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Mary Kay Inc., one of the largest direct sellers of skin care and color cosmetics, achieved another year of record results in 2007 with $2.4 billion in wholesale sales. Mary Kay® products are sold in more than 35 markets worldwide, and the company's globa ... more
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Greensburg Daily News
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Sharon Kay Alverson of Greensburg has earned the use of the exclusive Mary Kay pink cadillac, the most coveted incentive awarded by the company and one of the most recognized brand symbols in the world.The new Cadillac comes in pearlized pink-a color unique to the Mary Kay Career Car Program.
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That's A Good Look: 8 Celebs Who Are Burning Up The Beach
I've been anticipating summer for months now, but this time, I think it actually is almost here. As the temperature inches ever closer to 80 degrees and sunny, I've been casting a critical eye on my beach style. This year, it's time for a reboot. I'm ready to purge the limp sundresses and faded bathing… More »

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2011-05-18 11:53:00
Jefferson County Sheriff Jim Adkins said there was a big celebration in madras when they heard the results of the Jail Bond Levy passing. An extensive of an operating levy for the jail means they won't be forced to start letting out inmates when the current levy expires next month. Adkins want to thank the citizens who supported the levy. "I hope I can live up to their expectations. I've really cut back on different expenditures. I'm running a really lean machine. I've cut back on food costs, electricity, we're trying to do that, watering, I've laid off seven and a half people. We're cutting everywhere so we can meet the expectations of the voters." The levy passed by about a 2 to 1 margin.
Jones Road, full road closure between Bennington Lane and NE Butler Market Road. May 18 – August 18, local access only.
Orion Drive closed in two locations for sewer work; at the intersection with Avery Lane and between Desert Woods Drive and King Hezekiah Way. From July 11 to Sept. 6. Detours marked.
Valhalla Sewer Relocation Project, Mt. Washington Drive at Shevlin Park Road intersection and North to Regency Street. Nighttime closures with detours marked during roundabout construction. Daytime closures for construction towards Regency Street. 7 p.m. – 7 a.m., July 11 – November.
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Marion News
Local news for Marion, IA continually updated from thousands of sources on the web.
Flourishing In The Face Of Growing Competition
Friday Jul 29 | Shooting Industry | Comment?
Mystery residue in Marion neighborhood now believed to be fungicide
Thursday Jul 28 | KWWL-TV Waterloo | Comment?
Powerful weed control solution sprayed on Marion neighborhood
Wednesday Jul 27 | KWWL-TV Waterloo | Comment?
Marion news is powered by NewsRank™
Updated: Tue Aug 23, 2016 05:45 pm
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1. The voting system was hacked.
The voting for this year's Miss Hong Kong was supposed to be American Idol-style, with viewers calling in and voting online for their favorite contestant. But the system crashed due to an exceptionally high volume of voters, which organizers say was orchestrated by hackers. The panel of judges, who were only supposed to choose the three finalists, were forced to pick a winner.
2. People think judges chose the wrong winner.
Judges chose Carat Cheung (pictured) as the winner, but the favorite in the Hong Kong blogosphere was Tracy Chu.
3. Contestants apparently got infections due to forced sharing of unsanitary makeup.
According to a Chinese report, during a recent press conference, two women in the pageant were suffering from cold sores, which they blamed on unsanitary makeup that they were required to share.
4. The emcee was rumored to be hooking up with one of the contestants.
Emcee Amigo Chui was allegedly romantically involved with contestant Christy Chan. They both denied it.
5. And of course, some pretty bold fashion offset all the drama.
- Brazilian police have charged swimmer Ryan Lochte with falsely reporting a crime. He'll be summoned to Rio to testify.
- Hillary Clinton came closer than ever to attacking Donald Trump's character and tied her opponent to the "alt-right" movement.
- The death toll from Italy's earthquake rose to 250 people amid efforts to dig out residents still trapped in rubble.


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Honeymoon Suitcase Christmas Ornament
Personalized Christmas Ornament
The first trip a couple takes together is a milestone in their marriage and this suitcase brings the tradition of the honeymoon to your tree when taking a vacation after the wedding was an adventure for the newlyweds. This personalized honeymoon ornament permanently says JUST MARRIED on the front with a pair of golden wedding bands and the back permanently says HONEY MOON. You will love the fine details of this Polish glass ornament that makes a great gift for the newlyweds or even a bridal shower gift!
Material: Polish Glass
Read what our customers say about our Personalized Wedding Ornaments and their shopping experience!Hover over testimonials to stop scrolling
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Huntington Park Guided Bike Tour Saturday March 29
Thursday, March 27, 2014 - 02:20 Updated 2 years ago From Press Release
The Greater Huntington Park and Recreation District will sponsor this casually paced ride which rolls through the scenic Fourpole Creek, crosses two bridges, and moves into the Harveytown neighborhood park.
Riders will meet at the Ritter Park fountain. The ride is free and open to all ages and abilities. For more info, email email@example.com.


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Headphone Amplifiers
Marantz HD- DAC1High Definition USB DAC / Headphone Amp
"Hello Fellow Headfiers, I own this DAC for atleast 7 months now and so I thought I would make a review cuz I'm planning to sell this :) (which I'll tell you why at the end of this review). I haven't wrote a review for a DAC/AMP so go easy on me. Lets get started with the usual stuff. Build - If you have owned Marantz products before then you will really appreciate how the..." --Gamergtx260
Monoprice 113194 25 Watt AB Power Amplifier Stereo Hybrid Tube Amp with Bluetooth
"Introduction: A few months ago, Monoprice released their multi-function amp for the budding audiophile looking for a classic tube sound. I say multi-functional because it includes Bluetooth! Standard RCA-in is great and all, but sometimes you just wanna connect it to your Spotify playlist running on your phone. You can plug in headphones or hook up speakers in the back as well, making it a..." --Midgetguy
SMSL SD-192 Pro WM8805 + ES9023 Optical Coaxial Mini DAC Coaxial Decoder Black
"The packaging is surprisingly nice for this price point. It looks nice, and offers adequate protection. Sparse documentation, only what looks like a QC card. Sounds clean, works as expected. I've tried lots of files in wasapi and asio mode. Most files play fine, exception being 88200hz files, so no 88.2 support. The device is about the size of a soft pack of filterless cigarettes. It's very..." --bigx5murf
Lyr 2 Headphone Amplifier
"The Schiit Audio Lyr 2 was my first desktop amp and its a fantastic sounding amp. This amp comes in a neo industrial brushed aluminum chassis. This design chooses function over flash. The front of this fantastic amp, has a large volume knob and a SE headphone jack. The volume knob works great, although, at night, in low light conditions, I have a hard time noticing the volume indicator,..." --reddog
Audioengine D3 24-bit Digital to Audio Converter & Headphone Amplifier (Silver)
"This is my first product made by Audioengine and you can color me impressed. It's the third USB stick-style amp/DAC I've used (others are Dragonfly v.1 and GO1000), and honestly I think I like it best. It's got power for days, a tiny footprint, and it's plug-and-play! As for the sound? Well, just read on... The Breakdown: Test Songs (all ALAC either..." --JoeDoe
Cypher Labs AlgoRhythm Trio Portable Vacuum Tube Headphone Amplifier
"Thank You's and Sorries A big thank David Maudlin for sending me the Cypher Labs AlgoRhythm Trio to me back in late May and I apologise that it's taken me 3 months to put something up about it. Introduction Cypher Labs as a company needs no introduction. It's been in the portable audio business being one of the first few companies to release an iOS approved DAC back in 2011 which..." --AnakChan
AUNE S16 USB DAC Headphone Amplifier HiFi DIY 32Bit / 384KHz DSD128
"Intro: I have been so fortunate as to participate in a tour with the aune s16 on the Danish sister site Hoved-fi.dk. I what to thank Claus from Hoved-Grej.dk for putting this unit up for a tour. Reviewer background: I am a farther of 3 at the age of 6, 4 and 1 and a half, I listen to music 5 to 7 hours during the day at work as an electrician, and when the time allows it during the evening..." --walbum4262
xDuoo XD-03 Portable Headphone amplifier 24Bit/96KHz USB DAC
"I feel as though the sectioned layout is best, so I will apply that here. I tested this using a pair of Beyetdynamic T90s. Introduction These can be purchased for $75 + $10 shipping from eBay, $85 from Penon Audio, or around $97 from Shenzenaudio via Amazon on their website. I personally chose Penon and they were good, the processing took a little bit of time..." --xskugga
Auvio Headphone Amplifier
"I stumbled across this little portable amp in radioshack while I was on vacation and while I was in the store I did my absolute best to hate it about right until I got it out of the box. When I pulled it out of the box I realized it was the exact same size as my Sansa Clip Zip which I had retrieved from the car along with my grado sr80i that I genuinely believe sound fine without..." --PatchMan
Yulong Audio DA8 II
"This review is the summary section of Yulong DA8II in-depth review here: http://www.head-fi.org/t/779702/yulong-da8ii-in-depth-review Please visit the above thread for more information. Many thanks to Yulong and Qubes Audio Singapore for the loan of Yulong DA8ii demo unit! I had the demo unit for more than a month for proper review and comparison with other..." --earfonia


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Capital Markets
Company Overview of Pharos Capital Partners II, L.P.
Company Overview
Pharos Capital Partners II, L.P. specializes in later stage, middle market, mature, and buyout investments. It is an SBIC fund. The fund prefers to invest in business services and healthcare, with opportunistic investments in other sectors. It typically invests in the United States. The fund seeks to invest in companies with enterprise values between $50 million and $500 million. It comprises of a side fund Pharos Capital Partners II - A, L.P.
8 Cadillac Drive
Suite 180
Brentwood, TN 37027
United States
Founded in 2005
Key Executives for Pharos Capital Partners II, L.P.
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Eli Young Band's Mike Eli Endures Worst Interview Ever [Watch]
If awkward videos make you uncomfortable, then this might not be for you. Unfortunately for Mike Eli of Eli Young Band, he couldn't escape this extremely uncomfortable radio interview.
If awkward videos make you uncomfortable, then this might not be for you. Unfortunately for Mike Eli of Eli Young Band, he couldn't escape this extremely uncomfortable radio interview.
Eli Young Band's "Saltwater Gospel" is all about finding inner-peace away from the pulpit. The group's first new single in a year is lighter than most of what they've released to date. Like rays from the sun, the song's message soaks in deep.
It couldn't have been any more beautiful outside as Eli Young Band took the stage for their set at WE Fest 2015. The sun was starting to set, and the Saturday night (Aug. 8) fans were certainly feeling good.
Headliners like the Band Perry, Tim McGraw and Keith Urban made 2015 Country Jam a summer festival to remember. And Sunday (June 21), the fourth day of the event, was no exception. Toby Keith arrived in Grand Junction, Colo. to blow fans away — and succeeded.
With "Turn It On," Eli Young Band reveal they were just hoping to write a fun love song for their live show. They overachieved. The uptempo Texas country-rocker may be Mike Eli's sharpest storytelling moment.
The 2015 Country Jam lineup got bigger and even more impressive.
Eli Young Band fans have a lot to look forward to in March.
It's getting closer, folks! The full 2015 Taste of Country Music Festival lineup is now available, and in addition to headliners Tim McGraw, Keith Urban and Toby Keith, 14 other acts have been revealed!
A handful of country's biggest stars will appear on the soon-to-be-released soundtrack for the upcoming Nicholas Sparks film, 'The Best of Me.'
Grammy-nominated country rockers Eli Young Band hit up 'The Late Show With David Letterman' on Tuesday night (July 22), bringing with them their new rising single 'Dust.'
Eli Young Band's 2013 plans included making new music in the studio -- and they did just that. They've been hard at work, and now, a release date, along with track listing, have been revealed for their next mainstream country album.
Touring artists like Eli Young Band know what it feels like to be away from home too often. But even with their jam-packed travel schedules, their time apart from family is nothing compared to the burden that our soldiers overseas face -- something they realize.


text: AdChoices Terms of Use Privacy Policy Hide TOP 10 Top 10 Dating Chivalry In Film © Warner Bros. Chivalry In Film What The 10 Greatest Gentlemen In Film Can Teach You About Chivalry Jaime Rojo January 10, 2014 Share Tweet 0 Shares Before the 20th century, the best examples of chivalry came from myth -- stories of knights and heroes told late at night around a camp fire or collected in books. These days, some of our finest examples of chivalry come from characters in our favorite movies and TV shows. While it seems like someone is always complaining about how modern pop culture is bad for our society, the truth is that there are scores of great role models out there. I've collected a list of some of films most notable gentlemen, including choice lines that embodies each character's gentlemanly prowess. Start With #10 TOP 10 9 8 7 6 5 4 3 2 1 Romance Chivalry Better Man film Movies Comments Share your opinion Your name More Like This Recommended Is The New Ghostbusters Actually Any Good? Here's Our Spoiler-Free Verdict Read More Career These Star Wars Quotes Will Help You Succeed In All Aspects Of Life -- Really Read More Top 10 Better Man The 10 Most Ridiculous Myths In The World, Debunked Read More Top 10 Dating Sorry, You're Not A Real Man Unless You Can Do These 10 Things Read More Top 10 Entertainment 10 Surprising Uses For Drones You Never Knew About Read More Top 10 Travel 10 Honeymoon Destinations That Will Win You Brownie Points For Life Read More Around the Web Special Features Sponsored Content How To Dress Like The World's Most Stylish Men Read More Grooming Guide The Best Razors Of 2016 Read More Guy Gear The Best Watches For Men Under $500 Read More Fitness Gear Finding The Right Gym Bag Read More Dating The Ultimate Guide To Hooking Up Online Read More Groming Guide 15 Best Beard Trimmers On The Market Read More


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Watch Featured Movies
John Carter: Transplanted to Mars, a Civil War vet discovers a lush planet inhabited by 12-foot tall barbarians. Finding himself a prisoner of these creatures, he escapes, only to encounter a princess who is in desperate need of a savior.
|IMDB: 6.6/10 Metascore: 51% RT: 51%
|March 09, 2012
|132 mins
|Action Adventure Fantasy
|Bryan Cranston Ciarán Hinds Daryl Sabara Dominic West James Purefoy Lynn Collins Mark Strong Polly Walker Samantha Morton Taylor Kitsch Thomas Haden Church Willem Dafoe
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John Carter Comments
|Posted by CountessCarnage 4 years, 5 months ago
Does anyone notice John Carter's outfit is pretty much a total rip off of He-Man?
|Posted by hik 4 years, 5 months ago
thats tooooooooooooooo gud ;)
|Posted by GeminiMadness 4 years, 5 months ago
It was pretty decent, but after the hour, I started to get bore with the concept of a heroic earthling hooking up with a Mars chick.
|Posted by edmanman 4 years, 5 months ago
This was a great movie I can't wait for a sequel...5/5
|Posted by jholl99 4 years, 5 months ago
Very enjoyable and exciting movie! Looking forward to a sequel.
|Posted by apm120 4 years, 5 months ago
out of sync
|Posted by cece16 4 years, 5 months ago
Wow i was taken on a roll with this movie, every part of it keeps you entertained with its awesome adventure this movie is BRILLIANT, just grab a snack sit back and enjoy 10/10
|Posted by martinpochhit 4 years, 5 months ago
this movie is awesome... it does give u hope about the whole sci-fi movies... its good. and eventhough it does look a bit (just a bit) like avatar it creates its own world ... a little bit long but worth watching it.. 8/10
|Posted by dairyman638 4 years, 5 months ago
good movie just what i expected it to be 8/10
|Posted by ExTaCy 4 years, 5 months ago
Thnxs for the comments i am glad i read it before watching the movie
|Posted by awesomejohn49 4 years, 5 months ago
are the links good?
|Posted by clearbluewatergal 4 years, 5 months ago
Saw it today in the theater - had to watch it again tonite * Loved it.
|Posted by thunderbolito 4 years, 5 months ago
excellent movie, well done a nice story along with a good projection of the character, 4/5
|Posted by varshanandamuri 4 years, 5 months ago
Waited For long time happy to see in here ASAP..
|Posted by mahdinajem 4 years, 5 months ago
good movie stupid ending
|Posted by Ink_spot 4 years, 5 months ago
Put the old upload back up, this one is worse than the (cam) links. I feel like i'm wearing beer goggles.
|Posted by Birddog6424 4 years, 5 months ago
Saw it in the theater in 3D. Thought it was awsome. The critics are whack. I give it five four-armed Tharks out of five. I would even toss in the really fast "dog".
|Posted by marvellegund 4 years, 5 months ago ( Edited 4 years, 5 months ago )
I saw this in theaters and Wow was it visually stunning. The Cgi is aweSome and the story is EPIC! U gotta watch this movie, it was s0 fun. 5/5 stars :D
|Posted by slackermcmahon 4 years, 5 months ago
saw it in 3d in the theatre the other night... was pretty sweet. def worth the watch
|Posted by user06 4 years, 5 months ago
i just saw it in theater it was one of the best movies i have ever seen 1000/10
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- //Home
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- //Mary J. Blige
After the success of her last album, No More Drama, Mary J. Blige has become more of a crossover urban pop star than an R&B icon. But like all pop musicians, the obligatory b-sides and singles result in a plethora of unnecessary dance remixes. The nine songs from this album, six of which are from the latest album, are not as horrid as some may suspect, but to be compared to the original versions would be a foolhardy idea. Although there are touches of Latin, samba and hip-hop beats on the record, there isn't a large musical thread running through the album.
Starting off with "No More Drama (Thunderpuss Remix)", the initial opening is promising, a percussion heavy Latin and African flavoring that should lead to a danceable and infectious track. But this is shelved two minutes in for a rather mundane and routine remix. The percussion and beats are a bit more predominant, but only in certain instances is there any hint of creativity. The bridge portion is beefed up considerable and some tension is created in Blige's being echoed into dance-house feeling. It has an aerobic-workout beat to it while hitting all of the notes of a Ricky Martin remix. The conclusion seems worthy of praise, but it fades for far too long.
Mary J. Blige
Dance for Me
US: 13 Aug 2002
UK: Available as import
The Spanish Fly remix of "Family Affair" has a nice groove in it, similar to a New Order or Depeche Mode '80s-era track. It evolves (devolves?) into a '70s-style disco floor beat as Blige begins to be heard. The funk of the original is replaced by a rather watered-down bass line and, as a result, loses some of the song's original assets. It picks up slightly when the chorus is added to the mix, but the sound is far too cliched to be credible. "Everything" has the team of Curtis & Moore remixing this song and they have far greater success than the previous tracks. Leaving most of the melody and song in tact for the introductory, the remix only accentuates some of the percussion and adds a slightly orchestral tone to it. It's also the first of the three tracks not from No More Drama.
"Rainy Dayz" begins with a horrid pace and structure, but thankfully moves into a much better vibe as some dense layering and keyboards gives it a decent tune. Remixed again by Thunderpuss, which is actually Barry Harris and Carl Cox, the track eclipsed seven minutes with a Latin rhythm that is lost in the middle section for some unknown reason. "He Think I Don't Know (hq2 Club Remix)" is the weakest of the remixes here, trying to be too ambient for its own good despite having a great vocal by Blige. Often her vocals are not the centerpiece of the song, instead relying on an ambient and Eno-esque feeling that doesn't work. One of the remixes that stays truer to the feel of most of Blige's material is "Never Been", which is a great track because it doesn't succumb to the typical dance beats, allowing it to evolve gradually. Done by Al B. Rich (Albert Castillo and Rich Pangilinan}, it's a sensual and very smooth interpretation of the original. The title track, which is dubbed the "G-Club Remix" has a Prince funk sense about it but also has a tinge of British house music to it. The bass line and horn section is far more pronounced here, much to the tune's benefit. A similar comparison to its sound is Dee-Lite's "Groove is in the Heart".
One of the warmer sounding songs here is "Give Me You (Extended Nino Radio Mix)", an upbeat song that stays away from the too often formulaic dance sound. It sounds more like a track that wouldn't seem out of place on an official album, especially given the tempo and backing vocals. Rounding out with "Let No Man Put Asunder", the track has all the feeling of a '70s Commodores track in its guitar and tone. The Pointer Sisters would be another fair comparison. On the whole the remixes are for the diehard fans of the dynamic singer, but there are some worth checking out.
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Classical CDs Weekly: Bach, Berlioz, Mythos Accordion Duo | Classical music reviews, news & interviews
Classical CDs Weekly: Bach, Berlioz, Mythos Accordion Duo
Choral spendour, both modestly proportioned and on a vast scale. Along with the best accordion duo on the planet
Bach: Cantatas for Ascension Day The Monteverdi Choir, English Baroque Soloists/John Eliot Gardiner (SDG)
The final volume in John Eliot Gardiner's mammoth Bach Cantata sequence is one of the very best. Gardiner's recent BBC2 documentary placed rightful emphasis on Bach's humanity, his normality. The devout will find plenty of weighty religiosity in the four cantatas assembled here, but they're also full of zest and vigour. Sample the opening chorus of Gott fähret auf mit Jauschen and smile at Bach's unerring ability to compose music which exactly reflects the texts he sets. "God is gone up with a shout", sing the Monteverdi Choir. The first minute is a little staid, before the music suddenly lurches forward into an exuberant, trumpet-led dance. Bass Dietrich Henschel's solos are magnificent, and Gardiner's sprightly direction allows him to soar. These cantatas do peculiar things with one's sense of time; each one packs an inordinate amount of musical and philosophical content into a compact space.
Marvel at the opening of Lobett Gott in seinen Reichen, a brassy eruption of joy complemented in sublime fashion by a closing chorus which carries an emotional weight wholly out of proportion to its four-minute duration. This disc is full of such small miracles. The performances are incredibly assured, with tight, rich choral singing and orchestral playing full of felicitous detail. Several wonderful oboe da caccia solos stand out, and all is contained within the not-too-resonant acoustic of St Giles' Cripplegate where it was recorded in May 2012. These cantatas were to have been recorded in Salisbury in 2000, but "noise issues" intervened - this disc was made possible by 2500 volunteer donors offering £20 each to fund the concerts.
Berlioz: Grande Messe des morts Barry Banks (tenor) London Symphony Choir, London Philharmonic Choir, London Symphony Orchestra/Sir Colin Davis (LSO Live)
This is superb stuff – a wondrous, fitting swansong from one of the most consistent artistic partnerships of the last 20 years. Berlioz's Grande Messe des morts has to be one of the least depressing of Requiem settings. This was a composer incapable of writing maudlin music, and this work teems with subversive quirkiness. Berlioz's instrumentation is suitably lavish at key moments, and the futuristic sonic eruptions in the Dies irae, with extra brass groups placed at the four corners of the performance space, sound suitably apocalyptic, the resonance of the St Paul's acoustic magnificently tamed by producer James Mallinson. This pair of CDs really needs to be enjoyed through a set of decent speakers; listening through crap headphones would be the sonic equivalent of sipping an expensive single malt from a polystyrene cup.
Sir Colin Davis's grip on the score is as sure as it ever was, the massed choral forces coordinated with unerring precision. He's always had an ear for Berlioz's quirky sense of orchestral colour. Soft cymbal strokes punctuate each phrase of the Sanctus with unearthly delicacy, and those spooky trombone and flute notes in the Hostias are bone-chilling. Tenor Barry Banks is excellent, his repeated cries in the ninth movement nicely set against the soft choral backing. This is an essential purchase – a first-rate reading of a religious work that combines both entertainment value and spiritual uplift.
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Hear, hear! Mythos Duo's
Hear, hear! Mythos Duo's Petrushka already on my provisional best of year list too. Nothing's going to displace it.
I've delightedly bought both
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HTC M8 is 2014's flagship handset, but first will be an updated HTC OnePocket-lint
HTC is planning to release an updated version of the HTC One later in 2013, according to a source familiar with the matter. The source also confirmed that, internally, the 2014 flagship HTC One model will go under the M8 codename.
Starting with the plans for 2014, our source reports that HTC is already in discussions regarding the HTC M8, although it is using different codenames for the device with external contacts - presumably to keep things under wraps and try to cut down on some of the leaks.
But with the M8 name out of the bag, we're hoping to see a repeat of the sort of rapturous chanting that greeted the HTC M7 before launch while gripped in CEO Peter Chou's hands. But at this stage, aside from confirmation of the codename, we have no details on the M8 specs or design.
However, we've also been tipped off that HTC is looking at releasing an updated HTC One. While there's currently a run of software updates going through, it looks like HTC might be making some more-serious internal hardware changes to update the current handset.
Again, we've no details on what specs might change, but with the HTC One launching with a Qualcomm Snapdragon 600 chipset, it's a possibility that it might be moving to Snapdragon 800, like the recently launched Sony Xperia Z Ultra.
In 2012, HTC updated its flagship HTC One X handset is a similar way, tweaking many aspects of Sense, as well as boosting the hardware with a new front-facing camera and chipset in the HTC One X+.
With both the updated HTC One and HTC M8 details being a little on the sketchy side, we're not getting too excited as we've very little to go on at the moment and our source did say that plans could be changed. But as always, we'll keep you posted if we hear any more from our little birds.
Earlier today, we brought you news that HTC was looking to merge the One and Butterfly lines, which will result in a plastic HTC One handset, again scheduled for 2014.
READ: HTC looking to merge One and Butterfly: Plastic HTC One incoming
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General Manager takes part in strategic energy discussions in the Republic of Kazakhstan
15 August 2016
Dr Andrew Minchener OBE
Kazakhstan is a country that is larger than the European Union in geographical terms but with a population of just 17.5 million people. Its major energy source is coal, which represents over 70% of its national mix and there are also oil and gas resources although these have only been partly assessed.
Earlier this year, I took part in an UNECE/UNDP mission to Kazakhstan to determine how best to tie in work on advanced coal technologies with the Kazakhstan Government's Green Bridge Initiative. In early August, I had the privilege to return to Kazakhstan to participate in a national strategic discussion forum on how best to utilize coal in an economically and environmentally improved way. The forum was chaired by the Prime Minister of Kazakhstan and was well attended by several ministers and various national experts on coal production and utilization, as well as the national press. I was the only person from outside of Kazakhstan and it was my role to provide a succinct global commentary on the role of coal and to highlight the various utilization routes and the various technology advances that have been made, especially in power generation.
Arising from the meeting, the Prime Minister has charged the Ministry of Energy to set up two strategic working groups, with one to look at short term issues associated with coal mining covering commercial issues (tariffs, trade deals, taxes) and technical issues (more effective extraction and subsequent transport). The other group will consider longer term issues as to how best to exploit the massive coal resource within the country, taking into account practical issues such as infrastructure needs, investment requirements, scope/need for international cooperation while also considering COP21 requirements. Both are expected to report later this year, the short term group during September and the longer term group during November. The Prime Minister encouraged both groups to introduce international experts into the discussions so I hope that I might be involved in the longer term considerations.
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General Manager takes part in strategic energy discussions in the Republic of Kazakhstan
Posted: 15 August 2016
Fine particulate emissions - legal limits and how to meet them
Posted: 29 July 2016
Alternative water supplies for coal-fired power plants
Posted: 4 July 2016
Successful conclusion of the 8th International Freiberg Conference in Cologne, Germany
Posted: 4 July 2016
VGB Workshop on Mercury Control, Berlin, Germany, 15-16 June 2017
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|Publication number
|Publication type
|Application number
|Publication date
|Jun 5, 1979
|Filing date
|Nov 29, 1977
|Priority date
|Nov 29, 1977
|Also published as
|Publication number
|Robert D. Lundberg, Henry S. Makowski, Jan Bock, Thomas Zawadski
|Original Assignee
|Exxon Research & Engineering Co.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (10), Referenced by (34), Classifications (13)
|External Links: USPTO, USPTO Assignment, Espacenet
1. Field of the Invention
This invention relates to a process for the uniform sulfonation of elastomeric or thermoplastic polymers. More particularly, this invention is directed to a process for the preparation of sulfonated elastomeric or thermoplastic polymers from hydrocarbon polymers characterized before sulfonation by the presence in said polymers of sulfonatable sites selected from the group consisting of: olefinic unsaturation, which may be located in the polymer backbone chain of carbon atoms or in acyclic or alicyclic hydrocarbon groups pendant to the polymer backbone chain and arylene groups pendant to the polymer backbone chain of carbon atoms in which said backbone chain may be saturated, contain olefinic unsaturation and have appended to it unsaturated acyclic and alicyclic groups.
Most particularly, this invention is directed to a process for the bulk sulfonation of said unsaturated and aromatic ring containing polymers and mixtures of hydrocarbon polymers including said polymers which include:
(A) MECHANICALLY MIXING, AT AN INTENSITY WHICH CAN VARY FROM SIMPLY KNEADING OR MASTICATION TO A HIGH DEGREE OF SHEAR, ONE OR MORE OF THE POLYMERS, OR A MIXTURE OF HYDROCARBON POLYMERS INCLUDING THE POLYMERS WITH A SULFONATION REAGENT INCLUDING SULFURIC ACID OR SULFUR TRIOXIDE, IN THE SUBSTANTIAL ABSENCE OF A SOLVENT FOR THE POLYMERS, AT A TEMPERATURE WHICH IS HIGHER THAN THE GLASS TRANSITION TEMPERATURE (Tg) of the polymers or mixture of polymers including the polymers in the case of amorphous polymers and is higher than the crystalline melt temperature (Tm) of the polymer or mixtures of polymers which are crystalline for a time sufficient to effect the desired degree of sulfonation; followed by
(C) NEUTRALIZATION WITH A BASIC MATERIAL SELECTED FROM THE GROUP CONSISTING OF AMMONIA, MONOALKYL AND POLYALKYLENE AMINES, THE COMPOUNDS IN WHICH THE CATION IS AN ELEMENT SELECTED FROM THE GROUP CONSISTING OF Groups I-A, I-B, II-A and II-B of the Periodic Table of Elements, aluminum, antimony and lead; and the anion is selected from the group consisting of oxides, hydroxides, C1 to C5 alkoxides, carbonates, and carboxylic acids.
Sulfonated polymers made by the process of this invention when neutralized with monovalent and polyvalent cations can yield ionically cross-linked products which are elastomeric at ambient temperatures but are thermoplastic at elevated temperatures permitting the products to be extruded, blow molded, injection molded, sheeted and vacuum formed. Sulfonated polymers such as polystyrene, for example, yield on neutralization with alkalies, lower amines and the like, products useful as thickening agents as rigid foams and plastic-like applications. Sulfonated elastomers having 10 mole percent or less, preferably 0.2 to 5.0 mole percent of sulfonic acid groups incorporated therein, when ionically cross-linked or neutralized, may be blended with other polymers which may be amorphous or crystalline to yield compositions having novel physical properties.
2. Prior Art
Sulfonated polymers, varying in utility from water-soluble resins to ionically cross-linked thermoplastic elastomers are old in the art but virtually all processes described in patents and the chemical literature utilize a solvent for the polymer or synthesize the polymer from monomers possessing a sulfonic acid group. Exceptions involve surface sulfonation of covalently cross-linked polymers lacking thermoplastic or elastomeric properties. Examples of these processes include:
U.S. Pat. No. 2,533,210 describes the preparation of a water-soluble sulfonated polystyrene by sulfonating a polymer of styrene dissolved in a chlorinated solvent with a complex of SO3 and bis (β-chloroethyl) ether.
U.S. Pat. No. 3,322,734 discloses the preparation of plastic polymers containing ionic cross-links by the copolymerization of styrene sulfonic acid with other monomers.
Vinyl sulfonic acid readily forms water-soluble homopolymers and copolymers with a variety of polar monomers but with the exception of styrene (Kern et al; Makromol. Chem. 32, 37 (1959)) attempts to copolymerize this monomer with hydrocarbon monomers, e.g. isobutylene and butadiene, failed. See Breslow et al, J. Poly. Sct. 27, 295 (1958).
The preparation of water-soluble sulfonic acids of natural rubber by reaction of a rubber cement with oleum or chlorosulfonic acid complexed with an ether or ester is described in German Pat. Nos. 550,243; 572,980; 582,565; and 585,623.
U.S. Pat. No. 3,218,301 discloses the sulfonation of a cross-linked vinyl polymer in the absence of solvent by passing gaseous SO3 upwardly through a reactor containing particles of the polymer having a macroreticular structure and a size in the micron range at rate sufficient to fluidize the reactor contents.
British Patent No. 1,100,712 describes the production of an antistatic surface treatment for polystyrene articles using a bath of an aliphatic hydrocarbon and chlorosulfonic acid.
Recently, U.S. Pat. Nos. 3,072,618; 3,642,728; and 3,836,511, which are herein incorporated by reference, have disclosed the preparation of novel sulfonic acid ionomers of unsaturated elastomers by reaction of the polymers in solution with a variety of organic complexes of sulfuric acid and sulfur trioxide.
In contrast to the solution, gaseous diffusion or surface sulfonation processes of the prior art we have now found that a wide variety of unsaturated and aromatic ring containing polymers may be sulfonated in the bulk, in the substantial absence of solvents for the polymers, by intimately mixing with the aid of a mechanical device to a degree which may result in shear of the polymer, a mixture of the polymer and a sulfonation reagent, for e.g. sulfuric acid, chlorosulfonic acid or sulfur trioxide or both, at a temperature in which the polymer is in a plastic state, defined herein as a temperature which is above the glass transition temperature (Tg) of the polymer or mixture of polymers; in the case of amorphous (non-crystalline) polymers will generally be at a temperature which is intermediate to the Tg and below 250� C. and in the case of polymers having a fair degree of crystallinity (greater than 10%) will be higher than the crystalline melting point and below 250� C. A satisfactory reaction temperature where most polymers will have the desired degree of plasticity preferably will generally be in the range between 1 and 2.5 times the glass transition temperature when both are measured in degrees Kelvin.
Preferred reagents for sulfonating the polymers comprise organic complexes and coordination compounds of sulfuric acid or sulfur trioxide with acid anhydrides and Lewis bases. The sulfonated polymers can be recovered as the free sulfonic acid or neutralized and ionically cross-linked with a variety of cations or counterions. Those polymers which have Tg's>250� C. or have crystalline melting points (Tc)>250� C. generally will not fall within the scope of this invention unless a nonvolatile additive present in minor amounts effectively reduces the Tg or Tc below 250� C. under the conditions of reaction.
Polymers which are conceptually suitable for the bulk sulfonation process of this invention include:
(a) homopolymers and copolymers of one or more conjugated diolefins such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, piperylene, cyclopentadiene, myrcene and ocimene. Enchainment, using a variety of catalysts for the polymerization, includes 1,4-cis; 1,4-trans; 1,2- and 3,4- types of additions and mixtures thereof. Non-limiting examples include: natural rubber; 1,4-cis poly(1,3-butadiene); 1,4-cis polyisoprene; and a random 1,4-cis and 1,4-trans polybutadiene having equal parts of each stereoisomer made by Ziegler catalysts as disclosed in Belgian Patent No. 543,292 (1955).
(b) homopolymers and copolymers of one or more alkenyl aromatic hydrocarbons and substituted derivatives thereof having the general formula Ar-C(R)═CH2 wherein Ar is a monovalent sulfonatable aromatic radical and R is hydrogen or methyl. Non-limiting examples include: solid, thermoplastic polymers and copolymers of styrene, α-methyl styrene, vinyl toluene, vinyl naphthalene, and vinyl ethylbenzene.
(c) copolymers of one or more C4 to C10 conjugated dienes with one or more C8 to C12 vinyl aromatic hydrocarbons. Non-limiting examples include: copolymers of 1,3-butadiene with styrene, e.g. GRS rubber and graft polymers of styrene or polybutadiene.
(d) random copolymers of one or more C8 to C12 vinyl aromatic hydrocarbons comprising about 40 to 60 wt. % of the vinyl aromatic with one or more C4 to C8 Type III monoolefins. Non-limiting examples include the copolymers of styrene and isobutylene.
(e) random elastomeric copolymers of one or more C4 to C10 conjugated dienes with one or more C4 to C8 Type III monoolefins. Non-limiting examples include the family of rubbers comprising copolymers of isobutylene with butadiene, isoprene and piperylene.
(f) random interpolymers of one or more Type I C2 to C18 monoolefins and one or more C6 to C12 non-conjugated acyclic or alicyclic diolefins. Non-limiting examples of commercially available polymers include: terpolymers of ethylene, propylene and 1,4-hexadiene; ethylene, propylene and dicyclopentadiene; and terpolymers of ethylene, propylene and 5-ethylidene-2-norbornene. Olefin types are in accordance with the Schmidt and Boord Classification, JACS 54, 751 (1932).
While the above polymers provide a broad range of materials which are conceptually suitable for this reaction, we have observed that those polymers containing substantial levels of unsaturation are prone to be cross-linked much more readily than those having reduced unsaturation levels. Therefore, it is preferred that those polymers having unsaturation ranges suitable to provide polymer sulfonic acid products with acid functionality in the range of about 10 meq up to about 200 meq be employed in this invention.
It is apparent, therefore, that this limitation excludes homopolymers having high unsaturation levels such as polybutadiene, polyisoprene, polypentamine, etc.
All of the above polymers are either thermoplastic or elastomeric and may range in their degree of crystallinity at ambient temperatures from amorphous solids to a crystallinity in excess of 90 percent. The polymers may be blended prior to, or after sulfonation and ionic cross-linking, with other polymers such as polyethylene, polypropylene, and copolymers of ethylene and propylene having a range of crystallinity.
In addition to sulfuric acid having a range of concentrations of from 95.5 percent to Oleum (104.5 percent) a variety of organic addition, coordination and complex compounds of sulfuric acid, chlorosulfonic acid and sulfur trioxide have been described in the chemical and patent literature which are suitable as sulfonating reagents in the process of this invention. Non-limiting examples of suitable reagents include: sulfuric acid having a strength in the range of about 95 wt. % to Oleum containing 20 wt. % of SO3 ; chlorosulfonic acid; stabilized liquid SO3 ; and 1:1 or 1:2 addition compounds of 100 percent sulfuric acid, chlorosulfonic acid and sulfur trioxide with: acyl compounds, e.g. carboxylic acids; acid anhydrides; perfluorinated acids; ethers; thioethers; alkyl esters; dialkylformamides; and a variety of Lewis bases. Non-limiting examples of specific compounds which form adducts or complexes with the said acids and sulfur trioxide are: diethylether, acetic acid, acetic anhydride, trifluoroacetic acid, benzoic anhydride, trifluoro acetic anhydride, benzoic acid, propionic acid, η-butyric acid, dioxane, tetrahydrofuran, 1,4-oxathiane, pyridine, dimethylaniline, N-ethylmorpholine, dimethylformamide, dimethyl sulfone, dimethyl sulfoxide, sulfolane, triethyl phosphate, hexamethyl phosphoramide and bis (βchloroethyl) ether. Preferred, is acetic anhydride and sulfuric acid.
A wide variety of machines are available in the plastics and rubber industry for mixing, with varying degrees of shear (from about 10 sec-1 to greater than about 1000 sec-1) resinous and elastomeric materials with solid or liquid reagents under controlled conditions of temperature, mechanical pressure and atmosphere. Prior to reaction with a sulfonation reagent, thermoplastic polymers such as polystyrene may be in bead form as a result of the method used for polymerization, or reduced to a small particle size by pelletizing, and elastomeric polymers granulated by passage through a mechanical chopper. The equipment used for mixing the polymer with the sulfonation reagent, whether done in a bath, semi-continuous, or fully continuous process must exert sufficient stress at the temperature of operation in order to ensure plasticity of the mixture. Non-limiting examples of suitable batch equipment are: the Banbury Mixer; similar mixers equipped with helical "sigma" blades rotating in opposite directions in a divided trough or saddle with either overlapping blades rotating at the same speed, or non-overlapping blades rotating at differential speeds; and the Bramley Beken Blade Mixer equipped with input shaft speeds of about 20 to 80 rpm. All of the above types of mixers may be fitted with jackets or cored blades through which heat-exchange media may be circulated for controlling the temperature. The Brabender Plasticorder having a mixing head made from stainless steel with a capacity of about 25 cc and auxiliary constant water or oil bath is particularly suitable for small-scale laboratory sulfonations.
Continuous or semi-continuous sulfonations are preferably performed in temperature controlled single or multiple screw extruders fabricated from hardened, corrosion resistant alloys. The screws may have variable geometry such as helix angle, root diameter, lead or pitch, interrupted flights and ratios of length to diameter (L/D). The barrel may be fitted with injection ports for addition of reagents and vent ports connected to a vacuum system downstream from the reaction zone for the removal of volatile by-products of the reaction. Screws comprising a reactor section having individually spaced apart, offset, discontinuous, helical flights of the type disclosed in U.S. Pat. No. 3,884,451, which is herein incorporated by reference, are particularly preferred.
A. Reagent Formulation and Addition
The method used for formulation and addition of the sulfonation reagent to the polymer may vary depending on the composition of the reagent, the rapidity with which the particular polymer sulfonates, and whether a batch or continuous process is used.
In a batch process, using for example "acetyl sulfate" which may be prepared by the addition of sulfur trioxide to acetic acid at a temperature below 0� C., or by the addition of 1.0 mole of 100 percent sulfuric acid to 1.0 mole of acetic anhydride, the entire amount of externally prepared reagent required to obtain the desired level of sulfonation of the polymer may be added to the polymer after the polymer has been mixed to the desired degree of plasticity in a single dump or the externally prepared reagent may be added to the plasticized polymer in increments at intervals.
Alternatively, the reagent may be prepared in situ by the serial addition of all of the acetic anhydride to the plasticized polymer, mixing thoroughly and then adding the sulfuric acid in a slow stream or in discrete incremental amounts. Another method is the alternate addition of incremental amounts of acetic anhydride and sulfuric acid to the plasticized polymer beginning with the acetic anhydride.
In a continuous process, using again "acetyl sulfate" as the sulfonation reagent, and an extruder having one or more reaction zones, the reagent prepared externally may be added to the polymer after it has reached the desired degree of plasticity in a single stream in a single reaction zone or in split streams when more than one reaction zone is used. Alternatively, the acetic anhydride may be added to a first mixing or reaction zone, followed downstream in a second mixing or reaction zone with the sulfuric acid. Other complexing agents can be handled in a similar manner when used in batch or continuous processes. Alternatively, the sulfonation reagent may be "dry blended" at ambient or lower temperatures with the polymer, previously reduced to a fine particle size, in an atmosphere free of oxygen and moisture and the mixture fed to the extruder for reaction.
B. Reaction Temperature and Time
In the bulk sulfonation of polymers as encompassed in the process of this invention, it is essential that the polymer be in a state of plasticity to permit uniform distribution of the sulfonation reagent throughout the entire mass of the reaction mixture. The temperature at which reaction occurs will accordingly be above the glass transition temperature (Tg) and for a completely amorphous polymer will generally be above Tg and below 250� C. Polymers having a measure of crystallinity or comprising crystalline segments will be sulfonated at temperatures which will be generally above the crystalline melt temperature (Tc) and below 250� C. Expressed in terms of Absolute Temperature, the preferred temperature range for the sulfonation is between 1 and 2.5 times the glass transition temperature of the polymer when both are measured in degrees Kelvin, but below 523� K.
While sulfonation reactions, particularly with aromatic compounds, are generally exothermic the use of complexes of sulfuric acid and sulfur trioxide results in an attenuation of the reaction and some heat must be supplied to the reaction mixture. However, the major source of the heat developed in the reaction mixture is due to the stress and resulting shear induced by the mechanical action of the mixing equipment and heat-exchange means must be supplied to maintain the reaction mixture within the desired temperature limits. For a number of polymers which have been studied, such as EPDM, polystyrene, copolymers of isobutylene and isoprene, an initial mixing temperature in the range of about 100� C. to 180� C. appears to be satisfactory.
In these reactions, many factors influence the selection of suitable reaction conditions. Specifically, the major factors which are important in conducting these bulk sulfonation reactions are:
(a) polymer backbone type
(b) sulfonation reagent, and concentration
(c) reaction temperature
(d) reaction time
The preferred polymer backbone in conducting these reactions are those containing relatively low levels of unsaturation, as have already been described, or those saturated polymers containing aromatic groups. Polymers which contain levels of unsaturation sufficient to give a sulfonic acid level of about 10 to about 200 meq are preferred with levels of 10 to 50 being most preferred. Ethylene propylene terpolymers (EPDM) are available commercially that can fall into this range of unsaturation. When using polymers which have this level of unsaturation, it has been observed that the reactions between sulfonation reagent and polymer can be very rapid at moderate temperatures (50� to 100� C.). It is preferred to conduct these reactions between unsaturated polymer and sulfonating reagent under the most moderate conditions which are possible, yet being consistent with the fluidity of the polymer melt and high conversion of the sulfonation reaction. The data shown below demonstrate that this can be accomplished with EPDM and Butyl rubber at temperatures between 50 and 125� C. for times ranging from 1 minute and 30 minutes.
If higher temperatures are employed, it is desirable to conduct the reaction with more intensive mixing and for shorter periods of time to avoid degrading the polymer prior to the addition of the neutralization agent. For example, it would be conceptually feasible to conduct the sulfonation of EPDM at 225� C. However, under these conditions, the employment of a very reactive sulfonation reagent would induce undesirable side reactions. Therefore, with this system, it is necessary to employ less extreme conditions for sulfonation (i.e. lower temperatures, less reaction time with the sulfonation agents--preferably 1 to 10 minutes, and moderate sulfonation agents or complexes).
On the other hand, we have observed that the polymer sulfonic acids derived from polystyrene are more stable than those derived from EPDM and other unsaturated polymers. As a consequence of this apparently better stability and, possibly the slower reaction between sulfonating agent and the aromatic moiety, these reactions can be conducted at somewhat higher temperatures than would be the case with EPDM. However, it should be emphasized that there is evidence that these sulfonating agents (specifically acetyl sulfate) can undergo side reactions at moderate temperatures and, therefore, this can provide an upper limit to the temperature and residence time for this reaction. Obviously, these side reactions involving the sulfonating complexes will be quite dependent on the nature of the particular complex, the temperature of its utilization, and the time during which it is reacted before neutralization. The specific examples delineated below provide information on the conditions for sulfonation of both EPDM and polystyrene. Based on the discussion above and the data below, we prefer an upper temperature limitation for these reactions as being less than 250� C., and preferably less than 225� C. In the case of unsaturated polymers, it is most preferable that the upper temperature for sulfonation be less than 150� C. In the case of aromatic polymers, it is most preferred that the upper temperature limit for sulfonation be less than 200� C.
Depending on the amount and type of polymer to be sulfonated, the composition and manner of addition of the sulfonation reagent, the temperature of the reaction mixture and the intensity of the mixing supplied by the mechanical equipment, reaction times in the range of 2 minutes to 1 hour, e.g. 6 to 30 minutes have been found to be adequate for the sulfonation of a broad spectrum of polymers.
In continuous sulfonations where the initial mixing of the polymer and the sulfonation reagent is conducted for example in an extruder, additional time for the completion of the reaction, if necessary, may be obtained by discharging the extrudate into a jacketed Banbury or kneader maintained at reaction temperature and operated under vacuum to remove volatiles.
The mole ratio of the sulfonation reagent to either the number of aromatic rings or the olefinic unsaturation or both used to effect sulfonation may be varied over a wide range, e.g. 0.2-5.0 moles of reagent calculated on the basis of the SO3 content per mole of aromatic or double bond. With certain Lewis bases (e.g. tetrahydrofuran, THF) the ratio of available SO3 to the Lewis base in the complex may also be varied from an equimolar complex to one having 3 moles of THF per mole of SO3. In the case of unsaturated polymers having an unsubstituted allylic methylene the sulfonation reaction can be nearly quantitative under optimum conditions of sulfonation. The conversion obtained varies with the type of polymer, composition and mole ratio of the sulfonation reagent and the specific conditions and equipment employed.
This invention has been described as a bulk sulfonation process. This is meant to distinguish such a process from the prior art process of sulfonations conducted on polymer solutions. These solution sulfonations are normally conducted with a minor amount by weight of polymer dissolved in non-reactive solvent. As such, the viscosities of such solutions are in the range of 2000 to 10,000 centipoise. These are considered the viscosities of solutions in which chemical reactions can be conducted in a reproducible manner to achieve homogeneous products.
The instant invention is substantially different from these solution sulfonations. The viscosity of the reaction medium is many times higher, ranging from 20,000 up to 1,000,000 centipoise or more. Under these conditions the reaction of polar sulfonating reagents in the non-polar medium is not readily predictable. It is essential for the products of this invention that this reaction be controlled sufficiently to provide products which are homogeneously sulfonated (as opposed to surface sulfonation), of uniform sulfonation level, that the products be substantially free of covalently crosslinked product (e.g. sulfones) and that the reactions be effected in a reproducible manner. Aside from the extremely high viscosities of these reaction media, and the lack of homogenity between the polar sulfonating agents and the relatively non-polar polymers, there is also the problem of the extreme rapidity of the reaction which could lead to gelled products of little utility. In view of all of the obstacles to this reaction, it is indeed surprising that the bulk sulfonation reaction proceeds smoothly and controllably.
The reaction of certain sulfonating agents such as gaseous SO3 with undissolved polymer is not unknown. It is important to distinguish the instant invention from that prior art. The instant invention does not contemplate the use of gaseous sulfonating agents. In fact, they are undesirable because they are extremely reactive are non-discriminatory in attack crosslinking degradation. Furthermore, the instant invention is not concerned with solid state sulfonation, i.e. surface sulfonation, wherein it is not relevant whether a crosslinked polymer is formed since generally it will be employed in the shape it is in when contacted with the sulfonating reagent.
In the instant invention it is required that the polymer be in a state of flux, i.e. the instant process depends on such polymer fluxing to disperse the sulfonating reagents throughout the reaction environment. It is important to note that certain non-volatile hydrocarbon additives can be incorporated into the polymer to be sulfonated in order that the fluxing be effected more readily or at a lower temperature. For example, the addition of hydrocarbon paraffinic oils to ethylene propylene terpolymer will lower the melt viscosity and expedite the reaction. It is important to note that such a mixture constitutes a bulk sulfonation system since the oil or additive will constitute less than 100 parts per 100 parts of polymer to be sulfonated. Furthermore, these additives will be non-volatile and thereby be compatible with and part of the sulfonated polymer phase. In addition to the oils, selected polymers can be added, e.g. ethylene propylene copolymer, polyethylene, polypropylene and the like can be incorporated into the EPDM to be sulfonated. These additives will not normally react with the sulfonating or neutralization agents. For other polymers, similar oils or plastic additives can be incorporated.
In all cases, the reactions envisioned in this invention will be conducted in a very viscous polymer melt. The viscosity of this melt will preferably be in the range of 50,000 centipoise up to and exceeding 10,000,000 centipoise when measured at shear rates of about 1 sec-1. This range of viscosities will generally be those manifested by the polymer before sulfonation or neutralization. It is even more preferred that this range of viscosities be about 100,000 centipoise up to 5,000,000 centipoise. Obviously, the temperature of the reaction medium can be adjusted to achieve these viscosity ranges. It is intended that this description of melt viscosities be descriptive of the characteristics of the reaction medium. However, under exceptional conditions, reactions can be conducted outside of these ranges. It is intended that such reactions fall within the scope of this invention.
C. Neutralization and Recovery
The sulfonated polymers made by the process of this invention may be recovered in the form of the free sulfonic acid or neutralized and recovered as a salt of the hereinbefore stated cations or counterions.
The free sulfonic acid may be recovered by dissolving the sulfonation mixture in a mixed solvent, for example toluene to which has been added between 5 to 10 volume percent of isopropanol, ethanol or methanol, at a concentration in the range of about 5 to 20 weight percent, and adding the solution of the sulfonated polymer to about 20 volumes of boiling water. The sulfonated polymer is precipitated in the form of small particles which can be filtered and at the same time the solvents are flashed off and can be recovered overhead. The polymer may be dried by kneading in acetone followed by solvent removal under vacuum or dewatered through an extruder.
Neutralization or ionic crosslinking with an appropriate cation or counterion may be done directly in the same equipment used for the sulfonation at the completion of the sulfonation reaction after which other polymers, fillers, antioxidants, plasticizers, extenders and the like may be blended with the neutralized polymer.
Polymers having olefinic unsaturation prior to sulfonation, retain in large part their olefinic unsaturation after sulfonation and can be covalently crosslinked by conventional vulcanizing agents such as sulfur. The advantages of the bulk sulfonation process of this invention will be more readily appreciated by reference to the following examples.
Seventeen grams of a terpolymer of ethylene, propylene and 5-ethylidene-2-norbornene (EPDM) in the gum state having an ethylene content of 51 weight percent, determined by the method of Gardner, Cozewith and VerStrate: Rubber Chem. & Tech. 44, 1015 (1971), an ethylidene norbornene content of 4.2 weight percent, a number average molecular weight (Mn) of 65,000 and a crystallinity of less than 20 weight percent as determined by the method of VerStrate and Wilchinsky: J. Poly. Sci A-2, 9, 127 (1971) which had incorporated therein about 0.5 weight percent of 2,2'-methylene-bis (4-methyl-6-ter-butylphenol) as an antioxidant was sheeted on a two roll mill, cut into strips and added to a 25 cc Brabender Plasticorder fitted with a constant temperature bath maintained at 50� C. and worked until the temperature of the melt had reached 85� C. which required about 1 minute, whereupon 0.70 grams of acetic anhydride having a strength of 97.4 weight percent was added dropwise to the molten polymer over the course of 4 minutes at the end of which time 0.51 grams of 96.5 weight percent of sulfuric acid was added dropwise over the course of 3 minutes followed by an additional mixing time of 10 minutes at the end of which time the temperature had risen to 103� C. and the mixture had a viscosity on the recorder of 1630. To the mixture was now added 4.68 grams of finely powdered zinc stearate (ZnSt2) and the mixing continued for 12 minutes at the end of which time the temperature had risen to 116� C. and the viscosity had leveled out at 2170. When cooled and milled, the product had a light tan to caramel color and surface roughness and snap-back characteristics of crosslinked elastomers. The high torque values obtained on the Brabender are also characteristic of solution sulfonated EPDM as the free sulfonic acid and when ionically crosslinked with zinc stearate.
Four experimental runs were made in the 25 cc Brabender Plasticorder in which Example 1 was essentially repeated with the exception that the acetic anhydride to sulfuric acid ratio were varied. Seventeen grams of the same EPDM and 4.68 grams of ZnSt2 were used in all runs, the bath temperature was 50� C. and the order of addition of the reagents was the same as in Example 1. The experimental details of Examples 1-5 and the results obtained are given in Table 1.
TABLE I__________________________________________________________________________Example No. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5__________________________________________________________________________Reactants - Gms.EPDM 17 17 17 17 17Ac2 O 0.70 0.70 0.70 2.8 0.23H2 SO4 0.51 2.03 0.16 0.51 0.51ZnSt2 4.68 4.68 4.68 4.68 4.68Time for Ac2 O Addition 4.0 min. 4.0 min. 4.0 min. 4.0 min. 4.0 min.Time for H2 SO4 Addition 3.0 min. 10.0 min. 2.0 min. 3.0 min. 3.0 min.Condition Before ZnSt2AdditionTemperature, �C. 103 87 98 82 95Brabender Viscosity 1630 1510 1350 920 1500Final ConditionsTemperature, �C. 116 106 105 101 103Brabender Viscosity 2170 1860 1660 1400 1880Total Blend Time, Min. 30 24 19 28.5 20.5__________________________________________________________________________
Examination of the torque measurements is indicative of the sulfonation efficiencies that were obtained. Prior experience has shown that the higher the free-acid and final neutralized viscosities, the higher the degree of sulfonation. From the above, it is apparent that from the variety of conditions that were studied in this series of experiments that the reagent ratios used in Example 1 in which the mole ratio of acetic anhydride to sulfuric acid is close to unity gave the best results. On the other hand, when either reagent was present in substantial excess poorer sulfonation efficiencies, as judged by torque determinations, were obtained.
Two experimental runs were made in the Brabender Plasticorder in which the procedure used in Example 1 was repeated with the exception that the absolute level of the sulfonation reagent was increased while the mole ratio of acetic anhydride to sulfuric acid was the same as in Example 1. The results are given in Table II. The data of Example 1 are included for comparison.
TABLE II______________________________________Example No. Ex 1 Ex. 6 Ex. 7______________________________________Reactants - Gms.EPDM 17 17 17Ac2 O 0.70 1.40 2.10H2 SO4 0.51 1.01 1.52ZnSt2 4.68 4.68 4.68Time for Ac2 O Addition 4.0 min. 4.0 min. 4.0 min.Time for H2 SO4 Addition 3.0 min. 3.0 min. 3.0 min.Conditions before ZnSt2AdditionTemperature, �C. 103 95 78Brabender Viscosity 1630 1620 580Final ConditionsTemperature, �C. 116 118 125Brabender Viscosity 2170 2480 2430Total Blend Time-Minutes 30 20.5 23______________________________________
It will be observed from the data in Table II that the use of higher levels of the sulfonation reagent result in increased viscosity after neutralization. The results are consistent with a higher degree of sulfonation of the polymer and as a consequence an indication of a higher degree of ionic crosslinking.
Samples, suitable for testing for tensile strength and elongation were prepared from a quantity of EPDM ionomer prepared as in Example 1 by injection molding the ZnSt2 neutralized bulk sulfonated EPDM at 150� C. into a cold mold using a 60 gram Watson-Stillman injection molding machine. The tensile strength of the sample was 36.5 kilo/cm2 at a cross-head speed of 5.0 cm per minute and the elongations at break were on the order of 300%. The results demonstrate that ionically crosslinked ionomers prepared by the bulk sulfonation process of this invention can be injection molded using conventional melt fabrication equipment to yield elastomeric products having good physical properties.
Example 1 was repeated except that the temperature of the constant temperature bath was raised from 50� C. to 100� C. but was the same in all other respects. The observed temperatures at the completion of the sulfonation was 111� C. and at the completion of the ZnSt2 addition was 124� C. The observed torque at the end of the run was 2140 which is within the experimental duplication of Example 1. This experiment illustrates that the bulk sulfonations can be conducted over a range of temperatures.
In order to determine the effect of alternative methods of reagent addition, Example 1 was repeated except that the acetic anhydride and the sulfuric acid were alternately added dropwise to the molten EPDM over the course of 1 minute, the reaction mixture held for 2 minutes from the time the viscosity leveled out, the zinc stearate added in 0.5 minute and the neutralized reaction mixture held for an additional 4 minutes. The results are given in Table III. The data from Example 1 are repeated in Table III for comparison.
A third method for sulfonating the EPDM used in Example 1 employed pre-formed acetyl sulfate made by the dropwise addition of 51.6 grams of 96.5 weight percent sulfuric acid, precooled to -10� C. to 50.0 grams of 97.4 weight percent of acetic anhydride, with stirring, while maintaining the mixture at a temperature of -10� C. Example 1 was repeated, except that 1.35 grams of the preformed acetyl sulfate was added over the course of 18 minutes. It was observed that the oily character of the reagent, which was maintained at a low temperature, acted as a lubricant for the walls of the mixing chamber and necessitated a longer mixing time before the viscosity leveled out. The overall effect was a lower final viscosity which was related to the mixing efficiency of the equipment. The results are given in Table III.
TABLE III______________________________________Example No. Ex. 1.sup.(a) Ex. 10.sup.(b) Ex. 11.sup.(c)______________________________________Reactants - Gms.EPDM 17 17 17Ac2 O 0.70 0.70 --H2 SO4 0.51 0.51 --CH3 COOSO3 H -- -- 1.35ZnSt2 4.68 4.68 4.68Time for Ac2 O Addition 4.0 min. 1 --Time for H2 SO4 Addition 3.0 min. 1 --Time for AcOSO3 -- -- 1Conditions Before ZnSt2AdditionTemperature, �C. 103 90 92Brabender Viscosity 1630 1670 1450Final ConditionsTemperature, �C. 116 115 --Brabender Viscosity 2170 2300 1900Total Blend Time-Minutes 30 8.5 32______________________________________ .sup.(a) Dropwise addition of all of the Ac2 O followed by dropwise addition of all of the H2 SO4. .sup.(b) Alternate dropwise addition of Ac2 O and H2 SO4. .sup.(c) Dropwise addition of preformed acetyl sulfate
While the lower viscosity of the neutralized product obtained in Example 11 would suggest that the use of preformed acetyl sulfate is less efficient than serial addition or alternate addition of the reagents, the slippage and poorer mixing accounts for the lower viscosity.
A blend of zinc stearate-neutralized sulfonated EPDM, prepared as in Example 1 was made with a high density polyethylene (HDPE) which had a density of 0.96 g per cc., a crystalline content in excess of 80 wt. % and a melt index of 6.0. The compounded blend had an overall composition of 27.4 grams of the ZnSt2 neutralized sulfonated EPDM; 14.8 grams of the HDPE; 6.6 grams of zinc oxide; 0.5 grams of magnesium oxide; and 0.4 grams of 2,2'-methylene-bis (4-methyl-6-ter-butylphenol) antioxidant.
The procedure employed in preparing the blend was as follows: To the Brabender mixing head, maintained at 180� C. by means of the constant temperature bath was added the HDPE, followed by the neutralized sulfonated EPDM within 0.5 minutes, the antioxidant within 1 minute, followed by the zinc oxide and magnesium oxide for a total mixing time of 10 minutes. The compounded blend was then sheeted on a cold two roll mill and samples for tensile strength prepared by injection molding at 150� C. in a Watson-Stillman press into a cold mold.
The tensile strength as measured was found to be 105.5 Kg/cm2 at a cross-head speed of 5.0 cm per minute and the elongation at break was 208%. The above compositions, which are disclosed in U.S. patent application, Ser. No. 524,502 filed Nov. 18, 1974, which is herein incorporated by reference, possess improved processability and compression set properties.
Seventeen grams of an unmodified general purpose polystyrene was added to the mixing head of the Brabender Plasticorder with the constant temperature bath maintained at 165� C. After about 2 minutes of mixing, the melt temperature had reached 156� C. and the fluxed polymer gave a torque reading of 2200. To the molten resin was then added over the next 7 minutes, 0.91 grams of acetic anhydride followed by 0.66 grams of concentrated sulfuric acid. The temperature remained unchanged and the torque reading had decreased to 1100. At this point, 0.60 grams of zinc oxide was added to the reaction mixture and mixing continued for an additional 8 minutes at which time the torque reading had leveled out at 2800. The high torque reading is consistent with data obtained with zinc oxide-neutralized sulfonated polystyrenes having the same degree of sulfonation, made by a solution process.
The above examples clearly show that polymers comprising olefinic unsaturation or aromatic rings can readily be sulfonated in the bulk with suitable sulfonating reagents. While zinc stearate and zinc oxide have been used in the above examples to neutralize the sulfonated polymers, other metallic salts, oxides and hydroxides are also suitable. Similarly, while acetic anhydride and sulfuric acid, used serially or alternately or in the form of pre-formed acetyl sulfate have been used in the above examples as the sulfonation reagent, other reagents detailed above are also suitable, particularly in those instances where isolation of the polymer in the form of the free sulfonic acid is desired.
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|U.S. Classification
|International Classification
|Cooperative Classification
|European Classification


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