text: tag:blogger.com,1999:blog-242178852015-10-06T20:53:57.899-04:00Citrine's Blog - Lip gloss, lipstick and all that good stuff...Citrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-3973348899201934722015-10-05T22:15:00.000-04:002015-10-05T22:15:01.025-04:00Maybelline Color Sensational Creamy Matte in Mesmerizing Magenta Back in Spring when I saw Lena's review on Chanel Rouge Allure La Romanesque , I became momentarily infatuated with the idea of matte magenta/deep plum lipstick. I couldn't justify buying a high end lipstick, especially one that I mostly likely not going to reach for very often. I decided to head back to the trusted Maybelline, who made (and discontinued!) several of my favorite lipsticksCitrinehttp://firstname.lastname@example.com:blogger.com,1999:blog-24217885.post-65172870775217267252015-10-04T11:45:00.000-04:002015-10-04T11:45:00.053-04:00Dior Mystic Metallic Eyeshadow Palette - Bonne Etoile Before you go "Whoa! What's with all the palettes?" Let me tell you that this is a palette I won 2 years ago from the Makeup Museum blog anniversary giveaway. After keeping it next to my bed (and taking a look at it once a while) for 1.5 years, I finally decided to just dig in. I am pretty sure the MM Curator keeps a pristine copy kept somewhere for you to admire in an upcoming exhibition. Citrinehttp://firstname.lastname@example.com:blogger.com,1999:blog-24217885.post-16903474519238653212015-10-03T15:25:00.000-04:002015-10-03T15:25:00.126-04:00Wet n Wild We're the Wild Cats Limited Edition for Fall 2015 I wonder if Wet n Wild hired someone new, because I really like their limited editions (and their punny names)! The one for Fall 2015 is called We're the Wild Cats (appeared right after their 40% off sale last week, which means they will be probably gone before the next one). There are four shades of liquid eyeliner - Black, purple, cobalt and bronzey brown Four limited Color Citrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-50380568999317525892015-10-02T17:30:00.000-04:002015-10-02T17:30:01.250-04:00Nivea Limited Tins, Burt's Bees Mint Cocoa, Ardell, Sally Hansen and More A collective spy cam for the newish sightings. Limited Edition Nivea Creme tins - They are actually really cute this time? I think I will pick up a few since they are so affordable (back in the dog days, I was able to get a bunch of these for free thanks to CVS red coupon machine...Now there isn't that many good promotion any more). I stopped by TJ-Maxx to look ...craps to buy. Look at Citrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-14771997442147486722015-10-02T17:05:00.000-04:002015-10-02T17:05:25.210-04:00Sinful Colors Glitz and Garlands Holiday 2015 Collection Spotted at Rite Aid - Sinful Colors Glitz and Garlands I never keep track of Sinful Colors' releases but the rose gold kind of looks new So does the chunky red-green hexagonal glitter Citrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-8547236475805232182015-10-02T15:15:00.000-04:002015-10-03T14:45:01.888-04:00Bonita Forget Me Not, Gel On and Snowman Nail Polish Spotted at Rite Aid - Bonita Forget Me Not Golden Girl, Tinman's Brew, Mo' Money Do the Flamingo, You're My Lobster and Forget Me Not Updated Oct 3rd - Spotted the Gel On Display in another Rite Aid Random red, green on the left, Purple Craze, Feeling Lucky One and Only ( I think), Tech Savvy, Hollywood High Rise and Bleau (what is that?) Bar Holiday Helpers minis Citrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-63711825657886947092015-10-01T22:00:00.000-04:002015-10-01T22:02:16.450-04:00Jurlique Skin Balancing Face Oil Upon the arrival of fall, the humidity finally dropped so much that my face is in the Sahara mode again (time to load on oils, most and hydrating serum). Anyway, Jurlique is spamming my mailbox about their sale again (15 off 50 with code FALL15)so this review would be somewhere timely. I first discovered Jurlique Skin Balancing Face Oil when I was still in Texas (about to move up north). Citrinehttp://firstname.lastname@example.com:blogger.com,1999:blog-24217885.post-81877869575524808882015-09-30T21:15:00.000-04:002015-10-01T10:30:48.317-04:00Visee Glossy Rich Eyes in PU-4 I normally keep the (lengthy) palette reviews for the weekend but here is a mid-week special since it's the last day of the month...I have been going crazy with the palettes lately so I am trying to play them through (catching up the rate of buying). Visee Glossy Rich Eyes (released in fall 2013) is probably the most popular Japanese drugstore eyeshadow releases of recent years, consider Citrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-60653118042236848472015-09-29T19:05:00.000-04:002015-09-29T19:08:24.438-04:00Maquillage Essence Glamorous Rouge Neo in PK 323 Maquillage Essence Glamorous Rouge PK-323 was a cart-filler from my Rakuten haul(I was buying a palette and a lip brush and felt like I needed to even out the ems shipping). When the range first got released in 2011, it was almost thirty bucks (with the exchange rate and markup at the time) and now it's around 18. So no buyers guilt! See? I am trying not to buy high end lippie when I have so Citrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-50170346108974115822015-09-28T19:35:00.000-04:002015-09-28T19:35:05.247-04:00Maybelline BabySkin & Super Stay 24HR Spotted at Rite Aid - Maybelline Baby Skin Instant Cheek Flush (cream blush that's not retractable and shaped like dome). Super Stay 24 Color in Limited Edition (I totally thought these got discontinued). Citrinehttp://firstname.lastname@example.com:blogger.com,1999:blog-24217885.post-87496046177986730342015-09-28T13:30:00.000-04:002015-09-28T13:30:01.516-04:00L'Oreal Chateau Royale by Colour Riche Spotted at Rite Aid - Chateau Royale nail color by L'Oreal Colour Riche Vineyard Blush, Wine Spritzer, High Spirit, Pinot Purple Wicked Wine, Sangria Splash, Pass the Vino Citrinehttp://firstname.lastname@example.com:blogger.com,1999:blog-24217885.post-85921495062935072642015-09-24T22:00:00.000-04:002015-09-24T22:00:01.328-04:00Majolica Majorca Majolook Illuminator Eyeshadow BE700 Majolica Majorca is a brand that always grabbed my eye balls with their seasonal releases. Not only I dig the brand's whimsical, ornate and girly "Majo" (enchantress) brand image. They always come up with interesting theme for each of their seasonal collections. Quality(for product and packaging) is usually quite good, as with Shiseido brands in general. BE700 is one of the two limited Citrinehttp://firstname.lastname@example.com:blogger.com,1999:blog-24217885.post-37189403202524565212015-09-23T22:00:00.000-04:002015-09-23T22:00:01.938-04:00Fresh Tinted Sugar Lip Treatment in Honey, Petal, Tulip, Rose and Berry Since my Rose Extreme just became unusable straight out of the tube(still have some left if I dig with a lip brush). It was time to crack open the Sugar Addict Mini Lip collection (five half sized minis for 36 dollars/doesn't take a maths major to figure out it was a good deal), which I got almost four months back. The set contains Berry, Tulip, Rose(can't get that accent to appear now on Citrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-53436552990877800482015-09-21T13:05:00.000-04:002015-09-21T13:05:12.137-04:00Butter London Cream Blush in Piccadilly Circus Another budget find from TJ-Maxx (at 4 bucks!) - Butter London Cream Blush normally retails for around 20 dollars and can be found in ULTA (which I no longer live closed to). The blush comes with a shiny square compact with round edges, which doesn't take much space and is easy for storage. To illustrate the mirror shine. I was having too much fun hiding in that corner of bush (how else amCitrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-70548326186858000422015-09-18T08:45:00.000-04:002015-09-18T09:24:32.323-04:00Shiseido Luminizing Satin Eye Color Trio in Bouquet I am on a Japanese eye palette binge lately and after dropping a few bombs here and there, I think maybe it was time to look around and shop local. Sometime, you forget that Shiseido is a Japanese brand when it's so widely available in the US. Shiseido's Satin Luminizing Eye Trio is an extensive range of eyeshadow palettes that I found a little hard to bite into: The color combos are Citrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-27190016684381475742015-09-17T06:00:00.000-04:002015-09-17T06:00:02.596-04:00Lipstick Queen Butterfly Ball - Sigh Finally getting to the last item in the Introductory Kit - Lipstick Queen Butterfly Ball is a range of semi-sheer lipstick that flashes teal. The tube is a metal with rubberized coating (same as Saint formula), it has an inner sleeve inside the lid (no scratching) and it hasn't turn sticky yet. So far most of the Lipstick Queen are unscented but this smells a little like mechanical grease.Citrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-12812914703661440262015-09-16T06:00:00.000-04:002015-09-16T06:00:03.597-04:00Lavshuca Happy Playing Cheek PK-3 Since Lavschuca is getting discontinued according credible source (Rouge Deluxe), I guess I should just finish up this (another) overdue review. The Happy Playing Cheek is a small pan of firmly pressed powder blush in a cute compact. There is no mirror, no useless brush and the clear window lets you to see what's inside (and collect a few while not getting confused which shade is which). ICitrinehttp://firstname.lastname@example.com:blogger.com,1999:blog-24217885.post-70743426453679453462015-09-15T19:35:00.002-04:002015-09-15T19:35:53.537-04:00Sinful Colors Dressed to Kill, Sinful Shine and Phantom Fright Spotted at Rite Aid - Sinful Colors Dressed to Kill Halloween Collection Nothing looks new here Maybe that chunky copper glitter is? Sinful Shine Gel Tech color with a top coat Glow in the Dark polish from Phantom Frights Pumpkin Glitter Cllose up of the glitter (the pink ones looks like it could work on Valentine's) Citrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-65494818430933214482015-09-15T18:45:00.000-04:002015-09-15T18:45:00.143-04:00MUA Brush Cleansing Balm, Covergirl, Lip Smacker and Asian Skincare in Marshalls Spotted at CVS, UA brushes and a cleansing balm (I guess it's a waxy/oily formula to dissolve cream product in synthetic brushes, should be disastrous with natural hair). It's 11.5 bucks with a 2 dollar coupon availabe New balm from Lip Smacker New outlast longwear lipstick by Covergirl From Marshalls - They have My Beauty Diary masks (lol at that "calling the white with the blackCitrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-71834459773526164352015-09-14T19:55:00.002-04:002015-09-14T19:55:50.473-04:00Majolica Majorca and Canmake Eyelash Curlers Lash curlers are items that both lasts for a long while(don't expire like makeup) and eventually need replacements (as the spring action wears off). I don't feel bad hoarding them a bit, as I get to "use them up" at my own pace. I got two last year while trying to find my favorite so here is a quick run down for both of them. The Majolica Majorca curler was a freebie with a set (came with Citrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-85389055080428147792015-09-13T20:00:00.000-04:002015-09-13T21:21:02.625-04:00Laura Geller Color Drenched Lip Gloss in Berry Crush Laura Geller has never been a brand that I give much thoughts to (well, that applies to the majority of the non-drugstore brands in US)but when I saw a berry set at Marshalls for 15 bucks. I kind of had to grabbed it...I am currently working that problem, the problem of hoarding craps I don't normally buy, just because they are cheap. The Color Drenched Lip Gloss is 1/2 of that set (The Citrinehttp://firstname.lastname@example.com:blogger.com,1999:blog-24217885.post-19971172187734102152015-09-12T07:00:00.000-04:002015-09-12T14:10:44.245-04:00Lunasol Vivid Clear Eyes in Pink Beige Collection After buying mainly eyeshadow singles (and only use one shade at a time) for so many years. I had been contemplating on a neutral palette, since my then-go to (Maybelline Strut it Suede and Sunbaked Neutral) were a little too smoked-out for everyday wear. I wanted something a little more refined and knew I wanted to start with Lunasol. Not only the brand is known as the granddaddy of Citrinehttp://firstname.lastname@example.com:blogger.com,1999:blog-24217885.post-80066371924528474802015-09-11T18:25:00.000-04:002015-09-11T18:25:23.449-04:00Revlon Fiery Temptress Fall 2015 Color Collection The long awaited Revlon Fall 2015 Collection, Fiery Temptress is here and it's kind of meh. Mante Balm in Fiery (sold out so I want it =_=) , Fierce, Passionate and Enchanting. Photoready Kajal eyeliner pencil in Matte Expresso Nail colors in Untamed, Uninhibited and Blush in Peach Glow Photoready Eyeshadow palette in Rustic. Citrinehttp://firstname.lastname@example.com:blogger.com,1999:blog-24217885.post-62788972023520978172015-09-11T14:10:00.000-04:002015-09-11T14:10:00.843-04:00Essie Summer Sunset, Lip Smacker Coke and Phantom Fright Halloween Spotted at Rite Aid - Essie Summer Sunset collection Lip Smacker Coke flavored balm Phantom Fright Halloween Collection I kind of want to try the red lip gloss (since it's just 2 bucks) Nail color, body paint and lip gloss pot. Citrinehttp://email@example.com:blogger.com,1999:blog-24217885.post-18426716089577400812015-09-10T23:20:00.000-04:002015-09-10T23:20:00.892-04:00Milani Blossomtime Rose Powder Blush Quick review (because I don't have much to say about blushers). Milani released three limited rose powder blush this summer, I picked one up as it was affordable and… limited thus highly desirable. The three shades all happen to be shimmery so they should also apply better. To this day, I have yet to see a wonderfully executed drugstore matte, be it lipstick or eyeshadow. The Rose Citrinehttp://firstname.lastname@example.com


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Koi RestaurantNovember 2, 2011Sushi • Las Vegas, United States
Ask about the bottle specials - best deals in town!
Ask about the bottle specials - best deals in town!
Monday is Local's Night! Open bar from 10:30-12 and NO COVER all night for my locals!!
No power? Wet cardboard and stolen electricity make a great refrigerator.
Edit: Open Bar for Locals 10:30-Midnight! $100 bottle specials!
$20 open bar for ladies EVERY NIGHT!!! Monday is Local's Appreciation Night - No Cover and Open Bar for locals 10:

subset: commoncrawl


text:
Who won the first Democratic debate?
BROKEN ARROW, Okla. — Police in Oklahoma say they have turned to social media posts for clues about the motive of a teenager accused in the stabbing deaths of his parents and three siblings during a late-night attack that left bodies strewn through the family's home.
BROKEN ARROW, Okla. - Oklahoma police responding to a 911 call in which no one spoke found a gruesome scene at a suburban Tulsa home - five members of a family dead or dying from stabbing and a sixth wounded but alive near the front door.
TULSA, Okla. — Authorities say one person is dead and multiple others are injured after tornadoes hit Oklahoma and Arkansas.
OKEMAH, Okla. — A man accused of killing two girls along a rural Oklahoma road in 2008, but who wasn't arrested until after being questioned in his fiancée's death three years later, pleaded guilty in both cases Thursday.
TULSA, Okla. - A federal judge on Tuesday struck down Oklahoma's gay marriage ban, ruling that it violates the U.S. Constitution. U.S. District Judge Terrence Kern handed down the ruling in a lawsuit filed by two same-sex couples.
TULSA, Okla. - Gunfire that left five people injured at a traditional Hmong New Year's festival rattled a peaceful, tight-knit east Tulsa community, where some feared Sunday the rampage could deter others from attending upcoming cultural celebrations.
When Woody Guthrie's dilapidated boyhood home was ordered torn down in the late 1970s, the demolition reflected the strained relationship between conservative Oklahoma and the native son famous for his folk singing and progressive politics.
TULSA, Okla. - Hundreds of patients of an Oklahoma oral surgeon accused of unsanitary practices showed up at a health clinic Saturday, looking to find out whether they were exposed to hepatitis or the virus that causes AIDS.
TULSA, Okla. (AP) - Hundreds of patients of an Oklahoma oral surgeon accused of unsanitary practices showed up at a health clinic Saturday, looking to find out whether they were exposed to hepatitis or the virus that causes AIDS.
TULSA, Okla. — About 150 to 200 patients of a Tulsa oral surgeon accused of unsanitary practices queued outside a health clinic Saturday, hoping to discover whether they had been exposed to hepatitis or the virus that causes AIDS.
Letters began going out Friday to 7,000 patients who had seen Dr. W. Scott Harrington during the past six years, warning them that poor hygiene at his clinics created a public health hazard. The one-page letter said how and where to seek treatment but couldn't explain why Harrington's allegedly unsafe practices went on for so long.
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text:
I am working on PHP and database MySQL. I have two tables in SQL Server 2005 and I want to move them into MySQL.
These two tables contain fields with Unique Identifier and MySQL doesn't have a Unique Identifier data type. So I am not able to convert it into MySQL.
Please help me to solve this problem.


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Music instruments keyboard
Upright Piano YP48
Professional upright 48 " Ebony Polished Mahogany Brown Satin Bubinga Yellow Satin Rosewood Yellow Satin Cherry Special Satin Young Chang uses More detailed
Casio CTK 3200 Keyboard
Brand: Casio. Description: The Casio CTK-3200 - High tone quality and versatile functions to help you play your best! All b More detailed
Casio Privia Digital Piano PX410R
Brand: Digital. Description: • 32-note polyphony (maximum) More detailed
Yamaha U2G Upright Piano
Brand: Yamaha. Description: Specification: Size:127(H) x More detailed
Keyboard, Casio CTK-230
Brand: Casio. Description: Casio's NEW entry level 49 note keyboard. 100 tones, 50 built-in songs, LCD display, 2 speakers, More detailed
Create lead and sellers will contact you
For last 30 days 25925 leads received the offers from the companies


text:
2012-12-16 Sweet Baby Jesus! By: Mike Webb
Greeley Vineyard
The Church in the City
1015 9th Ave Greeley, Colorado
Senior Pastor: Mike Webb
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text:
Dr. Kenrich works in Scottsdale, AZ and 2 other locations and specializes in Podiatric Medicine. Dr. Kenrich is affiliated with Mayo Clinic Hospital.
Podiatric Medicine
Medical School: Not Available
*This physician has multiple office locations. See Office Information for details.
9817 N 95th St Ste 115
Scottsdale, AZ 85258
9331 E Hillery Way
Scottsdale, AZ 85260
10250 N 92nd St Ste 114
Scottsdale, AZ 85258
9070 E Desert Cove Ave Ste 104B
Scottsdale, AZ 85260
10789 N 90th St Ste 103
Scottsdale, AZ 85260


text:
'Fantastic Beasts' Lands Ron Perlman as a Goblin
Ron Perlman has joined the growing cast of Warner Bros.' 'Harry Potter' prequel 'Fantastic Beasts and Where to Find Them'.
Ron Perlman has joined the growing cast of Warner Bros.' 'Harry Potter' prequel 'Fantastic Beasts and Where to Find Them'.
The 'Power Rangers' movie launches an official Instagram account to announce the first official cast member.
Ellen Page is in talks to headline a remake of the 1990 thriller 'Flatliners', about a group of Med students who meddle with the afterlife.
Gemma Chan has joined the cast of 'Fantastic Beasts and Where to Find Them', alongside Jon Voight and Carmen Ejogo, as production continues.
'John Wick' director David Leitch has signed on to direct 'The Coldest City', which has Charlize Theron attached to star.
Joseph Naufahu has been cast for a multiple-episode arc in Season 6 of 'Game of Thrones'.
A new report claims that there are two female lead roles for 'Star Wars 8', with Gugu Mbatha-Raw revealed as one of the contenders.
Jeremy Irons has signed on to play Marion Cotillard's father, while Brendan Gleeson plays Michael Fassbender's father in 'Assassin's Creed'.
Matthew Vaughn has signed on to direct 'I Am Pilgrim', MGM's new thriller about a spy who comes out of retirement to assist an odd investigation.
The villains continue to rise in 'Gotham' Season 2 as yet another iconic DC Comics villain is added to the popular Fox series.
'Barbie' producer Laurie MacDonald thinks the movie's independent spirit will appeal to feminists.
'Mr. Robot' star Stephanie Corneliussen has signed on to play a character from DC Comics in 'Legends of Tomorrow'.
Mila Kunis and Rob Zombie will both executive produce the new Starz' TV series 'Trapped', centering on a family who is attacked by a cult.
Liam Neeson has signed on to star as a businessman who gets caught up in a conspiracy in the new action-thriller 'The Commuter'.
Tracy Morgan is in talks to star in 'Fist Fight', which would mark his first role since being severely injured in a 2014 car crash.
Kristen Bell signs on to join her husband Dax Shepard in Warner Bros.' comedy remake 'CHiPs' in an unspecified role.
Warner Bros. signs a new distribution deal with Chinese Media Capital for a new slate of Chinese-language movies.
Phillip Iscove is bringing H.G. Wells' book 'The Island of Dr. Moreau' to CBS.
Original 'Ghostbusters' star Ernie Hudson will join Bill Murray and Dan Aykroyd in the all-female reboot arriving in 2016.
Keanu Reeves is in talks to star as an American race car driver in 'Rally Car', which is compared to 'Cannonball Run' set in China.
Amanda Seyfried has landed a 'major role' on Showtime's 'Twin Peaks' revival, described as a brand new character.
Iain Glen, Shawn Roberts, Ruby Rose, Eoin Macken and William Levy have all come aboard the sequel 'Resident Evil: The Final Chapter'.
Megan Fox will appear in a multi-episode guest arc on Season 5 of Fox's 'New Girl' as Zooey Deschanel takes maternity leave.
Originally conceived as a sequel to cult crime thriller 'Layer Cake', 'Viva La Madness' will now be an episodic TV series.
Originally conceived as a sequel to cult crime thriller 'Layer Cake', 'Viva La Madness' will now be an episodic TV series.


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Andrea Leigh Model
BedrichSetlik-retoucherRetoucher Male Ãstà nad Labem, Ãstecký, Czech Republic My MM URL: http://www.modelmayhem.com/shapramseyretouch
Mayhem # 1423698
About MeHi all,
I am from Czech republic and work as retoucher for a long time. (Especially body skin retouch) Working for lot of models, photographers and everybody else :-)))
My motto is "satisfaction for both of us" ;-)
Feel free to contact me!! Projects or individual images, both is possible.
I am here as a model too, so check out both of my ports ;-)
Paypal prefered.
Andrea Leigh Model
Sarah Olivia Model
Elsa Day Model
Ashley Wilke Model
Kristin Ways Model
Erika Nicole Model
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text:
See: http://onlinepsychologydegrees.org/100-best-blogs-for-psychology-students/
Social Psychology Eye
Compass Journals
- Issue Information September 28, 2015
- Spatial Imaginaries Research in Geography: Synergies, Tensions, and New Directions September 28, 2015
- Innovation Policy for Grand Challenges. An Economic Geography Perspective September 28, 2015
- Participatory Action Research: Coproduction, Governance and Care September 28, 2015
- The Feminisation of Mining September 28, 2015
Top Posts
- Why do we join groups?
- Does isolation reduce violent behavior among psychiatric inpatients?
- Confirmation Bias, Satire, and Stephen Colbert
- Truck driver... no wait a professor! Can glasses really change impressions of you?
- Ostracism and School Shootings: What's the Connection?
- Political Ideology is Alive and Well
- Is love blind? Positive illusions in romantic relationships
- Banksy vs. the 'viewer's maxim'
- Featured Journals
- It's Complicated: The Realm of On & Off Relationships
Twitter Updates
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Published April 29, 2015
(SportsNetwork.com) - Heading into the 2014-15 season the two favorites to win the Western Conference title were the Chicago Blackhawks and Los Angeles Kings.
However, a year after beating Chicago in the conference finals and winning its second Stanley Cup in three seasons, the Kings failed to make the postseason altogether. That left the Blackhawks as the heavy favorite to win the West and potentially claim their third Cup in six seasons.
Chicago began its 2015 playoff run with a six-game victory over the Nashville Predators. It wasn't a dominating performance by any means and it could dissuade some people from picking the Blackhawks to win it all.
The Blackhawks didn't earn many style points in downing the Predators. In the end, the 2010 and '13 Cup champions were able to fight through bad starts and shaky goaltending to advance past the first round for a third straight year.
The bad news was Chicago allowed Nashville to score 21 times through six games. The good news: only 10 of those goals came after the first period. The Blackhawks and Predators were tied at 10-10 in scoring over the second and third periods, but the big difference was Chicago won both times the teams played beyond regulation.
Head coach Joel Quenneville will go with Corey Crawford over Scott Darling in net to start the second round. Crawford struggled mightily as the No. 1 option to begin the series with Nashville, but he later bailed out Darling in Game 6, stopping all 13 shots to pick up the round-clinching victory.
Crawford has the edge in playoff experience after anchoring Chicago's Cup run in 2013, but he gave up nine goals on just 60 shots in the opening round. Darling, meanwhile, posted a 2.21 goals against average and .936 save percentage against Nashville despite yielding three goals on nine shots before getting yanked from Game 6.
To be fair, Chicago's problems in Round 1 extended beyond the crease. The club's defensemen, particularly depth guys like Johnny Oduya and Michal Rozsival, who combined for a minus-six rating, struggled to limit Nashville's chances in the offensive zone.
Making up for the defensive lapses, however, were Duncan Keith and Brent Seabrook, who paced the blue line with seven and four points, respectively. Keith averaged over 32 minutes of ice time per game and finished with two goals and five assists.
Oduya, Seabrook and Niklas Hjalmarsson each logged over 25 minutes of ice time per game versus the Predators. Meanwhile, 40-year-old defenseman Kimmo Timonen was used for only 10 minutes, 22 seconds on average.
Chicago's star forwards clearly were its strength against the Preds. Captain and top centerman Jonathan Toews led the team with eight points on three goals and five assists, while speedy winger Patrick Kane had two goals and five helpers.
Kane had missed the final 21 games of the regular season with a shoulder injury, but made his return for the playoff opener and seemed no worse for wear. The 2013 Conn Smythe winner has amassed 98 points (39G, 59A) over 99 career playoff games.
Patrick Sharp added three goals and two assists in the opening round, while Marian Hossa provided five helpers. Hossa hasn't scored a goal in 12 straight games dating back to the regular season and is mired in an 18-game playoff goal-scoring drought.
Brandon Saad recorded two goals for the Blackhawks to follow up his best regular season as an NHLer with a solid showing in the first round. The 22- year-old recorded career bests in both goals (23) and assists (29) while playing in all 82 games in 2014-15.
In addition to the star players, Chicago boasts tremendous all-around depth up front. Additional forwards like Bryan Bickell, Brad Richards, Andrew Shaw, Antoine Vermette and Kris Versteeg allow Quenneville to roll with four lines and give the opposing defense all it can handle.
Despite all its scoring depth, the Blackhawks have struggled on the power play. They were ranked 20th in the league with a success rate of 17.6 percent during the regular season, and against Nashville they scored three times on 19 chances with the man advantage (15.8 percent).
REGULAR SEASON RECORD: 46-28-8 (1st Wild Card)
2015 PLAYOFFS: Defeated St. Louis 4-2 in conference quarterfinals
For a second straight spring, the Minnesota Wild found themselves matched up with the Central Division champions in the opening round of the playoffs. Just like in 2014, the Wild showed the division title guaranteed nothing in the postseason.
The Wild ousted the Colorado Avalanche last season before losing in six games to the Blackhawks in the conference quarterfinals. This time around, Minnesota beat St. Louis in six games to earn a second-round rematch with Chicago and the upcoming series will mark the third straight season with a playoff series between the Blackhawks and Wild.
One difference for Minnesota in 2015 is the situation in net. The Wild faced Chicago last year with Ilya Bryzgalov between the pipes, but expect to be in much better shape this spring thanks to the mid-season acquisition of Devan Dubnyk.
The often shaky Bryzgalov actually performed admirably in last season's series, but Dubnyk enters this matchup with a chance to be a real difference- maker for the Wild.
Dubnyk resurrected Minnesota's playoff hopes after coming over from Arizona in a trade on Jan. 14. He went 27-9-2 with a 1.78 GAA, .936 save percentage and five shutouts over 39 games to help the Wild nab their fourth straight playoff berth. The 28-year-old wasn't quiet as good in the opening round against the Blues, but ended his first career playoff series with a .913 save percentage and 2.32 GAA while recording one shutout.
Darcy Kuemper is the No. 2 option in net, but head coach Mike Yeo is hoping he won't need him.
The Wild offense, and the power play in particular, helped Dubnyk out tremendously in Round 1. Minnesota averaged 2.83 goals per game against the Blues while scoring on one-third (4-of-12) of its chances with the man advantage.
It should come as no surprise that Zach Parise led the scoring attack in the opening round, pacing the Wild with seven points on three goals and four assists. Parise also was the team's leading scorer in the regular season with 62 points and a team-best 33 goals.
Parise plays the left wing on the top line alongside centerman Mikael Granlund and right winger Jason Pominville. Granlund tied Parise for the team with four assists in the opening round and also scored once. Pominville, meanwhile, was second on the team with five points on two goals and three helpers.
In the first round, Nino Niederreiter was the club's most dangerous forward outside of the top-line guys. The Swiss winger brings both size and speed to the table and he was able to match Parise with three goals in the opening round.
The Wild would like to get more production from winger Thomas Vanek, who only had two assists in six games against the Blues. The Austrian veteran posted 21 goals in 2014-15, but has failed to score a goal in 10 consecutive games dating back to the regular season.
Marco Scandella had a productive first-round series from the back end, leading the defense with a pair of goals. He also added an assist and sported a club- leading rating of plus-five. Jared Spurgeon also contributed three points (1G, 2A) from a blue-line position.
Yeo's most reliable all-around defensive pairing is still the partnership of Ryan Suter and Jonas Brodin, who were the top two minute-eaters for the club despite combining for just one assist against the Blues.
Suter logged 26:05 of ice time per game in Round 1, which was down from 29:03 in the regular season. Brodin logged 22:30 of action per tilt against the Blues.
Jordan Leopold and promising young Mathew Dumba will likely serve as the third pairing.
Minnesota had a solid showing on the penalty kill in Round 1, killing off 9- of-11 St. Louis power plays. Parise also recorded a short-handed goal to give the Wild an early lead in the series-clinching Game 6 victory.
A year before losing in six games to the Blackhawks in the 2014 conference semis, the Wild lost 4-1 to Chicago in the opening round. With Dubnyk in the crease, Minnesota is hoping the third time is a charm when it comes to pulling off an upset over its Central Division rivals.
Dubnyk certainly gave Chicago fits in his two meetings against the Blackhawks since moving to Minnesota. The Blackhawks won the first three games against the Wild in 2014-15, but then only scored one goal against Dubnyk in losing the final two tilts of the season series.
Chicago was blanked by Dubnyk in a 3-0 road loss on Feb. 3 and only managed to get one of its 33 shots by the goaltender in a 2-1 setback on April 7 in the Windy City. Dubnyk recorded a .983 save percentage over those two outings.
Crawford put up solid numbers against the Wild this season, going 2-2-0 with a 2.02 GAA and .948 save percentage. In light of Crawford's struggles in the first round, we could see Darling at some point in this series, but the rookie netminder has never faced Minnesota.
The Wild are hoping Dubnyk is the guy who can get them over the hump against Chicago. However, Parise also needs to perform at a higher level in this series than he did in the previous two playoff meetings against the Blackhawks. He has five points (2G, 3A) in 11 postseason tilts against Chicago and had two assists in four regular-season meetings in 2014-15.
Mikko Koivu led Minnesota with four points on a goal and three assists in this season's series, while Jason Zucker and Granlund potted three and two goals, respectively.
Kane torched Minnesota for eight points (2G, 6A) in four games this season. He has nine points on three goals and six helpers over 11 career postseason outings against the Wild.
Toews added six points (1G, 5A) in five games against the Wild in 2014-15, while Bickell had four goals and an assist.
The tough series against the Predators knocked Chicago down a peg and Quenneville's club doesn't have that air of invincibility around it at the moment.
Still, betting against a team like the Blackhawks because of one down series doesn't seem like a smart move. This will be a much closer battle than the previous two playoff meetings between these clubs, but in the end, Chicago should have enough firepower to move past the Wild.
Sports Network predicted outcome: Blackhawks in 7


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Went with the wife and kids, ordered drinks but couldn't get as far as ordering food. The servers outfits were diturbingly reminiscent of a halloween "slutty schoolgirl" outfit, and I came there to have dinner with my wife and 3 young teenagers. Nope. Not to mention the fact the girls looked too young to even be attempting wearing them.
Ask me about the food, I couldn't tell you. Won't be going back unless I read an article somewhere about how they changed the server attire.
Kelli's Grill & Wings
Serving Nesconset
235 Smithtown Blvd
Nesconset, NY 11767-2425
Main (631) 656-6087
Latest Reviews of Kelli's Grill & Wings
#1 Dec 15, 2012
#2 Dec 16, 2012
Ok I will be checking that place out thanks for the review!!!!
#3 Feb 19, 2013
The wings are fantastic, meaty and the hot sauce is zesty with excellent flavor not painful. The restaurant is very casual with the waitresses dressed in tank tops and very short skirts, not a plus or a minus. The atmosphere is relaxed with sports on the many easily viewed flat screen tvs. They also feature a complimentary endless salad bowl at the tables. How can you go wrong with that? I'm going to go back and try other menu items. The restaurant is very clean with spotless restrooms.
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|Número de publicación
|Tipo de publicación
|Número de solicitud
|Fecha de publicación
|12 Jul 1983
|Fecha de presentación
|10 Nov 1981
|Fecha de prioridad
|18 Nov 1980
|También publicado como
|Número de publicación
|Paul A. Holmes, Frank M. Willmouth, Alan B. Newton
|Cesionario original
|Imperial Chemical Industries Plc
|Exportar cita
|BiBTeX, EndNote, RefMan
|Citas de patentes (5), Otras citas (3), Citada por (93), Clasificaciones (39), Eventos legales (5)
|Enlaces externos: USPTO, Cesión de USPTO, Espacenet
This invention relates to polymer blends and in particular to polymer blends containing a β-hydroxybutyric acid polymer.
Poly(β-hydroxybutyric acid) is a thermoplastic polyester consisting of repeat units of the formula
which is accumulated by many micro-organisms, particularly bacteria, for example of the genera Alcaligenes, Athiorhodium, Azotobacter, Bacillus, Nocardia, Pseudomonas, Rhizobium, and Spirillium, as an energy reserve material.
The polymer is conveniently prepared by cultivating the micro-organism in an aqueous medium on a suitable substrate, such as a carbohydrate or methanol, as an energy and carbon source. The substrate must, of course, be one that is assimilable by the micro-organism. In order to promote accumulation of the polymer, at least part of the cultivation is preferably conducted under conditions wherein there is a limitation of a nutrient that is essential for growth of the micro-organism but which is not required for polymer accumulation. Examples of suitable processes are described in European Patent Specification No. 15669 and in European patent application No. 81.303373.
Polymers containing both β-hydroxybutyric acid units and other hydroxycarboxylic acid units, such as β-hydroxyvaleric acid units, can also be produced microbiologically. Thus a microbiologically produced heteropolymer containing β-hydroxybutyric acid and β-hydroxyvaleric acid residues is described by Wallen et al. in "Environmental Science and Technology" 8 (1974) 576-9. Also, as described in United Kingdom patent application No. 81.20991 various copolymers can be produced by cultivating the micro-organism on certain substrates, such as propionic acid which gives rise to β-hydroxyvaleric acid units in the copolymer.
While cells containing the polymer can be used as such as a moulding material, for example as described in U.S. Pat. No. 3,107,172, it is generally desirable to separate the polymer from the remainder of the cell material.
Methods that have been proposed to effect this separation include breakage of the cells by methods such as treatment with acetone, followed by extraction of the polymer from the broken cells by treatment with a solvent in which the polymer is soluble. Examples of such processes are described in U.S. Pat. Nos. 3,036,959 and 3,044,942 in which the solvents employed are pyridine or mixture of methylene chloride and ethanol. Other extraction solvents for the polymer in the form in which it is produced in the cells include cyclic carbonates such as 1,2-propylene carbonate (see U.S. Pat. No. 4,101,533); chloroform (see U.S. Pat. No. 3,275,610); and 1.2-dichloroethane (as disclosed in European Patent Specification No. 15123).
U.S. Pat. No. 3,275,610 discloses other methods of cell breakage viz. ultrasonic vibration, grinding, French pressing, freezing/thawing cycles and lysozyme treatment, while, as described in the aforementioned European Patent Specification No. 15123, spray or flash drying of the suspension of cells as produced by culturing the micro-organism can also cause sufficient cell breakage to enable the polymer to be extracted from the cells.
Copolymers can also be made containing units of other hydroxycarboxylic acids and/or units derived from diols, e.g. ethylene glycol, and/or dicarboxylic acids, e.g. isophthalic acid, by ester interchange occuring when the microbiologically produced polymer or copolymer is melted with such a hydroxycarboxylic acid, lactone thereof, e.g. pivalolactone, diol, dicarboxylic acid and/or polyester produced therefrom.
In the following description therefore by the term HB polymer we mean not only the homopolymer, poly(β-hydroxybutyric acid) but also copolymers as described above, provided that the β-hydroxybutyric acid residues form at least 50 mole %, and preferably at least 60, particularly at least 80, mole % of the polymer chain.
When polymeric materials are used to form shaped articles by fabrication processes such as solution casting or processes involving melt shaping, for example injection or compression moulding, or extrusion, it is often useful to incorporate additives into the polymer in order to modify its properties and/or to assist the processing operation. Such additives may in some cases be other polymers.
We have found that HB polymers are useful additives for incorporation into certain other polymers and, likewise, certain other polymers are useful as additives for HB polymers.
In order to give the optimum physical properties, the HB polymer should be of high molecular weight, above 50,000, as determined by intrinsic viscosity measurements in chloroform at 30° C. using the intrinsic viscosity--molecular weight relationship derived by Einaga et al. (Macromoles 9 (1976) page 774-780, viz (η)=1.18×10-4 Mw0.78. By intrinsic viscosity we mean the value obtained by plotting values of the fraction:
(t-io)/to c
where t is the flow time of a "c" gms deciliter-1 solution of the PHB in a given solvent through a given viscometer, and to is the flow time of the same volume of pure solvent through the same viscometer under the same conditions, against the concentration c for various values of c, and extrapolating the curve obtained to zero concentration.
Synthetic HB polymers, e.g. as prepared by polymerising β-butyrolactone, in common with other synthetic lactone polymers such as polypropiolactone or polycaprolactone, generally have only low molecular weights, below 50,000, which adversely affects the physical properties of articles made from blends containing such synthetic polylactones. In contrast, microbiologically produced HB polymers generally have a high molecular weight, above 50,000, and often above 200,000. We have found that the best results are achieved using HB polymers of molecular weight above 100,000.
In general, in order to obtain a benefit in the processing or other properties, the base polymer and additive polymer should exhibit some compatability: for this reason the polymers, for which HB polymers are useful additives, or which are usefully incorporated into HB polymers, are those containing at least 25% by weight of chlorine and/or nitrile groups. The chlorine atoms or nitrile groups appear to render the polymer capable of interaction with HB polymers, possibly by enabling hydrogen bonding to occur with the carbonyl groups of the HB polymer, resulting in at least partial miscibility between the polymers.
In general, although not exclusively so, the chlorine or nitrile group containing polymer should be used at a concentration at which it is miscible with the HB polymer. In fact, it may be advantageous to exceed the bounds of miscibility and a proportion of immiscible material may have desirable effects.
A useful test of miscibility is derived from examination of the characteristics of the blends as examined using differential thermal calorimetry or dynamic mechanical analysis techniques. The observation of a single, compositional dependent, peak characteristic of the glass transition temperature (Tg) is evidence that the polymers of the blend are miscible. The presence of two distinct Tg's at the temperatures characteristic of the Tg's of the pure homopolymers indicates immiscibility between the phases.
Accordingly we provide a polymer blend comprising (i) 0.2 to 95% by weight of an HB polymer of molecular weight above 50,000 and containing at least 50 mole % of β-hydroxybutyric acid residues in the polymer chain, and (ii) an organic polymer containing at least 25% by weight of chlorine atoms and/or nitrile groups.
We have found that such blends exhibit interesting characteristics; the properties of the blend naturally depend upon the nature and amount of the polymer blended with the HB polymer.
Examples of polymers that may usefully be blended with HB polymers include
(i) polymers containing at least 50% by weight of units derived from vinyl chloride, vinylidene chloride and/or acrylonitrile, and 0 to 50% by weight of units derived from at least one ethylenically unsaturated monomer. Examples of such comonomers include olefins such as ethylene, propylene, and styrene; vinyl acetate; vinyl ethers; and ethylenically unsaturated acids and alkyl esters thereof wherein the alkyl group contains up to 6 carbon atoms, such as acrylic, methacrylic, maleic, or itaconic acids, ethyl acrylate, methyl acrylate, butyl acrylate, and methyl methacrylate.
(ii) chlorinated or chlorosulphonated hydrocarbon polymers. Examples of such hydrocarbon polymers include polyolefins such as polyethylene, polypropylene, and ethylene/propylene copolymers; polyisoprene; and polybutadiene. Preferred chlorinated hydrocarbon polymers include chlorinated polyethylene and chlorosulphonated polyethylene. The hydrocarbon polymers may be chlorinated or chlorosulphonated, in solution (which gives homogeneous products) or in suspension (which tends to give more heterogeneous materials).
(iii) chlorine containing polyethers.
The polymer blend contains 0.2 to 95% by weight of the HB polymer, based on the combined weights of the HB polymer and the chlorine or nitrile group containing polymer.
Addition of minor amounts, i.e. up to 50% by weight, of the HB polymer to the chlorine or nitrile group containing polymer generally assists the processing of the latter. Benefits in processability may be achieved by the addition of relatively small amounts of the HB polymer, e.g. 0.2 to 10, particularly 0.5-5, % by weight, and so here the HB polymer acts as a high molecular weight processing aid.
Hence addition of HB polymers, even in such relatively small amounts, enables polymers containing a major proportion of acrylonitrile, vinyl chloride, or vinylidene chloride units, that are difficult to melt process, to be melt processed more readily. Such polymers often have to be melt processed at a temperature relatively close to their melting points and often this means that the melt viscosity is relatively high. The addition of a small amount of a HB polymer causes, inter alia, the melt viscosity to be reduced and assists processability in other respects. To be effective as a processing aid, the HB polymer should have a melting point below the processing temperature: therefore, where the desired processing temperature is very near to, or below, the melting point, circa 180° C., of β-hydroxybutyric acid homopolymer, a lower melting copolymer containing β-hydroxybutyric acid units and a minor proportion, e.g. 1 to 40, particularly 2 to 20, mole %, of comonomer units, e.g. β-hydroxyvaleric acid units, is preferably employed. Such copolymers are particularly useful as processing aids for vinyl chloride polymers.
To avoid thermal degradation of the HB polymer, the processing temperature should be below 220° C.
HB polymers, both β-hydroxybutyric acid homopolymer and copolymers containing β-hydroxybutyric acid residues and comonomer residues, are useful as processing aids for the so-called high acrylonitrile resins often used because of their good impermeability to water and gases. Such resins, which contain at least 50% by weight of acrylonitrile, often present processing difficulties. Examples of such high acrylonitrile resins are graft copolymers obtained by the polymerisation of (a) 99.5 to 50% by weight of a monomeric material containing (i) at least 50% by weight of acrylonitrile and (ii) 0 to 50% by weight of at least one comonomer, such as styrene or an alkyl acrylate or methacrylate, e.g. methyl acrylate, in the presence of (b) 0.5 to 50% by weight of a butadiene) acrylonitrile copolymer. The incorporation of HB polymers, particularly a homopolymer of β-hydroxybutyric acid, as a processing aid is very effective in improving the processability and yet the impermeability characteristics of the acrylonitrile resin are not unduly affected.
Articles made by melt processing compositions containing a major proportion of a HB polymer are often relatively highly crystalline, although where copolymers containing, for example β-hydroxyvaleric acid residues, are employed, the crystallinity may be somewhat reduced. This high crystallinity often renders brittle articles fabricated from the polymer. It is therefore often desired, when using HB polymers as moulding materials, to improve the toughness of the HB polymer by incorporation of an impact modifier.
Rubbery chlorine or nitrile group containing polymers, for example chlorinated or chlorosulphonated polyolefins, such as polyethylene or ethylene/propylene copolymers, or chlorinated polyethers can exhibit a toughening effect on HB polymers and so act as impact modifiers therefor. To be effective as an impact modifier, the additive polymer should have a glass transition temperature, Tg, below 10° C. Preferably the amount of impact modifier forms 10 to 50% by weight, based on the combined weight of the impact modifier and the HB polymer.
It is thought that the toughening effect results since, although the rubbery polymers may not be completely miscible, in the proportions employed, with the HB polymer, the chlorine atoms or nitrile groups enable hydrogen bonding between the HB polymer and the rubber to occur, hence promoting interaction between the phases.
Other impact modifiers commonly used, such as ethylene/vinyl acetate copolymers, and ABS resins, which contain less than 25% by weight of nitrile groups, appear not to be effective as impact modifiers for HB polymers.
The preferred impact modifiers are chlorinated polyolefins, particularly chlorinated polyethylene containing up to 50% by weight of chlorine. However materials containing up to 70% by weight, or more, of chlorine may be used provided the Tg is below 10° C. In general, there should be sufficient chlorine present to lower the crystallinity of the polymer with respect to the unchlorinated polyolefin, but insufficient to increase Tg to above 10° C. Other suitable chlorinated rubbers are chlorinated polyethers containing the recurring unit: ##STR1## These materials may be homopolymers or copolymers with comonomers, such as ethylene oxide. These copolymers may contain units, such as the ethylene oxide units in random or block distribution.
Because of the interaction occuring between HB polymers and vinyl chloride polymers, particularly interesting materials can be produced by blends thereof. The vinyl chloride polymer is preferably a homopolymer of vinyl chloride or a copolymer containing at least 80% by weight of units derived from vinyl chloride.
As mentioned hereinbefore, the HB polymers act as processing aids. In addition, with larger amounts of HB polymers, the properties depend on whether or not crystallisation of the HB polymer is suppressed. If crystallisation is suppressed so that the composition is essentially amorphous, the HB polymer can act as a toughening agent for vinyl chloride polymers and can be considered as a polymeric plasticiser as well as a processing aid. While other polyesters, e.g. polycaprolactone, are known as polymeric plasticisers for vinyl chloride polymers, they are not satisfactory as processing aids.
At some levels, particularly in the range 10 to 30% by weight of HB polymer, vinyl chloride polymers reduce the rate of crystallisation of the HB polymer thus enabling tough articles to be fabricated. This is of particular utility where the article has a relatively thin section, e.g. less than 2 mm thickness, so that it can be produced by solution casting or by a melt fabrication process where the melt is cooled rapidly as part of the fabrication process to minimise crystallisation. Of course, if such articles are subjected to prolonged periods above the glass transition temperature, Tg, which will vary depending upon the composition and the method by which it is made, crystallisation will occur with consequent loss of the toughening effect. However articles made from such compositions can be used for applications where the temperature is unlikely to exceed Tg. HB copolymers, which are generally less crystalline than the HB homopolymer are particularly useful for toughening vinyl chloride polymers.
At higher HB polymer levels, e.g. above 35% HB polymer, based on the combined weights of the HB polymer and the vinyl chloride polymer, if crystallisation of the HB polymer is induced, e.g. by annealing where necessary, the HB polymer serves to increase the softening temperature of the vinyl chloride polymer enabling vinyl chloride polymer articles to be used at higher service temperatures.
It will be appreciated that the polymer blends may also contain other polymers. For example where a HB polymer is added to a vinyl chloride polymer as a processing aid, or to enhance the heat distortion temperature, an impact modifier such as those normally used for vinyl chloride polymers may also be present: in some cases this impact modifier could be another polymer containing at least 25% by weight of chlorine or nitrile groups, e.g. a chlorinated polyolefin.
When the compositions of the invention contain a substantial amount of chlorine in the form of a chlorine containing polymer, the composition has enhanced fire retardancy relative to the HB polymer itself.
The compositions of the invention may be blended by any of the known techniques for producing an intimate blend of polymers. These techniques include solution blending using a common solvent or melt blending using equipment capable of shearing the melt of polymers. Screw extruders or mills are commonly used for melt blending polymers. It will also be appreciated the blend of polymers may be a simple powder blend providing that the blend is subjected to a homogenising process before or during the process of fabricating an article from the blend. Thus, for example, where an article is formed from the composition in a screw-fed injection-moulding machine, the feed to the hopper of the screw may be a simple mixtue of the two components since an intimate blend may be achieved in the screw portion of the machine.
In addition to the polymeric constituents of the compositions there may also be present any of the auxiliary materials known for use in polymeric compositions such as antioxidants, heat and light stabilisers, plasticisers, pigments reinforcing and non-reinforcing fillers, foaming agents and fire retardants.
Even where the component polymers of the blend are completely miscible (in the thermodynamic sense), as is the case of blends with vinyl chloride polymers, this thermodynamic ideal may not always be realised in practice so that the blends will not be completely mixed but rather have a HB polymer rich phase and a chlorine or nitrile group containing polymer rich phase. The properties of the blends will therefore to some extent depend on the intimacy of mixing of the components.
HB polymers produced by solvent extraction from bacterial cells followed by precipitation are generally in the form of a fine fibrous powder. While this powder may be mixed with the chlorine or nitrile group containing polymer and melt compounded, the fine fibrous HB polymer powder is somewhat difficult to handle and so may be densified, e.g. granulated, before mixing with the chlorine or nitrile group containing polymer. However melt compounding a mixture containing such a densified HB polymer may give inferior dispersion.
We have found that an improved method of obtaining good dispersion of the HB polymer and the chlorine or nitrile group containing polymer is to mix the latter with the precipitated HB powder to which a small amount, e.g. 10% by weight of the blend, of a volatile liquid, e.g. chloroform, has been added. The resultant paste or slurry may then be densified by granulation at a temperature below the melting point of the polymers: before, during, or after granulation the liquid may be removed by volatilisation. This given a densified product that may be readily melt processed.
Even better dispersion may be achieved by mixing the chlorine or nitrile group containing polymer with a solution of the HB polymer in a volatile solvent, e.g. chloroform, followed by such a low temperature granulation process, before, during, or after which the solvent is volatilised. Precipitated HB polymers are generally only poorly soluble in cold solvents and so, where such a solution blending step is required, the precipitation step may be omitted, blending the chlorine or nitrile group containing polymer with the solution obtained by solvent extraction of the HB polymer from the bacterial cells. Alternatively the HB polymer solution may be obtained by heating the precipitated HB polymer with the solvent.
Even more intimiate dispersion may, of course, be achieved by mixing solutions of the polymers in a common solvent or in miscible solvents. This is of particular utility where it is desired to fabricate articles by solution casting.
Blends of HB polymers with vinyl chloride polymers may also be made by polymerising the vinyl chloride (and comonomers, if any) in the presence of the HB polymer.
The invention is illustrated by the following examples in which all parts and percentages are expressed by weight, unless the contrary is indicated or implicit. In the examples blends are made from an HB polymer and an additive polymer. In Examples 1 to 15 a complex tin thiooctyl stabiliser based on a di-N-dithioglycollic acid ester (except in Examples 4 and 5a where the stabilizer was a 2,2,4-trimethyl 1,2-dihydroquinoline polymer) was added to the additive polymer, when the latter is used alone, or when blended with the HB polymer, at a level corresponding to 2% of the total composition (except in Examples 1-3 where the amount of stabiliser was 1%).
Various compounding or blending methods are utilised in the Examples as follows:
(a) "Solution" blending.
The precipitated HB polymer is dissolved by refluxing with chloroform followed by cooling to room temperature to give a solution of the HB polymer. The additive polymer and stabiliser is mixed with the solution, the chloroform evaporated off, and the mixture granulated at room temperature in a domestic mincer. The granules are then dried at 60° C. under vacuum for 24 hours, and then melt extruded at 190° C. and regranulated.
(b) "Slurry" blending.
The precipitated HB polymer is dry blended with the additive polymer powder and then about 10% of the blend of chloroform is added to form a paste. The stabiliser is then added and the paste granulated in a domestic mincer at room temperature. The chloroform is removed by volatilisation at 60° C. under vacuum for 24 hours. The granules are then melt extruded at 190° C. and regranulated.
(c) "Melt" blending.
The precipitated HB polymer is made into a paste by addition of 10% of chloroform and granulated and dried as in "slurry" blending. The additive polymer powder, and the stabiliser, are then added to the HB polymer granules and melt compounded, by extrusion followed by granulation unless otherwise indicated.
In the Examples (Except Examples 16b and 16c) the HB polymer was a β-hydroxybutyric acid homopolymer, hereinafter termed PHB, produced by cultivation of Alcaligenes eutrophus mutant S 301/C5 (NCIB 11599) on glucose. The PHB was isolated by extraction from the aqueous cell suspension with 1,2-dichloroethane at room temperature followed by separation of the solvent layer, containing the dissolved PHB, from the aqueous layer by decanting. The solution was filtered and then the PHB was precipitated by adding the solution to a methanol/water mixture. The precipitated PHB was separated by filtration and dried. The PHB had a weight average molecular weight (Mw) of about 290,000.
All tensile and impact tests were performed at 23° C. Tensile tests in Examples 1-17, e.g. Tensile Strength (TS), Young's modulus (YM), Elongation to Break (EB) were in accordance with ASTM D638-77a (50 mm/min).
Blends were made from PHB and various amounts of an amorphous chlorinated polyethylene (CPE) obtained from Dow Chemicals containing 36% chlorine and having a Tg of about -15° C. by "solution" blending. The resultant granules were injection moulded at 190° C. into standard test bars of 3 mm thickness, the properties of which are shown in Table 1.
TABLE 1______________________________________ Izod Impact (a)Composi- Strengthtion % Tensile Properties (J/m) HDT (b)PHB CPE TS(MNm-1) EB (%) 1 mm notch (°C.)______________________________________1a 100 0 38 4 27 1511b 90 10 31 5 32 1421c 80 20 24 7 37 1481d 70 30 18 20 59 1381e 60 40 13 64 96 113______________________________________ (a) according to ASTM D256 78 (b) Heat Distortion Temperature, according to ASTM D648 using 0.45 N load
PHB, and the CPE as used in Example 1, were "melt" blended by extrusion at 190° C. to give granules containing 30% CPE. The granules were injection moulded at 190° C. into standard test pieces of 3 mm thickness using a mould maintained at (a) 25° C. and (b) 65° C. The test pieces were annealed at 50° C. for 48 hours before testing. The results are shown in Table 2.
TABLE 2______________________________________ Izod ImpactMould Tensile Properties Strength (J/m)temp. YM TS 1 mm un-% (GNm-2) (MNm-2) EB % notch notched______________________________________2a 25 2.0 16 9 75 3502b 65 2.0 18 15 130 710______________________________________
Example 2 was repeated but using as the additive polymer
(a) a chlorosulphonated polyethylene (CSPE) of chlorine content (i) 35% and (ii) 43%
(b) an acrylonitride/butadiene/styrene (ABS) polymer which contained less than 25% of nitrile groups.
The mould temperature was 60° C.: the results are shown in Table 3.
TABLE 3__________________________________________________________________________Composition (%) Tensile Properties Izod Impact StrengthCSPE CSPE YM TS EB (J/m)PHB 35% Cl 43% Cl ABS (GNm-2) (MNm-2) (%) 1 mm notch unnotched__________________________________________________________________________3a 1000 0 0 3.3 40 10 65 1153b 90 10 0 0 2.7 31 19 55 2203c 70 30 0 0 2.2 21 8 120 5503d 90 0 10 0 3.0 31 12 70 4203e 70 0 30 0 2.0 25 50 210 >10003f 90 0 0 10 3.3 37 4 22 74__________________________________________________________________________
This shows that while the CSPE acted as an impact modifier for PHB, the ABS polymer did not.
Blends of PHB and a chlorinated polyether (CP ether) having a Tg of about -13° C. and containing the repeat unit ##STR2## were prepared by "melt" blending on a Brabender Plastograph for 3 minutes at a block temperature of 203° C. and a rotor speed of 90 rpm. Samples of the compositions obtained were each formed into plaques of dimensions 10 mm×10 mm×1 mm by compression moulding at 180° C. for 2 minutes. The plaques produced were optically clear. The Tg values of the samples and the individual polymeric constituents of the blend were determined using a Du Pont Dynamic Mechanical Analyser using a sample heating rate of 10° C./min. Elongation values were also determined on the plaques. The results are tabulated in Table 4.
TABLE 4______________________________________Composition (%)PHB CP ether Tg °C. EB %______________________________________4a 100 0 27 24b 80 20 18 44c 70 30 -1 3664d 50 50 -3 316______________________________________
The DMA showed only a single Tg peak for each sample indicative that the CP ether is miscible with PHB.
Blends were made from PHB and
(a) the chlorinated polyether used in Example 4
(b) the chlorinated polyethylene used in Example 1
(c) a butyl acrylate rubber,
by "slurry" blending. The resultant granules were injection moulded at 190° C. using a mould temperature of 75° C. into discs of 3 mm thickness and the Impact Strength was measured by the Instrumented Falling Weight Test (IFW). In this test the sample is supported on an annular ring of internal diameter 50 mm and is impacted by dropping an impactor having a weight of 100 N and having a round nose of radius 6 mm. The impactor is dropped from a height such that the velocity at impact is 5 meters/sec. A force transducer is connected to the impactor to give a record of the load on the specimen during the time that it is deformed by the impactor. A permanent record is made of the load-deformation behaviour and the impact strength is calculated from the area under this curve.
The results are shown in Table 5.
TABLE 5______________________________________Composition (%) IFW butylacrylate Energy to breakPHB CP ether CPE rubber (Nm)______________________________________5a 100 0 0 0 6.55b 70 30 0 0 20.25c 80 0 20 0 11.35d 70 0 30 0 20.15e 60 0 40 0 30.45f 80 0 0 20 2.95g 70 0 0 30 3.65h 60 0 0 40 5.7______________________________________
It is seen from the above examples that the chlorine containing rubbers show a significant toughening effect on PHB. However the butyl acrylate rubber, which is a commonly used impact modifier, shows no toughening effect.
A series of blends containing 75% PHB were prepared by "melt" blending on a Brabender Plastograph for 2 minutes at a block temperature of 200° C. and a rotor speed of 90 rpm. Samples of the compositions were compression moulded at 200° C. into 1 mm thick test pieces which were then permitted to crystallise isothermally by maintaining the test piece at 60° C. for 5 minutes. The mouldings were examined by optical microscopy and the physical nature assessed manually. The results are set out in Table 6.
TABLE 6______________________________________Other polymer Structure Product nature______________________________________6a rubbery ethylene/vinyl two phase sticky; brittle acetate copolymer containing 28% vinyl acetate6b chlorinated polyether (as single phase tough used in Example 4)6c chlorinated polyethylene two phase tough (as used in Example 1)______________________________________
Example 6 demonstrates that a conventional impact modifier, viz a rubbery ethylene/vinyl acetate copolymer exhibits no toughening effect whereas the rubbery chlorine containing polymers do act as impact modifiers for PHB.
Blends of PHB and a vinyl chloride homopolymer (PVC) powder of K-value 67 were made by "slurry" blending. After drying, the granules were melt extruded at 180° C., and regranulated, dried overnight at 60° C. in a vacuum oven, and then injection moulded into test samples of 1.5 mm thickness on an Arburg Allrounder injection moulding machine Model No. 220E--35/90 using a barrel temperature varying from 170° C. at the hopper to 190° C. at the nozzle. A mould temperature of 65° C. and a cooling time of 15-30 seconds was used. The properties of the mouldings are shown in Table 7.
TABLE 7__________________________________________________________________________ Tensile Properties Flexural IFW EnergyComposition (%) TS Modulus to break HDT Vicatx (°C.)PHB PVC (MNm-2) (GNm-2) (Nm) (°C.) 1 kg load__________________________________________________________________________7a 100 0 38 2.30 1.0 144 >1507b 75 25 36 3.0 0.4 76 1407c 50 50 47 3.8 0.1 68 1357d 30 70 30 2.3 5.9 62.5 1117e 25 75 28 2.8 24.0 56 102.57f 20 80 27 3.1 24.0 55 87.57g 10 90 41 4.4 1.2 58.5 827h 0 100xx 38 3.8 3.9 71.5 86__________________________________________________________________________ x Vicat Softening point according to ASTM D 1525. xx The K 67 PVC was not mouldable under the conditions used to mould the other samples and so a lower viscosity grade PVC, of Kvalue 57, was used as the control.
Examination of the products containing 20 and 25% PHB showed that they were essentially amorphous, indicating that the vinyl chloride polymer retarted the rate of crystallisation, enabling the PHB to act as a polymeric plasticiser.
The fact that the K-67 PVC was not mouldable under the conditions used, whereas the blends could be moulded, demonstrates that the PHB also acts as a processing aid.
The procedure of Example 7 was repeated except that the mouldings had a thickness of 3 mm and a mould temperature of 75° C. was employed. The results are shown in Table 8.
TABLE 8______________________________________Composition (%) Cooling time IFWPVC PHB (sec) Energy to Break (Nm)______________________________________8a 90* 10 30 3.28b 80* 20 40 3.18c 70* 30 40 3.38d 65* 35 35 3.18e 95** 5 15 2.38f 90** 10 20 29.48g 80** 20 25 33.48h 70** 30 30 2.38i 65** 35 30 1.8______________________________________ *K-67 **K57
With the exception of mouldings 8f and 8g, the mouldings were essentially crystalline. This shows that if the cooling rate is too slow, crystallinity can develop, rendering the products brittle.
Blends of PHB with various polymers were made by "slurry" blending. The granules were examined by differential scanning calorimetry as follows:
The test sample was first heated to 200° C. and held at that temperature for 1.5 minutes and then cooled at a rate of 320° C./min to the desired crystallisation temperature, Tc, and held at that temperature. The time taken at Tc to achieve the maximum rate of crystallisation was measured. The results are shown in Table 9.
TABLE 9__________________________________________________________________________ Time to maximum crystallisationComposition (%) rate (min) atPHB PVC CPE1 CP ether2 50° C. 60° C. 70° C. 80° C. 90° C. 100° C. 110° C.__________________________________________________________________________9a 100-- -- -- 1.65 0.95 0.74 0.65 0.7 0.75 4.39b 60 -- 40 -- 3.1 2.45 1.85 2.25 2.8 4.45 11.29c 60 -- -- 40 6.2 4.35 4.25 5.25 9.0 22.8 --9d 35 653 -- -- -- -- 9.8 8.5 8.5 11.5 16.59e 35 654 -- -- -- -- 4.9 4.5 6.1 9.8 14.19f 20 804 -- -- too slow to measure9g 5 944 -- -- too slow to measure__________________________________________________________________________ 1 As used in Example 1 2 As used in Example 4 .sup. 3 K57 4 K67
It is seen that all the additive polymers retarded the rate of crystallisation.
A weries of blends of PHB and K-57 PVC were made by (a) "solution" blending, (b) "slurry" blending, and (c) "melt" blending by extrusion at 190° C. followed by granulation. The intimacy of mixing is thus expected to be in the order
The resulting granules were moulded into test pieces of thickness 1.6 mm by
(i) compression moulding for 2 minutes at 200° C.; the mould and moulding were then quenched in iced water and the mouldings stored at -20° C. until tested to prevent any further crystallisation occuring;
(ii) injection moulding at 190° C. using a mould temperature of 20° C. and a cooling time of 15-30 seconds. The mouldings were stored at -40° C. until tested.
For testing the samples were cooled to -120° C. and Tg determined by dynamic mechanical analysis over the increasing temperature range -120° to 100° C. Further quenched mouldings were annealed at 80° C. in a vacuum oven for 16 hours to develop maximum crystallinity prior to dynamic mechanical analysis. The results are shown in Table 10.
TABLE 10______________________________________ Tg (°C.) of blend of PVC/PHB compositionBlood Moulding An- 65/ 80/ 95/ 100/method method nealed 35 20 5 0______________________________________10a solution injection yes 73.5 78 78.510b slurry injection yes 81 85 78.510c slurry compression yes 89.5 86 82 92.510d melt compression yes 94.510e solution injection no 27.5 42.5 8010f slurry injection no 36.5 55.5 75.510g slurry compression no 77.5 78 81.5 89.510h melt compression no 85______________________________________
It is seen that the "solution" blending method gives a lower Tg in the quenched (i.e. unannealed) samples but, on annealing little difference in Tg is obtained. Quenched compression moulded samples do not exhibit such a large depression of Tg. This is probably because the degree of mixing between the two components is not so good as in the case of the injection mouldings.
The Tg of an ideally mixed quenched sample can be predicted from the Fox equation (Bull. Am. Phys. Sec. 1, 1956, page 123) ##EQU1## where x is the weight fraction of PVC fraction of PVC and the Tg's are in °K. (362.5° K. for PVC and 294° K. for PHB). Comparing the observed Tg's for the quenched "solution" blended samples with values predicted by the Fox equation gives
______________________________________Composition (%) Tg °C.PVC PHB predicted observed______________________________________65 55 62 27.580 20 73 42.595 5 85 80______________________________________
showing that the Tg depression is greater than predicted by the Fox equation.
"Solution" and "slurry" blended compositions containing PHB and a K-57 PVC were injection moulded at 190° C. into 1.5 mm thick test pieces using a mould temperature of 20° C. to produce mouldings that were as amorphous as possible. The mouldings were stored at -40° C. until required for testing whereupon they were left at room temperature for 1 hour before impact testing. The 5 kg Vicat softening temperature was also measured. Similar samples were annealed at 75° C. for 16 hours before testing. The results are shown in Table 11.
TABLE 11______________________________________ Unannealed AnnealedCom- IFW Vi- Vi-position energy to cat IFW cat% Blending Break 5 kg energy to 5 kgPVC PHB method (Nm) (°C.) break (Nm) (°C.)______________________________________11a 95 5 slurry 9 52.5 0.5 5811b 95 5 solution 9 60 0.5 6511c 80 20 slurry 8 51 0.7 76.511d 80 20 solution 26.4 43 0.3 7011e 65 35 slurry 19.3 39 0.8 81.511f 65 35 solution 21.7 37 0.7 71______________________________________
The data for the compositions containing 20% PHB show that the intimacy of mixing has a marked effect on the performance of PHB as a toughening agent, i.e. as in the unannealed samples.
1400 parts of vinyl chloride were polymerised at 61° C. in aqueous suspension in the presence of 120 parts of precipitated PHB powder and 2.55 parts of azodivaleronitrile as initiator, to give 600 parts of a polymer blend containing 20% PHB. A sample of the polymer blend was extracted with cyclohexanone. The soluble portion had a K-value of about 57.
Injection moulded test pieces made as described in Example 10 from the polymer blend were compared with the annealed mouldings of Example 10 made from the "solution" blend of K-57 PVC and PHB containing 20% PHB. The properties are shown in Table 12.
TABLE 12______________________________________Test Polymerised blend Solution blend______________________________________IFWEnergy to break (Nm) 1.2 0.3TS (MNm-2) 33.9 27.6EB (%) 9 225 kg Vicat (°C.) 62 701 kg Vicat (°C.) 120 --opacity transparent translucent______________________________________
These properties are indicative that the polymerised blend is more intimately mixed than the solution blend.
To illustrate the improvements in processability given by the addition of PHB to K-67 PVC, blends were made up by the "solution" and "melt" blending (extrusion at 190° C. techniques and their melt viscosities measured on a melt extruder at 190° C. at a shear stress of 2×105 Nm-2. The results are shown in Table 13.
TABLE 13______________________________________Composition (%) ViscosityPVC PHB Blending method (Nsm-2)______________________________________13a 80 20 solution 1.4 × 10413b 80 20 melt 3.4 × 10413c 90 10 solution 5.2 × 10413d 90 10 melt 3 × 10513e 100* 0 -- 1 × 106______________________________________ *K-62 PVC the K67 PVC was not melt extrudable at 190° C. in the absence of processing aids.
These results also show that the better mixing technique, "solution" blending, gives a greater viscosity decrease than "melt" blending.
The procedure of Example 6 was repeated using various chlorine containing polymers:
(i) a chlorinated polyether containing the repeat units ##STR3##
(ii) a chlorinated polyether containing the repeat unit ##STR4##
(iii) a chlorinated polybutadiene of Tg about 100° C. and 66% chlorine,
(iv) a chlorinated polyisoprene of Tg about 130° C. and containing 66% chlorine,
(v) a vinylidene chloride/acrylonitrile/methyl methacrylate copolymer containing about 90% vinylidene chloride units, and 3% acrylonitrile units.
In all cases the blends processed readily: in some cases more readily than the additive polymer alone; indeed some of the additive polymers could not be fabricated by themselves satisfactorily at 200° C.
"Solution" blends were made of K-67 PVC, PHB and chlorinated polyethylene (CPE) as used in Example 1, or a methyl methacrylate/butadiene/styrene rubber (MBS) PVC impact modifier. The resulting granules were injection moulded at 190° C. into test samples of thickness 3 mm using a mould temperature of 60° C. The samples were annealed at 70° C. for 16 hours prior to testing. The results are shown in Table 14.
TABLE 14______________________________________ Izod Vicat Impact Strength Softening (J/m) PointComposition % 1 mm (°C.)PVC PHB CPE MBS notch unnotched 1 kg 5 kg______________________________________15a 100 0 0 0 181 >1000 86 8115b 65 35 0 0 36 316 129 7815c 60 30 0 10 80 437 122 7815d 50 40 10 0 156 286 113 7115e 45 35 20 0 56 767 103 68.515f 0 70 30 0 130 >1000 151 8515g 0 100 0 0 60 200 174 152______________________________________
A PVC formulation was made by room temperature dry blending the following ingredients:
______________________________________ parts______________________________________(1) K-62 vinyl chloride homopolymer 100(2) complex tin thiooctyl stabiliser 1.5 based on a di-N--dithioglycollic acid ester(3) methyl methacrylate/butadiene/styrene 8 PVC impact modifier(4) wax (external lubricant) 0.8(5) glyceryl monoester (internal lubricant) 1(6) processing aid 2______________________________________
The processing aids were:
(a) the β-hydroxybutyric acid homopolymer (PHB) as used in the previous examples.
(b) a copolymer (A) containing 75 mole % of β-hydroxybutyric acid units and 25 mole % of β-hydroxyvaleric acid units. This copolymer was prepared in the same manner as the homopolymer except that propionic acid was used as the substrate instead of glucose. The copolymer had a weight average molecular weight (Mw) of about 300,000 and had a melting range, as determined by differential scanning calorimetry of about 120° C. to about 160° C. with a peak in the melting endotherm at 132° C.
(c) a copolymer (B) containing 80 mole % of β-hydroxybutyric acid units and 20 mole % of β-hydroxyvaleric acid units. This copolymer was prepared in the same way as the homopolymer except that, when the aqueous fermentation medium became depleted of a nitrogen source, cultivation was continued using a mixture of glucose and propionic acid as the substrate instead of only glucose. This copolymer had a weight average molecular weight (Mw) of about 300,000 and a melting range of about 100° C. to about 180° C., with a peak in the melting endotherm at 168° C.
(d) polycaprolactone of melting point 60° C.
The processing aids were melt extruded and ground to a particle size below 150 μm before incorporation into the PVC dry blend.
The dry blends were tested as follows:
(1) 50 g of the mixture was poured into the mixing head of a Brabender Plastograph maintained at 180° C. rotating at 18 rpm under a pressure ram loaded with a 5 kg weight. The time taken for gelation to occur was measured.
(2) The mixture was cold compressed to form a candle which was then charged to an extrusion rheometer maintained at 170° C. and fitted with a die having a circular orifice of 1 mm diameter and 20 mm land length. After the charge had heated to 170° C., it was extruded at increasing rates. The appearance of the extrudate was noted and the melt extensibility assessed by attempting to draw the extrudate away from the die.
The results are shown in Table 15.
TABLE 15______________________________________ Gelation time Extrusion at 170° C.Processing (min) at Melt ex-aid 180° C. Appearance tensibility______________________________________16a none 12 Severe sharkskin at Poor low extrusion rates; ripple at higher rates16b homopolymer 9.5 poor with a lot of Poor unmelted polymer clearly visible16c copolymer A 1.0 excellent - very good smooth16d copolymer B 1.5 smooth but occas- fair ional unmelted particles16c polycaprol- 1.5 fair at low extru- fairactone sion rates; se- vere ripple at higher rates______________________________________
The results for the homopolymer and copolymer B are indicative that the processing temperature of 170° C. was too low for complete melting of the processing aid to occur. Likewise, for the homopolymer, the long gelation time at 180° C. is indicative that 180° C. is too low a processing temperature.
In this Example PHB was assessed as a processing aid for a high acrylonitrile resin obtained by the graft polymerisation of about 75 parts of acrylonitrile and 25 parts of methyl acrylate in the presence of about 9 parts of a butadiene/acrylonitrile rubber containing 70% butadiene. This high acrylonitrile resin thus contains about 35% nitrile groups.
Blends were made from 100 parts of the acrylonitrile resin and 2 parts of β-hydroxybutyric acid homopolymer (PHB), as used in the previous examples, by mixing the acrylonitrile resin with PHB powder obtained by melt extruding PHB followed by grinding to a particle size below 150 μm.
The resulting blend was (i) extruded at 200° C., and (ii) injection moulded into standard test bars of thickness 3 mm at 200° C. using a mould temperature of 60° C. For comparative purpose the extrusion and injection moulding were repeated with the acrylonitrile resin alone, i.e. with no processing aid.
Addition of the processing aid significantly reduced the power required for extrusion and increased the extrusion rate. In injection moulding, the screw back time and injection pressure were significantly reduced by addition of the PHB.
The mouldings were tested (a) as made and (b) after annealing for 24 hours at 50° C.
The results are shown in Table 16.
TABLE 16__________________________________________________________________________Composition(parts) Tensile properties Izod Impact Strengthnitrile YM TS EB (J/m)resin PHB Annealed (GNm-2) (MNm-2) (%) 1 mm notch Unnotched__________________________________________________________________________17a 100 0 no 3.63 57 10-20 110-150 350-65017b 100 2 no 4.18 68 26-33 370-500 100017c 100 0 yes 3.50 65 8-10 90-130 300-40017d 100 2 yes 3.86 70 20-23 250-320 1000__________________________________________________________________________
The above results indicate that not only does the PHB assist processing but also improves the mechanical properties.
Tubular film of thickness 0.12 mm was made from the acrylonitrile resin blends made as described in Example 17 containing varying amounts of PHB as a processing aid by melt extrusion at 200° C. through an annular die. As in Example 17, incorporation of the PHB reduced the power required for extrusion and increased the extrusion rate.
The tensile strength and Young's modules (measured according to ASTM D882-79); and tensile impact strength (measured according to ASTM D1822-68) were determined. Measurements were made in both the machine and transverse directions and as the direction of testing gave little difference in the results, the measurements were averaged. The permeability to oxygen was measured according to ASTM D1434-75.
TABLE 17______________________________________Composition Perme-(parts) Tensile properties abilityacrylo- Impact ml · m-2 ·nitrile TS YM strength day-1 ·resin PHB (MNm-2) (GNm-2) (kJm-2) atm-1______________________________________100 0 52 3.04 181 3.299.5 0.5 51 2.90 168 3.299 1 49 2.80 186 2.998 2 52 3.12 184 3.1______________________________________
These results show that while the addition of PHB improved processability, it had no adverse effect on the film properties.
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|Clasificación de EE.UU.
|525/64, 525/190, 525/415, 525/450, 525/186, 525/412
|Clasificación internacional
|Clasificación cooperativa
|Clasificación europea
|10 Nov 1981
Owner name: IMPERIAL CHEMICAL INDUSTRIES PLC, MILLBANK, LONDON
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|16 Dic 1986
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|29 Abr 1994
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