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prints, race prints, competition prints, contest prints, chase prints, run prints, running prints, marathon prints, robot prints, android prints, cyborg prints
"Race" print by Augustinas Raginskis. Ships within 3 - 4 business days and arrives rolled in a tube. Choose from multiple print sizes, papers, mats, and frames.
All prints ship in durable cardboard tubes.
Fine Art America is one of the largest, most-respected giclee printing companies in the world with over 40 years of experience producing museum-quality prints. All of our prints are produced on state-of-the-art, professional-grade Epson printers.
We use acid-free papers and canvases with archival inks to guarantee that your prints last a lifetime without fading or loss of color. Paper prints include a 1" white border around the image to allow for future framing and matting. Canvas prints include a 2.5" white border to allow for future stretching on stretcher bars.
Prints ship within 3 - 4 business days in durable cardboard tubes.
This is not the kind of race where normal people come to participate just because it is fun. Nor is this the kind of race in which all participants are highly trained professional athletes. This is the kind of race there only crazy people participate and do whatever it takes to win, because whoever wins becomes disgustingly rich and whoever is dragging behind gets shot in the arm for some extra motivation.
My name is Augustinas Raginskis. I specialize in digital drawings and paintings. I am interested in weird, strange, unexpected, surreal. What I am best at is creating unusual, detailed, sometimes confusing at first artwork. Often in my works you don't see everything there is to see at the first sight. As you keep looking, you notice more of the detail and story hidden in the picture.
Our return policy is very simple:
If you're not happy with a purchase that you made on FineArtAmerica.com, for any reason, you can return it to us within 30 days of the order date. As soon as it arrives, we'll issue a full refund for the entire purchase price. Please note - Fine Art America does not reimburse the outgoing or return shipping charges unless the return is due to a defect in quality.
Fine Art America sells thousands of pieces of artwork each month - all with a 100% money-back guarantee.
If you've hesitated to purchase artwork online in the past, why not give us a try? You have nothing to lose!
We take great pride in the fact that 337,879 artists have chosen Fine Art America to fulfill their orders, and we look forward to helping you select your next piece!
Customer Service: 877-807-5901
(Call Any Time - 24 Hours Per Day)
All prints ship from our production facility within three business days of your order.


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The flags in downtown Tifton are old and worn out according to long-time business owner Jack Stone.Stone has owned Western Auto Parts for over 50 years and takes pride in how downtown looks, especially Main Street where his business is.Stone says the flags that are on every light post are dirty, frayed, and need replacing and he wants them all replaced by November.He's working to get everyone in the community to make a small contribution towards these flags.Stay connected to MySouthWestGA.com as stories develop and the FOX 31 Newscast at 10 PM. Visit us on Facebook and Twitter to join in on the conversation and connect with FOX 31!
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subset: commoncrawl


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CPSC 410: Advanced Software Engineering is offered by the Department of Computer Science at the University of British Columbia.
Important: this is a group-based, development-heavy course. You will be required to propose, design, build, validate, and demonstrate a large software product to the class, the TAs, and the instructor. Do not take this project lightly as it will be a huge amount of work and comprises the majority of your final grade.
Lectures are held Monday, Wednesday, and Friday 1300 to 1350 in Dempster 110. My office hours are TBD but will be held in ICCS 309. Official administrative entry.
While the course does not have a required textbook, much of the materials will be sourced from the first two texts; additional books are supplementary.
- Richard N. Taylor, Nenad Medvidovic, and Eric Dashofy. Software Architecture. Foundations, Theory, and Practice. Available in the library or for purchase (e.g., through Amazon.ca). Slides for this book are available online.
- Ian Gorton. Essential Software Architecture. Available online or for purchase (e.g., through Amazon.ca). Slides for this book are available online.
- Fred P. Brooks Jr. The Mythical Man Month. Available in the library or for purchase (e.g., through Amazon.ca).
- Fred P. Brooks Jr. The Design of Design. Unfortunately not in the library but still available through Amazon.ca.
The best way to get help is via Piazza; please prepend your questions with your TAs name to ensure you get a quick response (TAs will be assigned to project groups after they are all formed). Sign up for piazza here. You can reach me at rth.se2(at)gmail.com for questions not appropriate for Piazza.
Course Schedule
|In Class
|Sept 9
|Sept 11
|Architecture intro
|Kitchen Design
|Sept 14
|Architectural views & decomposition
|System Decomposition
|Sept 16
|Non-functional properties
|NFP Alternatives
|Sept 18
|NFP Stakeholders
|Sept 21
|Sept 23
|Game Show
|Sept 25
|Game Show
|Sept 28
|Deliverable 1
|Project Proposals
|Sept 30
|Project Proposals
|Oct 2
|Project Proposals
|Oct 5
|Architectural Styles Intro
Architectural Styles (complete)
|Oct 7
|Oct 9
|Oct 12
|No Class (Thanksgiving)
|Oct 14
|Living Architectures & Style Activity
|Oct 16
|Oct 19
|Guest Lecture: Testing in Practice
|Oct 21
|Oct 23
|Oct 26
|TBD (was NFP Measurement but was covered along with Specifications)
|Oct 28
|Testing: Coverage
|Oct 30
|Mutation Testing
|Nov 2
|Prototype Demos
|Nov 4
|Prototype Demos
|Nov 6
|Prototype Demos
|Nov 9
|Cloud + Rest**
|Nov 11
|No Class (Remembrance Day)
|Nov 13
|Nov 16
|Analytics & A/B Testing
|Nov 18
|Nov 20
|SOLID Activity
|Nov 23
|Dependency Injection
|Nov 25
|Guest Lecture: Scrum Master
|Nov 27
|Course Review
|Nov 30
|Final Demo
|Dec 2
|Final Demo
|Dec 4
|Final Demo
|Final Exam
The projects will be completed in teams of four. You are free to select your own team; if you do not have a team or your team has less than four members, please talk to me and I will set you up.
Projects will have a difficulty scale applied to them by the instructor and TAs. The scale formula will be:
(project + bonus) * scale = final project gradeScale will range between 0.75 and 1.0. The components of the scaling mark will be determined by:
- 5: completeness (compared to proposal)
- 5: utility
- 5: polish
- 10: difficulty
- Best pitch
- Best prototype demo
- Best final demo
- Accepted to curated App Store (iOS, Blackberry, Windows Phone)
|SE Impressions
|Sept 9
|In Class
|D0: Project Groups
|Sept 25
|D1: Proposal Presentations
|Sept 28/30/Oct 2
|In Class (+ online)
|Oct 16
|In Class
|D2: Prototype Demonstration
|Nov 2/4/6
|In Class
|D3: Architecture & Design
|Nov 2
|Oral Exam (+ online)
|D4: Project Acceptance Test
|Nov 30
|Oral Exam (+ online)
|D5: Presentation + Video
|Nov 30/Dec 2/4
|In Class
|Final Exam
2014 Project Videos
A selection of project videos from 2014 are included in this playlist to help you get an idea of the scope of projects suitable for the course.
You must pass the final exam and all pass/fail assignments to pass the course.
- Late submissions will not be accepted except in case of documented emergency.
- For special accommodation for the exam or midterm, contact the Access and Diversity Office.
- In order to maintain a culture of academic integrity, members of the University of British Columbia community are expected to promote honesty, trust, fairness, respect and responsibility. [See the academic integrity site for more information.]
- Everyone involved with CPSC 310 is responsible for understanding and abiding by the University's Respectful Environment Statement. [See the complete statement.]
- As this course is heavily oriented around the group project, and the groups are formed early, it is a difficult class to join late. As such, the advisors will not place new students into CPSC 410 after Sept 14.


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I don't blame you. I blame bad policy. I blame the interventionists. I blame the neoconservatives who preach this stuff, who believe in it like a religion -- that they have to promote American goodness even if you have to bomb and kill people. In short, I dont blame America; I blame neocons." Ron Paul
Watching his step does not mean the shoes are already dirty. There is a 54 to 46 majority what is he going to do?


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Registration is now open online for WINTER sports.
Set for Monday, October 5th, The 3rd Annual Gavin Rupp Open will take place at Chantilly Golf & Country Club. Help fight pediatric cancer by registering as a participant and/or a sponsor for this worthy cause. Click here for more information.
Starting Monday morning, September 28, Bull Run Post Office Road will be closed from Cedar Ridge Boulevard to just south of the entrance to Cardinal Ridge Elementary School in order to replace the gravel road surface with pavement, according to the Virginia Department of Transportation.
Congratulations to the SYA Babe Ruth players who were recently recognized to the All Babe Ruth World Series Team! Pitcher Joe Larimer and shortstop Jacob D'Ercole were named to the team, along with All World Series Defense Team selection catcher Zack Bright.
Your SYA wants you to be informed. You can find vital concussion info from the CDC by following this link. Also, go to the following link to get important concussion training for coaches
Reports of vehicles parking illegally at schools and parks for SYA activities may lead to ticketing and/or towing at the owner's expense.
A former SYA coach and volunteer, Jay Coakley has started a non-profit program for kids with leukemia called Ellie's Hats. What started out as collecting hats for an individual child with cancer has blossomed into a cause that brings joy to thousands of kids going through cancer treatments.
All SYA Members: Please be aware that recently we have had reports of four wheelers accessing our SYA Fields of Dreams Sports Park. If you are not aware, several years ago we had four wheelers who damaged two of our fields and cost SYA thousands of dollars and delayed opening the fields by almost a year.
Congratulations to the SYA 5th grade girls travel basketball team who recently won the Fairfax Stars summer league.The girls are from the Centreville and Clifton area and are coached by Kerry Womack-Lajdel.
Professionally done course maps for the cross country 1-4 k courses. These include the new fitness stations.
Check out this article about our SYA Sports Park written by Mary Stachyra, editor of the Centreville Patch. While you're there, be sure to sign up to get this great local newsletter on a regular basis!
Has your address, email, phone number, etc... changed? Or do you have an unpaid registration that you would like to pay now? Use this link to update your family information or make a payment: Update family information
Registration is now open for WINTER sports. WINTER sports include basketball, travel basketball, wrestling and track & field. Fall clinics are open for rugby, soccer and lacrosse.
For WINTER & FALL player registration, please click here.
For WINTER & FALL coaches & other volunteers, please click here.
For upcoming clinics, please click here.
SYA is a non-profit organization serving southwestern Fairfax County. SYA provides the youth of Centreville and Clifton, Virginia and the surrounding communities with the opportunity to participate in sports activities. The number of sports offered by SYA now numbers thirteen and the list will continue to grow in the coming years.
Among the most important purposes of SYA are:
PRIVACY POLICY The information that we collect will be used for business purposes only, and we do not share your information with other organizations.


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Devern Fromke Ultimate Intention
|Devern Fromke Ultimate Intention[Full DOWNLOAD]
June 2013 News Letter Little Lambs Inc.
Finding several books by DeVern Fromke I was intrigued to read "Ultimate Intention". This book was first printed in 1963 it is astounding how more and .
[ Read more ] [ Donwload pdf ]
CONNAITRE CHRIST SELON L'ORDRE DIVIN Connaitrechrist.net
3 H.J. Stanley Ces mots ont été écrit par H.J. Stanley dans l'Introduction à The Ultimate Intention by. DeVern Fromke. Finalement j'ai écrit ce livre pour tous les .
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ovdje Logos
DEVERN FROMKE. O?e pomozi mi razumjeti tvoju OSNOVNU ... ULTIMATE INTENTION by DeVern Fromke. © Copyright 1963 by Sure Foundation Inc..
[ Read more ] [ Donwload pdf ]
DeVern Fromke Frank Viola Author
from the ministry of. DeVern Fromke . preparatory word as to the meaning of the term ultimate. In this present day when ... intention of God. In this book we will ....
[ Read more ] [ Donwload pdf ]
The following is Frank Viola's 3 part response to Ben Witherington's
them (b) take time out of his grueling schedule to review them on his blog. And not just review them but ... addressed clearly in the chapter entitled ? Reimagining the Eternal Purpose.? Not sure how ..... I'd recommend DeVern. Fromke's book ?Ultimate Intention? as an introduction on this point. 13) I don't recall saying ....
[ Read more ] [ Donwload pdf ]
David D. Flowers - elris.fr
CONNAITRE CHRIST SELON L'ORDRE DIVIN Pou ceux ui voient le besoin d'une évolution spiituelle au lieu d'une éfome eligieuse David D. Flowers.
[ Read more ] [ Donwload pdf ]


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My Moody Gardens "Ice Land" Experience
My family and I went to Moody Gardens Galveston over the weekend to check out the "Ice Land" ice sculptures. It was amazing! Here's a look at my photos.
My family and I went to Moody Gardens Galveston over the weekend to check out the "Ice Land" ice sculptures. It was amazing! Here's a look at my photos.
SEXY! There, I said the word. Now, quick -- what's the first place that comes to mind.
The City of Sulphur, right? Sexy, sexy Sulphur.
Jimmy Carrey stops by Jimmy Kimmel to reveal the secret of the Illuminati, well kinda…
When satisfying your hunger is dependent on someone else's indecisiveness, drastic measures must be taken.
Rappers Shad Moss (Bow Wow), Kevin Gates, Young Thug, and Rich Homie Quan get parodied in the latest installment of the animated series 'We Are Young Money,' part 7.
Check out the latest commercial featuring legendary martial arts movie star Chuck Norris, as he shows you just how much of a bad man he is in a very funny way.
Watch as kids react to their parents telling them they ate their Halloween candy! The reactions are priceless!
It's time for another installment of 'The Dumbest Tweets 2014,' this time it's the dumbest Ebola tweets.
Check out the best news bloopers of the last month, some will fill you with laughter, others will make you just shake your head.
Check out Anthony Hamilton and his background singers hilarious rendition of 'Momma I Love You… P.O.P., Hold It Down!'
Jimmy Kimmel gives rapper Ice Cube some nice things to say, except he has to say them in a angry way. Watch the hilarious bit here!
Female is caught in a mans chimney after meeting him through a social media site.


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Cross-talk effects on the Regenerator Allocation optimization
Document typeConference report
Date issued2011
Rights accessOpen Access
This paper studies the impact of considering crosstalk effects in the IA-RWA process and in the regenerator allocation algorithms. First of all, we evaluate if the regenerator allocation optimization is still useful when the crosstalk effects are considered. For this end we improve a simple physical model which computes the quality of the signal factor for each optical connection. Until now this physical model was unaware of the physical layer impairments depending on the interference between different optical connections, such as the crosstalk. Following the same simple methodology we add the switching node crosstalk effect to the computation of the quality of the signal factor. Once the new physical model is enhanced we evaluate the impact of the crosstalk on the performance of IA-RWA algorithms that optimize the use of the regenerators; and also we evaluate the impact of different e wavelength assignation techniques.
CitationMarín, E. [et al.]. Cross-talk effects on the Regenerator Allocation optimization. A: International Congress on Ultra Modern Telecommunications and Control Systems and Workshops. "2010 International Congress on Ultra Modern Telecommunications and Control Systems and Workshops". Moscou: 2011, p. 1206-1211.
Publisher versionhttp://ieeexplore.ieee.org/stamp/stamp.jsp?tp=&arnumber=5676672
Aquest ítem (excepte textos i imatges no creats per l'autor) està subjecte a una llicència de Creative Commons: Attribution-NonCommercial-NoDerivs 3.0 Spain


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Related quotes
"The idea that other perspectives exist may not be obvious to those who are in an emotional state of mind. ~Nabil N. Jamal"
"If ever there is tomorrow when we're not together.. there is something you must always remember. you are braver than you believe, stronger than you seem, and smarter than you think. but the most important thing is, even if we're apart.. i'll always be with you."
"We're obviously disappointed that it has been sent back to Judge Robertson that it is just not over."
"Likewise also was not Rahab the harlot justified by works, when she had received the messengers, and had sent them out another way? / For as the body without the spirit is dead, so faith without works is dead also."
"Teachers don't want to have a letter sent home saying that they are not highly qualified, ... We likely will have a few of those letters that will have to go out. Hopefully in that letter, somehow we can explain to parents that we still feel like the teacher we have in that classroom is a very good teacher, who will do an excellent job."
"And he stayed yet other seven days; and sent forth the dove; which returned not again unto him any more."


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Cookout Party
These delicious recipes include spicy and sticky baby back ribs and crunchy coleslaw.
Yogurt-Marinated Lamb Skewers
More ∨
This dish is great for entertaining: The spiced lamb marinates overnight, and the sauce can be made ahead of time. All you have to do right before serving is grill the skewers for seven minutes.


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Put together a banner for a League of Legends forum. Bronze is a ranking in the game and is harder than hell to advance in rank from bronze to silver, so I made this as a joke.
I went for a purposefully busy composition. Felt like elements and colours meeting each other would be appropriate for a forum.


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Mike Bennett not signing yet
For a while there, Mike Bennett was hotly rumored to be joining WWE through their developmental program. Things have been quiet on that front recently. The belief is that the silence is due to Bennett himself. He knows that his reputation in the industry is rocketing skywards, so he might wait until he has as much leverage as possible before going into negotiations with World Wrestling Entertainment again.
August 14, 2015
Traci Brooks farewell
House of Hardcore took place in Toronto over the weekend, and it was the final public appearance made by Traci Brooks. The former TNA Knockout was in the corner of her husband, Frankie Kazarian, and Christopher Daniels. They went up against Matt Taven and Mike Bennett. Traci ended up getting an enjoyable cat fight with Maria Kanellis.
July 19, 2015
Mike Bennett on Tom Brady
A post on Instagram where Mike Bennett chooses a side in the Tom Brady debate. The New England Patriots quarterback has been accused of cheating by having the footballs deflated. Some are defending him, while others want to take away his accomplishments.
June 11, 2015
Mike Bennett dating Maria
During a recent interview, Mike Bennett opened up a bit about his relationship with Maria Kanellis. He revealed that when they first met one another, there was a strong connection between the two. However, they were unable to do anything about it at that moment because they were both involved with someone else. Once those relationships ended, the two of them started communicating via social media. Things moved forward from there on.
May 15, 2015
Mike Bennett on Ric Flair
A post on Instagram where Mike Bennett reveals a very important lesson that Ric Flair taught him.
April 29, 2015
Mike Bennett to TNA
If you follow international wrestling at all, you'll know that Mike Bennett and his stock are rising. He is becoming a hot commodity in the industry. Those rumors are about signing a contract with TNA in the near future are heating up once again. The promotion would provide him with a bigger platform than the one he has in ROH. Bennett also knows that working with an opponent like Kurt Angle could definitely make him even more known.
April 27, 2015
Mike and Maria at Ribera
A photo on Instagram of ROH star Mike Bennett taking his lovely wife Maria Kanellis out to dinner at the world famous Ribera steak house that the wrestlers all go to when they visit Japan.
April 5, 2015
Bennett and Taven win IWGP titles
During their first reign, the Bullet Club held the IWGP Tag Team Championship for an entire year. Their second reign wasn't nearly as successful. Karl Anderson and Luke Gallows were defeated by Matt Taven and Mike Bennett, who were accompanied by the lovely Maria Kanellis at Invasion Attack 2015 over the weekend. The ROH stars are making quite a name for themselves in New Japan and could opt to work more there than in the United States.
April 5, 2015
Hardy on Bennett and Taven
A post on Twitter where Matt Hardy talks about what it means to him now that Matt Taven and Mike Bennett have captured the IWGP tag team championship.
April 5, 2015
Mike Bennett on Perro Aguayo
A post on Twitter from ROH star Mike Bennett about how hard it is for professional wrestlers to deal with the death of a peer after the tragic passing of Perro Aguayo.
March 22, 2015


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Gaitley Previews Fordham Women's Basketball
Defending Atlantic 10 Champion Fordham hits the hardwood to open their 2014-15 campaign against Iona College at the Rose Hill Gym.
Defending Atlantic 10 Champion Fordham hits the hardwood to open their 2014-15 campaign against Iona College at the Rose Hill Gym.
Kelly Kultys and Matt Rosenfeld spoke with Bob Ryan (@GlobeBobRyan) on One on One to discuss his latest book, Scribe: My Life in Sports. They talk about the book itself, his career in the media from basketball to baseball, how media coverage has changed over the years and much more.
Brett Pollakoff (@BrettEP) of NBCSports.com joined the podcast to dissect the early results from the Nets and Knicks, plus project a realistic season for the injury-laden Thunder.
Jared Dubin (@JADubin5), of Hardwood Paroxysm called in to our 2014 Season Preview to provide some insight into the prospects of the Knicks and Nets, plus Kenny Ducey, Matt Rosenfeld, and Kevin Kelly give a full slate of season predictions.
Fordham athletic director David Roach joined Mike Watts to discuss Fordham and the larger intercollegiate athletic landscape in his monthly Roach Report update.
Jason Concepcion (@netw3rk) of Grantland joined the podcast to discuss his experience at Summer League, realistic expectations for the Knicks, the favorite in the East, and more.
I've always casually watched the NBA Summer League. In a time where the focus is almost entirely on baseball, watching a couple of basketball games per day is a good way to have a change of pace and scout some young talent. But after being courtside in Las Vegas for five days, my appreciation for the Summer League has grown immensely.


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|Publication number
|Publication type
|Application number
|Publication date
|Nov 19, 1991
|Filing date
|Jun 7, 1990
|Priority date
|Jun 9, 1989
|Fee status
|Publication number
|Katherine S. Clement, David A. Babb, Bobby R. Ezzell
|Original Assignee
|The Dow Chemical Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (9), Non-Patent Citations (10), Referenced by (52), Classifications (35), Legal Events (4)
|External Links: USPTO, USPTO Assignment, Espacenet
This is a continuation-in-part of U.S. application Ser. No. 364,667 now abandoned filed June 9, 1989.
This invention relates to polymerizations of perfluorovinyl compounds and to compositions containing more than one perfluorocyclobutane ring, more particularly to crosslinked polymeric compositions containing more than one perfluorocyclobutane ring.
It has long been recognized that perfluorovinyl compounds having more carbon atoms than tetrafluoroethylene are very difficult to polymerize into aliphatic chains. Such difficulties are discussed, for instance in U.S. Pat. Nos. 2,848,504 and 2,958,685; and in J. Polymer Science, Part 1-A, pp. 481-492 (1952) and vol. 6, pp 711-717 (1968).
Dimerization of certain perfluorovinyl compounds has been reported and is discussed, for instance, in Chambers, Fluorine in Organic Chemistry, John Wiley, N.Y., 1973, pp. 173-191; S. Patai, The Chemistry of Alkenes, Wiley Interscience Publishers, 1964, p. 779: M. Hudlicky, Chemistry of Organic Fluorine Compounds, 2nd ed., Halsted Press (John Wiley and Sons), 1972, p. 450; and Tarrant ed., Fluorine Chemistry Reviews, Vol. 2, Marcel Dekker, 1968 pp. 1-52. In general, the dimerizations are easily sterically hindered and have not been used to prepare long chain molecules. A report of dimerization linking two molecules of such compounds as perfluoropropylene and perfluoropentene-1, included speculation that the reaction could be used for perfluoroalkyl perfluorovinyl compounds wherein the alkyl radical has 1 to 20, "or even a higher number" of carbon atoms. See, McCone et al., U.S. Pat. No. 3,316,312.
Such dimerization has not previously been reported to produce compounds having more than one perfluorocyclobutane ring. In fact, few compounds having multiple perfluorinated four carbon-rings have been reported. U.S. Pat. No. 3,303,145 discloses a number of polyethers formed from cyclic fluorocarbon epoxides, which polymers can have perfluorocyclobutane rings separated by oxygen atoms. The polymers are said to have good thermal stability and chemical inertness as well as dielectric properties. Use as solvents, heattransfer media and lubricants as well as insulators in the form of films and moldings is suggested. U.S. Pat. No. 3,682,876 discloses polyperfluorocyclobutene and halogen terminated polyperfluorocyclobutadienes. The solid polyperfluorocyclobutadienes are reported to be thermally stable, chemically inert and useful as coatings, ablatives, gaskets, bearings, potting compounds and sealants. U.S. Pat. No. 3,900,380 discloses polymers prepared by coupling certain perfluoroalkyl or perfluoroalkyl ether chains with iodine terminated perfluorocyclobutanes to prepare polymers having double bonds suitable for cross linking. The liquids are reported to be useful as hydraulic fluids, and the solids as gaskets and ablatives. Certain polymers containing radical-initiated rings, assumed for steric reasons to be four-membered rings are reported by Brown et al. in J. Polymer Sci: Part A vol. 3, pp 1641-1660 (1965) and vol. 4, pp 131-140 (1966). None of these reported polymers having perfluorocyclobutane rings is formed by thermal reaction of perfluorovinyl groups. Also, none has aromatic structure.
In one aspect the invention is a polymer having perfluorocyclobutane rings comprising the steps of:
(a) contacting monomers having at least two dimerizable perfluorovinyl groups; and
(b) exposing the monomers to sufficient heat and for a sufficient time that a polymer containing perfluorocyclobutane rings is formed
wherein at least about 0.05 mole percent of the monomers have at least three dimerizable perfluorovinyl groups.
In another aspect, the invention includes polymers formed by the process.
In another aspect the invention is a polymer having a backbone comprising perfluorocyclobutane rings being formed from monomers having at least two dimerizable perfluorovinyl groups per molecule wherein at least 0.05 mole percent of the monomers have at least three dimerizable perfluorovinyl groups per molecule.
Polymers of the invention are formed by thermal reaction of monomers having at least two dimerizable perfluorovinyl groups such that perfluorocyclobutane groups are formed. A dimerizable perfluorovinyl group is a perfluorovinyl group which reacts with another such group to form a perfluorocyclobutane ring. Thus, resulting polymers have at least two perfluorocyclobutane groups, in particular sufficient perfluorocyclobutane groups to achieve physical and electrical properties desired for specific uses of the polymers. The term polymer is used herein to refer to any compound having at least two perfluorocyclobutane groups formed from perfluorovinyl groups, and includes oligomers which have from about 2 to about 100 repeating units and preferably have a molecular weight of from about 300 to about 30,000. It is within the scope of the present invention to form lower molecular weight oligomers useful as fluids or prepolymers and higher molecular weight polymers exhibiting general plastic properties. Within this scope and depending on the molecular structure connecting the perfluorocyclobutyl groups, the number of perfluorocyclobutane groups can vary from as few as two up to thousands. The process of forming polymers or oligomers by the process of the present invention is general and capable of forming products having wide ranges of utility. Physical and electrical properties of the resulting products are highly dependent on the choice of the molecular structure between the perfluorocyclobutane groups as well as the number of perfluorocyclobutane groups.
The relative proportion by weight of the perfluorocyclobutane groups to the other molecular components of the resulting products can vary over a wide range of from about 12 to 1 to about 0.01 to 1, preferably from about 5 to 1 to about 0.02 to 1 and most preferably from about 2 to 1 to about 0.03 to 1. High proportions of perfluorocyclobutane groups are desirable for instance, when fluorocarbon character such as low dielectric constant is beneficial in the products. Exemplary of such products are low dielectric fluids and lubricants. Medium ranges of ratios of weights of perfluorocyclobutane groups to other molecular structures of about 2 to 1 to about 1 to 4 are desirable, for instance, when higher physical strength and relatively lower dielectric constants (e.g. relative to conventional engineering thermoplastics) are desired, e.g. in low dielectric plastics. These relatively low dielectric plastics are particularly preferred and are preferably achieved by using aromatic compounds substituted with trifluorovinyl groups, most preferably, with trifluorovinyl ether groups. Very low proportions of the perfluorocyclobutane groups result, for instance, when low molecular weight oligomers (e.g. in the range of 1000 to 20,000) are terminated by trifluorovinyl groups which are then thermally dimerized to form higher molecular weight polymers.
Any monomer having at least two dimerizable perfluorovinyl groups is suitably used in the practice of the invention. Whereas polyaddition of perfluorovinyl groups to form perfluoroaliphatic polymers (like polytetrafluoroethylene), not generally having perfluorocyclobutane groups, takes place in the presence of free radicals or free radical generating catalysts, dimerization to form perfluorocyclobutane groups takes place thermally.
When a perfluorovinyl group is dimerizable, dimerization is preferably favored over other thermal reactions either kinetically or in equilibrium. In perfluorobutadiene, isomerization and formation of perfluorocyclobutane is favored: it is, therefore, preferable in the practice of the invention that the perfluorovinyl groups on a monomer used in the practice of the invention be separated by at least one atom or group of atoms, which group does not facilitate isomerization. The atom or group of atoms preferably includes at least one carbon atom, more preferably at least one carbon atom in an, optionally substituted, hydrocarbyl group, that is a group containing at least one carbon-hydrogen bond for instance a methylene group, a phenylene group, a phenylene ether group, a pyridinyl group and the like. Furthermore, when the perfluorovinyl groups are attached to aliphatic carbons or separated from aliphatic carbons by single atoms such as oxygen, the perfluorovinyl groups are preferably primary or secondary because tertiary perfluorovinyl groups are generally sterically hindered with respect to formation of perfluorocyclobutane rings, more preferably the perfluorovinyl groups are primary because secondary perfluorovinyl groups tend to rearrange. Preferably, to avoid rearrangement and facilitate polymer formation the monomers have structures such that resulting polymers have hydrocarbyl groups (preferably aromatic rings), perfluorocyclobutane rings and at least one non-carbon atom such as oxygen, silicon, boron, phosphorus, nitrogen, selenium, tellurium and/or sulfur atom (each optionally substituted) in the backbones.
The monomers preferably have a structure represented by Formula I:
CF2 ═CF--X--R--(X--CF═CF2)m
wherein R represents an, optionally inertly substituted group; each X is independently a bond or any group which links R and a perfluorovinyl group (hereinafter linking structures), said structure is independently a bond or any group which links R and a perfluorovinyl group (hereinafter linking structures), said structures being inert; m+1 is the number of --X--CF═CF2 units. Advantageously, m is an integer of from about 1 to about 3, preferably from about 1 to about 2. While compounds represented by Formula I wherein m is one are especially useful for forming linear polymers, compounds wherein m is 2 or more particularly 2 or 3 are especially useful for preparing crosslinked polymers. By "inert" it is meant that the structures or substituents do not react undesirably with perfluorovinyl groups or interfere undesirably with polymerization (perfluorocyclobutane formation) of the monomers.
Linking structures X are each independently a linking structure such as a bond, an oxygen atom, carboxylic and thiocarboxylic ester groups, other sulfur containing structures, perfluoroalkylene, perfluoroalkylene ether, alkylene, acetylene, phosphorus containing groups such as phosphines, carbonyl and thio carbonyl groups; seleno: telluro: nitrido; silicon-containing groups such as silanediyl, trisilanediyl tetrasilanetetrayl, siloxanediyl, disiloxanediyl, trisiloxyl, trisilazanyl, or silylthio groups; boron-containing groups such as boranediyl or methylboranediyl groups; a combination thereof, or any other group which is inert, which molecularly links R to a perfluorovinyl group, and which provides a molecular structure in which the perfluorovinyl group is sufficiently reactive to form a perfluorocyclobutane ring. For instance, X is preferably other than a perfluoroalkylene group because perfluorovinyl groups attached to perfluoroalkylene groups generally require temperatures greater than about 300� C. to dimerize and are subject to isomerization.
It is preferred that at least one of X is not a bond. More preferably, X is independently selected from the group consisting of groups having at least one noncarbon atom between the perfluorovinyl groups and R, such as groups containing oxygen, sulfur, selenium atoms, tellurium atoms, silicon, boron, phosphorus or nitrogen between R and the perfluorovinyl group, e.g. oxygen atoms, sulfur atoms, (thio) carboxylic ester groups, phosphines, (thio) carbonyl groups, seleno, telluro, silanediyl, trisilanediyl, trisilazanyl or silylthio, boranediyl groups. Preferred groups have S, O, Si, N or P, more preferably S, O or Si between R and the perfluorovinyl group, such as carbonyl, thiocarbonyl, sulfone, sulfoxy, silanediyl, amines (optionally inertly substituted), oxygen or sulfur atoms. Most preferably there is a single atom other than carbon; even more preferably it is oxygen or sulfur, among those groups preferably an ether or sulfide linkage, because monomers having such linking structures advantageously form perfluorocyclobutane groups at lower temperatures than are needed with such groups as perfluoroalkyl groups and are more stable than monomers where the perfluorovinyl group is attached directly to R, particularly when R is aromatic. Monomers having such linking structures are also relatively easily prepared.
R is suitably any inert molecular structure, preferably a molecular structure which facilitates formation of perfluorocyclobutane rings and/or imparts desirable physical properties to polymers or oligomers prepared from the monomers. For the purpose of imparting desirable physical properties to polymers, R preferably contains at least one carbon atom. Preferably, the carbon atom is in the molecular chain between X's because monomers having at least one carbon atom between X's when X is other than a bond, tend to have desirable stability and to produce polymers having desirable physical properties. Alternatively, the carbon atom is in a side chain: for instance, --R-- can be --N(CH3)--, --N(CH2 CH3)--, --P(CH3)--, --P(CH2 CH3)-- and the like. The carbon atoms(s) in R are suitably in aliphatic, cycloaliphatic, aromatic, heterocyclic groups and the like and combinations thereof. Additionally, R optionally contains groups or has substituents which are inert, that is which do not undesirably interfere with the formation of perfluorocyclobutane rings from perfluorovinyl groups. Inert substituents include ether, carbonyl, ester, tertiary amide, carbonate, sulfide, sulfoxide, sulfone, nitrile, alkyl phosphonate, tertiary amine, alkyl phosphate, alkyl silyl, chlorine, bromine, fluorine, alkyl, arylalkyl, alkylaryl, cycloalkyl, aromatic, heterocyclic, alkoxyl, aryloxy groups and the like, which inert substituents are suitably in any position, for instance, in a polymer backbone between X's and/or appended to such a backbone. Carbon-containing inert substituents on R preferably contain from about 1 to about 50, more preferably from about 1 to about 12 carbon atoms because of the stability and ease of working with monomers of lower molecular weight. R, including inert substituents preferably has a molecular weight (MW) of from about 14 to about 20,000, more preferably from about 75 to about 15,000 and most preferably from about 75 to about 5,000. These ranges include monomeric and oligomeric R groups. In the case of monomers which are other than oligomeric, R preferably has from about 1 to about 50, more preferably from about 6 to about 50, carbon atoms because molecular weights above this reduce the contribution to properties made by the fluorinecontaining substituents when R is alkyl or aromatic hydrocarbon. As previously discussed, the nature of R as well as the perfluorocyclobutane content of the polymers can vary broadly according to the type of products desired.
Preferably, for polymers having good plastic properties such as tensile strength and flexibility, at least one carbon atom of R is in the molecular chain between X's and is part of an aromatic nucleus. Aromatic groups are desirable because of improved physical properties of the polymers and ease of manufacture of the monomers. For both ease of manufacture of the monomer and monomer stability, when R is aromatic, each X is preferably independently sulfur or oxygen. The aromatic group can be any molecular structure having aromatic character, advantageously having at least one six membered aromatic ring, suitably having any number of such six-membered rings fused together or connected by bonds or linking structures. R preferably has from about 1 to about 50 such rings, more preferably from about 1 to about 10 rings, more preferably containing from about 6 to about 25 carbon atoms, most preferably R has at least 2 to about 4 aromatic rings to impart properties such as hardness and/or stiffness to a polymer. The aromatic fragment is suitably unsubstituted or inertly substituted. Inert substituents on an aromatic R include, for instance, the inert substituents listed for R generally. Exemplary aromatic molecular fragments include, for instance, perchlorophenylene, phenylene, biphenylene, naphthylene, dichlorophenylene, nitrophenylene, p,p'(2,2-diphenylene propane) [--C6 H4 --C(CH3)2 --C6 H4 ]; p,p'--(2,2-diphenylene-1,1,1,3,3,3 hexafluoropropane) [--C6 H4 --C(CF3)2 --C6 H4 --], preferably biphenylene; phenylene: 9,9-diphenylenefluorene, oxydiphenylene: thiodiphenylene; 1,1,1-triphenyleneethane; 1,3,5-triphenylene benzene; 1,3,5-tris(2-phenylene-2-propyl)benzene: 1,1,1-triphenylenemethane: 1,1,2,2-tetraphenylene-1,2-diphenylethane, 1-(2-phenylene-2-propyl)-4-(1,1-diphenyleneethyl)benzene; 2,2-diphenylene propane: 2,2-diphenylene-1,1,1,3,3,3-hexafluoropropane; 1,1-diphenylene-1-phenylethane; naphthalene; and anthracene. Molecular weights of aromatic ring containing polymers are preferably at least about 10,000. Such aromatic groups are preferably present because they generally impart high temperature glass transition properties (Tg) and good mechanical strength (e.g. as measured by differential scanning calorimetry (DSC) and tensile/flexural tests) to the polymer.
Most preferably, at least one aromatic carbon atom of R is bonded directly to X, most preferably aromatic carbon atoms of R are bonded directly to each X because perfluorovinyl groups bonded to X, said X being bonded to aromatic groups are generally more reactive in forming perfluorocyclobutane rings.
Some specific combinations of X and R are especially preferred: when R is aromatic, at least one X is preferably other than a bond, more preferably neither X is a bond, because attachment of perfluorovinyl groups directly to aromatic R renders the perfluorovinyl groups more thermally and oxidatively unstable than when said groups are attached, for instance, to oxygen or sulfur. When R is a perfluoroalkyl group or a perfluoroalkylether group, at least one X is preferably other than a bond, most preferably no X is a bond or a perfluoroalkyl group, because perfluorovinyl groups linked directly to perfluoroalkyl groups require temperature in excess of about 300� C. to dimerize and are subject to isomerization.
Monomers useful in the practice of the invention are suitably prepared by any method which links molecular structures having perfluorovinyl groups to other molecular structures or which forms perfluorovinyl groups.
Perfluorovinyl groups are formed, for instance by elimination of halogens from terminal dihalotrifluoroethyl groups. Halogens such as bromine or iodine may be eliminated, for instance, using metallic reactants as illustrated by Cohen's synthesis of trifluorostyrene by the reaction of zinc with dichlorotrifluoroethylbenzene in absolute ethanol (J. Am. Chem. Soc., 71, 3439, (1949)). Additionally, pentafluoroethyl (substituted) phenyl ethers can be reacted with certain phosphorus compounds to form perfluorovinyl ethers as reported by Kawaguchi et al. in Japanese Kokai 77 89,603. Structures suitable for elimination of halogens to form perfluorovinyl groups are prepared, for instance, by processes such as those taught in Rico et al. U.S. Pat. No. 4,377,711 and Carl et al. in U.S. Pat. No. 4,423,249 which patents are incorporated herein by reference. Additionally perfluorovinyl groups are formed by decarboxylation of perfluorocarboxylic acids with concomitant loss of hydrogen fluoride, as taught by R. N. Griffin and M. I. Bro, J. Org. Chem., 25, 1068 (1960), and also by T. S. Reid, G. H. Smith, and W. H. Pearlson, in U.S. Pat. No. 2,746,997 which are incorporated herein by reference. Electrochemical elimination of halogens from certain substituted alkyl-1,2-dihalo-1,2,2-trifluoroethyl ethers according to the procedures taught in European Patent document EP 293,856 is also useful for forming perfluorovinyl compounds.
Tetrafluoroethylene and chlorotrifluoroethylene are reacted with suitable compounds, for instance by procedures taught by Prober in J. Amer. Chem. Soc., 75, 968 (1953): by Plumer et al. (U.S. Office Saline Water, Res. Develop. Prog. Rep. #481, 1969): by Dixon in J. Org. Chem., 21, 400 (1956); Wall et al. U.S. Pat. No. 3,277,068.
Linking of molecular structures containing perfluorovinyl groups to other molecular structures is illustrated by reaction of (trifluorovinyl)trimethyltin aryl iodides in the presence of palladium complexes, as taught by R. S. Sorokina, et al. in Zh. Org. Khim. 18, 2458, (1982); by the reaction of trifluorovinyl zinc reagents with certain substituted phenyl iodides as taught by R. S. Sorokina et al. in Izv. Akad. Nauk SSSR, Ser. Khim., 1647, (1985); and Heinze and Burton in J. Fluorine Chem., 31, 115, (1986), and J. Org. Chem., 53, 2714, (1988).
Preferred monomers are preferably prepared by the process taught in copending application Ser. No. 364,665, filed June 22, 1989, filed simultaneously herewith and incorporated herein in its entirety.
An exemplary method of preparing a trisperfluorovinyl ether (exemplary of monomers having three perfluorovinyl groups) is illustrated by a process having the following steps:
A) A trihydroxy compound such as 1,1,1-tris(4-hydroxyphenyl)ethane is converted to its sodium or potassium salt in a solvent such as a methanol/water mixture The methanol or another solvent for the trihydroxy compound is used when, as in the case of 1,1,1-tris(4-hydroxyphenyl)ethane, the compound is not water soluble. Sufficient alcohol is used to keep the trihydroxy compound in solution; in the case of 1,1,1-tris(4-hydroxyphenyl)ethane from about 20 to about 50 volume percent based on total volume of alcohol and water is convenient. Alternatively, the trihydroxy compound is combined with aqueous sodium or potassium hydroxide and stirred vigorously until salt formation reaches the desired state, advantageously as indicated by dissolution. Salt formation occurs conveniently at from about 0� C. to about 100� C. at atmospheric pressure, preferably under a nitrogen atmosphere to avoid oxidation.
B) The methanol if used is removed under reduced pressure at any convenient temperature and pressure with replacement of water as it is lost.
C) The salt is dried and powdered e.g. in a drum dryer.
D) The salt is slurried in a polar, aprotic solvent suitable for achieving reaction such as DMSO (dimethyl sulfoxide), dioxane, DMF (dimethyl formamide), HMPA (hexamethylphosphoramide), diglyme, tetraglyme or glyme and an aprotic azeotropic medium such as toluene or chlorobenzene in a solvent to azeotropic medium ratio of from about 10 to 1 to about 1.5 to 1 and dried by the azeotropic removal of water.
E) About half of the azeotropic medium is removed, e.g. by distillation and the mixture is cooled below about 50� C., preferably below about 20� C.
F) A dihalotetrafluoroethane such as 1,2-dibromotetrafluoroethane is added to form a mixture as the reaction temperature is controlled at a temperature suitable for the reaction to occur substantially without the side reaction of ring halogenation; in the case of 1,1,1-tris(4-hydroxyphenyl)ethane preferably below about 20� C. initially. The mixture is stirred at 18-25� C. for 36 hours.
G) The mixture is poured into about an equal volume of cold water, conveniently from about 0.5 to about 3 times the volume of the solution, and the product falls out as the lower layer. There is preferably sufficient cooling to offset the heat generated by admixing DMSO (or other solvent) and water.
H) The product, a tris-bromide, is distilled, e.g. at about 190-195� C./0.05 mm Hg. When tris-bromides are heat stable as observed in the case of 1,1,1-tris(4-(2-bromotetrafluoroethoxy)phenyl)ethane, the degree of vacuum is selected to give a convenient boiling point. Such selection is within the skill in the art.
I) The tris-bromide is used directly or, if desired, in cases where the tris-bromide is a solid for ease of addition it may be dissolved in a polar, aprotic solvent such as diglyme, tetraglyme, or glyme and added to a hot (e.g. 120� C.) mixture of the same solvent and granular zinc to form the tris-perfluorovinyl ether (TVE). Alternatively, the tris-bromide can be added to a hot (e.g. 120� C.) mixture of for example, diglyme and granular zinc as a melt without dilution if heated above its melting point, e.g. to about 120� C. in the case of 1,1,1-tris(4-(2-bromotetrafluoroethoxy)phenyl)ethane. Temperatures above about 125� C. are preferably avoided to avoid dimerization of perfluorovinyl groups.
J) The TVE is isolated by removing the zinc salts e.g. by centrifugation, evaporating the diglyme under reduced pressure, diluting the TVE with a, preferably low boiling, solvent such as hexane, and flushing the solution through a pad of neutral alumina. Alternatively, the zinc salts are removed by filtration and the TVE distilled under vacuum, e.g. in two stages, the first to remove solvent and the second to purify the TVE. Preferably, temperatures above about 110� C. are avoided to avoid dimerization of perfluorovinyl groups. Especially when a very pure product is desired, these methods of purification are suitably combined.
K) The hexane, if used, is removed from the TVE by evaporation under reduced pressure.
Alternatively, the TVE is isolated by removing the zinc salts by filtration, evaporating the diglyme under reduced pressure, diluting the TVE with hexane and purifying by countercurrent extraction with polar organic materials such as acetonitrile or DMSO. The pure TVE in hexane is then flushed through a pad of alumina and isolated by concentration under reduced pressure.
The monomers are heated to a temperature and for a time sufficient to form perfluorocyclobutane rings. Temperatures suitable for forming perfluorocyclobutane rings differ with the structure of the monomer. In general, temperatures above about 40� C. are suitable for formation of perfluorocyclobutane rings, preferably the temperature is above about 50� C., more preferably above about 100� C., because these temperatures result in formation of the rings at successively faster rates. Temperatures above about 450� C. are preferably avoided because perfluorocyclobutane groups are generally thermally unstable above such temperatures. More preferably a temperature of from about 105� C. to about 350� C., most preferably from about 105� C. to about 250� C., is used to produce the perfluorocyclobutane rings at a convenient rate. Within that range, a temperature of from about 100� C. to about 230� C. is generally most preferred for cyclization of perfluorovinyl aromatic or aliphatic ethers or sulfides, while a temperature of from about 50� C. to 80� C. is needed to form perfluorocyclobutane groups when the perfluorovinyl group is attached directly to an aromatic ring. In the case of perfluoroalkylperfluorovinyl groups, however, temperature of at least about 300� C. preferably at least about 350� C., is generally required.
Preferably, especially when the perfluorovinyl compounds are capable of radical initiated addition polymerization, conditions conducive to free radical polymerization, e.g. presence of oxygen, ozone, peroxygen compounds and other free radical generating compounds are avoided so that the perfluorovinyl groups will dimerize into perfluorocyclobutane groups rather than undergoing addition polymerization. Compounds known in the art for stabilization against free radical polymerization are alternatively used. Similarly, especially when the perfluorovinyl groups are capable of addition polymerization in the presence of anions or cations, compounds which supply such anions or cations are avoided. For instance, fluoride ions (e.g. from carbonyl fluorides), chloride, hydroxide, phenoxide and the like are preferably avoided. To avoid such compounds as carbonyl fluorides, oxidative conditions such as presence of oxygen, hypochlorite, dichromate, permanganate and the like are preferably avoided because the perfluorovinyl groups are known to oxidize to form carbonyl fluorides. Perfluorovinyl ethers, thioethers, sulfones, sulfoxides and the like are relatively stable with regard to addition polymerization and oxidation; and, therefore, such precautions are generally unnecessary when such perfluorovinyl compounds are used.
Monomers or admixtures thereof are suitably neat or, optionally, in admixture with other materials such as in solution, in emulsion, in dispersions or in any other form in which monomer molecules can be contacted with one another to form a polymer. Neat polymerization is preferred when the monomers or prepolymers are formed in the final desired shape of the polymer article before final thermal treatment. This is especially true when monomers having more than two perfluorovinyl groups are used in whole or in part to form crosslinked, thermoset materials.
Suitable solvents are those which are inert to the conditions encountered in the polymerization reaction and include xylene, mesitylene and perfluorotetradecahydrophenanthrene (MULTIFLUOR� APF 215 commercially available from Air Products Corp.). At atmospheric pressure, preferred solvents are those which attain temperatures of 170�-250� C. such as dichlorobenzene, trichlorobenzene, diphenyl oxide and perfluorotetradecahydrophenanthrene. Although solvents such as 1,2-dichlorobenzene and 1,2,4-trichlorobenzene give less satisfactory results such as discoloration of the finished polymer, they are suitably used when their disadvantages are tolerable in a final product. When a solvent is used the concentration of monomers in solvent is advantageously from about 0.1 to about 99.9 weight percent preferably, from about 10 to about 90 percent by weight monomer.
Polymerization or dimerization suitably takes place at any pressure. Pressures are generally chosen such that the monomers and any solvents and/or dispersing media remain liquid at the temperatures used for polymerization. When the monomers or other materials evaporate at temperatures used, then it is generally preferable to maintain a pressure at least sufficient to maintain the materials liquid.
Monomers having three or more dimerizable perfluorovinyl groups (hereinafter referred to as polyfunctional) are especially useful to form polymers having relatively high Tg believed to be due to crosslinking. From about 0 to 100 percent by weight of such monomers are suitably used, preferably sufficient of the monomers having at least three perfluorovinyl groups to measurably increase the Tg of the polymer over that of a polymer of monomers having corresponding structures but with only two perfluorovinyl groups, more preferably at least about 0.5 mole percent, most preferably from about 0.1 to about 100 mole percent of such monomers is used. While use of lower proportions of polyfunctional monomer(s) produces generally thermoplastic polymers having crosslinking and corresponding properties of toughness and solvent resistance, use of sufficient polyfunctional monomer to form thermosetting polymers is useful to produce crosslinked polymers having higher Tg. The relative proportions of polyfunctional monomer which produce such polymers varies with the structure of the monomers. However, from about 0.05 to about 75 mole percent polyfunctional monomers used with monomers having 2 perfluorovinyl groups is sufficient to result in sufficient crosslinking in a thermoplastic polymer to reduce its solubility in a solvent. Thermoset polymers, however, are advantageously formed from monomer mixtures having from about 75 to about 100 weight percent, preferably from about 85 to about 100 mole percent, of the polyfunctional monomers. For instance, a polymer of 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane which is about 97 weight percent pure, with the major impurity being 1,1-bis(4-trifluoroethenyloxyphenyl)-1-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)ethane, is polymerized at about 180-240� C. for 30 min. and produces a colorless, transparent polymer having a Tg of 286� C.
While monomers of the invention are conveniently polymerized in a single stage polymerization, use of more than one stage is often advantageous. A first stage can advantageously be used to react some of the perfluorovinyl groups to reduce the exotherm frequently observed when large quantities of monomers, particularly of monomers having at least three perfluorovinyl groups are polymerized in a single stage. A first stage is also useful to produce a monomer (or monomer mixture of solution) having increased viscosity and lower volatility than those of the initial monomer. A liquid or a solid of relatively lower melting point than that of a completely cured polymer is suitably formed. Such a first stage of polymerization is conveniently carried out at temperatures of from about 50� C. to about 400� C., preferably from about 105� C. to about 250� C., more preferably from about 120� C. to about 170� C. At least one later stage follows the first stage and is preferably carried out at a higher temperature than the first to allow the polymerization to proceed toward completion. Such later stage(s) are conveniently carried out at temperatures from that sufficient to result in additional polymerization up to the decomposition temperature of a resulting polymer, preferably from about 100� C. to about 450� C., more preferably from about 120� C. to about 400� C., most preferably from about 200� C. to about 375� C. Those skilled in the art will recognize that the first and later stages can represent more than one stage or can be carried out using two or more temperatures and that a series of stages or a continuum of temperatures are suitably used. In addition to these stages, a postcure at a relative high temperature such as from about 200� C. to about 450� C. is optionally used. The postcure is suitably of any duration sufficient to change physical properties and insufficient to decompose the polymer, preferably from about 1 minute to about 1 week, more preferably at higher temperatures such as from about 240� C. to about 450� C. for duration of from 1 minute to about 24 hours. Stages of polymerization are conveniently run under conditions previously described for polymerization of the monomers. When a solvent is used in an early stage, and it is desirable to avoid bubbles that may occur as a solvent is driven off, advantageously the solvent removed before or during a later stage.
In a preferred embodiment of the invention, conditions suitable for all or part of the dimerization can occur in a polymer shaping apparatus, for instance, an extruder, injection mold or compression mold. This embodiment of the invention is particularly useful when materials containing perfluorovinyl groups, for instance, monomers, oligomers or polymers, have a viscosity suitable for introducing into the polymer shaping apparatus and the material resulting from the formation of perfluorocyclobutane groups in the apparatus has a higher viscosity or is solid, which is less suitable for introduction into the apparatus. More specifically, a perfluorovinyl containing oligomer or relatively lower molecular weight polymer, including the result of partial dimerization of perfluorovinyl groups is introduced into a shaping apparatus wherein it is heated sufficiently for formation of sufficient perfluorocyclobutane rings to form a solid polymer.
Another preferred embodiment of the present process is to form perfluoropolymers, preferably having ether atoms incorporated in the polymer backbone. Polymers of this general class of compounds are generally prepared by fluoride ion catalyzed reactions of perfluorinated epoxides (U.S. Pat. Nos. 3,214,478 and 3,322,826). These type products have perfluorocyclic groups, including perfluorocyclobutane groups, are taught in U.S. Pat. No. 3,303,145. While the methods taught are suitable for preparing low molecular weight materials, the method is generally unsuitable for producing higher molecular weight products (e.g. average molecular weights at least about 10,000). Elimination of fluoride to form acid fluoride terminal groups in the growing chains generally limits molecular weight. This deficiency can be offset somewhat by lowering reaction temperature, but nevertheless the only commercially significant products produced using a process like that taught in the prior art patents are oligomeric fluids such as Krytox� commercially available from I. E. DuPont and Company. Formation by the cyclopolymerization process of the present invention makes possible production of higher molecular weight polymers. Preferably perfluoro polymers of this embodiment of the present invention are thermally produced from monomers of Formula I wherein R is perfluoroalkyl, X is oxygen. These monomers are conveniently produced by known chemistry involving reaction of perfluoroalkyl compounds having two acid fluoride groups with fluoropropyl epoxides followed by decarboxylation to form vinyl ethers. (See U.S. Pat. Nos. 3,450,684 and 4,554,112). The resulting monomers, perfluoroalkyl diperfluorovinyl ethers, CF2 ═CFO(CFRf)n OCF═CF2, where Rf is branched or linear fluoroalkyl (preferably of from about 1 to about 10 carbon atoms), or fluorine; and n is preferably between 1 and about 10, are then thermally polymerized to form polymers, or if desirable, oligomers having the repeating unit, ##STR1## and terminated trifluorovinyl ether groups. The polymers having average molecular weight above about 10,000, preferably above about 25,000 are useful in elastomer applications, particularly when cured by a crosslinking reagent. Suitable crosslinking reagents are monomers described herein where m is greater than 1. The terminal groups are conveniently further reacted, if desired, by a variety of processes within the skill in the art including radical initiated reactions or, alternately, are rendered inert by halogenation, preferably with fluorine. It is within the scope of the present invention to copolymerize the foregoing monomers, oligomers or polymers with other compounds of the present invention having two or more trifluorovinyl groups. For instance, oligomers of the divinylperfluoroethers are formed and cured with a perfluorovinyl compound, particularly of Formula I wherein R is aromatic, m is 2 and both X's are oxygen. This technique is useful for forming thermoset resins or elastomers depending on the proportion of multifunctional (m greater than 1) material used.
Polymers of the invention are suitably solids, fluids or gels, preferably solids or fluids, most preferably solids. The solids preferably maintain plastic characteristics such as tensile strength well above ambient temperatures (e.g. above about 25� C.) and have glass transition temperatures from well below ambient to well above ambient temperatures. A particularly preferred group of such polymers have glass transition temperatures (Tg) above ambient (25� C.), preferably above 60� C. and most preferably above 100� C. In general, the polymers having Tg above ambient result from monomers of Formula I wherein R is aromatic, and the polymers having Tg above 60� C. when R contains more than one aromatic ring. A particular desirable property of polymers where R is aromatic and not substituted with polar substituents (e.g. nitro, sulfonate, carboxy) is the combination of good physical properties and good electrical properties. Dielectric constants and static dissipation factors (as measured according to the procedures of ASTM D150-87) preferably range from about 2.2 to about 3.0 and from about 0.0001 to about 0.005 respectively. Glass transition temperatures increase from about ambient when R is phenyl to about 170� C. when R is biphenyl to 230� C. when R is 9,9-diphenylfluorene, to about 286� C. or higher when R is 1,1,1-triphenylethane.
The linear polymers are advantageously thermoformed as by molding or extruding or are cast from solvents such as ethers and chlorinated solvents, for instance, tetrahydrofuran or dichloromethane. The polymers possess processing advantages over other polymers having similar low dielectric properties such as polytetrafluoroethylene. The advantages include extrudability, suitability for injection molding, and solvent casting.
The following examples are offered to illustrate but not to limit the invention. In each case, percentages are weight percent unless otherwise indicated. Examples (Ex.) of the invention are indicated numerically, while comparative samples (C.S.) are not examples of the invention and are indicated with letters.
All gas chromatography/mass spectrometry (GC/MS) analyses of monomers and intermediates are performed on a Finnigan 1020 GS/MS using a 30 meter RSL-150 fused silica capillary column. All gas chromatography/mass spectrometry (GC/MS) analyses of fluid polymer samples are performed on a Finnigan 4500 GC/MS using a 60 meter DB-1 fused silica capillary column, with the GC program run at 290� C. isothermal. Mass to charge (m/e) ratios and percentage of peak height relative to tallest (parent) peak are given.
Differential scanning calorimetry (DSC), thermomechanical analysis (TMA) and thermogravimetric analysis (TGA) are performed on a Perkin Elmer 7000 thermal analysis system unless otherwise indicated.
Dielectric constant and dissipation factor measurements are conducted according to the procedures of ASTM D150-87. Tensile strength and modulus and percent elongation were measured on an Instron model 1125 according to the procedures of ASTM D 882-83.
Granular zinc is activated by washing in 0.1 N hydrochloric acid (HCl) followed by drying in a vacuum oven at 0.5 torr and 140� C. for 10 hours.
Infrared (IR) spectra are measured on a Beckman Microlab 600 model spectrophotometer. Nuclear Magnetic Resonance (NMR) spectra are measured on a Varian EM360L spectrometer using 19F (fluorine 19) or 1H (hydrogen) mode.
A 1 liter 5-necked round bottom flask is fitted with a mechanical stirrer, a Dean Stark trap topped with a nitrogen padded reflux condenser, and a thermocouple attached to a temperature controller. A mixture of DMSO (450 ml), toluene (150 ml), and 1,1,1-tris(4-hydroxyphenyl)ethane (55.1 g, 0.18 mole) is added to the flask under nitrogen purge. After stirring for 15 minutes under a vigorous nitrogen purge, potassium hydroxide (85% pellets, 80.0 g, 1.2 mole) is slowly added to the reaction flask. The mixture is then stirred at reflux for 48 hours with azeotropic removal of water. The resulting suspension is cooled to 35� C. in an ice bath and 1,2-dibromotetrafluoroethane (155 g, 0.60 mole) is added at a rate that maintains a temperature of 30�-35� C. When the addition is complete, the mixture is heated to 50� C. with continuous stirring for 3 hours. After filtration, the solvents are removed by heating under vacuum on a rotary evaporator. The brown residue is purified by column chromatography on neutral alumina using hexane as eluent to provide as product 1,1,1-tris(4-[2-bromotetrafluoroethoxy]phenyl)ethane (18.3 g, 0.022 mole, 12% yield).
Identity of the product is confirmed by a GC/MS spectrum, the following peaks; m/e: parent ions m/e 840-842-844-846 (ratio 1:3:3:1) too heavy to detect. Structure determined from fragmentation: 573 (32.3%); 571 (58.3%); 569 (31.5%); [indicating parent--PhOCF2 CF2 Br]). 299 (58.1%); 297 (52.7%); 279 (32.3%); 228 (43.5%); 227 (31.5%); 226 (36.0%); 215 (59.5%); 181 (82.1%); 179 (100.0%); 165 (50.3%); 152 (43.7%); 131 (47.1%); 129 (50.4%); 100 (38.8%).
Into a 500 ml 5-necked flask fitted with a mechanical stirrer, a reflux condenser, and a thermocouple attached to a temperature controller is placed freshly activated granular zinc (4.3 g, 0.066 mole) and 25 ml dry diglyme. This mixture is stirred and heated to 110� C. under nitrogen while the product from the above reaction (18.0 g, 0.021 mole) is dissolved in 21 ml diglyme and added dropwise. The resulting mixture is stirred at 115� C. for 3 hours, then cooled and filtered. The filtrate is evaporated at 60� C. under vacuum to remove the diglyme, and the residue is purified by column chromatography on neutral alumina using hexane as eluent to provide the product 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane (9.98 g, 0.018 mole, 87% yield).
The GC/MS spectrum has the following peaks: m/e: 546 (3.2%); 531 (44.0%); 434 (17.9%); 373 (24.4%); 276 (16.9%); 240 (28.1%); 239 (73.9%); 199 (19.3%); 178 (100.0%); 177 (17.8%); 176 (25.4%); 163 (17.3%); 152 (31.9%); 151 (17.8%); 127 (20.3%); 126 (28.7%); 120 (39.1%); 119 (70.3%); 118 (25.6%); 113 (27.3%); 107 (18.8%); 102 (31.7%); 77 (15.9%); 76 (29.5%).
This example illustrates preparation of a trifunctional monomer, 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane. This monomer is useful alone or mixed with a bifunctional monomer to produce a crosslinked perfluorocyclobutane polymer.
4,4'-bis(trifluoroethenyloxy)biphenyl is prepared according to the following procedure:
Dimethyl sulfoxide (DMSO) (1800 ml) is placed in a 5-liter 5-necked flask fitted with a mechanical stirrer, a Dean-Stark phase separating trap topped with a nitrogen padded reflux condenser, and a thermocouple attached to a temperature controller. The solvent is stirred and purged of oxygen by blowing in nitrogen through a dip-tube placed below the surface of the liquid while 4,4'-dihydroxybiphenyl (454 g, 2.44 mole) is added to the flask.
The system is stirred and purged for 20 minutes, then potassium hydroxide (85% pellets) (322 g, 4.88 mole) is added slowly. The stirred mixture is then heated to 120� C. The temperature is held at 120� C. for 1.5 hours, then the heat is turned off and the mixture is allowed to cool to room temperature. Toluene (600 ml) which has been thoroughly purged with nitrogen is added to the solution and the resulting mixture is heated to reflux (135� C.). Water is axeotropically removed from the reactor through the Dean-Stark trap for a total of 4 days, cooling the reactor once after 24 hours to allow for salt formation to be broken up by opening the flask under a nitrogen sweep and scraping the sides with a spatula. After 4 days the Dean-Stark trap is removed and replaced with a Soxhlet extractor containing anhydrous sodium sulfate. The toluene is then refluxed through the Soxhlet extractor for 7 hours to dry the toluene. After 7 hours, the Soxhlet is replaced with a Dean-Stark trap, and toluene (300 ml) is removed from the reactor by simple distillation. The reaction mixture is then cooled to 30� C. in an ice water bath and 1,2-dibromotetrafluoroethane (1300 g, 5.00 mole) is added slowly dropwise over three hours at a rate that maintains a reactor temperature of 35��2� C. When the addition is complete the reaction temperature is allowed to stabilize (not increasing in temperature when the ice bath is removed) and then a heating mantle is applied to the flask. The reactor is heated to 50� C. for 8 hours, then allowed to cool to room temperature with constant stirring. The crude reaction mixture is filtered to remove the potassium bromide salts, and the precipitate is washed with acetone. The filtrates are combined and thoroughly evaporated to remove acetone, DMSO and residual toluene. The solid residue is subjected to a 2 liter Kugelrohr bulb-to-bulb distillation to provide the crude product. This material is dissolved in 750 ml of methylene chloride and is washed first with mild aqueous potassium bicarbonate (500 ml, approximately. 0.2M), then with mild aqueous hydrochloric acid (HCl) (500 ml, approximately 0.05M), then twice with distilled water (500 ml each). After complete phase separation the product layer is removed and evaporated, and the residue is fractionally distilled (138�-148� C., 0.35 torr) to provide 1031.1 g (1.90 mole, 77.9% yield) of 4,4'-bis(2-bromotetrafluoroethoxy)biphenyl, melting point 71�-73� C. The Infrared (IR) spectra of the product has the following peaks (cm-1); 1601,1492 (indicating an aromatic double bond); 1199-1107 (indicating carbon-oxygen and carbon fluorine bonds), 842, 788 (indicating aromatic character). The gas chromatograph/mass spectrometer (GC/MS) indicates peaks at the following mass to charge ratios (m/e)=545 (29.8%); 543 (48.9%); 541 (23.8%); 365 (48.7%); 363 (50.9%); 337 (30.3%); 335 (34.7%); 168 (33.7%); 156 (78.3%); 140 (36.7%); 139 (90.1%); 129 (37.4%); 128 (100.0%); 127 (33.2%); 102 (32.9%); 76 (41.1%); 63 (34.3%), consistent with a product of 4,4'-bis(2-bromotetrafluoroethoxy)biphenyl.
Bromine is eliminated from this product by the following procedure:
Into a 1-liter 5-necked flask equipped with a mechanical stirrer, a thermocouple attached to a temperature controller, a powder addition funnel and a reflux condenser, is placed freshly distilled diglyme (200 ml) and fresh zinc powder (36.0 g, 0.55 mole).
The mixture is stirred and heated to 130� C. Powdered 4,4'-bis(2-bromotetrafluoroethoxy)biphenyl (100 g, 0.184 mole) is added very slowly via the powder addition funnel over 3.5 hours. The mixture is then stirred mechanically at 115� C. for 1 hour, after which heating is turned off and the mixture is allowed to cool to room temperature. The solution is centrifuged to remove the zinc salts. Then the liquid is decanted, and the zinc salts are washed with acetone and centrifuged again. The liquid portions are combined and evaporated thoroughly, and the residue is dissolved in methylene chloride and washed with 0.05M hydrochloric acid. The methylene chloride solution is evaporated to provide 62.45 g (0.180 mole) of 4,4'-bis(trifluoroethenyloxy)biphenyl of 94.5% purity in 98% yield.
The product is then recrystallized in an ethanol/water mixture to give product of 99.8% purity in greater than 70% recovery, melting point 44�-46� C.
The IR spectrum shows peaks at (cm-1): 1833 (indicative of a perfluorovinyl group); 1601, 1491 (indicative of an aromatic double bond); 1231, 1196-1132 (indicative of carbon-oxygen and carbon-fluorine bonds respectively); 818 (indicative or aromaticity).
The GC/MS spectrum has the following peaks: m/e: 346 (31.3%); 153 (13.8%); 152 (100.0%); 151 (27.0%); 150 (11.7%); 76 (14.9%); 63 (14.9%).
A mixture of the 4,4'-bis(trifluoroethenyloxy)biphenyl (4.50 g, 0.013 mole) and the 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane (0.79 g, 0.0014 mole) are combined in a 100 ml single necked round bottomed flask topped with a nitrogen padded reflux condenser. The flask is purged thoroughly with nitrogen, and the mixture is heated without stirring. After reaching a temperature of 200� C., the mixture sets into a rigid plastic within 15 minutes. This material is then cured an additional 40 minutes at 220� C.; then the heat is removed. The resulting plastic is rigid, inflexible and does not dissolve in tetrahydrofuran (THF) or methylene chloride, but swells into a gel in these solvents.
DSC analysis (25�-350� C., 20� C./min.) of this polymer sample shows a slight endothermic event at 125� C. followed by a broad exotherm beginning at about 210� C., indicative of an incompletely cured polymer. After this sample is cured during the first DSC scan, a second scan is run which clearly indicates a Tg transition at 151� C. and no subsequent exothermic activity at higher temperatures.
Example 1 illustrates preparation of 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane and copolymerization 4,4'-bis(trifluoroethenyloxy)biphenyl therewith. The resulting polymer is stiff and brittle, as well as insoluble, compared to a thermoplastic prepared from 4,4'-bis(trifluoroethenyloxy)biphenyl alone, which is flexible and soluble in THF and methylene chloride.
Monomer 4,4'-bis(trifluoroethenyloxy)biphenyl (16.2 g, 0.047 mole) prepared as in Example 1 is placed in a 500 ml round bottom flask along with a magnetic stirring bar. A nitrogen padded reflux condenser is placed on the flask, and the monomer is heated at 200�-205� C. with stirring for 20 minutes, to form a low molecular weight polymer resembling a thick fluid at 200� C. The fluid is allowed to cool to room temperature where it sets into a brittle glass. The glass is dissolved in methylene chloride and 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane (0.51 g, 0.00094 mole) prepared as in Example 1 is added to the solution. The methylene chloride is evaporated and the residue is dried and devolatilized on a Kugelrohr bulb-to-bulb apparatus at 120-140� C. and 0.20 torr pressure. While still hot, the fluid mixture is poured into a mold and cured on a hot press at 250� C. and 20,000 psi for one hour. The mold is removed from the press and cooled. A coupon is removed from the mold. The coupon is a strong and flexible plastic, and does not dissolve in THF but swells into a gel therein.
DSC analysis of this crosslinked polymer sample indicates a Tg value of 149� C., with no subsequent thermal activity up to and including 350� C.
Example 2 illustrates polymerization of 4,4'-bis(trifluoroethenyloxy)biphenyl with subsequent addition of 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane. It is notable that crosslinked polymers are prepared either by copolymerizing difunctional and multi-functional monomers, as in Example 1, or by combining a multifunctional monomer with a low molecular weight polymer containing trifluorovinyl end groups as in Example 2.
Potassium hydroxide (678.72 g, 10.28 mol, 85%) is dissolved with cooling into 630 mL of water in a 5 liter round-bottomed flask fitted with a thermometer and stirrer. Methanol (400 mL) is added and the mixture is stirred under nitrogen in an ice bath as a solution of THPE [1,1,1-tris(4-hydroxyphenyl)ethane] (1051 g, 3.43 mol) in 1650 mL of warm methanol (40� C.) is added. Methanol is then removed from the resulting solution of the potassium salt of THPE in water/methanol by distillation under reduced pressure (140 mmHg, 55-60� C.) with addition of a total of 1245 mL of water to make up for losses and to obtain a solution of THPE potassium salt in water with the consistency of light syrup. The potassium salt of THPE is isolated by evaporation of this water solution (48% solids by weight) in a drum dryer. The resulting dried THPE salt contains about 4% water by weight.
The dried THPE salt is transferred to a 12 L round-bottomed flask fitted with a condenser and water trap along with 5 L of dimethysulfoxide (DMSO) and 1.5 L of toluene. This slurry is stirred and heated to reflux under nitrogen to remove residual water by azeotroping it with toluene. After 6 hours of reflux no further water collection is seen in the water trap and the water trap is replaced with a Soxhlet extractor containing dry sodium sulfate. The mixture is refluxed through the Soxhlet extractor for a total of 5.5 h with the sodium sulfate being replaced with an equivalent amount of dry sodium sulfate once at the halfway point, during this process. About 1 L of toluene is then removed by distillation and the remaining mixture is cooled to 18� C. by means of an internal cooling coil containing either tap water or chilled glycol as needed. The temperature of the stirring mixture is maintained at 16-18� C. by means of this internal cooling coil as 1,2-dibromotetrafluoroethane (3000 g, 11.54 mol, 1382 mL) is added over 1 h and the resulting mixture is stirred at 18� C. for 36 hours (h).
The reaction is worked up by pouring the mixture into an equal volume of cold water with stirring and then allowing the layers to separate. The lower layer containing the product is drained and the upper aqueous layer is washed with hexane. The hexane wash is combined with the product layer and evaporated under reduced pressure to remove solvents. The crude product solidifies into a crystalline mass melting at ca. 100� C. This mass is melted and distilled at reduced pressure (190-195� C., 0.05 mm Hg) to yield the product, 1,1,1-tris(4-(2-bromotetrafluoroethoxy)phenyl)ethane, as a yellowish viscous oil which crystallizes upon standing. The yield of this reaction is 88.1% and the product is 93% pure with the remaining 7% being the byproduct 1,1,-bis(4-(2-bromotetrafluoroethoxy)phenyl)-1-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)ethane which results form the replacement of one of the bromine atoms of the product with a hydrogen atom. The byproduct may be removed by melting the distilled crystalline mass and pouring it into an equal volume of methanol with stirring. The product preferentially crystallizes into fluffy white needles which can be filtered from the methanol solution. Alternatively, the 93% pure product may be used directly in the dehalogenation reaction. The crystalline 1,1,1-tris(4-(2-bromotetrafluoroethoxy)phenyl)ethane is found to have the following properties:
White needles, m.p. 100� C.
F-19 NMR: delta -10.4 (t, J=6 Hz, which is attributed to --CF2 BR), 7.5 (t, J=6 Hz, which is attributed to OCF2)
H-NMR: delta 2.2 (bs, 3 H), 7.1 (bs, 12 H)
IR: cm-1 1501, 1329, 1312, 1206, 1173, 1126, 1100, 1012, 929, 784
Granular zinc (213.3 g, 3.26 mol, 10-20 mesh) is weighed into an oven-dried 3 L round-bottomed flask. The flask is then fitted with a stirrer, thermometer, septum, and a 1 L pressure-equalizing addition funnel containing 1,1,1-tris(4-(2-bromotetrafluoroethoxy)phenyl)ethane (833.7 g, .989 mol, 97% purity). Dry diglyme (1045 g, 1115 mL) is added to the flask via canula and also to the addition funnel (384 g, 410 mL). The septum is replaced with a stopper, and the zinc/diglyme slurry is stirred and heated to 115� C. as the contents of the addition funnel are heated by means of heating tape to ca. 80� C. to form a homogeneous solution. The solution of 1,1,1-tris(4-(2-bromotetrafluoroethoxy)phenyl)ethane in diglyme is added slowly to the hot stirring zinc/diglyme slurry over 2 h, maintaining the reaction temperature at 115-125� C. by varying both heating rate and rate of addition. After addition is complete the mixture, which now contains precipitated zinc salts, is heated at 120-125� C. for an additional 5 h. The mixture is allowed to cool and the precipitated zinc salts are removed by centrifugation. Ethyl acetate is used to rinse the flask.
The resulting diglyme solution of the tris-perfluorovinyl ether product, 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane, is concentrated under reduced pressure by rotary evaporation and the resulting mixture of product and zinc salts is slurried in hexane and flushed through a 6"�6" column of neutral alumina commercially available from Aldrich Chemical Company under the trade designation Brockmann I. The product is isolated by evaporation of the hexane solution under reduced pressure. The product is isolated as a colorless oil (yield 85-90%, 89-97% purity). The remainder of the material (7-10%) is a bis-perfluorovinyl ether, 1,1,-bis(4-trifluoroethenyloxy)phenyl)-1-(4-(1,1,2,2-tetrafluoroethoxyphenyl)ethane.
The bis-perfluorovinyl ether is removed by countercurrent extraction to obtain up to 99.9% pure tris-perfluorovinyl ether. A countercurrent extractor is constructed form PFA (Perfluoroalkoxy) tubing (1 in. i.d., 4 ft. length) packed with stainless steel packing, commercially available from Metex Corp. under the trade designation Goodloe™, two electronic pumps commercially available from Pennwalt Corp. under the trade designation CHEMPULSE™ (Pennwalt model #45-050-K1M), two solvent reservoirs filled respectively with mutually saturated hexane and acetonitrile, and two receivers.
A sample of impure tris-perfluorovinyl ether ("tris") (180.8 g, 93.5% tris-, 6.5% bis-perfluorovinyl ether; purity as determined by gas chromotography corresponding to mole percent) is diluted with 1500 mL of hexane to make an approximately 10% (by volume) solution. The pumps are started, with hexane pumped into the bottom of the column (above the acetonitrile take-off) and acetonitrile pumped into the top of the column (below the hexane take-off). The flow rates are adjusted to 90 mL/min for hexane and 45 mL/min for acetonitrile. The hexane reservoir is allowed to drain until nearly empty, and the solution of impure tris-perfluorovinyl ether is transferred to the reservoir. After this is transferred onto the column, the reservoir is filled again with 1500 mL of hexane (saturated with acetonitrile). This is allowed to pump through the column and into the product reservoir to ensure complete washing of the product from the column. The hexane solution which exits the column contains tris-perfluorovinyl ether (99.5% purity, 49% recovery). The acetonitrile solution which exits the column contains the remainder of the product (88.35 g, 85.5% tris- and 14.5% bis-perfluorovinyl ether) and is concentrated by rotary evaporation, rediluted in hexane (750 mL) and purified by running it through the countercurrent extractor to give 50.55 g of tris-perfluorovinyl ether (98.2% purity). The acetonitrile solution from this pass contains 25.7 g of material which is 71% tris- and 28.5% bis-perfluorovinyl ether. The ether is found to have the following properties:
Colorless, mobile oil
F-19 NMR: delta 42.7 (dd, J(cis)=60 Hz, J(gem)=100 Hz, which is attributed to ═CF (terminal vinyl fluorine), cis to F; 49.3 (dd, J(trans)=120 Hz, J(gem)=100 Hz, which is attributed to ═CF, trans to F; 55.3 (dd, J(cis)=60 Hz J(trans)=120 Hz, which is attributed to OCF groups)
H-NMR: delta 2.1 (bs, 3 H), 6.95 (bs, 12 H)
IR: cm-1 1830 which is attributed to (CF═CF2) groups, 1500, 1313, 1273, 1205, 11781, 1138, 1011
The 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane polymerizes at 140-350� C., with a peak exotherm at 235� C.
A polymer is prepared by degassing a 9 g. sample of the 97.5% pure product obtained before purification. 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane is held under vacuum until no visible bubbles form at room temperature, then heated to 150-160� C. for 2 hours. The sample is then allowed to cool to room temperature. The sample is a solid which is then chipped out of its container and ground into a powder using mortar and pestle. The powder is poured into a mold measuring about 4�5�1/32 inches (10.2�12.7�0.008 cm), put in a press, and compression molded at 240� C. and 10,000 psi (pounds per square inch on the gauge) for 15 minutes. A resulting plaque is removed without cooling and is observed to be clear, flexible and colorless. The polymer is found to have a Tg of 282.1� C. as measured by thermomechanical analysis (TMA) Mettler TA 3000.
A 30 g sample of the material prepared in Example 3 which is 99.5% pure 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane is filtered and poured into a vertical casting mold measuring 3�4�1/8 inches (7.6�10.2�0.3cm). The mold is placed in a vacuum oven at 140-160� C. for a period of 2 hours after which, the heat is increased to 240-250� C. for a period of 1 hour. The heat is turned off and the mold allowed to cool to room temperature. The molded polymer is removed and found to have the following properties:
Colorless, transparent Tg (as measured by Thermomechanical Analysis on a Mettler TA 3000)=300� C.; Dielectric Constant (as measured by the procedure of ASTM D150-87)=2.45 (1 MHz) Dissipation Factor (as measured by the procedure of ASTM D150-87)=0.0005 (1 MHz). Upon postcuring by heating twice from 250� C. to 360� C. at a rate of 10� C. per minute, a Tg of 414� C. is obtained.
The procedure of Example 3 is repeated obtaining a samples of 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane having a purity of 97 mole percent after having been flushed through alumina using hexane.
A sample of the 97 percent pure 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane is poured into a compression mold and heated to 160� C. for a period of 2 hours then 240� C. for a period of 30 minutes, after which it is cooled to 25� C. and removed from the mold. The resulting polymer is found a Tg of 286.1� C. and a dielectric constant as determined (as measured by the procedure of ASTM D150-87) of 2.55 and dissipation factor (as measured by the procedure of ASTM D150-87) of 0.001 (1 Megahertz (MHz).
The procedure of Example 3 is repeated obtaining samples of 1,1,1-tris(4-trifluoroethenyloxyphenyl)ethane having the following purities after the steps indicated in Table 1.
Each sample is poured into a pan and put into a vacuum oven at 140� C. for a period of 2 hours, after which the temperature is raised to 240� C. for a period of 1 hour. The pan is removed from the oven and the resulting polymer is cooled to room temperature and removed from the pan. By TMA using a Mettler TA 3000 System, the samples are found to have the Tg's indicated in Table 1.
______________________________________ PurityStep MoleNo. Step Percent* Tg �C.______________________________________6 catalyst and solvent (hexane) removal 89.6 2767 counter current extraction using 99.8 300hexane/acetonitrile, first cut inhexane8 recovery from acetonitrile without 73.6 242further purification9 acetonitrile sample after purification 85.9 251by second extraction in hexane10 recovery from acetonitrile portion of 50 178hexane extraction of Step 8______________________________________ *as determined by gas chromatography
During TMA analysis, Examples 8 and 10 are observed to soften, indicative of thermoplastic character. Examples 6, 7 and 9 are observed to undergo a change in rate of expansion indicative of thermoset character.
These examples show that various purities of tris-perfluorovinyl monomers are obtained using various purification methods and that Tg increases with percentage of polyfunctional monomer. Counter current extraction is particularly useful for removing such impurities as bis-perfluorovinyl ethers. With such extractions, tris-perfluorovinyl monomers exceeding 99.9 percent in purity are obtained and are particularly useful, for instance in electronics applications. Generally such counter current solvent extractions require two solvents which are substantially immiscible, one of which preferentially dissolves the desired product. Solvent combinations useful for the separation in the practice of this invention include solvents for the desired monomer paired with solvents in which the monomer is less soluble, but in which at least some of the impurities are more soluble. Such solvent pairs include hexane/acetonitrile, hexane/dimethysulfoxide, and hexane/dimethylformamide.
Alternatively, the monomers are suitable for polymerization after preparation without purification, preferably with removal of solvent(s) used in preparation. Such monomers in combination with by-products of their preparation are suitable, for instance, for applications wherein lower Tg's are suitable such as molded objects.
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|Nov 15, 2011
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|Polymer dispersant addition to fuel cell electrode inks for improved manufacturability
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|Jan 15, 2013
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|Co(II)tetramethoxyphenylporphyrin additive to PFSA PEMS for improved fuel cell durability
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|Dec 17, 2013
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|Poly(perfluorocyclobutane) ionomer with phosphonic acid groups for high temperature fuel cells
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|Sodium stannate additive to improve the durability of PEMS for H2/air fuel cells
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|Bausch & Lomb
|Polymerization products and biomedical devices containing same
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|U.S. Classification
|526/242, 526/250, 526/243, 526/245, 528/86, 526/247, 526/251, 568/669, 526/252, 526/255, 526/253, 526/248
|International Classification
|Cooperative Classification
|European Classification
|Jul 17, 1991
Owner name: DOW CHEMICAL COMPANY, THE A CORPORATION OF DE, MI
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:CLEMENT, KATHERINE S.;BABB, DAVID A.;EZZELL, BOBBY R.;REEL/FRAME:005770/0596;SIGNING DATES FROM 19900605 TO 19900607
|Jan 12, 1995
|Fee payment
Year of fee payment: 4
|Mar 2, 1999
|Fee payment
Year of fee payment: 8
|Apr 14, 2003
|Fee payment
Year of fee payment: 12