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Bryan Adams' Hit-Heavy Fox Show
By Jeremy Essig
Lightning Bolt's Sharp New Sound
By Jason Robinson
Fleetwood Mac Back with Classic Lineup
By Hans Morgenstern
Here's Who's Making STL Noisy This Spring
By Joseph Hess
Beatles Sister Louise Harrison Departs the Midwest
By Peter Gilstrap
By Julia Burch
Working Class Dogs to Honor Rick Springfield
By Jeremy Essig
Torche Gets Back Into Its Heavy Groove With Restarter
By Nathan Smith
Of course, each deal is customized, and for artists like Potzee, who is signed to Asylum Records through the production company Unauthorized Entertainment, going through a middleman has certain advantages. He says he has learned from cautionary tales like Ebony Eyez's.
"I'm not in a rush at all," he says. "Our situation? We're gonna stretch it out as much as we can."
But other artists signed through a production company aren't nearly so sanguine. Signed in February 2006 to Rap-a-Lot Records, Maurice Hines, known as Raw Resse, says he has no idea when his album will be released.
He says the label has yet to set a date in part because his single, "24's," isn't getting the radio play it deserves.
"The label's been calling us, telling us they're going to give us a release date," says the dark-skinned, slender rapper, who grew up in East St. Louis. "But the messed-up thing about the situation is that we're really not getting the spins that we should be getting. The streets and everybody love us, but without the spins it makes our label look at us like we're not doing our job. Our buzz can be real big in the street, but [Rap-a-Lot Records] wants to see what the radio's doing, what the people are requesting."
Raw Resse is not alone. Working with the Atlanta rapper Gipp, St. Lunatic Ali's terminally forthcoming album, Kinfolk, though released last December in Europe, has already missed several domestic release dates.
Asked about the delay, Shirronda Sweet, the duo's publicity representative at Universal, says, "They started putting new songs on the album. They just needed to change some things."
J Records, a division of Sony BMG, shows no signs of releasing an album by St. Louis rapper Clyph, who has been signed since mid-2005. J Records publicity representative Viola Borden says she's unsure of Clyph's status with the label, adding that J Records has no clear plans regarding how to move forward with the artist.
"So far we've done nothing with him," says Borden. "He might come out fourth quarter; he might not, but right now I don't have him on my release schedule."
It was these sorts of delays that prompted DJ Kaos, who in 2002 landed a deal with MCA/Universal with his band Da Hol' 9, to drop outside production companies for good.
"We got signed and everything was great. We were supposed to be the next big thing," says Kaos, whose 2002 hit single "Urbody in the Club Up" became a local anthem. "But we were going back and forth with lawyers: The producers' lawyers were talking to the label's lawyers who would get back to our lawyers. All of this was going on while our song was peaking: We've already done shot the video. Everything's ready to go, but we can't play the video until we've got the clearance on the producer agreements so the producer can hold your whole project up."
In the end, Kaos (who declines to provide his given name) says the song's popularity began to wane and the label decided to hold off on releasing the album. Undeterred, he walked away from MCA/Universal with the rights to the album's masters.
But when he tried to release the album independently, it wasn't the same.
"We didn't have the muscle that the big label gave us," Kaos says. "What did I learn from that? I don't deal with producers anymore."
In late January the Adam's Mark hotel in downtown St. Louis hosted the first annual Midwest Monsters Music Conference. Aspiring rappers from around the state paid the $25 admission fee to listen to panels of rappers, distributors, DJs and producers discuss issues like how to make it in the industry without a major-label deal, how to get a deal and how to negotiate publishing rights and radio play.
Outside the conference rooms, companies like Hollow Wear Apparel Inc., which makes music videos for many unsigned artists, hawked their wares. Derrty Entertainment had a booth selling Pimp Juice products and the end of the conference was marked by a showcase of unsigned St. Louis acts.
The conference was organized by an unsigned St. Louis rapper known as Ruka Puff, who knows more than a little about the pitfalls of modern music contracts. In the summer of 2005, Ruka Puff (real name: Byron Waters) signed with Los Angeles artist Mack 10's Hoo-Bangin' Records. At the time Mack 10 had a deal with Capitol Records. The plan was that once Mack 10's album was released, he'd promote Ruka Puff to the label.
"It didn't go as expected. He sold 40,000 or 50,000 but for Capitol that was a flop. And he couldn't get Capitol to bite on my record because his record didn't do what it was supposed to do," says Ruka, who only recently got out of his deal with Hoo-Bangin'. "It was real ghetto. We never even got around to the recording process because, you see, it was a waiting game."
A beefy rapper who wears his hair braided but for a spiked mohawk and is given to pronouncements like "This is the age of the overweight MC," Ruka Puff has gone on to place his music with Fox Sports as well as the Indiana Pacers basketball team. He says he has come to realize there are plenty of ways to pull money from the music, and he's convinced that getting signed is only half the battle.
Sponsor Content


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Gear Review
Dig the phones, hate the mic!
- Gender: Male
- Familiarity: I've put it through the wringer
These work great to throw in my Smith Vantage helmet. Good sound quality for the price. The downfall is the Mic 1 is just dumb. No volume control on it. and if you dont click it just right youll end up calling people when you were trying to change the track. I just dont even use it.
Overall its an inexpensive way to get tunes in dat helmet!
View More Details on Skullcandy Cassette Headphones w/ Mic1

subset: commoncrawl


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The Rev. Robert Roland Sauer, 74, of Allen, Texas, passed away on Sunday, Nov. 7, 2010.
Graveside services will be held at 11 a.m. on Thursday, Nov. 11, 2010, at Roscoe Cemetery with Pastor Gordon Illausky officiating. Arrangements are under the direction of Cate-Spencer & Trent Funeral Home.
The memorial service, with a reception following, will be held at 11 a.m. on Saturday, Nov. 13, 2010, at Christ the Servant Lutheran Church, 821 South Greenville Avenue in Allen, Texas.
Olney ~ Dawson Payne Boydstun, age 6, died Wednesday, Nov. 3, 2010, at his home in Olney.
Funeral services were held at 10:30 a.m. on Saturday, Nov. 6, 2010, at the First Baptist Church of Olney with the Rev. Andy Graham of Southside Baptist Church officiating, assisted by the Rev. Charles Fischer of Abilene, Texas. Interment followed at Restland Cemetery under the direction of Lunn Funeral Home of Olney.
Dawson was born on Jan. 21, 2004, in Sweetwater to Misty Donn (Walters) Schneider and Trey Boydstun. He was a student at Olney Elementary School.
Sweetwater's football season may be over, but Mustang Bowl will be a busy place this weekend.
The Texas high school playoffs are set to begin and three bi-district games will be played here, including two on Saturday, said Danny Escobar with the Sweetwater Chamber of Commerce playoff committee.
The local postseason play starts Friday when Canyon Randall and Lake Dallas meet in a Class 4A, Division II matchup at 7 p.m. Hereford and Denton meet in another Class 4A, Division II contest at 3 p.m. Saturday.
The TSTC Board of Regents appointed Michael L. Reeser as Chancellor of the Texas State Technical College System. Reeser will begin his tenure as the ninth CEO of the TSTC System immediately. "Mike has a history of innovative student-focused leadership," said TSTC Board Chair Rolf Haberecht, Ph.D. "His passion and boldness will serve the entire system well as TSTC becomes the leader in building the economic vibrancy of Texas by striving to develop the technical competence of all Texans," added Dr. Haberecht.
Nine Sweetwater Middle School choir students and two Sweetwater High School choir students recently auditioned for and earned a place in the Texas Music Educators Region 16 Honor Choir. Auditions were held in Abilene at Craig Middle School on Oct. 23, 2010. The students will participate in an all day clinic and perform an evening concert on Nov. 20, 2010, at First Baptist Church in Abilene. Participants are from Abilene, Clyde, Snyder, Sweetwater and Wylie schools. The students are directed by Kathy Pogue, SMS choirs, and Melody Squires, SHS choirs.


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Charles Burchfield letter to Alan M. Pensler, 1966 Aug. 3
Physical Details: Letter : 6 p. : handwritten ; 21 x 16 cm.
Sender: Charles Ephraim Burchfield (1893-1967)
Recipient: Alan Pensler
Description: Burchfield describes how he happened to paint The Shed, explaining: "I often say that I do not choose my subjects for my pictures, that they choose me ..."
Letter is six pages on three sheets of paper.
Donated 2011 by Alan M. Pensler whose family owned the painting The shed.
Forms part of: Miscellaneous manuscripts collection,
Rights Statement: Current copyright status is undetermined
Citation: Charles Burchfield letter to Alan M. Pensler, 1966 Aug. 3
Digital ID: 14678
View all Image Gallery items from the Miscellaneous manuscripts collection


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Vogue Theatre
3290 Sacramento Street,
San Francisco,
11 people favorited this theater
The Elite Theatre was opened in 1910. It was renamed Rex Theatre in 1919. In 1939 it was renamed Vogue Theatre, when at that time it was operated by Blumenfeld Theatres. It was later operated by United Artists. In 2002 UA installed a new floor in the auditorium and put in brand new seats with cupholders. In August 2002, the roof was repaired and plaster work was done on the ceiling of the auditorium.
Recent comments (view all 18 comments)
The SF Theatre Foundation just bought the Vogue and will operate it as Peerless Entertainment.
I hope they go back to using the stage lights and the red curtains before the movie.
here is a link with more info http://www.sfntf.org/images/vogueflyer.pdf
The current seating capacity is 240 seats.
The Vogue in 1997: View link
History from the theatre's website (provided by LostMemory above) states that this theatre was built in 1910, and only became the Vogue in 1939 (the era of most of the Vogue theatres). Also alternate names: Elite Theatre from 1910, at some point was also known as the Rex, then the Vogue. I can't wait to check this theatre out next time I'm in SF!
Here's a photo from 2006
The Vogue- Nothing Dies With Blue Skies.com
A 2012 photo can be seen here.
The Vogue is alive and well and under the auspices of the San Francisco Neighborhood Theatre Foundation
"The San Francisco Neighborhood Theater Foundation (SFNTF) is dedicated to preserving and maintaining the City's last remaining neighborhood cinemas. Movie theaters make important contributions to the unique character of San Francisco's neighborhoods and are important economic engines for local commercial districts. Today, only a dozen neighborhood movie theaters remain in San Francisco."
The website should be listed as…
I visited this theater yesterday in my quest to visit single-screen theaters around the country. It is a very nice theater with excellent projection, and I enjoyed my visit. My only complaint is that the curtain was already open and there were no stage lights. The front of the auditorium was just dark. I feel that if a theater has a curtain, they should use it, along with stage lights. It would make the place much more attractive and inviting. Too many of the single-screen theaters I visit are so dark that you can't appreciate the decor and ornamentation of the place. It's always disappointing.
The history page of the Vogue's web site says that the house opened in 1910 as the Elite Theatre and was known as the Rex Theatre before becoming the Vogue in 1939.
San Francisco Theaters, Cinemas, Dancehalls, after 1906 lists 3290 Sacramento Street as the home of the Elite Theatre from 1912-1919, the Rex Theatre from 1919-1927, the Plaza Theatre from 1927-1939, the United Artists Vogue From 1939 to an unlisted date, and simply the Vogue Theater in 1982.
Around 1916 there was an Elite Theatre on Market Street opposite 7th in downtown San Francisco, so the two Elites must have overlapped for some time. The post-1906 web page doesn't list the Market Street Elite Theatre.
Just login to your account and subscribe to this theater


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This 1968 Porsche 911L Targa is an extremely rare find and a superb original car. Tangerine with black interior. Matching numbers. The 911 L was... More
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This 1967 Porsche 912 is matching number example and a one owner California car from new. An excellent car to restore for only $26,500... More
1978 PORSCHE 911SC TARGA INCREDIBLE CONDITION! ONLY 37,104 DOCUMENTED MILES! RARE AND DESIRED EUROPEAN EDITION WITH HIGHER HORSEPOWER ENGINE! IMPORTED IN 1988 WITH ALL EPA DOT CERTIFICATIONS! GORGEOUS ORIGINAL... More
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Turbo Cabriolet Tiptronic With Black Full Leather Interior. Fitted With: Full Leather Interior, Tiptronic S Transmission, Heated Front Seats, Floor Mats In Interior Color,... More
2002 Porsche Carrera Cabriolet is a highly attractive drop-top 996 in Carrara White over Metropol Blue Supple Leather Interior, with Blue Soft Top. 3.6L/320hp... More
1983 Porsche 911 SC SportsCar LA is pleased to offer this very nice Porsche 911 SC. This is an excellent running and... More
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Porsche 911 Targa 3.0 1980 Fuchs wheels in good condition 1980 Porsche 911 Targa from Hawaii. The car is in a beautiful and well maintained... More
Porsche 356 B Coupe matching numbers 1963 Porsche 356 B coupe. The car is in a very original and solid condition. Needs some cosmetical and... More


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An independent study commissioned by the organisers of The Open Championship, The R&A, forecasts that this years event, to be staged at Muirfield (14-21 July 2013), will deliver a total economic benefit of £70m in the East Lothian and Edinburgh regional economy.
The headline figure includes a forecast economic impact of £25 million and an estimated destination marketing benefit of £45 million gained through global television exposure of the week-long event.
Researchers at the Sport Industry Research Centre at Sheffield Hallam University base their economic impact forecast on 170,000 spectator admissions and the spending patterns of players, the media, event staff, sponsors and organisers established in studies of the last three Championships.
Announcing the forecast to coincide with a tourism and retail customer care conference in Musselburgh, organised by East Lothian Council, The R&As Executive Director Championships Johnnie Cole-Hamilton said:
The Open Championship is staged at Muirfield to provide the best players in the world with a true test of golf and it is good to know that we also bring an important financial boost to the host economy.
Welcoming The Open Championship economic impact forecast Cllr. John McMillan, East Lothian Council Cabinet Spokesperson for Economic Development and Tourism said:
Having The Open Championship in town is clearly beneficial for local people and businesses in East Lothian and we look forward to welcoming the many thousands of spectators destined to attend this years event.
Already our East Lothian Food and Drink members are actively engaged in supply discussions with The R&A and local employment agencies, university and college authorities are gearing up to help with the recruitment of temporary staff.
Scottish companies are demonstrating their enthusiasm to do business at Muirfield with the Official Open Championship Hospitality Programme reporting sales up 20 percent on last year at this time.


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Berry: Does SB5 restrict bargaining for emergency equipment and training?Written by Thomas Berry | | firstname.lastname@example.com
Opponents to Issue 2 are making a series of claims meant to frighten voters into repealing SB5.
One such claim is that it will make emergency equipment and training less readily available. Quoting from the opposition's website, http://action.weareohio.com/page/s/issue2primer <http://action.weareohio.com/page/s/issue2primer> : "Issue 2 puts all our families' safety at risk. It makes it harder for emergency responders, police and firefighters to negotiate for critical safety equipment and training that protects us all."
Since no citation for this claim (or, for that matter, any other claim on that page) is provided, I searched the issue's text for "equipment" and "training." Rather than finding any such language as this, I learned that, according to Sec. 4117.08(C), SB5 does not "[impair] the right and responsibility of each public employer" to "(8) Determine the type of equipment used and the sequence of work processes," and, "(9) Determine the making of technological alterations by revising either process or equipment or both." More to the point, Sec. 4117.08(F) states, "Notwithstanding division (C) of this section, equipment issues directly related to personal safety are subject to collective bargaining." So much for the myth that SB5 bans collective bargaining.
As for training, most of the citations involving training of emergency personnel make such training mandatory; see Sec. 505.38 and 505.49. And none in any way support the claim that SB5 makes it harder to negotiate for training.
If you will pardon a double negative, Sec. 4117.08 (B) completely omits equipment and training from the list of subjects that are not, "appropriate subjects for collective bargaining." In other words: Under SB5, both equipment and training for emergency personnel are subject to collective bargaining; and We are Ohio evidently thinks that making public employers responsible to manage equipment and work processes is a limitation on that process.
But since the opponents mention public safety: Where are their concerns about this when politicians make cuts to emergency services the means of choice in resolving budget deficits that were largely induced by increasingly unaffordable employee benefits and pensions? We are Ohio laughably claims that Issue 2 proponents think "teachers, nurses, firefighters" are to blame for these deficits. The fault clearly lies elsewhere: With politicians, and with the voters.
Politicians are at fault for committing government entities to lavish contracts with growing numbers of present and past employees. If you want to argue this, let's start with the 23 Chicago labor officials who stand to collect $56 million in city pensions because, under laws crafted in 1991 by politicians, their pensions are based not on wages earned as public employees, but on what their unions pay them as executives.
They are also at fault for fulfilling the oft-quoted but oft-ignored warning from 18th century Scottish historian Alexander Tytler, "A democracy cannot exist as a permanent form of government. It can only exist until a majority of voters discover that they can vote themselves largess out of the public treasury." They accomplish this by pandering to public employees for votes, then rewarding those votes by keeping the largess coming at taxpayer expense.
We, the voters, are at fault for time and again electing people who engage in these practices. If we even bother to vote, we habitually push the button next to a name solely because we recognize it, or it's followed by the correct party abbreviation, or the power brokers said to, or that person has promised us sufficient goodies to buy our votes; and we ignore to our detriment the record of incompetence, addiction to power and faithlessness to the Constitution that trails so many politicians. Our fault exceeds theirs, because if not for us they would not be in power.
We are Ohio is using Chico Marx's classic flimflam line: "Who ya gonna believe? Me, or your own eyes?" In the grand style of voter dereliction just described, they expect you to believe their claims solely because they made them. I don't want you to believe them, or me. Do what I did: Study the bill for yourself and see what it says. SB5′s text is athttp://www.legislature.state.oh.us/BillText129/129_SB_5_EN_N.pdf <http://www.legislature.state.oh.us/BillText129/129_SB_5_EN_N.pdf> and it's fully searchable.
I am Ohio, and so is every Ohioan who favors Issue 2.
Thomas Berry, for the Children of Liberty, http://www.meetup.com/The-children-of-liberty/ <http://www.meetup.com/The-children-of-liberty/> .


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Looking for an organization that cares about the same issues as you do? Do you believe in equal pay for equal work? Advancing education for women and girls? Then AAUW is for you!
AAUW of Murfreesboro is a company of college-educated individuals from all walks of life who share a common purpose—To work toward equity for women and girls in education and in the workplace. We are part of a national and state network that makes a difference both locally and nationally.
Our mother organization in Washington, D. C. (200,000 members strong) is a powerful voice on women's issues (http://www.aauw.org/ ). Our Tennessee organization (http://aauw-tn.aauw.net/) supports legislation in the General Assembly that will make positive changes for women in the workplace.
AAUW of Murfreesboro meets monthly—September through May, excluding January—on the second Thursday of the month, 5:00 to 7:00 PM. At these meetings, we learn about women's issues, plan activities to advance women and girls, and share a meal. We make lifelong friends, have fun, and enjoy good eats!
We welcome members from all professions and businesses who care about equity for women and girls in education and in the workplace. The only requirement for membership is a college degree, including an associate's degree.
Our activities include raising funds for local and national scholarships and for legal advocacy for women and educating the public about the pay gap for women and lobbying for paycheck fairness. We also partner with other community organizations to create opportunities for women and girls, such as co-sponsoring "Expanding Your Horizons," the science and mathematics conference for middle school girls, and adopting the Rutherford County Domestic Violence and Sexual Assault Program.
For more information, contact Tanya Peres Lemons, firstname.lastname@example.com. In principle and in practice, AAUW values and seeks a diverse membership. There shall be no barriers to full participation in this organization on the basis of gender, race, creed, age, sexual orientation, national origin or disability.
Featured News
"Report: Murfreesboro closing gender pay gap"
Daily News Journal, April 5, 2014
Featured Events
NWHM panel "Serving the Local Community: Women in Murfreesboro City and Rutherford County Governments," March 20, 2014, at MTSU. Those pictured L to R are:
Laura Bohling, Circuit Court Clerk, Rutherford County
Donna Scott Davenport, Juvenile Court Judge Rutherford County
Joyce Ealy, Commissioner, District 19, Rutherford County Commission
Madelyn Scales Harris, Councilwoman, Murfreesboro City Council
Lisa Nolen, Finance Director, Rutherford County


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The invention herein relates to unsaturated monohydroxylated polydiene polymers which are comprised of at least two polymerizable ethenically unsaturated hydrocarbon monomers wherein at least one is a diene monomer which yields unsaturation suitable for epoxidation. The invention also encompasses partially hydrogenated and/or epoxidized derivatives of these novel monohydroxylated polydiene polymers. The preferred monohydroxylated polydiene polymer of the present invention has a structural formula
wherein A and B are polymer blocks which may be homopolymer blocks of conjugated diolefin monomers, copolymer blocks of conjugated diolefin monomers, or copolymer blocks of diolefin monomers and monoalkenyl aromatic hydrocarbon monomers. These polymers may contain up to 60% by weight of at least one vinyl aromatic hydrocarbon, preferably styrene. Generally, it is preferred that the A blocks should have a greater concentration of more highly substituted aliphatic double bonds than the B blocks have. Thus, the A blocks have a greater concentration of di-, tri-, or tetra-substituted unsaturation sites (aliphatic double bonds) per unit of block mass than do the B blocks. This produces a polymer wherein the most facile epoxidation occurs in the A blocks. The A blocks have a molecular weight of from 100 to 6000, preferably 500 to 4,000, and most preferably 1000 to 3000, and the B blocks have a molecular weight of from 1000 to 15,000, preferably 2000 to 10,000, and most preferably 3000 to 6000. S is a vinyl aromatic hydrocarbon block which may have a molecular weight of from 100 to 10,000. x and y are 0 or 1. Either x or y must be 1, but only one at a time can be 1. z is 0 or 1. Either the A or the B block may be capped with a miniblock of polymer, 50 to 1000 molecular weight, of a different composition, to compensate for any initiation, tapering due to unfavorable copolymerization rates, or capping difficulties. These polymers may be epoxidized such that they contain from 0.1 to 7.0 milliequivalents (meq) of epoxy per gram of polymer.
1. An epoxidized monohydroxylated polydiene polymer which is comprised of at least two polymerizable ethenically unsaturated hydrocarbon monomers, wherein at least one is a diene monomer which yields unsaturation suitable for epoxidation, and wherein the polymer has been epoxidized at aliphatic double bonds to have from 0.1 to 7.0 meq of epoxy functional groups per gram of polymer.
2. The epoxidized monohydroxylated polydiene polymer of
3. The polymer of
4. The epoxidized monohydroxylated polydlene polymer of
5. The epoxidized monohydroxylated polydlene polymer of
6. The epoxidized monohydroxylated polydiene polymer of
7. The epoxidized monohydroxylated polydiene polymer of
This is a division of application Ser. No. 08/320,807, filed Oct. 11, 1994.
This invention relates to novel monohydroxylated diene polymers which are suitable for use in a variety of applications including adhesives, sealants, coatings, modification of other polymers or asphalt, etc., as well as to be further functionalized to produce useful polymers. More specifically, the invention relates to particular epoxidized monohydroxylated polydiene polymers and their epoxidized derivatives.
Monohydroxylated polydienes are known. Most of these polymers are homopolymers of one diene or another. For example, monohydroxlated polybutadienes are known in the art for use in adhesive formulations. U.S. Pat. No. 4,242,468 describes solventless polyurethane coatings having improved flexibility resulting from incorporation of monohydroxylated polybutadienes. Epoxidized versions of hydroxylated polybutadienes are known as well. Low viscosity epoxidized polydiene polymers are also known, especially for use in adhesives. Such polymers are described in commonly assigned U.S. Pat. Nos. 5,229,464 and 5,247,026.
While the low viscosity polymers of the prior art are useful in applications where aliphatic epoxies are generally employed., they suffer the disadvantage of not being reactive via a broader class of chemistry. Further, epoxidation is costly and many examples of the prior art required high levels of epoxy functionality to be of utility. Incorporation of a more economical moiety which would provide the same or broader chemical utility is highly desirable. The present invention provides polymers which overcome the disadvantages of the aforementioned limited chemical reactivity. Further, in applications requiring epoxy functionality for chemical compatibility these polymers reduce the necessary epoxy levels.
This invention is a monohydroxylated polydiene polymer which is comprised of at least two polymerizable ethenically unsaturated hydrocarbon monomers wherein at least one is a diene monomer which yields unsaturation suitable for epoxidation. The invention also contemplates partially unsaturated and/or epoxidized derivatives of these novel monohydroxylated polydiene polymers. The hydroxylated polymers are preferably block copolymers of at least two diene monomers, preferably isoprene and butadiene, and, optionally, a vinyl aromatic hydrocarbon wherein a hydroxyl group is attached at one end of the polymer molecule. These polymers may be hydrogenated or unhydrogenated but they are preferably epoxidized.
The preferred monohydroxylated polydiene polymer of the present invention has the structural formula
wherein A and B are polymer blocks which may be homopolymer blocks of conjugated diolefin monomers, copolymer blocks of conjugated diolefin monomers, or copolymer blocks of diolefin monomers and monoalkenyl aromatic hydrocarbon monomers. These polymers may contain up to 60% by weight of at least one vinyl aromatic hydrocarbon, preferably styrene. Generally, it is preferred that the A blocks should have a greater concentration of more highly substituted aliphatic double bonds than the B blocks have. Thus, the A blocks have a greater concentration of di-, tri-, or tetra-substituted unsaturation sites (aliphatic double bonds) per unit of block mass than do the B blocks. This produces a polymer wherein the most facile epoxidation occurs in the A blocks. The A blocks have a molecular weight of from 100 to 6000, preferably 500 to 4,000, and most preferably 1000 to 3000, and the B blocks have a molecular weight of from 1000 to 15,000, preferably 2000 to 10,000, and most preferably 3000 to 6000, S is a vinyl aromatic hydrocarbon block which may have a molecular weight of from 100 to 10,000, x and y are 0 or 1. Either x or y must be 1, but only one at a time can be 1, z is 0 or 1. Either the, A or the B block may be capped with a miniblock of polymer, 50 to 1000 molecular weight, of a different composition, to compensate for any initiation, tapering due to unfavorable copolymerization rates, or capping difficulties. These polymers may be epoxidized such that they contain from 0.1 to 7.0 milliequivalents (meq) of epoxy per gram of polymer.
Polymers containing ethylenic unsaturation can be prepared by anionically copolymerizing one or more olefins, particularly diolefins, by themselves or with one or more alkenyl aromatic hydrocarbon monomers. The copolymers may, of course, be random, tapered, block or a combination of these.
Diene containing polymers, having residual unsaturation suitable for epoxidation, may also be obtained by other means of polymerization, such as by cationic polymerization or free radical polymerization. Using cationic polymerization, monomers such as substituted 1-butenes, 1-pentenes and dienes such as isoprene and butadiene can be copolymerized. Like anionic polymerization, living cationic polymerization allows the copolymers to be block copolymers such that the residual diene double bond can be localized within the polymer. Dienes may be polymerized together with acrylic monomers by initiation with a free radical initiator, such a peroxide or AIBN. For pressure sensitive adhesive applications, monomers such as n-butyl acrylate, 2-ethyl-hexyl acrylate and isoprene may be used, and other modifying monomers, such as acrylic acid or 2-hydroxy-ethyl acrylate may also be used. Other polymerization methods including coordination/insertion mechanisms such as Ziegler-Natta polymerizations, metallocene polymerizations, and metathesis polymerizations can also be used to make polymers such as these.
The polymers containing ethylenic unsaturation or both aromatic and ethylenic unsaturation may be prepared using anionic initiators or polymerization catalysts. Such polymers may be prepared using bulk, solution or emulsion techniques. When polymerized to high molecular weight, the polymer containing at least ethylenic unsaturation will, generally, be recovered as a solid such as a crumb, a powder, a pellet or the like. When polymerized to low molecular weight, it may be recovered as a liquid.
In general, when solution anionic techniques are used, copolymers of conjugated diolefins, optionally with vinyl aromatic hydrocarbons, are prepared by contacting the monomer or monomers to be polymeized simultaneously or sequentially with an anionic polymerization initiator such as group IA metals, their alkyls, amides, silanolates, napthalides, biphenyls or anthacenyl derivatives. It is preferred to use an organo alkali metal (such as sodium or potassium) compound in a suitable solvent at a temperature within the range from about −150° C. to about 300° C., preferably at a temperature within the range from about 0° C. to about 100° C. Particularly effective anionic polymerization initiators are organo lithium compounds having the general formula:
wherein R is an aliphatic, cycloaliphatic, aromatic or alkyl-substituted aromatic hydrocarbon radical having from 1 to about 20 carbon atoms and n is an integer of 1 to 4.
Conjugated diolefins which may be polymerized anionically include those conjugated diolefins containing from about 4 to about 24 carbon atoms such as 1,3-butadiene, isoprene, piperylene, methylpentadiene, phenyl-butadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene and the like. Isoprene and butadiene are the preferred conjugated diene monomers for use in the present invention because of their low cost and ready availability. Alkenyl (vinyl) aromatic hydrocarbons which may be copolymerized include vinyl aryl compounds such as styrene, various alkyl-substituted styrenes, alkoxy-substituted styrenes, vinyl napthalene, alkyl-substituted vinyl napthalenes and the like.
The monohydroxylated polydienes are synthesized by anionic polymerization of conjugated diene hydrocarbons with lithium initiators. This process is well known as described in. U.S. Pat. No. 4,039,593 and Re. No. 27,145 which descriptions are incorporated herein by reference. Polymerization commences with a monolithium initiator which builds a living polymer backbone at each lithium site. Typical monolithium living polymer structures containing conjugated diene hydrocarbons are:
wherein B represents polymerized units of one conjugated diene hydrocarbon such as butadiene, A represents polymerized units of another conjugated diene such as isoprene, and either A or B may contain one or more vmyl aromatic compounds such as styrene, and X is the residue of a monolithium initiator such as sec-butylithium. The hydroxyl groups are added by terminal capping the polymerization with oxiranes such as ethylene oxide followed by termination with methanol.
Monohydroxy diene polymers can also be made using a mono-lithium initiator which contains a hydroxyl group which has been blocked as the silyl ether. Details of the polymerization procedure can be found in U.S. Pat. No. 5,396,745, which is herein incorporated by reference. A suitable initiator is hydroxyporoyllithium in which the hydroxyl group is blocked as the tert-butyl-dimethylsilyl ether. This mono-lithium initiator can be used to polymerize isoprene or butadiene in hydrocarbon or polar solvent. The living polymer is then terminated with methanol. The silyl ether is then removed by acid catalyzed cleavage in the presence of water yielding the desired monohydroxy polydiene polymer.
When one of the conjugated dienes is 1,3-butadiene and it will be hydrogenated, the anionic polymerization of the conjugated diene hydrocarbons is typically controlled with structure modifiers such as diethylether or glyme (1,2-diethoxyethane) to obtain the desired amount of 1,4-addition. As described in U.S. Pat. No. Re 27,145 which is incorporated by reference herein, the level of 1,2-addition of a butadiene polymer or copolymer can greatly affect elastomeric properties after hydrogenation. The hydrogenated polymers exhibit improved heat stability and weatherability in the final adhesive, sealant or coating.
The most highly preferred polymers for use herein are diblock polymers which fall within the scope of formula (I) above. The overall molecular weight of such diblocks may range from 1500 to 20000, preferably 3000 to 7000. Either of the blocks in the diblock may contain some randomly polymerieed vinyl aromatic hydrocarbon as described above. For example, where I represents isoprene, B represents butadiene, S represents styrene, and a slash (/) represents a random copolymer block, the diblocks may have the following structures:
where EB is hydrogenated butadiene, -EB/S-OH means that the hydroxyl source is attached to a styrene mer, and -S/EB-OH signifies that the hydroxyl source is attached to a hydrogenated butadiene mer. This latter case, -S/EB-OH, requires capping of the S/EB "random copolymer" block with a mini EB block to compensate for the tapering tendency of the styrene prior to capping with ethylene oxide. These diblocks are advantageous in that they exhibit lower viscosity and are easier to manufacture than the correponding triblock polymers. It is preferred that the hydroxyl be attached to the butadiene block because the epoxidation proceeds more favorably with isoprene and there will be a separation between the functionalities on the polymer. However, the hydroxyl may also be attached to the isoprene block if desired. This produces a more surfactant-like molecule with less load bearing capacity. The isoprene blocks may also be hydrogenated.
Certain triblock copolymers are also preferred for use herein. Such triblocks usually include a styrene block or randomly copolymerized styrene to increase the polymers glass transition temperature, compatibility with polar materials, strength, and room temperature viscosity. These triblocks include the following specific structures:
The latter group of polymers specified in the last line above wherein the styrene block is external are represented by the formula
where A, B, S, x, and y are as described above.
Epoxidation of the base polymer can be effected by reaction with organic peracids which can be preformed or formed in situ. Suitable preformed peracids include peracetic and perbenzoic acids. In situ formation may be accomplished by using hydrogen peroxide and a low molecular weight fatty acid such as formic acid. Alternatively, hydrogen peroxide in the presence of acetic acid or acetic anhydride and a cationic exchange resin will form a peracid. The cationic exchange resin can optionally be replaced by a strong acid such as sulfuric acid or p-toluenesulfonic acid. The epoxidation reaction can be conducted directly in the polymerization cement (polymer solution in which the polymer was polymerizedy or, alternatively, the polymer can be redissolved in an inert solvent. These methods are described in more detail in U. S. Pat. Nos. 5,229,464 and 5,247,026 which are herein incorporated by reference. In particular, we have found that when using peracetic acid for the epoxidation, the rate of epoxidation of residual aliphatic double bonds in polyisoprene and polybutadiene is the following, 1,4-polyisoprene mers (tri-substituted aliphatic double bonds)>1,4-polybutadiene mers (1,2di-substituted aliphatic double bonds)>3,4-polyisoprene mers (1,1-di-substituted aliphatic double bonds)>1,2-polybutadiene mers (mono-substituted aliphatic double bonds). Neither 1,2-polybutadiene mers nor polystyrene mers have been observed to epoxidize.
The molecular weights of linear polymers or unassembled linear segments of polymers such as mono-, di-, triblock, etc., arms of star polymers before coupling are conveniently measured by Gel Permeation Chromatography (GPC), where the GPC system has been appropriately calibrated. For anionically polymerized linear polymers, the polymer is essentially monodisperse (weight average molecular weight/number average molecular weight ratio approaches unity), and it is both convenient and adequately descriptive to report the "peak" molecular weight of the narrow molecular weight distribution observed. Usually, the peak value is between the number and the weight average. The peak molecular weight is the molecular weight of the main species shown on the chromatograph. For polydisperse polymers the weight average molecular weight should be calculated from the chromatograph and used. For materials to be used in the columns of the GPC, styrene-divinyl benzene gels or silica gels are commonly used and are excellent materials. Tetrahydrofuran is an excellent solvent for polymers of the type described herein. A refractive index detector may be used.
If desired, these block copolymers can be partially hydrogenated. Hydrogenation may be effected selectively as disclosed in U.S. Pat. No. Reissue 27,145 which is herein incorporated by reference. The hydrogenation of these polymers and copolymers may be carried out by a variety of well established processes including hydrogenation in the presence of such catalysts. as Raney Nickel, nobel metals such as platinum and the like, soluble transition metal catalysts and titanium catalysts as in U.S. Pat. No. 5,039,755 which is also incorporated by reference. The polymers may have different diene blocks and these diene blocks may be selectively hydrogenated as described in U.S. Pat. No. 5,229,464 which is also herein incorporated by reference. Partially unsaturated hydroxylated polymers are preferred for further functionalization such as to make the epoxidized polymers of this. invention. They can also be chlorinated, brominated, or reacted with maleic anhydride, or used directly for vulcanization or reaction with amino resins. The partial unsaturation preferably is such that 0.1 to 7 meq/g of aliphatic double bonds remain for subsequent epoxidation.
The epoxidized derivatives of these polymers may be used in pressure sensitive adhesives, films, sealants, coatings, structural adhesives, laminating adhesives, pressure sensitive structural adhesives, printing plates, and in the modification of other polymers and/or asphalt (i.e., blends with other polymers andor asphalt for the purpose of altering the properties of those materials). The unepoxidized polymers may be used in applications for which other monohydroxlated polymers have been commonly used, including as part of a binder system for adhesives. However, their primary utility is to be functionalized, such as by epoxidation, to form useful functionalized derivatives.
In the examples several adhesives tests are used to demonstrate the properties of test formulations using the improved binders of this invention. The degree of covalent cure obtained for each of the adhesive samples was measured by use of a polymer gel content test developed by J. R. Erickson for radiation curing adhesives, and first described in the article "Experimental Thermoplastic Rubbers for Enhanced Radiation Crosslinkng of Hot Melt PSA's", TAPPI 1985 Hot Melt Symposium Proceedings, June 1985. The method as practiced for the present examples is essentially identical to the method as published, but for a few minor improvements and corrections. The w % values indicate the weight percentage of the binder polymers that are covalently attached to the three dimensional gel network. 180° Peel from polished steel was determined using Pressure Sensitive Tape Council Method No. 1. Large values indicate high strength when peeling a test tape form the substrate. Loop Tack (LTD.) was determined using a TLMI Loop Tack Tester. Polyken Probe Tack (PPI) was determined by ASTM D2979. High values for LTD. and PPT indicate aggressive tack. Holding Power (HP) is the time required to pull a standard area (1 in×1 in) of tape from a standard test surface (Mylar, steel) under a standard load (500 g, 2 Kg), in 2° antipeel (Pressure Sensitive Tape Council Method No. 7), at a certain temperature (23° C., 95° C.). Long times indicate high adhesive and cohesive strength. Shear Adhesion Failure Test (SAFT) is similar to HP, except that the temperature at which failure occurs is recorded. SAFT is carried out in a oven that ramps up at a rate of 40° F. per hour. High temperature values indicate high cohesive and adhesive strength.
A number of the polymers are used in the binder systems for examples 1 and 2. Many of their important characteristics are given in the table below.
A number of other formulation ingredients are also used in the examples, and they are described in the table below.
Adhesive 1-Q, shown in Table 1, was prepared, cast, and cured by solvent mixing all of the ingredients at room temperature using tetrahydrofuran (THS) as the solvent. The adhesive solution was cast onto a clean 1 mil Mylar sheet. Final dry film thickness of the adhesive was 5 mils. The test film was directly UV cured, with the adhesive facing the incoming radiation at 30 feet per minute (fpm) conveyor speed under a single medium pressure Hg bulb, using a Linde Photocure processor. A nitrogen atmosphere was used only for the purpose of reducing ozone from the bulb, as cationic systems do not need an oxygen free atmosphere to cure. A lightbug was also passed under the lamp to measure the radiation dose. A dose of 150-160 mJ/cm was recorded. Immediately after the UV exposure, the test adhesive was postbaked for 10 minutes at 121° C. It was tested for properties which are also shown in Table 1.
Adhesive 1-Q is an example where the epoxidized diene polymer also contains a hydroxy group. The cure of 1-Q is excellent, as are its aggressive tack and SAFT. It gives all indications of having excellent cohesive strength, yet it exhibited viscous splitting during the room temperature HP test, an apparent spurious result.
Adhesives 2-3, 24, and 2-8, shown in Table 2, were prepared, cast, and cured as in experiment 1. No 180° Peel testing was done because of equipment malfunction. Adhesive 2-4 had no cohesive strength at all. It remained a "goo" even after UV cure and postbake and was not sufficiently handleable to even perform the gel test, probably because neither polymer was epoxidized. Adhesive 2-4 used Polymer 5, a polymer like Polymer 3 except that it was not epoxidized. Adhesives 2-3 and 2-8 have good PSA properties.
Formulations were prepared to test the concept of using blends of epoxidized diene polymers with diene monools and diols as laminating adhesives. Laminating adhesives seem to operate via an entirely different mechanism than PSA's which are cast in relatively thick layers. This thick layer is capable of absorbing much energy through viscous flow during deformation and this provides the strength of PSAs. In laminating adhesives, the layers are relatively thin and these adhesive layers must strongly join two substrates together. Because of the thinness, viscous dissipation of energy within the adhesive layer is not a dominant strength mechanism. Rather, the adhesion between adhesive and substrate must provide the required strength.
The polymers used in the laminating adhesive formulations are described in Table I and in Example 1. In particular, Polymer 13 is epoxidized I-S/EB-EB-OH, with segment molecular weights 2000-2500/1350-150-OH. The random S/EB block has a strong tendency to taper, where the styrene polymerizes last. In making Polymer 13, it was arbitrarily decided to attach the hydroxy source to a hydrogenated butadiene mer. Therefore to assure that the hydroxy source (ethylene oxide) adds to a butadiene mer, the 150 molecular weight EB miniblock was added. Polymer 13 is made by polymerizing the isoprene in cyclohexane, without ether, and after all the isoprene is polymerized, adding diethyl ether to give 6% of the total solvent. The styrene and butadiene are then added over time and polymerized to completion, followed by the remaining butadiene, after completion of the polybutadiene miniblock polymerization, the ethylene oxide is added, and then the living polymer is terminated with methanol. The polymer is partially hydrogenated to completely hydrogenate the butadiene mers and some of the isoprene mers. The styrene mers are not hydrogenated. The polymer is washed to remove the hydrogenation catalyst, and then epoxidized with peracetic acid. The epoxidized polymer is washed, stabilized with a small amount of Irganox® 1010 antioxidant, and recovered by solvent evaporation.
Formulations were made according to Table II. The ingredients were dissolved in THF to prepare a 10% solids solution. Preliminary work indicated that our curing agent, Leecure B1310, would completely dissolve in THF. Partial solubility was found using toluene as the solvent. All ingredients except the B1310 (a blocked BF3 catalyst from Leepoxy, Inc.) were dissolved in THF. Once dissolved B1310 was added and the solution was placed on a roller for several minutes. The formulation was then cast on a poly(ethylene terephthalate) film to give a nominal adhesive layer thickness of 0.3 mils. The film was allowed to air dry for 1 hour. When dry, another poly(ethylene terephthalate) film was laminated to the top of the adhesive layer. The laminate was pressed together using a 2 lb roller. One inch strips were cut and then heat treated under moderate pressure at 50° C. for 60 seconds. The laminates were then tested for strength using a T-peel geometry on an Instron tensile tester. The peel rate was 10 inches per minute.
Table III shows the results for laminates as made and then aged at room temperature. The total molecular weight of Polymer 13 is low and so must experience substantial chemical crosslinking to form a load bearing network. With Polymer 13, an improvement was found by adding a monool. Compare control 2 and formulations 3-3 and 3-4. Incorporation of the monool alone (formulation 3-4) gave an increase from immeasurably low strength to 124 gli. Additional incorporation of a diol gave a further increase to 211 gli.
After aging 24 hours the cure reaction continued to proceed. Some increase in T-peel value is seen for all samples. The mode of failure is 'still cohesive (that is the adhesive layer fails (viscous splitting) rather than the interface). The trends observed for the initial T-peel values are continued at 24 hours.
Incorporation of monool or diol served to increase the strength of the laminating adhesive when the epoxidized polymer was hydroxyl terminated. The best strengths achieved are in the range of 100-400 gli initial T-peel strength.
Several performance properties of cured modified epoxy resin compositions of the present invention are important. The tensile properties such as strength, elongation, and Young's modulus are measured according to ASTM D-638. The flexural properties such as flexural modulus, stress and strain at failure are measured according to ASTM D-790. The tensile fracture toughness as characterized by the stress intensity factor (CKIC) for crack propagation is measured according to ASTM E-399-83. Using the value of KCIC so measured, the fracture energy (GIC) was calculated for the plane strain conditions employed. The adhesive properties such as lap shear stress are measured according to ASTM D-1002. The glass transition temperature (Tg) is measured using torsional bar dynamic mechanical analysis.
Table IV below describes the composition of the epoxidized polydiene polymers used herein. Monohydroxylated and unhydroxylated epoxidized polydienes are compared.
In the base polymer architecture column of Table IV, B represents poly(1,3-butadiene) blocks, I represents polyisoprene blocks, and OH represents monohydroxyl functionality. Homopolymer blocks are separated by a dash.
The cloud points of blends of the,example polymers in EPON® 828 resin at a 1/9 ratio by weight are shown,in Table IV. A clear and significant advantage is shown for the monohydroxylated epoxidized polymer. Very similar cloud points are achieved for the two polymers but the polymer of the present invention achieved that cloud point with only 3.4 meq/g of epoxy, 1.4 meq/g less than the comparative unhydroxylated polymer.
11 parts of monohydroxylated epoxidized polymer A or 11 parts of the comparative monohydroxylated polymer, both having the base structure I-B were added to 100 parts of EPON® 828 resin, a diglycidyl ether of bisphenol-A. 33 parts of EPICURE® 3140 (a polyamide curing agent) per hundred parts of EPON® 828 resin plus epoxidized polymer were added to the mixture and stirred by hand. A small amount (less than 1 part per hundred parts of EPON® 828 resin plus epoxidized polymer) of PC-1344/monofunctional glycidyl epoxy solution was added to aid in defoaming the mixture. The blend was degassed in vacuum and centrifuged. The blend was cast between glass plates to make ⅛″ plaques which were cured at room temperature for 7 days before testing. The mechanical properties of the resultant rubber modified epoxy resins are listed in Table V which provides a comparison of these blends and the cured epoxy resin without added epoxidized polymer.
Incorporation of Polymer A and the comparative polymer leads to increases in fracture energy (GIC) of 192% and 92%, respectively, while maintaining good tensile and flexural properties. These results demonstrate that the these epoxidized polymers are effective at achieving a superior balance of properties in epoxy resins cured with polyamides and that the monohydroxylated epoxidized polymer gives superior results to those of the unhydroxylated epoxidized polymer even though the latter has a higher epoxy content.
The following examples demonstrate the utility of the epoxidized monohydroxylated polymers in amino resin cured compositions. The amino resin used was CYMEL® 1156, a melamine-formaldehyde resin where R is C4H9. The acid used to catalyze the amino resin/hydroxyl and amino resin/epoxy reactions was CYCAT® 600, dodecyl benzene sulfonic acid (a 70%weight solution in isopropyl alcohol). The compositions were mixed and coated from a 65 percent by weight (% w) solids solution of the ingredients in a solvent blend composed of 90% w of an aliphatic hydrocarbon solvent, VM&P naphtha, and 10% w n-butanol. The following formulation, given in parts by weight, was used.
The following polymers were tested in this formulation. Polymers 3, 4, 5, and 7 are described in Example 1. Polymer 14 was a 2000 MW polyisoprene (1)-4000 MW polystyrene/hydrogenated polybutadiene (S/EB) copolymer having a single OH on one end. The 4000 MW S/EB block in Polymer 14 was 2500 MW S and 1500 MW EB. Polymer 13 was an epoxidized version of Polymer 14 (1.5 meq of epoxy/gm polymer). Polymer 16 was a triblock polymer which had the same S/EB copolymer block as Polymer 14. However, Polymer 16 had a 1000 MW block of epoxidized polyisoprene on each end of the S/EB center block and had no OH group.
Coatings, about 2 mil thickness dry, were drawn onto aluminum panels with a #52 wire wound rod. The coatings were cured by baking 20 minutes at 175° C. They were evaluated qualitatively for their suitability for use as coatings. The following are the results.
The results with Polymer 4 clearly show that a melamine cured EB-OH monohydroxylated polydiene polymer made from only one diene monomer is not suitable for use as a coating because it is very sticky. Results with Polymers 5 and 14 show that a monohydroxylated polydiene polymer made from at least two diene monomers and subsequently selectively hydrogenating it, thereby putting an unsaturated I block on the end opposite the OH, performs significantly better than Polymer 4. However, these coatings are still not suitable because they are still sticky. Results for Polymers 3 and 13 show that epoxidation of the I block on the end opposite the OH converts the monohydroxylated polydiene polymers made from at least two diene monomers into useful coating compositions. The results for Polymers 16 and 7 confirm that a polymer with epoxy groups on both ends or an OH group on both ends is useful in coatings, as is already well known.
Coatings made according to the. present invention were evaluated for mechanical properties. The appearance (gloss) of the coatings was judged visually. The pencil hardness (gouge) of the coatings was measured according to the ASTM D3363 method of pushing successively softer pencil leads across the coating until the pencil lead will no longer gouge through the coating. The hardness scale (softest to hardest) is 6B<5B<4B<3B<2B<B<HB<F<H<2H<3H<4H<5H<6H. The methyl ethyl ketone (MEK) resistance of the coatings was measured according to the ASTM D4752 method of rubbing an MEK-moistened cloth across the coating for 200 cycles, or until breakthrough to the aluminum substrate occurred (one cycle equals one forward and one backward stroke). Adhesion of the coatings was measured with the cross hatch adhesion test, ASTM D3359, Method B. In this test, a lattice pattern is scribed through the coating, pressure sensitive tape is applied and removed, and the amount of coating removed with the tape is rated. The scale ranges from 5 (no adhesion loss) to 0 (greater than 65% adhesion loss).
The effectiveness of the monohydroxylated diene polymers in improving properties of coatings was tested in two acrylic urethane formulations using the acrylic polyol and two different triisocyanate curing agents. The hydroxyl (OH) equivalent weight of IONCRYL® 510 (80% w solids) is 500. The isocyanate (NCO) equivalent weight of DESMODUR® Z4370 (70% w solids) and DESMODUR® Z-3390 (90% w solids) are 365 and 216, respectively. The acrylic polyol and the triisocyanate curing agents were mixed at 1.1 to 1 NCO to OH molar ratio, the DABCO T-12 catalyst was added, and coatings were applied onto steel panels.
Four different polymers, all having 6000 molecular weight, were compared in the following experiments. Polymer S was an epoxidized I-EB-OH (epoxy content 1.5 meq/gm). Polymer 13 was an epoxidized I-S/EB-OH (epoxy content 1.5 meq/gm) and Polymer 14 was its unepoxidized precursor (double bond content 1.7 meq/gm). Polymer 16 was an epoxidized I-S/EB-I (epoxy content 1.2 meq/gm). The polymers were dissolved at 70% w solids content in 2-heptanone which had been previously dried with mol sieves. The polymer solutions were mixed with the triisocyanates and catalyst for about 24 hours before the acrylic polyol was added and coatings were applied onto steel panels.
The solutions were checked to see if they were phase stable and those which did not phase separate were drawn down onto steel panels (D36 CRS panels from Q-Panel Corp.) using a #22 wire wound rod. The coatings were tested after being held at room temperature for two weeks. The following result were obtained.
In formulation 6-1, the solution with Polymer 5 phase separated. All the other polymers gave phase stable solutions and so were cast as coatings, the properties of which are shown in the following table.
The fact that Polymer 5 phase separated shows that the polymer must have some styrene in order to gain compatibility with this acrylic/isocyanate system. Polymers 13 and 14, with and without epoxy, both influenced the properties of the acrylic urethane to about the same extent—both reduced the hardness and increased the adhesion. The results on Polymer 16 show that, although its styrene content was sufficient to give a phase stable solution, it made the cured coating tacky and therefore is unsuitable. Thus, the hydroxyl group on Polymers 15 and 14 is required to achieve satisfactory performance.
In formulation 6-2, the only polymer which gave a phase stable blend was Polymer 13. These results clearly show that, in this case, styrene is required in the polymer, the I block must be epoxidized and the OH group is required. The coating properties for Polymer 13 in Formulation 6-2 are shown in the following table.
These results show that Polymer 13 gives a dramatic improvement in adhesion with no apparent reduction in other properties.
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i think you have a point stomp, so todays mission is to go and buy a good burner!
It's better to stick with DVD -R Verbatim or Taiyo Yuden because the lower quality DVD manufatcures perfer quantity over quality and not every disc in the spindle may be good. Sony media may be a good third choice. I burn Verbatims with one computer at 6x, because my burner don't go lower speed, and the games work fine. Then on another computer, same verbatims, I get all kinds of errors. Both computers are HP and not very old, both burners don't get used much, both burners came with the computers. So I don't burn with the burner that gives errors. I have a few Sony burners in other computers with Windows XP, these burners have lots of burn time on them and they burn games without a problem. You may want to buy a good quality burner. I wouldn't copy on the fly, could create problems with the burned disc. As for copying a copy, could be problems too, if the first copy had some errors, then the second copy has some errors, then it seems like the errors are just multiplying. I have copied a copy and it works fine. I used Nero 7, even though your computer may not recognize the burned copy, it is still copyable. I use the copy disc function and it will copy the disc, I'm sure that IMGburn does too, just never tried with that program. I mainly use USB Loader, so I rarely burn a disc.
But I think that I never get a bad burn because of my method, you just have to find your method. Quality media, 4x, no multi tasking, and a burner other than what came preinstalled in your computer.
i think you have a point stomp, so todays mission is to go and buy a good burner!
ok todays mission complete and new lite-on burner + verbatim dvd-r's = 100% copy rate so far, not one failure!! so it seems that all you do is trial and error to find a combo that works for you and away you go! thanks to all for there sugestions
Yea, I can say that I never get a bad burn. I used to burn a lot of movies, not much different than games, it's all data. The verbatim and taiyo yuden will last for years if taken care of, and burning at 4x or slower, I found that burning faster than that will shorten the life of data on the disc. I had a bunch of discs I had to throw out because they wouldn't work any more, I noticed that it was the discs I burned at 8x and the ones I burned at 4x were still good, not to mention, early on I used CMC MAG and Ritek which were Memorex, TDK, Office Depot, Maxell, and other various store brands all lower quality. Sony manufactures their own media but not top rated media. I think taiyo yuden are best but everybody here likes verbatim, they're probably equals.


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There are several scholarships that are available only to students enrolled at the Purdue Polytechnic Institute at Richmond. These scholarships are awarded based on academic merit and/or need. To be considered for these scholarships, beginning and continuing students must submit a scholarship application each year of their attendance.
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