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Pretty Little Liars
Getting Teens Right: Why ABC Family Deserves More Credit Than It Gets
Let's be honest: When most people hear "ABC Family," they think "cheesy teen TV that isn't worth a second glance if you're not a thirteen year old girl." Most people, it turns out, are dead wrong.
I'm not here to tell you ABC Family is churning out reams of Emmy-worthy television programs (though, for what it's worth, it is the home of Descendants breakout star Shaliene Woodley, and long-time Hollywood favorites like Marlee Matlin and Molly Ringwald). What ABC Family does do, however — and what it does better than most of the major networks — is tell stories featuring the kinds of characters who are painfully underrepresented on the small screen.
This is a network that believes teenage girls (even popular, stylish ones) care about more than boys and gossiping. It's a network that employs deaf actors not named Marlee Matlin (although Marlee Matlin, who is wonderful, does star in ABC Family's Switched at Birth), handles issues of sexuality with grace, that once aired a show where the majority of the cast was overweight (Huge).
Most importantly, it's a network that does all of these things while avoiding over-sentimentality. Its shows are, if not always artistically magnificent, at least fun and engaging, integrating diversity seamlessly amidst all the mysteries, switched identities, and generally addictive drama. It teaches a lesson of inclusively without ever making you realize you're in class.
The Daily Beast's Jace Lacob recently wrote a wonderful feature highlighting the myriad ways Switched at Birth is truly groundbreaking in its portrayal of deaf and hard-of-hearing characters. I encourage you to read it. I don't have much to add, but I want to reiterate the biggest takeaway: Switched at Birth features several deaf main characters, portrayed by deaf actors, who are allowed to speak in subtitled ASL. That is unprecedented, and it's happening on a show many people don't give a second glace because its soapy premise — two girls were, well, switched at birth — doesn't seem serious enough to adult audiences.
While Switched at Birth is the most obvious example of ABC Family pushing boundaries, it's hardly the only one. Another noteworthy case is 2010's Huge, a smart, wistful show about teens attending a weight loss summer camp. Almost every significant character was obese, and they were all allowed to be individuals, dealing with body image issues in their own specific way.
Importantly, though, people dealing with body image issues wasn't all Huge was about. While it didn't have a flashy premise like Switched at Birth, it dealt with so much more than weight. From gender-identity to fraught friendships, from family drama to good old fashioned heartbreak, Huge captured the small cruelties and deep joys of teenage life better than almost any show, ever. In doing so, it avoided becoming a PSA about loving yourself. The fact that Huge was cancelled after one season is an overlooked TV tragedy; the fact that it made it on air at all should be applauded.
Huge and Switched at Birth do things that are practically unheard of elsewhere on TV. Of course, not every ABC Family actively features actors who are normally relegated to the sidelines; not every script can be groundbreaking. However, something ABC Family shows almost universally do, and something that is very, very heartening to see in a network aimed at young women, is put female characters and female relationships front and center.
As someone who spends an inordinate amount of time hanging out in feminist TV-geek circles (yes, they exist, and yes, they are awesome), I constantly hear the complaint that TV is really bad at representing female relationships. Individual kick-butt female characters are all over the place on major network shows, but too often they aren't shown interacting with other women, and when they do, the spend their time talking about men, men, and more men.
While this is hardly a universal truth, it is a notable, and disappointing, pattern on TV. Not so on ABC Family. Every one of its current shows has a female protagonist and, more importantly, female friendships are often given the spotlight. For a prime example, you need to look no further than one of the network's biggest hits, teen murder-mystery Pretty Little Liars.
Part Veronica Mars, part Gossip Girl, Pretty Little Liars centers on a group of girlfriends being stalked and tortured by the omnipresent, texting "A." Also, their friend was murdered a while ago, and basically every authority figure they meet is out to nail them for said murder.
However, lurking under the veneer of tangled mysteries is a web of genuinely felt relationships, at the center of which is the bond between the four (female) protagonists. Each girl has important love interests, and those relationships — from Aria's (Lucy Hale) illicit affair with her teacher to Hanna's (Ashley Benson) teenage dream of a relationship with bad-boy Caleb (Tyler Blackburn) — get plenty of screentime.
But in the end the girls always return to each other. Their friendship is what drives the plot; they rely almost entirely on each other to navigate the never-ending challenges "A" throws at them.
If any of the men of Pretty Little Liars were to leave the show tomorrow, some shippers might moan, but the main story would remain relatively unchanged. And it's easy to imagine that whichever Little Liar lost a boyfriend would, eventually, move on. If one of the Liars left, however, the show and other characters would be profoundly changed. The girls are essential, the boys are, for the most part, not (unless it turns out one of them is "A"...). How many network shows can say that female relationships are at the core of their shows? More disturbingly: How many can say the exact opposite?
And I haven't even touched on Emily's (Shay Mitchell) coming out arc, which was a beautifully nuanced exploration of the difficulties of coming out to a parent who doesn't understand, but still loves their child.
I'm not saying this network is flawless (one only has to scan their show page to notice how white its protagonists tend to be); nobody gets everything right all the time. What I am saying is this this: ABC Family may produce teen TV, but it's definitely worth a second look from adults.


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Barb's Caringbridge site: www.caringbridge.org/visit/barbreierson
Barb's Benefit Facebook site: www.facebook.com/benefitforbarb
Barb's Story:
In August 2012, Barb went into the Dr. for a swollen lymphnoid, they told her it was an infection and gave her antibiotics. After the swelling continued to grow, we convinced her to go to the ER where she was originally treated for mono and then was diagnosed with AML – Acute Myeloid Leukemia with a rare chromosomal abnormality. At the time of diagnoses we had learned that the cancer had already taken over 70%+ of her blood cells. The doctors quickly took action and put Barb on a very aggressive chemo plan where she would receive multiple types of chemo over a one week/24 hour drip. Barb spent a total of 5 weeks at Abbott in the Oncology area, where many weeks she was confined to her room, while she recovered from the chemo. Finally the results of her chemo treatment came in and it was good news. No cancerous cells were found in her blood!
While Barb was preparing for her bone marrow transplant in November, she learned her cancer had already returned. So the bone marrow transplant was put on hold and Barb was sent back to Aboott to receive another round of chemo - one of the most agressive chemo treatments a person can take.
In January while going through the bone marrow testing week, again she learned the cancer is still present,.this time it is confirmed she has both AML and ALL. The best Doctor's at the U of M are diliberating over the next steps for Barb, in the meantime she will be tested again to see how fast the cancer had grown in a 2 week period before determining if she will once again go through Chemo or begin Radiation. The ultimate goal is to have a bone marrow transplant. Without this transplant she has only a 10% chance of survival.
Barb is only 33 years old. She is married to Brent Reierson, has 2 small children; Benjamin (11) and Bethany (3), and they live Barb's small home town of Arlington, MN. Barb has a hard time saying "no" so she volunteers to help so many people in the community. She has taught Sunday school, she volunteered for Sibley County Human Services and is currently the President of the local Arlington-Green Isle Women of Today Chapter, where she has Lead the yearly scrapbook fundraiser that has been supporting her local community for the past 4 years.
Please keep Barb and her family in your prayers. We appreciate your support.

subset: commoncrawl


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Castle Makahuena Condominium Resort at Poipu
1661 Pe'e Road
Poipu, HI US 96756 Map It
Poipu, HI US 96756 Map It
Kauai South Shore :Poipu
Makahuena at Poipu is on the southernmost point of the island of Kauai and offers the rare opportunity for viewing both sunrise and sunset from its oceanfront location .
This oceanfront all-suite condominium consists of beautifully furnished one, two and three bedroom suites with full kitchen, and offers swimming pool, sundeck, jet spa, and tennis court and barbecue area . With Keoniloa Bay and Shipwreck Beach to the East and Brennecke's and Poipu Beach to the West, Makahuena is within walking distance to some of the most beautiful beaches on the island ..
Castle Makahuena Condominium Resort at Poipu Features
- Tennis Courts
- Safe Deposit Box
- Swimming pool
- Elevators
- Free parking
Castle Makahuena Condominium Resort at Poipu Reservation Policies:
- Check-In: 1500
- Check-Out: 1200


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The first question anyone would ask is "what in the heck is "Moral Monday" and why would it want to come to South Carolina?"
When I first heard about Moral Monday, I had no idea what it was and thought it must have something to do with a bunch of Bible-thumping TV evangelists who didn't get enough of the thumping on Sunday and kept it all going till Monday.
Unfortunately, we live in a world in which pedicures and funeral parlor bathrooms are serious issues for state government.
Last week, the Regulatory Review Task Force, established by Gov. Nikki Haley earlier this year, met at the Statehouse to hear comments and concerns by citizens. Among the citizens were representatives of the S.C. Board of Funeral Service and the S.C. Board of Cosmetology.
The nation learned in May that the Justice Department secretly obtained the phone records of more than 100 Associated Press reporters and monitored Fox News reporter James Rosen's personal email and cell phone records, branding him a "possible co-conspirator" in a classified leak case for asking questions of a government source.
These revelations sent shockwaves throughout newsrooms nationwide. Reporters can no longer assure their sources that interviews will remain confidential because there is no way to tell whether the government is listening.
I confess: I used to make the choice to drive while distracted. Every time we get behind the wheel, we have a choice: the wise one to focus on the serious responsibility of operating a motor vehicle or the hazardous one to use the "down time" of driving doing other things.
The worst part is that we all depend on the other drivers to make the wise choice – conscious or not.
Over the past six fiscal years, medical businesses with ties to five S.C. lawmakers collectively have received more than $10 million in Medicaid payments, The Nerve found in a review of state Medicaid records.
Two of the lawmakers – Rep. Kris Crawford, R-Florence and an emergency room doctor, and Rep. Kit Spires, R-Lexington and a pharmacist – didn't report any of their Medicaid amounts on their six most recent annual statements of economic interests filed with the State Ethics Commission, though Spires contends he is not required to do so.
The Bible contains pictures of saving faith, the faith which brings people into a right relationship with God. In 2 Kings 5, Naaman, a leprous Syrian general, found cleansing through obeying the command of the Hebrew prophet Elisha.
Naaman was the courageous pagan commander of the Syrian army, highly regarded because through him God had given deliverance to Syria.
A young Jewish girl worked in Naaman's home as a servant to his wife. She felt compassion for Naaman and mentioned to his wife that there was a prophet in Samaria who would heal him of his disease.
When I was a young boy growing up and my mother confronted me with something that I knew I had done wrong, I often stammered around, making excuses and trying to avoid fessing up. My mom's response was always the same: "Let's begin by just telling the truth."
When it comes to the Statehouse debacle over so-called "ethics reform," they should simply follow mom's wisdom – let's begin by just telling the truth.
The S.C. Department of Transportation has decided to close the crossover at the entrance of Black Horse Run on U.S. 521 due to "safety concerns."
This affects 150-plus families who use the crossover daily.
Black Horse Run has been developed for more than 40 years, long before Indian Land became the "hot spot" for development of strip shopping centers with little or no planning as to what the area, which is beginning to look like Cherry Road, might look like in the future.
What's the best way to explain or analyze what a moderate Republican and a liberal Democratic represent?
The word I find in Roget's New Thesaurus (expanded edition) is "hypocrite."
Words such as hypocrisy, hypocritical, hypocriticalness, complacent, smug and self-contented best explain the actions and thinking of moderate Republicans and Democrats.
One of the major mistakes in development that has led to the difficult situation in Indian Land is the failure to anticipate and provide for the infrastructure required to support that development.
Developers build houses and houses become homes because people come to live in them. Those people need roads, traffic control, schools, libraries, water and sewers, police and fire protection and EMS and 911 services.
Copyright © 2015
The Lancaster News is your source for local news, sports, events, and information in Lancaster County and Lancaster, South Carolina, and the surrounding area..


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Workout Tips During Cold and Flu Season, Part 1
The New Year is here and with it comes aspirations of getting fit no matter what. In some cases, this may mean working out when you don't feel like it – literally! If you're under the weather does it make sense to workout and if so, how hard do you push it? In my first of two posts I will discuss ways to workout when you're under the weather and when to just say no.
Go to any gym and you're bound to hear someone coughing across the room.
In some cases you may see someone sneeze in his hand and then grab some
free weights and start pumping (happens more often than you think). The
bottom line is to take these sneezes and coughs seriously - it doesn't take
much to spread a cold or flu. However,
if you're not experiencing any sick symptoms you still need to be careful
amongst sick gym-goers. Here are some must-do tips to practice at the gym
during flu season.
Scenario 1: Symptom free, you're not sick
Tip #1: Wash your hands - often. This tip is the most helpful, effective yet overlooked step that can prevent you from getting sick. In fact, studies show that hand-washing works better than hand sanitizer to remove those germs associated with illness in vulnerable areas like schools, hospitals, and you name it: gyms.
Wash your hands before and after your
workout. Don't put it off until you get home -- clean those hands right
away. Don't assume that you're a hand-washing expert though. It's
always good to get a refresher
course from the Centers for Disease Control and Prevention.
Tip #2: Wear gloves. Weightlifting gloves are not just for the Muscle & Fitness wannabes. I recommend you make gloves a staple in you gym bag. Weightlifting gloves serve the obvious function of protecting your hands from those mean callouses but they also provide a barrier when you use gym equipment. Granted, your fingers are still exposed so you'll still need to wash your hands after a workout anyway.
That said, the more barriers you use,
the better. Be sure to wash your gloves regularly, 2-4 times per month is
Tip #3: Maintain a clean workout surface. Never assume that equipment is clean. Err on the side of caution and use a towel to prevent any bodily fluid exchange (a little personal, but you get my point). If the gym has a sanitizer you can use to wipe off equipment, by all means use it. Trust me, you're not an elitist if you do, you're just doing the right thing.
In my next post, I'll discuss workout options when you have the cold or flu and what you can do to help a speedy recovery. Until then, stay healthy and keep moving.


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I moved away from Michigan and then moved back. I was amazed at the amount of hurdles I had to jump through to get my driver's license and reinstate my Michigan residency. But you know what, I did it and would do it again happily. My grandfather always taught me that you do what it takes to do what's right. He was a township treasurer and oversaw voting in his area for years. Even though he knew almost everyone by name, he still said there needed to be more accountability in voting and this was many years ago.
How does this have ANYTHING to do with the Tea Party? Pretty sure ICE is a federal program run by... wait for it... NOT the Tea Party. I'm sure it's still Bush's fault after four years, right?
23 years of breaking the law doesn't make everything okay. Would I rather he be able to become a U.S. citizen? Yes, but the system as it is, UNDER OBAMA, doesn't allow for that. Can't blame anyone else but himself.
Seems that you're all well to willing to take this on face value, but you're missing the point here. What business does a union have issuing ANY kind of statement on an event, whether it actually happened or not, that has nothing to do with the professional lives of those involved. She was mowing her yard and he was at a party. It didn't happen in the work place or either of them.
Doesn't matter if you're a republican or a democrat, if you don't see that as wrong, you're an idiot.
I love it that having to show a picture I.D. will cause some to be disenfranchised with voting... Yeah, the lies, political garbage and outright lousy job the politicians are doing aren't enough to disenfranchise the voter, it's having to show an I.D.
Fine. Make free I.D.s available, oh wait, we already do that...
But voter fraud can't happen. Democrats are smarter than all of us and socialism works, too. And the moon is made of cheese, too.
The law he broke was spread out over several pages of the Alaska rule book. His guide didn't know about it and several other guides asked didn't know about it. Even the officers investigating were not sure of it.
I don't always agree with Ted and how he handles things. BUT, he is a great advocate of guns, safety and teaching kids.
I honestly think this whole thing was less about catching a criminal than it was a bit of character assassination.
Hey, I didn't say red...
I'm just happy we a bit of a playoff rivalry brewing. We've lacked one since the Avs.
I can see it now. The Wings will score a goal and the ice will be pelted with ping pong balls.
I heard a tree knock. There's a squatch right outside my door. No, wait... Just the UPS guy.
The researchers that do the show should run for office. They spend tons of money, totally believe what they say and never offer or find one shred of proof.
I thought I saw a Bigfoot once. It was hairy and smelly and scary... Turned out to be my Mother-in-law. I would have rather it been a Bigfoot.
Ferris' trip to the Finals reminds me of another small Michigan team around 1994. Granted Lake State had been to the Finals the previous year, but they still got NO respect from Boston University fans, or the Harvard or Michigan fans that LSSU had to go through to get there.
What was that final score again... Oh yeah, 9-1 LSSU.
BC is going to be tough, but I'm behind the Bulldogs... SHould be a good game.
The only reason unemployment went down under Obama is that they don't count the people who aren't willing to work anymore. The real number is closer to 16%, worst in history.
It took both parties, working together, to screw things up this bad. But to blame Bush after 4 years is idiotic.
Isn't the issue one of the people of this country not wanting the Government to do EVERYTHING for us? Isn't the issue those who work not wanting to pay for those who won't? (Note, I didn't say can't...)
And no, I didn't read the entire health care reform bill that was rammed through and signed into law. But then again, neither did the people who voted for it! "We can read it after we pass it." - Nancy Pelosi
I do know that when it passed, my health insurance got more expensive and my coverage went down. Want to blame the "big, bad" insurance company? Go right ahead. Want to blame "big business?" Go right ahead. Blame whomever makes you sleep at night. Whatever you do, however, don't blame yourself.
I find it disgusting that this law was enacted. Now the Supreme Court is reviewing it, as they should, and is divided on party lines. Politics has NO place in the court. And that the president seems to threaten the court is also disgusting.
I have a job and pay for health insurance for me and my family. I work 5 days a week plus extra on the weekends and evenings as does my wife so we can support our family.
My sister-in-law works 2 days a week. She pays for nothing and gets irate when she "has to use her own money for food and stuff." She has better health coverage than my family does. She has her Bridge card and her free cell phones and got an $6,000 tax refund. She didn't even MAKE $6,000 last year. She has had multiple opportunities to take a full-time job, but has no interest in doing so.
The gravy train needs to stop. Those that TRULY need help should get it. Those that take advantage of a broken system need to get the boot.
I don't make a ton of money. I am not wanting to protect the rich or any of that other garbage liberals like to say about conservatives. I'm highly educated, intelligent and have studied history. We can't continue to go on in this fashion as a country.
One thing not often taken into account when looking at issues like this is the legal side of what would happen if an event took place. Say you're called upon to protect yourself and/or a loved one in a school or other public place. Even if everything were legitimate, there is going to be a legal mess, not to mention the amount of lawsuits that would arise from "mental trauma."
Should more places be open to concealed carry? Yes. BUT, the consequences need to be fully understood by gun owners before they make the decision to carry into such places.
Democratic idiots use public forums as a way to try to prove to others how intelligent they aren't.
Saying that anyone who carries a handgun is a nutcase shows just how intelligent you are not.
Criminals and nutcases generally don't go to the effort to LEGALLY obtain and carry firearms.
Here's a thought, the state already has licensed waterfowl hunters. Add a $5 Mute Swan tag and let the hunters do the job. The swan problem goes away and the state makes money.
Thanks for changing the photo MLive... Still doesn't get you guys off the hook for the terrible story on concealed carry, but that's another discussion.
Nice picture of a gun for a story on crime. This kind of thing and the recent pile of stories you ran on concealed carry offenders is why I'm canceling my subscription to your newspaper.
I know it's trendy to associate gun ownership with being a criminal, but I would think you would know better.


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King of the Band
Capillary Action's leader takes his band through rock and jazz and back again
Brownies are great," enthuses Capillary Action's guitarist and vocalist, Jonathan Pfeffer, relaxing at his mother's house on a rare holiday break. Just back from a grueling tour where his band played 55 shows in 55 days, he's a bit worn out. The shell-shocked musician seems even more flummoxed when asked how he'd describe his band to a neophyte who isn't schooled in the lexicon of indie-rock taxonomy.
"You mean, basically, what you're asking me to do is to describe the band to my grandmother, right?" Yes, Jonathan. This is an especially tricky question for Pfeffer, whose enigmatic Philadelphia-based band regularly spans the stylistic globe two or three times over in the course of a single song.
"To describe Capillary Action, I'd say it would be like a picture of your typical rock band that had been cut into different pieces, mixed up, and stuck back together," says Pfeffer. "It's a weird rock band, with all of the parts interpreted by jazz musicians. Every part has a purpose, and it's purposely eclectic—the eclecticism isn't for its own sake, but the different parts are chosen to fit purposes of the songs."
The group came together at Oberlin College, where Pfeffer, a self-trained musician, was a regular student and the other players were enrolled in the music conservatory. While one might think that this dichotomy is key to the band's odd style, Pfeffer claims that he's always written off-kilter songs.
There is not a single band on this earth that likes to be classified. Every group purports to defy categorization, even though the majority of bands are just chasing whichever bandwagon came down the pike last week. And the only thing worse, usually, than bandwagon-jumping is self-conscious eclecticism. Believe it or not, though, Capillary Action really is different, without employing too many Dadaistic tendencies or straying into novelty-music territory.
"I usually just tell people that my biggest influences are my parents' divorce and that saying, 'When life gives you lemons, make lemonade,'" Pfeffer says.
Pfeffer and his band mates have been making lots of lemonade of late, apparently throwing sundry other musical fruits and vegetables into the mix, and bringing along the blender just for the heck of it. The group's newest album, So Embarrassing, delivers a selection of tunes that—just as soon as you think you've gotten a handle on a riff or rhythm—switch from sounding like The Locust to Oneida to Miles Davis, or something.
With a couple of years of incremental, albeit modest, triumphs, Capillary Action seems to be on the verge of progressing from the indie ghetto into some kind of success. The group is hot off of two tours with Fugazi's Joe Lally, outings that exposed the band to larger audiences. "Those were our first somewhat major tours," says Pfeffer. "It was an amazing opportunity.... And as of now the tours are finally sort of paying for themselves—but I'm still living with my mother when I'm not on the road."
Capillary Action's jarring musical complexity means that the band is something of an acquired taste, which is sometimes a hard sell in traditional rock venues. Pfeffer explains that while audiences are generally accepting wherever the band performs, sometimes alternative spaces really are more suited for the group's paradoxical sound. While it's unlikely that the group will ever find a niche on commercial rock radio, Capillary Action is moving into a phase where they might actually join the much dreaded and maligned music business. Stranger things have happened.
"We're on a record label, but it just happens to be a label that I run," explains Pfeffer. "I would love to be on a 'real' record label for the sole purpose of having someone else take up the slack on the business end. As of now, I've taken this band as far as I can on my own."
And that's yet another way that Capillary Action is different. While most bands at least claim to be democratic, Pfeffer has no qualms about claiming his status as the group's driving force. "I am the king of the band," he says. "That's a way of avoiding problems. We don't have problems with democratic issues because I'm responsible for everything. The other musicians [Sam Krulewitch on keyboards and Noah Hecht on drums] all do their jobs. If you think about it, that's the way it always is: With every single successful band, it's either one or two people who call the shots."


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Bodmin Town's late double denies Witheridge win over Peninsula League champions
Posted: March 14, 2013|
BODMIN TOWN scored twice in stoppage time to deny Witheridge a famous win in the Carlsberg South West Peninsula League premier division.
Richard Groom's 77th-minute header gave Witheridge a 1-0 lead away to the premier division leaders and champions, who have lost only once in the league this season.
But as more than five minutes were added on at the end, Luke Hodge headed an equaliser for Bodmin and Lewis Reed's cross-shot found the far corner to snatch a 2-1 win.
Witheridge might have been out of sight long before the late double blow, but for Bodmin goalkeeper Kevin Miller.
He produced fine saves from efforts by Richard Blake, twice, and Jamie Dirrane.
After winning their first six games under manager Chris Vinnicombe, Witheridge have won only one of the last six.
They will try to climb back into the top half of the table when they go to Saltash United on Saturday and Cullompton Rangers on Tuesday.


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Novel polyacrylic acid resins are prepared by polymerizing H2 C═CHCO2 H, H2 C═CRCO2 X, or HRC═CHCO2 X, wherein R is an aliphatic or aromatic hydrocarbon, halogenated hydrocarbon, or sulfonated hydrocarbon of from C1 to C20, phenol, naphthol, sulfonated phenol, sulfonated naphthol, or a halogen, and X is hydrogen, alkyl, or a hydroxylated, ethoxylated, sulfonated, or halogenated aliphatic or aromatic hydrocarbon of from C1 to C20, sodium, potassium, ammonium, or quaternary amine, in the presence of aromatic sulfonic acid or its salt to form a polymer in which the sulfonated aromatic compound is covalently bound to the polymer. In an alternative embodiment, a textile processing or cleansing compound is included in the polymerization reaction along with the acrylic acid and aromatic sulfonic acid or its salt. The resulting polymers have superior properties for use in textile processing and cleaning, and can be used as detergents, acid dye levelers, surfactants, emulsifiers, yarn lubricants, copolymerizing agents, polymer after treat agents, defoamers, chelating agents, flocculants, anti-static agents, flame retardants, metal cleaners, metal coatings, and as multipurpose acids.
1. A water soluble composition comprising a polymer prepared by polymerizing monomers consisting essentially of methacrylic acid, or its sodium, potassium, or ammonium salt, in the presence of at least 10% by weight of reaction components of an aromatic sulfonic acid selected from the group consisting of xylene sulfonic acid, toluene sulfonic acid, benzene sulfonic acid, cumene sulfonic acid, dodecylbenzene sulfonic acid, dodecyl diphenyloxide disulfonic acid, naphthalene sulfonic acid, methylnaphthalene sulfonic acid, trimethylbenzenesulfonic acid, aminobenzene sulfonic acid, halobenzenesulfonic acid, alkoxybenzenesulfonic acid, benzophenone sulfonic acid, halonaphthalene sulfonic acid, alkylnaphthalene sulfonic acid, alkoxynaphthalene sulfonic acid, 3-sulfobenzoic acid, hydroxybenzenesulfonic acid, hydroxynapthalenesulfonic acid, or carboxymethylbenzene sulfonic acid, or mixtures of these aromatic sulfonic acids or their sodium, potassium, or ammonium salts, and wherein the polymerization reaction is performed in the absence of a sulfonated formaldehyde condensation polymer of sodium naphthalene sulfonate and 4,4'-dihydroxydiphenylsulfone.
2. A method for preparing a water soluble composition comprising polymerizing monomers consisting essentially of methacrylic acid, or its sodium, potassium, or ammonium salt,, in the presence of at least 10% by weight of reaction components of an aromatic sulfonic acid selected from the group consisting of xylene sulfonic acid, toluene sulfonic acid, benzene sulfonic acid, cumene sulfonic acid, dodecylbenzene sulfonic acid, dodecyl diphenyloxide disulfonic acid, naphthalene sulfonic acid, methylnaphthalene sulfonic acid, trimethylbenzenesulfonic acid, aminobenzene sulfonic acid, halobenzenesulfonic acid, alkoxybenzenesulfonic acid, benzophenone sulfonic acid, halonaphthalene sulfonic acid, alkylnaphthalene sulfonic acid, alkoxynaphthalene sulfonic acid, 3-sulfobenzoic acid, hydroxybenzenesulfonic acid, hydroxynapthalenesulfonic acid, or carboxymethylbenzene sulfonic acid, or mixtures of these aromatic sulfonic acids or their sodium, potassium, or ammonium salts, and wherein the polymerization reaction is performed in the absence of a sulfonated formaldehyde condensation polymer of sodium naphthalene sulfonate and 4,4'-dihydroxydiphenylsulfone.
3. The composition of claim 1, wherein the aromatic sulfonic acid is cumene sulfonic acid, or its sodium, potassium, or ammonium salt.
4. The method of claim 2, wherein the aromatic sulfonic acid is cumene sulfonic acid, or its sodium, potassium, or ammonium salt.
5. The composition of claim 1, wherein the aromatic sulfonic acid is xylene sulfonic acid, or its sodium, potassium, or ammonium salt.
6. The method of claim 2, wherein the aromatic sulfonic acid is xylene sulfonic acid, or its sodium, potassium, or ammonium salt.
7. The composition of claim 1, wherein the aromatic sulfonic acid is selected from the group consisting of toluene sulfonic acid, benzene sulfonic acid, and dodecylbenzene sulfonic acid, or their sodium, potassium, or ammonium salts.
8. The method of claim 2, wherein the aromatic sulfonic acid is selected from the group consisting of toluene sulfonic acid, benzene sulfonic acid, and dodecylbenzene sulfonic acid, or their sodium, potassium, or ammonium salt.
This invention is in the area of polymer chemistry, and in particular relates to a group of novel polyacrylic acid derivatives that can be used in a variety of applications, including textile applications.
Polymethacrylic acid and polyacrylic acid, as well as their copolymers, are important polyelectrolytes that are widely used in industry for a number of applications, including as thickening agents for paints, suspending agents for inorganic pigments, flocculants in metal ore recovery, and in ion-exchange resins, coatings and dispersants. For example, Dickson U.S. Pat. No. 4,043,965 describes a copolymer of acrylic acid and 1,1-dihydroperfluorooctyl methacrylate that is useful as a soil-release finish in the rinse cycle of a home laundry process. Portnoy U.S. Pat. No. 4,680,128 discloses low molecular weight copolymers of acrylic acid and salts of vinylsulfonic acid for use as dispersants and deflocculants.
Polymethacrylic acid and a number of copolymers and blends thereof have been used increasingly to impart stain resistance to nylon (polyamide) fibers. The anionic moieties of the polymers ionically bind to protonated terminal amines in the polyamide, blocking subsequent ionic bonding by anionically charged dyes. Chang, et al. U.S. Pat. No. 4,937,123 assigned to Minnesota Mining and Manufacturing Company, describes the use of polymethacrylic acid and copolymers of methacrylic acid with other ethylenically unsaturated monomers to impart stain resistant properties to nylon fibers. Olson U.S. Pat. No. 4,822,373 also assigned to Minnesota Mining and Manufacturing Company, describes a stain resistant composition prepared by blending a partially sulfonated novolak resin with a polymethacrylic acid, or a copolymer of methacrylic acid with ethylenically unsaturated monomers. Moss, et al. U.S. Pat. No. 4,940,757 assigned to Peach State Labs, Inc., describes a stain resistant polymeric composition prepared by polymerizing an α-substituted acrylic acid in the presence of a sulfonated aromatic formaldehyde condensation polymer using a free radical generating agent. The resulting product imparts to polyamides improved resistance to acid dyes, while exhibiting little discoloration over time, and can be used at levels of application less than other compositions that are composed of a mere blend of polymethacrylic acid and a sulfonated aromatic formaldehyde condensation polymer.
A number of chemical agents other than stain resist agents are required during textile processing and handling. Examples include dye levelers, acids to adjust pH, cleaning agents (detergents, shampoos, and surfactants), emulsifiers, yarn lubricants, defoamers, antistatic agents, flame retardants, ultra-violet absorbing agents, and finishing resins A substantial amount of the agents currently used typically remain in the wastewater after use, increasing the B.O.D. (biological oxygen demand) and C.O.D. (carbon oxygen demand) of the wastewater. The agents also increase the hazardous nature of the wastewater, which significantly increases the burden of water purification placed on the company and on the publicly owned treatment facilities.
It would be of significant environmental benefit to develop textile processing chemicals that adhere to the carpet fiber (that would be exhausted onto the fiber) instead of remaining in the wastewater to be removed later at significant expense. It would be of even greater value to have an exhaustible processing chemical that improves the properties of the textile fiber for residential or commercial use.
It is therefore an object of the present invention to provide textile processing and handling agents that have improved performance over the currently used agents.
It is another object of the present invention to provide processing chemicals for textile applications that are exhausted onto synthetic and natural fibers and substrates
It is still another object of the present invention to provide an exhaustible processing chemical that improves the properties of the synthetic and natural fibers and substrates.
New polyacrylic acid resins are prepared by polymerizing acrylic acid, H2 C═CRCO2 X, or HRC═CHCO2 X, wherein R is an aliphatic or aromatic hydrocarbon, halogenated hydrocarbon, or sulfonated hydrocarbon of from C1 to C20, phenol, naphthol, sulfonated phenol, sulfonated naphthol, or a halogen, and X is hydrogen, alkyl, or a hydroxylated, ethoxylated, sulfonated, or halogenated aliphatic or aromatic hydrocarbon of from C1 to C20, sodium, potassium, ammonium, or quaternary amine, in the presence of an aromatic sulfonic acid or its salt. In a second embodiment, a textile processing or cleansing compound is included in the polymerization reaction, along with the acrylic acid and sulfonated aromatic compound. Increasing the relative ratio of the acrylic acid and methyl methacrylate to the other components in the polymerization reaction mixture increases the aqueous solubility and reduces viscosity of the reaction product.
The polymerization reaction components are selected based on the desired properties of the resulting polymeric product for a specific application. The choice of aromatic sulfonic acid or its salt and textile processing or cleansing agent will influence the aqueous solubility, wettability, ionic character, surfactant capability, exhaustibility, soil and grease absorption, chelation ability, flame retardancy, and detergency of the polymer.
The resulting polymers have superior properties for use in textile processing and cleaning, and can be used as detergents, dye levelers, surfactants, emulsifiers, yarn lubricants, copolymerizing agents, polymer after treat agents, finishing agents, leather tanning and finishing auxiliaries, defoamers, chelating agents, flocculants, anti-static agents, flame retardants, metal cleaners, metal coatings, and as multipurpose acids (replacing or supplementing, for example, phosphoric, acetic, formic, sulfonic, or sulfamic acid in a processing procedure).
An important advantage of the polymers described herein are that they can replace current textile processing and finishing chemicals that can have a harmful effect on the environment. For example, laundry detergents now commonly include phosphoric acid salts or their esters as surfactants. These compounds are very difficult to remove from wastewater and are often released into fresh water, where they accelerate the aging of rivers, streams, and lakes. In certain countries, phosphoric acid esters are being replaced with acrylic and methacrylic acid polymers. An alternative laundry detergent can be prepared as described herein by polymerizing an acrylic acid in the presence of a sulfonated aromatic compound and a phosphoric acid ester. The resulting laundry detergent retains the advantages of the phosphoric acid ester but is easily removed from wastewater using conventional wastewater treatment processes.
The polymers described herein can also be used in fiber finishing processes to replace or supplement the acid dye levelers, surfactants, emulsifiers, and acids for pH adjustment that are now used. These compounds are eliminated in the waste stream, significantly increasing the biological oxygen demand (B.O.D.) and the chemical oxygen demand (C.O.D.) of the wastewater. The polymers described herein can be exhausted onto nylon fiber, wool, silk, or leather, so that they are not eliminated in the waste stream, thereby decreasing the B.O.D. and C.O.D. of the wastewater, and at the same time actually improving the physical properties and durability of the fiber.
As used herein, the term polyacrylic acid includes polymers prepared by the polymerization of H2 C═CHCO2 X, H2 C═CRCO2 X or HRC═CHCO2 X, or mixtures of these monomers, with X and R as defined above. The term acrylic acid as used herein includes H2 C═CHCO2 X, HRC═CHCO2 X, and HC═CRCO2 X. The term aromatic sulfonic acid or sulfonated aromatic compound refers to any aromatic compound in which a sulfonic acid group is covalently bound to an aromatic moiety.
Acid dye levelers are compounds that allow uniform distribution of a dye during the coloring process. If a leveler is not used, the dyestuff tends to adhere in a nonuniform fashion, causing blotching of the color and Barre'. Textile processing acids are compounds used to adjust the pH during dyebath and finishing treatments. Surfactants and emulsifiers are surface active agents that modify the surface energy between two liquid phases. A yarn lubricant is an oil or emulsion finish that is applied to a fiber to prevent damage to the fiber during textile processing or applied to knitting yarns to make them more pliable. A defoamer is a chemical that reduces the foamability of a solution. An antistatic agent is a reagent capable of preventing, reducing, or dissipating static electrical charge that is produced on materials. A flame retardant is a chemical that is incorporated into a textile fiber during manufacture or use to reduce flammability. Ultra-violet absorbers are chemicals that absorb ultra-violet radiation, and are used to protect the fiber from damage caused by uv absorption. A finishing agent is a chemical applied to a substrate for dimensional stability and other desired aesthetic effects.
Acrylic acid resins prepared as described herein can also be used as copolymerizing agents in the polymerization reaction with any ethylenic unsaturated monomers, including H2 C═CHCO2 X, HRC═CHCO2 X, H2 C═CRCO2 X, and styrene. The monomers useful for copolymerization with the methacrylic acid are monomers having ethylenic unsaturation. Such monomers include, for example, monocarboxylic acids, polycarboxylic acids, and anhydrides; substituted and unsubstituted esters and amides of carboxylic acids and anhydrides; nitriles; vinyl monomers; vinylidene monomers; monoolefinic and polyolefinic monomers; and heterocyclic monomers.
Representative monomers include, for example, acrylic acid, itaconic acid, citraconic acid, aconitic acid, maleic acid, maleic anhydride, fumaric, acid, crotonic acid, cinnamic acid, oleic acid, Palmitoleic acid, vinyl sulfonic acid, vinyl phosphonic acid, alkyl or cycloalkyl esters of the foregoing acids, the alkyl or cycloalkyl groups having 1 to 18 carbon atoms such as, for example, ethyl, butyl, 2-ethylhexyl, octadecyl, 2-sulfoethyl, acetoxyethyl, cyanoethyl, hydroxyethyl and hydroxypropyl acrylates and methacrylates, and amides of the foregoing acids, such as, for example, acrylamide, methacrylamide, methylolacrylamide, and 1,1-dimethylsulfoethylacrylamide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, p-hydroxystyrene, chlorostyrene, sulfostyrene, vinyl alcohol, N-vinyl pyrrolidone, vinyl acetate, vinyl chloride, vinyl ethers, vinyl sulfides, vinyl toluene, butadiene, isoprene, chloroprene, ethylene, isobutylene, vinylidene chloride, sulfated castor oil, sulfated sperm oil, sulfated soybean oil, and sulfonated dehydrated castor oil. Particularly useful monomers include, for example, alkyl acrylates having 1-4 carbon atoms, itaconic acid, sodium sulfostyrene, and sulfated castor oil. Of course, mixtures of the monomers, such as, for example, sodium sulfostyrene and styrene, and sulfated castor oil and acrylic acid, can be copolymerized with the methacrylic acid.
Methods to polymerize a monomer in the presence of a polymer are described in a number of sources, including Moss U.S. Pat. No. 4,940,757, incorporated by reference herein.
The polyacrylic acid resin is prepared with a H2 C═CHCO2 X, H2 C═CRCO2 X, or HRC═CHCO2 X or mixtures of these, wherein R is an aliphatic or aromatic hydrocarbon, halogenated hydrocarbon, or sulfonated hydrocarbon of from C1 to C20, phenol, naphthol, sulfonated phenol, sulfonated naphthol, or a halogen, and X is hydrogen, alkyl, or a hydroxylated, ethoxylated, sulfonated, or halogenated aliphatic or aromatic hydrocarbon of from C1 to C10, sodium, potassium, ammonium or quaternary amine. A preferred starting material is H2 C═CRCO2 X, wherein R is methyl, ethyl, propyl, butyl, phenyl, phenol, sulfonated phenol, naphthol, chloro, or fluoro, and X is hydrogen, lower alkyl (C1 to C10), sodium, potassium or ammonium.
Mixtures of α and or β-substituted acrylic acids, with or without acrylic acid, can also be reacted together. Esters of substituted acrylic acids can be polymerized in combination with unesterified substituted acrylic acids. If the alcohol from which the ester is prepared is hydrophobic, as the percentage of ester in the composition increases, water solubility and affinity for the polyamide fiber will decrease. If the alcohol from which the ester is prepared is hydrophilic or basic, water solubility is not adversely affected or is improved. Acrylic acid derivatives with low water solubility can be polymerized using emulsion polymerization techniques known to those skilled in the art.
In an alternative embodiment, an unhalogenated acrylic acid is copolymerized with a partially halogenated or perhalogenated acrylic acid or acrylate. In another embodiment, an acrylic acid or anhydride is esterified with a halogenated alcohol, and then polymerized or copolymerized in the presence of the textile processing or cleansing chemical. In yet another embodiment, fluorinated C8 -C12 esters of acrylic acids are polymerized or copolymerized. It is preferable to copolymerize a fluorinated acrylate with at least some free acrylic acid.
Fluorinated alkyl esters of acrylic acid have low water solubility. When polymerizing these esters, an emulsifying agent such as a nonyl phenol, an ethoxylated oleic acid ester, or a sorbitan monooleate should be included in the reaction mixture.
The acrylic acid monomers can be used as the free acids, as mixtures of the salt and free acid or as all salts. The free acids are used when water solubility is desirable or the compound is to be used with surfactants, emulsifiers, or acids. The salts are used in detergents and as hydrotropes. Alpha-substituted acrylic acids are preferred when used as acid dye levelers and to increase substantivity.
Aromatic sulfonic acids are included in the acrylic acid polymerization reaction to impart a number of characteristics to the polymer, including, but not limited to, anionic character (when in the salt form) suitable for ionic bonding with protonated terminal amines, acidity when used as the free acid, viscosity adjustment, prevention of precipitation and clumping, hydrotropic effects, and increased exhaustibility.
Nonlimiting examples of aromatic sulfonic acids that do not have ethylenic unsaturation include xylene sulfonic acid, toluene sulfonic acid, benzene sulfonic acid, cumene sulfonic acid, dodecylbenzene sulfonic acid, dodecyl diphenyloxide disulfonic acid, naphthalene sulfonic acid, benzaldehyde sulfonic acid, methylnaphthalene sulfonic acid, trimethylbenzenesulfonic acid, aminobenzene sulfonic acid, halobenzenesulfonic acid, alkoxybenzenesulfonic acid, benzophenone sulfonic acid, benzophenone disulfonic acid, halonaphthalene sulfonic acid, alkylnaphthalene sulfonic acid, alkoxynaphthalene sulfonic acid, carboxybenzene sulfonic acid (3-sulfobenzoic acid), hydroxybenzenesulfonic acid, hydroxynapthalenesulfonic acid, carboxymethylbenzene sulfonic acid, alkylbenzene disulfonic acid, dicarboxybenzene sulfonic acid, acetamidobenzene sulfonic acid, acetaminonaphthalene sulfonic acid, naphthalene disulfonic acid, alkyl naphthalene disulfonic acid, dialkylbenzene disulfonic acid, biphenyl-4,4'-disulfonic acid, benzene and naphthalene sulfonic acids that contain combinations of halo, alkyl, hydroxy, carboxy, alkoxy, and acetamino groups, as well as the salts of all of these compounds. Preferred salt cations are sodium, potassium, and ammonium. Examples of aromatic sulfonic acid salts include sodium xylene sulfonate, ammonium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, ammonium cumene sulfonate, potassium toluene sulfonate, potassium cumene sulfonate, and potassium xylene sulfonate.
The choice of aromatic sulfonic acid to be included in the acrylic acid polymerization reaction will be determined by a variety of factors, including aqueous or organic solubility, degree of sulfonation, viscosity, solidification temperature, and pH. One of skill in the art will know how to select the appropriate aromatic sulfonic acid based on known properties of these compounds. Mixtures of sulfonated aromatic compounds, including salts, can be used to attain the desired properties. Diphenyl esters or diphenyl oxide disulfonates are preferred for use as levelers. Xylene sulfonic acids are preferred for use in exhaustible acids. Dodecylbenzene sulfonic acids are preferred for use in shampoos and detergents.
A wide variety of textile processing and cleansing compounds can be included in the acrylic acid polymerization reaction to improve the properties of the polymeric composition. Examples of the families of chemicals that can be included are described in more detail below. None of these families of compounds include the traditional ethylenically unsaturated monomers, as described in Olson U.S. Pat. No. 4,937,123, that are typically copolymerized with acrylic acid or its derivatives.
As noted above, polymers prepared by the polymerization of acrylic acid in the presence of an aromatic sulfonic acid and a surfactant can be used in a wide variety of applications, including as acid dye levelers, pH adjusters, in shampoos and detergents, as defoamers, yarn lubricants, and in metal cleaners and coatings. The polymer can be exhausted onto fibers with terminal protonated amino groups, such as nylon, during textile treatment processes, to reduce the concentration of the polymeric material in the wastewater, thereby reducing the B.O.D. and C.O.D. (biological oxygen demand and carbon oxygen demand, respectively) of the effluent.
Surfactants contain both a hydrophobic (or lyophobic) end and a hydrophilic (or lyophilic) end. Surfactants are typically characterized by the nature of its hydrophilic portion. Anionic surfactants have a negatively charged moiety in the hydrophilic end of the molecule, such as a carboxylate or sulfonate salt. Cationic surfactants have a positive charge in the hydrophilic portion of the molecule, provided by, for example, an ammonium salt or a quaternary amine. A zwitterionic surfactant has both positive and negative charges in the hydrophilic portion. Examples of zwitterions are long chain amino acids and sulfobetaines. Nonionic surfactants do not have a formalized charge. Examples include the monoglycerides of long chain fatty acids and polyoxyethylenated alkyl phenol.
The hydrophobic end of the surfactant can include a wide variety of structures, for example, straight or branched long chain alkyl groups, long chain alkyl benzenes, alkyl naphthalenes, rosins, high molecular weight propylene oxide polymers, long chain perfluoroalkyl groups, polysiloxane groups and lignin derivatives. In general, as the length of the hydrophobic group increases, solubility in polar or ionic solvents decreases. Branching and unsaturation typically increases the solubility of the surfactant in all solvents. Aromatic nuclei increase adsorption onto polar surfaces. Polyoxypropylene chains also increase adsorption onto polar surfaces, and increase solubility in organic solvents. Perfluoroalkyl and polysiloxane moieties are hydrophobic groups that reduce the surface tension of water to lower values than those attainable with a hydrocarbon-based hydrophobic group. Perfluoroalkyl surfaces are both water and hydrocarbon repellent.
The characteristics of surfactants and their applicability for a wide variety of applications are described by Rosen in Surfactants and Interfacial Phenomena, 2nd Edition (John Wiley and Sons, N.Y.), incorporated herein by reference. In general, the desired chemical structures of the hydrophilic and hydrophobic portions of the surfactant will vary with the nature of the solvent and the conditions of use. As discussed by Rosen, in a highly polar solvent such as water, the hydrophobic group can be, for example, a hydrocarbon, fluorocarbon or siloxane chain of proper length, whereas in a less polar solvent such as an alcohol, a very nonpolar moiety is required in the hydrophobic part of the surfactant. If a surface is to be made hydrophobic by the use of a surfactant, a cationic surfactant is usually preferred. If a surface is to be made hydrophilic, in general, then anionic surfactants should be considered. Nonionic surfactants adsorb onto surfaces with either the hydrophilic or hydrophobic group oriented toward the surface, depending on the nature of the surface.
It is important to understand that surfactant activity in a particular system is highly dependent on the nature of the two immiscible materials. The surfactant must have a chemical structure that is amphipatic in that solvent system. Methods to select and manipulate the surfactant for a given system are well known to those of skill in the art, and are described in a large number of textbooks, for example, Surfactants and Interfacial Phenomena.
Families of surfactants are also well known to those skilled in the art, and can be used with the polymers described herein. Common ionic surfactant families include sodium and potassium salts of straight chain fatty acids (soaps), sodium and potassium salts of coconut oil fatty acids, sodium and potassium salts of tall oil acids, amine salts, acylated polypeptides, linear alkylbenzene sulfonates, higher alkyl benzene sulfonates, aromatic sulfonates, petroleum sulfonates, paraffin sulfonates (secondary n-alkanesulfonates), olefin sulfonates, sulfosuccinate esters, alkylnaphthylsulfonates, isethioates, sulfuric acid ester salts, including sulfated linear primary alcohols, sulfated polyoxyethylenated straight chain alcohols, sulfated triglyceride oils, phosphoric and polyphosphoric acid esters, perfluorinated anionics, long chain amines and their salts, diamines and polyamines and their salts, quaternary ammonium salts, polyoxyethylenated long-chain amines, quaternized poyoxyethylenated long chain amines, and amine oxides.
Common nonionic surfactants include polyoxyethylenated alkylphenols, alkyl phenol ethoxylates (such as the polyoxyethylenated derivatives of nonylphenol, octyl phenol, and dodecylphenol), alcohol ethoxylates, polyethylenated polypropylene glycols, polyoxyethylenated polyoxypropylene glycol, polyoxyethylenated mercaptans, long chain carboxylic acid esters, glycerol and polyglycerol esters of natural fatty acids, propylene glycol, sorbitol, and polyoxyethylenated sorbitol esters, polyoxyethylene glycol esters and polyoxyethylenated fatty acids, alkanolamine condensates, alkanolamides, alkanolamine fatty acid condensates, tertiary acetylenic glycols, polyoxyethylenated silicones, N-alkylpyrrolidones, and alkylpolyglycosides.
Common zwitterionic surfactants include β-N-alkylaminopropionic acid, N-alkyl-β-iminodipropionic acids, imidazoleline carboxylates, N-alkylbetaines, amine oxides, sulfobetaines and sultaines.
Preferred surfactants include polyethylene glycols, phenol ethoxylates, ethoxylated alcohols, and phosphoric acid esters. These families of compounds are discussed in more detail below.
Ethylene glycol esters, ethylene glycols and polyethylene glycols can be used in the preparation of acrylic acid resins to be used as surfactants, emulsifiers, and lubricants (i.e., detergent builders).
Ethylene glycol can be in the form of a mono or diester, for example, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol (mono or di)-isopropyl ether, ethylene glycol (mono or di)-n-propyl ether, ethylene glycol (mono or di)-n-butyl ether, ethylene glycol (mono or di)-sec-butyl ether, and ethylene glycol (mono or di)-isobutyl ether. Also appropriate are the mono- and di- alkyl ethers of diethylene glycol.
Polyethylene glycols (referred to as "PEG") can be purchased from any of several commercial sources in molecular weights ranging from 100 to 6,000. Polypropylene glycols are also available from a number of sources.
Long chain alkyl phenol ethoxylates are known surfactants. These compounds can be added to the acrylic acid polymerization reaction to form a polymer that can be used as an exhaustible surfactant or emulsifier, exhaustible acid dye leveler, liquid laundry detergent, or liquid detergent additive. A commonly used phenol ethoxylate is nonylphenol ethoxylate, which is commercially available having a wide range of ethoxylation, including 4 mole, 6 mole, 9 mole, 15 mole, and 30 mole. All of these are suitable for incorporation into the acrylic acid resins. Various types of ethoxylated octylphenol and dodecylphenol are also commercially available. Combinations of long chain alkyl phenol ethoxylates are also suitable.
The greater the extent of ethoxylation of the long chain phenol ethoxylate, the higher its water solubility. Therefore, phenol ethoxylates with high ethoxylation values should be used in the acrylic acid polymerization reaction when a product is desired that has high wettability or aqueous solubility. In contrast, a phenol ethoxylate with a low ethoxylation value should be used to prepare a product with low solubility and high exhaustibility. For example, a nonyl phenol with a low extent of ethoxylation is suitable for inclusion in a product used as a defoamer, in which low solubility is an important factor.
Ethoxylated alcohols can be included in the acrylic acid polymerization process to provide a product that is useful as a surfactant, emulsifier, low foam detergent or wetting agent. Preferred compounds are ethoxylated decyl alcohol and tridecyl alcohol. These compounds are commercially available with ethoxylation values of approximately 4 mole, 6 mole, 8.5 mole, 9 mole, 12 mole, 15 mole, and 30 mole. Decyl alcohols are preferred for use as low temperature surfactants and tridecyl alcohols are preferred for use as high temperature surfactants.
Phosphoric acid and its salts, as well as phosphoric acid esters and their salts, can be included in the acrylic acid polymerization reaction to provide a product that is a superior chelating agent, flocculant, flame retardant, metal cleaner, antistatic agent, emulsifying agent (for example, in pesticides, herbicides, and in liquid fertilizer), dry cleaning solution, or hydrotrope. Preferred phosphoric acid esters are phosphated polyoxyethylenated alcohols (acid or salt), phosphated polyoxyethylenated phenols (acid or salt), and sodium alkyl phosphates. A preferred phosphoric acid ester is 2-ethylhexyl phosphoric acid. Any cation can be used to form the salt, including sodium, potassium, ammonium, substituted ammonium, and quaternary amine. Other suitable phosphoric acid esters include phosphated decyl alcohol with ethoxylation values of 4 and 6 mole for use as flame retardants and antistatic agents.
Ultra-violet absorbing agents can be included in the acrylic acid polymerization reaction to provide a product that provides a protective coating against ultra-violet radiation. Any aromatic ultra-violet absorbing molecule is suitable. Examples include 2,4-dihydroxy-benzophenone (Uvinol™ -400, BASF Corporation), 2hydroxy-4-methoxy-benzophenone (Uvinol™ M-40, BASF Corporation), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Uvinol™ D-49, BASF Corporation), Uvinol™ 490 (BASF Corporation, mixture of Uvinol™ D-49 and other tetrasubstituted benzophenones), 2,2',4,4'-tetrahydroxybenzophenone (Uvinol™ D-50), 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid (Uvinol™ MS-40), disodium 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone (Uvinol™ DS-49), ethyl-2-cyano-3,3-diphenylacrylate (Uvinol™ N-35), 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (Uvinol™ N-539), and 4-methoxy-5-hydroxy-benzophenone-3-sulfonic acid.
Fluorochemicals are also useful with the polymers described herein. A number of compositions are commercially available and known to those skilled in the art. Fluorochemical coatings have been developed that prevent wetting of the carpet surface, by minimizing chemical contact between of the carpet surface, and substances that can stain the carpet, making the substance easier to remove. Typical fluorochemicals contain a perfluoroalkyl radical having three to twenty carbons, and are produced by condensation of a fluorinated alcohol or fluorinated primary amine with a suitable anhydride or isocyanate, for example, N-ethyl perfluorooctyl-sulfonamidoethanol and toluene diisocyanate reacted in a 2:1 molar ratio.
Examples of commercially available fluorochemical coatings include Scotchgard™ 358 and 351 (Minnesota Mining & Mfg. Co.) and Zepel™ (E. I. DuPont Nemours & Co.). Wang, et al. U.S. Pat. No. 4,518,649 discloses releasing finishes for textiles. A number of water and soil repellents for fabrics are reviewed by Sodano in Chemical Technology Review No. 134, Noyes Data Corporation, Park Ridge, N.J. 1979. European patent application by Allied Corporation describes an oil and soil repellent finish based on a mixture of a quaternary ammonium salt containing trialkyl dodecyl ammonium anion and cocotrialkyl ammonium anion and a fluorochemical consisting of polycarboxybenzene esterified with fluorinated alcohols. British patent numbers 1,379,926 and 1,405,268 to Ciba-Geigy report several fluorocarbons useful for treatment of fibers to increase oil and water resistance.
The reaction mixture typically contains at least H2 C═CHCO2 X, H2 C═CRCO2 X, or HRC═CHCO2 X, an aromatic sulfonic acid, a free radical initiating agent, and water. A textile processing or cleansing chemical as defined above should be added as appropriate to produce a polymeric composition with the desired characteristics. Any ratio of components is suitable that provides a product with the desired properties. One of ordinary skill in the art can easily manipulate the ratio of components to determine the best mix for a given application without undue experimentation.
Table 1 provides typical range percentages by weight for the reaction components. It should be understood that these ranges are not limitations, but exemplary, and superior products for certain applications can be formulated using the components described herein at concentrations other than in these ranges.
TABLE 1______________________________________Ranges of Percent Composition for Polymeric Mixtures ofAcrylic Acids and Aromatic Sulfonic Acids.Component Percent Composition by weight______________________________________acrylic acid 15-22free radical initiating agent 3-5water remaining percentagearomatic sulfonic acid or its salt 5-40textile processing chemical 0-40ethylene glycol esterethylene glycolpolyethylene glycolethoxylated phenolethoxylated alcoholphosphoric acid/esterUV absorbing agentsfluorochemicals______________________________________
In general, as the ratio of sulfonated aromatic compound increases, the molecular weight of the resulting polymer decreases, since the sulfonated aromatic compound acts as a chain terminating reagent for the acrylic acid polymerization. Polymers of lower molecular weight are desirable for exhaustible textile treatments because they tend to penetrate the shank of the polyamide fiber more easily than high molecular weight polymers. Polymers of higher molecular weight give good exhaustion and high substrate surface concentration.
Any known free radical initiating agent can be used to initiate the acrylic acid polymerization reaction, including sodium persulfate, potassium persulfate, ammonium persulfate, benzoyl peroxide, hydrogen peroxide, sodium peroxide, acetyl peroxide, lauryl peroxide, azobisisobutyronitrile, t-butyl peracetate, cumyl peroxide, t-butyl peroxide, and t-butyl hydroperoxide.
The appropriate weight percent of free radical agent to be used in the polymerization reaction will be a function of the molecular weight of the initiator. In general, the amount of initiator needed for polymerization increases as the percent of monomer in the reaction solution increases. However, in a concentrated reaction solution, the need to use a substantial amount of initiator must be balanced against the tendency of high quantities of initiator to actually decrease molecular weight and viscosity. Typically, the weight of the initiator used is approximately 15-30% that of the weight of the monomer, but the optimal amount can be determined in a given reaction by routine experimentation.
In a preferred embodiment, all reaction components are mixed and heated to a temperature ranging from approximately 50� C. to 100� C., depending on the temperature required for free radical generation of the initiator. The initiation of polymerization is sufficiently exothermic to raise the temperature of solution to between 100� and 115� C. The heat of reaction is controlled by reflux. The reaction temperature is allowed to stabilize, and then maintained at 100� C. for at least 30 minutes. Preferably, polymerization is allowed to proceed until one percent or less monomer is left in the reaction solution. The thickness of the reaction mixture, or tendency to gel, can be adjusted by increasing the ratio of sulfonated aromatic compound in the reaction mixture.
Once the reaction is complete, the reacted material is diluted to the desired solids concentration and viscosity, based on cost of product, effective concentration, and ease of handling. A wide variety of viscosity adjusting reagents can be used, including water and sulfonated aromatic acid or salt solutions. Preferred viscosity adjusting reagents include water, and the sodium, potassium, and ammonium salts of xylene sulfonate, cumene sulfonate, toluene sulfonate, and dodecyldiphenyl disulfonate. The resulting polymeric solution is acidic. If desired, the pH of the solution can be adjusted with a base such as ammonium, sodium, or potassium hydroxide. Acrylic acid monomer can also be added to the product mixture to increase the aqueous solubility and reduce the viscosity.
The reaction can be performed in one batch or by dose feed. In a dose feed process, the reaction is started by adding a percentage of the starting material to the reactor, and heating to initiate reaction. After the reaction creates an exotherm, additional reactants are added. The dose feed process can be used to control the vigorous nature of the reaction. As an example, one-third to one-half of the starting materials is added to the reactor. After the solution boils, one-third of the remaining material is added. The final two-thirds of the remaining material is added in at a rate so as not to reduce the reaction temperature below the initiation temperature.
The following examples provide representative formulations for a wide variety of textile applications. The ratios of reactants in these formulations can be modified as necessary by one skilled in the art to optimize a product for a specific use. Other components can also be added as required without altering the scope of the polymeric composition described herein. These formulations are merely illustrative of the types of products that can be prepared by using the method described herein, and are not intended to limit the scope of the invention. All percentages are by weight unless otherwise specified.
A superior tanning agent for leather was prepared by blending and reacting, in order:
______________________________________Water 38.0%Sodium Xylene Sulfonate 30.0%Xylene Sulfonic Acid 10.0%Ammonium Persulfate 4.0%Methacrylic Acid 18.0% 100.0%______________________________________
The product mixture had an active solids content of approximately 39%. The product was diluted to approximately 20% active solids before use with a mixture of water and sodium xylene sulfonate.
An exhaustible surfactant was prepared by blending and reacting:
______________________________________Methacrylic acid 15.0%Sodium cumene sulfonate 30.0%Ammonium persulfate 5.0%Nonyl phenol 20.0%ethoxylate (9 mole)Water 30.0% 100.0%______________________________________
The product had an active solids content of approximately 51%. It was diluted to a 45% active solids content with sodium cumene sulfonate and water.
An exhaustible acid was prepared by blending and reacting:
______________________________________Methacrylic Acid Monomer 22.0%Xylene sulfonic acid 33.0%Ammonium persulfate 3.0%water 62.0% 100.0%______________________________________
The product had an active solids content of approximately 55%. It was diluted before use to a 35.5% active solids content with water and sulfamic acid.
An alternative formulation for an exhaustible acid is:
______________________________________Methacrylic Acid Monomer 16.0%Xylene sulfonic acid 20.0%Ammonium persulfate 4.0%Water 60.0% 100.0%______________________________________
The reaction was performed as described in Example 3. The reacted product was diluted with 2:1 water to xylene sulfonic acid.
An alternative formulation for an exhaustible acid is:
______________________________________Methacrylic Acid Monomer 28.0%Xylene sulfonic acid 30.0%Ammonium persulfate 5.0%Water 37.0% 100.0%______________________________________
The reaction was performed as described in Example 3. 500 ml of product solution was diluted to 748 ml by the addition of 200 ml of water and 30 grams of powdered sulfamic acid. To this was added 18 ml of dodecylbenzenesulfonic acid to form the final product.
An exhaustible shampoo that does not diminish the soil and stain characteristics of nylon carpets was prepared by reacting:
______________________________________Methacrylic acid 12.5%Acrylic acid 12.5%Xylene sulfonic acid 8.0%Sodium xylene sulfonate 17.5%Ammonium persulfate 3.0%Isopropyl alcohol 4.5%Water 21.5%Sodium dodecyl benzene 20.5%sulfonate 100.0%Dilution & NeutralizationReaction Product 62.5%Sodium xylene sulfonate 13.5%Water 17.0%NaOH 50% 7.0% 100.0%______________________________________
Final product 38% solids' and pH 5.
A powder or liquid laundry detergent or builder was prepared by reacting as mixture of:
______________________________________Acrylic Acid 18%Xylene sulfonic acid 5%Ammonium Persulfate 4%Sodium cumene sulfonate 23%Water 30%Nonylphenol (9 mole ethoxylate) 20% 100%______________________________________
The product is spray dried to be used as a powder or used as is in the liquid state as a liquid laundry product. The product functions as both a detergent and a detergent builder. It can also serve the function of surfactant, hydrotrope, soil absorber, or redeposition agent.
A hard plastic material is prepared by mixing and heating to 80� C. all of the components listed in Formulation A or B below except methacrylic acid, and then adding the methacrylic acid to the heated components. After the reaction is completed and the water is driven off, the product can be hot pressed or molded to a desired shape. Methyl methacrylate, acrylic acid, or another acrylic acid derivative described in Section II, can be substituted for methacrylic acid.
______________________________________Formulation A:Ammonium Persulfate 3%Methacrylic acid 18%Xylene Sulfonic Acid 5%Sodium Xylene Sulfonate 10%Phosphoric Acid (75%) 20%Water 44% 100%Formulation B:Ammonium Persulfate 3%Methacrylic acid 18%Xylene Sulfonic Acid 5%Sodium Xylene Sulfonate 10%Sulfamic Acid (powder) 20%Water 44% 100%______________________________________
An acrylic acid resin that is useful as an exhaustible surfactant or exhaustible acid dye leveler was prepared by reacting:
______________________________________Water 30%Sodium cumenesulfonate (45%) 30%Nonyl phenol (9M) 20%Methacrylic acid 15%Ammonium Persulfate 5% 100%______________________________________
The product made from this formulation had a solids content of approximately 51%. The solids content was diluted to approximately 45% with water. This product can be used instead of standard wetting agents and dye levelers in textile applications to reduce the B.O.D. and C.O.D. of the wastewater. It can also be used as a surfactant for liquid laundry detergent and dishwashing detergents, as well as an emulsifying agent for yarn lubricants. The product forms a stable emulsion when poured in water at a pH from pH 4.3 to pH 12. This formulation can also be used as an industrial wetting agent for synthetic and natrual fibers, particularly cotton.
An acid dye leveler was prepared by reacting:
______________________________________Sodium cumene sulfonate (40%) 60%Isopropyl alcohol 7%Dodecyl diphenyloxide disulfonate 10%Methacrylic acid 15%Xylene sulfonic acid 4%Ammonium persulfate 4% 100%______________________________________
500 milliters of the reaction mixture was diluted to 640 ml with water to provide the final product.
A yarn lubricant was prepared by reacting
______________________________________Methacrylic Acid 15%Hydrogen peroxide (35%) 6%Water 54%Polyethylene glycol 400 20%Xylene sulfonic acid 5% 100%______________________________________
A copolymerizing solution is prepared using the stain resistant composition NB-31-150, the reaction product of methacrylic acid and the formaldehyde condensation polymer of sodium naphthalene sulfonate and 4,4'-dihydroxydiphenylsulfone. Glacial methacylic acid (99% in water, 22.3 grams), water (48.7 grams), formaldehyde condensation polymer of sodium naphthalene sulfonate and 4,4'-dihydroxydiphenylsulfone (Erinal™ NW-LQ; 37-40% solution; 12.3 grams), potassium persulfate (5.7 grams), and sodium xylene sulfonate (40% solution; 11.0 grams) were placed in a two liter round bottom flask equipped with a mechanical stirrer, reflux condenser, thermometer, and water bath. The brownish solution was heated to 65� C. with stirring. A large exothermic reaction rapidly raised the temperature of the reaction mixture to 100� C. The temperature was maintained at 90-100� C. for 30 minutes. The resulting viscous, yellow/red solution was diluted with water to give a final total solids concentration of 32 weight percent.
The reaction product (20%) was reacted with:
______________________________________Methyl Methacrylate monomers 15%Hydrogen peroxide (35%) 6%Water 54%Xylene sulfonic acid 5%______________________________________
The vessel was charged with water, xylene sulfonic acid, the 32% composition, the methyl methacrylate monomers, heat to 50� C. and add hydrogen peroxide. The temperature was raised to 100-105� C. and run 30 minutes. Water was added to gain desired solids level.
The product is useful as a textile coating, resin curring agent, and paint additive.
A defoamer is prepared by reacting:
______________________________________Methacryclic or acrylic acid 12%Water 43%Benzoyl peroxide 5%Nonyl phenol 1-5 mole (EO) 40% 100%______________________________________
A chelating agent is prepared by reacting:
______________________________________Acrylic acid monomer 15%nitryl triacetic acid 15%sodium phosphate 15%Ammonium persulfate 3%Water 52% 100%______________________________________
Product can be partially neutralized with diethylamine or triethylamine to pH 5, or more amine can be added to get to pH 8.
A flocculant is prepared by reacting:
______________________________________Acrylic acid monomer 18%Xylene sulfonic acid 5%Ammonium persulfate 3%Water 74% 100%______________________________________
Product can be added to a waste stream in the presence of aluminum sulfate to form a bond with positively charged ions to form a precipitant mass for sludge press removal.
An anti-static agent is prepared by reacting:
______________________________________Methacrylic Acid 15%Sodium xylene sulfonate 20%Xylene sulfonic acid 5%Phosphated 2-ethylhexanol 20%Ammonium persulfate 3%Water 37% 100%______________________________________
The product can be used as an after treatment agent for textile fabrics and nylon carpets. The product can also be used as a component in nylon yarn manufacturing as a lubricant additive for static control.
A flame retardant is prepared by reacting:
______________________________________Methacrylic Acid 18%Sodium xylene sulfonate 25%Ammonium persulfate 4%Ammonium sulfamate 15%Naphthalene sulfonic acid 10%condensateWater 28% 100%______________________________________
The product can be used on nylon and cotton, in exhaust after treat cycles, and spray dried on all other fabrics in small quantities for flame retardation.
A metal cleaner is prepared by reacting:
______________________________________Acrylic acid monomer 15%Xylene sulfonic acid 5%Sodium xylene sulfonate 15%Ethylene glycol 2%Benzene sulfonic acid 10%Sodium phosphate 5%Water 48% 100%______________________________________
A metal coating is prepared by reacting:
______________________________________Methyl methacrylate 5%Methacrylic acid monomer 10%Acrylic acid monomer 5%Xylene sulfonic acid 5%Sodium xylene sulfonate 10%Fluoropolymer (Zonyl ™ 5180, Du Pont) 10%Water 55% 100%______________________________________
and diluting the reaction product to 60% by blending with 20% isopropyl alcohol and 20% ammonium thiocyanate (50% solution). Spray on metal for quick drying protective coating.
The processes described in Examples 11 through 17 used the reaction process, adding the reaction products as follows: water, individual components, monomer acid, initiator.
Although all examples were performed in a batch process continuous methods can also be used. Surfactants can also be incorporated for use in the emulsion processes.
Modifications and variations of the present invention, new acrylic acid derivatives and their method of use, will be obvious to those skilled in the art from the foregoing detailed description of the invention. Such modifications and variations are intended to come within the scope of the appended claims.
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Dear all, I bring my humble question:
What is the difference between these two paints? I can see that raw umber is 'browner' than raw sienna, raw sienna a touch warmer, but if one had a limited palette or limited space, which would you choose and why? (Ochre only adds to the confusion....)
P.S., I primarily use watercolors, so oil paints/acrylics may have different considerations.
Thank You!
The major difference is that Raw Sienna is transparent while Raw Umber is opaque. So a glazing effect can be achieved with raw sienna which is not so easy with raw umber.
I alo find raw sienna to be significantly warmer.
I am an oil painter so please take that into consideration, however as far as I know the transparency, or lack of, is the same for these colors both mediums.
I hope this helps.
Christopher M. Grimes - join me on Facebook
Hmm, It depends on what other colors are in your limited palette. It also depends on what your painting. Neither are my favorite and I usually have neither.
Thank you - That's exactly the type of answer I was looking for!! Very helpful On another note, my books show raw umber to be significantly darker than I find it in real life, so I got confused.
Hello mariettetb
Although Helen Van Wyk was an oil painter, her books offer information, I think, that can be helpful to most painters. What she had to say about Raw Umber in her book "Helen Van Wyk's Favorite Color Recipes" is: "A dark dull color that can be classified as a yellow. Usually thought of as brown. Mistakenly used as a shadowing agent, and becomes the villain of many muddy pictures. Should only be used to represent things that are described as brown. Extremely transparent. Has a greenish hue. In admixture, not as strong as the more substantial Burnt Umber."
Raw Sienna: " A darker, more orange version of Yellow Ocher. Very transparent. Can omit from a very basic palette since it can be somewhat matched by mixing Cadmium Yellow Light and Burnt Umber. To get the full volume and beauty of the colours in nature Raw Sienna can be a great friend."
Working with Acrylics I find burnt umber a necessary colour (works nicely with blue for a black colour), and I also like raw sienna a lot. I also have Burnt Sienna which I use a lot, and find her suggestion for mixing the cadmium yellow light and burnt sienna to get a colour similar to raw sienna quite interesting. I do have Raw Umber, and have used it sparingly.
On Golden's site it made a brief mention of Raw Umber as having a granular effect in watercolour.
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Larry Raymond, the Coordinator of Copyright Permission Services, works closely with Dwayne K. Buttler, the Evelyn J. Schneider Endowed Chair of Scholarly Communication and Professor in University Libraries, to identify solutions to a variety of shared copyright concerns and to develop educational opportunities for the UofL community to better understand copyright and how it relates to teaching and learning. Making appropriate uses of copyrighted materials is the responsibility of all in the UofL community, and making reasonable and good faith decisions is an important foundation for supporting those uses and making them appropriate.
For more information on about securing permission to use copyrighted works in teaching and learning, you can contact Larry Raymond at 852-5099 or at email@example.com . You may also wish to consult the University's Copyright Guidelines and Resources page.
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2014-2015 Undergraduate Catalog
College of Performing and Visual Arts
College of Performing and Visual Arts
Contact: Lisa Stocker, Administrative Assistant
Location: Guggenheim 103
Telephone: 970.351.2143
Fax: 970.351.2299
Website: www.arts.unco.edu/artanddesign
Advising Information:
Students must consult with their assigned major advisor each semester prior to registering.
Please note that in Art & Design, all classes are closed until a student is released by the professor to register for each Art course. That is accomplished by meeting with their major advisor on or by Advising Day (scheduled each semester).
Contact the Art office for more information.
The program consists of three parts:
Program Description:
The art history emphasis is a program preparing the student for an academic career in Art History, and provides the student with the basic skills needed for graduate level coursework. This emphasis requires the student to be competent in the visual arts, including an understanding of artistic techniques, styles, historical context and various research methodologies. The student will also demonstrate competency of an appropriate foreign language for continual research and scholarly development.
Program Admission Requirements:
Admission. Students planning to major or minor in Art & Design must apply and be accepted into the School of Art & Design. Interested students need to submit an application and an Entry Portfolio, consisting of artwork and essay. A written essay alone will be considered if no artwork is available. Application form and instructions are available in the School of Art & Design office, or on their webpage, www.arts.unco.edu/artanddesign. The deadline for applications is March 1 to attend the Fall Semester, and October 31 to attend the Spring Semester. Late applications may be accepted depending on availability of space in the program.
Declaring an Art & Design major or minor without applying does not assure admission to the program.
Students needing a resource in creating a portfolio may consider taking Art 121, Introduction to Art & Design Studies. The class serves as an exploration of Art studies and assists students in developing a portfolio.
Program Requirements:
Degree Requirements — 120 Credits
Take all of the following courses:
First complete the following five Freshman Foundation Courses:
ART 181 and ART 182: (LAC area 3.a.)
Complete the following course:
Choose one of the following Art Studio courses:
And choose three Art Studio courses (9 hours) at the 200-level or above.
Choose six of the following courses:
Choose 3 credits from the following courses:
1 - 5
1 - 4
ART 422: (Research, internship, or other academic experience)
Complete additional credits to achieve the minimum credits needed for this degree at UNC; for this degree, that will typically be 23 credits.
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OHP: Bartlesville man dead following Osage County crash
BARNSDALL, Okla. - The Oklahoma Highway Patrol is investigating the cause of a deadly accident in Osage County that left a Bartlesville man dead.
31-year-old Donald Lee Hogue was pronounced dead at the scene after he was ejected from his vehicle and it rolled on top of him, crushing him.
The collision happened shortly after 10 p.m. Monday on State Highway 123 just north and east of the Barnsdall city limits.
According to the trooper that worked the scene, Hogue was driving northbound in a 1996 Ford Explorer when his vehicle swerved left then right, departed the roadway to the right and struck an embankment, causing the car to roll twice before coming to rest on its wheels.
Hogue was was transported to Stumpff Funeral Home in Bartlesville.
According to the Oklahoma Highway Patrol, Hogue was not wearing his seatbelt at the time of the accident.


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Shows filmmakers and audio engineers how to import, edit, mix, and export the dialogue, sound effects, and music for a short film and provide the best audio impact for the video's story.
Takes an in-depth look at the new and enhanced features in Audition CS6.
Demonstrates all of the major features of Audition and prepares sound editors to start enhancing and correcting audio—whether it's music, dialogue, or other sound effects.
"As a teacher, I respect the way that your tutorials are hands-on and interactive. They are quick and to-the-point, and the teachers you have chosen are patient and concise." —Joshua M.
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We are looking for software reviewers to write for us.
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GiliSoft File Lock is designed for protecting your sensitive files,folder and drives on your local computer.In factly, it protects but does not encrypt the protected files and folders, so it will never have the chance to destroy your data and nobody can access or destroy your private data without password.
1 Hide File/Folder/Disk : You can hide your private files folders and drives to make them completely invisible to users and programs.
2 Lock File/Folder/Disk : The locked files/folders/drives are protected from accessing, users can not open, read, modify, move, delete, copy, rename the protected files/folders. Files and sub-folders in a locked folder are also protected.
3 Write-Protect File/Folder/Disk : The protected files/folders/drives are protected from editing, users can not modify, delete, rename the protected files/folders. Files and sub-folders in a locked folder are also protected.
4 Password Protected:There's no other way to run or unstall it if you have not the password .
5 Integration with Windows Shell.
Keywords: Folder Lock, File Lock, Password Protect, Disk Lock, Hide File, Hide Folder, Hide Drive, file encryption, protect file folder drive
Recent Changes: Not Established
Install Support: Install and Uninstall
Supported Languages: English
Additional Requirements: Intel Pentium II 350MHz or above, or any Athlon
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text: Brazil Brazil Amy Silverstein on Nov 19, 2012 @ 10:56 AMNov 19, 2012 @ 10:56 AM PublishedRio Gay Pride Parade brings over one million Two transvestites pose during the gay pride parade at Copacabana beach in Rio de Janeiro, Brazil on November 18, 2012.Brazil's gay rights Rainbow Group said that over one million people attended Rio de Janeiro's Gay Pride Parade on Sunday, BBC News reported. The parade was a party but also aimed to highlight homophobia that plagues Brazilian society."The Lesbian-Gay-Bisexual-Transgender community spends most of the year in Brazil hiding, deprived of many of their rights," activist Julio Moreira told Jornal do Brasil. "We need to discuss this issue in the schools and in the National Congress."More from GlobalPost: When the BRICs CrumbleAmid the activism was also a massive street party, the AFP reported, with techno music, wigs and carnival costumes.Fifteen floats blaring music lined the beach, Gay Star News reported. Despite Brazil's reputation as a liberal place, the Roman Catholic country has seen an explosion of evangelical Christian group membership in the past decades, the AFP said.