
Ages Eligible for Study: | 22 Years and older (Adult, Senior) |
Sexes Eligible for Study: | All |
Accepts Healthy Volunteers: | No |
Inclusion Criteria:
- Meets DSM-IV criteria for schizophrenia
- Speaks English
- Stable medication regimen
- Able to receive medical clearance for moderate exercise
Exclusion Criteria:
- Hospitalized within 1 year of study entry for angina, heart attack, or cardiac surgery
- Diagnosed with congestive heart failure
- Has a pacemaker
- Heart rate less than 50 bpm or more than 100 bpm at rest
- Uncontrolled hypertension
- History of spinal or hip fracture
- Unable to walk or move around without assistance
- Any other medical condition, in the opinion of primary care provider, that would prevent safe participation in the study
Please refer to this study by its ClinicalTrials.gov identifier: NCT00559572
United States, Tennessee | |
Helen Ross McNabb Center | |
Knoxville, Tennessee, United States, 37917 |
Principal Investigator: | Lora L. Beebe, PhD, PMHNP, BC | University of Tennessee |
Responsible Party: | Brenda Lawson, Compliance Officer, IRB Administrator, The University of Tennessee Knoxville |
ClinicalTrials.gov Identifier: | NCT00559572 History of Changes |
Other Study ID Numbers: |
R03MH079047 ( US NIH Grant/Contract Award Number ) |
Study First Received: | November 14, 2007 |
Last Updated: | January 14, 2013 |
Keywords provided by The University of Tennessee, Knoxville:
Exercise Group Counseling Obesity |
Additional relevant MeSH terms:
Schizophrenia Schizophrenia Spectrum and Other Psychotic Disorders Mental Disorders |
ClinicalTrials.gov processed this record on March 27, 2017


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Milwood Branch
Milwood Branch
Monday - Thursday: 10:00 am - 9:00 pm
Friday: 10:00 am - 6:00 pm
Saturday: 10:00 am - 5:00 pm
Automated Laptop/Electronic Device Checkout Kiosk
Try out the new automated laptop and electronic device kiosk at the Milwood Branch. Customers who have a Library Card in good standing can use the kiosk to check out a Chromebook, Ultrabook, MacBook Air or iPad for up to two hours for use inside the Library building.
About the Milwood Branch
When the Milwood Branch of the Austin Public Library celebrated its grand opening on July 26, 1997, the event was not only considered a triumph, but also the end of a long road – for both the Milwood community and the Austin Public Library. In the mid-1980s, concerned citizens and neighborhood organizations began lobbying for the much needed Branch in far North Austin. Their campaign continued into the 1990s until voters finally approved funds for the branch in the 1992 bond election. The Branch officially opened its doors to the public in 1997. The 8,266 square foot facility is situated on a beautiful wooded site of over seven acres. On those seven acres you will find Lori Norwood's sculpture, Learning to Fly, part of the Austin Art in Public Places program.
The Milwood Branch is located in Council District 7 of the City of Austin.
Events Listing
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General Information
Library Locations
- Faulk Central Library
- Austin History Center
- Carver Branch
- Cepeda Branch
- Hampton Branch at Oak Hill
- Howson Branch
- Little Walnut Creek Branch
- Manchaca Road Branch
- Milwood Branch
- North Village Branch
- Old Quarry Branch
- Pleasant Hill Branch
- Recycled Reads Bookstore
- Ruiz Branch
- St. John Branch
- Southeast Branch
- Spicewood Springs Branch
- Terrazas Branch
- Twin Oaks Branch
- unbound: sin fronteras
- University Hills Branch
- Willie Mae Kirk Branch
- Windsor Park Branch
- Yarborough Branch


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Friday, December 2, 2011
Vintage Inspiration Friday # 66 Toile, Plaid and the Winners!
64 comments:
Lots of beautiful things going on in your page Debra! Congratulations to Robin for winning! I knew I couldn't be the luckiest person in the world by winning your giveaway a second time around! I love the necklace that I won from you last time and keep wearing it! Still deciding what to use the lovely notebook for! Patsy from
HeARTworksHi Debra... oooh, your tree is so pretty!... I too love toile and plaid, especially mixed together...can't wait to see what else you do... congratulations to your lucky winners!... and thanks for another peek from last weeks party... love to you, xoxo Julie Marie PS I have waited FOREVER for these parties of yours again... so of course I linked today!
ReplyDeleteSo funny, I have been working today on a tablescape with a plaid tablecloth with blue in it. I love the red, green and blue. I made a tree shirt out of one of the plaid fabrics you featured today. It is hard to find those now and how I wish I had bought the napkins to match. Anyway, we like so many of the same things. I always enjoy your posts. Have things scattered all over the house so I must get busy! Thanks for all your fun ideas.
ReplyDeleteHi Debra! I can't wait to see more of your Christmas decor next week!!! I am loving the toile especially! I used to have a pretty purple toile guest room before little guy #2 came long. I loved that room...but I love my little guy more. lol! Thanks for hosting today!
Best Wishes and Blessings,
AmandaHi Debra,
First of all, so excited to have won that darling bag! It will be perfect to hold my stitching projects that I'm working on. Can't wait to show it off to all of my friends!
I love toile and plaid. Your tree turned out so lovely. I like mixing things up a bit each year also. Thanks again!
WooHoo, I'm so excited I finally had my act together enough to post on VIF! I love your red toile & plaid. That pic of the sunroom from pinterest you showed has been in my inspiration file for ages. Love everything about it. Your home is so elegant but warm & cozy too. I love seeing how you decorate for each season. Thanks for hosting this party. It's the only one I make an effort to join.
LIsaThanks to a very dear friend, I LOVE the vintage look - AND I love using unique, personalized, and vintage Christmas tree ornaments on my tree. Thanks so much for a fun visit to your site to enjoy even more of these treasures. I've added you to my Christmas blog party roundup for the Sandwich Generation caregivers who aren't always able to get out and about for the holidays. Have a delightful week.
ReplyDeleteHi Debra! You know, I keep thinking about participating in Vintage Friday since I have a number of interesting items in my collections, but since I started school in September, I've barely been able to keep posts on - down to only two a week! Difficult to visit regularly, too - though I have been lurking . . .
So, I'm checking in here with my tree and my vintage angel on top - plus all things nostalgia. More vintage things to come this month, too! Loving all the inspiration with you - as always - and your sweet spirit. Thank you for hosting so many talented and inspiring decorators and collector!


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Blended iced coffee drinks are like chocolate milkshakes for grownups. Your favourite coffee shop puts coffee, ice and flavourings like chocolate syrup into a blender to mix the drink, and whipped cream is added on top. Making your own blended iced coffee at home would save time and money, and this simple recipe needs a few simple ingredients and a blender.
- Skill level:
- Easy
Other People Are Reading
Things you need
- 1 cup strong coffee
- 1/3 cup milk
- 1/4 cup sugar
- 1 squirt of chocolate syrup
- 1 cup ice
- Blender
- Whipped cream
Show More
- 1
Brew a strong cup of your favourite coffee. Let cool and put into the refrigerator for 20 minutes or freezer for 10 minutes.
- 2
Place coffee, milk, sugar, chocolate syrup, and ice into a blender. Turn onto high for one minute or until ice is finely crushed.
- 3
Pour your drink into a tall glass and add whipped cream on top.
Tips and warnings
- For a stronger coffee flavour, pour brewed coffee into an ice cube tray and use frozen coffee cubes instead of regular ice in this recipe. Experiment with different flavours and syrups to recreate your favourite coffee shop blended ice drinks. A high-quality blender crushes the ice better when making these drinks.
- Never stick anything hard, like a spoon, into the blender while it is working, and do not open the blender top while using. Use caution when brewing hot coffee.


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Pin It | |||||
Part Number:PSP-ISN1133 Item Size:5.875" x 9.125" | |||||
Sweet Blue Cupcake Invitations
This sweet flat white baby shower invitation looks good enough to eat! A background of brown, yellow and blue stripes and dots border the card next to a large chocolate cupcake with vanilla frosting, sprinkles and a cherry on top. A blue polka dotted ribbon ties the center of the cupcake together. Includes white unlined envelopes.
Ideal For:Baby Shower Invitations, Baby Boy Invitations
Delivery Time
To determine your delivery time, add the ground shipping time to your location, as shown on the map below, to the listed processing time. To speed up your delivery, you can select rush processing(details below in the form) and/or upgrade shipping to next day or second day air during the checkout process. If you have requested a proof, the processing time listed begins after you have approved your proof.
Processing Time:Approximately 2-3 business days
Ships From:North Carolina
Font Shown:Zipty Do
Font Color:Black
Paper Thickness:100# White Cover
Printing Method:Digital Press
Min. Order Quantity:10


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Stephen King's Dark Tower #6
November 2, 2013 1 Comment on Stephen King's Dark Tower #6
The Dark Tower Book 6: Song of Susannah by Stephen King King's magnum opus is not a series that you can jump into midway through, so if you've not read it, I suggest you start at the beginning. See my series of posts: Vol 1, Vol 2, Vol 3, Vol 4 and Vol 5 and find your starting point, don't read on. * * * * *… Read more »


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As residents of one of the world's most exciting and dynamic capital cities, our students have plenty to enjoy in their leisure time.
London has an incredible history stretching back to AD43 when it was originally founded by the Romans. Amazing architecture and centuries of history abound, from the imposing Tower of London and the Houses of Parliament to the numerous museums and art galleries. It is truly a world cultural centre, with a packed calendar of cultural events including London Fashion Week, and Frieze London, one of the world's leading contemporary art fairs.
It is a uniquely cosmopolitan city too, with over one in four Londoners having been born outside the UK. This makes for a wonderfully vibrant and tolerant society in which people of all creeds, backgrounds, orientations and interests can feel at home. It is no surprise that London is consistently voted one of the very best cities in the world in which to live.
To help our new students make the best of the leisure opportunities available to them we provide them with membership of International Students House, a social centre that specialises in providing social and leisure facilities for those new to London.


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After the success of Così fan tutte and The Marriage of Figaro, René Jacobs' CD recording of this centrepiece of the Mozart/Da Ponte trilogy offered us his reflections on Classical opera and garnered serious acclaim worldwide. Performed at the Innsbruck festival in August 2006 and filmed in Baden-Baden, this production is nourished by his thoughts on Don Giovanni as taboo-breaker but still respects Mozart's intentions as closely as possible.
In the documentary Looking for Don Giovanni, the director Nayo Titzin follows the creation of this production in the search for musical truth.
Thirty years after its publication, The Death and Life of Great American Cities was described by The New York Times as "perhaps the most influential single work in the history of town planning….[It] can also be seen in a much larger context. It is first of all a work of literature; the descriptions of street life as a kind of ballet and the bitingly satiric account of traditional planning theory can still be read for pleasure even by those who long ago absorbed and appropriated the book's arguments."


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Kids @ Work - A Lego Brick Building Club | |
Event Type: Children Age Group(s): Children Date: 2/4/2017 Start Time: 2:00 PM End Time: 3:15 PM Description: Build with the Library's Lego Bricks around our monthly theme or build something else of your choosing! Children under 8 must be accompanied by an adult. No registration is necessary
Library: Main LibraryLocation: James R. Garfield Room (Main - Lower Level) Contact: Mary Detling Presenter: Mary D |


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See Why Virginia Is For Lovers with our Hampton Romance Package
Enjoy a relaxing and romantic escape on the beautiful Hampton waterfront. Rendezvous under the stars in our rooftop pool, or stroll along the marina hand in hand. Enhance the romance with a bottle of sparkling champagne and chocolate-covered strawberries and breakfast for two at the Regatta Grill. Enjoy an intimate evening in a beautifully-appointed room, where breathtaking marina views inspire romance and togetherness on the Virginia coast.Our Special Includes:
- Marina View King Room
- Bottle of Champagne
- 2 Complimentary Breakfast Vouchers
- Chocolate-covered Strawberries


text: U.S. Grand Prix Formula 1 Track, Financier RevealedMatt Hardigree7/27/10 12:00pmFiled to: MotorsportsUs Grand PrixGrand Prixus formula 1Formula 1Formula OneRed McCombsTavo Hellmundus f1usf1AustinAustin Grand PrixTop1971EditPromoteShare to KinjaToggle Conversation toolsGo to permalink The mysterious circumstances bringing the U.S. Grand Prix to Austin, Texas and the location of the track were both revealed today. Big-bucks former Vikings/Saints owner Red McCombs will provide the funding, and the track will be out in the sticks. The selection of Austin as the home of the U.S. Grand Prix for the next ten years was a complete surprise to most — especially those in New York — and few could explain how an unknown event organizer named Tavo Hellmund could find the space or money to host such an event. We later learned the state of Texas was going to fork over $250 million over ten years, almost directly to F1 manager Bernie Ecclestone's coffers, a key part of the equation. But it wasn't until this morning we learned Red McCombs was going to be a major investor and "quarterback" of the event. McCombs currently runs the largest car-dealership network in Texas and, through a radio station startup, was a co-founder of Clear Channel Communications. The wealthy businessman is a major contributor to local schools in the area (the University of Texas's business school is the Red McCombs School of Business) and former owner of the Denver Nuggets, San Antonio Spurs, and Minnesota Vikings. Advertisement Advertisement His interest in this event, therefore, brings together two of his passions: sports and Austin.As for the site, the Austin American Statesman leaked the location this morning. It'll be in a a mostly undeveloped area ten miles southeast of downtown Austin called Elroy, north of FM 812 near the new Texas 130 toll road. Most of the 900-acre plot was purchased in 2007 with the purpose of eventually building a track.There's still a question of how what the neighbors will think about having an F1 track in their backyard (so far they seem happy it's not tract housing), and of how they can possibly build a track in less than two years. According to McCombs, Ecclestone asked the same question this morning, and the Texan businessman told him, "This is Texas." It's still a stretch, but all levels of government seem to be in line with this goal, including the superintendent of the local school district who was on hand and, one can imagine, counting the tax dollars. Organizer Hellmund also hinted at numerous other uses for the facility: conference, other racing, R&D offices, etc. Sponsored Rather than downplaying the plans for the F1 facility, everyone speaking at the event seemed to raise expectations. Everything's bigger in Texas, including the promises. Also pretty big? The disappointment if everything doesn't work perfectly.If you want tickets for the event at a track that hasn't been built yet, you can enter your information here at the newly unveiled F1 website. Advertisement Photo Credit: Paul Gilham/Getty ImagesReply197 repliesLeave a reply


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640 Vital Statistics. 25 Condition Alerts found.
Americana Dr / Patriot Dr median real estate price is $225,249, which is more expensive than 46.9% of the neighborhoods in Virginia and 59.3% of the neighborhoods in the U.S.
The average rental price in Americana Dr / Patriot Dr is currently $1,548, based on NeighborhoodScout's exclusive analysis. The average rental cost in this neighborhood is higher than 66.4% of the neighborhoods in Virginia.
Americana Dr / Patriot Dr is a densely urban neighborhood (based on population density) located in Annandale, Virginia.
Americana Dr / Patriot Dr real estate is primarily made up of small (studio to two bedroom) to medium sized (three or four bedroom) apartment complexes/high-rise apartments and townhomes. Most of the residential real estate is occupied by a mixture of owners and renters. Many of the residences in the Americana Dr / Patriot Dr neighborhood are older, well-established, built between 1940 and 1969. A number of residences were also built between 1970 and 1999.
In Americana Dr / Patriot Dr, the current vacancy rate is 3.6%, which is a lower rate of vacancies than 84.7% of all neighborhoods in the U.S. This means that the housing supply in Americana Dr / Patriot Dr is very tight compared to the demand for property here.
When you see a neighborhood for the first time, the most important thing is often the way it looks, like its homes and its setting. Some places look the same, but they only reveal their true character after living in them for a while because they contain a unique mix of occupational or cultural groups. This neighborhood is very unique in some important ways, according to NeighborhoodScout's exclusive exploration and analysis.
Did you know that the Americana Dr / Patriot Dr neighborhood has more South American and Iranian ancestry people living in it than nearly any neighborhood in America? It's true! In fact, 16.7% of this neighborhood's residents have South American ancestry and 3.3% have Iranian ancestry.
Americana Dr / Patriot Dr is also pretty special linguistically. Significantly, 7.7% of its residents five years old and above primarily speak Korean at home. While this may seem like a small percentage, it is higher than 99.4% of the neighborhoods in America.
The freedom of moving to new places versus the comfort of home. How much and how often people move not only can create diverse and worldly neighborhoods, but simultaneously it can produce a loss of intimacy with one's surroundings and a lack of connectedness to one's neighbors. NeighborhoodScout's exclusive research has identified this neighborhood as unique with regard to the transience of its populace. What is interesting to note, is that the Americana Dr / Patriot Dr neighborhood has a greater percentage of residents born in another country (54.8%) than are found in 98.6% of all U.S. neighborhoods.
The real estate in the Americana Dr / Patriot Dr neighborhood really stands out in the way it looks for a unique reason: this neighborhood has a higher proportion of apartment complexes or high-rise apartments than nearly every neighborhood in the country. Most neighborhoods are a mixture of real estate and housing types, but here it is almost entirely dominated by big apartment buildings and complexes. In fact, 83.7% of the real estate here is classified as apartment complexes or high-rise apartments, which is more than is found in 97.8% of American neighborhoods.
One of the really interesting characteristics about the Americana Dr / Patriot Dr neighborhood is that, according to NeighborhoodScout's exclusive research, it is an excellent choice in which to reside for college students. Due to its popularity among college students who already choose to live here, its walkability, and its above average safety from crime, the neighborhood is ideal for prospective or already-enrolled college students. Between semesters and during school breaks, you'll notice that the excitement here fluctuates with the college seasons. Despite the excitement however, parents of college-age children can rest easy knowing that this neighborhood has an above average safety rating. For each of these reasons, the neighborhood is rated among the top 2.8% of college-friendly places to live in the state of Virginia.
How wealthy a neighborhood is, from very wealthy, to middle income, to low income is very formative with regard to the personality and character of a neighborhood. Equally important is the rate of people, particularly children, who live below the federal poverty line. In some wealthy gated communities, the areas immediately surrounding can have high rates of childhood poverty, which indicates other social issues. NeighborhoodScout's analysis reveals both aspects of income and poverty for this neighborhood.
The neighbors in the Americana Dr / Patriot Dr neighborhood in Annandale are upper-middle income, making it an above average income neighborhood. NeighborhoodScout's exclusive analysis reveals that this neighborhood has a higher income than 65.9% of the neighborhoods in America. With 38.4% of the children here below the federal poverty line, this neighborhood has a higher rate of childhood poverty than 81.6% of U.S. neighborhoods.
A neighborhood is far different if it is dominated by enlisted military personnel rather than people who earn their living by farming. It is also different if most of the neighbors are clerical support or managers. What is wonderful is the sheer diversity of neighborhoods, allowing you to find the type that fits your lifestyle and aspirations.
In the Americana Dr / Patriot Dr neighborhood, 30.4% of the working population is employed in sales and service jobs, from major sales accounts, to working in fast food restaurants. The second most important occupational group in this neighborhood is executive, management, and professional occupations, with 29.0% of the residents employed. Other residents here are employed in manufacturing and laborer occupations (21.6%), and 19.1% in clerical, assistant, and tech support occupations.
Culture is the shared learned behavior of peoples. Undeniably, different ethnicities and ancestries have different cultural traditions, and as a result, neighborhoods with concentrations of residents of one or another ethnicities or ancestries will express those cultures. It is what makes the North End in Boston so fun to visit for the Italian restaurants, bakeries, culture, and charm, and similarly, why people enjoy visiting Chinatown in San Francisco.
In the Americana Dr / Patriot Dr neighborhood in Annandale, VA, residents most commonly identify their ethnicity or ancestry as Asian (27.7%). There are also a number of people of South American ancestry (16.7%), and residents who report English roots (4.4%), and some of the residents are also of Irania ancestry (3.3%), along with some Irish ancestry residents (3.2%), among others. In addition, 54.8% of the residents of this neighborhood were born in another country.
The languages spoken by people in this neighborhood are diverse. These are tabulated as the languages people preferentially speak when they are at home with their families. The most common language spoken in the Americana Dr / Patriot Dr neighborhood is English, spoken by 38.3% of households. Other important languages spoken here include Spanish, Vietnamese, Korean and Tagalog (the first language of the Philippine region).
How you get to work – car, bus, train or other means – and how much of your day it takes to do so is a large quality of life and financial issue. Especially with gasoline prices rising and expected to continue doing so, the length and means of one's commute can be a financial burden. Some neighborhoods are physically located so that many residents have to drive in their own car, others are set up so many walk to work, or can take a train, bus, or bike. The greatest number of commuters in Americana Dr / Patriot Dr neighborhood spend between 15 and 30 minutes commuting one-way to work (32.7% of working residents), which is shorter than the time spent commuting to work for most Americans.
Here most residents (74.2%) drive alone in a private automobile to get to work. In addition, quite a number also carpool with coworkers, friends, or neighbors to get to work (9.6%) and 9.5% of residents also ride the bus for their daily commute. In a neighborhood like this, as in most of the nation, many residents find owning a car useful for getting to work.
44 Vital Statistics. 3 Condition Alerts found.
136 Vital Statistics. 0 Condition Alerts found.
(100 is the most diverse)
67 Vital Statistics. 2 Condition Alerts found.
(100 is safest)
Violent | Property | Total | |
Number of Crimes | |||
Crime Rate
(per 1,000 residents) |
(100 is safest)
Index |
Index |
Index |
Index |
100 is safest |
100 is safest |
100 is safest |
100 is safest |
Crime | |
Americana Dr / Patriot Dr | 0.101011101001110 |
Annandale | 0.101011101001110 |
Virginia | 1.96 |
Murder | Rape | Robbery | Assault | |
Report Total | ||||
Rate per 1,000 |
Murder | Rape | Robbery | Assault | |
Report Total | ||||
Rate per 1,000 |
(100 is safest)
Index |
Index |
Motor Vehicle
Theft |
100 is safest |
100 is safest |
100 is safest |
Crime | |
Americana Dr / Patriot Dr | 0.101011101001110 |
Annandale | 0.101011101001110 |
Virginia | 18.67 |
burglary | theft | motor vehicle theft | |
Report Total | |||
Rate per 1,000 |
burglary | theft | motor vehicle theft | |
Report Total | |||
Rate per 1,000 |
Crime | |
Americana Dr / Patriot Dr | 0.101011101001110 |
Annandale | 0.101011101001110 |
Virginia | 19 |
65 Vital Statistics. 12 Condition Alerts found.
Adults In Neighborhood With College Degree Or Higher | |
Children In The Neighborhood Living In Poverty |
SEE ALL SCHOOLSDiscipline | District | State |
Proficiency in Reading and Math | 0.101011101001110 | 0.101011101001110 |
Proficiency in Reading | 0.101011101001110 | 0.101011101001110 |
Proficiency in Math | 0.101011101001110 | 0.101011101001110 |
Ethnic/racial Groups | This District | This State |
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328 Vital Statistics. 8 Condition Alerts found.
Appreciation Potential (3 years)
1=Very Low
5=Rising Star
Time Period | Total Appreciation | Avg. Annual Rate |
Compared To
Metro* |
Compared To
America* |
3 Year Forecast:
Latest Quarter:
Last 12 Months:
Last 2 Years:
Last 5 Years:
Last 10 Years:
Since 2000:
* 10 is highest |
Factors likely to drive home values upward over the next few years or indicators of upward trends already underway.
Impediments to home value appreciation over the next few years or indicators of negative trends already underway.
Price advantage score
1=Strong Disadvantage
3=Similar Price
5=Strong Advantage
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Millennium Madejski Hotel Reading
- 關於酒店
- 酒店信息
- 賓客評價
Set in the business district, Millennium Madejski Hotel Reading occupies a wonderfully convenient location. It's next to The Royal Berkshire Conference Centre and Madejski Stadium, 5km away from Oracle Shopping Centre and Reading Abbey Ruins, and just a short drive from LEGOLAND® and Windsor Castle.A 4-star hotel, our spa offers a range of body treatments and facials, we have a health club and indoor pool, and for a gourmet dining experience, Cilantro Restaurant & Champagne Bar serves 2 AA Rosette award-winning international cuisine. As a family-friendly hotel, our Ask Alfred Children's Concierge is also always on hand to provide expert advice on nearby attractions.Book here for our Best Price Guarantee promise. Earn and spend loyalty points on all qualifying stays. The level of points, benefits and privileges are subject to availability and may vary at certain participating hotels.


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Dinner Delivered
Pre-order healthy meals sourced from local ingredients with our Dinner Delivery program.
We craft meals based on your specific dietary preferences and locally sourced ingredients.
3-Day Detox
Nourish yourself with wholesome, healthy, and organic cuisine delivered to your door. Sugar, soy, gluten, dairy, and corn free.
A one-time delivery. Green juices are the same daily, but all other foods rotate each day.
Earth Day Brunch
Come vividly celebrate the harvest on alongside farmers, artisans, and community members as spring comes along.
A multiple course brunch sourced from local and organic farms will be served.
Salad Days C SA
In our Salad Days CSA, you sign up for the program and prepay for four weeks of salads and high energy snacks. Yum!


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Behold! I finished my very first sweater: Teva Durham's Lace Leaf Pullover from Loop-d-Loop. I made it roomy, but not huge. It's perfect for those occasional days when I can't seem to get warm.
I'm head over heels for it. I'm very pleased with myself!
Not long after we finished shooting these photos, the s.o. and I had to grab the dogs and run into the bathroom. Our town's brand-new tornado siren (conveniently located three houses away) was wailing. We had a real honest-to-goodness tornado warning. Good thing nothing happened, because nobody around here has a basement.
One nice thing about not having a basement is that we do not currently have a flooded basement.


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Controllers or starter units are required when you wiish to use fluorescent tubes in your vivarium. These are available in a wide range of different wattages to suit different tube lengths.
Controller units are required if you wish to use T5 fluorescent tubes in your enclosure.
The Arcadia Reptile Ultraseal lamp holders offer both keeper and animal total security against dangerous water ingress. To comply with the new waterproof lighting regulations we have designed and made this system to be IP67 or waterproof. This does however mean that the lamp holders must be tight.
Northern Invertebrate Show
Thursday 02 March 2017
Introducing the Northern Invertebrate Show; Huddersfield 9th April (11am - 4pm).


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Russian River Jazz and Blues Festival - Sonoma County Events
Russian River Jazz and Blues Festival
The Russian River Jazz and Blues Festival is a combination of Jazz on the River and the Russian River Blues Festival. Jazz is performed on Saturday. Blues is performed on Sunday.
The Russian River Jazz and Blues Festival is a great way to spend the weekend. Bring your chair, blankets, sunscreen, picnic foods and head down to Johnson's Beach situated on the the warm Russian River with giant Redwoods surrounding you. Sit in an easy chair on the rivers edge and enjoy music from top name acts on the main stage. In between sets go to the wine garden and enjoy music and dancing there too. Or you can just wade around in the Russian River. Whatever the case, The Russian River Jazz and Blues Festival is unique because it mixes great music with the natural beauty of the outdoors.
Lots of food and drinks available for sale at reasonable prices, check out the International Food Court where you will find world-class cuisine. While dining on your favorite grub, browse the surrounding Vendor Village featuring art, apparel and unique gifts.
General Admission (unreserved open seating only)
Single Day - $55
2-Day Pass - $90
GOLD Pass (reserved seat in preferred viewing section, 3 complimentary wine tastings, 2 stages of music)
GOLD Single Day - $110
GOLD 2-day Pass - $190
Kids 6 and over are same price as adults
Kids 5 and under Free
Purchase tickets here. Tickets are $10 more at the gate (while supplies last).
Saturday September 12, 2015
Jazz Festival:
10:30am-11:00am - Sabor De Mi Cuba
11:00am-12:00pm - Klye Eastwood
12:00pm- 12:35pm - Sabor De Mi Cuba
12:40pm-1:55pm - Karen Briggs and Mike Phillips
2:00pm-2:30pm - Quinn DeVeaux
2:30pm-3:50pm - WAR
3:50pm-4:30pm - Quinn DeVeaux
4:30pm-6:00pm - Dave Koz & Rick Braun with Kenny Lattimore
Sunday September 13, 2015
Blues Festival:
10:30am-11:00am - Jimmy Smith Band
11:00am-12:00pm - The Rad Trads
12:00pm- 12:35pm - Jimmy Smith Band
12:40pm-1:55pm - Jackie Greene
2:00pm-2:30pm - B.B. & The Blues Shacks
3:50pm-4:30pm - B.B. & The Blues Shacks
4:30pm-6:00pm - Buddy Guy


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Floor 60
Regular price
Out of Stock
The Floor 60 is currently out of stock. Don't worry though, more are already on the way and will be available soon!
Receive In-Stock Notification:-
Product Description
'The Perfect Killing Machine. Now you have to smoke him. The longer the barrel the straighter the aim.'
Also known as the Straight Shooter, this massive and deadly accurate bong has no gimmicks or crazy designs. It is has one single purpose. One mission. It lives to hit.
Standard interchangeable parts such as the bowl, downpipe, base and grommets are easily replaced in our Spare Parts section. -
Technical Specifications
brand Killer Bongs diameter 46mm height 591mm joint Female material Acrylic mouthpiece Straight


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PHOTOS: The world turns whiteWinter has tightened its grip across North India and many parts of the world with fresh bouts of snowfall. The national capital recorded the season's lowest temperature on Tuesday. Snow covered many parts of Jammu and Kashmir and Himachal Pradesh. Here are some of the beautiful snow pics from across the globe. (Photographs: PTI Photo and Umar Ganie/Rediff.com) Jammu and Kashmir The mercury has gone down to the freezing point in Kashmir and Ladakh regions, with most places ... Rediff.com, 2 months ago |
48 images for yannis behrakis | ||||
What lies ahead for the world in 2017?With 2016 officially behind us, let's look forward and speculate about the events, people and issues that will shape 2017. >> RUSSIA'S GROWING INFLUENCE Russian leader Vladimir Putin looks to position his nation as an alternate ally to countries such as the Philippines and Turkey who have been traditionally allied with the United States. Putin's Russia, accused of influencing the US presidential election, could seek to cement their influence by providing support to ... Rediff.com, 2 months ago


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What can you do to protect your brain? Two studies out of Rush University Medical Center in Chicago provide some interesting fodder to consider.
Mental Activities
Not surprisingly, mental activities have been found to preserve the structural integrity in elders' brains. This study included 152 participants who, on average, were 71 years of age. These participants have been participating in the rush Memory and Aging Project, a large-scale study that is focused on the risk factors for Alzheimer's disease. The researchers used a detailed clinical evaluation to ensure that participants did not have dementia or mild cognitive impairment. Participants were asked to rate on a scale of one to five how often they participated in a list of mentally stimulating activities, such as reading, writing letters and play games, during the previous year.
The researchers then used magnetic resonance imaging to determine diffusion anisotrophy, which is a measurement of how water molecules move through the brain. The level of anisotropy drops with aging, injury and disease. The participants participated in a brain MRI within one year of their clinical evaluation. Data analysis found that there were significant associations between the frequency of mental activity in later life and higher diffusion anisotrophy values.
"Several areas throughout the brain, including regions quite important to cognition, showed higher microstructural integrity with more frequent cognitive activity in late life," said lead researcher Dr. Konstantinos Arfanakis in a Rush press release. "Keeping the brain occupied late in life has positive outcomes."
Being Hungry as a Child
Although I wouldn't advise trying it, I did want to share the findings of another study out of Rush University Medical School. Researchers found that people who were occasionally hungry as children actually had slower decline when they reached old age as compared to people who always had enough food to consume.
The study involved 6,158 people who were, on average, 75 years of age, and living in Chicago. Sixty-two percent of the participants were African-Americans. The researchers asked the participants about their health as children, their family's financial status and the home learning environment (i.e. how often they were read to, told stories or played games with family members). The researchers then administered cognitive tests to measure any changes every third year during a 16-year period.
The researchers found that 5.8 percent of the African American participants who had reported that they didn't always have enough food to eat as a child were more likely to have a slower rate of cognitive decline than participants who often or always had enough to eat. Furthermore, the 8.4 percent of African American participants who said they were thinner than other children at the age of 12 also were more likely to experience slower cognitive decline than study participants who said they were approximately the same size or heavier than other children when they were young. There was no relationship found between any of the adverse conditions during childhood and cognitive decline for study participants who were Caucasian. -
"These results were unexpected because other studies have shown that people who experience adversity as children are more likely to have problems such as heart disease, mental illness and even lower cognitive functioning than people whose childhoods are free of adversity," study author Lisa L. Barnes, PhD, an associate professor in the departments of Neurological Sciences and Behavioral Sciences at Rush University and a cognitive neuropsychologist in the Rush Alzheimer's Disease Center of Rush University Medical Center, said in a hospital press release.
The researchers hypothesize that calorie restriction may delay the onset of age-related changes in the body or that there is a selective survival effect that make these participants hardier and more resilient.So what's the takeaway from these research efforts? I wouldn't suggest underfeeding children, but I would suggest starting to feed your brain with lots of activities and opportunities.
Primary Sources for This Sharepost:
Rush University Medical Center. (2012). Can going hungry as a child slow down cognitive decline in later years?
Rush University Medical Center. (2012). Reading, writing and playing games may help aging brains stay healthy.
Published On:
December 19, 2012
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1601 Sansom Street
Philadelphia, PA 19103
The YIP Running Club is a monthly running club that **usually** meets the first Tuesday of each month at Philadelphia Runner at 6:30PM. Each month we run 2-5 miles to an interesting place in the city (historic, public space, point of interest, anything really!) where we will do a brief 5-10 minute tour or Q & A before heading to bar in the neighborhood for post-run camaraderie.
Check the YIP website or YIP Running Club facebook page to see where we are heading next!
The goal of the YIP running club is to provide a new avenue for conversation and networking while exploring interesting locations throughout Philadelphia (and hey, you get a workout in too!).
The YIP running club is organized by Young Involved Philadelphia whose mission is to build relationships and increases civic engagement to empower and connect young Philadelphians.
Runners of all levels are welcome!


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Australia captain Steve Smith reckons Mitchell Starc will be fit to face South Africa in November despite a freak accident in training last week that left the pace bowler with a "gruesome" injury.
Left-armer Starc required 30 stitches to close a gash in his left leg caused by a stump that had been dug into the ground, and will be in a leg brace for another two weeks.
Australia are expected to touchdown in South Africa today, where they will play a lone one-dayer against Ireland followed by five ODIs against the hosts.
And skipper Smith says: "It wasn't nice at all. It was actually probably one of the most gruesome things I have ever seen.
"I guess for Mitch, he's got no tendon or ligament damage so given everything goes well over the next couple of weeks, we're confident that he'll be okay for the first Test match."
Starc, who was being rested from the trip to South Africa along with fellow quick Josh Hazlewood, has established himself as the leader of Australia's pace over the last couple of years.
The 26-year-old's absence for the first of three Tests against the Proteas in Perth from November 3 would be a major setback for the hosts, who also face the Proteas in Hobart and a day-night match in Adelaide.
Smith explains the incident as follows: " As he was catching it [the ball] a few of us were saying 'don't go for it' but he took the catch and then what happened after that wasn't great."


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I's been 9 years since I watched this, i cried a river with this one. <3 ;A; (first drama btw)
Tahara Mika is an ordinary high school girl. One day, out of the blue, one of her classmates kisses her. His name is Sakurai Hiroki also known as Hiro. Hiro stands out because of his bleached hair and piercing. Apparently he is also dating someone. Mika is shocked and hurt that her first kiss had to happen this way. She desperately tries to forget about it. Then, her friend tells her that read moreshe should find somebody else and suggests Tatsuya, another boy in their class. However, before she even realizes it, Mika is already in love... --TBS


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Shakoor, A and Lo Savio, R and Portalupi, SL and Gerace, D and Andreani, LC and Galli, M and Krauss, TF and Ofaolain, L (2012) Enhancement of room temperature sub-bandgap light emission from silicon photonic crystal nanocavity by Purcell effect. Physica B: Condensed Matter, 407. pp. 4027-4031. ISSN 0921-4526
Full text not available from this repository.Abstract
We report the enhancement of sub-bandgap photoluminescence from silicon via the Purcell effect. We couple the defect emission from silicon, which is believed to be due to hydrogen incorporation into the lattice, to a photonic crystal (PhC) nanocavity. We observe an up to 300-fold enhancement of the emission at room temperature at 1550 nm, as compared to an unpatterned sample, which is then comparable to the silicon band-edge emission. We discuss the possibility of enhancing this emission even further by introducing additional defects by ion implantation, or by treating the silicon PhC nanocavity with hydrogen plasma. © 2011 Elsevier B.V.
Item Type: | Article |
Subjects: | UNSPECIFIED |
Divisions: | Div B > Photonics |
Depositing User: | Cron Job |
Date Deposited: | 09 Dec 2016 17:42 |
Last Modified: | 27 Mar 2017 03:29 |


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【budapest】travel collections (Travelog)
This is a summary of all the Logbooks (Travelogs) related to budapest that we have available for the Andalusia(Spain) area. Please go ahead and click on them if you want to read their contents. Does reading about budapest in Andalusia(Spain) make you want to go there too? In that case let's start planning your next trip!
2013-01-18 - 2013-01-31


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Languedoc-Roussillon covers a large region of southern France, from the Rhone to the Pyrenees. For many years its wines had a poor reputation and the over-production filled the European wine lake. Now, with attention to yields and new wine-making techniques, Languedoc-Roussillon is producing first rate wines from the traditional grapes of the region as well as from France's classic grapes - Cabernet Sauvignon, Chardonnay and Sauvignon blanc. Liz Berry looks at these developments - the creation of new applications, the advance of new technology, and new investments as the New World wine wizards move into Europe. Languedoc-Roussillon is perhaps the most exciting and forward-looking wine region in Europe today, and its wines offer remarkable value for money.
"synopsis" may belong to another edition of this title.
Book Description Ebury Press, 1992. Hardcover. Book Condition: New. Bookseller Inventory # P110091774497
More Information About This Seller | Ask Bookseller a Question


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Oficinas Centrales Avda de Burgos 12 Madrid 28036 España-Spain Tel: + 34 91.480.64.00 Fax: +34 91.302.14.37 firstname.lastname@example.com
Catálogos del grupo
Prointec, as the main consultant company, is carrying out the "Development of Sharm El Sheikh International Airport Project", whose client is the Egyptian Airport Company (EAC). In this moment, we are developing the Airport Planning and Design Stage, and the remaining phases are: Tender Process and Construction Phase. In case that any provider is interested in offering his services for any of these phases, we would be pleased to meet you and collaborate together. To arrange an appointment please get in touch with the following personnel.


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Publication number | US6576297 B1 |
Publication type | Grant |
Application number | US 09/590,847 |
Publication date | Jun 10, 2003 |
Filing date | Jun 9, 2000 |
Priority date | Dec 9, 1997 |
Fee status | Lapsed |
Also published as | CA2313326A1, CA2313326C, CN1281491A, CN1286930C, DE69833789D1, DE69833789T2, EP1047740A1, EP1047740B1, WO1999029790A1 |
Publication number | 09590847, 590847, US 6576297 B1, US 6576297B1, US-B1-6576297, US6576297 B1, US6576297B1 |
Inventors | Colin Cameron, Anna Thomas, Alastair Robert Marrion, Ian David Fletcher, Stefan Norbert Rudiger Niedoba |
Original Assignee | International Coatings Ltd. |
Export Citation | BiBTeX, EndNote, RefMan |
Patent Citations (13), Non-Patent Citations (1), Referenced by (18), Classifications (28), Legal Events (6) | |
External Links: USPTO, USPTO Assignment, Espacenet | |
This is a continuation of International Application No. PCT/GB98/03639, with an international filing date of Dec. 7, 1998, designating the United States of America, expressly abandoned after the filing and acceptance of the present application. This application claims priority of Great Britain Patent Application No. 9726076.4, filed Dec. 9, 1997.
This invention relates to ambient temperature curable compositions, comprising an epoxy resin and an amine-functional curing agent and useful as coatings, adhesives or sealants, and to a process for curing the compositions.
The use of heterocyclic secondary amines such as piperidine, pyrrolidine, aminoethylpiperazine or anabasine as curing agents is discussed in the textbook "Handbook of Epoxy Resins" by Lee and Neville published by McGraw-Hill, 1967. They are generally used in small amounts to promote mainly self-condensation of epoxide groups. Piperidine, for example, is customarily used at 5-7% by weight based on an epoxy resin such as the diglycidyl ether of bisphenol A (DGEBA). 2,3-Bipiperidine is described by Forostyan et al. in Plasticheskie Massy, 1965(1), 16-17 as providing cures with DGEBA in 2 hours at 80° C.
US-A-4581454 describes adducts of aminohydrocarbyl piperazines and urea which are used as curing agents for epoxy resins, particularly in reaction injection moulding.
According to one aspect of the present invention, a process for forming a layer of cured epoxy resin on a substrate comprises coating the substrate with a composition comprising an epoxy resin and an amine-functional curing agent and allowing the coating thus applied to cure at ambient temperature, and it is characterised in that the curing agent comprises a material containing at least two heterocyclic secondary amine groups. By a heterocyclic secondary amine group we mean a secondary amine group in which the amine nitrogen atom forms part of a heterocyclic ring.
The invention also provides for the use of a compound containing at least two heterocyclic secondary amine groups as curing agent for an epoxy resin, characterised in that the epoxy resin and the compound containing at least two heterocyclic secondary amine groups are applied together as a coating to a substrate and allowed to cure on the substrate at ambient temperature.
The ambient temperature at which the coating is cured is generally below 40° C. and frequently below 25° C., and it may be below 10° C. or even below 0° C., down to −20° C. for example. At these low temperatures the epoxy resin compositions of the invention cure more rapidly than known epoxy resin compositions such as those using a diprimary amine as curing agent. We believe that initial curing of the epoxy resin is essentially through epoxide/amine reaction rather than self-condensation of epoxide groups.
The epoxy resin of the composition can in general be any of the epoxy resins described in the above textbook by Lee and Neville, preferably a glycidyl-type epoxy resin containing glycidyl ether or ester groups. The epoxy resin can for example be a glycidyl ether of a bisphenol such as DGEBA or can be a condensed or extended glycidyl ether of a bisphenol. Such glycidyl ethers derived from a bisphenol generally have an epoxy functionality of 2 or slightly less, for example 1.5 to 2. The epoxy resin can alternatively be a glycidyl ether of a polyhydric phenol, for example an epoxy novolak resin, or an aliphatic or cycloaliphatic di- or poly-glycidyl ether. Examples of epoxy resins containing glycidyl ester groups are homopolymers or copolymers of a glycidyl ester of an ethylenically unsaturated carboxylic acid such as glycidyl methacrylate or glycidyl acrylate, or the diglycidyl ester of dimerised fatty acid.
In most cases the curing agent preferably contains more than two, for example at least three, heterocyclic secondary amine groups, although mixtures of a curing agent with at least three such groups and a curing agent with at least two but less than three such groups can be used. It is strongly preferred that either the epoxy resin contains an average of more than two epoxy groups per molecule or the curing agent contains an average of more than two heterocyclic secondary amine groups per molecule, for example at least 2.5 or 3 heterocyclic secondary amine groups per molecule. The heterocyclic secondary amine groups can for example be part of a heterocycle containing 3 to 12 atoms in the ring, for example a saturated heterocycle such as a piperidine, piperazine, pyrrolidine, azetidine, aziridine, imidazolidine, oxazolidine, thiazolidine or homopiperazine (1,4-diazacycloheptane) ring, an unsaturated heterocycle such as an imidazoline ring or even an aromatic ring having a secondary amine group such as pyrrole or imidazole. For rings containing two hetero-N-atoms such as piperazine or imidazolidine, it is usually preferred that only one N atom in an individual ring is present as a secondary amine group; the ring can be attached to the remainder of the curing agent molecule through the other N atom, for example the other N atom of a piperazine ring.
Thus, according to another aspect of the invention a coating, sealant or adhesive composition curable at ambient temperatures of 40° C. or below comprises an epoxy resin and an amine-functional curing agent and is characterised in that the curing agent comprises a material containing at least three heterocyclic secondary amine groups.
The curing agent can for example be the reaction product of a primary amino-substituted heterocyclic secondary amine with a compound containing two or more, preferably at least three, groups which are reactive with primary amine groups but substantially unreactive with heterocyclic secondary amine groups. The primary amino-substituted heterocyclic secondary amine can for example be N-(2-aminoethyl)piperazine, 2-(2-aminoethyl)imidazoline, N-(3-aminopropyl)piperazine, 4-(aminomethyl)piperidine, 2-(aminomethyl)piperidine, 3-(aminomethyl)piperidine or 3-aminopyrrolidine, or a substituted derivative of any of the above containing for example one or more alkyl or alkoxy substituents. The groups which are reactive with primary amine groups but not with heterocyclic secondary amine groups can for example be beta-dicarbonyl groups such as acetoacetate groups and similar beta-ketoester groups or beta-diketone groups, other aldehyde or ketone groups, for example the aldehyde groups of glutaraldehyde, terminal urea groups —NHCONH2 or imide- forming groups such as cyclic anhydrides or half-esters of vic-dicarboxylic acid groups capable of forming cyclic imides. Acid groups, particularly carboxylic acid groups, and their lower alkyl esters will also react preferentially with primary amine groups rather is than heterocyclic secondary amine groups. The curing agent can alternatively be formed by reaction of a polyfunctional reagent with pyridine substituted by a reactive functional group, followed by hydrogenation of the pyridine ring to generate secondary amine groups.
A di- or poly-acetoacetate ester, for example, can be reacted with N-aminoethylpiperazine or another primary amino-substituted heterocyclic secondary amine to bond the heterocylic secondary amine to the acetoacetate ester through an imine or enamine linkage. The reaction is shown below for trimethylolpropane tris(acetoacetate).
trimethylolpropane tris(2-piperazinoethyl)aminocrotonate (may exist in ketimine or enamine form)
Trimethylolpropane tris(acetoacetate) can be prepared from trimethylolpropane and a lower alkyl acetoacetate such as t-butyl acetoacetate by heating to transesterify, with removal of the volatile alcohol such as t-butanol by distillation. Poly(acetoacetate)esters can similarly be formed from other polyols such as pentaerythritol, 1,6-hexanediol, trimethylolethane or sorbitol or hydroxy-functional polymers such as acrylic polymers having pendant hydroxyl groups, for example homo- and co-polymers of 2-hydroxyethyl acrylate or methacrylate and polyesters, including hyperbranched or dendritic polymers having surface hydroxyl groups and 2,4,6-tris(hydroxymethyl)phenol and other compounds and oligomers formed by novolak condensation of an optionally substituted phenol and formaldehyde.
Glutaraldehyde will react with a primary amine to form one imine linkage followed by aldol condensation of the other aldehyde group to form a hydroxy-substituted polymer chain, provided that the reaction is carried out without having a significant molar excess of glutaraldehyde over amine at any stage. The hydroxy-substituted polymer chain may undergo further dehydration to form an unsaturated polymer chain. If glutaraldehyde is reacted with aminoethylpiperazine, a polymer is formed having pendant imine groups of the formula:
A di- or poly-urea can be reacted with N-aminoethyl-piperazine or other primary amino-substituted heterocyclic secondary amine to replace the terminal —NH2 of the polyurea with elimination of ammonia. The reaction is shown below for hexamethylenediurea.
Di- and poly-ureas such as hexamethylenediurea can be prepared by heating a di- or poly-amine such as hexamethylenediamine with an excess of urea. The amino groups of the di- or poly-amine are preferably primary amino groups, although secondary amino groups will also react. The di- or poly-amine can for example be ethylene diamine, diethylene triamine or tris(2-aminoethyl)amine.
Examples of compounds and polymers containing carboxylic acid or lower alkyl ester groups which will react preferentially with primary amine groups are polyesters having terminal acid or ester groups, acrylic acid polymers or methyl or ethyl acrylate polymers, Michael-type adducts of an unsaturated carboxylic acid ester such as dimethyl maleate with a Michael donor such as a thiol or a malonate or acetoacetate ester, ester-substituted lactone reaction products of an epoxy resin with dimethyl malonate, or dimer fatty acids or acid-terminated low melting polyamides derived from them. The lower alkyl ester groups are ester groups of a lower boiling alcohol such as an alcohol having 1 to 4 carbon atoms, especially methyl or ethyl ester groups. The acid or ester groups react with primary amine groups to form amide linkages.
Although carboxylic acid groups react preferentially with primary amine groups, they will react with heterocyclic secondary amine groups under more forcing conditions, and a compound or polymer containing at least two heterocyclic secondary amine groups can be formed by reaction of a compound or polymer, for example a copolymer of acrylic acid with one or more acrylate or methacrylate ester monomers, having at least two carboxylic acid groups with piperazine. The piperazine reacts predominantly to form a monoamide of each piperazine unit.
The curing agent can alternatively be the reaction product of a hydroxy-substituted heterocyclic secondary amine such as N-(2-hydroxyethyl)piperazine with a compound or polymer containing at least two groups reactive with hydroxy groups under conditions in which the heterocyclic secondary amine does not react. For example, hydroxyethyl piperazine can be reacted with a polyisocyanate to form a urethane having at least two piperazine secondary amine groups if the amine group is first deactivated by salt formation with a strong acid. The amine groups need to be reactivated by removal of the acid before the reaction product is used as an epoxy curing agent.
When reacting a primary amino-substituted heterocyclic secondary amine such as aminoethyl piperazine with a multifunctional cyclic anhydride to form imide linkages, care should be taken to avoid gelation. The multi-functional cyclic anhydride can for example be ring-opened with an alcohol to form a half-ester, which will itself form imide linkages with aminoethyl piperazine on heating. Examples of multi-functional cyclic anhydrides are maleic anhydride polymers, for example copolymers with styrene or with an alpha-olefin such as 1-octene or with one or more acrylate or methacrylate ester monomers. Itaconic anhydride polymers can be formed from itaconic acid as described in GB-A-2137637.
The curing agent can be a polymer or oligomer containing secondary amine-containing heterocyclic rings either pendant from a polymer chain or linked in a polymer chain. Examples of heterocyclic rings pendent from a polymer chain are described above. Further examples can be derived by hydrogenation of a polymer containing pyridine groups such as poly(vinyl pyridine). Another example is a siloxane polymer containing pyridine groups which can be formed by reaction of vinyl pyridine with a polymer containing Si-H groups, for example a poly (methyl hydrogen siloxane), in the presence of a hydrosilylation catalyst such as a platinum compound. Compounds and polymers containing 3 or more pyridine groups can be formed by reaction of vinyl pyridine with a polythiol such as pentaerythritol tetra (3-mercaptopropionate). 4-Aminopyridine can be reacted with di- or poly-acid to form a di- or poly-amide containing pyridine groups or with a diacrylate to form a Michael-type adduct containing pyridine groups or with a diepoxide to form an adduct containing pyridine groups. Any of these materials can be hydrogenated to form a poly(piperidine), as can terpyridine. Analogous polymers and oligmers containing 5-membered secondary amine heterocycles can be formed from 2- or 3- vinyl pyrrole or vinyl imidazole followed by hydrogenation.
Polymers and oligomers containing pyrrolidine groups can be produced by lithium aluminium hydride reduction of maleimide or succinimide groups. An addition copolymer of maleimide (whether formed by polymerisation of maleimide or by polymerisation of maleic anhydride followed by reaction with ammonia) can be reduced to a polymer containing pyrrolidine groups linked in a polymer chain. A maleinised polymer or maleinised polyene, for example polybutadiene maleinised by reaction with maleic anhydride, or an itaconic anhydride polymer, can be reacted with ammonia to form maleimide groups which can be reduced to pyrrolidine groups. The polyene can for example be a cyclic polyene such as cyclododecatriene. A cyclic oligomer containing pyrrolidine groups can alternatively be prepared by hydrogenation of a macrocycle containing pyrrole groups, for example an acetone pyrrole reaction product.
which can be hydrogenated to form a tetrapyrrolidine useful as a curing agent.
A polymer containing piperidine and/or pyrrolidine groups in the polymer chain can be produced by the free is radical initiated cyclopolymerisation of diallylamine.
Epoxy resins cure particularly rapidly with the cyclopolydiallylamine polymerisation product. This can be valuable for a coating or sealant required to cure at particularly low temperature. The cyclopolydiallylamine can be partially reacted with a monofunctional reagent such as an epoxide or acrylate prior to the curing reaction with an epoxy resin to reduce its reactivity.
Heterocyclic amines can alternatively be formed by the reaction of ammonia with 1,2,5,6-diepoxides. The diepoxides can for example be derived from a sugar-derived polyalcohol such as D-mannitol, as described by L. Poitout et al in Tet. Lett. 35 3293 (1994). Heterocyclic secondary amines are formed as shown below:
where P=protecting group.
Reaction of the diepoxide with ammonia leads to ring opening of one of the epoxides followed by spontaneous intramolecular ring closure to give the piperidine and/or the azepine. The central hydroxyl groups may be used, for example by prior reaction with isocyanate groups, to link the piperidine and/or azepine to an appropriate core unit to give multifunctionality. The diepoxide can is alternatively be derived from a polydiene, for example from 1,2- or 1,4-polybutadiene.
A curing agent containing oxazolidine groups can be prepared from a polyepoxide by reaction with ammonia followed by reaction with formaldehyde as shown below for one of the epoxide groups:
The curing agent can comprise a simple di(secondary amine heterocycle) such as 1,3-bis(4-piperidino)propane or the 1:2 molar adduct of urea and N-(2-aminoethyl)piperazine.
In general, these curing agents have the disadvantage that they are only di-functional and are often solids which are difficult to mix into curing compositions. They are preferably not used as the only amine curing agent for epoxy resins having an average epoxide functionality of 2 or less. They can advantageously be used mixed with other heterocyclic secondary amine curing agents having a functionality greater than 2, particularly liquid oligomers and polymers. The di(secondary amine heterocycle) curing agents can also be used as curing agents for epoxy resins of higher functionality such as glycidyl acrylate or methacrylate polymers or epoxy novolak resins. The di(secondary amine heterocycle) compounds can alternatively be reacted with a polymer to form a polymeric curing agent tipped with heterocyclic secondary amine groups, for example 1,3-bis(4-piperdino)propane can be reacted with a polyepoxide at a ratio of at least two piperidine groups per epoxy group to form a curing agent.
When the curing agent and epoxy resin are mixed to form a coating, sealant or adhesive composition the curing agent and epoxy resin are usually used in amounts s such that the composition contains at least 0.5 heterocyclic secondary amine groups per epoxide group, although lower amounts of amine can be used if the epoxy resin contains many epoxy groups, for example a glycidyl acrylate or methacrylate polymer. The composition preferably contains at least 0.6 up to 1.5 or 2.0 heterocyclic secondary amine groups per epoxide group, although higher amounts of the curing agent can be used if it contains many heterocyclic secondary amine groups.
The curing agent according to the invention can comprise a blend of different heterocyclic secondary amines. Normally the total curing agent present has an average of at least two heterocyclic secondary amine groups per molecule. When the epoxy resin has high functionality, for example a glycidyl acrylate or methacrylate polymer, the curing agent can be used in conjunction with a heterocyclic secondary amine having only one secondary amine group, and in these circumstances the total curing agent may have an average of less than two heterocyclic secondary amine groups per molecule.
A curing agent containing heterocyclic secondary amine groups can also be used in conjunction with another curing agent for the epoxy resin such as a primary amine. Examples of such primary amines are 1,3-bis(aminomethyl)cyclohexane, m-xylylene diamine, isophorone diamine, bis(4-aminophenyl)methane and bis(4-aminocyclohexyl)methane or even a simple primary monoamine such as n-hexylamine, n-octylamine or benzylamine. Preferably, the other curing agent does not constitute more than 50 percent of the total amine nitrogen of the curing agent.
The compositions of the invention are used as coatings, adhesives or sealants (including potting compounds used for sealing electrical and electronic components) and are particularly suitable for curing at ambient temperature, for example below 40° C. and particularly below 25° C. and including cold climates where the ambient temperature is below 10° C. or even below 0° C. down to −10° C. or −20° C. The compositions of the invention cure and harden more rapidly than epoxy resin compositions based on conventional primary amine curing agents, for example they cure 2 to 10 times faster at 10-20° C. than similar compositions based on bis(aminomethyl)cyclohexane as curing agent. The compositions of the invention can be prepared at sprayable viscosity at high solids (250 g/L or less of volatile organic material). Despite the tendency of high solids coatings to cure more slowly, coatings according to the invention can cure more rapidly than conventional amine-cured epoxy coatings of higher solvent content. The reaction rate of compositions according to the invention is about 8 times faster than that of epoxy resins cured by a hydrogenated aralkyl primary diamine, as measured by ASTM E698-79.
The compositions of the invention can for example be used as the binder of anticorrosive primer coating compositions applied to steel used in shipbuilding or structural steel used in buildings, bridges or oil rigs. Such compositions generally have to be cured at ambient temperature. The epoxy resin and the curing agent are generally stored separately and are mixed shortly before application together as a coating to the substrate, for example 10 minutes to 2 hours before application, or they can be mixed at application in a twin-feed spray and applied together. The coatings generally harden sufficiently rapidly at 10° C. (often at 0° C.) that a 200 μm coating film can be trodden on 24 hours after application, usually 8 hours after application, without gouging of the film.
The compositions may optionally contain compounds known to accelerate the epoxy-amine reaction if even faster cure is desired. Many additives tested as cure accelerators, for example Lewis acids, are described in the list compiled by Inoue in the Proceedings of the 21st Japan Congress on Materials Research, page 251 (1979) Hydrogen bond donor materials such as alcohols, phenols and acids accelerate the cure. A common example is 2,4,6-tris(dimethylaminomethyl)phenol. Metal salt catalysts such as calcium nitrate can alternatively be used.
The coatings may contain an anticorrosive pigment such as metallic zinc, zinc phosphate, wollastonite or a chromate, molybdate or phosphonate, a barrier pigment such as micaceous iron oxide, glass flake, aluminium flake or mica and/or a filler pigment such as iron oxide, barytes, talc, calcium carbonate or titanium dioxide. The coatings may also contain other coating additives such as a wetting agent, a thixotrope, a reactive diluent, for example a monoepoxide, a flow control agent, solvent or diluent. Sealant compositions generally contain a filler and/or pigment such as those listed above, and sealant or adhesive compositions may contain additives such as those listed for coating compositions. The pigments and other additives can be mixed and stored with the epoxy resin or with the curing agent or with both.
The invention is illustrated by the following Examples, in which percentages are by weight unless otherwise indicated:
1(a) Preparation of Curing Agent
77.4 g (0.6 mole) N-aminoethylpiperazine was added to 77.2 g (0.2 mole) trimethylolpropane tris(acetoacetate) in a Buchi flask and rotated at 80° C. for 1 hour before stripping under vacuum. 5.4 g water was removed, leaving 150 g trimethylolpropane tris(2-piperazinoethyl)-aminocrotonate as a very viscous yellow oil.
1(b) Preparation of Coating
100 parts by weight trimethylolpropane piperazinoethyl) tris(2- aminocrotonate and 80 parts by weight DGEBA-type epoxy resin of equivalent weight 185 were dissolved in 75 parts xylene/25 parts butanol (by weight) to form a coating composition having a ratio of piperazinoethyl to epoxide groups of 0.97:1. This coating, when applied at 200 μm wet thickness (130 μm dry thickness) at an ambient temperature of 23° C. on a glass plate, cured overnight to a scratch-resistant coating.
This coating composition could be pigmented with anticorrosive pigment at a pigment volume concentration of 35% to form an ambient temperature curable primer for steel.
An epoxy resin paint base was prepared from the following ingredients:
Liquid DGEBA-type epoxy resin 45.25 g
Solvents (xylene benzyl alcohol, 12.19 g methoxypropanol)
Hydrocarbon resin plasticiser 3.80 g
Pigments and fillers (talc, barytes, 37.72 g yellow iron oxide)
Modified hydrogenated castor oil thixotrope 1.04 g
57.38 g trimethylolpropane tris(2-piperazino-ethyl)aminocrotonate was dissolved in 30 g xylene/10 g butanol and mixed with 4.28 g hydrocarbon resin plasticiser and then with the above paint base.
The resulting paint was applied to steel panels at 400 μm dry film thickness and allowed to dry at 0° C. The paint was touch dry after 5.5 hours, through dry after 26.5 hours and dry enough to walk on without gouging the paint film after 53 hours.
By comparison, when a paint of similar Tg and amine hydrogen to epoxide ratio was made from the same paint base with 18.75 g xylene, 6.25 g butanol and 12.23 g of the primary amine curing agent H2N(CH2)3O(CH2)4O(CH2)3NH2, the 400 μm paint film was not touch dry after 6.5 hours (it became touch dry overnight) and was not through dry after 53 hours.
Diallylamine (110 g), water (200 g) and concentrated hydrochloric acid (140 g) were mixed cautiously and sparged with nitrogen for 2 hours. Bisazoamidinopropyl hydrochloride (2 g) was added and sparging continued for 30 minutes. A partial vacuum was applied to the flask and it was placed in an oven controlled at 60° C. and held for three days.
Potassium hydroxide (84 g) was added in portions with cooling. The water was evaporated to yield a crusty product which was digested with butanol (100 g), filtered and evaporated to yield a leathery yellow material (60 g). It was used as a 45% solution in butanol.
No residual unsaturation could be detected by NMR spectroscopy. Spectra were consistent with a predominantly 5-membered ring structure:
The glass transition temperature of the polymer was −53° C. (by DSC). Gel permeation chromatography of the derivatised product prepared by reacting the cyclopolymer with excess butyl acrylate gave comparative molecular weights, Mn=6000, Mw=20500 using polystyrene standards.
Mixtures of the cyclopolydiallylamine polymerisation product with epoxy resins gelled extremely rapidly. A mixture of cyclopolymer solution (2.16 g, 0.01 mole), "Epikote 828" liquid DGEBA-type epoxy resin (0.57 g; 0.003 mole) and "Cardura E10" monofunctional epoxide (1.75 g, 0.007 mole) gelled within 15 minutes. The film on glass was totally unaffected by 200 acetone double rubs after 56 hours' curing at room temperature.
Aminoethylpiperazine (AEP) (12.9 g, 0.1 mole) was dissolved in water (40 g) and 25% aqueous glutaraldehyde (40 g, 0.1 moles) was added dropwise. The mixture remained homogeneous until the end of the process, when the amine had been consumed and a small amount of gel separated. The gel was strained off, the water was removed by rotary evaporation, and the residue was dissolved in butanol to give a solution of NVC (non-volatile content) 46.5%. GPC of the product suggested a comparative Mn of 1500.
Epikote 828 (3.74 g, 0.02 mole), the reaction product solution (3.3 g, 0.02 mole), xylene (1.0 g) and butanol (1.0 g) were mixed. The solution became clear after about 15 minutes, and it started to gel after 20 minutes. A film cast on glass was hard and glossy and was totally unmarked by 200 acetone double rubs after 72 hour' curing at room temperature.
Dimethyl maleate (14.4 g, 0.1 mole), ethanedithiol (4.7 g, 0.05 mole), xylole (45 g), and "DMP 30" (2,4,6-tris(dimethylaminomethyl)phenol catalyst) were warmed together for 2 hours until there was no evidence of a C═C band in the infrared spectrum. AEP (25.8 g, 0.2 mole) was added and the mixture boiled under partial distillation conditions for 4 hours. 5.9 g of the expected 6.4 g of methanol were recovered. Rotary evaporation, yielded 42 g of an amber gum which was dissolved in butanol to give a solution of NVC 55.9%. Infrared spectroscopy showed a strong amide signal at 1651 cm−1 and a trace of ester at 1725 cm−1. NMR showed that the AEP was attached predominantly through its side-chain primary amine group.
Dimethyl maleate (7.2 g, 0.05 mole), dimethyl malonate (6.6 g, 0.05 mole) and a molar solution of sodium methoxide in methanol (0.5 g, 0.0005 mole) were held at 100° C. for 2 hours. AEP (25.8 g, 0.2 mole) and xylole (40 g) were added and the mixture was refluxed for 8 hours. Vacuum stripping yielded 39 g of an amber oil, which could be used without dilution though it hardened to a wax over several weeks. Infrared showed the presence of ester groups and the absence of unsaturation in the first stage. In the second stage there was evidence of amide (1655 cm−1) and some imide (1696, 1772 cm−1)
Epoxy Malonate Reaction Product
Sodium metal (3.45 g, 0.15 mole) was dissolved in ethanol (100 g). Dimethyl malonate (21.78 g, 0.615 mole), was added dropwise over 15 minutes. Epikote 828 (28.05 g, 0.15 equiv) dissolved in toluene (30 g) was added dropwise over 30 minutes. On completion the temperature had risen from 20° C. to 30° C. After 2 hours a viscous mass separated. Further toluene (45 g) was added and warming applied to disperse the mass. Glacial acetic acid (13.5 g, 0.225 mole) was added and the reaction product partitioned between water (200 g) and further toluene (100 g). The organic fraction was separated and washed with water (50 g). Vacuum stripping yielded 46.3 g of a clear, almost colourless, viscous oil. IR showed two equal-sized sharp bands at 1736 and 1780 cm−1, suggesting substantial conversion of epoxy groups to lactone groups of the formula:
NMR was consistent with the formation of about 80% of the possible lactone.
Stage 2 Preparation of Heterocyclic Secondary Amine
Stage 1 product (14.35 g), aminoethylpiperazine (12.9 g) and xylole (25 g) were mixed and held at reflux temperature for 3 hours. The lactone signals in the infrared disappeared rapidly, followed by the ester signals. A new amide signal appeared at 1664 cm−1, indicating that the lactone and ester groups had both been converted to amide. Vacuum stripping yielded a stiff amber liquid (28.4 g), which was dissolved in butanol to yield a 48.7% NVC solution.
Stage 1 product of Example 7 (14.35 g, 0.05 mole) was mixed with dimethyl maleate (7.2 g, 0.05 mole), and 1 molar sodium methoxide in methanol (0.5 g, 0.0005 mole) was added. The mixture was held at 60-68° C. for 3 hours and became very viscous. Xylene (20 g) and AEP (25.8 g, 0.2 mole) were added and heating started. Within 1 hour large amide (1656 cm−1) and imide (1700, 1776 cm−1) peaks were visible, and lactone and ester signals were almost completely removed. Processing was continued for a further 2 hours with little change.
The formation of imide under such mild conditions was a surprise and was possibly due to the presence of geminally substituted precursor. To the extent that imide was formed, up to 25% of the AEP was unrequited and remained free in the reaction product.
The polyfunctional heterocyclic secondary amine solutions prepared in Examples 5 to 8 were mixed with Epikote 828 in a stoichiometric amount based on the nominal amine functionality to form clear coating compositions. The compositions were cast on glass and allowed to cure at ambient temperature. The gel time was noted and the solvent resistance was measured (by means of double acetone rubs resisted without marking after specified curing time at ambient temperature). The results are shown in Table 1.
Weight %
Solids of
of amine
100 (24 hr)
100 (24 hr)
200 (72 hr)
200 (16 hr)
**Because of imide formation, functionality probably closer to 6, with some free AEP.
(100 g), and "Luperox 575" (tert-amyl peroxy-2-ethylhexanoate, 2.0 g) were mixed and added to refluxing oct-1-ene (60 g, 0.54 mole) over 2 hours. After 3 hours at reflux a further portion (0.2 g) of "Luperox" was added. After another hour at reflux the mixture was vacuum stripped and the viscous product dissolved in xylole to provide a solution of 42.2% NVC. The molecular weight of the polyanhydride produced was measured as Mn 2600, Mw 5780 by GPC relative to polystyrene standards.
The above solution (49.8 g, 0.1 equivalent), isopropanol (50 g) and triethylamine (0.15 g) were refluxed together for 10 hours, at which stage anhydride signals in the infrared spectrum were reduced to negligible intensity. AEP (12.9 g, 0.1 mole) was added and distillation started, with the progressive addition of xylole until a reflux temperature of 140° C. was achieved. After 12 hours at reflux, imide signals (1699, 1775 cm31 1) had become intense and amide signals (1638 cm−1) weak. A fluid solution of 33.0% non-volatile content resulted.
A styrene-maleic anhydride copolymer of equivalent weight per anhydride group 224 (22.4 g, 0.1 equiv.) was dissolved in xylene (50 g), isopropanol (18 g) and triethylamine (2.0 g). After 3% hours at reflux the anhydride peak had become negligible. Aminoethyl-piperazine (12.9 g, 0.1 mole) was added, followed by a further 20 g of xylene to restore fluidity. After 10˝ hours of distillation and removal of volatile solvents, a solid product was recovered by filtration and dissolved in butanol to give a solution of 27.5% non-volatile content, showing strong imide signals (1697, 1768 cm−1)
A mixture of vinyl neodecanoate ("Veova 10", Shell, 66.9 g, 0.338 equiv.), xylene (30 g) and tertiary-butyl peroxide (2.0 g) was run into refluxing xylene (70 g) and maleic anhydride (33.1 g, 0.338 mole) over 2 hours. After 3 hours, tert-butyl peroxide (0.2 g) was added and ref lux maintained for a further hour. Vacuum stripping yielded 108 g of a golden glassy solid, showing anhydride (1786, 1863 cm−1) and ester (1729 cm−1) signals in the infrared and having Mn 750, Mw 790.
This polyanhydride (16.0 g, 0.05 equiv.), isopropanol (12 g, 0.2 mole) xylene (20 g) and triethylamine (0.15 g) were mixed, and reflux was started. The reaction mixture took on an intense purple coloration. After 6 hours at reflux the anhydride signals were negligible and ester and acid bands were predominant at 1730, 1704 cm−1 respectively. Aminoethylpiperazine (6.45 g, 0.05 mole) was added and distillation started. After 13 hours at 140° C., infrared spectroscopy showed a strong signal at 1700 cm−1. Vacuum stripping yielded a black liquid which was dissolved in butanol to yield a solution of 45.8% NVC.
A mixture of vinyl neodecanoate (63.9 g, 0.323 equiv.), xylene (30.0 g) and tert-butyl peroxide (2.0 g) was run into refluxing xylene (70.0 g) and itaconic acid (41.9 g, 0.322 mole) over 2 hours. After 3 hours a further 0.2 g tert-butyl peroxide was added, followed by two further portions at hourly intervals. Reflux was continued for a further 13 hours when a fluid homogeneous product resulted. Vacuum stripping yielded 103 g of a clear golden viscous liquid. Its infrared spectrum showed strong ester (1724 cm−1) and anhydride (1784, 1861 cm−1) signals. Molecular weight was measured as Mw 1630 by GPC relative to polystyrene standards. The liquid was re-dissolved in xylene to yield a solution of 58.0% non-volatile content.
The polyanhydride solution, (53.45 g, 0.1 equiv.) was refluxed with butanol (29.6 g, 0.4 mole), and triethylamine (0.15 g). After 2 hours, infrared a:spectroscopy showed complete removal of the anhydride bands. Aminoethylpiperazine (12.9 g, 0.1 mole) was added and reflux continued. Within 30 minutes a strong imide band appeared at 1702 cm−1 and the ester band reduced in intensity. Reflux was continued for 2 hours in butanol to provide a pale amber solution of 55.9% non-volatile content.
Coating compositions were prepared from the polyfunctional heterocyclic secondary amine solutions of Examples 9 to 12, cast on glass and tested for solvent resistance as described for Examples 5 to 8. The results are shown in Table 2.
Weight %
weight of
solids of
Gel Time
200 after 72 hrs
200 after 16 hrs
80 after 72 hrs
100 after 72 hrs
**Solvent resistance determined as the number of acetone double rubs required to produce slight marring after curing at ambient temperature for the specified time.
An epoxy resin paint base was prepared from the following ingredients:
Weight %
Liquid diglycidyl ether of bisphenol A epoxy resin
Solvent (3:1 butanol:xylene)
Pigments and filler (talc, barytes, yellow oxide)
The following polyfunctional heterocyclic secondary amine solutions were then mixed with the above paint base on a 1:1 stoichiometric ratio to form a paint.
Polyfunctional Amine
Weight % of solids
Example No.
of Example No.
in amine solution
Some of each paint was drawn down onto degreased steel panels, using 300 μm and 600 μm drawdown bars, and was placed in a refrigerated cabinet at 5° C. Walk-on time was assessed for each coating, being determined as the time at which the coating can be walked on without gouging of the coating occurring. The average dry film thickness (DFT) of the cured coating was also measured. The results are shown in Table 3 below:
Example No.
DFT in μm
Walk-on Time/hrs
A standard paint base, containing both liquid and solid diglycidyl ether of bisphenol a epoxy resins, when mixed with a standard curing agent, containing primary and secondary amine functionality, gave the following walk-on times when cured at 5° C.
120 μm DFT=8 hours
260 μm DFT=16 hours.
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U.S. Classification | 427/372.2, 544/358, 528/122, 548/400, 528/408, 528/117, 528/88, 528/87, 528/118, 546/184 |
International Classification | C08G59/50, C08G59/54, C09D163/00, C08F8/30, C09K3/10, C08L63/00, C08G59/40, C09J163/00 |
Cooperative Classification | C09K2200/0647, C08L63/00, C08G59/5046, C09K3/10, C08F8/30, C09K2200/0476 |
European Classification | C08L63/00, C09K3/10, C08F8/30, C08G59/50K |
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