text:
Posted by: Adam Male on 2 October 2015
Comments: 0
Twenty residents of a Hertfordshire street were lefts scratching their heads today when a 20 meter wide sinkhole opened in the middle of their suburban street!
The first sign that something was amiss on Fontmell Close, a quiet St Albans street, came five days ago, with residents noting that a man hole cover appeared to be 'sinking'.
This was followed by a small hole appearing, which the council had plans to fill on Thursday. However at 1am on Thursday morning, residents woke to the crashing sound of a 20 meter wide hole eating through their street and gardens, rupturing a gas main and demolishing brick walls. The chaos led to the emergency evacuation of six homes and has left a further 50 families without gas, water or electricity.
It is believed that the 10 meter deep crater opened due to the road being built on the site of a former rubbish dump from the Victorian era. Historically the clay soil had been excavated to make bricks, and the space filled with the town's waste - in time the waste has degraded and compacted leaving an underground cavity which filled with rainwater. This caused a larger void to open, eventually the structure because sufficiently weak that the 'roof' (the road above!) suddenly collapsed in a very dramatic fashion.
There are plans to carry out full archaeological and geological records before repairs take place, however the council believe that they will have utilities back online within the next couple of days and have the hole filled in as soon as possible.
Read more
Posted by: Adam Male on 1 October 2015
Comments: 0
Some estate agents are famous for re-branding small properties as 'bijou' or 'charming', here at Urban.co.uk we like to be open and honest, and this London let, which was made famous online by a disgruntled viewer earlier this week is, quite frankly, a cupboard under the stairs.
The current tenants of the property, which is located in desirable Clapham, tried to convince the poor viewer that the advertised space was indeed a fully furnished bedroom, and was worth every penny of the advertised price of £500 pcm, with an additional share of the household bills on top!
The tenants describe their ideal new flatmate as someone 'friendly, open-minded and outgoing' who is 'not looking to stay in their room a lot.' Although presumably they will be allowed in their room when the Hoover, football boots, coats and washing power are out for the night.
For rental properties with a bit more space, check out what's available on our website.
Posted by: Adam Male on 30 September 2015
Comments: 0
Q: I have to have a Carbon Monoxide detectors, but I'm not sure where to put it? I want to make sure that the detector safeguards not only my tenants, but the rest of the people who share the building too. Where does it have to go?
A: The location of carbon monoxide detectors is a common problem with rental properties, and one that is essential to get right. Carbon monoxide poisoning kills up to 14 people in the UK every year, and it's not something to be taken lightly.
We spoke to GasElec, specialists in Gas Safety and certification, who were able to give us the most up-to-date information for our confused customer, taking into account the floorplan of her property. However, it is worth noting that every case is different and there is no definitive 'best place' for a detector. However, we have drawn up a best practise guide to advise us on the best plan of action.
The first thing to make sure is that you have purchased the correct type of alarm. They are widely available from all good DIY/hardware stores and most large supermarkets, and are priced from around £15. It is important to make sure that your alarm complies with British Standard EN 50291, and make sure you take note of the alarm's life span – most units are built to last three to ten years, and they must be replaced once this life span has come to an end.
Once you have the correct alarm, there is a few rules you can follow to make sure that you give it the very best chance of performing properly.
If you are unsure of the best place to position your alarm, you should seek advice from a Gas Safe Capita registered engineer, who will be able to visit your property and advise you on the perfect location to maximise effectiveness.
There are serious changes due to the way landlords are allowed to operate within the UK, and it is important that you are aware of what is happening, and how it affects you, and your tenants.
What's it all about?
It surrounds the Section 21 act, a section of the Housing Act 1988 that allows landlords to seek recovery of possession of a property which has been let on an assured shorthold tenancy.
The new legislation, which will be enforced with heavy fines if not adhered to correctly, will ensure that both tenants and landlords are protected by a more effective paper trail throughout the duration of a lease, and will help ensure that you and your tenants are able to communicate
When is it happening?
All new assured shorthold tenancies in England that start on or after 1 October 2015 will be affected, whilst all remaining assured short hold tenancies in England will be have to comply with the under the new rules from the 1st October 2018
What's changing?
The new act signals fairly significant changes to the way landlords serve notice, and tenants communicate issues within the property.
What do I need to do?
From these dates, a valid Section 21 Notice of Eviction can only be served on a tenant if that individual has been served with the following:
Can you help!?
It sounds like it is going to be a very confusing time, but don't worry – the regulations have been introduced in order to ensure a more secure industry for both tenants AND landlords.
Urban.co.uk are able to assist you however you require – if you have any questions ensuring you have all of the relevant paperwork in place before you undertake a new tenancy – our lettings team are more than happy to handle any questions you may have.
We work hard to ensure than not only the tenants we help place, but also our landlords are protected and able to rent their properties
We would always advocate a lick of paint, and a spruce up of your property to ensure you stand out from the crowd when you're marketing your property for sale, but there are some properties that even the most immaculately presented semi is going to struggle to stand out against!
Plans for the floating 'City of Meriens', an ocean-going 'designer city' with the capacity to house 7,000 residents in sleek, contemporary style, have been making a splash onto the housing market, with French designer Jacques Rougerie certain that turning to the sea is the answer to the housing shortage on land.
Shaped like a manta ray, the floating city will be powered by renewable energy sources and operate a 'zero waste' programme, as well as planning to boast Aquaculture tanks to farm fish and hydroponic gardens for growing fruit and vegetables, allowing residents to be primarily self-sufficient.
Residents will be able to moor their boats in inner lagoons (allocated parking is always a selling feature!) which would also house research vessels, such as Mr Rougerie's SeaOrbiter, an ocean skyscraper and floating lab which is currently under construction.


text:
IOS Special Announcements
NEW Dear Colleague Letter: Special Guidelines for Submitting Collaborative Proposals under the US NSF/BIO/IOS - US-Israel BSF International Opportunity. Click here for this funding opportunity.
Cracking the Olfactory Code – An Ideas Lab Activity A solicitation for an Ideas Lab to facilitate the generation and execution of innovative research projects aimed at understanding the nature of olfactory processing and sensory representations in the brain in general.
Frontiers for the Integrative Study of Animal Behavior. - See the Workshop report for further details.
Grand Challenges in Organismal Biology: How Organisms Walk the Tightrope Between Stability and Change - See the Workshop report for further details.
Find more IOS news on our blog, IOS in Focus. Follow us at http://nsfiosinfocus.wordpress.com.
If you're a new visitor to the Directorate for Biological Sciences website or just want a quick visual and textual summary of our areas of support, please visit the "About BIO" web page where we have added a new interactive organization chart.
See "Additional BIO Resources" for other items of interest including BIO's Guidance on Data Management Plans and BIO Dear Colleague Letters.
BIO Program Director and Reviewer Opportunities
NOTE: March 1 annually (or next business day if that is a weekend or holiday) is the target date for most IOS programs for REU, RET, RAHSS, and ROA supplements as well as proposals for Conferences, Symposia and Workshops (Meetings). Guidance for IOS PIs preparing supplemental requests is posted at: http://www.nsf.gov/bio/ios/suppopp.jsp For Guidance on preparing Proposals for Conferences, Symposia and Workshops (Meetings) visit http://www.nsf.gov/bio/ios/confworkshopguidance.jsp
Please be sure to check the Division of Emerging Frontiers (EF) for additional grant competitions.
Programs and Funding Opportunities
Key: Crosscutting | NSF-wide
Featured NSF-wide Programs
Faculty Early Career Development Program
International Research Fellowship Program
Facilitating Research at Primarily Undergraduate Institutions:
View All NSF-wide Programs
NSF Educational Opportunities by Audience
For Undergraduate Students
For Graduate Students
For Postdoctoral Fellows
For K-12 Educators
Graduate Research Fellowship Program
Full Proposal:
October 26, 2015, Geosciences; Life Sciences
Graduate Research Fellowship Program
Full Proposal:
October 27, 2015, Computer and Information Science and Engineering; Engineering; Materials Research
Graduate Research Fellowship Program
Full Proposal:
October 29, 2015, Psychology; Social Sciences; STEM Education and Learning
Graduate Research Fellowship Program
Full Proposal:
October 30, 2015, Chemistry; Mathematical Sciences; Physics and Astronomy
ADVANCE: Increasing the Participation and Advancement of Women in Academic Science and Engineering Careers
Full Proposal:
November 3, 2015, Institutional Transformation Catalyst (IT Catalyst)
September 10, 2015
- January 21, 2016
ADVANCE IT and IT-Catalyst pre-proposal Technical Assistance Webinars
October 15, 2015
Committee on Equal Opportunities in Science and Engineering (CEOSE)
Advisory Committee Meeting
October 21, 2015
- October 22, 2015
Advisory Committee for Geosciences
Advisory Committee Meeting
November 2, 2015
- November 3, 2015
NSF Grants Conference - Arlington, VA
November 3, 2015
NSF Day at Spelman College in Atlanta Georgia

subset: commoncrawl


text:
- August 23: General Motors Recalls Chevrolet Impala Over Airbag Problems
- August 14: GM Recalls 73,000 Chevrolet Cobalt Cars Over Airbag Failures
- July 20: GM Recalls 10 Chevy Cruze and Chevy Volt Cars
- July 11: GM Recalls 98,000 Cars For Radio and Seat Belt Problems
- July 10: GM Recalls 686,000 Vehicles With Liftgates That Fall On You
Engine Seized And Died
CarComplaints.com Notes: The Trailblazer emerged from an "upscale trim line" of the Blazer, but there's nothing upscale about its transmission problems or its wonky, unpredictable headlights.
8.8pretty bad
- Typical Repair Cost:
- $4,580.00
- Average Mileage:
- 71,800 miles
- Total Complaints:
- 5 complaints
Most Common Solutions:
- new engine!!! (5 reports)
engine problem
Helpful websites
- No one has added a helpful site for this 2002 Trailblazer problem yet. Be the first!


text:
Sewickley Valley Student Ministries
…for middle school and high school students (6-12th grade) throughout the Sewickley Valley!
Student Ministry
… for middle school and high school students (6th-12th grade) throughout the Pittsburgh area!
Student Ministry every Sunday at 4pm in the Ministry Center (5941 ½ Penn Ave). Expect hang out time with students from area schools, crazy games, biblical teachings from Ryan Lancia, and food. Questions? E-mail Ryan at firstname.lastname@example.com
Laurelville Student Retreats
Middle School Nov 13-15, 2015
High School Nov 20-22, 2015
Its time for Laurelville! This is going to be an awesome weekend hanging out with friends & leaders, playing games, worshiping, connecting at Club and of course a strictly friendly game of mud football! The price is $150. Regsiter for middle school or high school then dowload a permission slip and return signed form by Nov 9th.
For more information about our High School & Middle School Ministries contact Ryan Lancia


text:
David Lat
Gay Marriage, SCOTUS, Supreme Court
The (Monday) Morning After: A Conversation About Obergefell With David Lat
ReplyAll conversationalist Zach Abramowitz chats with Above the Law managing editor David Lat about the Supreme Court's big gay marriage ruling.
Law Schools, Money, Student Loans
Good Grief: These Law School 'Debt Per Job' Numbers Are Ugly
For every job obtained by a graduate of these law schools, an extraordinary debt burden has been accrued.
Inventors Will Lead the Legal Future not Licensees
David McCullough's The Wright Brothers serves as an ideal case study on the requirements to innovate; a desire to learn, perseverance, and work ethic. I read it in route to a wonderful opportunity to serve as visiting lecturer for Professor and Parsons Behle & Latimer attorney Randy Dryer's innovative Technology and Modern Litigation course at […]
* Following his surprise resignation, the University of New Hampshire School of Law has banned the former director of its public policy center from stepping foot on campus. There must be something more to this story. Tipsters: time to assemble! [New Hampshire Union Leader]
* With his divorce lawyer's blessing, George Zimmerman released a video where he says he still doesn't think he did anything wrong when he killed Trayvon Martin, and that he feels victimized by President Obama's "racially charged comments." Paint a picture and get that angst out, Georgie. [Gawker]
* You were gonna walk your dog, but then you got high? You've heard of medical marijuana for people, but you probably haven't heard of medical marijuana for pets. Nevada has a bill that'll allow animal owners to smoke a bowl with sick pets. [LXBN]
* In case you missed our Converge conference last week, here are four essential tips that you'll need to know if you intend to make a pitch to members of the mainstream media or legal press in the future. Tip #3 here is clutch. [Hellerman Baretz Communications]
* What's so bad about Biglaw gossip? Absolutely nothing! In fact, ATL's managing editor thinks that "Biglaw firms should [only] be afraid of us if they have something to hide." You can thank us for your firm's transparency, lawyers. [Big Law Business / Bloomberg BNA]
* Many Biglaw firms seem to be dragging their feet to match Davis Polk's generous bonus scale. Why's that? According to one partner, these bonus matches have cut into his firm's profits by about 4 percent. Yikes! [The Economist]
* Total 1L enrollment in law school is the lowest it's been since 1973, when there were 53 fewer schools. The next step would be to reduce tuition to 1973 levels, and then no one would have any more complaints. [DealBook / New York Times]
* Just because Bingham McCutchen bit the big one, it doesn't mean that all of its pro bono cases will have to suffer the same fate. Not only did Morgan Lewis rescue most of the firm's attorneys, but it's also saving 500 of its pro bono cases. [Am Law Daily]
* Now that President Obama has decided to reopen diplomatic relations with Cuba, lawyers are champing at the bit for more business opportunities. Love Cuban cigars? Well, lawyers love trademark disputes involving those cigars. [National Law Journal]
* Greenberg Traurig reminds Florida clerks that if they issue gay marriage licenses, they could be criminally charged. Plaintiffs' attorneys remind Florida clerks that if they refuse to issue gay marriage licenses, they could be sued. [Tampa Bay Times]
* Our managing editor, David Lat, sat down with Vivia Chen to dish about some of his favorite things, from his new book, Supreme Ambitions (affiliate link), to his new fiancé. Her book review: "I liked it! It's a fun, breezy read." Hooray! [The Careerist]
An Outsider's Perspective: A Review Of David Lat's Supreme Ambitions
Why should someone who will have a hard time relating to the duties of a federal law clerk read Supreme Ambitions?
From Lawyer To Blogger To Novelist: An Interview With David Lat, Author Of Supreme Ambitions
According to the New York Times, "for an elite niche," Supreme Ambitions "has become the most buzzed-about novel of the year."
* "[I]t's hard to find anybody as handsome as Antonin Scalia." Some would beg to differ, but as it turns out, legal scholar Bryan Garner can brown-nose with the best of them. [WSJ Law Blog]
* For the third year in a row, Cooley Law graduates have mostly failed the July administration of the Michigan bar. So much for it being a "highly prestigious" law school. [Crain's Detroit Business]
* In a lawsuit filed against real estate database Zillow, a former employee claims she was subjected to the "most heinous acts of sexual harassment imaginable" and "sexual torture." That's just lovely. [LAist]
* Law firm merger activity is still going strong as 2014 winds down to a close. Aside from big-name tie-ups like Bingham / Morgan Lewis and Locke Lord / Edwards Wildman, other firms like Verill Dana also had the urge to merge. [Am Law Daily]
* "Does it really surprise me? Not all that much." University of Memphis School of Law students are on high alert during finals time after one of their own was almost robbed at gunpoint across the street from campus this week. Yikes. [WMC Action News 5]
* In case you've been sleeping under a rock, Above the Law's managing editor, David Lat, wrote a book called Supreme Ambitions (affiliate link), and it's been receiving rave reviews. If you dig clerkship lit, you should try to check it out. [National Law Journal]
Associate Salaries, Biglaw, Money
Is there something fishy about the reported salaries of first-year associates in Biglaw?
Antonin Scalia, Biglaw, Books, Boutique Law Firms, Crime, Department of Justice, Immigration, Mergers and Acquisitions, Morning Docket, Pro Bono, SCOTUS, Supreme Court
* Justice Scalia spoke at CU-Boulder last night. For his sake, we certainly hope he didn't speak about any issues that might someday appear before SCOTUS, lest he be asked to recuse. [Boulder Daily Camera via How Appealing]
* Another one bites the dust over at Main Justice: David O'Neil, the head of the criminal division, is stepping down in the wake of the BNP Paribas case, and will likely have many white-shoe law firm suitors. [DealBook / New York Times]
* Fox Rothschild picked up a 18-lawyer boutique firm in Texas, which will serve as the home of its first outpost in the Lone Star State. Energy law, surprisingly, wasn't the driving factor. [Legal Intelligencer]
* "I have a heart and I have two kids." That's a pretty damn good reason for Biglaw attorneys to take a break from their corporate billable hours to represent undocumented children pro bono. [WSJ Law Blog]
* Scott Greenfield reviews Lat's forthcoming novel, Supreme Ambitions (affiliate link). Of course, in SHG style, it contains a spoiler. Try to skip that clearly marked paragraph. [Simple Justice]
Lean Legal: Three Techniques for the Agile Lawyer
A growing number of attorneys are turning to a set of project management and process improvement techniques commonly known as "Agile."
Admin, Announcements, Events, Shameless Plugs, Texas
Above The Law Is Coming To Houston
If you'll be in Houston on September 15, please come by and say hello!
Advertising, Billable Hours, Events, General Counsel, In-House Counsel, Job Searches, Shameless Plugs, Technology, This Is an Ad
What Is It Like To Work As The General Counsel Of A Startup Company?
Words of wisdom from in-house lawyers at some of the country's most exciting startup companies.
Advertising, Events, General Counsel, In-House Counsel, Shameless Plugs, Technology, This Is an Ad
Innovative Lawyers: You're Invited To A Night With NYC's Premier Start-Up GCs
You are invited to a riveting panel and networking event on life as a start-up GC. Get the details here!
Advertising, Drinking, Events, Fabulosity, Holidays and Seasons, Parties, Pictures, Shameless Plugs, This Is an Ad
The ATL Valentine's Day Party: A Photo Essay
Here are some pictures from our fabulous event. Join us at the next one!
Advertising, Drinking, Events, Fabulosity, Holidays and Seasons, Parties, Pictures, Shameless Plugs, This Is an Ad
The ATL Holiday Party: A Photo Essay
Thanks to our guests and to our sponsors, Prestige Legal Search and Superior Discovery. Here are some pictures from our fabulous event.
Abortion, Events, Gay Marriage, Health Care / Medicine, SCOTUS, Supreme Court, Thomas Goldstein
Supreme Court Cheat Sheet: An ATL Infographic
A visual look at the major cases on the Supreme Court's docket for the current Term.
9th Circuit, Biglaw, Cozen O'Connor, Divorce Train Wrecks, Gay, Gay Marriage, Job Searches, Jury Duty, Law Schools, Lesbians, Litigators, Morning Docket, SCOTUS, Supreme Court, Women's Issues
* The number of women arguing before the Supreme Court is still small, but most of its appellate practitioners follow sage advice like this: "Clerk, work, and don't be a jerk." [National Law Journal]
* If you were curious about whether gays and lesbians could be excluded from juries on the basis of their sexual orientation, the Ninth Circuit is about to lay down the law. [New York Times]
* Now that the Supreme Court has ruled in Windsor, Cozen O'Connor will be forced to give a deceased partner's profit-sharing benefits to her wife, and not her parents. [Legal Intelligencer]
* Who are Biglaw's top innovators of the last 50 years? There are many familiar names, but one of them is near and dear to our own hearts at Above the Law: It's our managing editor, David Lat. Congratulations! [Am Law Daily]
* If you're making a career change to go to law school, you should think about why the the hell you'd do such a thing right now — or try to leverage it in applications. [Law Admissions Lowdown / U.S. News]
* In a surprise move, Wendi Murdoch, better known as Rupert Murdoch's soon-to-be ex-wife, has hired William Zabel to represent her in the divorce. This is going to get very, very messy. [New York Times]
* "Why you mad, bro?" Brian Zulberti, the man with the muscles, is trying to make the most of his 15 minutes of fame. He's lined up several job interviews, so wish him good luck. [Delaware News Journal]
Bankruptcy, Deaths, In-House Counsel, Law Schools, LSAT, Morning Docket, Pro Bono, Trials
* Under the leadership of emergency manager Kevyn Orr, Detroit is now the biggest U.S. city to declare bankruptcy in history. Unfortunately, not even the strict Jones Day dress code could save them. [Am Law Daily]
* As one of our columnists David Mowry told us weeks ago, New York wants to close the justice gap by looking to the state's best untapped resources for pro bono work: in-house counsel. [New York Law Journal]
* It turns out the "new employer survey" to be used by U.S. News is really just the old employer survey that's been used in the rankings since 1990. How incredibly anticlimactic. [Morse Code / U.S. News & World Report]
* Law schools are officially ready to scrape the bottom of the barrel when it comes to filling their classes. Some are now accepting first-time June LSAT scores for fall admission. [National Law Journal]
* Our managing editor, David Lat, comes to the defense of fictional representations of the law, but seeing as he's writing a fictional legal novel, we think he's kind of biased. [Room for Debate / New York Times]
* Mobsters really don't like rats, and it looks like someone who was planning to testify against Whitey Bulger may have been whacked after having been dropped from the prosecution's witness list. [CNN]
Advertising, California, Events, Gay, Parties, Pictures, Shameless Plugs, This Is an Ad
Thanks To Our West Coast Readers And To Recommind
Thanks to all of the readers who attended our event in San Francisco last week and to our friends at Recommind for sponsoring.


text:
Recent Articles
- What are Encrypted Forms and how to use them as expert?
- How to Set Up the Configurable List Widget
- Whitelisting JotMails IP Addresses
- How to Capture Stripe Payment Authorization
- Submissions report: How to change submissions date and time to local?
- How to Downgrade Subscription back to Free Account
- Upload to Dropbox with JotForm
- How to upgrade my account
- Adding Form To SharePoint Site
- How can I receive SSL Submissions?
Getting Started
Learn how to use JotForm, create your first web form, and discover the form builder.
Payment Forms
Create order forms to collect donations or sell single/multiple products, and subscriptions.


text:
Kitten for sale, including essential items
Male kitten, approximately 10 weeks old in need of a loving homr. Very playful and is used to being around children. Has been flea'd and comes with litter box, food bowl, kitten leash and whatever food and litter we have left. Only being sold because
- DOB:27 Jul 2015
- Rehome date:21 Sep 2015


text:
Women Helping Women, Inc. Women Helping Women, Inc.
Here's a sample of our volunteer opportunities:VIEW AS
Mission Statement
Women Helping Women, Inc. serves Southwestern Ohio as a unique provider of crisis intervention and support services for direct and indirect victims of sexual assault, domestic violence and stalking and takes a leading role in educationg the community in order to promote awareness and help prevent these types of abuse.
The agency provides 24-hour crisis line, short term crisis intervention, support groups, court and law enforcement advocacy, hospital accompaniment for rape victims and information and referral. The agency also offers child sexual abuse and date rape/dating violence prevention programs. Women Helping Women, Inc. is funded in part by the City of Cincinnati, Hamilton County, the United Way and other sources of public and private support.
Women Helping Women, Inc. accepts donations. Donate Now.
- Valerie Louis
- (513) 977-5541
- Need admin access?
(513) 977-5544


text: Delvin Choice: "A Song for You" (The Voice Audition) by Free Britney at February 26, 2014 6:02 am. Comments Barista Delvin Choice comes back to audition again, striking gold with his take on Donny Hathaway's "A Song for You." Share Tweet Email Edit Delete Follow The Voice? Facebook Disqus Tag: The Voice Related Videos: The Voice Videos Uploaded by: Free Britney Uploaded: February 26, 2014 Duration: 284 seconds


text:
|Publication number
|Publication type
|Application number
|Publication date
|20 Dec 1983
|Filing date
|15 Dec 1980
|Priority date
|15 Dec 1980
|Fee status
|Also published as
|Publication number
|Jitka Solc nee Hajna
|Original Assignee
|The Dow Chemical Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (25), Non-Patent Citations (2), Referenced by (144), Classifications (75), Legal Events (4)
|External Links: USPTO, USPTO Assignment, Espacenet
This invention relates to colloidal size particulates containing particles of an inorganic material and to polymerization processes used to prepare such particulates.
Metals, metal oxides, pigments, fillers and other inorganic particulates that tend to agglomerate are often coated with or encapsulated in hydrophobic polymers. These coated or encapsulated particles are often used in a wide variety of applications such as electroconductive additives to plastics, toners in electrophotographic applications, pigmented paints as well as many other applications.
Conventionally, such particulates are prepared by (1) treating the inorganic solid with acid, a combination of acid and base, alcohol or a polymer solution; (2) dispersing an addition polymerizable monomer in an aqueous dispersion of a treated inorganic solid and (3) subjecting the resulting dispersion to emulsion polymerization conditions. Examples of such methods are described in U.S. Pat. Nos. 4,048,136; 3,383,346; 3,935,340; 3,544,500 and 3,884,871. Unfortunately, these methods are deficient in that they often require expensive multi-step procedures, anchoring agents, functional additives, stabilizing agents and the like. Also, the polymeric particulates often must be employed as viscous pastes or dry powders.
In view of the deficiencies of the prior art methods for preparing such particulates, an improved method which eliminates or substantially reduces the adverse affects of the aforementioned procedure deficiencies is highly desirable.
In one aspect, the present invention is such an improved method which comprises the steps of (1) emulsifying a hydrophobic, emulsion polymerizable monomer in an aqueous colloidal dispersion of discrete particles of an inorganic solid and (2) subjecting the resulting emulsion to emulsion polymerization conditions to form a stable, fluid aqueous colloidal dispersion of the inorganic solid particles dispersed in a matrix of a water-insoluble polymer of the hydrophobic monomer. Surprisingly, dispersion of the inorganic solid particles into the polymer matrix is achieved by a process having an emulsion polymerization step without pretreating the particles with polymer, acid or other conventional anchoring agent prior to the emulsion polymerization step. Also, in the colloidal size polymer matrix having the inorganic solid dispersed therein, the inorganic solid particles remain in a discrete, essentially nonagglomerated form. Hereinafter, this colloidal-size matrix is called "matrix particulate" or "matrix particles." Thus, the discrete inorganic solid particles are entirely coated with polymer. Moreover, in many particles of the particulate (colloidal-size polymer matrix), two or more inorganic particles reside in a spaced apart relationship.
In another aspect, this invention is the aforementioned matrix particulate. In the matrix particles, the inorganic particles exist as discrete (nonaggregated) particles, each being surrounded by the polymer matrix.
The matrix particulates of this invention are particularly useful in applications requiring a colloidal size particulate having magnetic properties. Examples of such applications include (1) the separation of a water-miscible fluid from a water-immiscible fluid as described in U.S. Pat. No. 4,108,767; (2) clarification processes as described in U.S. Pat. Nos. 4,089,779 and 4,110,208; and (3) the absorption of e.l.m. radiation. Such matrix particulates are also useful in magnetic paints, electrically resistive barriers and moldable magnetic powders, as toners in electrophotographic applications, electroconductive additives for plastics, pigments in paint and ink formulations and pigmentary core latexes. Such particulates are suitably employed as diagnostic materials in human and animal health applications such as described in Nature, Vol. 270, pp. 259-261 (Nov. 17, 1977); Science, Vol. 200, pp. 1074-1076 (June 2, 1978) and U.S. Pat. No. 4,157,323; and as catalysts such as described in U.S. Pat. No. 4,157,323.
Inorganic solids suitably employed in the practice of this invention are inorganic materials in the form of colloidal particles, i.e., have diameters generally less than about 0.6 micrometer, preferably from 0.005 to about 0.4 micrometer, most preferably from about 0.005 to about 0.1 micrometer, which particles tend to form aggregates if not treated with a dispersant or surface active agent. When dispersed in water, these inorganic particulates tend to aggregate or agglomerate upon standing. Often, as a result of such agglomeration, the inorganic particles settle to the lower region of the aqueous dispersion. These solids are insoluble in water and hydrocarbon and are incapable of adsorbing more than 5 weight percent of hydrocarbon based on the weight of the solid. Examples of such inorganic solids are inorganic pigments such as titanium dioxide, zinc oxide, antimony oxide, magnesium oxide, fly ash, red oxide, yellow oxide, lemon chrome and cobalt blue; powders of metals including titanium, copper, brass, gold and stainless steel; carbonates such as calcium and magnesium carbonates; phosphates such as calcium and lead phosphates; silica and silicates such as clay and glass particles; chromates such as lead chromate; metal salts such as silver chloride; inert filler materials such as titanates and talc; ferrites; aluminum hydrates; and the like. Of particular interest are powders of metals and metal alloys such as aluminum, cobalt, iron, copper, nickel, chromium, zinc, palladium, silver, ruthenium, platinum, gold, rhodium, lead and alloys of these metals. Also of interest are the oxides of such metals, particularly magnetic oxides such as iron, nickel, cobalt or alloys thereof, as well as oxides of other elements such as titanium dioxide and silica. Of special interest are titanium dioxide that is preferably in the form of particles having an average diameter in the range from about 0.2 to about 0.4 micrometer, silica that is preferably in the form of particles having an average diameter from about 0.005 to about 0.2 micrometer, and the magnetic iron oxides of the formula Fe3 O4 which are in the form of finely divided magnetic particles or ferrofluids as such are disclosed in U.S. Pat. No. 3,981,844, preferably those having an average particle diameter in the range from about 0.005 to about 0.1 micrometer. Typically, such fluids are aqueous dispersions of magnetic particles which are prepared by methods normally employed in comminuting metals and their ores, e.g., grinding and electrolysis or by precipitation methods. In both instances, chemical dispersants and/or surfactants as described hereinafter are used to maintain the aqueous dispersions in a reasonably stable state. Similar aqueous colloidal dispersions of nonmagnetic, inorganic solids are prepared by conventional techniques used in the manufacture of colloidal gold, calcium carbonate, titanium dioxide, silica and the like. Examples of such methods are described by A. King in Inorganic Preparations, Van Nostrand (1936); H. N. Holmes in Manual of Colloid Chemistry, MacMillan (1922); R. R. Myers et al. in Pigments, Marcel-Dekker (1975) and Angew. Chem., International Ed., Vol. 19, 190-196 (1980).
The hydrophobic monomers employed in the practice of this invention are essentially water-immiscible, i.e., the monomer forms a separate phase when 5 g of monomer is mixed with 100 g of water. Such water-immiscible monomer(s) will polymerize under emulsion polymerization conditions to form a water-insoluble polymer which will exist in the form of a stable aqueous colloidal dispersion, usually with the aid of suitable surface active agents. Examples of suitable hydrophobic monomers include monovinylidene aromatic monomers such as styrene, vinyl toluene, t-butyl styrene, chlorostyrene, vinylbenzyl chloride and vinyl pyridene; alkyl esters of α,β-ethylenically unsaturated acids such as ethyl acrylate, methyl methacrylate, butyl acrylate and 2-ethylhexyl acrylate; unsaturated esters of saturated carboxylic acids such as vinyl acetate, unsaturated halides such as vinyl chloride and vinylidene chloride; unsaturated nitriles such as acrylonitrile; dienes such as butadiene and isoprene; and the like. Of these monomers, the monovinylidene aromatics such as styrene and the alkyl acrylates such as butyl acrylate are preferred. In addition to the aforementioned hydrophobic monomer, relatively minor portions, e.g., less than 10, preferably less than 5, weight percent based on total monomer component, of a water-soluble monomer such as an ethylenically unsaturated carboxylic acid or its salt such as acrylic acid or sodium acrylate; methacrylic acid, itaconic acid and maleic acid; an ethylenically unsaturated carboxamide such as acrylamide; vinyl pyrrolidone; hydroxyalkyl acrylates and methacrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate; aminoalkyl esters of unsaturated acids such as 2-aminoethyl methacrylate; epoxy functional monomers such as glycidyl methacrylate; sulfoalkyl esters of unsaturated acids such as 2-sulfoethyl methacrylate; ethylenically unsaturated quaternary ammonium compounds such as vinylbenzyl trimethyl ammonium chloride may be employed. It is critical, however, that such water-soluble monomers not be employed in amounts sufficient to render the resulting polymer soluble in water. Particularly effective monomer recipes for the practice of this invention are those containing from about 20 to about 90 weight percent of styrene, from about 10 to about 80 weight percent of alkyl acrylate such as butyl acrylate and from about 0.01 to about 2 weight percent of the unsaturated carboxylic acids such as acrylic acid, with said weight percentages being based on the weight of total monomers.
In the practice of this invention, it is preferred to initially prepare an aqueous colloidal dispersion of the inorganic solid by contacting said solid with an aqueous solution of a water-soluble surfactant or emulsifier thereby forming the dispersion which contains from about 5 to about 70 weight percent of the inorganic solid. Typically, suitable surface active agents or emulsifiers include salts of fatty acids such as potassium oleate, metal alkyl sulfates such as sodium lauryl sulfate, salts of alkyl aryl sulfonic acids such as sodium dodecylbenzene sulfonate, polysoaps such as sodium polyacrylate and alkali metal salts of methyl methacrylate/2-sulfoethyl methacrylate copolymers and other sulfoalkyl acrylate copolymers, and other anionic surfactants such as the dihexyl ester of sodium sulfosuccinic acid; nonionic surfactants such as the nonionic condensates of ethylene oxide with propylene oxide, ethylene glycol and/or propylene glycol; and cationic surfactants such as alkylamine-guanidine polyoxyethanols, as well as a wide variety of micelle generating substances described by D. C. Blackley in Emulsion Polymerization, Wiley and Sons, Chapter 7 (1975) and other surfactants listed in McCutcheon's Detergents and Emulsifiers, 1980 Annual, North American Edition, McCutcheon, Inc., Morristown, N.J. Also included among the suitable surfactants are the surface active polymers (often called polysoaps), e.g., those described in U.S. Pat. No. 3,965,032. Of the suitable surfactants, the anionic varieties such as the potassium salts of functionalized oligomers, e.g., Polywet varieties sold by Uniroyal Chemical, are preferred. Such surface active agents or emulsifiers are employed in amounts sufficient to provide a stable dispersion of the inorganic solid in water. Preferably, such surface active agents are employed in concentrations in the range from about 0.2 to about 10, most preferably from about 1 to about 6, weight percent based on the aqueous phase. Particularly desirable processes for forming such aqueous colloidal dispersions of inorganic solids are described in U.S. Pat. Nos. 3,826,667; 3,981,844; 3,843,540 and Industrial Engineering Production and Research Development, Vol. 19, 147-151 (1980).
The aqueous dispersion of inorganic solid is then combined with the water-immiscible monomer to form the desired emulsion by normal mixing procedures, for example, passing both the dispersion and monomer through a high shear mixing device such as a Waring blendor, homogenizer or ultrasonic mixer. Alternatively and preferably, the monomer is added continuously to the aqueous dispersion of inorganic solid during the polymerization. Advantageously, the monomer is in the form of an aqueous emulsion of the monomer which emulsion is maintained by a water-soluble monomer and/or a water-soluble emulsifier such as described hereinbefore. As another alternative, the aqueous emulsion of inorganic solid and water-immiscible monomer can be prepared by adding colloidal size inorganic particles to an existing aqueous emulsion of monomer. In such instances, it is often desirable to add additional emulsifier to the emulsion prior to or simultaneous with the addition of the inorganic solid. In the emulsion of inorganic solid and water-immiscible monomer, the aqueous phase is present in a proportion sufficient to be the continuous phase of the emulsion. The inorganic solid is present in proportions sufficient to provide the matrix particulate, with the desired characteristics, e.g., magnetic properties, pigmentation, etc. The water-immiscible monomer is present in proportion sufficient to enclose or encapsulate the inorganic solid when polymerized, and sufficient emulsifier and/or surface active agent is present to provide an aqueous colloidal emulsion which is sufficiently stable to be subjected to emulsion polymerization conditions. Preferably, the emulsion contains from about 0.1 to about 25 weight percent of inorganic solid, from about 1 to about 30 weight percent of monomer and a remaining amount of the aqueous phase including emulsifier (surfactant), catalyst and the like.
The emulsion polymerization conditions employed in the practice of this invention are generally conventional free-radical type polymerizations carried out in the presence of a radical initiator such as a peroxygen compound, an azo catalyst, ultraviolet light and the like. Preferably, such polymerization is carried out in the presence of a water-soluble peroxygen compound at temperatures in the range from about 50� to about 90� C. The emulsion is generally agitated during the polymerization period in order to maintain adequate feed transfer. The concentration is normally in the range from about 0.005 to about 8, preferably from about 0.01 to about 5, weight percent based on total monomer. Examples of suitable catalysts include inorganic persulfate compounds such as sodium persulfate, potassium persulfate, ammonium persulfate; peroxides such as hydrogen peroxide, t-butyl hydroperoxide, dibenzoyl peroxide and dilauroyl peroxide; azo catalysts such as azobisisobutyronitrile, and other common free-radical generating compounds. Also suitable are various forms of free-radical generating radiation means such as ultraviolet radiation, electron beam radiation and gamma radiation. Alternatively, a redox catalyst composition can be employed wherein the polymerization temperature ranges from about 25� to about 80� C. Exemplary redox catalyst compositions include a peroxygen compound as described hereinbefore, preferably potassium persulfate or t-butyl hydroperoxide and a reducing component such as sodium metabisulfite and sodium formaldehyde hydrosulfite. It is also suitable to employ various chain transfer agents such as mercaptans, e.g., dodecyl mercaptan; dialkyl xanthogen disulfides; diaryl disulfides and others listed in Blackley, supra, Chapter 8 in concentrations as described therein.
Following emulsion polymerization, the emulsion polymerizate can be withdrawn from the polymerization vessel and (1) the emulsion is employed as is or (2) the unreacted monomer and other volatiles are removed to form a concentrated emulsion and then used or (3) the matrix particulate can be separated from the aqueous continuous phase of the dispersion by conventional means such as drying under vacuum. The dried matrix particulate preferably contains from about 1 to about 70 weight percent of inorganic solid and from about 99 to about 30 weight percent of polymer matrix.
The following examples are given to illustrate the invention and should not be construed as limiting its scope. Unless otherwise indicated, all parts and percentages are by weight.
An aqueous dispersion of iron oxide (Fe3 O4) is prepared by the procedure described in Table I, footnote (2).
To a 3-neck flask equipped with a stirrer, two addition funnels and a condenser is added a mixture of 507 g of the 28.3 percent solids dispersion of Fe3 O4 (200 gauss and average particle size less than 0.5 micrometer) and 203 g of deionized water. The mixture is then heated under nitrogen atmosphere to 90� C. while stirring the mixture. At this temperature of 90� C., a monomer stream and an aqueous surfactant stream are separately introduced via the two addition funnels into the flask, each stream being introduced at the rate of 5.5-6.0 ml/min over a period of 90 minutes. The monomer stream consists of 64 g of styrene, 16 g of butyl acrylate and 3.0 g of t-butyl hydroperoxide. The aqueous stream consists of 80 g of deionized water, 1.25 g of a potassium salt of a functionalized oligomer sold by Uniroyal Chemical under the trade name "Polywet KX-4" and 2.0 g of sodium formaldehyde hydrosulfite. The resulting reaction mixture is stirred and maintained under nitrogen at 90� C. for an additional half hour. The resulting 24.6 percent solids latex is concentrated by distillation under vacuum to a 29.7 percent solids latex having dispersed particles with a polymeric as well as magnetic characteristic. The particles have a narrow particle size distribution and an average particle diameter of 0.107 micrometer as determined by hydrodynamic chromatography. The latex remains stable in an applied magnetic field of 60 gauss and exhibits properties common to magnetic colloids. For example, such magnetic colloids are magnetizable liquids that are instantly demagnitized upon removal of a magnetic field and levitate an object upon application of a magnetic field. Magnetization of the latex by a Collpits oscillator circuit technique, described by E. A. Peterson et al. in the Journal of Colloidal and Interfacial Science, 70, 3 (1977), is estimated to be 135 gauss.
A mixture of 7 g of Ferrofluid A-05 (200 gauss, 25.7 percent solids) sold by Ferrofluidics Corporation, Burlington, MA; 1 g of a 10 percent aqueous solution of the dihexyl ester of sodium sulfosuccinic acid and 140 g of water are converted to an aqueous dispersion with an ultrasonic probe operating at 90 percent capacity for 2 minutes. The resulting dispersion is added to 15 g of styrene containing 0.1855 g of t-butyl peroxide. The dispersion is heated with agitation under a nitrogen atmosphere to 93� C. A 0.05-g portion of sodium formaldehyde hydrosulfite dissolved in 2 ml of water is introduced into the dispersion. The polymerization reaction is continued for 2 hours to form an aqueous colloidal dispersion containing 10.3 percent solids. The resulting matrix particulate is recovered in the form of an aqueous dispersion which is responsive to a magnetic field. Electromicrographs of individual matrix particles show them to have a polymer matrix enclosing discrete particles of the Ferrofluid. Many matrix particles are observed to contain more than one discrete particle of magnetic iron oxide. The average particle diameter of the matrix particulate is about 0.085 micrometer.
A 40-g portion of Ferrofluid A-01 (50 gauss) containing 7.2 percent solids is centrifuged on a high speed laboratory centrifuge for 6 hours at 17,000 rpm. A 3.8-g portion of sediment (60 percent solids) is recovered from the centrifugation and redispersed in 15 g of an aqueous solution containing 5 percent of potassium oleate and 3.2 g of an aqueous solution containing 4 percent of the dihexyl ester of sodium sulfosuccinic acid. The resulting dispersion is combined with 230 g of deionized water and then agitated using an ultrasonic probe. To the resulting dispersion is added 25 g of styrene and 0.2 g of t-butyl peroxide. The dispersion is heated under nitrogen with agitation to a temperature of 90� C. The dispersion contains 0.88 percent of Fe3 O4, 0.3 percent of potassium oleate, 0.04 percent of the dihexyl ester, 9.1 percent of styrene and 0.76 percent of t-butyl peroxide. At this point, 0.05 g of sodium formaldehyde hydrosulfite dissolved in 2 ml of water is introduced into the dispersion and the polymerization reaction is allowed to proceed for 30 minutes. Following this time, a 9.4 percent solids polymer matrix latex of polymer matrix iron particles is recovered wherein the average particle diameter of the matrix particles is 0.08 micrometer.
A 3.8-g sample of the sediment as prepared in Example 2 is dispersed in 15 g of an aqueous solution of 5 percent of potassium oleate. This dispersion is combined with 220 g of deionized water and agitated with an ultrasonic probe. To this dispersion is added 25 g of styrene and 0.196 g of t-butyl hydroperoxide. This dispersion contains 0.9 percent of F3 O4, 0.28 percent of oleate, 9.47 percent of styrene and 0.07 percent of t-butyl peroxide. The resulting dispersion is heated under nitrogen with agitation to 90� C. and 0.05 g of sodium formaldehyde hydrosulfite is added to the dispersion. The reaction is allowed to proceed for 30 minutes. The resulting latex of encapsulated iron particles contains 7.4 percent solids.
Similar results are achieved with the foregoing procedure when sodium lauryl sulfate, sodium dihexyl sulfosuccinate, methyl methacrylate/2-sulfoethyl methacrylate/acrylic acid (67/6/27) terpolymer, methyl methacrylate (80/20) copolymer, methyl methacrylate/2-sulfoethyl methacrylate (85/15) copolymer or mixture of two or more of same is substituted for the potassium oleate. In the aforementioned polymers, the numbers in parenthesis represent mole percentages of the individual monomers.
I. Dispersion of Inorganic Solid
Except for the magnetic iron oxide of Sample No. 11 of the following table, several pigment dispersions are prepared by dispersing the pigment specified in Table I in an aqueous solution of a potassium salt of a functionalized oligomer sold by Uniroyal Chemical under the trade name "Polywet KX-4." The dispersion of magnetic iron oxide is prepared according to footnote (2) of the following table. Dispersion is achieved by using an ultrasonic probe 3 times operating at 90 percent capacity for 5 minutes each time. The dispersion is allowed to stand overnight and the top layer containing the colloidal dispersed pigment is decanted and retained for the subsequent polymerization.
II. Polymerization
Each of the aforementioned pigment dispersions is subjected to the following emulsion polymerization procedure.
A mixture of 14.5 g of one of the pigment dispersions specified in Table I, 150 g of deionized water and 1.7 g of 1N NaOH is prepared by using an ultrasonic probe operating at 90 percent capacity for 4 minutes. This mixture is charged to a one-liter, 3-neck flask equipped with a stirrer, condenser and 2 addition funnels. The mixture is heated with agitation under nitrogen to 90� C. A monomeric stream consisting of 20 g of styrene and 20 g of butyl acrylate and an aqueous stream consisting of 45 g of deionized water, 1.5 g of a 40 percent solution of Polywet KX-4 in water, 1 g of 1N NaOH and 0.75 g of sodium persulfate are each added at the rate of about 2 ml/minute. After addition of the monomer and aqueous stream is completed, the resulting reaction mixture is maintained under nitrogen and with agitation at 90� C. for 40 minutes. The resulting latex is placed under vacuum with agitation to remove unreacted monomer and water thereby providing a latex, herein called "a dispersion of a matrix particulate."
The several aqueous dispersions of matrix particulates are described in Table I.
TABLE I__________________________________________________________________________Pigment DispersionPigment.sup.(1) Dispersant.sup.(2) Monomer.sup.(3) Emulsifier.sup.(4) AverageSam- Amt Amt Amt Amt Initiator.sup.(5) % Particleple Avg Part Wt Wt Wt Ratio Wt Wt Amt Solids DiameterNo. Type Size, μm % Type % Type of Monomer % Type % Type Wt % .sup.(6) μm.sup.(7)__________________________________________________________________________1 TiO2 <0.45 2.3 KX-4 0.6 S/BA 1:1 15.7 KX-4 0.43 Na2 S2 O8 0.29 17.8 0.53 (0.114)2 TiO2 " 5.5 " 2.0 S/BA 1:1 18.4 " 0.20 " 0.13 24.3 0.65 (0.15)3 TiO2 " 10.2 " 0.25 S/BA 1:1 17.0 " 0.78 " 0.16 28.1 0.74 (0.12)4 TiO2 " 11.7 " 0.36 S/BA 1:1 7.8 " 0.58 " 0.20 20.2 0.68 (0.118)5 CaCO3 <0.09 1.3 " 0.036 S/BA 1:1 12.7 " 0.30 " 0.20 14.0 0.426 ZnO <0.11 5.6 " 0.50 S/BA 9:1 18.7 " 0.48 " 0.16 23.8 0.387 ZnO " 13.6 " 0.64 S/BA 9:1 13.5 " 0.35 " 0.11 27.2 0.318 Clay <0.38 6.5 " 0.70 S/BA 1:1 19.2 " 0.23 " 0.12 25.0 0.859 Silica <0.045 5.6 " 1.0 S/BA 1:1 18.7 " 0.20 " 0.07 23.5 0.1210 Silica " 6.5 " 1.2 S/BA 1:1 12.9 " 0.06 " 0.05 19.5 0.11611 Magnetic <0.035 7.3 " 4.5 S/BA 4:1 8.1 " 0.01 TBHP 0.18 19.6 0.09 Iron Oxide__________________________________________________________________________ .sup.(1) Average particle size in micrometers (μm) as measured by electron microscopy. Weight percent of pigment based on weight of aqueous dispersion of matrix particulate. .sup.(2) KX-4 = Polywet KX4 sold by Uniroyal Chemical. Weight percent of dispersant based on weight of aqueous dispersion of matrix particulate. I the preparation of the iron oxide dispersion of Sample No. 11, an aqueous solution of ferric and ferrous salts are mixed in amounts to maintain the Fe+3 /Fe+2 molar ratio at ˜2:1. Magnetic iron oxide is then precipitated at 0�-10� C. by rapid addition of 1N NH4 OH and vigorous agitation until pH of 9-10 is reached. Immediately thereafter, the dispersant is introduced with agitation to th aqueous medium containing the precipitated iron oxide and the mixture is heated at 90� C. for one hour. During this period, hydrochloric acid is added until the pH of the mixture reaches 7.5. The particles of precipitated iron oxide are washed with deionized water and redispersed i deionized water containing additional dispersant by using an ultrasonic probe. Magnetization of the dispersed iron oxide is measured by a Collpit oscillator circuit technique. .sup.(3) S = styrene, BA = butyl acrylate. Weight percent of monomer base on weight of aqueous dispersion of matrix particulate. .sup.(4) KX-4 = same as in .sup.(2) of this Table. Weight percent of emulsifier based on weight of aqueous dispersion of matrix particulate. .sup.(5) TBHP = tertbutyl hydroperoxide. Weight percent of initiator base on weight of aqueous dispersion of matrix particulate. .sup.(6) % Solids determined by freezing aqueous dispersion of matrix particulate in methylene chloride/dry ice bath and drying the dispersion at 1 mm Hg for 36 hours. The solids (matrix particulate) are then weighed and converted to % solids by dividing weighed solids by weight of the aqueous dispersion of matrix particulate. The dried matrix particulate is compression molded at 125� C. to form a disk (2.54 cm diameter and 1.27 cm thick). .sup.(7) Average particle diameter determined by hydrodynamic chromatography. Sample Nos. 1-4 represent bimodal systems with the diameter for each mode being shown separately.
Using a Waring blender, a 150-g portion of titanium dioxide having an average particle size in the range of 0.2-0.4 micrometer is dispersed in 350 g of deionized water containing 0.3 g of an ethanolated alkylguanidine amine complex sold by American Cyanamid under the trade name Aerosol C-61. The resulting dispersion is then combined with mixing with 240 g of deionized water containing 15 g of a 40 percent solution of Polywet KX-4 in water.
This dispersion (471 g) is combined with 248 g of deionized water, 4 g of a 40 percent solution of Polywet KX-4 in water, 3 g of 1N NaOH and 0.8 g of a 1 percent solution of the pentasodium salt of (carboxymethylimino) bis(ethylenenitrilo)tetraacetic acid in water. The resulting mixture is charged to a 3-neck flask equipped with a stirrer, two addition funnels and a condenser. The mixture is stirred and heated under nitrogen to 90� C. At this temperature, (1) a monomer stream consisting of 40 g of styrene and 40 g of butyl acrylate and (2) an aqueous stream consisting of 80 g of deionized water, 10 g of a 40 percent solution of Polywet KX-4 in water, 2.2 g of Na2 S2 O8 and 9 g of 1N NaOH are introduced into the flask with each stream being introduced at the rate of ˜2 ml/min. After the addition of the monomer and aqueous streams is completed, the resulting mixture is maintained at 90� C. under nitrogen and agitation for an additional 30 minutes. The resulting latex which contains 19.4 percent solids is concentrated via evacuation to a 55 percent solids dispersion which is a bimodal dispersion wherein one mode has an average particle diameter of 0.65 micrometer and the other mode has an average particle diameter of 0.11 micrometer.
A coating is prepared from the latex that exhibits excellent opacity.
|Cited Patent
|Filing date
|Publication date
|1 Mar 1949
|7 Jul 1953
|Pabco Products Inc
|Method of coating mineral particles
|3 Jun 1957
|16 May 1961
|Monsanto Chemicals
|Composition comprising alumina particles coated with polymer of ethylenically unsaturated monomer
|27 Aug 1963
|25 Oct 1966
|Chevron Res
|Colloidal suspension of ferromagnetic iron particles
|24 Mar 1961
|31 Jan 1967
|Exxon Research Engineering Co
|Isoolefin-multiolefin copolymers through ultrasonic homogenizers
|7 Apr 1965
|14 May 1968
|Goodyear Tire & Rubber
|Particle size control in seed technique emulsion polymerization using hydroxyl group-containing modifier
|19 Jun 1967
|24 Mar 1970
|Xerox Corp
|Imaging systems
|10 Nov 1966
|1 Dec 1970
|Ici Ltd
|Polymer coated particles
|28 Mar 1969
|20 Apr 1971
|Dow Corning
|Method of stabilizing catalyzed organopolysiloxanes
|29 Jun 1973
|20 May 1975
|Nl Industries Inc
|Process for coating pigment particles with organic polymers
|4 Aug 1972
|29 Jul 1975
|Du Pont
|Polymer coated pigment particles and a process for their preparation
|4 Jun 1975
|17 May 1977
|Produits Chimiques Ugine Kuhlmann
|Process for the preparation of pigmentary metallic particles coated with an organic polymer and compositions resulting therefrom
|7 Apr 1976
|19 Jul 1977
|Sun Chemical Corporation
|Encapsulated pigments
|26 Jan 1976
|13 Sep 1977
|Star Paper Limited
|Cast coated paper and its production and compositions for it
|24 May 1976
|10 Jan 1978
|Desoto, Inc.
|Signal coating suitable for lead-based paint hazard abatement or the like and formulations therefor
|2 Aug 1976
|31 Jan 1978
|Xerox Corporation
|Method of sizing monomer droplets for suspension polymerization to form small particles
|20 Apr 1977
|5 Jun 1979
|California Institute Of Technology
|Metal containing polymeric functional microspheres
|17 Aug 1977
|28 Aug 1979
|Minnesota Mining And Manufacturing Company
|Tacky polymeric microspheres
|15 Feb 1979
|25 Mar 1980
|Marion Darrah
|Intrachromoleucospheruloid pigment compositions and processes for producing same
|18 Sep 1978
|3 Jun 1980
|California Institute Of Technology
|Method for producing a biological reagent
|16 Jun 1978
|22 Jul 1980
|Aktiebolaget Bofors
|Bonding agent for sheet-formed fibre products
|23 Jan 1978
|9 Sep 1980
|Imperial Chemical Industries Limited
|Composite materials
|27 Apr 1979
|3 Mar 1981
|Ricoh Company, Ltd.
|Pressure sensitive adhesive toner of clustered encapsulated porous particles for use in electrostatic photography
|22 Oct 1979
|28 Apr 1981
|Xerox Corporation
|Method of forming magnetic toner particles having a concentration of magnetic particles greater than 45 percent by weight by dispersion polymerization techniques
|15 Aug 1980
|13 Jul 1982
|Rhone-Poulenc Industries
|Process for the preparation of magnetic beads of vinylaromatic polymers
|16 Apr 1981
|9 Nov 1982
|Rhone Poulenc Industries
|Magnetic polymer latex and preparation process
|Derwent Abst. 57718V/32 (7-13-74) Mitsubishi (J74026938).
|Citing Patent
|Filing date
|Publication date
|28 Mar 1984
|25 Jun 1985
|Henkel Kommanditgesellschaft (Henkel Kgaa)
|Use of bis-semiesters of sulfosuccinic acid with polyether diols based on ethylene oxide/propylene oxide or their salts as surface-active agents
|14 Dec 1983
|24 Sep 1985
|Shin-Etsu Chemical Co., Ltd.
|Plastic magnets impregnated with a dye-coated magnet alloy powder
|26 Jul 1985
|26 Aug 1986
|Union Carbide Corporation
|Method of encapsulating finely divided solid particles
|15 Feb 1985
|2 Sep 1986
|The Dow Chemical Company
|Colloidal size hydrophobic polymer particulate having discrete particles of a metal dispersed therein
|10 Oct 1985
|14 Oct 1986
|Bayer Aktiengesellschaft
|Inorganic-organic fillers for polymerizable compositions
|21 Mar 1986
|12 May 1987
|Koh-I-Noor Rapidograph, Inc.
|Pigment encapsulated latex aqueous colorant dispersions
|7 Apr 1986
|30 Jun 1987
|The Dow Chemical Company
|Composite pigmenting particles as thermostabilizers of plastic materials
|22 Jul 1985
|14 Jul 1987
|The Dow Chemical Company
|Method for preparing colloidal size particulate
|19 Sep 1985
|7 Jun 1988
|Ricoh Co., Ltd.
|Fine particle substance-containing microgel dispersions
|22 Aug 1986
|13 Sep 1988
|Union Carbide Corporation
|Encapsulating finely divided solid particles in stable suspensions
|29 Jul 1986
|27 Sep 1988
|Process for preparing magnetic polymer particles
|21 Aug 1986
|8 Nov 1988
|Mitsubishi Rayon Co., Ltd.
|Method for preparing a polymeric composition
|17 Apr 1987
|29 Aug 1989
|Sulfochem S.P.A.
|Process for preparing antirust components with improved flowability and penetration
|25 Nov 1987
|3 Oct 1989
|Minnesota Mining And Manufacturing Company
|Colloidal metals in monomers or polymers
|21 Mar 1986
|2 Jan 1990
|Koh-I-Noor Rapidograph, Inc.
|Electrophoretic display particles and a process for their preparation
|20 Sep 1988
|20 Mar 1990
|Mitsubishi Rayon Co., Ltd.
|Method for preparing a polymeric composition
|18 Aug 1987
|31 Jul 1990
|Koh-I-Noor Radiograph, Inc.
|Thermosetting dyed latex colorant dispersions
|29 Feb 1988
|5 Mar 1991
|Lark John C
|Colloidal composition and method of preparing same
|23 May 1989
|19 Mar 1991
|Vincenzo Petrillo
|Process for preparing antirust components with improved flowability and penetration
|6 Mar 1989
|15 Dec 1992
|Union Carbide Chemicals & Plastics Technology Corporation
|Micro composite systems and processes for making same
|23 Oct 1990
|2 Mar 1993
|Nippon Zeon Co., Ltd.
|Emulsion having dye developing property
|30 Mar 1992
|20 Apr 1993
|Crown Decorative Products Limited
|Aqueous surface coating material prepared by emulsion polymerization
|6 Mar 1992
|10 Aug 1993
|Revlon Consumer Products Corporation
|Method of encapsulating pigment particles useful in the manufacturing of cosmetic products and the products thereof
|20 Aug 1991
|23 Nov 1993
|Commissariat A L'energie Atomique
|Material based on an electronic conductive polymer incorporating magnetic particles and its production process
|28 Dec 1990
|21 Dec 1993
|Westinghouse Electric Corp.
|System and method for remotely heating a polymeric material to a selected temperature
|31 Aug 1990
|25 Jan 1994
|Xerox Corporation
|Ink compositions containing modified pigment particles
|11 Feb 1992
|19 Apr 1994
|Elf Technologies, Inc.
|Plateable toner and method for producing the same
|1 Jun 1993
|18 Oct 1994
|Rhone-Poulenc Chimie
|Magnetizable composite microspheres of hydrophobic crosslinked polymer, process for preparing them and their application in biology
|28 Dec 1990
|25 Oct 1994
|Xerox Corporation
|Process for producing electrophotographic toners containing passivated pigments
|3 Mar 1994
|21 Feb 1995
|Westinghouse Electric Corporation
|System and method for remotely heating a polymeric material to a selected temperature
|4 Oct 1993
|28 Feb 1995
|Rtd Corporation
|Preparation of stable aqueous emulsions of water-insoluble particles
|20 Dec 1993
|16 May 1995
|Revlon Consumer Products Corporation
|Surface coating compositions containing fibrillated polymer
|24 May 1994
|24 Oct 1995
|Hodogaya Chemical Co., Ltd.
|Toner for developing electrostatic image and process for the preparation thereof
|7 Sep 1994
|26 Mar 1996
|Rohm And Haas Company
|Polymer emulsion agent for cross-linking a polymer emulsion and method for making a polymer film
|20 Jul 1994
|20 Aug 1996
|Bioquest, Incorporated
|Preparation and use of novel injectable RES avoiding inorganic particles for medical application
|17 Mar 1995
|11 Mar 1997
|Deetz; Dayton J.
|Magnetic paint additive
|13 Feb 1996
|22 Apr 1997
|Micap Technology Corp.
|Duplicating inks for digital duplicators
|22 Oct 1993
|1 Jul 1997
|Copytele, Inc.
|Black electrophoretic particles and method of manufacture
|13 Nov 1995
|22 Jul 1997
|E. I. Du Pont De Nemours And Company
|TiO2 light scattering efficiency when incorporated in coatings
|29 Jul 1996
|26 Aug 1997
|Basf Magnetics Gmbh
|Magnetic coating dispersion
|20 May 1996
|26 Aug 1997
|Bic Corporation
|Erasable ink composition containing a polymer-encapsulated colorant derived from monomer containing dissolved colorant
|3 Dec 1991
|2 Sep 1997
|Rohm And Haas Company
|Process for preparing an aqueous dispersion
|16 Jan 1996
|10 Nov 1998
|Solid Phase Sciences Corp.
|Composite magnetic beads
|12 Dec 1996
|24 Nov 1998
|Sumitomo Metal Mining Company, Limited
|Coating solution for a heat-ray shielding film and a process for forming a heat-ray shielding film by employing the same
|21 Feb 1997
|1 Dec 1998
|Deetz; Dayton J.
|Magnetic paint or ink additive
|20 May 1996
|22 Dec 1998
|Bic Corporation
|Erasable ink composition containing a waterborne polyurethane urea
|20 May 1996
|22 Dec 1998
|Bic Corporation
|Erasable ink composition containing a polymer-encapsulated colorant obtained by polymerizing monomer in the presence of solid colorant particles
|27 May 1997
|9 Feb 1999
|Copytele, Inc.
|Black electrophoretic particles and method of manufacture
|11 Oct 1996
|9 Mar 1999
|Ecc Internatinal Ltd.
|Paper coating
|8 May 1997
|23 Mar 1999
|E. I. Du Pont De Nemours And Company
|Titanium dioxide particles having substantially discrete inorganic particles dispersed on their surfaces
|20 May 1996
|4 May 1999
|Bic Corporation
|Erasable ink composition containing a polymer dye obtained from ethylenic monomers and marking instrument containing same
|20 Jun 1996
|2 Nov 1999
|Societe Prolabo
|Latex of calibrated monodisperse magnetizable microspheres, process of preparation and use of the said latex in chemistry or in biology
|30 Jul 1998
|15 Feb 2000
|Clariant Gmbh
|Colloid dispersion mixtures as protective colloid for aqueous emulsion polymerization, processes for preparing them and their use
|3 Dec 1991
|27 Jun 2000
|Rohm And Haas Company
|Process for preparing an aqueous dispersion of composite particles including polymeric latex adsorbed to titanium dioxide
|5 Jan 1998
|27 Jun 2000
|Basf Aktiengesellschaft
|Injection-molding compositions containing metal oxides for the production of metal moldings
|20 Jul 1999
|10 Apr 2001
|Rohm And Haas Company
|Polymer-pigment composites
|21 Feb 1997
|15 May 2001
|Seiko Epson Corporation
|Ink jet recording ink
|12 Nov 1998
|22 May 2001
|James T. Lowder
|Composite magnetic sheet
|16 Apr 1996
|29 Jan 2002
|Foster Products
|Ultra violet light protective coating
|26 Apr 2000
|12 Feb 2002
|Xerox Corporation
|Toner processes
|2 Aug 1999
|23 Jul 2002
|Mds Proteomics, Inc.
|Ultrasonically generated paramagnetic polymer particles
|23 Dec 1997
|17 Sep 2002
|Nippon Shokubai Co., Ltd.
|Inorganic dispersion stabilizer and process for producing resinous particles using the same
|9 Jan 2001
|14 Jan 2003
|Mitsubishi Chemical Corporation
|Toner for the development of electrostatic image and process for the preparation thereof
|22 Dec 1999
|17 Jun 2003
|C. R. Bard, Inc.
|Dual mode antimicrobial compositions
|10 May 2000
|22 Jul 2003
|C. R. Bard Inc.
|Silane copolymer compositions containing active agents
|6 Dec 2000
|19 Aug 2003
|Nano-Tex, Llc
|Nanoparticle-based permanent treatments for textiles
|27 Mar 1997
|2 Sep 2003
|The Timken Company
|Colloidal suspensions for use as a lubricant or additive
|14 May 2002
|27 Jan 2004
|Mds Proteomics, Inc.
|Ultrasonically generated paramagnetic polymer particles
|15 Dec 1999
|6 Apr 2004
|C.R. Bard, Inc.
|Polymer compositions containing colloids of silver salts
|31 Aug 2000
|29 Jun 2004
|Basf Aktiengesellschaft
|Method for producing an aqueous dispersion of particles made up of polymerisate and fine inorganic solid material
|10 Oct 2000
|21 Dec 2004
|Basf Aktiengesellschaft
|Method for producing an aqueous dispersion of particles that are made up of polymers and inorganic solid matter which consists of fine particles
|14 Jun 2002
|22 Aug 2006
|Basf Aktiengesellschaft
|Method for producing an aqueous dispersion of particles composed of a polymer and a fine-particle inorganic solid
|26 Aug 2003
|20 Feb 2007
|C. R. Bard, Inc.
|Antimicrobial compositions containing colloids of oligodynamic metals
|21 Mar 2002
|8 May 2007
|Aviva Biosciences Corporation
|Composite beads comprising magnetizable substance and electro-conductive substance
|31 May 2002
|24 Jul 2007
|Amorepacific Corporation
|UV-scattering inorganic/polymer composite particles and a method for preparing the same
|15 Sep 2004
|16 Oct 2007
|Jsr Corporation
|Process for producing particles for diagnostic reagent
|24 Feb 2005
|31 Mar 2009
|Basf Aktiengesellschaft
|Method for improving the storage stability of composite particle dispersions
|25 Nov 2002
|11 Aug 2009
|Basf Aktiengesellschaft
|22 Jun 2005
|25 Aug 2009
|Rohm And Haas Company
|Opacifying particles
|18 Jul 2003
|18 May 2010
|Capitalbio Corporation
|DNA chip based genetic typing
|21 Feb 2008
|15 Jun 2010
|Lg Chem, Ltd.
|Method for preparing functional organic particle
|31 Dec 2002
|17 Aug 2010
|Capitalbio Corporation
|Magnetism based rapid cell separation
|15 Oct 2003
|28 Sep 2010
|Henkel Ag & Co. Kgaa
|Filler-containing polymer dispersion, method for its production and use
|3 Dec 2002
|26 Oct 2010
|C.R. Bard Inc.
|Microbe-resistant medical device, microbe-resistant polymeric coating and methods for producing same
|21 Nov 2006
|27 Sep 2011
|Evonik Degussa Gmbh
|Method of bonding materials of construction using nanoscale, superparamagnetic poly(meth)acrylate polymers
|10 Aug 2009
|11 Oct 2011
|C.R. Bard, Inc.
|Antimicrobial compositions containing colloids of oligodynamic metals
|17 Oct 2008
|4 Sep 2012
|Basf Se
|Process for preparing an aqueous composite-particle dispersion
|28 Apr 2008
|18 Sep 2012
|Basf Se
|Process for preparing an aqueous composite-particle dispersion
|18 May 2010
|9 Oct 2012
|Rohm And Haas Company
|Opacifying pigment particle
|18 May 2010
|6 Nov 2012
|Rohm And Haas Company
|Opacifying pigment particle
|8 Sep 2009
|15 Oct 2013
|Ppg Industries Ohio, Inc.
|Aqueous dispersions of polymer-enclosed particles, related coating compositions and coated substrates
|11 Aug 2009
|5 Nov 2013
|Basf Se
|Process for producing nanoscale organic solid particles
|3 Oct 2012
|17 Dec 2013
|Rohm And Haas Company
|Coating composition with high pigment volume content opaque polymer
|9 Jul 2002
|9 Sep 2014
|Reaxa Limited
|Microencapsulated catalyst methods of preparation and method of use thereof
|10 Nov 2010
|28 Oct 2014
|Wacker Chemie Ag
|Composite particles having organic and inorganic domains
|27 Oct 2009
|24 Mar 2015
|Ppg Industries Ohio, Inc.
|Aqueous dispersions of polymer-enclosed particles, related coating compositions and coated substrates
|13 Nov 2007
|14 Jul 2015
|Basf Aktiengesellschaft
|Method for production of a minisuspoemulsion or suspension of sub-micron core/shell particles
|26 Feb 2009
|28 Jul 2015
|Wacker Chemie Ag
|Method for producing composite particles
|15 Oct 2003
|22 Apr 2004
|Roberto Pavez Aranguiz
|Filler-containing polymer dispersion, method for its production and use
|14 Jun 2002
|2 Sep 2004
|Zhijian Xue
|Method for producing an aqueous dispersion of particles composed of a polymer and a fine-particle inorganic solid
|15 Sep 2004
|24 Mar 2005
|Jsr Corporation
|Process for producing particles for diagnostic reagent
|22 Jun 2005
|12 Jan 2006
|Brown Ward T
|Opacifying particles
|31 Dec 2002
|29 Jun 2006
|Xu Zhang
|Magnetism based rapid cell separation
|31 Dec 2002
|27 Jul 2006
|Xin Xie
|Magnetism based nucleic acid amplification
|19 May 2010
|15 Mar 2012
|E.I. Du Pont De Nemours And Company
|Phase change ink composition
|13 Sep 2010
|5 Jul 2012
|Akzo Nobel Coatings International B.V.
|Encapsulation of pigments with polymer latex prepared by mini-emulsion polymerization
|20 Mar 2013
|19 Feb 2015
|Rohm And Haas Company
|Binder thickened with xanthan gum
|12 Sep 1990
|15 Dec 1992
|Union Carbide Chemicals & Plastics Technology Corporation
|Encapsulating finely divided solid particles in stable suspensions
|3 Dec 1992
|21 Apr 1999
|Process for preparing aqueous dispersion of composite particle
|9 Jul 2002
|19 Aug 2009
|Microencapsulated catalyst, methods of preparation and methods of use thereof
|11 Sep 2009
|23 Jul 2014
|Surface modification of polymer particles
|21 Oct 1993
|27 Apr 1995
|Rotring Int Gmbh
|Wasserfeste Kosmetik
|10 Mar 2008
|17 Sep 2009
|Wacker Chemie Ag
|Verfahren zur Herstellung von Kompositpartikeln
|20 Mar 2008
|24 Sep 2009
|Merck Patent Gmbh
|Magnetische Nanopartikel und Verfahren zu deren Herstellung
|12 Nov 2009
|19 May 2011
|Wacker Chemie Ag
|Kompositpartikel mit organischen und anorganischen Dom�nen
|18 Feb 2011
|23 Aug 2012
|Wacker Chemie Ag
|Modifizierte Kompositartikel
|5 Nov 1992
|19 May 1993
|BASF Aktiengesellschaft
|Micro-capsules with solid matter cores
|15 Nov 2002
|25 Jun 2003
|Basf Aktiengesellschaft
|13 May 2010
|24 Nov 2010
|Rohm and Haas Company
|Opacifying pigment particle
|13 May 2010
|24 Nov 2010
|Rohm and Haas Company
|Opacifying pigment particle
|26 Sep 2012
|10 Apr 2013
|Rohm and Haas Company
|Coating composition with high pigment volume content opaque polymer particle and a polymer encapsulated TiO2 particle
|4 Nov 1992
|10 Jun 1993
|William D Emmons
|Process for preparing an aqueous dispersion including polymeric latex and titanium dioxide pigment
|12 Jan 1994
|20 Jul 1995
|Copytele Inc
|Black electrophoretic particles and method of manufacture
|19 Jan 2000
|24 Aug 2000
|Markem Corp
|Stable titanium dioxide containing ink jet ink composition
|31 Aug 2000
|15 Mar 2001
|Basf Ag
|Method for producing an aqueous dispersion of particles made up of polymerisate and fine inorganic solid material
|10 Oct 2000
|26 Apr 2001
|Basf Ag
|Method for producing an aqueous dispersion of particles that are made up of polymers and inorganic solid matter which consists of fine particles
|9 Jul 2002
|23 Jan 2003
|Avecia Ltd
|Microencapsulated catalyst, methods of preparation and methods of use thereof
|31 Dec 2002
|24 Jun 2004
|Univ Tsinghua
|Magnetism based nucleic acid amplification
|11 May 2005
|17 Nov 2005
|Seoul Nat Univ Ind Foundation
|Semiconductor nanoparticle-encapsulating vinyl polymer, vinyl polymer mixture includingthe same, and process of preparing the same
|31 Dec 2005
|13 Jul 2006
|Basf Ag
|Method for producing aqueous composite particle dispersions
|13 Nov 2007
|22 May 2008
|Basf Se
|Method for production of a mini suspoemulsion or suspension of sub-micron core/shell particles
|13 Nov 2007
|24 Jul 2008
|Basf Se
|Method for production of a mini suspoemulsion or suspension of sub-micron core/shell particles
|22 Apr 2009
|29 Oct 2009
|Basf Se
|Method for improving the storage stability of aqueous composite particle dispersions
|31 Mar 2010
|21 Oct 2010
|Basf Se
|Method for producing an aqueous composite particle dispersion
|10 Nov 2010
|19 May 2011
|Wacker Chemie Ag
|Composite particle having organic and inorganic domains
|24 Jan 2011
|4 Aug 2011
|Basf Se
|Coating means comprising composite particles
|1 Nov 2010
|15 Sep 2011
|Rohm And Haas Company
|Opacifying pigment particle
|1 Nov 2010
|15 Sep 2011
|Rohm And Haas Company
|Opacifying pigment particle
|11 Aug 2011
|23 Feb 2012
|Basf Se
|Process for improving the storage stability of aqueous composite particle dispersions
|16 Feb 2012
|23 Aug 2012
|Wacker Chemie Ag
|Modified composite particles
|15 Dec 2011
|17 Jan 2013
|E. I. Du Pont De Nemours And Company
|Method of preparing encapsulated pigment dispersions with minimal free polymer
|15 Feb 2013
|22 Aug 2013
|Rohm And Haas Company
|Polyurethane coating composition
|20 Mar 2013
|26 Sep 2013
|Rohm And Haas Company
|Binder thickened with xanthan gum
|24 May 2013
|5 Dec 2013
|Basf Se
|Binding agent
|U.S. Classification
|252/62.54, 524/800, 523/300, 524/783, 524/431, 524/832, 524/785, 524/458, 524/445, 524/425, 523/202, 524/435, 524/819, 524/773, 524/788, 524/780, 524/432, 524/836, 524/824, 524/789, 524/777, 524/461
|International Classification
|Cooperative Classification
|European Classification
|12 Sep 1983
Owner name: DOW CHEMICAL COMPANY, THE
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:SOLC, JITKA;REEL/FRAME:004168/0491
Effective date: 19801210
|3 Feb 1987
|Fee payment
Year of fee payment: 4
|31 Jan 1991
|Fee payment
Year of fee payment: 8
|12 Jan 1995
|Fee payment
Year of fee payment: 12


text:
"May you enjoy fantastic travels...
Welcome!!! "
WOW!!! - Into our 27th year of FULLTIMING - when my Retirement Phase2 rapidly hit me!"
However there is still a whole lot of Living in or out of an RV to do!
Enjoy YOUR Travels to the fullest while you still can
Peggi & Bratt (dachshund)
May you have a memorable 2015
Have a Super Safe Fun-Filled Summer - It is finally HERE!!!
Looking for Train Horns?
Mention 'RVLiving.net' and get 30% off the loudest train horns for your RV Make your RV or truck sound like a thunderous locomotive with a train horn.
Click Here to ENTER site OR Scroll down to see More
Add Sleek & Stylish LED Lights to motorbikes & more
Go Here for 2003-06 Pic's of 'LIFE ON THE MOVE -
'Friends we saw', 'things we did'!!! NOW SPAM FREE
OUR Complex detailed Picasa PICTURE ALBUMS (2007 * 2012) HERE
Shop Amazing Online Specials at Walmart.com!
Bratt helped me write going down the road
Bratilda (Bratt) - 10 -yrs
(Been with us (me) since April 2008)
GoodBye My Love - 21st July 2012 " You were One Of A Kind." & Yes "It Is Clearing Up Ahead"
Click Image to Enlarge
I can't have you with me in person, thanks for beingmy personal Guardian Angel. My life is still empty without you beside me,,
With your support, 21 OCT 13 "I SOLD THE LUXOR!" Thanks for standing beside me during the sale process.
John's rapid demise began late May - 6 weeks later - 21 June 2012 his cancer - that began with a tumor on outside of his colon spread to his liver, blood & bone took his life. Because his cancer moved so fast his intense suffering was brief.
RIP My Love
"I will always Love You John"
but I know I have your permission to move forward for the rest of my life.
Luxor is now sold -
She spent winter 2013/14 in Florida.
Not sure where she will be 2014/2015.


text:
Click on Thumbnails to see full size images.
Please note that over time links change or are no longer online. This is known as link rot or
link decay.
As such, links may appear that were valid originally, but no longer are.
Images that the Drudge Report links to often expire
after several weeks, consequently we usually only display the original link, not the images
after serveral weeks. You can still click on the link to see if the original image is still available.
DrudgeReportArchive.com © 2015 [DMCA]
CT Inc.
Tag cloud phrases:app tracks backtracks subways ban local city dispatches cuomo backtracks dispatches prison down travel inmates shovel prison inmates sexual liaisons shovel snow shut down snow off subway tracks subways shut tracks users train tracks travel ban uber tracks users sexual


text:
February 3, 2012
Thanks for helping us associate the correct Pornstars to this video!
Help Us: Do these Pornstars appear in this video?
Pornstar Name:
All Comments (12)
of course it's' 'best ever', That is Heather brooks!
I want Heather back!
That was one of the best videos I have ever seen!!! She is fucking sexy and she said ALL the right things!! The vocal comments of what she said and how got me rock hard!!! Thank you, Heather!!!!!!!
outdoor anal is a mess and i don't think heather really likes anal, but she truly loves to swallow
shes such a dedicated woman!
grande video
Ganz schoen Belag auf der Zunge die gute, perfekte Blasmaus
Great Vid. 10/10.


text:
Load cars, trucks, and other vehicles onto lower clearance trailers with car trailer ramps! These car trailer ramps come in 5 and 6 foot lengths and have unique hybrid hook-plate combo connecting ends! The ramps are constructed of lightweight aircraft quality aluminum for strength and easy maneuvering. All car trailer ramps have a 1 year warranty included with your purchase!
These car trailer ramps are perfect for loading wheeled equipment and vehicles onto lower clearance trailers! The ramps have a 2,500 lb weight capacity (per axle) for the 6' model and 3,000 lb per axle capacity for the 5' model. The trailer ramps are constructed of a lightweight aircraft grade aluminum for strength and durability and won't rust!
The surface of the trailer ramps have serrated cross bars for traction when tires are wet or covered in mud. The crossbars are wider than traditional rung designs allowing for greater weight capacities!
The ends of select models feature a unique hook/plate hybrid design and include two safety straps for securing the ramps to the trailer to prevent the ramps from kicking out when loading. The ramps include a one year warranty with your purchase and are guaranteed to be the strongest, lightest, trailer ramps on the market!
Rated at ,2500 lbs per axle for the 6' model & 3,000 lb max axle for the 5' model.
The best way to determine your vehicle's axle weight is to drive the heaviest axle on a scale. Normally the front of your car, SUV or pick-up truck is the heaviest axle weight because of the engine.
I wanted to replace my steel ramps which were too heavy and not long enough. These were a perfect solution for my requirement and fit into the ramp storage area on my trailer. I restore old British cars and these handle the car weight perfectly and my back is happier now. Nice solid construction. These will last me forever. Thanks for a nice set of ramps.
I bought the 5 ft ramps with hook ends to replace the 70+ lb steel ramps on my 18 ft LoadTrail trailer. At only 18 lbs each, the new ramps are easy to unload, hook up, and put back. They fit the storage bins in the trailer just right. My back thanks you for sparing it any more pulled muscles!
better than your add.
First the shipping was fast. Ramps where better than my steel rams , much easier to move around. .
Great product. Liked the knife edge at the beginning and the hook at the end. Overall an extremely well made product. Quality superb.
I purchased these ramps to replace the 50lb. steel ramps that came with my trailer and am so glad I did! I am extremely happy with the weight of these new ramps, as well as the design. They worked perfectly on my trailer and made loading/unloading my '68 Camaro a breeze. I am also impressed with how quickly these ramps were delivered after making my purchase. I would highly recommend these ramps and this company to anyone!
I had been looking for lightweight loading ramps that were heavier than the usual 1500lbs limited ones that other companies are selling. I was pleased when I found these HD Ramps for not much more than their lighter counterparts. They are engineered well and fit and finish are great. I was also pleasantly surprised with the quick shipping. I had bookmarked www.discountramps.com because I will be a repeat customer. Thank you for offering a well made product at a reasonable price.
Very good quality and the shipping was very quick.
Great ramps, work great for loading normal cars and trucks. But the ramp overall length is 72 inches, and the useable part of the ramp is only 67 inches. I really need about 77 inches of ramp like the old heavy ones, 72 inches of useable ramp would work.. We have low race cars. If I had known this I would of order different ramps.
Researched on-line and selected your product. Very happy with price, quality, and timely shipping.
The highest quality ramp I've ever bought and for the same price as heavy steel ramps... I would recommend to anyone
the ramps look great!!! I cant wait to put them to use. I have a 4 car hauler that's on the road everyday so we will see how they handle the weight. All the welds look great and the construction is first class.
My steel ramps were stolen, these light weight ramps are the perfect replacement. Fit the slots on my trailer, with all the strength and HALF the weight.....
Amazing built very well and durable love the weight and the pound capacity of the ramps we purchased will surely be doing more business in the future. thanks.
I picked up a set of the 2500lb 6' aluminum ramps to replace the heavy utility ramps that my trailer came with. Will use these to load our various racecars on and off the trailer. Ramps look well-built and should suit our needs well. Price was excellent and they only took 2 or 3 working days to show up on my porch, which was nice. Looking forward to using them next race season!
Just got my new ramps today. Six days shipping makes it real nice. These will make it real easy to load low cars on my trailer. The price was in my budget and they look great. I hope to get lots of use out of them.
Nice product, great price and lightning fast shipping. These ramps are very good quality and should work well with a new single car trailer we are having built.
My ramps came yesterday, really well made and more than I expected. The only thing that surprised me was on the Plate ends ( the one that measures 3 1/4 long) had not been buffed out very sharp edges with burrs. I'm sure I can file the edges smooth.
I received the 3000 pound aluminum loading ramps from my son and daughters for my birthday. These came with the safety straps. The ramps were lighter than any of the heavy duty ramps I had been using and were well made. I would recommend these to anyone wanting a pair of light-weight car ramps for their trailer.
These Ramps are built very nice and is perfect for our use with our car and motorcycles for access into our portable garage, I like them especially for their lightness and ease of set-up. Great job to the build of. Thanks
I have searched all over the internet for a deal like this and a set of ramps that can carry a load, all the others I found were limited to 1500 lns per pair.


text:
oil spill clean ups Companies in Latvia
OSEI - Oil Spill Eater International, Corp
based in Dallas, TEXAS (USA)
Oil Spill Eater II (OSE II) is the world's most environmentally safe and cost effective bioremediation process for the mitigation of hazardous waste, spills and contamination virtually anywhere of any size, large or small. OSE II is an environmentally safe cleanup method because it uses natures own bioremediation processes to effectively eliminate hazardous materials.
Oil Dissolver GmbH
based in Breddorf, GERMANY
A new international company, that has for decades experience in manufacturing, process engineering and manufacturing for the removal of oil spills collected by his company founder. As a manufacturer of bio-working, environmentally friendly products, the dissolution of crude oil and its derivatives, we have developed a worldwide unique technology. Previous methods disperse ...
Granite Environmental, Inc
based in Sebastian, FLORIDA (USA)
Granite Environmental provides products for pollution containment and collection, erosion control, industrial spill containment clean up applications, and emergency use as site specific solutions. We are customer focused by offering turbidity curtains, portable tanks, water pollution solutions, flexible fuel tanks, frac tanks, large capacity tank storage solutions, ...
The BioSolve Company
based in Lexington, MASSACHUSETTS (USA)
BioSolve is a proprietary, water-based, biodegradable formulation of surfactants and performance additives that work together to address hydrocarbon clean up in a broad range of settings: at sites with contaminated soil, in industrial repair and maintenance, and in emergency response. Biosolve has become the leader in hydrocarbon clean up because it is BOTH easy to use ...
Oil Spill Response Limited (OSRL)
based in London, UNITED KINGDOM
Oil Spill Response Limited is to provide resources to respond to oil spills efficiently and effectively on a global basis. Oil Spill Response will continue its pursuit of excellence in providing cost effective oil spill response, training and consultancy services. Oil Spill Response will work towards improving communication, awareness of resources and capabilities, and ...
Oil Cleaning Bio-Products Ltd
based in Royston, UNITED KINGDOM
Oil Cleaning Bio-Products is dedicated to supplying a complete range of safe, effective and biodegradable absorbents, bacterial bioremediation products, spill prevention and containment products, cleansers and degreasers.
Spill Source
based in Denver, NORTH CAROLINA (USA)
Sorbent pads, booms,spill kits, spill pillows, storm water protection, Hazmat pipe plugs, inflatable plugs, spill containment, oil spill clean upSpill Source manufacturers and distributes a complete range of spill control, spill cleanup and spill remediation products. Products include sorbent pads, socks, booms, spill kits, pillows, spill pallets, containment berms, storm ...
based in Noerresundby, DENMARK
DESMI is a global company specialised in the development and manufacture of pump solutions for marine, industry, oil spill combating, defence & fuel and utility both locally and globally. Our product range supplemented with agency products from other leading, world class manufacturers – is completed by related services such as the design and installation of pump plants, ...
Interactive Oil Spill Training Center Inc. (IOSTC)
based in West Vancouver, BRITISH COLUMBIA (CANADA)
IOSTC was founded in 2001 by professionals in the fields of marine science, oil spill management, interactive training, environmental consulting and business development. IOSTC team members have successfully developed and marketed interactive training projects, oil spill contingency planning and related training services to national and international clients. Through ...
UK Spill Association
based in Bramshott, UNITED KINGDOM
UKSpill is the national body for the UK Oil Spill Industry. UKSpill has grown rapidly as an independent organisation since 2004, leading to membership expanding 3 fold to over 100 companies and individuals by 2013. Members represent all aspects of the UK oil spill response and clean-up industry including not only the leading providers of manufacturing technology, ...


text:
Bass PasadenaSKU: #8125235
Product Information
- Get noticed in all the right ways when you walk into the room in the Bass® Pasadena.
- Leather upper in a classic plain-toe oxford style.
- Lace closure for an adjustable fit.
- Soft leather lining ensures an abrasion-free environment for all-day wear.
- Lightly cushioned removable insole massages the foot with each and every step.
- Rubber unit outsole for flexible comfort.
- Imported.
- Measurements:
- Heel Height: 1 in
- Weight: 1 lb 2 oz
- Product measurements were taken using size 11, width D. Please note that measurements may vary by size.


text:
The following tags exist in this scene. You can find similar scenes by combining tags in this scene together using the checkboxes, or just click a tag name to browse...
Starring Sunny Leone,
Do you recognise pornstars in this scene? Begin typing a pornstar name, then click on the button to suggest them!
Ethnic Sunny Leone massages and toys her soaking wet pussy to a state of pure sexual release.
Big boobs black beauty stripping and then showing how to masturbate lustrously with own finger.
This scene is available to stream or download High Definition Join now to unlock HD
Featured in playlists: Mexican (300 Videos), JerkOff Encouragement (130 Videos), JAPONEZE (51 Videos), Sunny Leone (5 Videos), --- TEASE --- (130 Videos), Busty Latinas ;-) (92 Videos), favorite pornstars stripping and masturbating (30 Videos), --- BRUNETTE --- (180 Videos), big titties (213 Videos), Sunny Leone (40 Videos)
Video Suggestions
- 8:03Big Titty Girl Sunny Leone Pleasures Herself With A Glass ToyApr 29, 2010
- 5:06Sexy Brunette With Glasses Enjoys Quality Pussy TimeMay 9, 2010
- 14:29Hot Slut Sunny Leone Plays With Her PussyOct 1, 2009
- 20:45Horny Lesbians Having Fun In The BedOct 1, 2009
- 28:14Ron Jeremy Interviews Smoking Hot Sunny LeoneOct 1, 2009
- 8:05Exotic Beauty Priya Rai Plays With Her Silky Wet SnatchJul 29, 2010
- 8:03Priya Rai Getting The Vibe In Her BedroomAug 24, 2010
- 8:02Smoldering Hot Brunette Audrey Bitoni Fingers HerselfApr 17, 2011
- 8:18Lela Star Masturbates Her Anal And PussyMay 1, 2009


text:
Donna & Markus by Markus Lupfer Designer girl's navy glasses print leggings
Item No.2320208513
Item No.2320208513
Up to 70% Off - Save up to £9.80
From our exclusive range of designer girlswear from Donna and Markus, these stylish leggings come in navy with an all over glasses print in black. Constructed from a stretch fabric for the ultimate in comfort, these stylish leggings make an instant statement and look great teamed with strappy tops and ballerina pumps.
UK Home Delivery Free (UK orders over £30) or £3.49
Delivered within 5 working days
Next or Named Day Delivery
7 days a week between 8am - 6pm
Sunday to Friday - order by 9pm - £3.99
Saturday - order by 6pm - £3.99
Next or Named Evening Delivery
7 days a week between 6pm - 10pm
Monday to Sunday - order by Midnight - £6.99
Collect from store the next day - FREE
Order before 9pm for next day collection after 12pm midday
Show participating stores
Show full delivery details
Subject to exceptions, Debenhams is happy to exchange or refund your purchase within 28 days of delivery. Please check here for more details on our returns policy and exceptions.


text:
Local Blogs
By John Raftrey And Lori McCormick
E-mail John Raftrey And Lori McCormick | Follow this Blog
Sort by: Most Recent | Most Popular
Oct 1, 2015 5:19 pm
Comments: 1 | Views: 1,080
(Written by Lori McCormick)
If you qualified for fee waivers to take the SAT or ACT, or are a participant in the free or reduced lunch program, then you should... More
Sep 22, 2015 10:16 pm
Comments: 2 | Views: 2,100
(written by guest blogger Patrick Hennes of AJ Tutoring, www. AJTutoring.com)
The redesigned SAT will debut in March 2016 and will affect the class of 2017 and... More
Sep 9, 2015 8:02 am
Comments: 7 | Views: 2,599
(written by Lori McCormick)
Students thoughtfully research colleges, attend college representative visits on their high school campuses, and gather information... More
Aug 26, 2015 7:24 am
Comments: 2 | Views: 2,731
(written by Lori McCormick)
Transitioning to college, while certainly exciting, can also feel a bit overwhelming. Here are some tips to help make your transition... More
Aug 12, 2015 9:30 pm
Comments: 0 | Views: 2,552
(Written by Lori McCormick)
In April 2015, UC Berkeley adopted a new freshman admission policy.
Starting with students applying to Berkeley this fall, some... More
Southern California chain snags La Boulange space in Palo Alto
By Elena Kadvany | 7 comments | 2,525 views
The Food Party! Top Ten List
By Laura Stec | 0 comments | 1,212 views
Fee Waivers
By John Raftrey and Lori McCormick | 1 comment | 1,080 views
Lessons in marketing yourself: "Making lemonade" from the Presidential campaigns
By Douglas Moran | 0 comments | 489 views
By Chandrama Anderson | 0 comments | 394 views


text:
All Headlines
Sep 30, 2015
LULAC Marks Hispanic Heritage Month with Hundreds of LULAC Members Meeting on Capitol Hill for Annual Advocacy Day
Sep 22, 2015
Iowa LULAC Members Gather to Protest Trump at the Annual Iowa Faith and Freedom Coalition
Sep 22, 2015
LULAC Urges Congress to Pass Clean Funding Bill and Cease Attacks on Planned Parenthood
Sep 11, 2015
LULAC Alarmed by Pasco, Washington Prosecutor's Decision to Not Indict Officers in Tragic Shooting of Antonio Zambrano-Montes
Aug 26, 2015
LULAC Meets with Department of Justice and Renews Call for Stronger Hate Crime Legislation
Aug 21, 2015
Trump's Hateful Rhetoric Inspires Criminal Assault Against Homeless Latino; Trump Refuses to Condemn the Hate Crime He Inspired
Aug 14, 2015
Action Alert: Protect Latino Preschoolers - Demand that Indiana Stop Discriminating Against Latino Children
Aug 6, 2015
On the 50th Anniversary of the Voting Rights Act, LULAC Celebrates Texas Victory And Calls for Congress to Protect Minority Communities who Remain Easy Mark for Voter Suppression
Jul 28, 2015
LULAC Hails Ruling Citing ICE Should Release 1,700 Immigrant Children and Parents Held in Detention Centers in Texas and Pennsylvania
Jul 24, 2015
LULAC Councils Gather at Laredo International Airport to Deliver Message to Donald Trump - LULAC Supports Veterans Not Bigots!
Jul 24, 2015
White House Recognizes "DACAmented" LULAC Teacher as a "Champion of Change" in Nation's Capital
Jul 22, 2015
LULAC Calls Upon the White House and Congress to Work with Puerto Rico to Solve the Territory's Debt Crisis
Currently reading page 1 of 27.
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 Next Page


text:
All Android applications categories
All Android games categories
by: Piotr Wosinek | 4
Hosanna Church is passionate about the local church; both yours and ours. We are about helping and inspiring people to find their place in His plan.
In this app you will find a collection of tweets, thraughts, photos and videos.
We'd like to invite you to interact with us and share content with the people in your world. Take a look around, make yourself at home and check back often.
from 4 reviews