text:
Perhaps I wouldn't have bought this book if it weren't for a friend of mine who insisted. After she read it she was very disappointed, so I was curious in reading it too. I must confess that it was slightly better than I thought and that I have enjoyed it to a certain point.
I really liked the way the narrator depicts interiors of the rooms, the school; she catches the atmosphere of that Romanian town at the border of the Danube, the good and bad habits of the locals, some of their problems - such as poverty, young people who decide to work abroad; the Roma population, etc. the historical information was interesting for me, because I didn't know too much about Vlad the Impaler,
The romance between the history teacher and Adelina is nice, youthful, but at a certain moment it begins to be a bit boring. The characters are okay, but I really couldn't feel for them either love or hate. They seem a little superficial, in my point of view, but maybe other readers will love them I know that this is a novel, but there are too many characters and too many subplots that confused me a little. As an avid reader, I would have preferred this book to be slightly shorter and a little straighter to the point.
P.S. Old Romanian people are indeed francophones, but that doesn't mean they speak French like in the period between the two WorldWide Wars. (Maybe the author wanted to show us that Mrs Dinescu was taught at a boarding school for young ladies, where the lessons were taught in French). At the graduation party, Romanian teenagers don't listen to French music, but the latest hits sung in English, house, drum and bass, techno and just a few ballads. (Those are also in English).
- File Size: 983 KB
- Print Length: 226 pages
- Page Numbers Source ISBN: 1466330333
- Publisher: DorionEpublishing (December 19, 2010)
- Publication Date: December 20, 2010
- Sold by: Amazon.com Services LLC
- Language: English
- Text-to-Speech: Enabled
- Word Wise: Enabled
- Lending: Enabled
Amazon Best Sellers Rank:
#3,738,282 Paid in Kindle Store (See Top 100 Paid in Kindle Store)
- #96477 in Romantic Suspense (Books)
- #54946 in Romantic Suspense (Kindle Store)
Would you like to tell us about a lower price?

subset: commoncrawl


text:
Get Discounts ! Latest Deals ! Allow Notifications to Stay Informed !!!❌
Dovekie Womens Denim Jegging Dark Blue
Rs 699 Buy from Amazon
best price Rs 699
Rs 699
No Cashback
Dovekie Women's Denim Jegging Dark Blue Details
Dovekie presents to you soft stretchable stylish womens denim Jeggings.Get a trendy look, with very comfortable, high quality and soft COTTON DENIM Jeggings. Our jeggings are stretchable and are perfect fit skinny jeggings. These jeggings are made of 100%% pure stretchable cotton and look great when worn. So get all set with a great collection of trend setting comfortable jeggings. Our range of coveted classics features jeans, jeggings, tees, jackets and Tops that are ready to be styled, layered, and lived in. Each piece is crafted with soft fabrics and is priced to make stocking-up a breeze-you'll want one in every color.
Similar Product From Amazon
Lucky Brand Women's HIGH Rise Bridgette Skinny Jean in Lonestar Destruct, 28Rs 15,330 Rs 15,514
( upto 1% Off )
Miss Chase Women's Black Distressed JeansRs 1,169 Rs 2,599
( upto 55% Off )
DL1961 Women's Emma Power Legging Jean, Melbourne, 28Rs 38,327 Rs 69,617
( upto 45% Off )
Lee Women's Sculpting Fit Slim Leg Pull On Jean, Voyage Embroidery, 6 ShortRs 8,194 Rs 14,665
( upto 44% Off )
RZ Lecort Cotton Comfertable Jegging for women & girls (Pack of 3)Rs 999 Rs 1,299
( upto 23% Off )
- Buy Now
PAIGE Women's Nellie Culotte Jean, Vintage California Rose, 23Rs 45,082 Rs 65,780
( upto 31% Off )
AG Adriano Goldschmied Women's The Legging Ankle Super Skinny Jean, serendipitous Destructed, 24Rs 41,093 Rs 76,239
( upto 46% Off )
- Buy Now
Frenchtrendz Cotton Modal Spandex Waistband Jegging (Black, Samall)Rs 848 Rs 2,220
( upto 62% Off )
Similar Product From Flipkart
FCK-3 Slim Women's Blue JeansRs 1,349 Rs 1,499
( upto 10% Off )
Pepe Jeans Regular Women's Blue JeansRs 1,199 Rs 2,399
( upto 50% Off )
Fck-3 Slim Women Blue JeansRs 1,299
ZUSH Slim Women's Light Blue JeansRs 1,495
Hoffmen Skinny Women's Blue JeansRs 1,015
manash Fashion Regular Women's White JeansRs 619 Rs 688
( upto 10% Off )
- Buy Now
Pepe Jeans Regular Women Blue JeansRs 1,679
- Buy Now
Xpose Slim Women's Blue JeansRs 849 Rs 1,019
( upto 17% Off )


text:
Sound like you?
You're an active adult who enjoys running, golf, tennis, swimming, yoga or other physical activities. As time moves forward, your body starts to wear and the aches and pains in your knees, elbows, feet, ankles or other joint areas are preventing you from the active lifestyle you love.


text:
2009 Heartland Sundance 3300BHS – Airdrie – 18155A
2009 Heartland Sundance 3300BHS
Used Fifth Wheel | Airdrie, AB | Stock # 18155A
Biweekly Payment
- RV Specs
- Overview
- Stock Number 18155A
- Model Number 3300BHS
- Status Sold
- Location Airdrie, AB
- Condition Used
- Class Fifth Wheel
- Floorplan Bunkhouse, Front Bedroom, Complete Kitchen
- Slide Outs 1
- Sleeping Capacity 10
2009 Sundance 3300BHS Fifth Wheel Travel Trailer by Heartland RV.
Bunkhouse model with two rear single-over-single bunks, front private master bedroom with a queen size bed, full ensuite bathroom, complete kitchen with a three burner range, convertible booth dinette and sofa slideout and more! Sleeps 8-10, 1 slide.
Similar RVs
Leave a ReplyWant to join the discussion?
Feel free to contribute!
Leave a Reply
You must be logged in to post a comment.


text:
Each and every weekend we bring you the deeper sounds of drum & bass, with Ben Soundscape & Collette Warren. Livestreaming from 9pm till we say when….
As we stay safe and stay apart from one another physically, this is an amazing way to connect virtually :) We won't be doing any clubnights for the forseeable, so it's the next best thing!
Listen live on Friday nights from 9pm BST and selected other dates, see below:
► Sun 7th June – Ben Soundscape history lesson
► Sun 14th June – All-Vinyl day session
► Fri 19th June – Mosaic in the house – Rich's b'day!
► Fri 26th June – Intrigue Music special – All-Intrigue mix
LISTEN LIVE LINK >>> http://www.facebook.com/intriguednb <<<
** SHARE THE LOVE! Please share the event and tell everyone you know so we can build up the audience **
We are taking donations in these difficult times.
If you'd like to donate, please paypal firstname.lastname@example.com However big or small, your donation will keep the music coming and directly support us. We'd like to take this opportunity to thank all of you who've donated so generously so far 🖤


text:
There are 2 Martial Arts Schools listed in Cortland. Karate is the most offered Martial Arts in Cortland area, followed by Kick Boxing and Mixed Martial Arts (MMA).
Popular Martial Arts in Cortland
Here is a Chart and list showing Martial Arts available in Cortland. This is based on information from 85 Martial Arts Schools in Cortland area that made style information available.
- Karate (41)
- Kick Boxing (23)
- Mixed Martial Arts (MMA) (11)
- Tae Kwon Do (9)
- Brazilian Jiu-jitsu (9)
- Aikido (9)
- Kempo/Kenpo (8)
- Goju Ryu Karate (7)
- Tai chi (7)
- Jiu-Jitsu (Jujutsu/Jujitsu) (7)
This list shows the Martial Arts Styles along with the number of schools offer that Style in Cortland area. If you are looking for specific Martial Arts in Cortland or looking to find a Martial Arts School closed to you, see a list of Martial Arts Schools in Cortland.


text:
Spesifikasi :
VIVOTEK's NR9581 is a full-featured high-performance H.265 NVR. Equipped with a 2U 32-CH 8 Bay Rackmount network appliance, standard RAID capability and H.265 video codec, the total storage capacity of the NVR also endows the NR9581 with scalability and flexibility, making it perfect for large-scale transport or industrial applications as well as public spaces such as campuses.
The NR9581's 8 hard-drive bay design provides for a storage capacity of up to 80TBs, offering greater than 30% ~ 50% more recording capacity than systems employing H.264 compression. This advance affords users larger storage space for longer durations of video recording. The RAID 0/1/5/6/10 configuration provides further data security in the rare event of a hard drive failure. Further, equipping the NR9581 with a DOM system has resulted in reliability and stability beyond the reach of other NVRs. Meanwhile, the NR9581 supports VIVOTEK's fisheye network camera "Fisheye Dewarp" function, which provides multiple de-warping modes in live view and playback, ensuring the correct angle of video view and detailed information for flexible usage. This ingenious NVR is also equipped to carry out remote management with a full range of the server/client structures and thus constitutes a robust system for diverse applications.
Moreover, the NR9581 features well-built ONVIF compliance and scalable configuration, with VAST CMS empowering users to set up and manage advanced IP surveillance systems with ease. The NR9581 also supports both remote and mobile access via iViewer app, for both iOS and Android handheld devices. The NR9581 represents a great advance in the field, providing users an open, intelligent and seamless NVR to meet market demands.
Rp 4.030.000
Rp 1.623.200
Rp 42.900
Rp 20.750
© 2015-  Indotrading - Indonesia B2B Marketplace.
All Rights Reserved.
Klik nomor untuk langsung menghubungi supplier
Bantu jadikan Indotrading.com B2B Marketplace yang lebih Aman dan Terpercaya.


text:
8 Search Results for "Local 610 Contract Fight"
At the Negotiating Table in Puerto Rico
Check out photos from negotiations in the contract fight against Hilton in Puerto Rico.
Union Victory in Puerto Rico
When members of Unite Here Local 610 in Puerto Rico entered into a contract fight with Hilton in June 2009, the life of their union was hanging by a thread.
The new contract that was ratified in February 2010 saved their union. It stopped decades of decline and concession bargaining. It significantly raised the members' standard of living and greatly increased their power.
Negotiations, Boricua style
Despite the fact that the union and management are still far from an agreement and that a strike is very possible, a joyous atmosphere characterized the workers' mood at the latest contract negotiating session on October 15th at the ILA building.
Contract negotiations: What's got to go
At the Hilton Membership Meeting last Thursday, Local 610 President, Felix Mejias shared his thoughts regarding the upcoming negotiations.
HTC, Local 6 and UNITE HERE Join in Relief Effort in Puerto Rico
After Hurricane Maria rampaged across Puerto Rico on September 20, leaving an unimaginable trail of destruction, HTC, Local 6 and UNITE HERE joined in a relief effort to assist members of the hotel union there, Local 610.
For immediate release: Rallies begin today in front of Hilton hotels in San Juan
Hundreds of hotel workers of the Caribe Hilton, Condado Plaza and the El San Juan hotels will be holding a series of protests and marches December 17, 18 and 19.
First 3 days of negotiations in Puerto Rico
Three days of extremely slow and contentious contract negotiations between the Union and Hilton have yielded some significant progress, but have also made clear that the road to a final agreement will be very difficult.
Water and decency for workers in short supply at the El San Juan
Hery Adorno, a doorman for almost 20 years at the El San Juan Hotel, wonders each day if it will be his last. "I am afraid I will die of a stroke because management will not allow me to take a sip of water so that I can take my medicine when I feel faint," he admitted to Liz Guerra, a union organizer.


text:
|Home Toys & Games Rc Drones Rc Drones Age 12+
12" Syma 4ch 2.4ghz 6 Axis Gyro Rc Quadcopter +2.0mp Hd Came...
Enjoy your wonderful flying time with our Syma X5C
Explorers 4CH 2.4GHz 6-Axis Gyro RC Quadcopter
With Flashing Light + 2.0MP HD Camera + 2G Micro SD Card + 5V 450mAh Battery.
The RC quadcopter allows video and camera at the same time for about 30 minutes.
It can easily implement...
2.4ghz 4ch 6 Axis Gyro Rc Quadcopter
Headless Mode, no need to adjust the position of aircraft before flying.
Lightweight airframe with nice durability
Fine workmanship endows the aircraft with smooth and delicate appearance
Flight time will be up to 8-10 minutes and offer you 100m remote control di...


text: Had my 2014 STX550 for a few months. Anyone know what the funny shaped weights are that are mounted on the front and rear of the rear springs..Front looks like a steel hockey puck..rear weight is shaped like a circle that's pinched in the middle. I think they must me some sort of anti-vibration. Only seems to be on the STX550 as I have checked quite a few standard D40's in the shopping centre carpark and they done seem to have them.


text:
#503 – Dem Debate Live, Annika O'Brien Drops Gonzalo Lira Dirt, + More
[Watch on BitChute] / [Listen on ZenCast] / [Download Podcast]
Annika O'Brien joins the show to drop all of the hot goss on everyone's favorite abortifacient promoting coach, Gonzalo Lira, or 'Gonzo' as she calls him! Turns out the ole coach got really salty over not receiving a Millenniyule invite and he joined JF Gariepy's New Years program to sperg out.
Featured Guests


text:
Menagerie Top
tie dye : check. beautiful purple color that Clemson fans will love: check.
This fun tie sleeve "faux tie front" blouse is just what you need for Spring and to carry into tailgating 2020. Seriously, we are obsessed. Make sure you pair with our Sona Earring in ORANGE
Meg is a size 2-4 wearing a SMALL
100% Rayon
Poppy Button Up Top
adorable floral button up square neckline top top that has aaall the fabulous colors for Spring! Looks great with our Moonshine Flares in White, new Bridgette Flares, the Carly Crop Denim in Capitola, .... ALL OF IT
Hope is 0-2 wearing the XS
Meg is a size 2-4 wearing the S
100% Viscose
Garden Party Top
the ultimate "garden party" ruffle top! how stinking cute. We love with white denim, layered under our Quinn Jacket in Sunshine Yellow...red palazzo pants. Bring on all the color because this top definitely has it!!! Great for work or play.
Meg is a size 2-4 wearing the SMALL
65% Cotton// 35% Polyester
Pick A Paisley Off The Shoulder Tunic
adorable paisley printed off the shoulder tunic that transitions perfectly into Spring! add your favorite flare jeans and fun earrings, you're set
100% Polyester
Fully Lined
Cotton Fields Ruffle Top
meet your new favorite white blouse! YES this is a must for Spring and Summer. Love the feminine, romantic lace + ruffle detail. Great worn with dressier shorts or tucked into a skirt, shown here with jeans...I mean the options are endless. She's gorgeous, trust me!
Brantlee is a size 2-4 wearing the SMALL // RUNS VERY TTS
100% Polyester
Darla Tank
aaaah the perfect eyelet cotton peplum top. Every gal needs one this Spring and Summer! Shown here with the printed Mayan Tassel Short but also great with your colored denim this Spring, regular denim, and more!
Meg is a size 2-4 wearing the SMALL // RUNS VERY TTS
100% Cotton
Golden Hour Twist Top
faux twist top in the prettiest shade of goldilocks yellow. love with white denim or pair back with our "Up and Away Pant"
Meg is a size 2-4 wearing the SMALL , runs very TTS
Nashville Embroidered Dress
fun, fully lined cotton shift with belle sleeves and the most stunning embroidery. From cowboy boots to nude wedges, there's SO many places you'll love wearing this one!
RUNS TTS // Brantlee is 5'6 , size 2-4 wearing a size SMALL
100% Cotton
Nirvana Hi-Lo Blouse
total 90 vibes in this plaid flannel button up blouse with hi lo hem and self tie detail at sleeve. Totally updated and elevated, this ain't ya boyfriend's flannel shirt that's for sure BUT it feels just as divine.
RUNS TTS // Brantley is a size 2-4 wearing the SMALL
Laura Side Slit Pant - Black
another palazzo party with this fun new pant by JoyJoy! talk about the most comfy work pant that's right on trend. Great side slit and lightweight so easy to transition into Spring and even wear throughout Summer.
Meg is 5'6 wearing the SMALL , size 2-4
RUNS VERY TTS // elastic waist + pockets
Pressley Short - Mustard Stripe
a cute (and comfy!) elastic waist short that looks great with everything from a white tee to our new Golden Hour Twist top for a more monochromatic look. Think navy....teal....black and more....
Meg is a size 2-4 wearing the SMALL and 5'4 height
100% Viscose
Halle Dress - Wine (1 XSMALL LEFT)
such a great puff sleeve dress in the most gorgeous wine/garnet for Carolina fans! Love the black exposed zipper and such an easy style to dress up for weddings or dress down for gameday...
RUNS TTS // Meg is a size 2-4 wearing the SMALL
70% Cotton// 30% Polyester
Pickens Swing Dress
fun, flirty and flowy bell sleeve swiss dot , off the shoulder dress by JoyJoy! They always do the best dresses that are so versatile - dress up with gold strappy heels for Fall weddings or dress down with cowboy boots for concerts. Seriously so many options and the prettiest shade of rust orange!!!!!
RUNS TTS // Hope is a size 0,2 - height 5'7 wearing the XS
100% Rayon | fully lined
Mayberry Top
polka dots? = obsessed. yellow? = obsessed. Soooo we need this top ASAP! So adorable for Summer and we love with a pop of color (like a pop of pink, shown here with our Key West Earring - Party Pink
100% Viscose // Brantlee is a size 2-4 wearing the SMALL
Tibet Embroidered Dress
gorgeous embroidery and fun pom pom detail too! This is a great off the shoulder dress to throw on with cute wedges and head out for Cinco De Mayo fun or a vacay in Cabo! No matter where you take it, it's always ready to party :)
Brantlee is a size 2-4 wearing the SMALL
Redfield Ruffle Dress
we love when Jade gives us a fabulous ruffle back dress with pockets! This style is a winner , year after year and now available in this gorgeous red floral just in time for the 4th!
Meg is 5'6 , size 2-4 wearing the SMALL | runs very TTS
County Fair Tie Top
adorable tie bottom top that's easy to pair with our Moonshine Flares but also great with shorts too!
RUNS TRUE TO SIZE // Brantlee is a size 2- 4 wearing the SMALL
Redfield Tank
the cutest swing tank by JoyJoy in a gorgeous red floral for Summer!
Emma is a size 2-4 wearing the SMALL
runs very TTS
cotton/poly blend
Perfect Pull On Short - Taupe
our bestselling JoyJoy short year after year...back in this beautiful "taupe" that's almost looks like a mauve/blush pink in these photos and pairs back perfectly with the Jocassee Star Tank (which has olive stars). So yes, we love this with olive but also it's going to go with so much in your closet this Summer!
elastic waist, front pockets and one back right pocket
Meg is a size 2-4, height 5'7 wearing the SMALL
Boardwalk Shirtdress
fabulous midi length shirtdress in a classic ticking stripe with front pocket detail and self tie sash. Hope is a size 0-2 , height 5'7 wearing the SMALL
Joy Joy styles always definitely run TTS , if not full
Paloma Multi Dot Top
such a cute ruffle trim button up top that's so easy to tuck into the Kristen Short in White (shown here) and I love that it actually has the pretty blues , orange and even tan!
Cocoa Beach Tassel Dress
grab a margarita , senorita and be ready to party in this oh-so-fun embroidered dress by JoyJoy! They seriously always have the BEST embroidered dresses and they always go fast. Don't miss it!
Meg is 5'6 , size 2-4 wearing the SMALL
Mayan Shirt Dress
a great fully lined shirt dress with cuffed sleeves, that you can throw on with sunnies + your big straw bag + sandals during the day, then dress up for dinner with wedges at night
Hope is 5'7 , size 0-2 wearing an XS
Arcade Stripe Crop Pant
such cute side slit palazzo pants with our Arcade Stripe Top , but also just with our simple Z Supply Tee that we tied up in a front knot for an a chic Spring/Summer look! The elastic waist + lightweight fabric = these pants are HEAVEN!
Arcade Stripe Tie Top
lightweight front tie top that pairs back perfectly with the Arcade Cropped Pant , but also looks amazing with white denim or shorts all through Summer!
Pink Lillies Top
the sweetest top that just screams Spring. Who doesn't love gorgeous pink Lillies? combine with a sky blue and you've got a gorgeous top that's just a dream! Pair with white denim and you're set. << shown here with the BuddyLove Moonshine Flares>>
height 5'6
Sweetheart Kimono
another fab kimono from JoyJoy, sized S/M and M/L - it's always a great style to not only layer over a top + jeans, but even dresses too. Shown here over the Z Supply Vagabond Tank in Slate Rose + Moonshine Flares
Meg is a size 2-4 wearing the S/M
Texas Button Top
the cutest little cropped top that's HOTTER than Texas ;) Love this burnt orange hue for Fall and the button detail. Add your favorite high waisted jeans, maybe some cowboy boots and you're set!
RUNS TTS // Meg is a size 2-4 wearing a SMALL


text:
Shop The SALE 10% to 30% Off Now. Local Delivery Available. Open Tuesdays, Thursdays and Saturdays 11AM to 6PM.
Regular price
Now 30% Off
Expertly made in lightweight stripe pattern, with a high threat count, these towels feel luxurious and modern.
Certified Fairtrade and GOTS 100% certified organic cotton.
Available in different sizes and colours.
Wash Cloth: 12" x 12" in 550gsm
Hand Towel: 20" x 40" in 550gsm
Bath Towel: 27" x 54" in 550gsm
Bath Mat: 20" x 35" in 900gsm


text:
If you want to enjoy a peaceful and quite place- this is the place for you! This cozy cottage is placed 7 minutes walk down a hill from Kasar Devi road, in Papersali village. It is located in nature. There are three rooms, 1st-Two bedroom cottage with kitchen,fireplace and bath. 2nd-New rooftop cottage with kitchen and bath. Himalaya and nature view from rooftop. From here you can go on daily hikes between villages, temples, mountains, Eco park, watch birds and listen to them from the balcony.
"素晴らしい言葉が正しい。 とても静かな場所 あなたはかなりの場所が好きではない場合は、これに行かないでください。 素晴らしいおもてなし。すべてのリクエストが聞かれ、実行されます。 harish jiは非常にシンプルで、地球上の人にダウンしています。"
10, Nautical Mile - as the name suggests, this is a Mountain Cottage of a Mariner. This has been made out of love for the mountains and a wish to slow down the pace of life. Ideal for family and 'me' time, this is a home away from a home; tucked away in the lush green forest 15km away from the cantonment Town of Ranikhet at Uttarakhand.
A mountain get away with pristine view of the snow clad mountains and an abode of the Devine on the Devbhoomi we all know of. Antique woodwork which comfortably beds 1-2 or if privacy is of no issue accommodation for more can be arranged. Owner is accessible any time need be with total privacy of being a priority. This bed & bath is accommodated with water heaters, heaters, kitchen and direct access to the Haidakhan temple, Hope you enjoy your stay .


text:
Use of organic oxyimide salts as flame retardants, flame-retardant plastic compositions, method for the production thereof and moulded part, paint or coating
First Claim
1. A method for imparting flame retardancy to a plastic material comprising incorporating an organic oxyimide salt having at least one structural element of formula I
1 Assignment
0 Petitions
Accused Products
The invention relates to the use of organic oxyimide salts as flame retardants for plastics and to a corresponding flame retardant plastic composition. The invention also relates to a method for producing said type of plastic composition or a molded part produced therefrom, a molding compound, a molded part, paint or a coating.
24 Citations
No References
|Branched polyphosphonates
Patent #US 7,816,486 B2
Filed 02/24/2004
Current AssigneeFRX Polymers Inc.
Sponsoring EntityFRX Polymers Inc.
|N-substituted imides as polymerization initiators
Patent #US 7,723,399 B2
Filed 10/31/2005
Current AssigneeCIBA Specialty Chemicals
Sponsoring EntityCIBA Specialty Chemicals
|Process for Preparing Diaryl Alkylphosphonates and Oligomeric/Polymeric Derivatives Thereof
Patent #US 20080045673A1
Filed 08/29/2005
Current AssigneeICL-IP America Inc.
Sponsoring EntityICL-IP America Inc.
|N-Substituted Imides As Polymerization Initiators
Patent #US 20080132600A1
Filed 10/31/2005
Current AssigneeCIBA Specialty Chemicals
Sponsoring EntityCIBA Specialty Chemicals
|Polyphosphonate Flame Retardant Curing Agent For Epoxy Resin
Patent #US 20070219295A1
Filed 05/19/2004
Current AssigneeICL-IP America Inc.
Sponsoring EntityICL-IP America Inc.
|Oligomeric, hydroxy-terminated phosphonates
Patent #US 20050020800A1
Filed 10/04/2002
Current AssigneeICL-IP America Inc.
Sponsoring EntityICL-IP America Inc.
|Branched polyphosphonates that exhibit an advantageous combination of properties, and methods related thereto
Patent #US 6,861,499 B2
Filed 02/24/2003
Current AssigneeFRX Polymers Inc.
Sponsoring EntityTriton Systems Inc.
|High refractive index thermoplastic polyphosphonates
Patent #US 6,288,210 B1
Filed 11/12/1999
Current AssigneeEssilor International SA
Sponsoring EntityJohnson Johnson Vision Products Inc.
|Method for producing a liquid formulation of tetraphenylphosphonium phenolate
Patent #US 6,291,630 B1
Filed 09/06/2000
Current AssigneeBayer AG
Sponsoring EntityBayer AG
|Polymetric film
Patent #US 5,690,994 A
Filed 06/05/1995
Current AssigneeImperial Chemical Industries PLC
Sponsoring EntityImperial Chemical Industries PLC
|Highly branched polyphosphonates based on melamine
Patent #US 5,334,692 A
Filed 11/24/1993
Current AssigneeBayer AG
Sponsoring EntityBayer AG
|Highly branched polyphosphonates
Patent #US 5,216,113 A
Filed 09/24/1990
Current AssigneeBayer AG
Sponsoring EntityBayer AG
|Process for the preparation of thermoplastic aromatic polyphosphonates with improved thermal ageing resistance
Patent #US 4,374,971 A
Filed 10/27/1980
Current AssigneeBayer AG
Sponsoring EntityBayer AG
|Thermoplastic, branched aromatic polyphosphonates, and a process for their production
Patent #US 4,415,719 A
Filed 12/07/1981
Current AssigneeBayer AG
Sponsoring EntityBayer AG
|Aromatic polyester phosphonates
Patent #US 4,328,174 A
Filed 06/19/1980
Current AssigneeBayer AG
Sponsoring EntityBayer AG
|Aromatic polyphosphonates and a process for their production
Patent #US 4,331,614 A
Filed 06/18/1980
Current AssigneeBayer AG
Sponsoring EntityBayer AG
|Tetrasulfide extreme pressure lubricant additives
Patent #US 4,218,332 A
Filed 03/20/1979
Current AssigneeUnited States Department Of Agriculture
Sponsoring EntityUnited States Department Of Agriculture
|Process for preparing polyphosphonate
Patent #US 3,946,093 A
Filed 12/26/1974
Current AssigneeNissan Chemical Industries Limited
Sponsoring EntityNissan Chemical Industries Limited
|Process for preparing poly(sulfonyl-phenylene)phenylphosphonate
Patent #US 3,919,363 A
Filed 04/30/1974
Current AssigneeNissan Chemical Industries Limited
Sponsoring EntityNissan Chemical Industries Limited
Patent #US 3,442,854 A
Filed 01/20/1966
Current AssigneeSchnell Hermann, Curtius Ulrich, Bottenbruch Ludwig
Sponsoring EntitySchnell Hermann, Curtius Ulrich, Bottenbruch Ludwig
|Process for preparing polymeric organo-phosphonates
Patent #US 2,682,522 A
Filed 09/10/1952
Current AssigneeHarry W. Coover Jr, Marvin A. Mccall
Sponsoring EntityHarry W. Coover Jr, Marvin A. Mccall
|Resinous polymeric phosphonates
Patent #US 3,326,852 A
Filed 08/10/1964
Current AssigneeIan M. Thomas
Sponsoring EntityIan M. Thomas
|Polymeric organo-phosphonates containing phosphato groups
Patent #US 2,716,101 A
Filed 09/10/1952
Current AssigneeHarry W. Coover Jr, Marvin A. Mccall
Sponsoring EntityHarry W. Coover Jr, Marvin A. Mccall
|Organophosphorus polymers
Patent #US 2,891,915 A
Filed 07/02/1954
Current AssigneeElbert Schroeder Herman, Brewster Mccormack William
Sponsoring EntityElbert Schroeder Herman, Brewster Mccormack William
15 Claims
- 1. A method for imparting flame retardancy to a plastic material comprising incorporating an organic oxyimide salt having at least one structural element of formula I
- 10. A flame-retardant plastic material composition, comprising or consisting of:
a) 60 to 99.9 parts by weight of at least one plastic material, b) 0.1 to 40 parts by weight of at least one organic oxyimide salt, comprising at least one structural element of the formula I,
- View Dependent Claims (11, 12, 14)
- 13. A method for the production of a flame-retardant plastic material composition, comprising introducing into the plastic material
a) 0.1 to 40 parts by weight of at least one organic oxyimide salt, comprising at least one structural element of the subsequently illustrated formula I,
1 Specification
This patent application is the U.S. national phase of International Application No. PCT/EP2015/071254, filed on Sep. 16, 2015, which claims the benefit of German Patent Application No. 10 2014 218 810.5, filed Sep. 18, 2014, the disclosures of which are incorporated herein by reference in their entireties for all purposes.
The present invention relates to the use of salts of organic oxyimides as flame retardant for plastic materials and also to a correspondingly flame-retardant plastic material moulding compound. In addition, the present invention relates to a production method for such a plastic material moulding compound or to a moulding part, paint or a coating produced herefrom.
Most plastic materials are combustible and comparatively easily inflammable. In order to reduce or exclude the risk of fire to plastic materials in specific applications, it is therefore absolutely necessary to reduce the flammability and to use flameproof plastic material compositions. For this purpose, generally flame retardants are added to the plastic material with the aim of inhibiting ignition for a specific time or significantly delaying the spread of fire. Traditional flame retardants are based on chlorine- and bromine-containing compounds (the latter generally in combination with antimony trioxide), on phosphorus-containing, on nitrogen-containing compounds and on metal hydroxides, such as aluminium hydroxide (ATH) or magnesium hydroxide (MDH). In recent times, halogen-free flame-retardant solutions are preferred for toxicological and ecotoxicological reasons.
For the production of flame-retardant plastic materials, there is a large number of flame retardants which are used generally substrate-specifically for a specific polymer and a specific field of use, corresponding to the national and international standards which form the basis thereof. Flame-retardant plastic materials are used for example in electrical and electronic applications, in the transport field (train, aircraft, car), in textiles, in upholstered furniture and in construction.
A new flame-retardant class, developed in the last few years and based on nitrogen, preferably for polyolefins, is based on selected alkoxyamines (e.g. WO 99/00450). Due to cleavage of the alkoxyamines, radicals are produced in the case of fire, which radicals intervene in the decomposition process of the polymer and hence cause the flame-retardant effect (C. R. Wilen, R. Pfaendner, J. Appl. Pol. Sci. 2013, 129, 925-944). Apart from alkoxyamines, in the meantime, also other radical generators have been described, which act as flame retardants or as flame-retardant synergists, such as azo compounds (Nicolas et al., Macromol. Rapid Commun. 2006, 27, 976-981, WO 2005/030852), hydrazones and azines (M. Aubert et al., Pol. Adv. Technol. 2011, 22, 1529-1538), azo-alkoxyamines (M. Aubert et al. Pol. Degr. Stab. 2012, 97, 1438-1446) azo-phosphonates (T. Tirri et al., Pol. Degr. Stab. 2012, 97, 375-382) or triazenes (W. Pawelec et al., Pol. Degr. Stab. 2012, 97, 948-954).
Furthermore, the use of new radical generators based on hydroxyimides and polymeric imides as flame retardant is described in the patent application DE 10 2013 005 307 or the as yet unpublished patent application DE 10 2014 210 214.
Many of the known and mentioned radical generators do not however fulfil all requirements for an effective flame retardant, such as e.g. sufficient thermal stability, i.e. during incorporation in plastic materials (compounding) at normal temperatures, in fact an undesired decomposition of the flame retardant occurs. As a result of this premature decomposition, the effect in the case of fire is reduced and/or, as a result of subsequent reactions, the properties of the plastic material to be protected are affected negatively. The wish exists therefore for radical generators which can be used as flame retardant or flame-retardant synergists, which have sufficiently high temperature stability during plastic material processing, i.e. generally above 300° C., but then achieve a particularly good effect in the case of fire due to rapid decomposition.
It was therefore the object of the present invention to make available new flame retardants and synergistic flame-retardant components which are highly effective and have very good thermal stabilities.
This object is achieved by the use of the organic imide salts, by a flame-retardant plastic material composition, by a method for the production of a flame-retardant plastic material composition and also by a moulded part, paint or a coating described herein, and advantageous developments thereof.
The present invention hence relates to the use of organic oxyimide salts, comprising at least one structural element of subsequently illustrated formula I
R1 being selected from the group consisting of inorganic or organic cations, as flame retardant for plastic materials.
The term "organic oxyimide salts" should thereby be understood synonymously with salts which are derived from an organic oxyimide. Such organic oxyimides are described for example in the already previously mentioned German patent application DE 10 2013 005 307. For further explanation of the structural principles of the organic oxyimides, reference is made to the entire content of this patent application. From these organic oxyimides, the salts of the organic oxyimides, which are used according to the invention, ergo the organic oxyimide salts, can be prepared for example by conversion with a base.
Preferred cations R1 are described in the following.
The inorganic cations are thereby selected preferably from the group consisting of metal cations, preferably monovalent, bivalent or trivalent alkali metal cations, alkaline earth metal cations, transition metal cations and/or rare earth metal cations, in particular Na+, K+, Mg2+, Ca2+, Zn2+ and/or Al3+.
Preferred organic cations are selected in particular from the group consisting of nitrogen and/or phosphorus-containing organic cations, in particular ammonium-, melaminium- and phosphonium cations. The organic cations can thereby be present in a low-molecular form or bonded to a polymer backbone.
Likewise, combinations of at least two different ones of the aforementioned cations are possible, i.e. the organic oxyimide salts can likewise be present as mixed salts. For example, the combination of two or more of the inorganic cations, two or more of the previously described organic cations, just as also a mixed salt which has both inorganic and organic cations, are thereby conceivable. Alternatively or additionally hereto, the salts relating to the present invention can also be present as mixed salt with at least two different anions. Hereby are for example the combination of two or more of the inorganic anions, two or more organic anions and also a mixed salt which has both inorganic and organic anions.
It is thereby particularly preferred if the organic oxyimide salt is halogen-free, i.e. the corresponding compound comprises no halogen atoms.
It is further advantageous if the organic oxyimide salt has the subsequent structure
R1 being defined as above and R1′, upon each occurrence, being the same or different and representing a linear or branched alkyl-radical, a linear or branched alkylene-radical, an aromatic radical, a heteroaromatic radical or both radicals R1′ being joined to form a ring, the ring being able to be saturated or unsaturated, substituted or unsubstituted and/or at least one or both radicals R1′ or the radicals R1′ joined to form a ring comprising at least one further structural element of the above illustrated formula I.
Preferred examples of organic oxyimide salts used according to the invention are described subsequently. Organic oxyimide salts which comprise only one structural element of the general formula I are conceivable. Compounds, given by way of example, are thereby selected from the subsequently illustrated compounds
It is likewise conceivable that the oxyimide salts comprise two structural elements of the general formula I. Compounds which correspond to the subsequent structural formulae are hereby possible
- n meaning 0, 1, 2, 3 or 4, and
- R2 being selected from the group consisting of possibly substituted alkylene-, cycloalkylene-, arylene-, heteroarylene- or bridging acyl-radicals.
The use of an oxyimide salt which has three structural elements of the general formula I is likewise conceivable, according to the subsequent formula
A combination or a mixture of a plurality of the previously described oxyimide salts is likewise possible.
In the oxyimide salt according to the subsequent formula
it is preferred if the moiety R2 is selected from moieties of the group consisting of
—(CH2)n— with n=1 to 18, —CH(CH3)—, —C(CH3)2—, —CH(CF3)—, —C(CF3)2—, —O—, —S—, —SO2—, —NHCO—, —CO—, —O—C(O)—O— and also the subsequently illustrated groups
- the cycloaliphatic or aromatic ring systems contained in the previously illustrated groups being unsubstituted or substituted by one or more alkyl- and/or alkoxy groups,
- Q upon each occurrence, being the same or different and being selected from the group consisting of a chemical bond and also the moieties —(CH2)n— with n=1 to 18, —CH(CH3)—, —C(CH3)2—, —CH(CF3)—, —C(CF3)2—, —O—, —S—, —SO2—, —NHCO—, —CO—, —O—O3—, and
- m being 0 or 1 to 3.
Preferably, the plastic materials to be protected are thermoplastic polymers and selected in particular from the group consisting of:
- a) polymers made of olefins or diolefins, such as e.g. polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene-PE (m-PE), polypropylene, polyisobutylene, poly-4-methylpentene-1, polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers and also copolymers in the form of statistical or block structures, such as e.g. polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene-acrylester, such as e.g. ethylene-butylacrylate, ethylene-acrylic acid and the salts thereof (ionomers), and also terpolymers, such as e.g. ethylene-acrylic acid-glycidylacrylate, graft polymers, such as e.g. polypropylene-graft-maleic anhydride, polypropylene-graft-acrylic acid, polyethylene-graft-acrylic acid, polyethylene-polybutylacrylate-graft-maleic anhydride,
- b) polystyrene, polymethylstyrene, polyvinylnaphthalene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers, such as e.g. styrene on butadiene, maleic anhydride on SBS or SEBS, and also graft copolymers made of methylmethacrylate, styrene-butadiene and ABS (MABS),
- c) halogen-containing polymers, such as e.g. polyvinyl chloride (PVC), polychloroprene and polyvinylidene chloride (PVDC), copolymers made of vinyl chloride and vinylidene chloride, or made of vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride,
- d) polymers of unsaturated esters, such as e.g. polyacrylates and polymethacrylates, such as polymethylmethacrylate (PMMA), polybutylacrylate, polylaurylacrylate, polystearylacrylate, polyglycidylacrylate, polyglycidylmethacrylate, polyacrylonitrile, polyacrylamides, copolymers, such as e.g. polyacrylonitrile-polyalkylacrylate, polymethacrylimide,
- e) polymers made of unsaturated alcohols and derivatives, such as e.g. polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral,
- f) polyacetals, such as e.g. polyoxymethylene (POM) or copolymers, with e.g. butanal,
- g) polyphenylene oxides and blends with polystyrene or polyamides,
- h) polymers of cyclic ethers, such as e.g. polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, polytetrahydrofuran,
- i) polyurethanes made of hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, in particular linear polyurethanes, polyureas,
- j) polyamides, such as e.g. polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 12.12, polyamide 11, polyamide 12 and also (partially) aromatic polyamides, such as e.g. polyphthalamides, e.g. produced from terephthalic acid and/or isophthalic acid and aliphatic diamines or from aliphatic dicarboxylic acids, such as e.g. adipic acid or sebacic acid, and aromatic diamines, such as e.g. 1,4- or 1,3-diaminobenzene, blends of different polyamides, such as e.g. PA-6 and PA 6.6 or blends of polyamides and polyolefins, such as e.g. PA/PP,
- k) polyimides, polyamideimides, polyetherimides, polyesterimides, poly(ether)ketones, polysulfones, polyethersulfones, polyarylsulfones, polyphenylenesulfides, polybenzimidazoles, polyhydantoins,
- l) polyesters made of aliphatic or aromatic dicarboxylic acids and diols or made of hydroxycarboxylic acids, such as e.g. polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate, polyethylene naphthylate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PVH),
- m) polycarbonates, polyestercarbonates and also blends, such as e.g. PC/ABS, PC/PBT, PC/PET/PBT, PC/PA,
- n) cellulose derivatives, such as e.g. cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate,
- o) non-thermoplastic, elastomeric or duroplastic plastic materials,
- p) and also mixtures, combinations or blends of two or more of the previously mentioned polymers.
Provided the polymers indicated under a) to o) concern copolymers, these can be present in the form of statistical ("random"), block- or "tapered" structures.
Provided the polymers indicated under a) to o) concern stereoregular polymers, these can be present in the form of isotactic, stereotactic but also atactic forms or in stereoblock structures.
Furthermore, the polymers indicated under a) to o) can have both amorphous and (partially) crystalline morphologies.
Possibly, the polyolefins mentioned under a) to o) can also be present crosslinked, e.g. crosslinked polyethylene, which is then termed X-PE.
The mentioned polymers a) to o) can thereby be present not only as virgin material but also in the form of recyclates, e.g. as production waste or "post-consumer" recyclates.
Preferred duromeric or elastomeric, non-thermoplastic plastic materials, which are listed further back under o) and in which the present flame retardants can be used, are thereby the following:
- q) epoxy resins, consisting of di- or polyfunctional epoxy compounds in combination with e.g. hardeners, based on amines, anhydrides, dicyanodiamides, mercaptans, isocyanates or catalytically acting hardeners,
- r) phenol resins, such as e.g. phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins,
- s) unsaturated polyester resins made of unsaturated dicarboxylic acids and diols,
- t) silicones,
- u) polyurethanes as reaction products made of di- or polyfunctional isocyanates and polyols, polyureas,
- v) alkyd resins, allyl resins.
For very particular preference, the flame retardants according to the invention are used in the case of polyolefins, preferably polypropylene and/or polyethylene and the copolymers and blends thereof.
For further preference, the organic oxyimide salts are used in combination with at least one further flame retardant. This at least one further flame retardant is thereby preferably selected consisting of
- a) inorganic flame retardants, such as e.g. Al(OH)3, Mg(OH)2, AlO(OH), MgCO3, layer silicates, such as e.g. montmorillonite or sepiolite, non- or organically modified, double salts, such as e.g. Mg—Al silicates, POSS (Polyhedral Oligomeric Silsesquioxane) compounds, huntite, hydromagnesite or halloysite and also Sb2O3, Sb2O5, MoO3, zinc stannate, zinc hydroxystannate,
- b) nitrogen-containing flame retardants, such as e.g. melamine, melem, melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, (poly)phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine-methane phosphonate, melamine-metal phosphates, such as e.g. melamine aluminium phosphate, melamine zinc phosphate, melamine magnesium phosphate, and also the corresponding pyrophosphates and polyphosphates, ethylene diamine methane phosphate, poly-[2,4-(piperazin-1,4,-yl]-6-(morpholin-4-yl)3,5-triazine], ammonium polyphosphate, melamine borate, melamine hydrobromide,
- c) radical formers, such as e.g. alkoxyamines, hydroxylamine esters, azo compounds, dicumyl or polycumyl, hydroxyimides or the derivatives thereof, such as e.g. hydroxyimide ester or hydroxyimide ether,
- d) phosphorus-containing flame retardants, such as e.g. inorganic or organic phosphonates, such as e.g. aluminium phosphonate, phosphonate ester, oligomeric and polymeric derivatives of methane phosphonic acid, red phosphorus, phosphates, such as e.g. resorcin diphosphate, bisphenol-A-diphosphate and the oligomers thereof, triphenylphosphate, ethylene diamine phosphate, phosphinates, such as e.g. salts of hypophosphorous acid and the derivatives thereof, such as alkyl phosphinate salts, e.g. diethylphosphinate aluminium or diethylphosphinate zinc or aluminium phosphinate, aluminium phosphite, aluminium phosphate, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and the substituted compounds thereof,
- e) halogen-containing flame retardants based on chlorine and bromine, such as e.g. polybrominated diphenyl oxides, such as e.g. decabromodiphenyl oxide, tris(3-bromo-2,2-bis(bromomethyl)propylphosphate, tris(tribromoneopentyl)phosphate, tetrabromophthalic acid, 1,2-bis(tribromophenoxy)ethane, hexabromocyclododecane, brominated diphenylethane, tris-(2,3,-dibromopropyl)isocyanurate, ethylenebis(tetrabromophthalimide), tetrabromobisphenol-A-bis(2,3)dibromopropylether), tetrabromobisphenol A, brominated polystyrene, brominated polybutadiene or polystyrene-brominated polybutadiene copolymers, brominated epoxy resin, polypentabromobenzylacrylate, brominated polyphenylene ether, possibly in combination with Sb2O3 and/or Sb2O5,
- f) borates, such as e.g. zinc borate or calcium borate, possibly on carrier materials such as silica,
- g) sulfur-containing compounds, such as e.g. elementary sulfur, disulfides and polysulfides, thiuram sulfide, dithiocarbamates, mercaptobenzothiazole and sulfenamides,
- h) antidrip agents, such as e.g. polytetrafluoroethylene,
- i) silicon-containing compounds, such as e.g. polyphenylsiloxanes,
- j) carbon modifications, such as e.g. carbon nanotubes (CNT) or graphene
and also combinations or mixtures hereof.
The halogen-containing flame retardants mentioned under e) frequently concern commercial products which are commercially available, e.g. from the companies Albemarle, Chemtura/Great Lakes or ICL-IP.
In particular in the case of combinations of the compounds used according to the invention according to formulae I to IV with at least one radical former as further flame retardant, synergistic effects result.
Radical formers in the sense of the present invention are compounds which can produce radicals by means of thermal and light-induced cleavage. Suitable radical formers for the applications present here are those which have sufficient thermal stability for the plastic material- or coating-processing processes, i.e. during processing, still form no or only very small quantities of radicals and produce radicals spontaneously only at higher temperatures, such as occur only in the case of fire. The respective processing processes and temperatures for coatings and plastic material processing processes are known to the person skilled in the art. Plastic material processing processes and associated temperatures can however also be obtained from the expert literature, such as e.g. H. Domininghaus, P. Elsner, P. Eyerer, T. Hirth, Kunststoffe (Plastic materials), 8th edition, Springer 2012.
The radical former is thereby selected preferably from the group consisting of N-alkoxyamines, —C—C— radical formers, radical formers with azo groups (—N═N—), radical formers with hydrazine groups (—NH—HN—), radical formers with hydrazone groups (>C═N—NH—), radical formers with azine groups (>C═N—N═C<), radical formers with triazene groups (—N═N—N<).
The production of suitable azo compounds is described for example in M. Aubert et al. Macromol. Sci. Eng. 2007, 292, 707-714 or in WO 2008101845, the production of hydrazones and azines in M. Aubert et al., Pol. Adv. Technol. 2011, 22, 1529-1538, the production of triazenes in W. Pawelec et al., Pol. Degr. Stab. 2012, 97, 948-954.
The radical former is thereby selected for particular preference from the group consisting of
- a) N-alkoxyamines according to the subsequently illustrated structural formula,
- R3 standing for hydrogen or a possibly substituted alkyl-, cycloalkyl-, aryl-, heteroaryl- or acyl-radical, in particular being a C1 to C4 alkyl radical,
- R4 standing for an alkoxy-, aryloxy-, cycloalkoxy-, aralkoxy- or acyloxy-radical,
- Z standing for hydrogen or a possibly substituted alkyl-, cycloalkyl-, aryl-, heteroaryl- or acyl-radical, the two radicals Z also being able to form a closed ring which can be substituted possibly by ester-, ether-, amine-, amide-, carboxy- or urethane groups,
- b) azo compounds according to the subsequently illustrated structural formulae,
- R5 meaning an alkyl-, cycloalkyl- or aryl-radical,
- R6 upon each occurrence, being the same or different and meaning a linear or branched alkyl-radical,
- R7 upon each occurrence, being the same or different and meaning hydrogen or a linear or branched alkyl-radical, and
- R8 upon each occurrence, being the same or different and meaning an alkyl-, alkoxy-, aryloxy-, cycloalkyloxy-, aralkoxy- or acyloxy-radical,
- c) dicumyl according to the subsequently illustrated structural formula
- R7 having the previously indicated meaning, preferably being methyl,
- d) and/or polycumyl according to the subsequently illustrated structural formula
- R7 having the previously indicated meaning, preferably being methyl, and 2<n<100.
Typical examples of the previously mentioned N-alkoxyamines of the indicated structure are thereby:
1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine; bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxyethylamino-S-triazine; bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)adipate; 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-S-triazine; 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine; 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine; 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine; bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)adipate; 2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-S-triazine); 4-piperidinol, 2,2,6,6-tetramethyl-1-(undecyloxy)-,4,4′-carbonate; the reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-S-triazine with N,N′-bis(3-aminopropylethylenediamine); the oligomer compound, which is the condensation product of 4,4′-hexamethylene-bis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethyl-4-yl)butylamino]-S-triazine, closed at the ends with 2-chloro-4,6-bis(dibutylamino)-S-triazine; aliphatic hydroxylamine, such as e.g. distearyl hydroxylamine; and also compounds of the formulae.
in which n=1-15.
The above-mentioned compounds are partially commercial products and are sold under the following trade names: FLAMESTAB NOR 116®, TINUVIN NOR 371®, IRGATEC CR 76® by BASF SE, Hostavin NOW® by Clariant or ADK Stab LA 81® by Adeka. Dicumyl and polycumyl are commercial products which are obtainable for example from United Initiators.
Sulfur-containing flame retardants are likewise radical formers with radical formers with disulfide- or polysulfide groups (—S—S—) or thiol groups (—S—H), and also thiuram sulfides, such as e.g. tetramethylthiuram disulfide, dithiocarbamates, such as e.g. zinc diethyldithiocarbamate or sodium dimethyldithiocarbamate, mercaptobenzothiazoles, such as e.g. 2-mercaptobenzothiazole and sulfenamides, such as e.g. N,N-dicyclohexyl-2-benzothiazolesulfenamide.
An example of a polysulfide is elementary sulfur, other polysulfides are described for example in U.S. Pat. No. 4,218,332.
Disulfides, polysulfides, thiols, thiuram sulfides, dithiocarbamates, mercaptibenzothiazoles and sulfenamides are commercially available.
Further suitable radical formers are hydroximides and the derivatives thereof such as hydroxyimide ester or hydroxyamide ether, as are described in WO 2014/154636.
The combination of the oxyimide salts according to the invention with another radical former can be in particular advantageous, since here the radical formation can be effected at different decomposition temperatures or adjusted according to requirement.
The at least one further flame retardant can be in particular also a phosphorus-containing flame retardant. Preferred phosphorus-containing flame retardants are thereby phosphinates of the following structures:
R1 and R2 preferably being identical or different and being selected from linear or branched C1-C6 alkyl and/or aryl; M being selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, Zn and/or a protonated nitrogen base, preferably calcium ions, magnesium ions, aluminium ions and/or zinc ions; and m=1-4, preferably 2 or 3; n=1-4, preferably 1 or 3; x=1-4, preferably 1 or 2. In a particularly preferred embodiment, R1=alkyl, R2=alkyl and M=Al or Zn.
A particularly preferred example of a phosphinate according to the invention are the commercially available products Exolit OP® by Clariant SE.
Further preferred phosphorus-containing flame retardants are metal salts of hypophosphorous acid with a structure according to the formula
Met being a metal, selected from groups I, II, III and IV of the periodic table of elements, and n being a number from 1 to 4 which corresponds to the charge of the corresponding metal ion Met. Met is for example Na+, Ca2+, Mg2+, Zn2+, Ti4+ or Al3+, wherein Ca2+, Zn2+ and Al3+ are particularly preferred.
The above-mentioned salts of hypophosphorous acid are partially commercially available, e.g. with the title Phoslite® by Italmatch Chemicals.
A further preferred group of phosphorus-containing flame retardants are phosphonates or phosphonic acid diaryl esters of a structure according to the following formula:
R8 and R10═H, alkyl, preferably C1-C4 alkyl, R9═C1-C4 alkyl, u=1-5 and v=1-5.
Corresponding structures can also be present in the form of phosphonate oligomers, polymers and copolymers. Linear or branched phosphonate oligomers and polymers are known from the state of the art. For branched phosphonate oligomers and polymers, reference is made to the U.S. Pat. Nos. 2,716,101, 3,326,852, 4,328,174, 4,331,614, 4,374,971, 4,415,719, 5,216,113, 5,334,692, 3,442,854, 6,291,630 B1, 6,861,499 B2 and 7,816,486 B2. For phosphonate oligomers, reference is made to the US patent applications US 2005/0020800 A1, US 2007/0219295 A1 and US 2008/0045673 A1. With respect to linear phosphonate oligomers and polymers, reference is made to the US patent documents U.S. Pat. Nos. 3,946,093, 3,919,363, 6,288,210 B1, 2,682,522 and 2,891,915.
Polymeric and oligomeric phosphonates are available for example under the trade name Nofia® by FRX Polymers.
A further preferred group of phosphorus-containing flame retardants are compounds based on oxaphosphorin oxide and the derivatives thereof with for example the following structures:
M being a metal, selected from the second, third, twelfth or thirteenth group of the periodic table of elements, x=2 or 3, n≥10, m=0-25, R═H, halogen or an aliphatic or aromatic radical with 1-32 C atoms and R1═H, C1-C6 alkyl.
Products based on oxaphosphorin oxide are marketed for example under the trade name Ukanol® by Schill and Seilacher GmbH. Further compounds can be produced for example according to the patent specifications WO 2013020696, WO 2010135398, WO 03070736, WO 2006084488, WO 2006084489, WO 2011000019, WO 2013068437, WO 2013072295.
Further synergistic phosphorus-containing flame retardants are cyclic phosphonates of a structure according to one of the following formulae:
A1 and A2, independently of each other, representing a substituted or unsubstituted, straight-chain or branched alkyl group with 1 to 4 carbon atoms, substituted or unsubstituted benzyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, and A3 and A4, independently of each other, being methyl or ethyl and A5 being a straight-chain or branched alkyl group with 1 to 4 carbon atoms or a phenyl- or benzyl group which can have respectively up to 3 methyl groups.
Cyclic phosphonates are marketed for example by the company Thor GmbH under the trade name Aflammit® or can be produced according to EP 2450401.
Further synergistic phosphorus-containing flame retardants are phosphacenes, in particular polymeric phosphacenes. A corresponding product is available commercially e.g. under the title SPB-100 by Otsuka Chemicals.
The at least one further flame retardant can be in particular also a nitrogen-containing flame retardant. Preferred nitrogen-containing flame retardants are melamine polyphosphate, melamine cyanurate, melamine-metal phosphates, poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine] and ammonium polyphosphate. These compounds are commercial products and available under the trade names Melapur® by BASF SE, Budit® by Budenheim Chemische Fabrik, Exolit AP® by Clariant, Safire® by J. M. Huber Corporation or MCA PPM Triazine by MCA Technologies GmbH.
The combination of the oxyimide salts according to the invention with a phosphonate and/or a (poly)phosphacene is very particularly preferred.
In the case of the previously described combined use of the organic oxyimide salt with at least one further flame retardant, it is preferred if the weight ratio of organic oxyimide salt or of the sum of all the organic oxyimide salts used and the at least one further flame retardant is in the range of 99:1 to 1:99, preferably of 5:95 to 50:50, particularly preferably of 10:90 to 30:70.
It is likewise possible and preferred that the previously mentioned organic oxyimide salts are used in combination with at least one phosphorus-containing compound. The phosphorus-containing compound is thereby not identical to the previously mentioned phosphorus-containing flame retardants. These phosphorus-containing compounds can thereby be selected in particular from the group consisting of organic phosphites or phosphonites. Suitable compounds are then for example:
triphenylphosphite, diphenylalkylphosphites, phenyldialkylphosphites, tri(nonylphenyl)phosphite, trilaurylphosphites, trioctadecylphosphite, distearylpentaerythritoldiphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, diisodecylpentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphite, bis(2,4-di-cumylphenyl)pentaerythritoldiphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite, diisodecyloxypentaerythritoldiphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritoldiphosphite, bis(2,4,6-tris(tert-butylphenyl) pentaerythritoldiphosphite, tristearylsorbitoltriphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocine, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphosphocine, 2,2′2″-nitrilo[triethyltris(3,3″,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], 2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl))phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.
Furthermore, it is advantageous that the organic oxyimide salts, relative to the plastic materials, are used at 0.01 to 30% by weight, preferably at 0.1 to 20% by weight, particularly preferably at 1 to 10% by weight.
In addition, the present invention relates to a flame-retardant plastic material composition, comprising or consisting of:
- a) 60 to 99.9 parts by weight, preferably 60 to 98, particularly preferably 70 to 95 parts by weight, of at least one plastic material, in particular of at least one thermoplastic polymer,
- b) 0.1 to 40 parts by weight, preferably 1 to 25 parts by weight, particularly preferably 2.5 to 15 parts by weight, of at least one organic oxyimide salt, comprising at least one structural element of the subsequently illustrated formula I,
- R1 being selected from the group consisting of inorganic or organic cations
- c) 0 to 25 parts by weight, preferably 1 to 20 parts by weight, particularly preferably 2.5 to 15 parts by weight, of at least one further flame retardant and also
- d) 0 to 25 parts by weight, preferably 1 to 20 parts by weight, particularly preferably 2.5 to 15 parts by weight, of at least one further phosphorus-containing compound.
The oxyimide salts and/or flame retardants used in the composition correspond to the above-described oxyimide salts or flame retardants. In particular, it is preferred if the flame retardant is a phosphonate or a (poly)phosphacene.
A preferred embodiment provides that the plastic material composition comprises in addition
- a) up to 40 parts by weight of at least one reinforcing- or filling material and/or
- b) up to 5 parts by weight of at least one additive from the class of phenolic antioxidants, phosphites, acid collectors, hindered amines, dispersants and also combinations hereof.
Preferably, the flame-retardant plastic material composition can comprise in addition additives, selected from the group consisting of UV absorbers, light stabilisers, stabilisers, hydroxylamines, benzofuranones, nucleation agents, impact strength enhancers, plasticisers, lubricants, rheology modifiers, processing aids, pigments, colourants, optical brighteners, antimicrobial active substances, antistatic agents, slip agents, antiblocking agents, coupling means, chain lengtheners, dispersants, compatibilisers, oxygen collectors, acid collectors, marking means or anti-fogging means. In a preferred embodiment, the compositions comprise in particular acid collectors, e.g. based on salts of long-chain acids, such as e.g. calcium stearate, magnesium stearate, zinc stearate, calcium lactate, calcium stearoyl-2-lactylate or of hydrotalcites and/or stabilisers from the group of phenolic antioxidants and phosphites and/or light stabilisers from the group of hindered amines (HALS) and/or dispersants.
Suitable light stabilisers are for example compounds based on 2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides and 2-(2-hydroxyphenyl)-1,3,5-triazines.
Suitable 2-(2′-hydroxyphenyl)benzotriazoles are for example 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl-5-chlorobenzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole, 2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole, 2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy) carbonylethyl]-2′-hydroxyphenyl)benzotriazole, 2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the product of reesterification of 2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R—CH2CH2—COO—CH2CH2—]—2, with R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl, 2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole, 2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.
Suitable 2-hydroxybenzophenones are for example 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy- and 2′-hydroxy-4,4′-dimethyoxy derivatives of 2-hydroxybenzophenones.
Suitable acrylates are for example ethyl-α-cyano-β,β-diphenylacrylate, isooctyl-α-cyano-β,β-diphenylacrylate, methyl-α-carbomethoxycinnamate, methyl-α-cyano-β-methyl-p-methoxycinnamate, butyl-α-cyano-β-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate and N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.
Suitable esters of benzoic acids are for example 4-tert-butylphenylsalicylate, phenylsalicylate, octylphenylsalicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.
Suitable oxamides are for example 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and the mixtures thereof with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
Suitable 2-(2-hydroxyphenyl)-1,3,5-triazines are for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl-1,3,5-triazine.
Suitable metal deactivators are for example N,N′-diphenyloxamide, N-salicylal-N′-salicyloylhydrazine, N,N′-bis(salicyloyl) hydrazine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene) oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N,N′-diacetyladipolydihydrazide, N,N′-bis(salicyloyl)oxylyldihydrazide, N,N′-bis(salicyloyl)thiopropionyldihydrazide.
In particular, the following structures are suitable as metal deactivators:
Suitable phenolic antioxidants are for example:
alkylated monophenols, such as e.g. 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols, such as e.g. 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures hereof;
alkylthiomethylphenols, such as e.g. 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol;
hydroquinones and alkylated hydroquinones, such as e.g. 2,6-di-tert-butyl-4-methyoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxylphenyl)adipate;
tocopherols, such as e.g. α-, β-, γ-, δ-tocopherol and mixtures of these (vitamin E);
hydroxylated thiodiphenylethers, such as e.g. 2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis(3,6-di-sec-amylphenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide;
alkylidenebisphenols, such as e.g. 2,2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2′-methylenebis(4-methyl-6-cyclhexylphenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4′-methylenebis(2,6-di-tert-butylphenol, 4,4′-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol-bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane;
O-, N- and S-benzyl compounds, such as e.g. 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzylether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate;
hydroxybenzylated malonates, such as e.g. dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate;
aromatic hydroxybenzyl compounds, such as e.g. 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol;
triazine compounds, such as e.g. 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroyphenylpropionyl)hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate;
benzylphosphonates, such as e.g. dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethylester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid;
acylaminophenols, such as e.g. 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate;
esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or multivalent alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane,
esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or multivalent alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane;
esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or multivalent alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
esters of 3,5-di-tert-butyl-4-hydroxyphenyl)acetic acid with mono- or multivalent alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as e.g. N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard®XL-1, marketed by Uniroyal);
ascorbic acid (vitamin C).
Particularly preferred phenolic antioxidants are:
octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, triethyleneglycol-bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, N,N′-hexan-1,6-diyl-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide.
Suitable phosphites/phosphonites are for example:
triphenylphosphite, diphenylalkylphosphites, phenyldialkylphosphites, tri(nonylphenyl)phosphite, trilaurylphosphites, trioctadecylphosphite, distearylpentaerythritoldiphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, diisodecylpentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphite, bis(2,4-di-cumylphenyl)pentaerythritoldiphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite, diisodecyloxypentaerythritoldiphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritoldiphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritoldiphosphite, tristearylsorbitoltriphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocine, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocine, 2,2′2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], 2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl))phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.
Particularly preferred phosphites/phosphonites are:
Further suitable stabilisers are aminic antioxidants. Suitable aminic antioxidants are for example:
N,N′-di-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N, N′-bis(1-methylheptyl)-p-phenylenediamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N, N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino) propane, (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene and also mixtures or combinations hereof.
Further suitable aminic antioxidants are hydroxylamines or N-oxides (nitrons), such as e.g. N,N-dialkylhydroxylamines, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearylhydroxylamine, N-benzyl-α-phenylnitron, N-octadecyl-α-hexadecylnitron, and also Genox EP (Addivant) according to the formula:
Further suitable stabilisers are thiosynergists. Suitable thiosynergists are, for example, distearylthiodipropionate, dilauryldipropionate or the compound according to the following formula:
Further suitable stabilisers, in particular for polyamides, are copper salts, such as e.g. copper(I)iodide, copper(I)bromide or copper complexes, such as e.g. triphenylphosphine-copper(I) complexes.
Suitable hindered amines are for example 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-di-chloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1′-(1,2-ethandiyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, linear or cyclic condensation products of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin.
Suitable dispersants are for example:
polyacrylates, e.g. copolyers with long-chain side groups, polyacrylate block copolymers, alkylamides: e.g. N,N′-1,2-ethandiylbisoctadecaneamide sorbitan ester, e.g. monostearyl sorbitan ester, titanates and zirconates, reactive copolymers with functional groups, e.g. polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene-co-glycidylmethacrylate, polystyrene-alt-maleic anhydride-polysiloxanes: e.g. dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers: e.g. polyethylene-block-polyethylene oxide, dendrimers, e.g. hydroxyl group-containing dendrimers.
Suitable nucleation agents are for example talc, alkali or alkaline earth salts of mono- and polyfunctional carboxylic acids, such as e.g. benzoic acid, succinic acid, adipic acid, e.g. sodium benzoate, zinc glycerolate, aluminium hydroxy-bis(4-tert-butyl)benzoate, benzylidenesorbitols, such as e.g. 1,3:2,4-bis(benzylidene)sorbitol or 1,3:2,4-bis(4-methylbenzylidene)sorbitol, 2,2′-methylene-bis-(4,6-di-tert-butylphenyl)phosphate, and also trisamides, such as e.g according to the following structures
Suitable fillers and reinforcing materials are for example synthetic or natural materials, such as e.g. calcium carbonate, silicates, glass fibres, glass balls (solid or hollow), talc, mica, kaolin, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite, carbon nanotubes, graphene, sawdust or fibres made of natural products, such as e.g. cellulose, synthetic fibres or metal fibres. Further suitable fillers are hydrotalcites or zeolites or layer silicates, such as e.g. montmorrillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite.
Suitable chain lengtheners for the linear molecular weight increase of polycondensation polymers such as polyesters or polyamides are for example diepoxides, bis-oxazolines, biz-oxazolones, bis-oxazines, diiosocyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, carbodiimides. Further suitable chain lengtheners are polymeric compounds, such as e.g. polystyrene-polyacrylate-polyglicidyl(meth)acrylate copolymers, polystyrene-maleic anhydride copolymers and polyethylene-maleic anhydride copolymers.
Suitable pigments can be of an inorganic or organic nature. Suitable inorganic pigments are for example titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, carbon black. Suitable organic pigments are for example anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines or pyranthrones. Further suitable pigments are effect pigments based on metal or pearlescent pigments based on metal oxide.
Optical brighteners are for example bisbenzoxazoles, phenylcumarines or bis(styryl)biphenyls and in particular optical brighteners of the formulae:
Suitable filler deactivators are for example glycidyl-based epoxides, such as e.g. bisphenol-A-diglycidyl ethers or bisphenol-F-diglycidylether and the oligomeric or polymer resins thereof, polysiloxanes, polyacrylates, in particular block copolymers, such as polymethacrylic acid-polyalkylene oxide or polystyrene-polyacacrlate-polyglycidal(meth)acrylate copolymers. Suitable antistatic agents are for example ethoxylated alkylamines, fatty acid esters, alkyl sulfonates and polymers such as e.g. polyether amides or copolymers, which comprise the salts of acrylic acid, such as e.g. polyethylene-polyacrylate-polyacrylate-Na copolymers.
Furthermore, the present invention relates to a method for the production of a flame-retardant plastic material composition, in which there is introduced
- a) 0.1 to 40 parts by weight, preferably 1 to 25 parts by weight, particular preferably 2.5 to 15 parts by weight, of at least one organic oxyimide salt, comprising at least one structural element of the subsequently illustrated formula I,
- R1 being selected from the group consisting of inorganic or organic cations,
- b) before, after or at the same time, with 0 to 25 parts by weight, preferably 2.5 to 15 parts by weight, of at least one further flame retardant and/or
- c) before, after or at the same time, with 0 to 25 parts by weight, preferably 1 to 20 parts by weight, particularly preferably 2.5 to 15 parts by weight, of at least one phosphorus-containing compound,
- in 60 to 99.9 parts by weight, preferably 60 to 98 parts by weight, particularly preferably 70 to 95 parts by weight, of at least one plastic material, in particular at least one thermoplastic polymer.
Furthermore, the present invention relates to a moulded part, paint or coating producible from a production of a previously described flame-retardant plastic material composition according to the invention, in particular in the form of injection moulded parts, foils, coatings, foams, fibres, cables and pipes, which are produced by extrusion, injection moulding, blow-moulding, pressing processes, e.g. for household and electrical appliances, vehicle parts, consumer articles, furniture, textiles.
The previously presented organic oxyimide salts according to the invention are suitable as flame retardant for thermoplastic, elastomeric and duromeric plastic materials, in particular in the form of injection moulded parts, foils or films, coatings or paints, foams, fibres, cables and pipes, profiles, hollow bodies, strips, membranes, such as e.g. geomembranes or adhesives, which are produced by extrusion, injection moulding, blow-moulding, calendering, pressing processes, spinning processes, roto-moulding or brushing and coating processes, e.g. for the electrical and electronic industry, construction industry, transport industry (car, aircraft, ship, train), for medical applications, for household and electrical appliances, vehicle parts, consumer articles, packaging, furniture, textiles. A further field of use is varnishes, paints and coatings.
For example, the compositions according to the invention can be used for marine applications (pontoons, planks, boats), auto applications (bumpers, batteries, trim parts, petrol tanks, cables, wires etc.), aircraft parts, railway parts, bicycle- and motor cycle parts, space applications, such as e.g. satellite parts, housing parts for electrical appliances, such as computers, telephones, printers, audio and video systems, plugs, printed circuits, switches, lamp shades, refrigerators, coffee machines, vacuum cleaners, rotor blades for energy production, ventilators, foils for roof constructions, building foils, pipes, such as e.g. waste water pipes and gas pipes, connection parts, drainage systems, profiles, such as e.g. window profiles or cable channels, wood composites, furniture, flooring, covering plates, artificial grass, stadium seating, carpets, nets, ropes, furniture parts, mats, garden seats, bottle crates, containers and barrels.
Incorporation of the above-described flame retardants and of the additional additives in the plastic material is effected by normal processing methods, the polymer being melted and mixed with the flame retardants and additives, preferably by mixers, kneaders and extruders. As processing machines, extruders, such as e.g. single-screw extruders, twin-screw extruders, planet roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing, are preferred. The processing can thereby be effected under air or possibly under inert gas conditions. Different flame retardants and additives can be added thereby separately or as a mixture, in the form of liquids, powders, granulates or compacted products or likewise in the form of master batches or concentrates which comprise for example 50-80% of the compositions according to the invention.
The present invention is explained in more detail with reference to the following examples, without restricting the present invention to the specially illustrated parameters.
Analogously to the literature (monthly journals for chemistry 137, 1591-1595 (2006)) there is added to a solution of N-hydroxyphthalimide (61.7 g; 378 mmol) in absolute ethanol (800 ml) with agitation, an equivalent quantity of sodium hydroxide (15.1 g; 378 mmol) which is subsequently heated for two hours with reflux. After cooling the solution, the formed product is filtered and washed with absolute ethanol. The product is obtained quantitatively as a red solid after drying in the vacuum oven at 100° C. for 12 hours.
1H-NMR (500 MHz, D20); δ=7.49 (dd, J=5.3, 3.0 Hz, 1H), 7.35 (dd, J=5.3, 3.0 Hz, 1H) ppm.
13C-NMR (126 MHz, D20); δ=169.11, 133.29, 129.08, 121.44 ppm.
To a solution of sodium N-oxyphthalimide (5.97 g; 32.2 mmol) in H2O (400 ml), zinc nitrate hexahydrate (4.8 g; 16.1 mmol) is added with agitation. After approx. half an hour, an orange-coloured precipitate is formed, whereupon the dispersion is stored for a further 12 hours at room temperature. The product is subsequently filtered off via a Büchner funnel, washed with H2O (100 ml) and dried at 140° C. for 12 hours under vacuum.
1H-NMR (300 MHz, DMSO-d6); δ=7.74-7.40 (m, 1H).
To a solution of melamine (10 g; 79.3 mmol) in hot H2O (200 ml), N-hydroxyphthalimide (12.93; 79.3 mmol) is added and the mixture thereupon heated for 3 hours with reflux. Subsequently, the mixture is stored for a further 12 hours at room temperature. The orange-coloured product is thereupon filtered off via a Büchner funnel, washed with H2O (100 ml) and dried for 12 hours at 140° C. under vacuum.
1H-NMR (300 MHz, DMSO-d6); δ=7.82 (s, 1H), 6.23 (s, 1H).
To a dispersion of poly-2-vinyl-4,6-diamino-1,3,5-triazine (5 g; 36.5 mmol) in hot H2O (50 ml), N-hydroxyphthalimide (5.95 g; 36.5 mmol) is added with agitation and the dispersion heated for 3 hours with reflux. Subsequently, the mixture is stored for a further 12 hours at room temperature. The yellowish and insoluble product is thereupon filtered off via a Büchner funnel and subsequently dried at 140° C. for 12 hours under vacuum.
Production and Testing of a Flame-Retardant Plastic Material Mixture According to the Invention
The extrusions of the polypropylene samples (DOW C766-03) are effected at a temperature of 190° C. and a screw speed of rotation of 150 rpm on an 11 mm twin-screw extruder (Process 11 of Thermo Scientific). The desired ratio of polymer and additives is firstly homogenised by mixing and supplied to the extrusion via volumetric metering.
Test pieces for the fire test are produced from the granulate at a temperature of 220° C. and a pressure of 2 t using a hydraulic 10 t press (Werner & Pfleiderer). For this purpose, the granulate is filled into the compression mould and this is transferred into the already preheated press. At a pressure of 0.5 t, the granulate is firstly melted for 60 s. After expiry of the melting time, the pressure is increased to 2 t and kept constant for a further 3 min. Whilst maintaining the contact pressure, the mould is cooled to 60° C. and thereafter the test pieces are removed. The test pieces have the following dimensions according to the standard: 127.5×12.5×1.5.
The examples and comparative examples according to the invention contained in Table 1 were tested according to DIN EN 60695-11-10 and the burning times and classification according to the standard were obtained:
Phosphazenes (SBP-100, Otsuka Chemical Co., Ltd.)
Aluminium diethylphosphinate (Exolit OP 1230, Clariant SE)
Phosphonate (Aflammit PCO 900, Thor GmbH)
The examples according to the invention are self-extinguishing after removal of the source of ignition and have surprisingly reduced burning times relative to the comparative example, a classification according to V-2 is obtained.


text:
Waban mass based firm telecom the WNBA continue
Box Lacrosse Assn.But I'm just ready for it to come.We're just ready for a battle on Sunday.The effort also includes a donation of 1 million meals to Feeding America, �?Tennis Channel will bring live matches back to viewers this weekend, May 1 through May 4, with the Tennis Point Exhibition Series in Germany.
�?MiLB has launched MiLB CommUNITY First, a national initiative developed in conjunction with Feeding America to raise funds for local food banks and to honor individuals risking their lives on the front lines of the COVID-19 pandemic.Leading to that event, Smith-Schuster will front a Doorbell Dance platform in which he will demonstrate ways he celebrates when the doorbell rings – meaning Pizza Hut pizza has arrived.Clyde Edwards RB LSU Kansas City Chiefs WNBA 2020 DRAFT 1.We're better than we were, and we have to keep getting better.
Other Madison Square Garden Company signature marketing partners include JPMorgan Chase, Delta Air Lines, Squarespace, Anheuser-Busch InBev, DraftKings, Kia Motors, Lexus and SAP.6 NBC �?Super Bowl LVII State Farm Stadium Glendale, AZ Feb.Kylian Mbappe 9.Players who have applied for early entry have the right to withdraw their names from consideration for the Draft by notifying the NBA of their decision in writing ten days prior to the 2020 NBA Draft.I try to bounce back each week and play the best ball that I can.
Tristan Wires T Iowa Tampa Bay Buccaneers 14.The other side of that is that �?every game, it doesn't matter who you're playing, you better bring it.Maria Sharapova 10.Brandon Alyuk WR Arizona State San Francisco 49ers 26.
Javon Kinlaw DT South Carolina San Francisco 49ers 15.Derrick Brown DT Auburn Carolina Panthers 8.Listen, we have our own wrinkles, and we like to think that we're doing some things that are going to give defenses some things to be concerned about, certainly within our personnel.Brandon Alyuk WR Arizona State San Francisco 49ers 26.Alex Morgan 5.
We had such a good group of guys there with Vinny and Wayne , Curtis Martin, Kevin Mawae, Tupa said.is a perfect example of a double bottom-line partnership �?great teams and a great partner in Coca-Cola, said Leonsis, founder of Monumental Sports & Entertainment and CEO and majority owner of the Capitals, Mystics and Wizards.Jerry Judy WR Alabama Denver Broncos 16.
Kitkja Laska G Latvia Seattle Storm 12.I don't know that yet either.As a three seed, the Mavericks went out and beat the feisty Blazers in the first round, swept the defending champion Lakers in the second round and beat down the up-and-coming Thunder in the conference finals.
Zack Snyder; Ben Affleck, Henry Cavill, Amy Adams Superman and Batman face-off in an epic battle of good vs.It is easier after the play or after the series to make calls; even I figured that out, he joked.Derrick Brown DT Auburn Carolina Panthers 8.He was voted the winner of the Selke Trophy as the best defensive forward in the NHL and the Conn Smythe Trophy as MVP of the playoffs, when he had 23 points in 26 games to help the Blues win the Stanley Cup for the first time in their history.The city council postponed the vote back in December after it received a public backlash.
ADDRESS Islanders Iceworks 175 Underhill Boulevard Syosset, NY 11791 Phone: 496 Fax: 496 ISLANDERS PRO SHOP.Tom Brady 8.He did not specify what activation might replace it except to say, We are still going through our planning process.Brandon Alyuk WR Arizona State San Francisco 49ers 26.


text:
1 to 1 sexchat Adultfriend cam
Here's how to get the most out of using them as an adult chat site: We felt the need to add Bubble Clips into our list as a bonus site because of their increasingly popular Live Sex Cams.We've talked about these guys before on our list of 3 Great Sites to Watch HD Sex Videos., but they also have a popular section to watch sex cams!Additionally, they provide sorting features that let you easily narrow down all the online cams and pinpoint exactly which video chat rooms you want to enter.Here's how to use their website: Chat-Avenue is a site that takes the traditional approach online chatting.Our sex chat rooms are always packed with thousands of people online at all times, so finding strangers to have webcam sex with is easier than ever.To top it off, we provide you with 100% free live porn, so you'll never have to spend a dime. There's usually at least one glaring issue on every site that sticks out like a sore thumb.This can totally ruin a user's experience and force them to constantly be in pursuit of a better alternative.
Additionally, we provide step-by-step guides on how you can use each website on our list to get the most out of them.Our #Java based #Digi Chat #Sex Chat is down for the moment but will be returning #ASAP!For now, a few regular users are meeting at the #Mobile #Chatroom at schat.321Sex which is our HTML5 based chat room. This is where you can start sex chatting exclusively with them and Tempocams is a sex chat roulette site that connects you exclusively with girls.Their roulette mode features your own private chat room where you're able to watch and talk to girls on cam doing free live sex shows.