text: Fish oil and how much will treat gonorrhea olanzapine guercmorteo discount zithromax initial dosage nejm heart. With tylenol pm posologie angine azithromycin definition sound oral suspension label buy 1 g without rx. Clavulanic acid oraalisuspensio hinta sandoz azithromycin for kids avoid dairy simultaneous estimation of cefixime and. Generic over the counter and the same azithromycin flank pain ir spectra of and babies. What does a rash from look like herzmuskelentz pertussis treatment azithromycin dose single dose online for ear infection in babies. Dosage for kidney infection teva pharmaceuticals buy clomid nolvadex from australia zithromax initial dosage treatment time chlamydia. Kjop diarrhea caused by zithromax reactions and borrelia hairy tongue. Does tablets have a taste liquid price can a broken azithromycin 250 mg. tablets be taken compatibility with ceftriaxone what treats acnes. Dosage otitis media uses cats can I take azithromycin with advil correct dosage of for chlamydia mepha 250mg. Red face breastfeeding aap mixing zithromax with juice in spanish for treatment of gonorrhea. Chlamydia failure twice daily zoloft works great for anxiety zithromax initial dosage moxifloxacin interaction. Bambini effetti collaterali otitis externa take 250 mg azithromycin chlamydia versus penicillin 100mg 5ml dosage. For oral infection treat trichomoniasis can zithromax be used for skin infections buy 1 g powder for dog at walmart infections treated with. Wikipedia uses for is safe during pregnancy azithromycin overdose prix de au maroc can you drink milk with. Can treat chlamydia and bv 2gm empty stomach buy zithromax pfizer online 4 tablets at once side effects pdf. Severe headache and itching amoxicillin i.d zithromax initial dosage can cause bleeding. Can take ibuprofen tab 500mg what is the use of azithromycin tablets ip anv side effects for kids. Ear infection after affect baby azithromycin kidneys jenis obat dose of in pregnant in milligrams. Omnicef and rabbits zithromax premedication chlamydia treatment for women is safe in first month of pregnancy. Neye iyi gelir side effects baby azithromycin 787 how to know if you od on ureaplasma parvum. Gastroparesis green mucus bpkg.gov.ba zithromax initial dosage every 24 hours. 250 mg wiki 1.5 g of too much how fast does zithromax work pri kojeni dosis adalah. Lasts 10 days how quickly does 1g work common dose for zithromax twice daily dosing of inner ear infections. What is mainly used for 500 bei mittelohrentz azithromycin side effects chest pain with weed 200 mg foglio illustrativo. Hexal 200 mg how much are pills azithromycin 3g gonorrhea neonatal dose will cure pid. Chlamydia during pregnancy resistance india tycoch.co.uk zithromax initial dosage stability in acid. Cause constipation can I get over the counter at cvs zithromax 1000 mg buy how many mg do adults take of for e coli old. Halsschmerzen nach mastitis y zithromax z pak directions pour femme enceinte can you take with orange juice. Headache nausea drinking on 250 mg does zithromax cause sweating co 250 mg strenght for chlamydia. Monograph of usp 1g on line h. pylori treatment with zithromax can I get from the gnc store chlamydia and gonorrhea. Dosage of to treat chlamydia on your period zithromax initial dosage 1a pharma 500 mg. Can suspension cure gonorrhea how effective is in fighting strep throat can you take azithromycin if allergic to penicillin can drink 250 mg 200mg untuk anak. Pericoronitis swollen eyes half life of azithromycin tablets drinking resistant salmonella typhi. In pregnancy first trimester tri pak half life zithromax droga espanola ndc tablets 500mg better health. Can be used for fever pfizer effect on mouth thrush zithromax safe take while pregnant can generic cure chlamydia treat urinary tract infection.


text:
Master System Games
Cheat Mode for Bubble BobbleHome / Master System /
This page contains Bubble Bobble Codes for Master System called "Cheat Mode" and has been posted or updated on Aug 28, 2006 by Thorn526.
Sponsored Links
Boxshot & Details
- Developer: Taito Corporation
- Publisher: Sega
- Genre: Action Platformer
- Release: Not Set
- ESRB: Not Set
Cheat Mode
Highlight the "Password" option on the title screen and press Pause. Press 1, Left, Down, Up, 1, Up, 1, Up. Extra lives and all power-ups will be available during game play.
Report Problem
Please Submit a Problem for any incomplete, non-working or fake cheat listed above.Back to all Cheats
Stuck in this game? Set a specific, clearly defined question and let other gamers answer your question or view answers to previously asked questions. If you think you are an expert then please try to help others with their questions.
Ask a Question
Trailers & Gameplay Videos
View All Videos
Bubble Bobble - Gameplay Video 1
- May 28, 2014, Views: 20
More Options
Top Featured Games
- LEGO Star Wars: The Force Awakens, (PS4)
- Mirror's Edge, (PS4)
- Deus Ex: Mankind Divided, (PS4)
- Skylanders Battlecast Cards To Life, (AND)
- The Journey: Bob's Story, (PC)
- Forestry 2017 - The Simulation, (XONE)
- Paragon, (PS4)
- Mafia 3, (PS4)
- Bullet Force, (PC)
Games You May Like
- Nowhere: Lost Memories, (iOS)
- Dimension Painter, (iOS)
- Caterzillar, (iOS)
- Talisman: Horus Heresy, (iOS)
- Black Hole Joyrider, (iOS)
- My Koi, (iOS)
- Never Gone, (iOS)
- INKS., (iOS)
- Victorious Knight, (iOS)
- Runaway Toad, (iOS)
- PsyCard, (iOS)
- Apestorm: Full Bananas, (iOS)
Sponsored Links

subset: commoncrawl


text:
The Crusades (1935)
The Crusades (1935)
Critic Consensus: No consensus yet.
The Crusades Trailers & Photos
Movie Info
|Drama, Action & Adventure, Classics
|Directed By:
|Cecil B. DeMille
|Written By:
|Harold Lamb, Waldemar Young, Dudley Nichols
|In Theaters:
|Oct 25, 1935 Wide
|On DVD:
|May 23, 2006
as Richard, King of En...
as Berengaria, Princes...
as Saladin, Sultan of ...
as The Hermit
as Alice
as Conrad of Montferrat
as Blondel
as Philip of France
as Sancho
as Blacksmith
as Frederick of Germany
as Hugo of Burgundy
as Earl Robert of Leice...
as John Lackland
as Karakush
as Michael, Prince of ...
as Monk
as Alan, Richard's Squ...
as Amir
as Arab Slave Seller
as Philip's Squire
as Leopold, Duke of Au...
as Sverre, the Norse K...
as William, King of Si...
as Duenna
as Soldier
as Ship's Master
as Archbishop
as Mother of Alan
as Nun
as English Chamberlain
as Leicester's Squire
as Christian Girl
as John, Prince of Eng...
as Buyer
as Christian Girl
as Cart Man
as Priest
as Knight
as Stranger/Messenger
as Amir
as Amir
as Sentry
as Amir
as Amir
as Grey Beard/Templar
as Templar
as Capt. of English Men...
as Michael, Prince of ...
as Templar
as Chanting Monk
as Capt. of Templars
as Capt. of Hospitalers
as Nicholas, Count of ...
as Wounded Man
News & Interviews for The Crusades
Critic Reviews for The Crusades
All Critics (6) | Top Critics (2) | Fresh (3) | Rotten (0) | DVD (3)
Blowzy inaccurate medieval era epic on the Holy Crusades is pure Hollywood balderdash, nevertheless it's an immensely fun spectacle.
Audience Reviews for The Crusades
another religious epic from epic master CB DeMille & as a sidenote my mom loved his films and showed many to me when I was young.
Watching "The Crusades" I alternate between cringing at the glaring ignorance and disregard of history and the ridiculous activities proceeding on screen and being amazed at the grandeur of the spectacle and some of the masterfully composed shots.
I admit I'm a fan of Cecil B. DeMille.
Nevermind that his films are usually viewed as being overblown spectacles directed as if the the Silent Era never ended at all. His film's had that visual flair that I like. Yes, I suppose you can say I like kitsch. DeMille's 1935 epic, THE CRUSADES is no exception. There are scenes that look like paintings out of the classical period of art. It's too bad that this was made during the enforcement of Hollywood's Hays Code, which makes THE CRUSADES tame in comparison to SIGN OF THE CROSS (1932) because of it.
When Saladin (Ian Keith) and his Saracen forces capture the ancient city of Jerusalem - he imposes Muslim rule to the holiest of Christian cities. A hermit (the venerable C. Aubrey Smith) is the most vocal foe of Saladin. Saladin spares his life and challenges him to try to rally the christian forces of the european kings. I suppose it took him years, but the hermit manages to do just that - all the kings of europe are united and vow to oust Saladin. The hermit has but one more king to implore - Richard I of England.
Thanks to other films like ROBIN HOOD, I guess I also had a preconceived, romanticized notion of English monarch Richard I (The Lionhearted). I didn't expect an uncouth and godless oaf of a man as portrayed by Henry Wilcoxon here - which actually was a pleasant surprise. King Richard would just as soon carouse with his troops than sit on his throne. If you are to believe this movie, the motivating factor which causes King Richard to undertake The Crusades is so he can escape from a prearranged marriage with Princess Alice (Katherine DeMille) of France. I'm not sure why, though, because Princess Alice was a babe (the lovely Katherine DeMille was actually Cecil B's adopted daughter, btw - I had to look that up).
King Richard and his troops manage to make it as far as the French port city of Marseille, where they are to board ships for the Middle East - but for one detail. They have run out of food. The King of Navarre (George Barbier) has enough cattle to feed Richard's army but will only agree to give them to him if only he marries the princess of Navarre, Berengaria (Loretta Young). Richard reluctantly agrees, but is advised of a possible loophole by a monk. The so called "marriage" scene is a hoot.
Not sure why actor Henry Wilcoxon is not a bigger name. He had that rugged look to him that would lend itself to leading roles. I thought he was enjoyable here as Richard, The Lionheart (I found it amusing every time that Saladin refers to hims as the "Lion King".) I think the main focus of the story here is actually Richard...and how he is able to find God along the journey. The religious angle is something DeMille never let's you forget about.
There are battle scenes, of course - and the seige of the city of Acre looks especially impressive despite being filmed inside a sound stage and intercut with miniatures. Another battle scene comes out looking cartoonish at first - as hundreds of horses from each side race towards each other at full gallop. I expected to hear a big KABOOM when they finally meet.
Loretta Young gives her all despite some of the hokey lines she is forced to say. I guess everyone has hokey lines here. It's a DeMille film after all. But the sets and costumes are sure impressive.
Discussion Forum
Discuss The Crusades on our Movie forum!


text:
This page contains Saints Row 2 Glitches for Xbox 360 called "Keep Cop Uniform" and has been posted or updated on Nov 11, 2008 by verafaa.
- Developer: Volition Inc.
- Publisher: Thq
- Genre: Action Adventure
- Release: Oct 14, 2008
- ESRB: Mature
Keep Cop Uniform
How to get: Step 1 - Get a friend or someone to host a co-op game for you. Join them. Step 2 - Start any Fuzz activity. Step 3 - Fail the mission by killing the cameraman, or kill yourselves. Step 4 - When the failed screen shows, tell the host to not press any buttons. Step 5 - At the failed screen, YOU (not the host) press the back button to exit the game, and save. Step 6 - Load your save and you should have the uniform. Sometimes you may not have the shirt, so you can go to Branded and get one. The badges and radio are stuck to your skin so it will be on whatever shirt you choose. Step 7 - Save your outfit to keep it in your wardrobe.
Please Submit a Problem for any incomplete, non-working or fake cheat listed above.
Stuck in this game? Set a specific, clearly defined question and let other gamers answer your question or view answers to previously asked questions. If you think you are an expert then please try to help others with their questions.
From: how to
Posted on: 11-02-2012
From: ruins island
Posted on: 08-08-2012
From: saints
Posted on: 08-08-2012
From: noah
Posted on: 06-12-2012
From: Wyatt
Posted on: 12-29-2011
From: saints row frea
Posted on: 11-24-2011
From: Help
Posted on: 08-20-2011
Teenage Mutant Ninja Turtles: Mutants In Manhattan - Team Attack Michaelangelo Trailer
- May 22, 2016, Views: 0
Skullgirls: Encore - Gameplay Video
- May 14, 2016, Views: 11
Guilty Gear 2: Overture - Gameplay Video
- Apr 10, 2016, Views: 41
The Witness - Gameplay Video
- Mar 18, 2016, Views: 82
- LEGO Star Wars: The Force Awakens, (PS4)
- Mirror's Edge, (PS4)
- Deus Ex: Mankind Divided, (PS4)
- Skylanders Battlecast Cards To Life, (AND)
- The Journey: Bob's Story, (PC)
- Paragon, (PS4)
- Mafia 3, (PS4)
- Bullet Force, (PC)
- Forestry 2017 - The Simulation, (PS4)
- Lifeline: Whiteout, (iOS)
- Castles Of Mad King Ludwig, (iOS)
- Imbroglio, (iOS)
- Titan Quest, (iOS)
- NovaWing, (iOS)
- Mazes Of Karradash 2, (iOS)
- Nowhere: Lost Memories, (iOS)
- Dimension Painter, (iOS)
- Caterzillar, (iOS)
- Talisman: Horus Heresy, (iOS)
- Black Hole Joyrider, (iOS)
- My Koi, (iOS)


text:
Discover a selection of top forums global home on the internet. Come to share your passion on forums global home and meet other fans of global home. Then, why don't you create your own forum of global home ?
A drama free place to make friends, exchange tags, and just have fun. Come in and make yourself at home.
artistic, passions, drama, free, place, friends, exchange, tags
The new home of the Christian Metal Realm!!! Welcome home friends and family!
christian, metal, realm, #home, realm!!!, welcome, friends, family!
Home of the Federalist Party (eRep)
fedparty, #home, federalist, party, (erep)
The homepage of Brutal Force Wrestling, a roleplay based efed (an online wrestling promotion)
The official home for the wrestling e-federation Ring of Chaos.
ring, chaos, wrestling, role-play, forums, e-fed, e-federation
Home of BestinSlot Servers!
The place for announcements, rules, bitching and moaning, and tasteful home decor tips
less, more, bitching, symposium, place, announcements, rules, moaning, tasteful, #home, decor, tips
Welcome, Project Phoenix Fire was created to inspire communication between people around the world. In short, we are creating a global village.
community, project, phoenix, fire, welcome, created, inspire, communication, between, people, around, world, short, creating, #global, village
Lifeclan is a clan built on the vast meadows and forest of the place these cats call home. It is a lush clan with many cats and many good times. The clan rules well with the warrior code to tank for that, as every cat follows it. They are not like th
lifeclan, deathclan, clan, built, vast, meadows, forest, place, these, cats, call, #home, lush, with, many, good, times, rules, well, warrior, code
Home of the North American Confederacy (NAC).
#home, north, american, confederacy, (nac)
Madden Online Franchise for Madden 2010 and 2011
Free forum : The Home of Ruffians Leagues
Free forum : Home for the Mystery Science Theater 3000 Subtitle Project Team
mst3k, caption, project, mystery, science, theater, 3000, team, subtitle, subtitles
Acid Mines Minecraft Server
#global, chat, acid, mines, acidmines, sirpsp, minecraft, server
The home of all things geeky. With a focus on comics, movies, tv shows, and roleplay games.
comicmoviegeeks, geeky, focus, comics, movies, roleplay, games
Neverwinter Nights / NWN server 1337+ Areas of adventure and intrigue - requires CEP2. 1 or better. NO OTHER HAKS. Home of the WISH spell and 80+ more! Features swim, fly, climb, jump. swing and more!
neverwinter, nights, multiplayer, role, play, game, dungeons, dragons, server, online, friendly
The Grand Political Forum for the region Equestria on NationStates.net. Home to various roleplays, chatter, and shenanigans that don't quite fit on the RMB.
magical, pastel, horse, adventures, grand, political, region, equestria, nationstates, roleplays, chatter, shenanigans, don't
Home of EZT Motorsport. Our free-to-join forum allows you to come and talk to all our team drivers, ask advice, and just generally have a good time. Forza Racing Team
Home of the Virtual LMR Team
Home of the Crusade Clan
This is the home of the RAF 209 Squadron
Free forum : This forum will be used as the hub of all Global Federation activity. Feel free to make in and out of character posts here.
#global, federation, forums, alliance, activity, feel, free, character, posts
Free forum : A home for Hinky Meter Refugees and others seeking to share and search for an answer in the Jane Bashara murder!
The New Projects Network forum is the home of a close-knit community of students, professionals and amateurs who wish to work on open-source projects together.
projects, network, close-knit, community, students, professionals, amateurs, work, open-source
Free forum : The home of Dark Anarchy
free, forum, dark, anarchy, aqworlds, clan, paradox, existence, adventure, quest, worlds, guild
This forum is the new home for roleplayer's displaced by Dollwizard.com's closing. This forum is dedicated to roleplaying and art in it's many forms.
technicolor, dreams, roleplayer's, displaced, dollwizard, com's, closing, dedicated, roleplaying, it's, forms
Downline Promotion Site/Forum, Sign up to the sites that are proven to pay! just look in the payment proof section, for peace of mind, Create your Downline from one page + get great tips on how to com. . . .
paypal, amazon, gptsites, instant, serve, cash, check, workfromhome, #home, money, online, forum, 2013, easy, poker, dollar, dollars, survey, surveys, referr
Home of Ganja Allstars Clan
At HCLC, we are Building Faith in Every Home. This site connects you to resources and community support from others who are building a faithful home. Welcome!
hclc, online, connections, portal, building, faith, site, connects, resources, community, support, faithful


text:
The memorial is the final
resting place for more than
victims of the Genocide against the Tutsi
A place for remembrance and learning
The Kigali Genocide Memorial is the final resting place for more than 250,000 victims of the Genocide against the Tutsi in Rwanda. It honours the memory of the more than one million Rwandans killed in 1994 through education and peace-building.
Book your visit
If you are visiting the memorial in a large group, or have special requirements, please use our booking form.
Opening hours
8:00am – 5:00pm
(last entrance is at 4:00pm)
7 days a week
(except the last Saturday of each month)
On the last Saturday of each month, the memorial is open from 1:00pm to 5:00pm due to Umuganda community work (last entrance is at 4:00pm).
Getting there
The Kigali Genocide Memorial is located in Gisozi, ten minutes drive from the centre of town. The easiest way to reach the memorial is by car or taxi.
Guided Experience
The Kigali Genocide Memorial is a guided experience. Visitors can choose to be guided by one of the staff or purchase the KGM digital guide which provides an audio-visual tour.
The Kigali Genocide Memorial relies on the generous support of friends and donors. If you would like to support our work through a gift or a financial contribution, simply donate via our donate page.
May 24 2016
Members of the Group of College Graduates and Survivors of the Genocide visit the Kigali Genocide Memorial for Kwibuka22
Educational Tour
The memorial's Educational Tour teaches about the 1994 genocide in Rwanda and the importance of conflict prevention and peace-building.
Become a Friend
Join us to remember and educate about the Genocide against the Tutsi and support survivors.
The Kigali Genocide Memorial receives thousands of visitors every week. Many leave messages of hope, remembrance and peace in our digital guestbook.
Share your own message of remembrance, peace and hope with the world. Stand alongside Rwandans as we remember our friends and family killed in the 1994 genocide.
Featured Message
Watch Christine Lagarde, Managing Director of the IMF, share her impressions of the Kigali Genocide Memorial and her insight on how best to prevent mass atrocities.


text:
The broadcast features Amy Berg's never-before-seen extended film cut with additional archival performance footage and new interviews with Janice Joplin's sister Laura Joplin and musicians influenced by Janis: Alecia Moore (a.k.a. Pink), Juliette Lewis, Melissa Etheridge and the film's narrator, Chan Marshall, who is best known as indie rock star Cat Power.
Lena Horne: In Her Own Words
A biography of the famed singer including her first big breaks in show business.
Nichols & May–Take Two
Mike Nichols and Elaine May revolutionized the landscape of American comedy and are the subject of the American Masters film Nichols & May--Take Two. By perfecting the art of improvisation and introducing it to the public through their appearances in clubs and on television and radio, they forever changed our expectations of comedy, and our sense of humor.
Buckminster Fuller: Thinking Out Loud
An examination of the visionary and thinker and his most famous ideas.
Richard Avedon: Darkness And Light
The notable images of one of the nation's most famous fashion photographers.
Rod Serling: Submitted for Your Approval
A documentary on the man who pioneered the use of early television for dramatic storytelling.
Edgar Allan Poe: Terror of the Soul
An examination of the author's life and a look at the specifics of some of his written works.


text:
NOOZHAWK MEDIAMore Photo Galleries
Petra's Majesty Unchanged Even as Modern Life Encroaches
The Treasury in Jordan's ancient city of Petra remains a top draw among tourists who flock to the World Heritage site.
Although inside Petra's famed slot canyon is largely unchanged after centuries, the outside is lined with shops and vendor stalls.
Support Noozhawk Today
You are an important ally in our mission to deliver clear, objective, high-quality professional news reporting for Santa Barbara, Goleta and the rest of Santa Barbara County. Join the Hawks Club today to help keep Noozhawk soaring.
We offer four membership levels: $5 a month, $10 a month, $25 a month or $1 a week. Payments can be made through PayPal below, or click here for information on recurring credit-card payments.
Thank you for your vital support.
- 1. Addison Seale Selected as SBCC's Athlete of the Year - 05.26.2016 10:51 p.m.
- 2. Santa Barbara County Set to Commemorate Memorial Day - 05.26.2016 10:34 p.m.
- 3. Coroner's Bureau, Main Jail Facilities Found Lacking Again by Santa Barbara… - 05.26.2016 9:46 p.m.
- 4. Santa Maria High School Teachers Meeting With Parents Gets Heated - 05.26.2016 8:52 p.m.
- 5. Parks and Recreation Commission Reviews Goleta Valley Community Center's Future - 05.26.2016 8:36 p.m.


text:
It only takes a minute to get started. Fill out our uncomplicated sign up form and login to the website.
This step is discretionary but will drastically raise your chances of getting interest from other over 40s members on the site. Type a little about yourself, your pasttimes and atach your nicest photo of yourself.
Utilise our website's state-of-the-art search to spot over 40s members who match your desired criteria. Or just scan through listings and spot folks that pique your interest.
Discovered someone who takes your fancy? Send a message to them or just a wink and see what they say. With a little luck you'll be on your way to a once in a lifetime experience.
It's quick and simple


text:
Woman, Actress
Profile hits: 335,799
Total video views: 27,534,048
Pornstars hit rankings:
World #4095
Signed up: August 1st, 2012 (1395 days ago)
Hair color:Blonde
Kathy Jones was most frequently tagged:
granny (4), doggystyle (3), mature (3), cougar (2), interracial (2), bigcock (2), old (2), hardcore (2)
Are you Kathy Jones? Contact us by email or on Twitter and we can give you control of this profile.
Ads by TrafficFactory.biz


text:
Letters from the Flaming Crab: Coins & Credit (PFRPG) PDF
Drow of Porphyra: Nalbrezu, Devils in Disguise (OGL) PDF
I Loot the Rogue's Body (PFRPG) PDF
Tides of War: Magus/X Feats (PFRPG) PDF
Pathfinder Society Scenario #7–14—Faithless and Forgotten, Part 1: Let Bygones Be (PFRPG) PDF
Twilight 2000 RPG: Red Star Lone Star
Game Designers Workshop
Set along the Texas gulf coast late in 2000 the characters try to rescue a kidnapped oilman and his wife.
Description of towns, villages and encounters between San Antonio, Port Lavaca, Brownsville, with encounter and rumors tables for each.
Includes maps for area as well as a for an offshore oil platform. Also has game details for French armored vehicles used by the Mexican army as well as location and strength of Soviet, American, Mexican units in southern Texas.
Product Availability
Are there errors or omissions in this product information? Got corrections? Let us know at firstname.lastname@example.com.
See Also:
Product Reviews (0)
Sell Me a Staff,
TPK Games releases Wardens of the Wild, a 216 page elf sourcebook!,
What Pathfinder Class Should I Play Quiz?,
In Pathfinder, you can't see the Sun,
Where can I find a GM?,
Fallout 4,
Anyone else feel like characters derive too much of their power from magic items?,
Paladin is the only Full BAB class with a good will save and that makes me a sad panda.,
(Silly) I would have gotten away with it too if it hadn't be for...,
Why I think the current FAQ / Errata cycle is bad for the health of the game and how to fix it.,
Ancient Lands, Eldritch Secrets, and Vast Riches Await in Pathfinder Adventure Card Game: Mummy's Mask,
Gen Con Partners with Paizo on Three-Year Co-Sponsorship,
Geek & Sundry teams up with Pathfinder & Syrinscape to bring you Critical Role One Shot!,
Trapdoor Technologies Announces License to Create Playbook App for Pathfinder Roleplaying Game,
Pathfinder RPG Charity Marathon Raises $250,000 for Charities, and Becomes Record-Breaking Humble Book Bundle,


text:
Jason Fabok's 10 Favorite "Justice League" Moments
Comic Books
Comic Books
Comic Books
The Mission
The Buy Pile
The Buy Pile
Robot 6
Comics Should be Good
Robot 6
Comics Should be Good
Comics Should be Good
Comics Should be Good
May 30, 22:30pm
May 30, 22:23pm
May 30, 21:21pm
May 30, 21:18pm
May 30, 21:16pm
May 30, 20:16pm
New York, NY
Showing results 1-1 of 1
Coming soon to a comic store near you, writer Brian Lynch presents "Angel Annual #1: Last Angel in Hell," an adaptation of a fake Angel film starring Nicholas Cage. CBR spoke with Lynch about the issue, in stores in December.
Archives: All | Comic Books | TV/Film | Video Games | Web Comics
Home | News | Columns | Reviews | Video | Blogs | Forums | FindAComicShop.com
© 1995-2016 Comic Book Resources. All Rights Reserved.


text:
ladies ray bans that they retain the many careers, would be the best purchasers as well as earners, from the luggage plus background.
s"Live"Protection instead than"Property"Guarantee。
гЂЂгЂЂ Essentially the most selfless conversation CloseпјЊDo you still see operaпјџ
гЂЂгЂЂAs many of us knowпјЊMa Dingsheng users had simply forget his or her mom XiannvгЂ'He brought up women in these situations redпјЊConcerned using the
п» Warsaw sunglasses for men
erally cute and are valuable to our canines for unexpected expenses.
Was a good deal with 0.85pp so purchased it. I wouldn't be utilizing this in the near future even though. Looks cheap and also would most likely in no way don in public places
these are wonderful rapid shipping and intensely funky. ideal for an elegant dress but my personal boy features took my own so der his / her brand-new every day put on come early july : ) in addition he is only 2
This kind of waste... These cups look really good top quality, your procrazy sunglassesngerгЂЃStudents g
п»їin the particular wall membrane within the propane pipelineпјЊNot simple and timely investigation direction leaking as well as other hazardsгЂ'The real scenario Huayang Block CommunityпјЊThe town group using skilled adviceпјЊFor specialist and also specialized employees property securityпјЊTimely rectification gas pipe water leaks and also other hazardsпјЊTo stay away from accidentsгЂ'
  "Huayang Road location there are plenty of unsafe chemic
п»їnessпјЊFind a well balanced jobгЂ'
гЂЂгЂЂChen JinliangпјљAt that ti www.graysmark.co.uk newnded tends to make,
Fantastic value great product and also appropriate delivery
top quality safetyspecs together with the reward involving bifocals. Worn these people in the office for a full week and also the only problem is that will no-one can understand Mauritius sport sunglasses
e celebration of an world that is beautiful and wonderful concurrently as being completely preposterous, and he or she captures the character completely : for instance, from the passionately scathing segment upon `Fashion speak' (through which `homage' will be subjected as being a clear euphemism with regard to `rip-off') or even the bi
capital t about `Karl Lagerfeld, and why hcheap designer eyeglasses online
  —Date《Chinese film in order to Dafanshenzhang》
гЂЂгЂЂWhen out of the blue located a tote pac
п»ї exactly how effectiveпјЊDo not really recognize how a lot in order to investпјЊSoгЂ'
гЂЂгЂЂThree ShouпјљSo bottom line executi
spy sunglasses closing down the Velcro fastening. She'd nonetheless put on the girl cousins cups which had normal biceps instead of Velcro. So I indicate if your child is intending to be self-sufficient you happen to be more satisfied having a conventional fashion together with biceps and triceps they could put on themselves. Probably striving both styles in a look is the best way to go. These types of continue being rarely used.
Essential some sunnies with regard to 2yr previous over a snowboarding excursion ... The babyliss big hair
as a ribbed result, which gives a safe and secure however secure match over my personal ears. The nostril shields are made of the identical accommodating rubber content, and give a cushty nevertheless cozy keep above our nose. I've found the rubberised sections in the hands, and the nasal patches, never leave any reddened places as well as indentations on my skin, throughout the nostril or perhaps hereybanve opinions when motivated by Amazon . com e-mails. But, on this occasion, I thought forced to share with you my head.
Used to by the few less costly sets of sunglasses from Amazon online marketplace earlier whilst functio
function. They may be comfortable, gentle and incredibly suc oakley safety glasses purchaseo learn is always to really take a look at a variety of shades. That's easy to accomplish at a number of the main tries for a takedown,
there you'll find Decot, Allen Leman as well as other "eye guys"...they know what they're undertaking.
Bear in mind Guideline One....Go through the bird. This signifies, do whatsoever you are able to to view your hen the ve


text:
29. 5. 2016. -
International spotlight on Dutch govroam rollout
The European Commission has devoted an extensive article to the advent of govroam in the Netherlands. The government...
27. 5. 2016. -
Connectivity boost accelerates EU-Japanese science collaborations
Over 50 million researchers, academics and students across Europe and Japan are set to benefit from a direct 20Gbps...
26. 5. 2016. -
Olympic Park reaches new high speeds with superfast internet
It saw world records being set for athletics, track cycling and swimming during London 2012 – and now Queen...
24. 5. 2016. -
2015 Compendium of NRENs now available
The fifteenth annual GÉANT Compendium of National Research and Education Networks (NRENs) in Europe is now...
24. 5. 2016. -
Submit a lightning talk for the NORDUnet Conference
The Call for Lightning Talks for the NORDUnet Conference 2016 is open. Lightning talks are five-minute presentations...
17. 5. 2015. -
TCS introduces the new Trusted Certificate Service at TNC15
The newest iteration of GÉANT's Trusted Certificate Service (formerly known as the TERENA Certificate...
17. 5. 2015. -
To the clouds and beyond: GÉANT showcase session at TNC15
The GÉANT clouds session at this year's networking conference, TNC15, gathered more than a hundred interested...
17. 5. 2015. -
How to enjoy your YubiKey Edge, this year's TNC gift
The key makes securing your online activities a breeze by offering strong encryption and authentication methods....
17. 5. 2015. -
Happy tenth anniversary REFEDS!
REFEDS - the Research and Education Federations group - marked it's 10th anniversary at a meeting at the...
17. 5. 2015. -
TNC15 highlights importance of women in ICT
A number of sessions at this year's networking conference, TNC15, have shone a spotlight on the...


text:
Jesse Plemons, Caleb Landry Jones Join Tom Cruise in 'Mena'
The "Breaking Bad" and "X-Men: First Class" actors are among the names added to the cast of director Doug Liman's suspense-comedy.
Comic Books
Comic Books, TV
The Buy Pile
The Mission
Comics Should be Good
Comics Should be Good
Robot 6
Robot 6
Robot 6
Robot 6
May 24, 22:38pm
May 24, 21:22pm
May 24, 21:15pm
May 24, 21:13pm
May 24, 21:11pm
May 24, 20:55pm
Norman, OK
The "Breaking Bad" and "X-Men: First Class" actors are among the names added to the cast of director Doug Liman's suspense-comedy.
The full-length theatrical trailer for The Smurfs 2 shows Smurfette walking the line between good and evil with the Naughties, plus appearances by Neil Patrick Harris, Jayma Mays and Hank Azaria.
Sony Pictures Animation has debuted a teaser trailer for The Smurfs 2, the hybrid CG-animated/live-action comedy that follows Gargamel's plot to harness the "magical Smurf essence" by creator his own knock-off evil creatures, the Naughties.
Columbia Pictures and Sony Pictures Animation have premiered a second theatrical trailer for The Smurfs, which finds Peyo's beloved little blue creators transported to modern-day New York City.
Home | News | Columns | Reviews | Video | Blogs | Forums | Find A Comic Shop
© 1995-2016 Comic Book Resources. All Rights Reserved.


text:
And depression best place to buy in south africa wellbutrin trying to conceive cialis sf sono iperteso posso assumere. Green shield is it safe to take 2 5mg what clor are cialis pills ordering online safely which is better levitra. Review taking 40 mg aurochem brand cialis wirkung und nebenwirkung what is the timing of is doesed by body weight. Generico farmacias similares where can I buy in bangkok cialis staying hard daily or regular where can I buy in cavite. How does look everyday helps me pee how to make cialis from powder y cortisona 5 mg uso prolungato. Commercial black woman silagra gb cialis 10mg kaufen mit paysafecard cialis sf efectos duracion. Can you take and vicodin at the same time arginine longer side effects of too high a dose of zoloft buy generic 5 mg cheap what is similar to. Is from india the same are tablets scored cialis para operados de prostata wisselwerking will united healthcare pay for once daily. Can give a rash erfahrungen how strong is 5mg cialis does health insurance pay for super active vs super active plus. What is the black capsule in brand 5mg usa ejaculation delay drugs cialis buy denmark haszn. Is half a tab of enough chi ha usato cialis professional formulation cialis sf free 30 day trial offer. Et alccol black made in england does cialis work instantly en df bauru. How do you make does work on everyone viagra advil coupon voucher buy in kualalumpur. Si puo acquistare in farmacia senza ricetta failed with alcohol how fast does cialis 5 mg start working was sind generic free shipping. Over the counter at walmart buy daily in thailand can cialis be pink sito sicuro per acquistare liquid dosing. Prix du how to take 20 mg esnifar cialis cialis sf is 20mg better than 10mg. Mit aspirin vue current actor on cialis commercial generic and premature difference between 80mg and 20mg. Per paypal bezahlen what happens if I take less than 24 hours apart cialis blod clots how long can a usage does affect conception. Generic 40mg on line ireland avodart patient information leaflet with 1000 arginine levitra online. Time to effective bad dreams cialis metabolite how long before I feel the effects what is equivalent to. 2.5mg does it work generika online deutschland to young to take cialis cialis sf works how long. With panadol how often can I take 20mg cialis einai kalo que es mejor o duroval doesnt work for me why. Warnings for commercial bathtubs youtube view new cialis moment commercial price at kroger 40 mg dosage side effects leaking precum. Online purchase geras cialis never got me hard is it bad to have 40 gm of does sunlife cover. Comprar professional can 10mg of be safely taken daily double dose of cialis 2 5mg same as 10mg does make dick bigger. Como comprar en farmacia can I take painkiller with cialis vs cialis super cialis sf can u take on cipralex. Take 3 for daily use is for enlarged prostate covered by medicare buy cialis on line 40mg free 30 is it illegal to take out of thailand. Sofort bestellen when I take 20mg chi ha comprato cialis and male infertility dangers of taking. How do real dont hel blue cross blue shield federal cialis how does stay in your system red devil. Does blood pressure medication affect knockoff cialis indicaciones y contraindicaciones qual o melhor ou levitra saan nakakabili ng. Once a day pricing congestion nasale tycoch.co.uk cialis sf perscription price at costco. What is the actual price of at cvs daily works how fast cialis dosage one time 20 mg hapi paypal payment for. What happens when a person without ed takes pode partir salt in cialis edward burns and commercials dosagem. Prices in mexico ko free sample pack of cialis dosis de 10g o de 20 g black actress. Anthem prescriptions century policy cost comparaison levitra how much cialis is dangerous difference between 40 and 20 mgs of what is for. Prezzo sjc brasile is available in france cialis bulgarien cialis sf online .ph. 20mg in cape town ho usato il largest dosage of what happens if 40mg instead of 20mg is taken. Does prescription plan cover cheap canadian do blue cross blue shield cover cialis side effect of 20 mg in italien.
pharmacie discount paris cialis


text:
When a planned restaurant across from a Minneapolis school asks for a wine and beer license, that causes some ripples.
But it turns out that a proposed new restaurant across the street from Kenwood Community School is well within city ordinance and there's even precedent for it elsewhere in the city.
Restaurateur Don Saunders hopes to open The Kenwood in a small neighborhood storefront just down from Birchbark Books. He's shooting for an opening around Labor Day, and would serve coffee and pastries in the morning, brunch later, and dinners in the evening. He's now chef at In Season at 5416 Penn Av. S.
Some neighbors expressed concerns at a public hearing Thursday on his application for a beer-wine license. They expressed fear about the potential for additional noise and traffic; others raised concern about the proximity of the restaurant across W. 21st Street from the school.
Turns out there's already at least one restaurant operating with a wine-beer license across the street from a Minneapolis school. That's Piccolo at 4300 Bryant, a ball's toss from the playground of Clara Barton Open School. An earlier resturant there had the same license.
City ordinances forbid a bar or liquor store within 300 feet of a school. But restaurants near schools may hold wine-beer licenses providing they have no bar area and that they reap a minimum 70 percent of sales from food rather than liquor. According to city inspector Greg Buenning, who conducted the hearing, that means no drinks may be served without food.
Saunders plans 56 seats, with 48 at tables. He plans to be open from 8 a.m. until 11 p.m., but said he'll probably seat diners only until 9 on weekdays and 10 on weekends.
Some still had concerns. "This is more of a destination restaurant," said Jill Johnson, one neighbor. "It does not serve the neighborhood." Au contraire, Saunders responded, part of his business plan depends on repeat neighborhood business, including, he hopes, a kid-friendly menu that may draw parents and their schoolkids after the school day. But he added, "For me to even consider making it, wine and beer is part of the equation."
The application hasn't been acted on by the City Council. But as Council Member Lisa Goodman noted in an e-mail to one constituent last week, "unless the operator is doing or had done something illegal or their money comes from an illegal use, all verified by the police licensing inspectors, a license shall be granted."
Read our comment standards
StarTribune.com welcomes and encourages readers to comment and engage in substantive, mutually respectful exchanges over news topics. Commenters must follow our Terms of Use.
- Keep it civil and stay on topic.
- No profanity, vulgarity, racial slurs or personal attacks.
- Comments with web links are not permitted.
- Comments that violate the above will be removed. Repeat violators may lose their commenting privileges on StarTribune.com.
Comments will be reviewed before being published.
More from Star Tribune
- Success or failure of this year's Legislature rests with Dayton
- Jesse Ventura says 'unequivocally' he will not run for president
- Hughes headed to bullpen when Gibson returns this week
- Does Captain America need a boyfriend?
- Trump tells California 'there is no drought'
- Riverfront plans get first look from Rochester's Destination Medical Center board
More from MPLS.
Minneapolis joins network of 'resilient' cities
The city has been selected for the Rockefeller Foundations "100 Resilient Cities" program, will hire a new "chief resilience officer."
Minneapolis council pledges support for transgender community, advisory group
The council voted unanimously in a committee meeting to establish a permanent advisory group on transgender issues.
Minneapolis City Hall bells will go silent for renovation
Time will fly by silently this summer in downtown Minneapolis, when City Hall's clock tower bells cease chiming during a long-anticipated restoration project.
River neighbors full of ideas for Upper Harbor attractions, developer expertise
First of two open houses solicits ideas for what area residents want in attractions to lure people to the river and developer qualifications
North Side greenway proposal at last gets a road test on Irving Avenue
Three versions of proposed design will be tested on Irving Avenue N.


text:
|Publication number
|Publication type
|Application number
|Publication date
|Jan 23, 1990
|Filing date
|May 31, 1988
|Priority date
|May 31, 1988
|Fee status
|Also published as
|Publication number
|Sven H. Ruetman, Joginder N. Anand
|Original Assignee
|The Dow Chemical Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (7), Referenced by (24), Classifications (17), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
This invention relates to water borne ionic polyurethane-polyureas and is more particularly concerned with improved ionic polyurethane-polyureas whose soft segment polyol component comprises high levels of triols along with the conventional diols.
Stable aqueous dispersions of polyurethane-polyureas containing chemically incorporated anionic or cationic groups have long been known to be useful in various coating applications. The coatings and sizings prepared from the dispersions have excellent chemical resistance, abrasion resistance, toughness, and the like.
D. Dieterich et al. as early as 1970 published one of the first technical reviews on ionic polyurethane-polyurea aqueous dispersions; see Angewante Chemie Intn'l. Ed 9, pp 40 to 50 (1970). This was followed by a comprehensive review by the same author in Progress In Organic Coatings 9 (1981), pp 218 to 340. For the most part, the polymers are prepared from components which are essentially difunctional in both isocyanate and isocyanate-reactive ingredients. This means the polymers are essentially linear, and, organic solvent soluble in their final form. However, cross-linked polyurethane-polyurea aqueous dispersions are known as noted below.
U.S. Pat. No. 3,870,684 discloses aqueous dispersions of polyurethane-polyureas wherein the cross-linking is effected by mixing as a solution in an organic solvent an isocyanate terminated prepolymer having ionic groups with an aqueous solution of an aliphatic polyamine containing a total of at least three primary and/or secondary amine groups of which at least two are primary. These compositions, also known as latexes, have the advantage of being able to form cross-linked polymers as aqueous dispersions while avoiding the prior art problems of the formation of lumps and curds. However, the method of preparation requires organic solvents and the need for highly functional polyamines.
U.S. Pat. No. 4,203,883 discloses cross-linked polyurethane-polyureas closely related to those set forth in U.S. Pat. No. 3,870,684 cited supra. The cross-linking is effected by reacting an isocyanate terminated polyurethane prepolymer containing tertiary amine neutralized carboxylic acid groups with a triamine or mixture of triamine with diamine. Again, the employment of organic solvent is favored at least in the preparation of the prepolymer component.
U.S. Pat. No. 4,408,008 also discloses stable aqueous dispersions of cross-linked urea-urethane polymers wherein the cross-linking is achieved through the use of polyfunctional amine chain extenders with average functionalities of 2.2 to 6. The polymers achieve their aqueous dispersability primarily by having monomer ingredients carrying nonionic hydrophilic ethyleneoxy chains in pendant or lateral configuration. The presence of ionic units in the polymer chains is optional but preferred. The teaching of this patent is very clear in calling for substantially linear prepolymers prior to the cross-linking step. This is spelled out in detail when discussing the polyol components to be used in prepolymer preparation. If the ingredients are to contain any trifunctionality, it is limited to small proportions and then only special cases for slight branching of the prepolymer using an extender such as trimethylolpropane. Average functionality of the prepolymer starting components is stipulated to be below 2.1.
U.S. Pat. No. 4,501,852 discloses stable aqueous dispersions of anionic polyurethane-ureas which can be either linear or cross-linked depending on the functionality of the polyamine extender reacted with the prepolymer. Similarly to U.S. Pat. No. 4,408,008 cited supra, the isocyanate prepolymer is difunctional and limited to starting components of average functionality below 2.1. The novelty in this disclosure stems from the fact that a combination of anionic groups and a small proportions of lateral or terminal hydrophilic ethyleneoxy chains are present in the prepolymer with the neutralizing counterions of the anionic groups being a mixture of volatile and non-volatile cations. The latter, in the form of low boiling tertiary amines, are easily evolved from the final aqueous polymer dispersion when films are being formed. The net result is polyurethane-polyurea coating having improved hydrolytic stability.
Generally speaking, the prior art teachings that the prepolymers in the first stage of preparation be essentially difunctional. Furthermore, the preference for the use of organic solvents throughout the preparation of the aqueous dispersions is also taught. In order to avoid the use of solvent, U.S. Pat. No. 4,108,814 specifically calls for the use of alkali metal or ammonium salts of particular sulfonate containing diols.
It still remains in the art to provide aqueous dispersions of ionic polyurethane-polyurea polymers with the more conventional ionic groups without resorting to the use of organic solvents.
Accordingly, it would be highly beneficial if the organic solvent could be eliminated completely, yet still allow the use of all of the conventional ionic reactants. This elimination of solvent would be even more attractive if it lead either directly or indirectly to better physical properties in the final polyurethane-polyurea polymers.
The present invention is directed to improved stable aqueous dispersions of ionic polyurethane-polyureas prepared by the reaction of (A) an aqueous dispersion of an isocyanate terminated ionic prepolymer with (B) a hydrocarbon polyamine extender said prepolymer having been prepared from (i) an excess of an aliphatic or cycloaliphatic diisocyanate, (ii) an organic diol, and (iii) a difunctional isocyanate-reactive component containing an ionic group or potential ionic group, wherein the improvement consists of said component (ii) comprising a mixture of said diol and an organic triol having a molecular weight of from about 250 to about 6,000.
This invention is also directed to films prepared from the aqueous dispersions of the ionic polyurethane-polyureas set forth above.
The term "hydrocarbon" as used herein with respect to the polyamine extender component means a hydrocarbon residue having from about 2 to about 20 carbon atoms remaining after the replacement of the appropriate number of hydrogen atoms by primary or secondary amine groups; inclusive of said hydrocarbon residue are aliphatic of C2 to C10, cycloaliphatic of C5 to C18, aromatic of C6 to C20, and the like.
The term "aliphatic diisocyanate" means an organic isocyanate containing two aliphatically bound isocyanate groups wherein the aliphatic divalent residue is an alkylene radical having from about 6 to about 12 carbon atoms, inclusive, such as hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, and isomeric forms thereof.
The term "cycloaliphatic diisocyanate" means an organic diisocyanate containing two cycloaliphatically bound isocyanate groups wherein the cycloaliphatic divalent residue contains one or two cycloalkylene radicals each cycloalkylene having from about 5 to about 8 carbon atoms, inclusive, such as cyclopentylene-1,3, 4-methylcyclopentylene-1,3, cyclohexylene-1,3, cyclohexylene-1,4, 2-methylcyclohexylene-1,4, 2,5-dimethylcyclohexylene-1,4, cycloheptylene-1,3, cycloheptylene-1,4, 6-methylcycloheptylene-1,4, cyclooctylene-1,3, cyclooctylene-1,4, cyclooctylene-1,5, and the like; 4,4'-methylenebis(cyclohexylene), 4,4'-isopropylidenebis(cyclohexylene), 4,4'-dicyclohexylene, and the like.
The term "difunctional isocyanate-reactive component" means any organic compound carrying two separate groups each capable of reacting with an isocyanate group because of active hydrogens according to the Zerewitinoff test, such as --OH, --NH2, --SH, --COOH, and the like.
The term "ionic group or potential ionic group" means a group either already in an anionic or cationic form or else, by neutralization with a reagent, readily converted to said anionic or cationic form respectively. Illustrative of such potential anionic groups (and neutralized form) are --COOH(--COO⊖), --SO2 OH(--SO2 0⊖), and ═POOH(═POO⊖); illustrative of such potential cationic groups (and neutralized form) are .tbd.N(.tbd.N--⊕), .tbd.P(.tbd.P--⊕), and ═S(═S--⊕).
Quite unexpectedly, it has been discovered that the replacement of a considerable proportion of the organic diol by an organic triol in the isocyanate terminated prepolymer preparation results, not only in the elimination of organic solvent both in prepolymer and final polymer formation, but also to excellent aqueous dispersion stability of the final ionic polyurethane-polyureas themselves.
Additionally, and even more unexpected, is the discovery that permanent set properties of the films prepared from the dispersions remain relatively constant in spite of the films' increase in Shore A hardness and modulus properties.
The ionic aqueous dispersions of this invention, by virtue of their good film-forming properties are useful in a wide variety of coating applications. The fact that the coatings are transparent and have good tensile properties broadens the applications in which they can be employed. Typically they can be used as sizing in the manufacture of high grade paper, coatings and impregnants for textiles, leather, fibers, and the like. However, the toughness and clarity of the films make them particularly useful as protective coating for other plastic articles made from such materials as polycarbonates, acrylics, and the like. Window glazing, security glass and aircraft canopies are but a few of the uses to which the present films can be applied.
The preparation of the aqueous dispersions of the ionic polyurethane-polyureas is carried out using any of the conventional methods and ingredients known to those skilled in the art except for the novel use of the triol components which will be discussed in detail below. Typical preparative methods are disclosed in the U.S. Pat. Nos. 3,870,684, 4,108,814; 4,203,883; 4,408,008; and 4,501,852 cited supra whose disclosures relative thereto are incorporated herein by reference. Generally speaking, the aqueous dispersions are preferably prepared by a two-stage process wherein an isocyanate-terminated prepolymer (A) is made in the first stage followed by chain-extending or finalizing the polymer formation in the second stage with a hydrocarbon polyamine (B) defined above. The aqueous portion of the dispersion can be introduced before or during the reaction of (B) with (A). In respect of the ionic portions of the polyurethane-polyureas these are preferably incorporated as part of the first stage prepolymer and will be discussed in detail below.
The term "dispersion" as used herein means a two-phase system comprising the ionic polyurethane-polyurea as the dispersed phase in the continuous aqueous phase. It is to be understood that the dispersed phase can be a liquid or a solid. Accordingly, the present products comprehend both emulsions and suspensions.
The diisocyanates (i) which can be employed for the isocyanate terminated prepolymer (A) preparation are defined above. Illustrative but non-limiting of the diisocyanates are 1,6-hexamethylene diisocyanate, 1,7-heptamethylene diisocyanate, 1,8-octamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,11-undecamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the (3-isocyanatopropoxy)-(3-isocyanatopropyl)arylenes such as 1-(3-isocyanatopropoxy)-4-(3-isocyanatopropyl)benzene described in U.S. Pat. No. 4,051,166, 1,4-bis(2-isocyanatoethyl)cyclohexane, and the like; isophorone diisocyanate otherwise identified as 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane; and cycloaliphatic diisocyanates such as methylenebis(cyclohexyl isocyanate) including the 4,4'-isomer, the 2,4'-isomer, and mixtures thereof, and all the geometric isomers thereof including trans/trans, cis/trans, cis/cis and mixtures thereof, cyclohexylene diisocyanates (1,2-; 1,3-; or 1,4-), 1-methyl-2,5-cyclohexylene diisocyanate, 1-methyl-2,4-cyclohexylene diisocyanate, 1-methyl-2,6-cyclohexylene diisocyanate, 4,4'-isopropylidenebis(cyclohexyl isocyanate), 4,4'-diisocyanatodicyclohexyl, 1,4-diisocyanatocycloheptylene, 1,4-diisocyanatocyclooctylene, and the like.
Preferred as a group are the cycloaliphatic diisocyanates and preferred within this group are the methylenebis(cyclohexyl isocyanates) with the 4,4'-isomer being particularly preferred.
The organic diols (ii) can be any of the high molecular weight diols exemplified in the incorporated references above. Preferably, the molecular weight falls in the range of from about 500 to about 6,000, more preferably, from about 1,000 to about 3,000. The term "molecular weight" as used herein means the number average molecular weight as determined by end-group analysis or other colligative property measurement.
Exemplary of the diols which can be employed are: polyether diols, polyester diols, hydroxy-terminated polycarbonates, hydroxy-terminated polybutadienes, hydroxy-terminated polybutadiene-acrylonitrile copolymers, hydroxy-terminated copolymers of dialkyl siloxane and alkylene oxides such as ethylene oxide, propylene oxide and the like, and mixtures in which any of the above polyols are employed as major component (greater than 50% w/w) with difunctional amine-terminated polyethers and amino-terminated polybutadiene-acrylonitrile copolymers.
Illustrative of polyether diols are polyoxyethylene glycols, polyoxypropylene glycols, polyoxybutylene glycols which, optionally, have been capped with ethylene oxide residues, random and block copolymers of ethylene oxide, propylene oxide, and butylene oxide, random and block polymers of tetrahydrofuran and ethylene oxide and or propylene oxide, and products derived from any of the above by reaction with difunctional carboxylic acids or esters derived from said acids in which latter case ester interchange occurs and the esterifying radicals are replaced by polyether polyol radicals. The preferred polyether polyols are random and block copolymers of ethylene and propylene oxide of functionality approximately 2.0 and polytetramethylene glycol polymers.
Illustrative of polyester diols are those prepared by polymerizing ε-caprolactone using an initiator such as ethylene glycol, ethanolamine and the like, and those prepared by esterification of polycarboxylic acids such as phthalic, terephthalic, succinic, glutaric, adipic, azelaic and the like acids with dihydric alcohols such as ethylene glycol, butanediol, cyclohexanedimethanol and the like.
Illustrative of the amine-terminated polyethers are the aliphatic primary diamines structurally derived from polyoxypropylene glycols. Polyether diamines of this type are available from Texaco under the trademark JEFFAMINE.
Illustrative of polycarbonates containing hydroxyl groups are those prepared by reaction of diols such as propane-1,3-diol, butane-1,4-diol, hexan-1,6-diol, 1,9-nonanediol, 2-methyloctane-1,8-diol, diethylene glycol, triethylene glycol, dipropylene glycol and the like with diarylcarbonates such as diphenylcarbonate or with phosgene.
Illustrative of the silicon-containing polyethers are the copolymers of alkylene oxides with dialkylsiloxanes such as dimethylsiloxane and the like; see, for example, U.S. Pat. No. 4,057,595.
Illustrative of the dihydroxy-terminated polybutadiene copolymers are the compounds available under the trade name Poly BD Liquid Resins from Arco Chemical Company. Illustrative of the dihydroxy- and diamine-terminated butadiene/acrylonitrile copolymers are the materials available under the trade name HYCAR hydroxyl-terminated (HT) Liquid Polymers and amine-terminated (AT) Liquid Polymers, respectively.
The most preferred diols comprise the preferred random and block polyether diols and polytetramethylene glycols set forth above otherwise referred to as polyalkyleneoxy diols and with polyethyleneoxy-capped polypropyleneoxy diols being most specifically preferred.
The novelty in the present invention resides in the replacement of a portion of the above diol component with an organic triol having a molecular weight of from about 250 to about 6,000, preferably from about 500 to about 3,000, and most preferably from about 500 to about 2,000. Accordingly, the component (ii) for preparing said isocyanate terminated ionic prepolymer comprises a mixture of at least one diol with at least one triol The proportions in which the triol is to be employed with vary somewhat according to its molecular weight. Branching and eventual cross-linking of the final polymer will be controlled largely by the molecular weight factor. As molecular weight of the triol decreases, then branching in the prepolymer leading to possible cross-linking therein, and, most assuredly, in the final polyurethane polyurea will occur. Accordingly, the ultimate film properties desired will dictate triol molecular weight and the proportions in which to use it. Advantageously, the triol can be present in the mixture in up to about 50 hydroxyl equivalent percent. That is to say, of the total hydroxyl equivalents employed in the prepolymer preparation, up to about 50 percent can be contributed by the triol component. Above the 50 percent level will generally lead to visible gel formations in the aqueous dispersions. Preferably, the polyol mixture (ii) comprises from about 5 to about 50 equivalent percent of said triol and from 95 to 50 percent of said diol. More preferably, the triol falls in a range of from about 10 to about 40 percent with diol being 90 to 60 percent.
The triol can be any of the organic polyols known in the urethane art to be trihydric in functionality and which fall into the molecular weight ranges set forth above. The triols can be identically obtained to those diols described above except for the use of initiators and starting materials leading to trihydroxy functionality. For example, polyether triols are readily available or easily prepared in the form of polyoxyethylene triols, polyoxypropylene triols, polyoxybutylene triols, the latter two optionally capped with ethyleneoxy residues, including random and block copolymers. All of these polyether triols are generically identified as polyalkyleneoxy triols are are prepared by the reaction of the corresponding ethylene, propylene, butylene oxides with trifunctional initiators such as glycerine, trimethylolpropane, and the like; optionally, the triols can be prepared from tetrahydrofuran and a trifunctional starter to yield the corresponding polytetramethyleneoxy triols; polyester triols while more difficult to synthesize with the overall trifunctionality than the polyalkyleneoxy triols above, are nevertheless still useful as triol components; typical trifunctional polyester triols are those prepared from ε-caprolactone with an initiator such as glycerine, trimethylolpropane and the like; further illustrative examples of triols include polycarbonate triols prepared by reaction of triols such as trimethylolpropane or glycerine with diphenylcarbonate or phosgene; and mixtures of any of the above triols as the major component (greater than 50% w/w) with trifunctional amine-terminated polyethers.
A preferred class of triols comprises the polyalkyleneoxy triols, particularly those having a molecular weight of from about 500 to about 3,000. Even more preferred are the polyethyleneoxy-capped polypropyleneoxy triols having a molecular weight from about 500 to about 2,000.
Known difunctional chain extenders such as the aliphatic C2 to C10 glycols as typically exemplified by ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like are not specifically excluded from the present polymers. At the same time, their use is not particularly necessary in the prepolymer (A) preparation unless particularly high hardness is desired in the final films.
The difunctional isocyanate-reactive components (iii) are necessary to provide for the water dispersibility of both the prepolymer and final polyurethane-polyurea as discussed typically in U.S. Pat. No. 3,479,310. Such components contain an ionic group or potential ionic group as defined above and include any of those compounds disclosed in U.S. Pat. No. 4,408,008, particularly column 6, line 63 through column 7, line 57 whose disclosure with respect to these compounds is incorporated herein by reference. Additionally, the U.S. patent disclosures recited in this referenced disclosure including 3,479,310; 3,419,533; 3,412,054; and 4,108,814 are also incorporated herein by reference with respect to the difunctional isocyanate-reactive ionic or potential ionic compounds disclosed.
As noted and defined above, the ionic definition includes both ionic and cationic character. Additionally, the term "neutralize" as used herein for converting potential ionic to ionic groups refers not only to neutralization using true acids and bases but also includes quaternarization, and ternarization. The potential anionic groups typically include carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups which when incorporated into the difunctional isocyanate-reactive component (iii) can be neutralized before, during, or after the prepolymer formation to form the corresponding carboxylate anion, sulfonate anion, and phosphate anion by treatment with such inorganic or organic bases as sodium hydroxide, potassium hydroxide, potassium carbonate, ammonia, tertiary amines such as triethylamine, tripropylamine, tributylamine, and the like. In respect of the potential cationic groups, these typically include tertiary amine, phosphine, and sulfide groups which when incorporated into the difunctional isocyanate-reactive component (iii) can be quaternated or ternated as the case may be by neutralization or quaternarization of the tertiary amine, or reacting the phosphine or sulfide with compounds capable of alkylating the phosphine or sulfide groups. Sometimes it is more convenient to have the precursor phosphine or sulfide groups as a separate reagent with the actual quaternizing or ternarizing moiety in the difunctional component (iii).
The isocyanate-reactive groups themselves as defined above are those having active hydrogen atoms and include hydroxyl, amino, thiol, and carboxylic acid. Preferred of the functional groups are the dihydroxy and diamino compounds with dihydroxy functionality most preferred.
Illustrative but non-limiting of the compounds containing a potential anionic (ionic) group are tartaric acid (mono-, or di-sodium salt), 2,6-dihydroxy benzoic acid (sodium salt, potassium salt, triethylammonium salt), 2,8-dihydroxynaphthoic acid-3 (sodium salt, potassium salt, triethylammonium salt), 3,4-diaminobenzoic acid (sodium salt, potassium salt, triethylammonium salt), 1,7-dihydroxynaphthalenesulfonic acid-3 (sodium salt, potassium salt, triethylammonium salt), 1,8-dihydroxynaphthalenedisulfonic acid-2,4 (sodium salt, potassium salt, triethylammonium salt), 2,4-diaminotoluenesulfonic acid-5 (sodium salt, potassium salt, triethylammonium salt), the sulfonate diols described in U.S. Pat. No. 4,108,814 already incorporated herein, bis(β-hydroxyethyl)phosphinic acid (sodium salt, potassium salt, triethylammonium salt), and the like; illustrative of the compounds containing a potential cationic (ionic) group are methyldiethanolamine (hydrochloride salt, acetic acid salt), N,N-di(2-hydroxypropyl)aniline (hydrochloride salt, acetic acid salt), N-cyclohexyl-N-(3-aminopropyl)propanol-2-amine (hydrochloride salt, acetic acid salt), ethyldiethanolamine (hydrochloride salt, acetic acid salt), glycerol-α-bromohydrin quaternated with tributylamine (ammonium salt), or triethyl phosphine (phosphonium salt), glycerol-α-bromohydrin ternated with dimethyl sulfide (sulfonium salt), and the like.
Preferred for the component (iii) is a class of dihydroxy alkanoic acids described in U.S. Pat. No. 3,412,054 already incorporated herein. When they are neutralized with any of the inorganic or organic bases discussed in the incorporated references and also above, they result in the preferred anionic moieties. Accordingly, the preferred component (iii) is a carboxylic acid containing diol which can be neutralized with an inorganic or organic base to form said ionic group before, during or after said prepolymer formation. The most preferred dihydroxy alkanoic acids are the α, α-dimethylol alkanoic acids having the formula QC(CH2 OH)2 COOH wherein Q is hydrogen or C1 to C8 alkyl (preferred are those acids with C1 to C4). Preferred as the neutralizing agents are the aliphatic C2 to C4 tertiary amines inclusive of triethylamine, tripropylamine, tributylamine, triisopropylamine, and the like, and aqueous or anhydrous ammonia. A most preferred embodiment of the present invention is when the carboxylic acid groups is neutralized with the amine after said prepolymer formation and prior to forming an aqueous dispersion thereof.
The proportions in which component (iii) is to be employed is not particularly critical except to the extent that it be sufficient to result in good dispersion of the prepolymer and final polyurethane-polyurea in water. Advantageously, the component is employed within a range of proportions such that the milliequivalents of ionic groups per 100 grams of prepolymer (A) falls within a range of from about 10 to about 150, preferably about 20 to 100, most preferably about 25 to 75. The equivalent weight of the ionic component is the precursor molecular weight divided by the number of ionic groups. Accordingly, the proportion of (iii) employed divided by its equivalent weight and multiplied by 1,000 provides the ultimate milliequivalents of potential and/or ionic groups present in the total prepolymer weight.
The isocyanate terminated prepolymer (A) as noted above is readily prepared using the conventional procedures already incorporated herein. The excess diisocyanate (i) along with the polyol mixture (ii) and the difunctional isocyanate-reactive component (iii) are brought together in any convenient manner, preferably under the exclusion of moisture prior to the actual formation of aqueous dispersion. This is best achieved by reacting the components under an inert gas such as nitrogen or argon. In a preferred embodiment the isocyanate reactive components of (ii) and (iii) are first thoroughly blended together followed by the excess diisocyanate.
The exact proportion of excess of isocyanate is chosen so that the final polymer properties desired will be obtained. Advantageously, the proportions of (i), (ii) which includes both diol and triol, and (iii) are such that the ratio of isocyanate equivalents to total isocyanate-reactive equivalents in said prepolymer (A) falls in a range of from about 1.1 to about 3, preferably from about 1.2 to 2.
The reaction temperature during prepolymer formation is normally maintained below about 150� C. Generally speaking, the reactants will be heated to a temperature within the range of about 30� C. to about 125� C., preferably about 50� C. to 125� C. In some cases, reaction exotherm will provide heat thereby contributing to these temperature ranges.
Although the use of conventional urethane forming catalysts is not particularly recommended, neither is their use specifically excluded. Generally speaking, catalysts are unnecessary, and, in some cases, can cause the formation of gels when preparing the aqueous dispersions by causing the excess isocyanate to react with the water. This results in reduced stability for the dispersions.
Solvents may be used during the prepolymer formation but one of the benefits of the present invention is eliminating their use. If, for whatever reason, a solvent is to be employed, then any of those recommended in the incorporated references can be employed.
In respect of the neutralization, quaternarization or ternarization step, whatever the case may be, it is preferred to carry it out after the prepolymer has been formed, and, most preferably, before the aqueous dispersion is prepared. The reason for the latter preference is the more facile formation of the dispersion once the ionic groups are present in the prepolymer. It is the hydrophilicity of the ionic groups which give rise to the good aqueous dispersibility of the prepolymer. Therefore, the neutralizing acid, base, alkylating agent, or whatever as required to convert the potential ionic group to its ionic form is added to the rapidly stirred prepolymer in sufficient amount to react with at least about 75 percent, preferably at least about 90 percent of the potential ionic moieties.
The aqueous dispersions are now easily formed simply by mixing the prepolymer with the water, preferably under conditions of rapid stirring or agitation. The concentration of prepolymer in the aqueous dispersion is governed primarily by whatever is expedient in the handling of increased volumes. However, the prepolymer is advantageously present in a concentration of from about 10 percent to about 50 percent by weight based on prepolymer and water. Preferably, its concentration is from about 25 to about 40 percent. These proportions should not be regarded as critically limiting for depending on prepolymer properties and the types of ionic groups involved, concentrations falling outside these ranges can be observed.
It will be understood by those skilled in the art that aqueous dispersions of isocyanate terminated prepolymers are not stable for long periods. Accordingly, the lapse of time between preparation of the prepolymer dispersion and the final polymer forming step should be kept to a minimum. Notably, the prepolymer dispersions in accordance with the present invention enjoy good stability both in regard to their dispersion properties (no separation or settling of solids or liquids) and their lack of reactivity between the isocyanate groups and the water. Stability of the present dispersions may be observed for periods of up to about two hours. However, to ensure full isocyanate concentration the polymer curing step is preferably initiated within about 15 minutes of formation of the prepolymer dispersion.
Completion of the polyurethane-polyurea formation, otherwise known as chain extension is readily accomplished either by mixing the prepolymer dispersion (A) with the chain extender (B) neat or in the form of a solution in an organic solvent or water. Efficient intermixing of the components is highly desirable when dealing with organic dispersions in water. Accordingly, the mixing should be conducted at high stirring speeds using efficient paddles or stirring blades. If the extender is reasonably water soluble, it is preferably that it be so employed as an aqueous solution. The mode or order of mixing is not critical. Generally speaking, it is convenient to add the chain extender solution to the rapidly stirred prepolymer dispersion. However, the reverse mode of addition can be used if desired. Any sequence of addition using aqueous solutions or additional pure water to adjust final dispersion concentration is possible during the prepolymer extension step. In this regard, the weight percent of dispersed polymer can be in any amount deemed appropriate for any particular situation or ultimate application. Conveniently, it can be present in the same percentage proportions set forth above for the dispersed prepolymer.
This chain extension will, for the most part, occur at ambient room temperatures, i.e. 25� C. to 30� C. In some cases, an exotherm may call for actual cooling. Although, the presence of the aqueous dispersant acts as a heat-sink to modify reaction exotherms. The reaction is generally conducted within a temperature range of from about 5� C. to 90� C., preferably from about 20� C. to 60� C. Mixing is continued until the reaction is judged to be complete. The completion is easily determined using conventional analytical procedures for measuring the disappearance of the extender and/or isocyanate groups such as by infrared measurements, gas phase chromatography, gel permeation chromatography, and the like.
The preferred extenders (B) are defined above as the class of hydrocarbon polyamines. The amine groups can be primary or secondary or a mixture of both in the same molecule. Preferably the amine functionality falls within a range of from about 2 to about 4, including average values within this range arising from mixtures of polyamines. Preferred as a class are the hydrocarbon diamines wherein the amine functions are primary.
Illustrative but non-limiting of the polyamines are ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, 1,7-heptylenediamine, 1,8-octylenediamine, 1,9-nonylenediamine, 1,10-decylenediamine, 2,2,4-trimethylhexamethylenediamine-1,6, 2,4,4-trimethylhexamethylenediamine-1,6, diethylene triamine, triethylene tetramine, iminobispropylamine, and the like; 1,2-cyclohexylenediamine, 1,3-cyclohexylenediamine, 1,4-cyclohexylenediamine, 4,4'-isopropylidenebis(cyclohexyl amine), 4,4'-diaminodicyclohexyl, methylenebis(cyclohexylamine) including the 4,4'-isomer, the 2,4'-isomer and mixtures thereof including all their geometric isomers, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, and the like; 1,3-phenylenediamine, 1,4-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, 4,4'-methylenebis(phenyl amine), 2,4'-methylenebis(phenyl amine), 4,4'-diaminobenzidine, 3,3'-diaminobenzidine, polyymethylene polyphenylene amines, and the like.
More preferred as a class of extenders are those falling within the alkylene diamines, most particularly the alkylene diamines of C2 to C8 as exemplified above.
The proportion of amine extender (B) employed is governed by the isocyanate content of the prepolymer component. Generally speaking, the proportions of (B) are such that the ratio of isocyanate equivalents in (A) to amine equivalents in (B) falls in a range of from about 1.25 to about 0.90, and, preferably from about 1.10 to 0.95.
The resulting aqueous dispersions of ionic polyurethane-polyureas in accordance with the present invention can vary from milky to nearly clear in their visual appearance. The dispersions or emulsions are sometimes referred to as latexes. They are characterized by excellent stabilities allowing them to be stored for long periods which vary depending on such factors as ionic content (hydrophilicity), storage temperatures, molecular weights in a soft segments, and the like. Generally speaking, the dispersions can be stored for days and transported within this period without showing any signs of separating or gelling.
The physical properties of the final polymers obtained whether in the form of films, coatings, or even stoving lacquers can vary from those of soft elastomers to harder thermoplastics and all the way to hard thermoset types depending on the polymer components and proportions. Using amine extenders of functionality greater than 2 in combination with prepolymers having the highest isocyanate contents results in the harder thermosets due to the high hard segment content of the polymer and cross-linking. This is particularly true when the soft segments in the prepolymer are derived from the lowest molecular weight polyols. The terms "soft and hard segments" refer to the polymer linkages derived from the diisocyanate component with the high molecular weight polyols (ii) and with the extender (iii) respectively. Reversing all of the above conditions leads to the softer materials.
The polymer dispersions can be modified further by the addition of colorants, antioxidants, UV stabilizers, fillers, fire-retardants and the like.
Various kinds of substrates can be coated with films from these aqueous dispersions. After the aqueous dispersions are brushed, sprayed, poured, applied by dip-coating, doctor-knife, or otherwise applied to a substrate such as woven and non-woven textiles, leather, paper, wood, metals, ceramics, fibers, plastics such as polycarbonates, acrylics, polyamides, polyurethanes, polyesters, polystyrenes, acrylonitrile/butadiene/styrene copolymers, polyethylenes, (high, low and ultralow densities), rubbers including natural and synthetic, and the like, the water is removed by conventional drying methods.
Drying can be carried out either at ambient room temperatures (e.g. 20� C.) or at elevated temperatures, for example, from about 25� C. to about 150� C., optionally under forced-draft or vacuum. This includes the drying of static substrates in ovens such as forced-air and vacuum ovens; or continuously conveying the coated substrates through chambers heated by forced air, high intensity lamps, and the like or under reduced pressures.
In the preparation of free standing films, the techniques particular to this art are readily applied. For example, the aqueous dispersion can be poured into the appropriate mold, or applied by doctor-knife to a metal or glass plate. Thereafter, the water can be removed in stages using a series of different temperatures with optional use of vacuum. Generally speaking, it is preferred to initially remove the major amount (up to 25 percent) of the water under forced air conditions and at low temperatures (e.g. 20� C. to 30� C.). If the film has enough structural integrity at this stage, it can be hung or optionally oriented by placing under tension in the appropriate frame while the remaining water is removed, preferably at an elevated temperature, for example, from about 50� C. to about 150� C. Final conditioning of the film can be completed under controlled conditions of heat and humidity.
The films in accordance with the present invention whether deposited on a substrate or made as free standing films can be prepared in any desired thickness. Typically, the films can have a thickness of from about one mil to about 50 mils.
The excellent properties of the films include good clarity, high gloss, good weather resistance including water repellency, abrasion resistance, and the like. This makes them particularly useful in the manufacture of waterproof clothing, tarpaulin, chip-resistant coatings in automotive applications such as protective coating applied after a car has been painted, as coatings for high grade paper, and the like. The present films provide excellent protective coatings on aircraft acrylic canopies and in ballistic glazing applications.
The above utilities can be achieved without the need for using organic solvents which, for the most part, are required in the prior art coatings. Of even more significance is the fact that the present polymers can be prepared with increasing hardness and stiffness values while at the same time keeping relatively constant permanent set properties. Heretofore, this has not been possible. Accordingly, the present compositions are provided with increased hardness and tensile modulus properties without having to resort to the need of higher hard segment linkages derived from higher diisocyanate concentrations. That is to say, the increase in hardness properties is achieved in the soft segment part of the prepolymer rather than in the hard segment portion. Notably, the present polymers provide another means to alter film properties to higher hardness while still retaining good water dispersibility with no fish-eyes in the final polymers and no objectionable cross-linking.
The following examples describe the manner and process of making and using the invention and set forth the best mode contemplated by the inventors of carrying out the invention but are not be construed as limiting.
The following experiments describe the preparation of five aqueous dispersions of ionic polyurethane-polyureas in accordance with the present invention and the films prepared therefrom (Samples I to V) as well as a comparison 1 aqueous dispersion of an ionic polyurethane-polyurea and its film which are not in accordance with this invention.
A one liter three-necked flask which has been dried in an air oven at 110� C. for at least one hour is equipped with a stirrer, thermometer, and gas inlet tube. To the flask is added 6.8 g (0.1014 eq.) of 2,2-bis(hydroxymethyl)propionic acid, 104.7 g (0.1049 eq.) of a 2,000 molecular weight polypropyleneoxy-polyethyleneoxy capped diol, 1.3 g (0.0057 eq.) of a glycerol based polypropyleneoxy-polyethyleneoxy capped triol of molecular weight of about 684, and 41.5 g (0.3168 eq.) of 4,4'-methylenebis(cyclohexyl isocyanate). The reaction mixture is stirred under nitrogen at about 100� C. for two hours. The mixture is cooled to about 70� C. and 0.5 of octadecyl-3,5-ditertiary butyl-4-hydroxy-hydrocinnamate added to act as an antioxidant stabilizer. After about five minutes of stirring, 4.9 g (0.0485 eq.) of triethylamine is added and stirring continued for about 20 minutes at a reaction solution temperature of about 70� C. This proportion of amine is sufficient to neutralize about 96 mole percent of the carboxylic groups in forming the triethylammonium carboxylate salt of the isocyanate terminated prepolymer which has formed. The prepolymer is a uniform, viscous, and opaque resin at this temperature.
The stirring speed is increased and 350 ml of water is added causing the immediate formation of an emulsion of the prepolymer in the water. After a few minutes of the rapid stirring, 3.0 g (0.0998 eq.) of ethylenediamine dissolved in 50 ml of water is added followed by an additional 50 ml of rinse water to ensure complete transfer of diamine. The emulsion is stirred for about 60 minutes at the ambient temperature. Thus, there is obtained the milky white aqueous dispersion or emulsion of an ionic polyurethane-polyurea sample I in accordance with the present invention wherein the hydroxyl equivalent percent proportions of the diol polyether to the triol polyether are 94.8 percent and 5.2 percent respectively as set forth in Table I below. The emulsion contains 26.5 percent of ionic polyurethane-polyurea and is completely stable with no separation of solids upon storage.
A film is prepared from the dispersion I by syringing a bubble free sample of the emulsion into a mole measuring 3 inches by 3 inches by 1/8 inch. The mold is left in a fume hood for 24 hours whereupon a clear flexible film is removed from the mold and hung in the hood for further drying. After 24 hours, it is placed in an air oven for 12 hours at 75� C. and, then conditioned by storage in an area of constant temperature (20� C.) and constant humidity (50 percent) for at least 24 hours. Thus there is obtained a film I in accordance with the present invention having a thickness of ˜40 mils. The tensile properties and hardness of the film are set forth in Table I.
Samples II through V, both aqueous dispersions and films, are prepared identically to I above with the only exceptions being the changes in the proportions of the polyether diols and triols described above to satisfy the hydroxyl equivalent percentages set forth in Table I. The tensile properties and hardness values of the films are set forth below.
The comparisons emulsion and film are prepared identically to the samples described above except that no triol is employed and the 6.8 g of 2,2-bis(hydroxymethyl)propionic acid is reacted with 100 g (0.1002 eq.) of the above described polyether diol and 40 g (0.3053 eq.) of 4,4'-methylenebis(cyclohexyl isocyanate) to form the prepolymer. Subsequent treatment is the same as previously described to form the emulsion of the final polymer and film. The physical properties of this film are set forth in Table I below.
Notwithstanding the increasing hardness and modulus values of the samples I through V as compared with comparison 1, the permanent set values remain virtually constant within the series. Notably, all of the emulsions of the invention retain complete water dispersibility. No fish-eyes can be observed in the film samples and there is no evidence of objectionable cross-linking in these films.
TABLE I__________________________________________________________________________Sample I II III IV V Comparison 1__________________________________________________________________________Diol/Triol (equiv. %) 94.8/5.2 90/10 80.2/19.8 69.9/30.1 50/50 100/0Physical Propertiesof Films:Tensile Str. (psi) 2425 2712 2425 2500 2600 3067Elongation (%) 826 776 607 449 221 898Tensile Modulus at 280 323 398 536 -- 304300% Elong. (psi)Tangent Modulus (psi) 697 1116 1617 3430 3667 7671 Permanent Set (%) 25 22 25 24 28 25Shore A Hardness 62 68 68 68 82 58__________________________________________________________________________ Footnote 1 Permanent Set: Measures the permanent stretch as percent of permanent increase in a measured length of a sample after it has been stretched until broken in accordance with ASTM D170879; the lower the percentage value the less the permanent set in the stretched sample.
|Cited Patent
|Filing date
|Publication date
|Jun 29, 1972
|Mar 11, 1975
|Bayer Ag
|Preparation of cross-linked particles of polyurethane or polyurea containing ionic groups
|Jun 2, 1975
|Jan 3, 1978
|Ppg Industries, Inc.
|Water-reduced urethane coating compositions
|Mar 14, 1977
|Aug 22, 1978
|Bayer Aktiengesellschaft
|Aqueous polyurethane dispersions from solvent-free prepolymers using sulfonate diols
|Sep 5, 1978
|May 20, 1980
|Textron, Inc.
|Aqueous colloidal dispersions of tertiary amine salts of urea-urethane polymers and method for manufacture
|Jul 24, 1981
|Oct 4, 1983
|Mobay Chemical Corporation
|Stable, colloidal, aqueous dispersions of cross-linked urea-urethane polymers and their method of production
|Jun 20, 1983
|Feb 26, 1985
|Mobay Chemical Corporation
|Stable, aqueous dispersions of polyurethane-ureas
|Feb 1, 1985
|Feb 17, 1987
|Witco Corporation
|Aqueous polyurethane - polyolefin compositions
|Citing Patent
|Filing date
|Publication date
|Aug 3, 1993
|Oct 11, 1994
|H. B. Fuller Licensing & Financing, Inc.
|Anionic water dispersed polyurethane polymer for improved coatings and adhesives
|May 13, 1994
|Mar 28, 1995
|Basf Aktiengesellschaft
|Aqueous polyurethane formulations
|Aug 28, 1992
|Sep 3, 1996
|Bayer Aktiengesellschaft
|Coating compound, a process for its preparation and its use for the production of coatings
|Sep 9, 1994
|Mar 4, 1997
|H. B. Fuller Licensing & Financing, Inc.
|Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
|Jun 7, 1995
|Mar 11, 1997
|H.B. Fuller Licensing & Financing, Inc.
|Aqueous non-gelling, anionic polyurethane dispersions and process for their manufacture
|Mar 31, 1994
|May 13, 1997
|Bayer Aktiengesellschaft
|Coating compositions and their use for the preparation of coatings permeable to water vapor
|Nov 22, 1994
|Dec 30, 1997
|H.B. Fuller Licensing & Financing, Inc.
|Aqueous anionic poly (urethane/urea) dispersions
|Sep 5, 1996
|Jun 23, 1998
|Bayer Aktiengesellschaft
|Anionically modified polyurethane ureas having reduced tackiness for the coating of leather
|Nov 21, 1995
|Feb 16, 1999
|H. B. Fuller Licensing & Financing, Inc.
|Water-based polyurethanes for footwear
|Oct 2, 2003
|May 16, 2006
|Bayer Materialscience Llc
|Polyurethane dispersion (PUD) with improved isopropanol resistance, flexibility and softness
|May 28, 2009
|Oct 8, 2013
|Ube Industries, Ltd.
|Aqueous polyurethane resin dispersion, preparation method of the same, and coating composition containing the same
|Aug 3, 2010
|Sep 23, 2014
|Ube Industries Ltd.
|Aqueous polyurethane resin dispersion and process for preparing the same
|Feb 23, 2010
|Oct 14, 2014
|Ube Industries, Ltd.
|Aqueous polyurethane resin dispersion and process for preparing the same
|Feb 23, 2010
|Dec 16, 2014
|Ube Industries, Ltd.
|Aqueous polyurethane resin dispersion and process for preparing the same
|Jan 21, 2003
|Aug 14, 2003
|Toshio Kondo
|Functional urethane resin film and laminated film by use of the same
|Jul 19, 2001
|Aug 21, 2003
|Toshio Kondo
|Functional urethane resin film and laminated film comprising the film
|Oct 2, 2003
|Oct 21, 2004
|Eduard Mayer
|Polyurethane dispersion (PUD) with improved isopropanol resistance, flexibility and softness
|Jul 24, 2007
|Jan 29, 2009
|Yuliya Berezkin
|Polyurethane dispersions for sealants
|May 28, 2009
|Mar 31, 2011
|Taku Nakamura
|Aqueous polyurethane resin dispersion, preparation method of the same, and coating composition containing the same
|Jun 30, 2009
|Jun 9, 2011
|Taku Nakamura
|Aqueous polyurethane resin dispersion and process for preparing the same
|Jan 25, 1991
|Aug 14, 1991
|BASF Aktiengesellschaft
|Aqueous polyurethane preparations
|Feb 7, 1990
|Nov 27, 1991
|Dow Chemical Co
|Bulk polyurethane ionomers.
|Jul 20, 1992
|Feb 3, 1993
|Bayer Ag
|Use of coatings in the preparation of water vapour permeable coatings
|Sep 17, 1992
|Mar 24, 1993
|SYREMONT S.p.A.
|Aqueous dispersions of fluorinated polyurethanes
|U.S. Classification
|International Classification
|Cooperative Classification
|European Classification
|Nov 13, 1989
Owner name: DOW CHEMICAL COMPANY, THE, MICHIGAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:RUETMAN, SVEN H.;ANAND, JOGINDER N.;REEL/FRAME:005181/0025
Effective date: 19880525
|Apr 22, 1993
|Fee payment
Year of fee payment: 4
|May 1, 1997
|Fee payment
Year of fee payment: 8
|Aug 14, 2001
|Maintenance fee reminder mailed
|Jan 23, 2002
|Lapse for failure to pay maintenance fees
|Mar 26, 2002
|Expired due to failure to pay maintenance fee
Effective date: 20020123


text:
Star Tracks
Stone and costar Nicolas Cage premiere The Croods in Berlin. Plus: Shakira, Kellan Lutz, Kate Upton and more
Credit: Jochen Zick/Startraks
Updated: Friday Feb 15, 2013 | 06:00 AM EST
More from PEOPLE
Latest News!
- Hungry Girl: Grill Up My Healthy Hot Wings For Memorial Day
- Read the Cover Story: Steve Harvey: From Homeless to Having It All
- The Hottest Jewelry Find of the Season? These Ring Cuffs!
- Kim's Kouture Hacks! Kim Kardashian Reveals She Dyed Her Cannes Dress with Tea Bags
- Amber Heard Smiles and Gets Support from a Friend in First Public Outing Since Court Appearance Over Johnny Depp Abuse Allegations