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Centara Blue Marine Resort & Spa Phuket
- Free WiFi and free parking
Main amenities
- 266 guestrooms
- Near the beach
- 2 restaurants
- Full-service spa
- 3 outdoor pools and 2 spa tubs
- Free children's club
- Free shuttle
- Fitness center
- Conference center
- Airport shuttle
- 24-hour front desk
- Air conditioning
What's around
- Patong Beach (1 mi / 1.7 km)
- Bangla Night Street (1.3 mi / 2.1 km)
- Kalim Beach (0.3 mi / 0.4 km)
- Sphinx Theatre (1 mi / 1.6 km)
- Royal Paradise Night Market (1.3 mi / 2 km)
Centara Blue Marine Resort & Spa Phuket
Hotel Info: 800 1205131from S$84
- Premium Deluxe 1 Bedroom Suite
- Superior Room
- Superior Room, Ocean View (Superior Ocean Facing)
- Classic Pool Access
- Premium Deluxe
- Deluxe Room, Ocean View (Deluxe Ocean Facing)
- Deluxe Room
- Deluxe Two Bedroom Family Suite
- Honeymoon Room (Premium Deluxe Honeymoon)
- Premium Deluxe Spa
- Deluxe Villa, 1 Bedroom, Private Pool (Deluxe 1 Bedroom Pool Villa)
- Premium Deluxe Ocean Facing
Recommended hotels
At a glance
Key facts
Hotel size
- This hotel has 266 rooms
- This hotel is arranged over 4 floors
- Check-in time starts at 2 PM
- Check-out time is Noon
Required at check in
- Credit card deposit required
- Government-issued photo ID required
- Minimum check-in age is 15
Travelling with others
- Babysitting/childcare *
- Free children's club
- No pets or service animals allowed
Extra people
- Rollaway beds available, charges may apply*
- Free WiFi in public areas
- Free WiFi in rooms
- Airport shuttle (available on request) *
- Free valet parking
- Free nearby parking
- Free beach shuttle
Nearby Four Star Patong hotels
In the hotel
- Children's club (free)
- Supervised childcare/activities (free)
- 2 restaurants
- Coffee shop/café
- Snack bar/deli
- Room service (during limited hours)
- Barbeque grills
- Free beach shuttle
- Beach towels
- Number of outdoor pools - 3
- Children's pool
- Fitness facilities
- Full-service spa
- Spa treatment room(s)
- Pool umbrellas
- Number of spa tubs - 2
- Steam room
- Sauna
- Arcade/game room
- Billiards or pool table
- Number of meeting rooms - 6
- Conference space
- Meeting rooms
- Conference center
- Computer station
- 24-hour front desk
- Concierge services
- Tours/ticket assistance
- Limo or Town Car service available
- Dry cleaning/laundry service
- Laundry facilities
- Hair salon
- Luggage storage
- Wedding services
- Number of buildings/towers - 8
- Year Built 2004
- Safe-deposit box at front desk
- Designated smoking areas
- Garden
- Library
- Fireplace in lobby
- In-room accessibility
In the room
- In-room climate control (air conditioning)
- Air conditioning
- Minibar
- Coffee/tea maker
- Bathrobes
- Slippers
- Iron/ironing board (on request)
- Blackout drapes/curtains
- Premium bedding
- Pillowtop mattress
- Fireplace
- Balcony
- Private bathroom
- Deep soaking bathtub
- Free toiletries
- Hair dryer
- 29-inch flat-screen TV
- Premium TV channels
- Desk
- Free WiFi
- Refrigerator
- Free bottled water
- Daily housekeeping
- In-room safe
Top Patong hotels
Recently reviewed hotels in Patong
- Rawai Palm Beach ResortFrom
"5th stay here, hotel management has improved, front desk service improved, room and pool standards maintained well. Keep up the good job!"Apr 17, 2016
- Sky Lantern HotelFrom
"It was an amazing stay at Sky Lantern! Located at a quiet area, it was very convenient to travel from the hotel to patong beach. "Apr 17, 2016
- Pimnara Boutique HotelFrom
"Stay for 3 days during songkran, very comfortable, convenient hotel. Location in the middle of shopping mall, beach & restaurant. Every room come with a unique design interiors.…"Apr 16, 2016
- Outrigger Laguna Phuket Beach ResortFrom
"Awesome 3D2N with Outrigger. We took club suite which provides us with breakfast with the choice of 2 of their restaurants, high tea, and a chef's sample with wine/cocktail during…"Apr 13, 2016
Nearby hotels
Special features
Blue Marine Spa has 10 treatment rooms including rooms for couples. Services include massages, facials, body wraps, and body scrubs. A variety of treatment therapies are provided, including aromatherapy, Ayurvedic, and hydrotherapy. The spa is equipped with a sauna and a spa tub.
Children under 15 years old are not allowed in the spa without adult supervision. Guests under 12 years old are not allowed in the spa.
DiningBlue Pacific Restaurant - This poolside restaurant serves breakfast, lunch, and dinner. Guests can order drinks at the bar and enjoy alfresco dining (weather permitting). A children's menu is available. Happy hour is offered.
Tub Tim Thai Restaurant - This poolside restaurant specializes in Thai cuisine and serves lunch and dinner. Guests can enjoy drinks at the bar. Happy hour is offered.
On Site
- Fitness facilities
- Sauna
- Steam room
- Aerobics on site
- Bicycle rentals on site
- Yoga classes/instruction on site
- Ecotours nearby
- Golfing nearby
- Parasailing nearby
- Sailing nearby
- Scooter/moped rentals nearby
- Scuba diving nearby
- Skydiving nearby
- Windsurfing nearby
Centara Blue Marine Resort & Spa Phuket's small print
Also known as
- Blue Marine Phuket Managed Centara
- Centara Blue Marine Resort And Spa Phuket Patong
- Blue Marine Phuket Managed Centara Kathu
- Blue Marine Resort Phuket Managed Centara
- Blue Marine Resort Phuket Managed Centara Kathu
- Centara Blue Marine Resort Phuket
- Centara Blue Marine Resort Phuket Patong
- Centara Blue Marine Phuket Patong
- Centara Blue Marine Phuket
- Blue Marine Hotel Patong
Children under 15 years old are not allowed in the swimming pool, fitness facility, or spa tub without adult supervision.
Children under 15 years old are not allowed in the spa without adult supervision.
Guests under 12 years old are not allowed in the spa.
This property does not have elevators.
For transfers, guests must contact the property 72 hours prior to arrival at the number on the booking confirmation.
Optional extras
Rollaway beds are available for THB 1177 per night
Babysitting/childcare is available for an extra charge
Airport shuttle service is offered for an extra charge
We have included all charges provided to us by this hotel. However, charges can vary, for example, based on length of stay or the room you book.
Is the description of this hotel not correct? Tell us


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TV on DVD: Archer, The Expanse, and War and Peace
Interested in the latest TV on DVD reviews? DVD Talk has you covered! This week's notable entries include:
Archer: Season 6 - returning to some of their covert ops roots in this season, the show is still funny and does a nice job of broadening its characters this time around; The Expanse: Season One - this is a bit unusual for a SyFy original series: not only is it actually sci-fi, but it's quite good at times and shows plenty of promise during this debut season; and War and Peace - shot on location in Russia, and boasting lavish sets and costumes, this six-hour, eight-episode miniseries give a shiny, new interpretation to Tolstoy's classic work.
Want more? Check out all of the TV on DVD reviews in the DVD Talk database.
This Week's Notable Releases: Son of Saul, Krampus, and The Kennedy Films of Robert Drew
Some great discs are being released this week. Check out these new movies:
Son of Saul [review] - the 2016 Oscar winner for Best Foreign Language Film this story of a man risking his life to give a dead young boy a proper Jewish burial in the Auschwitz concentration camp is powerfully undeniable and a stunning movie; and Krampus [review] - Michael Dougherty's film blends fantasy, horror, comedy, and demented visual whimsy in with a dysfunctional family Christmas flick... it is infectiously fun; and The Kennedy Films of Robert Drew & Associates [review] - this collection is a must-own both for history buffs and those interested in the development of documentary film.
Be sure to check out our DVD Talk Review Database for all the latest reviews including an entire section devoted to reviews of DVDs out this week.
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Some great DVD and Blu-ray reviews have been added to the the DVD
Talk Review Database recently including:
Thunderbolt and Lightfoot (Encore Edition) - this movie holds up as an entertaining road trip with great performances from Clint Eastwood, Jeff Bridges, and the supporting cast, while the film's "anything goes" attitude maintains a broad and lasting appeal for new and seasoned fans alike; Only Angels Have Wings - a superb drama about courageous airmail pilots in treacherous terrain and weather conditions over South America, starring Cary Grant, it is one of the all-time great American films, and among director Howard Hawks' best; and Try and Get Me! (The Sound of Fury) - an excellent, virtually unknown film noir-social commentary film from director Cy Endfield.
Visit the DVD Talk Review Database for all the latest reviews including an entire section devoted to reviews of DVDs out this week.
Movies in Theaters: The Jungle Book, Hardcore Henry, and The Huntsman: Winter's War
Check out DVD Talk's latest reviews of movies that are in theatrical release. This week's crop includes:
The Jungle Book [review of the 3D version] - this movie quickly takes shape as an energetic and spellbinding odyssey that shows reverence both to the spirit of Kipling's work and to the vibrancy of Disney's original animated film; Hardcore Henry - a movie that gets its inspiration from first-person shooter video games, you're going to be hard pressed to find anything as fast-paced and as enjoyable as this film; and The Huntsman: Winter's War - yet another massive disappointment for the blockbuster fantasy genre... the pieces to make something worthwhile were present, although they were never quite put together.
Other recent films include: 10 Cloverfield Lane, Deadpool, Zoolander 2, Hail, Caesar!, and Room.
Check out these, and more, in DVDTalk's Theatrical Review section.
TV on DVD: Veep, The Americans, and Silicon Valley
TV on DVD remains very popular with more and more favorites being released. New TV reviews include:
Veep: Season 4 - from beginning to end this season may have been its best yet... and if you have not seen the show at this point you should do yourself a favor and jump in; The Americans Season 3 - the third season continues to move the characters forward both in America and Russia, and the cast and creators continue to turn in excellent work on a show that deserves a wider audience; and Silicon Valley: The Complete Second Season - this second season is even better than the first, with a terrifically engaging, at times tension-filled, tale of corporate intrigue that's fantastically funny throughout.
Want more? Check out all of the TV on DVD reviews in the DVD Talk database.
This Week's Notable Releases: The Holcroft Covenant, The Texas Chainsaw Massacre 2, and The Stuff
This week several great movies are coming out, including a few that shouldn't be missed:
The Holcroft Covenant [review] - unexpectedly terrific, this movie benefits from John Frankenheimer's excellent direction, an outstanding performance by Michael Caine, a clever premise, and some marvelous black humor; and The Texas Chainsaw Massacre 2 [review] - Tobe Hooper's follow-up to his legendary horror classic changes tone dramatically, but offers an entertainingly frenetic mash-up of horror and dark comedy... horror fans will absolutely want to own a copy of Scream Factory's two-disc Collector's Edition Blu-ray; and The Stuff [review] - Larry Cohen's goopy satire of '80s consumerism remains addictively fun even after ringing in its thirtieth anniversary.
Be sure to check out our DVD Talk Review Database for all the latest reviews including an entire section devoted to reviews of DVDs out this week.
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Check out the latest reviews that have been entered into the DVD
Talk Review Database including:
Justice League vs. Teen Titans - this highly recommended DC animated adventure is a horror movie, a teen comedy, a coming-of-age flick, and a superhero spectacle all in one; Outlaw Gangster VIP: The Complete Collection - Arrow Video's boxed set collection does a very fine job of bringing to home video for the first time in English friendly editions six entertaining films that offer up romance, action, violence and intrigue in spades; and Barcelona: Criterion Collection - thanks to Whit Stillman's sharp, witty dialogue and the perfect casting of the lead actors, this film is a buoyant delight
Visit the DVD Talk Review Database for all the latest reviews including an entire section devoted to reviews of DVDs out this week.
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Russia's top health official has claimed that drinking and driving don't mix - even when the drink in question is kefir, a fermented milk beverage containing less than one per cent alcohol.
The comments by Gennady Onishchenko, Russia's chief sanitary inspector, sparked an outburst of criticism and ridicule on Twitter. Dozens of users circulated a picture of a glass of kefir with the caption, "Kefir? NO! I'm driving!"
Officials have scrambling to condemn drunk driving since an intoxicated driver in September killed seven people, including five orphans, after crashing into a bus stop in Moscow. Some lawmakers have proposed life sentences for drivers who cause death while under the influence. One has said drunk driving is a bigger threat than terrorism.
During a hearing of the Public Chamber, a governmental oversight body, on a proposal to raise the minimum blood-alcohol level for drivers, Onishchenko said kefir lovers "should decide - are you going to get behind the wheel, or drink kefir?"
"Here's a guy who loves kefir, poor baby, we've curbed his rights," Onishchenko went on. "But what about when he kills our children and our citizens?"
Getting drunk off kefir is practically impossible.
The comments mark an about-face for Onishchenko, previously a staunch supporter of kefir. During record heat waves in 2010, Onishchenko suggested that traffic policemen in southern Russia drink kefir to stay cool. Last year he suggested Russians choose the healthier option of kefir over sugar-filled, foreign-made soft drinks.
Russia's tolerated blood-alcohol level for drivers is zero, which means people who take certain medications or drink kefir can be found guilty of drunk driving. Critics allege that the law encourages police corruption, and have called for the level to be raised.
About 30,000 Russians die in road accidents each year - about the same as in the European Union, which has three times as many people and six times as many cars. Only 1000 of those are caused by drunk driving, according to official statistics, but given lax police enforcement, the real total is widely believed to be much higher.
Onishchenko is regularly mocked for supposed health concerns that curiously coincide with political disputes. He has issued blanket bans on Georgian wine and mineral water and Ukrainian cheese amid Russian spats with those countries. As the Kremlin issued increasingly anti-American pronouncements this summer, Onishchenko implored Russians not to eat hamburgers, which he said were "not our food."
And as Moscow prepared for unprecedented protests against President Vladimir Putin in December, Onishchenko warned Russians away from taking to the streets for fear of catching cold.
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Category Uniforms
Added September 28, 2013
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All of these guys couldn't wait to be alone together, as each of them took their places in this steamy gay orgy that has to be seen to be believed! You've got five sexy guys here with hard cocks that desperately need to be fucked on, and five guys that would love nothing more than to suck them off once they get out of their hot uniforms. They leave their leather accessories on to make it even kinkier, and after they made sure every dick was as aroused as it could get, they took turns filling up each other's butts. That made the room fill with orgasmic screams, as every guy got a butt to fuck, and every dick shot a hot load of jizz.
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This monster VW Beetle tops our list of the biggest bugs we've ever seen!
Generally, the Volkswagen Beetle is thought of as a fun woman's car, or brings back childhood memories of Herbie. While most people have given this Volkswagen model endearing terms, "cute" probably isn't the adjective the owner of this car was going for when he jacked his VW up with monster tires.
Also in the gallery is a jet power VW Beetle that is, for some astonishing reason, actually street legal! The last Beetle is a mesh cage shaped like a bug.
Stats for Modified VW Bugs
Trending: Older & Warm
Research: 48,148 clicks in 405 w
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By: Bianca Bartz - Published: Jul 30, 2008 • References: blog.makezine


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"The White Storm" crime thriller opens Hong Kong Asian Film Fest
October 28, 2013 - 13:17 AMT
PanARMENIAN.Net - The White Storm, a crime thriller starring three of Hong Kong's most prolific actors, has opened the Hong Kong Asian Film Festival, according to The Hollywood Reporter.
Lau Ching-wan, Louis Koo and Nicholas Cheung star in the action film about a clash between an undercover cop and a drug lord that director Benny Chan called his most defining work to date.
The three actors said at the opening ceremony of the festival that while the movie is filled with explosions and gunfights, some of the more memorable scenes showed the trio at their quietest and most emotional.
"Although the three of us just sit together without moving, I found that scene very hard to shoot, hard to write, hard to act. The result was very heartwarming. I think that was one of the most memorable scenes for me," Lau said.
Cheung said the support of his co-actors was touching, especially after he performed a dangerous stunt jumping off a cliff.
"They both saw me do a really dangerous stunt, so after I jumped and came back, they immediately gave me a beer and a cigarette. ... I felt really touched because they cared and they were worried about me," Cheung said.
The film will be released Nov. 29 in China and Dec. 5 in Hong Kong.
The film festival runs until Nov. 19, when it closes with South Korean director Bong Joon-ho's Snowpiercer, starring Tilda Swinton and Chris Evans.
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Opera brings built-in ad-blocking to its desktop, mobile browsers The company claims that native ad-blocking makes browsing the web even faster than using a third-party ad blocker or add-on.


text:
Clinical and molecular studies in full trisomy 22: Further delineation of the phenotype and review of the literature
Article first published online: 7 JUN 2005
DOI: 10.1002/ajmg.1320560404
Copyright © 1995 Wiley-Liss, Inc., A Wiley Company
American Journal of Medical Genetics
Volume 56, Issue 4, pages 359–365, 8 May 1995
Additional Information
How to Cite
Bacino, C. A., Schreck, R., Fischel-Ghodsian, N., Pepkowitz, S., Prezant, T. R. and Graham, J. M. (1995), Clinical and molecular studies in full trisomy 22: Further delineation of the phenotype and review of the literature. Am. J. Med. Genet., 56: 359–365. doi: 10.1002/ajmg.1320560404
Publication History
- Issue published online: 7 JUN 2005
- Article first published online: 7 JUN 2005
- Manuscript Revised: 26 OCT 1994
- Manuscript Received: 3 MAR 1994
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ContributorsJim Furtado
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Baseball Newsstand
— All the News That's Fit to Link
Monday, April 25, 2016
Founding Rules of 'Base Ball' Sell for $3.26 Million in Auction
Nothing about bat flips though.
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Walt Whitman, Baseball Reporter
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Primer Dugout (and link of the day) 4-25-2016
New York Evening World, April 25, 1916:
Touché. That hits a bit close to home, old-timey people. (I should mention that the "Answers to Queeries" below the linked blurb gave me a chuckle or two.)
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Rays notebook: Sternberg lauds Steinbrenner Field renovations | TBO.com and The Tampa Tribune
I am shocked that an owner of sports team would be in favor of tax dollars being put into the pockets of another owner.
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Orioles notes: Hyun Soo Kim more aggressive at plate; Tyler Wilson to start Thursday - Baltimore Sun
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Jim Furtado Posted: April 25, 2016 at 09:02 AM | 3 comment(s)
Beats: hyun soo kim, orioles
OTP 2016 April 25: Forget politics, baseball season in full gear
We all have our ways of marking the seasons. I know it's spring when in early April I start my morning by skipping The Washington Post front page and going right to the sports section. It's not until I've fully savored the baseball box scores that I resignedly turn to politics.
Bitter Mouse, Space Tyrant Posted: April 25, 2016 at 08:13 AM | 1946 comment(s)
Beats: bryce harper, politics, washington nationals
WaPo - Twins and Nats Combine for 16-innings of Wackiness
It was definitely not the cleanest game ever played, but there were so many uncommon events that this one will be remembered for quite some time.
Bote Man makes baseball fun again Posted: April 25, 2016 at 08:13 AM | 27 comment(s)
Beats: bryce harper, dusty baker, nationals, twins
Arrieta can join these six pitchers who threw two no-hitters in one season
The game was historic before Johnny Vander Meer even threw a pitch. It was the first regular season game played under lights at Ebbets Field. The game was preceded by great fanfare. There was a fife and drum corps that marched on the field, a parade of local politicians and officials of the power company who had installed the lights, which at the time were the most powerful lighting system at any sporting venue. Olympic champion Jesse Owens performed in a series of sprinting competitions that ...Read More...
Wahoo Sam Posted: April 25, 2016 at 08:13 AM | 55 comment(s)
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You won't believe what happened next!
Bote Man makes baseball fun again Posted: April 25, 2016 at 08:13 AM | 18 comment(s)
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AP: Cubs fan says arrest on field after no hitter was 'worth it'
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I never meant to cause you any sorrow
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Saturday, April 23, 2016
Townsend (BLS): No one is buying Derek Jeter's hole-in-one video
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Yankees' Jacoby Ellsbury steals home | MLB.com
It ties the game too.
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Jim Furtado Posted: April 23, 2016 at 07:05 AM | 32 comment(s)
Beats: jacoby ellsbury, steals home, yankees
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Too bad he missed the cutoff man.
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White Sox turn 9-3-2-6-2-5 triple play
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Worst TOOTBLAN ever?
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Beats: fundamentals, rangers, tootblan, white sox
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Beats: nolan arenado, rockies
MLB's replay rule can be challenging: When to challenge? | www.ajc.com
Yes, what we need is more replay. How about we cut the game time down to one hour so we can have two hours of replay and still get the game in under three hours?
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text:
|Publication number
|Publication type
|Application number
|Publication date
|Jul 13, 1999
|Filing date
|Aug 18, 1998
|Priority date
|Jul 2, 1998
|Fee status
|Also published as
|Publication number
|Carlton Edwin Ash
|Original Assignee
|Shell Oil Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (12), Non-Patent Citations (2), Referenced by (4), Classifications (12), Legal Events (4)
|External Links: USPTO, USPTO Assignment, Espacenet
This application claims the benefit of U.S. Provisional Application No. 60,091,569, filed Jul. 2, 1998, the entire disclosure of which is hereby incorporated by reference, now abandoned.
This invention relates to composites of aliphatic alternating polyketones and other polymers such as polyolefins.
Combinations of polymers are commercially important because of their potential to combine valuable attributes of a number of different polymers. Blending polymers can give desirable combinations of attributes such as barrier and cost, chemical resistance and dimensional stability, and toughness and strength. Some examples of applications in which multilayer structures of two or more polymers are widely used include barrier packaging and pipe applications where the barrier properties of one material are combined with the mechanical properties of less expensive materials. Most polymer combinations have poor miscibility resulting in blends that are not a single phase. Nonmiscible polymers frequently do not have enough interaction to generate strong interfacial bonding. This weak interfacial bonding can lead to delamination and loss of properties. Compatibilization of the polymer/polymer interface refers to lowering interfacial tension or improving the physical or chemical interaction of the polymers in combination. It is of critical importance since it leads to the strong interfacial bonds necessary to achieve and maintain the desired properties of the combination. For example, it prevents or reduces the ingress of water and other liquids such as hydrocarbons.
Polymers of carbon monoxide and ethylenically unsaturated hydrocarbons commonly referred to as aliphatic alternating polyketones (hereafter, "polyketones") are now well known. High molecular weight alternating aliphatic polyketones are of considerable interest because they exhibit a good overall set of physical and chemical properties. They have excellent mechanical properties, chemical resistance, and barrier properties which makes them particularly attractive for use in combination with other polymers. This class of polymers is disclosed in numerous U.S. patents assigned to Shell Oil Company as exemplified by U.S. Pat. Nos. 4,880,903 and 5,369,170 which are incorporated herein by reference.
U.S. Pat. No. 5,369,170 to Weinkauf discloses a polymer composition which is a combination of a polyketone polymer, a polymer which is not miscible with the polyketone, and a compatibilizing polymer obtainable by reacting a diamine with a polymer having carboxyl groups. A maleic anhydride graft copolymer reacted with a diamine having two primary amino groups is such a compatibilizer. Graft or copolymerized acid copolymers (e.g., acrylic acid copolymers) also comprise such compatibilizers. Further refinements of this technology are discussed by Ash et. al. in Bonding Aliphatic Polyketones to Incompatible Polyolefin Polymers, Research Disclosures, January 1997, pp. 11,12 (Kenneth Mason Publications).
U.S. Pat. No. 5,637,410 to Bonner et. al. is directed to adhesive blends of polyolefins. The blends are carboxylic acid derivative graft polymers and a low density polyethylene reacted in the presence of a diamine. The preferred graft polymer is a maleic anhydride graft polyethylene. Multilayer structures made of these blends together with polyketones are also described.
The polymer compositions of the U.S. Pat. No. 5,369,170 patent can be produced in the form of a blend obtained by a melt blending process. In this type of process the compatibilizing polymer is thought to be present as a layer between the polyketone and the polymer to which it is bound. Multilayer structures can also be prepared by coextrusion to make such articles as multilayer pipes and multilayer sheets and films. The compatibilizing polymer can also be used as a coating layer for a polyketone object, in which case no second polymer need be present.
The preparation and use of the compositions of the U.S. Pat. Nos. 5,369,170 and 5,637,410 patents is not trouble free. For example, when the compatibilizers comprise maleated polymers, a stoichiometric excess of amine is typically required. Further, when the compatibilizers comprise carboxylic acid groups, as they may under the U.S. Pat. No. 5,369,170 patent, lengthy processing times in the melt can lead to increases in melt viscosity and a tendency to form gels. This can lead to poor melt stability, the formation of bubbles or lumps and an uneven distribution of layers in multilayer structures resulting in the so-called wave pattern in processed polymer. Further, the gels may deteriorate polymer performance by, for example, acting as stress concentrators thereby decreasing impact resistance. Without being bound to theory, it is believed that melt stability problems are caused by crosslinking.
Recently it has been found that improvements to multilayer structures using polyketones can be obtained by employing a compatibilizing polymer which is the reaction product of a particular type of amine and a polymer comprising carboxylic acid groups (i.e., hydroxycarbonyl groups). The amine comprises a primary amino group which is attached to an aliphatic carbon atom which carries at most one hydrogen atom. This affords some measure of steric hindrance to the amine. Compositions made from this combination show a reduced tendency to crosslink in the melt. While the interfacial attraction of the materials used in this combination is acceptable for many applications, further enhancements in adhesion are still desirable for many other applications.
Additional methods and compositions for combining polyketones with different polymers that lessen the propensity towards crosslinking and poor melt stability yet display improved interfacial attractions would enhance the utility of polyketones. This is particularly true in the case of multilayer structures and articles made from them.
The invention is a composition comprising a polyketone, an optional second polymer which is not miscible with the polyketone, and an amine modified hindered acid copolymer.
In one embodiment of the invention, the acid copolymer comprises 0.015-2.04 mole % carboxylic acid groups (based on moles of carbolxylic acid monomer units per total number of moles of monomer units).
In another embodiment of the invention, the acid copolymer comprises 0.34-1.73 mole % carboxylic acid groups.
The invention is also a process for preparing the polymer compositions of this invention which comprises contacting polyketone and, optionally, the second polymer with the amine modified hindered acid copolymer.
In addition, the invention is a kit of parts suitable for producing a composition according to this invention comprising,
(a) a polyketone part,
(b) an optional, second polymer part which is not miscible with the polyketone, and
(c) an amine modified hindered acid copolymer.
The polyketone polymers which are employed in this invention are of an alternating structure and contain substantially one molecule of carbon monoxide for each molecule of ethylenically unsaturated hydrocarbon. The portions of the polymer attributable to CO alternates with those attributable to the ethylenically unsaturated hydrocarbon.
It is possible to employ a number of different ethylenically unsaturated hydrocarbons as monomers within the same polymer but the preferred polyketone polymers are copolymers of carbon monoxide and ethylene or terpolymers of carbon monoxide, ethylene and a second ethylenically unsaturated hydrocarbon of at least 3 carbon atoms, particularly an α-olefin such as propene. Additional monomers can also be used and still come within the scope of polyketone polymers described herein. That is, polyketone polymers can be made from four, five, or more combinations of monomers. Such polyketone polymers are aliphatic in that there is an absence of aromatic groups along the polymer backbone. However, alternating polyketones may have aromatic groups substituted or added to side chains and yet still be considered alternating aliphatic polyketones.
When the preferred polyketone terpolymers are employed, there will be within the terpolymer at least about 2 units incorporating a moiety of ethylene for each unit incorporating a moiety of the second or subsequent hydrocarbon. Preferably, there will be from about 10 units to about 100 units incorporating a moiety of the second hydrocarbon. The polymer chain of the preferred polyketone polymers is therefore represented by the repeating formula
-- --CO--(--CH2 --CH2 --)--!x -- --CO--(--G--)--!y --
where G is the moiety of ethylenically unsaturated hydrocarbon of at least three carbon atoms polymerized through the ethyllenic unsaturation and the ratio of y:x is no more than about 0.5. When copolymers of carbon monoxide and ethylene are employed in the compositions of the invention, there will be no second hydrocarbon present and the copolymers are represented by the above formula wherein y is zero. When y is other than zero, i.e. terpolymers are employed, the --CO--(--CH2 --CH2 --)-- units and the --CO--(--G)-- units are found randomly throughout the polymer chain, and preferred ratios of y:x are from about 0.01 to about 0.1. The precise nature of the end groups does not appear to influence the properties of the polymer to any considerable extent so that the polymers are fairly represented by the formula for the polymer chains as depicted above.
Of particular interest are the polyketone polymers of number average molecular weight from about 1000 to about 200,000, particularly those of number average molecular weight from about 20,000 to about 90,000 as determined by gel permeation chromatography. The physical properties of the polymer will depend in part upon the molecular weight, whether the polymer is a copolymer or a terpolymer, and in the case of terpolymers the nature of the proportion of the second hydrocarbon present. Typical melting points for the polymers are from about 175� C. to about 300� C., more typically from about 210� C. to about 270� C. The polymers have a limiting viscosity number (LVN), measured in m-cresol at 60� C. in a standard capillary viscosity measuring device, of from about 0.5 dl/g to about 10 dl/g, more frequently of from about 0.8 dl/g to about 4 dl/g. The backbone chemistry of aliphatic polyketones precludes chain scission by hydrolysis. As a result, they generally exhibit long term maintenance of their property set in a wide variety of environments.
The production of polyketone polymers is described in U.S. Pat. Nos. 4,808,699 and 4,868,282 to van Broekhoven, et al which issued on Feb. 28, 1989 and Sep. 19, 1989 respectively, and are herein incorporated by reference. U.S. Pat. No. 4,808,699 teaches the production of linear alternating polymers by contacting ethylenically unsaturated compounds and carbon monoxide in the presence of a catalyst comprising a Group VIII metal compound, an anion of a nonhydrohalogenic acid with a pKa less than 6 and a bidentate phosphorous, arsenic or antimony ligand. U.S. Pat. No. 4,868,282 teaches the production of linear alternating terpolymers by contacting carbon monoxide and ethylene in the presence of one or more hydrocarbons having an ethylenically unsaturated group with a similar catalyst.
The optional, second polymer may be an addition polymer or a condensation polymer. Where an addition polymer is used, preferably it is a polymer of one or more olefinically unsaturated compounds (i.e., a compound having carbon-carbon double bonds) polymerized through their olefinic unsaturation (or as a result of a rearrangement of the unsaturation during polymerization); for example, ethene, propene, butene-1, styrene, methyl(meth)acrylate, vinyl acetate or combinations thereof. Preferably the polymer is comprised of C1-10 olefinically unsaturated hydrocarbon monomers; the well known polyolefins such as polyethylene, polypropylene, poly(butene-1) and polystyrene are preferred among this group. High density polyethylene (HDPE), (i.e., having a density greater than 930 kg/m3) is desirable. Low density polyethylene and linear low density polyethylene (i.e., having a density less than 930 kg/m3 are also suitable. Isotactic polypropene is the preferred polypropene. Condensation polymers include, for example, polyamides such as polyamide-6, polyamide-6,6, polyamide-11 and polyamide-12, and poly(phenylene oxide). Another class polymersuseful as the second polymer of this invention are functionalized polymers wherein the functionality is reactive with amine component. Acid copolymers and derivatives thereof such as maleated polypropylene, maleated styrene, and maleated polybutylene are examples of such second polymers.
The weight average molecular weight of the second polymer is in the range of 2,000-1,000,000, preferably 10,000-500,000, as determined by gel permeation chromatography. The crystalline melting point is about 80� to about 300� C., as measured by DSC, or, if the second polymer does not possess a crystalline melting point, its glass transition temperature is about -80 to about 200� C., as measured by DSC.
If the optional second polymer is present, the amine modified polymer preferably has good compatibility with the second polymer. For example, if the second polymer is a polyolefin, it would be preferred that the amine modified polymer is a polyolefin which comprises carboxylic acid groups. On the other hand, if the second polymer is a poly(phenylene-oxide), it would be preferred that the amine modified polymer is a polymer such as a polystyrene having hindered carboxylic acid groups.
The amine modified polymer may be prepared by melt blending an acid copolymer with a suitable amine. The acid copolymer is a copolymer in which at least one of the monomer units used to make the polymer is an ethylenically unsaturated carboxylic acid. The alpha carbon (with respect to the hydroxycarbonyl group) of the acid monomer is bonded to a functional group and is not directly bonded to a hydrogen atom; polymers made of such compositions are referred to herein as hindered acid copolymers and offer significant advantages in adhesion to polyketones when applied as described throughout this specification.
Although monocarboxylic acids are preferred monomers for the acid copolymer, the acid monomer may comprise a polycarboxylic acid such as a dicarboxylic acid or a tricarboxylic acid. The other monomer units of the acid copolymer are preferably olefinically unsaturated hydrocarbons such as one or more of the following: ethene, propene, butene-1, styrene, methyl(meth)acrylate, and vinyl acetate. Random copolymers of ethene or propene and R--CR1 CO2 H, wherein R is a C1-10 olefinically unsaturated hydrocarbon and R1 is a C1-6 alkyl group are the preferred acid copolymers of this inventions with random poly(ethene-methacrylic acid) and random poly(propene-methacrylic) acid being the most preferred acid copolymers (particularly where the optional second polymer comprises polyethylene or polypropylene respectively).
The acid content of the acid copolymer is low. In the preferred embodiment in which the acid copolymer is an ethene-methacrylic acid copolymer, the acid content is, 0.015-2.04 mole % acid. Preferably, the acid content comprises 0.34-1.73 mole % and more preferably, 1.15-1.55 mole %. All references to mole % acid content herein are based on a calculation of the number of moles of the acid monomer relative to the total number of moles of all monomer units forming the polymer. Alternatively, a low molar content of acid (qualifying as low acid copolymer) can be attained by intermixing various quantities of acid copolymer such that the mole % acid content is in accord with the foregoing percentages based on the total acid content for the acid copolymer blend.
The melt flow index of the hindered acid copolymer is 0.1-35.0 g/10 min (based on ASTM D1238). Melt flow indices of 0.5-7 are preferred with 1-4 being most preferred.
The weight average molecular of the acid copolymer is 2000-1,000,000 as determined by gel permeation chromatography. The crystalline melting point of the acid copolymer is 80-300� C. (as measured by DSC) with 80-220� C. being preferred. If the acid copolymer does not have a crystalline melting point, its glass transition temperature is -80 to 200� C. (as measured by DSC). These parameters are preferably met through the use of poly(ethene-methacrylic acid) available from DuPont as "NUCREL" acid copolymers and having an acid content of about 4% wt and a melt flow index of about 3-7.
The amine component of the amine modified hindered acid copolymer has at least two amine functional groups and is of the form NH2 --R--NH2 wherein R comprises C4-24 substituted or unsubstituted aliphatic, cycloaliphatic, or aromatic groups or combinations thereof and may contain hetero atoms such as S, N, and O. Depending upon the composition of R, more than two amino groups may be present in the amine of this invention. It is most preferred that the amine component is an unhindered primary diamine. For the purposes of this specification, an unhindered amine component is of the form above wherein the carbon atoms to which each amine group is attached carries two hydrogen atoms. A few examples of suitable amines are 4,9-dioxadiamino-1,12-dodecane; 1,4-diaminobutane; 1,10-diaminodecane; 4,4'-diaminodiphenyl ether; 1,12-diaminododecane; 1,7-diaminoheptane; 1,6-diaminohexane; 1,3-diamino-2-hydroxypropane; 2,3-diaminonapthalene; 1,8-diaminooctane; 1,5-diaminopentane; 1,3-diaminopropane; 1,3-diamino-2-propanol; and 1,4-diamino-2-butanone. It is possible to use the amine in a wholly or partly neutralized form, i.e. as a salt of an acid. One or more amines can be used in combination. Additionally, the amine component can be a reagent which produces an amine of the type described above upon further chemical reaction such as hydrolysis. For example, imine reagents which produce amines upon contact with water can also be used to prepare the amine modified acid copolymers used in this invention.
An effective amount of amine is used to achieve the desired level of adhesion. The quantity of amine is preferably low. While a stoichiometric excess of acid copolymer can be used it is a particular advantage of this invention that as little as 0.01% mole amine/mole of acid (in the acid copolymer) can be used with good effect in some applications. One of ordinary skill in the art will recognize applications in which greater amounts of adhesion are required and will increase the relative proportion of amine accordingly. However, maximum adhesion is generally attained through the addition of no more than a stoichiometric quantity of amine.
The amine modified polymer of this invention may be made by melt blending the acid copolymer with the amine by any suitable means, for example via extruder or Brabender mixer. Suitable temperatures for melt blending are above 100� C., typically above 120� C., but generally below 300� C. A preferred temperature range is 150-220� C. If desirable, the preparation of the amine modified polymer may be effected simultaneously with a melt processing step which is carried out when preparing the composition of this invention as set forth below. It is also possible to perform the reaction between the amine and the third polymer by heating the reactants dissolved in a suitable solvent, for example, p-xylene, diethyleneglycol dimethylether and triethylene glycol dimethylether.
The polymer compositions of this inventions can be obtained by contacting the polyketone and (optionally) the second polymer with the amine modified polymer. Reaction of the polyketone with the amine modified polymer typically requires temperatures above 100� C. but generally below 300� C.
In one embodiment, the polymer composition of this invention is in the form of a blend in which the amine modified polymer acts as a compatabilizer. Such blends can be made by any melt blending process which affects an intimate blending of the components of the composition. Such processes are well known to those of ordinary skill in the art and include, for example, extrusion and combination in a Brabender mixer. The ratio of polyketone to the second polymer may vary within a broad range, for example between 5/95 and 95/5. Preferably, the range is between 10/90 and 90/10. A range between 20/80 and 80/20 is more preferred. The quantity of the amine modified polymer will generally relate to the quantity of the polyketone or of the second polymer if used as the minor component. Generally, it will comprise about 1-40% wt (based on weight of the minor component) with 2-20% wt being preferred.
In the preferred embodiment of this invention the polymer composition is in the form of a multilayer structure, in which the polyketone forms a first layer, the second polymer forms a second layer, and both layers are bonded together by an intermediate layer of amine modified polymer functioning as an adhesive layer. Compositions having four or more layers may also be formed with additional intermediate layers.
Such multilayer structures can be made, for example, by extruding a melt of the amine modified polymer in between the first and second layers which may be heated, e.g., at a temperature above 100� C. but below 270� C. simultaneously or in a later stage, thus effecting interfacial bonding. Other methods such as compression molding and co-injection molding can also be used. The most preferred method of making multilayer structures is a coextrusion process in which a melt of the amine modified polymer is extruded between a melt of polyketone and a melt of the second polymer. In such a coextrusion process, the three melts are brought together in a suitable multilayer manifold prior to exiting the die. The manifold is kept at a temperature of at least 150� C., preferably at least 180� C. but, generally less than 300� C. The most preferred range is 200-280� C. In the manifold the temperature is generally the highest of the extrusion temperatures. The total residence time in the manifold can vary from less than one minute to more than ten minutes. It is preferred that polymer having similar melt viscosities at the prevailing conditions be used. Making more extensive multilayer structures will require more streams of polymer melts be guided into the multilayer manifold. For example, a composite can be made from a layer of polyethylene followed by a layer of amine modified acid copolymer, followed by a layer of polyketone regrind, followed by a layer of amine modified acid copolymer, followed polyethylene regrind. Such composites improve the economics of multilayer constructions by using regrind layers but also permit the manufacturer to recognize the advantages of the properties of polyolefins together with those of polyketones.
The multilalyer structures may be processed further, for example, through regrind, by bending (e.g., tubes, pipes), by stretching (e.g., of sheet to form film) or by thermoforming or blow molding (e.g., to form a container).
In the multilayer structures of this invention, the thickness of the first and second layer will depend on application driven requirements. For example, the thickness may range from 5-5000 μm, for example, in a film or sheet application, to 0.1-100 mm in tubing and pipe applications. The thickness of the intermediate layer will frequently range from 5-1000 μm.
In another embodiment of this invention, no second layer is present. For example, the amine modified polymer can be applied directly to a polyketone layer (or vice versa) to be used as a coating. This can be done in any form in which either polymer may take. For example, tubes, pipe, and sheet can all be coated in this way.
In yet another embodiment of this invention, a multilayer structure is formed in which the amine modified poliymer is used as an adhesive between a layer of polyketone and a layer of another material which is not a thermoplastic polymer, for example glass, metal (such as aluminum or copper), or a thermosetting resin (such as a phenol-formaldehyde or epoxy resin). The considerations and conditions described above wherein a second polymer is used apply to the embodiments in which no second polymer is used. Additionally, successive applications of powder coatings of polyketone and aminated acid copolymer can also be used to adhere the combination to the surface of a substrate using well known powder coating techniques.
The polyketone, second polymer, and amine modified polymer may contain additives such as reinforcing fillers, non-reinforcing fillers, stabilizers, extenders, lubricants, pigments, plasticizers, and other polymeric materials to improve or otherwise alter its properties.
The compositions of this invention display excellent adhesion and an absence of gels, bubbles, or lumps. They also exhibit excellent performance properties such as impact resistance, chemical resistance and barrier properties. Multilayer structures can be formed with a good thickness of the various layers and do not show delamination in the presence of water or hydrocarbons.
The parts of the kit of parts suitable for producing the polymer compositions according to this invention may comprise any of the polymers in any suitable form. For example, liquids, powders, crumbs, and nibs are all suitable for this purpose.
The invention is further described by the following nonlimiting examples.
A terpolymer of carbon monoxide, ethene, and propene as produced in the presence of a catalyst composition formed from palladium acetate, the anion of triflouroacetatic acid and 1,3-bis(diphenylphosphino)propane. The melting point of the linear terpolymer was 220� C. and it had a limiting viscosity number (LVN) of 1.75 measured at 60� C. in m-cresol.
Various combinations of modified acid copolymers were coextruded with polyketones of Example 1 to form multilayer structures. The outerlayer was a HDPE commercially available from Petrothene as "LM60070" polyethylene. Acid Copolymer 1 is a random poly(ethene-methacrylic acid) copolymer having about 3.11 mole % acid content and a melt flow index of 3 and is commercially available from Du Pont as "NUCREL 903" polymer. Acid Copolymer 2 is a random poly(ethene-methacrylic acid) copolymer having about 1.34 mole % acid content and a melt flow index of 7 and is commercially available from Du Pont as "NUCREL 407" polymer. Acid Copolymer 3 is a random poly(ethene-methacrylic acid) copolymer having about 1.34 mole % acid content and a melt flow index of 3 produced by Du Pont. Acid Copolymer 4 is a randoom poly(ethene-acrylic acid) having an acid content of about 1.19 mole % and a melt flow index of 11 commercially available from Dow Chemical Co. as "PRIMACORE 3150" polymer. Amine A is 4,9-dioxadiamino-dodecane commercially available from BASF as "DODA" amine. Amine B is bis(4-aminocyclohexyl)methane commercially available as "AMICURE PACM" amine from Air Products. The polyketone (PK) comprised the inner layer.
The coextrusion was conducted using three single screw extruders (2�38 mm extruders and a 25 mm extruder) and a multilayer manifold and tubing die supplied by Geneca. A tubing of nominal outer diameter of 7.5-8.0 mm was produced with layer thicknesses of about 18 mil, 3-4 mil, and 16 mil for HDPE, tielayer, PK, respectively.
The polyketone was processed at a melt temperature between 240� C. and 260� C. The amine modified acid copolymer (as a tielayer) was processed through the 25 mm extruder at 160� C. except in Example 3 where it was processed at 200� C. The HDPE was processed at a melt temperature of 200-210� C. The three streams were processed through the die head at about 260� C.
A T-peel test was then conducted on the coextruded tubing. In this test, the tubing was sliced open longitudinally. The two main layers were separated on one end slightly by hand to produce two end tabs capable of being placed in an tensile tester. An Instron Model 1123 tensile tester was then used to determine the stress necessary to completely separate the layers at 90� to one another. The test was carried out at 23� C. with a crosshead speed of 127 mm/min. The T-peel adhesion is reported in units of force per unit width of the specimen.
Failure of the material under consideration was characterized as cohesive or adhesive by observation during the T-peel test. Cohesive failure occurs when the tielayer matrix itself is yielded and/or torn upon application of sufficient force. It indicates good interfacial adhesion between the tielayer(s) and the other polymers to which it is bound. Adhesive failure occurs when the tielayer simply separates from one or more other polymer layers to which it is bound during the course of the test. It indicates that the interfacial bond between tielayer and other polymer layers is lower than the overall tensile strength of the tielayer. The most desirable combination is high adhesion-cohesive failure, high adhesion, and a low rate of viscosity rise (preferably below about 75%). Materials which display adhesive failure may be acceptable provided that they display good adhesion and a low viscosity rise.
Viscosity rise was measured using a Kayeness capillary rheometer heated to 240� C. The sample was introduced and the apparent viscosities determined at a shear rate of 100 s-1. The percent viscosity rise was determined by comparing the viscosity at 25 minutes (unless otherwise indicated) to that at 3 minutes. A high rate of viscosity rise indicates a rapid rate of crosslinking.
Results are provided in the following Table.
______________________________________ % Viscosity Adhesion RiseEx. Acid Amine pli Type (240� C.,No. Copolymer (wt %) (N/mm) Failure 25 min)______________________________________ 2* 1 A (0.25%) 7.6 Cohesive 100 (10 min) 3* 1 A (0.25%) † -- --4 1 B (0.5%) 2.91 Adhesive 695 2 B (0.5%) 1.46 Adhesive 46 2 A (0.25%) 3.00 Adhesive 257 2 A (0.50%) 3.00 Cohesive 388 2 A (1.00%) 1.76 Cohesive9 3 A (0.25%) 5.06 Adhesive 2810 3 A (0.50%) 6.76 Cohesive 4011* 4 A (0.25%) † † 900 (15 min)______________________________________ *Comparative, not according to the invention. †Excessive crosslinking on extrusion, composite not functional.
Comparing examples 2 and 3 with examples 4-10, it can be seen that while the composites made with high acid content amine modified polymers can display good adhesion, their melt stability is an order of magnitude less than that of the materials made according to the invention. That is, they tend to crosslink in the melt. Example 11 shows instability in the melt when an unhindered acid is used in the tielayer.
Examples 4 and 5 show that a low acid content amine-modified polymer having a relatively low MW (compared to those of examples 6-10) and a hindered amine promote adhesion and improve melt stability. In example 6, low acid content/low quantity unhindered amine modified polymers are seen to promote adhesion without undue losses in melt stability. This situation is further improved with the increase in the quantity of amine used in Example 7. Example 8 shows that further increases in amine quantity (doubling that of Example 7) do not necessarily contribute to adhesion. Example 10 shows that a low acid content, higher molecular weight hindered acid polymer modified with unhindered amine most effectively increases adhesion without sacrifice to melt stability. Example 9 shows the same effect (to a lessened degree) obtained with a lower quantity of amine.
An amine modified polymer was prepared as follows. A random copolymer of ethene and methacrylic acid having an acid content of about 3.11 mole % (commercially available from DuPont as "NUCREL 903") was fed through a feed hopper to a 25 mm twin screw extruder. The feed rate of the random copolymer was 15 kg/h. 4,9-dioxa-1,12-diaminododecane (commercially available from BASF) was fed through the same feed hopper simultaneously at a rate of 38 g/h. The amine was used in a quantity of 0.023 mole/mole methacrylic acid present in the copolymer. The screw speed was 250 rpm. The barrel and the die were heated such that the melt temperature was 180� C. The melt was obtained in the form of a strand which was cooled in a water bath and granulated.
Multilayer pipes of polyketone/amine modified polymer/high density polyethene were produced in a coextrusion line as follows.
A commercial size coextrusion line comprised a 25 mm single screw main extruder equipped with a mulilayer manifold with a die suitable for producing pipe, two 20 mm single screw side extruders and a suitable haul-off/cooling unit. The polyketone of example 1 was fed to the main extruder, which was operated with a screw speed of 24 rpm. The amine modified polymer of Example 12 (3.11 mole % acid) above was fed to the first side extruder, which was operated with a screw speed of 20 rpm. A low density polyethylene (commercially available from Montell as "Grade 25-020FA") was fed to the second side extruder, which was operated with a screw speed of 98 rpm. The extruder barrels and further equipment in contact with the polymer melts were heated such that the polymer melts adopted a temperature of 240� C. in the multilayer manifold and die. The line speed was 0.7 m/min.
The adhesion between the layers of pipes was good. However, after 15 minutes of the coextrusion run, inspection of the inner surface of the pipes revealed the appearance of gels and that the pipes had serious irregularities in the thickness of the layers.
|Cited Patent
|Filing date
|Publication date
|Mar 24, 1987
|Feb 28, 1989
|Shell Oil Company
|Process for preparing polymers of carbon monoxide and ethylene under specified pressures
|Jun 8, 1988
|Mar 28, 1989
|Shell Oil Company
|Polymer blend of carbon monoxide/olefin copolymer and a polyacetal polymer
|May 5, 1988
|Sep 19, 1989
|Shell Oil Company
|Polyketone preparation from regulated quotient mixture of olefins
|Aug 5, 1988
|Nov 14, 1989
|Shell Oil Company
|Polyketone from carbon monoxide and mixture of olefins
|May 24, 1988
|Sep 4, 1990
|Shell Oil Company
|Polyketone polymer blend
|Oct 31, 1989
|Aug 27, 1991
|Shell Oil Company
|Blends of linear alternating polyketones, polyamides and olefin-carboxylic acid copolymers
|Jul 20, 1989
|Nov 12, 1991
|Shell Oil Company
|Blends of polyketones and carboxylated, hydrogenated block copolymers
|Nov 19, 1990
|May 11, 1993
|Shell Oil Company
|Polyketone polymer blends
|May 8, 1992
|Aug 3, 1993
|Shell Oil Company
|Multi-layer structures containing polyketone polymers
|May 8, 1992
|Apr 5, 1994
|Shell Oil Company
|Coextruded laminates containing polyketone polymers
|Dec 13, 1993
|Nov 29, 1994
|Shell Oil Company
|Composite systems of polyketone and aminated, modified polyolefins
|Sep 28, 1994
|Jun 10, 1997
|Bp Chemicals Limited
|Adhesive blends
|Bonding Aliphatic Polyketones to Incompatible Polyolefin Polymers, Research Disclosures, Jan. 1997, pp. 11 12.
|Bonding Aliphatic Polyketones to Incompatible Polyolefin Polymers, Research Disclosures, Jan. 1997, pp. 11-12.
|Citing Patent
|Filing date
|Publication date
|Jan 24, 2000
|Nov 14, 2000
|Freudenberg-Nok General Parnership
|Compatibilized blends of polyketones and polyolefins
|Jul 23, 2008
|Dec 25, 2008
|Rauwendaal Chris J
|Method of cooling material using an extruder screw configured for improved heat transfer
|Jun 7, 2002
|Dec 12, 2002
|Dupont Canada Inc.
|Low melt flow index, amine-modified polyolefins having superior processability and adhesion to ethylene/carbon monoxide copolymers
|Jun 7, 2002
|Feb 20, 2003
|Du Pont Canada
|Low melt flow index, amine-modified polyolefins having superior processability and adhesion to ethylene/carbon monoxide copolymers
|U.S. Classification
|358/1.15, 525/379, 528/392, 525/539, 528/220, 525/471
|International Classification
|Cooperative Classification
|European Classification
|Apr 19, 1999
Owner name: SHELL OIL COMPANY, TEXAS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ASH, CARLTON EDWIN;REEL/FRAME:009902/0917
Effective date: 19980722
|Jan 29, 2003
|Maintenance fee reminder mailed
|Jul 14, 2003
|Lapse for failure to pay maintenance fees
|Sep 9, 2003
|Expired due to failure to pay maintenance fee
Effective date: 20030713


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Harold D. Stolovitch
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In this "three-act webcast" Harold Stolovich, co-author of the best-selling Telling Ain't Training, presents practical methods for learning and performance professionals to avoid wasting valuable dollars and time in training, and improve learning, retention, and ROI. Th...
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July 06, 2011
Jack Wolf
Watch & Learn Webcasts
Sponsored By: Taleo
Whether you are a department of 100 or just one, if you are tasked with improving the performance of your managers, supervisors, and executives, attend this session to gather numerous proven techniques, strategies, exercises, and methodologies that you can successfully ...
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June 15, 2011
Rita Mehegan Smith
Watch & Learn Webcasts
Sponsored By: John Maxwell Co.
Is your learning viewed as a vital strategic tool or a cyclical expense? How would your senior executives respond to that question? Their response will directly reflect the strength of alignment you have with your business. As a result of the recent recession, businesse...
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February 09, 2011
Elliott Masie
Watch & Learn Webcasts
Sponsored By: GoToTraining
Today's learners are acquiring knowledge differently, and organizations are leveraging learning, training, and knowledge assets in new and diverse ways. As the pace of business continues to accelerate and work teams become more geographically dispersed, learning is evol...
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James Gonzalo Medina, 40, allegedly told FBI informant he wanted to bomb synagogue 'for the glory of Allah.'02:00 03.05.16 | 0 comments
What people are asking Israel to do is not just quit gambling in the middle of the winning streak, but to turn over much of his winnings to charity. What are the chances of that happening? For those that said ZERO, you are correct. Israel will bow to American pressure and engage in peace fakery. This has gone on before and has always satisfied the Americans. It will continue to satisfy the Americans.