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NORTHBRIDGE, Mass. - This season enjoy beautiful 24" diameter, double-faced, balsam
fir wreaths delivered to home or business and help the Whitin Community Center.
The fresh Maine wreaths, which are $20, arrive with a multi-loop red velvet bow and will be delivered, compliments of the Whitin Community Center, the week following Thanksgiving to your choice of location inthe Blackstone Valley (Blackstone, Douglas, Grafton, Hopedale, Mendon, Millbury, Millville, Northbridge, Sutton, Upton, Uxbridge, and Whitinsville).
"These wreaths make perfect timely holiday gifts for friends, neighbors, employees,
or for any special person on your holiday gift list," said Mike Robertson, president
and General Manager of New England Disposal Technologies, Inc. and chairman
of the WCC board of trustees.
"A Whitin Community Center gift certificate in any denomination may be requested
and delivered with the wreath." All proceeds go to support the Whitin Community
Center's mission of enhancing the health and well-being of individuals and families
and building a strong community in the Blackstone Valley,'' added Heather Elster, vice president of business operations,
Orders must be placed by Friday, Nov. 9. Download an order form at www.WhitinCommunityCenter.com or call 508.234.8184. Cash, checks, and credit
cards accepted.
The Whitin Community Center is a non-profit 50(c)(3) organization offering
social, recreational, educational, and outreach programs that bring community
members of all ages and backgrounds together. The Whitin Community Center
is the Blackstone Valley's most complete family and recreation center with
two swimming pools, a gym, a fitness center, aerobics studio, Spin/TRX studio,
childcare programs, summer camp, and a seven-acre park. To learn more, visit


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Kalamazoo Public Safety Officer Jason Gates is being hailed a hero after saving the life of a driver who was choking.
It all unfolded around 11:20 a.m. Saturday August 9, when Officer Gates pulled a woman over for a red light violation in the 4100 block of S. Burdick Street. As the officer approached the car, he found the driver in respiratory distress.
Dash cam video from the incident shows Officer Gates asking the woman if she was okay, and when he realizes she's in trouble, he administers a couple of back blows. When that doesn't work, you can see ,Gates quickly pull the woman from the car and administer the Heimlich maneuver.
A video was recently released of a man on a Seattle metro bus fighting back against a gunman who was robbing everyone of their cell phones. Immersed in his own phone, it wasn't until the gunman flashed the weapon in his face that he jumped into action, taking the gun from his hands and tackling him to the floor.

subset: commoncrawl


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Videos | Travel Accessories Guide | Travel Adapter Plug Guide
The Orv Trunk 36 is great for fitting all those longer pieces of gear that you want to bring along with you on your adventures. Fit a fishing pole with the collapsible mesh Pole Vault divider or other longer gear.
See All Eagle Creek Products
Copyright © 1999 - 2014 Going In Style Inc. All rights reserved


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Fates Warning
Progressive Metal legends FATES WARNING will be releasing 3 CD/DVD deluxe reissue of their critically acclaimed 1997 release 'A Pleasant Shade of Gray' October 2nd on Metal Blade Records.Read More
The Black Dahlia Murder
The Black Dahlia Murder have partnered with Revolvermag.com to exclusively debut the scathing, new track, 'Receipt,' from the band's new full-length album 'Abysmal,' which comes out on September 18th.Read More
Between the Buried and Me
Between the Buried and Me have debuted at #1 on the Hard Music Billboard Chart, as well as the iTunes Metal Chart, Vinyl Chart, Amazon Hard Rock Chart, and Amazon Metal Chart, with their latest release Coma Ecliptic.Read More
Progressive metal act Redemption have completed recording a new album and signed with Metal Blade Records! New music and more details will be released in the coming weeks.Read More
Don Jamieson
Comedian and That Metal Show co-host Don Jamieson will be hanging out with fans at the Rockstar Energy Drink Mayhem Festival on July 21st in Holmdel, NJ.Read More
Cattle Decapitation
As the official deployment of Cattle Decapitation's 'The Anthropocene Extinction' draws ever closer, today Vice Magazine's mega music portal, Noisey, premieres the official 'making of' documentary.Read More
Act of Defiance
Act of Defiance's highly anticipated debut offering simply delivers 100% in-your-face, uncompromising heavy metal. The group has partnered with Loudwire.com to exclusively debut the new track, 'Refrain and Re-Fracture'.Read More
New Releases
Upcoming Releases
Latest News
The Black Dahlia Murder and Suicide Silence co-headline tour this October!
- October 2nd, 2014 – Mark your calendars! The Black Dahlia Murder has...Read More
REVOCATION Post Third Video from the Making of "Deathless"
- October 1st, 2014 – Metal Blade Records Debut Out October...Read More
PRIMORDIAL to Release New Full-Length this November via Metal Blade Records
- September 30th, 2014 – Lyric Video Now Playing + Pre-order Packages...Read More
Ensiferum nearing completion on recording new album!
- September 29th, 2014 – Ensiferum have been locked away in Astia...Read More
In Solitude release "Sister" on white vinyl and cassette
- September 29th, 2014 – European tour with Beastmilk begins next...Read More
Nonpoint debut "Breaking Skin" video!
- September 29th, 2014 – Nonpoint have released their eighth studio...Read More
GWAR Eternal Tour Honors Lost Leader Oderus Urungus and Introduces New Scumdogs
- September 29th, 2014 – ANTARCTICA – 29th September 2014 –...Read More
Slipknot's Knotfest: Onsite Attractions And Activities Unmasked
- September 29th, 2014 – Three Day Destination Festival Held Friday,...Read More


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Click Here to Watch the Whole Video in HD at Defiant Boyz
We are famous for bringing you hot skaters, twinks, and straight boys exploring their first male-to-male action. Now we bring our entire video collection to the web with DefiantBoyz.
Brock Is Back and He Brought Along Another Defiant Exclusive, Nick Needs! the Boys Are Anxious to Get Started and Strip Down Right Away. Nick's Mouth Finds Its Way to Brock's Hardening Mushroom Tip and He Works That Cock Much to Brock's Obvious Pleasure! They Move Into a Hot 69 Before Brock Decides It's Time for Him to Try a Little Cock In His Tight Ass! Nick Is All Too Happy to Help Out, and He Struggles for a While to Get His Rod Into Brock's Hole. They Finally Give Up, but Nick Throws His Legs Back to Allow Brock's Dick Deep Inside. They Have Steamy Sex for a While, Before Stroking Out Their Own Loads One Right After the Other. Maybe Next Time, Brock!
Pixels: 320X240 | Bitrate: 350K
Pixels: 640X480 | Bitrate: 700K


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- Pro Sports Blogging - http://www.prosportsblogging.com -
Habs call up Yannick Weber; Doug Janik sent down
Posted By Corey Krakower On Apr 8 2009 @ 6:36 pm In Montreal Canadiens | No Comments
I'd like to thank Bob Gainey for reading my blog and taking my suggestion to call up Yannick Weber. Or maybe he got the advice from now assistant coach Don Lever who coached Weber all year. I'm looking into it.
The Swiss native has already set a Bulldogs record with 10 powerplay goals this season. He turned heads in training camp, and he turned even more heads when he put on an impressive performance at the Bell Centre against Binghampton. He was briefly called up, played one game at forward (?), and was sent down. With the loss of Markov and Schneider it was clear that the Canadiens' powerplay was going to take a hit, and was it ever awful last night! Weber will likely play minimal even strength minutes, but he will get plenty of time on the PP. I project that Komisarek and Gorges will stay together on the first pairing, Hamrlik – O'Byrne and Brisebois – Weber will make up the rest of the defense. Ryan O'Byrne is lucky that Dandenault is doing a good job up front, because otherwise Dandy would probably drop back on D and O'Byrne would grab a seat in the press box.
Weber will not be an immediate cure for the powerplay, but he will help, that's for sure. Worst case, this is good practice for next year where he will likely have a regular role in the top 6 and on the PP. For those who don't know; Weber is 20 years old and played his junior hockey for the Kitchener Rangers in the OHL. In 2 years, Weber accumulated 96 points in 110 regular season games. His OHL career culminated with a championship in 2008, and his coach Peter Deboer (now with the Florida Panthers) claimed that Weber was the best defenseman in all of junior hockey. He was drafted by Montreal in the 3rd round of the 2007 entry draft, and has spent his first year of pro hockey in Hamilton. In 68 AHL games; Weber has scored 16 goals and has added 28 assists. He has the potential to be a 2nd pairing defenseman who gets a lot of time on the powerplay.
About the Author
Article printed from Pro Sports Blogging: http://www.prosportsblogging.com
URL to article: http://www.prosportsblogging.com/2009/04/08/habs_call_up_yannick_weber_doug_janik_sent_down/
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Jimmy Choo shoes are in Italian sizing
The cut away detailing of these sandals plays on the idea of being both hidden and revealing. It offers a fresh, modern approach to an open toe sandal, with contrasting textured materials playing with both matt and shiny finishes. Heel measures 120mm/4.7 inches.
US Standard FREE
(2-7 working days, NY 2-3)
US Express $20 (1-3 working days, NY 1-2)
New York same day $25
(order by 2pm EST)
Canada $20 (1-3 working days)
Americas $30 (2-7 working days)
Please note; the above delivery times exclude pre-orders and made-to-order items.
Shop with confidence with free returns.
See full delivery and returns information.
Email Customer Care
or call us on (toll free):+1 877 955 2466
Italian sizing. Fits true to size. View Size Guide


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Upgrade your geek with Dwight Silverman
Posts filtered on Tag
Travel tech: Notes from the road and the sky
For the past two weeks, I've been taking some time off and taking to the road on a vacation that had me crisscrossing the country by both car and airplane. I wouldn't describe this as a restful holiday. While it began with a few days relaxing at my sister's lake house on the Virginia/North Carolina […] [Read More]
Mac users get pricier Orbitz offerings? Sometimes Windows users do, too.
For some time now, the Wall Street Journal has been running a series on how personal information gleaned from users' online activities can be used to shape digital marketing. The concept that site operators can personalize marketing messages on the Web is not earth-shattering – all advertising-based sites do it, including wsj.com – but users […] [Read More]


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UTSA's Selsor savoring transition to pro ball
Column by Richard Oliver : June 23, 2012 : Updated: June 23, 2012 10:03pm
Photo By Jeff Huehn/Courtesy UTSA
UTSA's Casey Selsor throws against Northwestern State at Roadrunner Field on April 15, 2011. Selsor, a Reagan High School graduate, was taken in the 23th round of the MLB first-year player draft by the Washington Nationals.
Photo By AP
Texas-San Antonio starting pitcher Casey Selsor throws to catcher Colby Braddock during a college baseball game against Stephen F. Austin State in Nacogdoches, Texas, on Friday, March 23, 2012. (AP Photo/The Daily Sentinel, Dustin Anderson) MANDATORY CREDIT
Photo By TOM REEL/San Antonio Express-News
UTSA's Casey Selsor throws back to get a runner as UTSA hosts Texas State University at Roadrunner Field on May 2, 2009.
Photo By EDWARD A. ORNELAS/San Antonio Express-News
UTSA's Ryan Hutson (center) celebrates with teammates Casey Selsor (left) and Ryan Dalton (right) after hitting a home run against Texas State during the fourth inning on May 8, 2011 at Roadrunner Field. Texas State won 7-6.
Photo By EDWARD A. ORNELAS/San Antonio Express-News
Portrait of Reagan pitcher Casey Selsor on May 12, 2008.
Photo By EDWARD A. ORNELAS/San Antonio Express-News
Portrait of Reagan pitcher Casey Selsor on May 12, 2008.
Photo By EDWARD A. ORNELAS/San Antonio Express-News
Portrait of Reagan pitcher Casey Selsor on May 12, 2008.
Photo By WILLIAM LUTHER/San Antonio Express-News
Reagan pitcher Casey Selsor lets go of a pitch May 14, 2008 at Wolff Stadium during the Rattlers' game against Stevens.
Photo By Express-News file photo
Reagan's Jordan Mengele (20) hugs Diego Flores (13) as Casey Selsor (5) hugs coach Chans Chapman after losing in the 5A Regional Finals to Lardeo United 5-4 in the third game at Whataburger Field in Corpus Christi on May 30, 2008.
Photo By Express-News file photo
Reagan pitcher Casey Selsor and catcher Santiago Ruiz bump fists on March 19, 2008 at Blossom baseball field.
Photo By Express-News file photo
Reagan's Casey Selsor and Derrick Walls share a laugh on March 19, 2008 at Blossom baseball field.
Photo By Express-News file photo
Express-News All-Area Baseball Player of the Year Casey Selsor of Reagan photgraphed on stage at Gruene Hall on June 2, 2008.
Casey Selsor landed in Florida last week with a scattering of other Washington Nationals draft picks. They loaded up in a van and headed to their assigned hotel near the team's East Coast training center at Viera.
But hearts had other ideas.
"We asked if we could bypass checking in at the hotel first," the former Reagan and UTSA headliner said this week. "We wanted to see the complex."
The driver complied, dropping the young players off at the Nationals' Rookie League minor-league operation adjacent to Space Coast Stadium. Selsor, 22, made his way directly to the locker room.
"It was awesome, a surreal feeling," he said by phone. "I walked up to the locker with my name plate on it, and it had my jersey hanging with my name and number on the back of it.
"I don't know how to describe it. I felt like I finally had arrived, felt like it was a dream come true. There's a long way to go, a lot of work to do, I understand that. But it's like one of our coaches said, we beat the odds."
The 6-foot-2 left-hander, who had rebuffed the Nationals after being drafted directly out of high school, signed a deal with the club when it selected him again in the 23rd round earlier this month. In his first few days in the Gulf Coast League, Selsor has seen work in the outfield, on the mound and at the plate.
Shortly after arriving at the team's training center, Selsor had a base hit and scored twice in his inaugural game. That first single shattered his bat, leaving him running to first with just the handle in his hand.
"I got every bit of the baseball and still broke the bat," he said. "I got the game ball and bat and shipped that back home."
Those trophies will be the latest for a player who seemingly has collected them since he was a toddler. Back then, he swung a small toy bat at stuffed balls his father, Willie, tossed at him in the living room of their San Antonio home.
Willie and his wife, Robin, both in sales management, have spent much of the past two decades following their boys to baseball games all over the landscape. Their younger son, Jace, was on the 2009 McAllister All-Star team that reached the Little League World Series.
"They dropped their weekends completely for us since I was 10 years old," Selsor said. "Summer ball, travel ball — thank God their jobs are flexible enough to get us wherever ... I don't know where I'd be without them."
It's further motivation for a star player who spearheaded Reagan's ascendant baseball program before staying at home to play four years for UTSA.
Selsor finished his UTSA career ranked among the school's all-time top five in triples and stolen bases. He hit .302 this past season, including 10 doubles, a record eight triples and 17 steals in 18 attempts.
Additionally, showcasing the versatility that the Nationals crave, Selsor ended among the Roadrunners' all-time top pitchers.
"This is my job now, and something I always dreamed about and wanted to happen," he said. "But it's not completely about the money. For me, a huge part of it is this game is what I love so much, and I'm getting paid to do what I love and not the other way around."
Twitter: @RichardCOliver


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Chapter 23 School records and handling informationThis chapter describes the role and responsibilities of the Board of Governors in terms of the keeping, maintaining and transfer of pupil records. It also includes the requirements of the Data Protection Act and the Freedom of Information Act relating to the handling of requests from members of staff, pupils, parents and the general public for information held by a grant-aided school.
In this chaper:
- Record keeping
- Records management
- Pupil records
- Access requests for information using legislation
- The law
- Guidance
Role of the Board of Governors
The role of the Board of Governors is to ensure that the arrangements operated by the school for the retention, management and release of public records comply with statutory requirements.
23.1. Record keeping and the storage of information are important functions of both the administration and teaching staff of a school. School records include those pertaining to personal details of pupils, along with those of their academic performance; assessments and examination results; school policies; minutes of school-based meetings; including information received from the Department of Education (DE) and other education bodies, solicitors, press organisations and public bodies.
23.2. The legislation which affects the retention, management and release of public records is listed at the end of this chapter.
Record keeping
23.3. Each school has a responsibility to maintain its records and record keeping systems. Although schools will have their own methods of creating and keeping records and sharing information with staff, students, parents and the general public, they should be aware that, in doing so, they need to take account of matters such as:
- the most efficient and effective way of storing records and information, in other words, paper or electronic forms
- the confidential nature of the records and information stored
- the security of the record system/s used
- privacy and disclosure
- their accessibility and to whom they are accessible
Records management
23.4. In reviewing their management of records, schools should consider:
- doing an information audit to identify the nature and scope of the information currently held by them
- ensuring that information is easily accessible to those who need access to it
- adopting a Records Management Policy on the management of records
- reviewing and implementing the disposal of information that is no longer required, by adopting a Disposal of Records Schedule
23.5. The Boards of Governors should be aware that each grant-aided school should have a Disposal of Records Schedule. A model 'Disposal of Records Schedule' has been approved for use by all schools in the North of Ireland (see Guidance documents below for access).
23.6. The school principal is responsible for ensuring that records and information systems conform to the agreed management policy of the school.
Pupil records
Legal requirements
23.7. Article 24 of the Education (NI) Order 2006 and the Education (Pupil Records and Reporting) (Transitional) Regulations (NI) 2007, set out the requirement for Boards of Governors to make arrangements for pupil records to be transferred, when a pupil transfers to another school.
Arrangements relating to the transfer of pupil information when leaving a school
23.8. Schools keep a formative record of progress and achievement for each pupil. The Department is currently considering how the scope of this record should be defined for the purposes of transferring information, when a pupil moves to another school. Following its consideration, the Department plans to make further regulations about this. The new regulations will build on the provisions currently set out in the Education (Pupil Records and Reporting) (Transitional) Regulations (NI) 2007.
23.9. The current requirements are for Boards of Governors to make arrangements to transfer a formal record of a pupil's academic achievements and progress, as well as their other skills and abilities, within 15 school days of a pupil transferring schools. This information should be transferred to the principal or Board of Governors of a school to which a pupil transfers. If a pupil transfers to an independent school, the information should be transferred to the principal or proprietor.
23.10. If the principal or Board of Governors of a school (or proprietor of an independent school) to which a pupil transfers, requests the disclosure or transfer of any other educational records kept by the school, these should be provided, again within 15 school days and a copy should also be provided to the pupil's parent. Any information requested by a parent relating to their child's formative record of progress and achievement, should be provided free of charge or, if the Board of Governors determines, for a fee which does not exceed the cost of supply.
23.11. Boards of Governors are required to keep a statement of the arrangements relating to the transfer of pupil records, when a pupil transfers to another school. The arrangements need to provide for the parent, pupil, or the principal or Board of Governors of a school (or proprietor of an independent school) to which a pupil is transferring, to appeal any decision refusing disclosure or transfer of information. Boards of Governors need to ensure, that in exercising their responsibilities, arrangements are not made for the disclosure, supply of copies, or transfer of any documents which are the subject of an order, under section 30(2) of the Data Protection Act 1998.
Access requests for information using legislation
23.12. Boards of Governors in all grant-aided schools have statutory duties under the Data Protection and the Freedom of Information Acts when dealing with requests for information from members of staff, pupils, parents and the general public.
The Data Protection Act 1998
23.13. The Data Protection Act 1998 requires schools which collect and process personal information, to comply with a number of important principles regarding privacy and disclosure. As processors of personal information, schools must comply with the following eight principles which state that information must be:
- fairly and lawfully processed
- processed for limited purposes
- adequate, relevant and not excessive
- accurate and up to date
- not kept for longer than necessary
- processed in line with individuals' rights
- secure
- not transferred to other countries without adequate protection
To comply with these principles every school processing personal data must notify the Information Commissioner under the terms of the Act. Failure to notify is a criminal offence. Schools may see their current notification by checking the Data Protection Register:
- Local telephone: 016 2554 5740
- International telephone: +44 (0)16 2554 5740
- Information Commissioner's Office
Your Employing Authority may be able to assist with this.
23.14. All schools must make sure that they comply with this Act which allows people such as members of staff, pupils and parents to find out what personal information is held about them in paper or electronic form. Members of the general public also have access to school information, such as minutes of meetings, policies and other types of non-personal information.
23.15. There are two distinct rights to information held by schools about pupils. in other words, the subject access right and the parent's rights to the child's educational records.
The subject access right
- A pupil has the right to see their own information. This includes information held on computer or in structured files or in their educational record or in unstructured loose correspondence.
- Personal information may be withheld when the information is covered by an exemption in the Act.
- The pupil must make a written request.
- The pupil is not required to be of any particular age but the school should take account of the ICO guidance regarding age and whether the child has requested the parent to act on their behalf and if the child properly understands what is involved in making the request and the type of information they will receive.
- Someone with parental responsibility can ask for the information on the child's behalf and receive a response but again the school should take account of the ICO guidance on responding to such requests.
- Parents will only be able to see all the information about their child when the child is unable to act on their own behalf or gives their consent. A pupil's information must only be released to a parent or guardian, where to do so, is in the best interests of the child.
Rights to educational records
The parent's right to a copy of their own child's educational records. This includes a formal record of the pupil's academic achievements, other skills, talents and achievements and educational progress and other records, defined in the Schedule 11 of the Data Protection Act. Information covered by an order under section 30 of the Data Protection Act does not have to be disclosed.
23.16. More detailed advice, including information about charges for the provision of information, exemptions and how an exemption applies and timescales for replies is available from:
- the Information/Data Protection officers of the Education Authority
- the Information Commissioner Office (ICO)
- Local telephone: 016 2554 5745
- International telephone: +44 (0)16 2554 5745
- Email: email@example.com
- Information Commissioner's Office
- the NI Regional Office
- Local telephone: 028 9051 1270
- International telephone: +44 (0)28 9051 1270
23.17. Where a person believes that they have been prevented from seeing or acquiring information to which they are entitled, they can complain to the Information Commissioner's Office.
The Freedom of Information Act 2000
23.18. The Freedom of Information Act came into force in 2005. In the context of schools, the Act deals with access to information and provides individuals or organisations with the right to request such information under the Act. Schools are also required to make information available proactively through a Publication Scheme. All requests for information should be handled promptly, but normally not later than 20 working days.
23.19. The Publication Scheme is a guide to the information which the school has committed itself to publishing, in other words, to make information routinely available on request. Schools must publish information in accordance with its scheme, which should be reviewed from time-to-time. In adopting or reviewing a publication scheme, Boards of Governors must have regard to the public interest in:
- allowing access to the information that schools hold
- the publication of reasons for its decisions
The Publication Scheme must set out:
- 'classes' or categories of information the school publishes
- the form in which the information is published
- whether or not charges apply
Schools are free to publish information over and above that described in the model scheme.
In some instances, schools may charge a fee (calculated according to the Fees Regulations), for the release of information.
A model Publication Scheme for schools and guidance can be accessed on the ICO website.
23.20. Some information is exempt from disclosure. The Act identifies exemptions categorised as 'Absolute' and 'Qualified'. For example, in relation to personal information belonging to the requestor or if disclosure would result in an actionable breach of confidence, these are regarded as absolute and it is not necessary to go on to consider disclosure in the public interest.
If a school believes that the information requested is covered by a qualified exemption, it must apply the public interest test, in other words, the information is withheld because it considers that the public interest in withholding the information is greater than the public interest in disclosing it.
Please refer to the FOI Act 2000 for list of 'Absolute' and 'Qualified' exemptions, or access the ICO website for guidance on the FOI Act, including exemptions.
Request for information not routinely published by a school
23.21. The public has the right to request information held by a school which has not already been made available through its Publication Scheme. Requests for information must:
- be made in writing or via email
- include the name and address (if in writing) of the applicant
- describe the information requested
Schools must tell the applicant whether it holds the information requested and normally provide it in the format requested as promptly as possible within 20 days.
23.22. Schools do not have to confirm or deny the existence of information requested or provide it if they can demonstrate that:
- the request is vexatious or similar to a previous request
- the cost of compliance exceeds an appropriate limit
If a school withholds information requested:
- it will usually be required to explain to the applicant why they are not releasing the information by citing the appropriate exemption and considering the public interest test, where applicable
- in all original decision notices, whether releasing information or not, schools should provide in their responses (normally issued by the principal), the contact details of an independent decision maker, to allow an applicant to seek an internal review of the decision, if they so desire. That person would ideally be the chairperson of the Board of Governors who will notify the applicant of their findings promptly, but normally not later than 20 working days. In the same decision notice, the applicant should also be advised, if they are not satisfied with the outcome of the internal review, then they have the right to complain to the Information Commissioner at
Water Lane
who will undertake an independent review.
It is a criminal offence for schools to alter, deface, block, erase, destroy or conceal information to prevent disclosure.
23.23. More detailed advice about the Freedom of Information Act including the Publication Scheme for Schools is available from:
- the Information/Data Protection officers of the Education Authority
- the Information Commissioner Office (ICO)
- Local telephone: 016 2554 5745
- International telephone: +44 (0)16 2554 5745
- Email: firstname.lastname@example.com
- Information Commissioner's Office
- the NI Regional Office
- Local telephone: 028 9051 1270
- International telephone: +44 (0)28 9051 1270
The law
Primary legislation
Data Protection Act 1998
Education (NI) Order 2006 - Article 24
(Provision of Information)
Freedom of Information Act 2000
Public Records Act (NI) 1923
Subordinate Legislation
Disposal of Documents Order SR&O 1925 No 167
Education (Pupil Records and Reporting) (Transitional) Regulations (NI) 2007 Statutory Rule No 43
(The keeping and transferring of pupil records)
Education (Pupil Reporting) Regulations (NI) 2009
- Data Protection Act 1998
- Accessing pupils' information
- DE Circular 2003/15: Education (School Information and Prospectuses) Regulations (NI) 2003 PDF 49 KB
- DE Circular 2007/10: Education (Pupil Records and Reporting) (Transitional) Regulations (NI) 2007 PDF 32 KB
(under review)
- DE: Disposal of school records, including schedule (June 2013)
- Freedom of Information Act 2000


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This is just a memo for everyone out there. As you may know, my research thesis is the fine-tuning argument in light of the multiverse and my suggestion is that the multiverse exponentially strengthens the argument. I've traced multiverse scenarios back to the Church Father Origen and Paley (read the second chapter of Natural Theology). It doesn't seem to be considered as actual until Hugh Everett in the mid twentieth century. If any of you have more information on the historical development I would greatly appreciate it. Thanks!
Needing Help in Research
No Dawkins? Don't be Daft!
There have been quite the development of criticisms of Richard Dawkins in the last few weeks in light of his denial to debate Christian philosopher William Lane Craig. I've been a participant in the blogosphere and in the forums and I'm familiar with what others are saying about everything. The basic principle that's being asserted is that Dawkins will have a monologue concerning his arguments against God but he will not dialogue about it. I mean really, why debate the existence of fictitious entities and fairies?
An Objection to Intelligent Design I've Never Heard
I was in a tweebate (tweet debate) with another person [whom shall remain anonymous] over a previous post of mine where I claimed that Ken Miller's argument against irreducible complexity was a bad argument (I really don't like Twitter debates/conversations either). This person went on about how Miller's argument convinced Judge Jones and my position was that it's actually quite embarrassing that the argument would convince anyone (see my post for the context). Then he claimed the type three secretory system is an objection to irreducible complexity in the bacterial flagellum, which prompted me to claim that it may indeed be IC itself and there are arguments that the flagellum may have come first. Anyways, those aren't what interests me. The argument that I had never heard before was:
ID claims are anything but modest. Incapacity to imagine other explanations of our beginnings is not evidence of ID. Non sequitur.
Let me be clear, I have never claimed anywhere at any time… ever… that one should be a proponent of intelligent design because of an incapacity to imagine other explanations. So first of all, this argument belongs in a cornfield scaring away the crows. Secondly, this is an utterly blatant attack on my imagination! I've got a great imagination! (Okay, the second point isn't really a part of my argument.) It's true, if anyone did make an argument for ID based on a lack of imagination it would be a non sequitur since one's capacity to imagine something has nothing to do with the truth claim (as long as the claim is sound/rational, I cannot imagine the actualization of a contradiction). I'm fairly confident anyone familiar with intelligent design and the state of the evolution controversy would never make an argument for intelligent design like this. In fact, no one should ever make such an argument for ID like this.
I've explained before in my post on God and Darwinism, the reasons why I'm not a Darwinist are for two reasons: 1) the origin of information must be mind and 2) there is objective teleology in the world and primarily human beings. I do believe the argument from irreducible complexity is a good argument for ID but I'm not going to die on that hill. I think intelligent causation is a legitimate scientific hypothesis and explanation. However, there are certain philosophical truths that press the argument. I could care less if man evolved from a common ancestor but this evolution could not have occurred without a mind acting on the origin of the information in DNA and I believe man [evolves] with an end goal in mind. That's why I reject Darwinism.
Theistic Evolution and Purposive Permission
This objection to intelligent design is within a theistic philosophy and theology. The theistic evolutionist would make the arguments for Darwinism just like the atheist would make his arguments for Darwinism; the only difference is that the former is a theist. Asa Gray (1810-1888) was a proponent of evolution who suggested that God guided evolution. The problem for the theistic evolutionist at this point is that if God guides evolution, it is design. Guidance implies purpose and involvement. The theistic evolutionist, so defined as God guiding evolution, is not really a detractor from design, rather he would be a proponent of common decent, which is entirely compatible with design.
It was not until the early twentieth century when a movement that emphasized Darwinian natural selection did theistic evolution attempt to reconcile unguided evolution with God. The following theistic evolutionist present an appropriate summation for the current understanding:
"An evolutionary universe is theologically understood as creation allowed to make itself."[1]
"Mankind's appearance on this planet was not preordained… we are here… as an afterthought, a minor detail, a happenstance in a history that might just as well have left us out."[2]
"Evolution could appear to us to be driven by chance, but from God's perspective the outcome would be entirely specified. Thus, God could be completely and intimately involved in the creation of all species, while from our perspective, limited as it is by the tyranny of linear time, this would appear a random and undirected process."[3]
It may be important to distinguish the last quote from Collins from the former quotes. It is difficult, even impossible, to distinguish Collins' position as not being intelligent design. Why would Collins use the human perspective as the objective standard for whether or not there actually is design? He willingly concedes that God could be intimately involved in creating yet it is illusory to the human perspective.
The argument from cognitive relations may be understood as an argument from omniscience or providence. If God allows any state of affairs to be actualized, and knows that it will happen, and then there is a teleology in that events actualization. The underlying principle is what is called "purposive permission." This principle makes a minimal commitment to any event X, such that X will come to be either by it being permitted to occur or by being strongly actualized to occur. Purposive permission assumes that if any event is permitted to happen then it is within the will of the knowing agent that the event be actualized. If the event were known that it would come to pass and it was not desired to come to pass, then it would not have been permitted to be and would not have happened. Under the current understanding of unguided evolution, the only way to reconcile that with theism is to adopt process theology, an understanding that God is not ontologically perfect and is literally evolving with the world.[4]
[1] John Polkinghorne, Faith, Science, and Understanding (New Haven, CT: Yale University Press, 2000), 23, 111, 197.
[2] Kenneth Miller, Finding Darwin's God (New York: Harper Perennial, 2000), 272-273.
[3] Francis Collins, The Language of God (New York: Free Press, 2006), 205.
[4] Even weak understandings of cognitive relations, or interactions, would still render design (categorically defined from an orthodox perspective). All that would require from the knowing agent (God) is that, within the mind, there must at least be two moments of knowledge: natural knowledge (the first logical moment) and free knowledge (the last logical moment). In the first moment the agent must know all tautologies and every possible circumstance. The final moment is knowing the actual world, the current, past, and future state of affairs. The only theistic model that does not hold to these two moments would be the process model. I want to note, that open theism would not even be compatible with a Darwinist understanding of evolution because God would only be ignorant of future contingencies that involved human freedom.
Ken Miller's Embarrassing Attempt to Disprove Irreducible Complexity
This video has been out for a while but I just saw it reposted on a blog I saw through Twitter. I'm not going to summarize the video here; rather, just give it a quick watch, it's only two minutes.
Honestly, it's a bit embarrassing and I feel bad for him. His attempt to disprove irreducible complexity demonstrates that 1) he doesn't actually understand it or 2) displaces the information. When he changed the mousetrap to function as a tie clip that tie clip then becomes a new mechanism. Whether that tie clip was actually irreducibly complex or not doesn't matter. His attempt would be correct if he could remove or change a part of the mouse trap while keeping it's function as a mouse trap.
As for the scholarship of intelligent design and irreducible complexity, he's simply incorrect there as well. Darwinists always do this and it's just annoying and dishonest (or simply wrong). For a list of peer-reviewed articles that have been published in regards to intelligent design and irreducible complexity (and yes, the words are used in the articles, sorry Ken) please see the Discovery Institute's list.
A Thank You Note to James White
James White is the director of Alpha and Omega ministries focused on apologetics. I've learned a lot about my own theological position as well as others because of his ministry and service. To be honest, I don't agree with a few things he believes. For instance, I'm a Molinist (he's not the biggest fan), evidentialist, and an old-earth creationist. Despite our disagreements he has my utmost respect and esteem. He is passionate about God, the gospel, the Church, and the unsaved. I'm a faithful listener of his podcast, The Dividing Line, and there have been moments when I shake my head at some points he makes and there are other times when I'm cheering him on.
I respect White for his defense of the faith from cults, atheists, Islam, Roman Catholicism, unitarians, and others. Where White earns my greatest respect is his integrity and honesty in scholarship and ministry. You won't find him quote mining or warping his citations. He does the work, he does the research, and he presents it well. Now, on another note, I'm a philosophy graduate student at Liberty University. For those who are familiar with White you'll know where I'm going with this. White demanded accountability from Caner, the university, and the church for so many discrepancies [and contradictions] Caner asserted about himself. All parties remained silent while all White did was demand honesty and integrity. Thank you, Dr. White.
For those of you who aren't familiar with White please check out his YouTube channel, his podcasts, and his website. You don't have to agree with him all the time but you will learn a lot.


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Carrie Serber honors husband's memory by 'running for life'Written by Julie Rubini | | firstname.lastname@example.com
We often wish we could turn back the clock and spend time with someone we've loved that no longer lives amongst us. However, the best we can do is to cherish the memories of those we've lost, while maintaining the balance of moving forward with our lives and embracing those who remain with us.
Carrie Serber is reaching that point in her life, several years following the untimely death of her husband Ryan as a result of a brain tumor.
The first time she met Ryan was at Doc Watson's, while she was on a girl's night out and he was out with his co-workers. She wasn't initially interested, yet, as was his nature, once Ryan set a goal for himself, there was no stopping him. They met in February 2001. They were married in October 2005.
"I was definitely drawn to him. He was extremely handsome, and he was confident and one of those terrific people that you could introduce to anybody and he could easily carry on a conversation with anyone. Being a journalist, that was one of his many talents. Also, his sensitivity, his thoughtfulness and perception of other people [were] attractive to me," Carrie shared.
Ryan moved to Toledo as news anchor for WUPW FOX Toledo, after serving stints in Bristol, Wichita Falls, Austin and then Orlando.
He took an interest in running a year before meeting Carrie, determining his ultimate goal would be running the 2001 Chicago Marathon. After successfully completing the 26.2 mile run, he went on to tackle the Toledo and Columbus long distance races before being diagnosed with a brain tumor in 2003. After the cancerous growth was removed, Ryan battled the disease with the same vengeance he took on the marathon training, enduring rounds of chemotherapy, radiation and, ultimately, a stem cell transplant.
He began training for the Chicago 2004 Marathon soon after the surgery, which he completed just 10 months after his last treatment. His running shirt read, "Ryan beat cancer in '03, Chicago Marathon in '04." He was encouraged by fellow runners along the way, as he inspired others.
"He was really upset that he was not in control of his body, so he was doing everything he could to top it, to reverse it," Carrie said.
Six months later the cancer returned, and despite his upbeat attitude, and the firm belief that he was going to beat the disease, he died on Jan. 9, 2006. He was 37 years old.
At his memorial services, Mayor Carty Finkbeiner suggested the community needed to remember and honor him. It didn't take long to determine that establishing a race in his honor was the solution.
Sept. 20 will mark the fourth annual Ryan Serber 8K Classic, an unusual distance, in reference to Ryan's desire to push himself beyond his limits and to encourage others to do so as well. The race, organized by the Toledo Roadrunners Club, along with Ryan's friends and family, attracts more than 250 runners inspired by his incredible, unforgettable spirit.
"I just wanted to thank you in more ways than you can imagine. It's your smile, your confidence, your sense of humor, your trust and the help that you do when I can't do it. It's been a tough few weeks, but after last year, we can do anything. This will make a good chapter in my book. I'm just glad you're by my side and I want to thank you from the bottom of my heart. I love you so much."
Carrie has this love note to hold on to, and her eyes swelled with tears as the sentiment was shared.
"It's [with] mixed emotions when we start planning the race. It's tough sometimes to open up and revisit everything. It's much easier just to go on every day. Yet, at the same time, it's good. It's good to share his life with people that knew him and those that didn't know him. As time goes on you meet new friends and get to tell people about him."
Carrie's last marathon was a tribute run to Ryan at the 2006 Chicago Marathon, accompanied by his sister Loren, and her sister Erica, along with 15 other friends. However, she continues to run, and left soon after the interview to participate in a team 200-mile race, running in shifts within a 24 hour period.
She'll be running with memories of Ryan in her heart and running to whatever life brings her way.
Ryan would be proud.
On the Web: visit www.ryanserber.blogspot.com and click on links for more information.


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It was a "Perfect Day" for The X Factor as the Top 12 took the stage with a Lou Reed tribute before finding out their fate. Then, it became Ladies' Night as Selena Gomez and Fifth Harmony gave killer performances, but it was a bummer when the results sent two acts - four ladies - home. See what went down in this radical recap.
Copyright 2013 Nexstar Broadcasting, Inc. All rights reserved. This material may not be published, broadcast, rewritten, or redistributed.


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About the Park Visitor Center
There are two floors of exhibits and a film.
Park Film
There are two Johnstown Flood-related sites in the area. Our park, Johnstown Flood National Memorial, preserves the ruins of the South Fork Dam, part of the old lakebed, and some of the buildings of the South Fork Fishing and Hunting Club. In our visitor center, we show a National Park Service-produced film, nicknamed "Black Friday," that tries to recreate the Flood. (For copyright reasons our film is not available for purchase.)
In an old Carnegie Library in Johnstown is the Johnstown Flood Museum, owned and operated by the Johnstown Area Heritage Association. It is a true museum, and features an Academy-Award-winning film by Charles Guggenheim called "the Johnstown Flood." (The Flood Museum's film is available for purchase.)


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Educational Resources
The Daniel Factor
This book was written to accompany Jacob's part in the film, "The Daniel Project". Jacob expands on that documentary and explains more fully about the world in which we live today and what it may mean in the light of those Biblical prophecies.
People are looking for answers, instinctively knowing that whilst great efforts are made to bring peace in our troubled world, all is not well. An increase in natural and man made disasters, geo-political tensions and an economic crisis create the sense of a gatherng storm which has become a part of us all.
Since 1948, hundreds of ancient predictions, written thousands of years ago, are now unfolding before us. News agencies from around the world beam satellite images into our homes that could have come straight from the pages of the Bible.
According to Daniel and other Biblical prophets, only the wise will understand how to read the signs and respond - as people around the world will continue to be so busy with their lives; buying and selling, planting and building, unaware of the terrible events that will overtake them.
Jews will be exiled and persecuted throughout the world
In the last days the Jews will return to their homeland
Jerusalem will become the centre of world tension
The lost language of Hebrew will be restored to Israel
In the last days, pools of water will appear in the desert
Fruits, forests, vineyards and olive groves arise from the dust
Man-made and natural disasters will increase
Lawlessness, moral and social breakdown
Christian apostasy, mass spiritual delusion, a great leader
A great leader to bring peace within a new world order
World government, a forced financial system, state control
A peace treaty signed - yet a military coalition attacks Israel
Earthquake to split Mount of Olives, water will flow from under Jerusalem
Near the end, a great temple is constructed in Jerusalem
The East Gate in the city wall will be sealed until the end
The kings from the East cross the Euphrates River for war
The war that will end all wars - Armageddon
Only the wise will escape
Please click here to place your order.
The Daniel Project
"In an age where evangelism has become so difficult in the developed world we must recall the instruction of Jesus to "Preach The Gospel of The Kingdom"—that is using eschatology and end time prophecy to engage in evangelistic dialogue, to proclaim the urgency of the need for salvation in the face of a returning Christ amidst a fast coming global cataclysm with the Middle East at its epicenter.
"This flies in the face of Kingdom Now theology with its latter day rain nonsense, and confronts the false and dangerous teachings of Rick Warren to reject the commands of Jesus to "be alert" for these signs—and it also counters the false doctrines of Replacement Theology propounded by such false teachers as John Stott and John Piper. In an age of ecumenical and emergent apostasy, the faithful Church must rally to the instructions of Jesus and preach the true Gospel in the face of His coming return and in light of the prophetic events encapsulated in Scripture, no place more than in the Book of Daniel from where most of the prophetic predictions of he Book of Revelation originate.
"The Daniel Project is a secular film production with a scriptural message, focus and theme which can reach non-believers in a post-modern world. A companion book will be published soon, but the producers have made available a special edition DVD set which is an effective tool for house groups, church groups and one-to-one dialogue. Even non-believers want to know the future. In an age of political, economic, strategic and environmental uncertainty, people sense something is happening and want answers; we have them. Bible codes and Da Vinci Codes are but fiction; the Book of Daniel, however, is true. Conspiracy theories are borderline lunacy while the Book of Daniel is cogent, plausible and coherent.
"I have prayed about such a project for years, and when the producers approached me I knew it was indeed God's time. Remember, this is a secular product and a secular production which takes the message into the secular world via the secular market. We would urge all who seek the salvation of the lost and who look to the return of Jesus to obtain a copy of the DVD and the soon to be published companion book for their benefit
"Time is getting short, and the time to raise our voices is now."
Jacob Prasch
Further Information: The Daniel Project documentary film made for TV and cinema is also available as a special edition boxed DVD set featuring Jacob Prasch, Dr. Siam Bhayro, Doug Harris, Rabbi Glick and others. The special Bonus DVD includes an interview with Jacob Prasch explaining "The Way of Escape" which is especially crucial viewing for non-believers.
Details including trailers can be seen at www.thedanielproject.tv.
If you have already seen this film you can support it and help the international distributor obtain public television viewings by leaving a review on the Facebook "Reviews" page atwww.facebook.com/thedanielproject.
This documentary simply presents the facts and leaves the viewer to make up his or her own mind.
DVD SETS AVAILABLE FROM www.thedanielproject.tv
Please click here to place your order.
The Dilemmaof Laodicia
There are "things which you have seen", "things which are", and "things which will take place".
The seven churches of the book of Revelation, which actually existed in the 1st Century ("things which you have seen"), also represent seven broad types of churches that can exist at any time in history ("things which are"), and seven generally overlapping periods of church history ("things which will take place"). These letters to the seven churches of Asia can be applied in four main ways:Z
• They existed literally and historically at the end of the 1st Century A.D. • They are seven types of churches which exist at any time throughout history. • They represent seven types of churches that will exist at the end of the age. • They correspond quite well to seven periods of church history.
This book examines the history of the church in light of the letters of Jesus Christ to the seven churches in Asia, as recorded by John in his Revelations. Unless learning can be achieved from the errors of the past it is a sure thing that those errors will be repeated.
Place your order
Israel,the Church & the Jews
Israel, The Church and The Jews is a themed assortment of biblical teachings and essays focused on providing a biblically balanced and comprehensive perspective on the major aspects of the relationship, theologically and historically, between biblical Christianity and Israel and the Jewish people—both the regenerate and as yet unregenerate. From the erroneous position of supercessionist Replacement Theology, to its Christian Zionist antithesis, to Messianic prophecy, to the origins of the Gospel within the Judaic culture which produced it, to eschatological and prophetic implications of contemporary events in the Middle East up to and including the Annapolis Summit, this book furnishes an up-to-date, multi-faceted and doctrinally solid compendium addressing the key issues which every Bible-believing Christian and every Jew should ponder in today's fast-changing world.
Place your order here
The Jews, Modern Israel and the New Supersessionism
Published May 2013 (Broadstairs, Kent: King's Divinity Press). xxiv + 356 pages. Paperback. 14.99 GBP.
Edited by Calvin L. Smith
This book explores the relationship between the Jewish people, the Church and Israel, from biblical times to the present. Its fifteen essays from contributors with considerable expertise and published work in the field provide readers with a careful and objective examination of the issue from various perspectives.
This timely volume is being published at a time when the debate surrounding the relationship between the Church and Israel raging within Evangelicalism is increasingly polemical and polarised.
"The unbiblical doctrine that the church replaces or supersedes the nation Israel in the plan of God must be challenged with the light of God's word. This work, written by an impressive international cast, continues the case against supersessionism and does so in a clear and compelling way."
Michael J. Vlach, Ph.D.
Associate Professor of Theology, The Master's Seminary and author of Has the Church Replaced Israel? A Theological Evaluation (Broadman and Holman, 2010).
Available on Amazon Kindle from 19 May 2013
Print version available from 1 June 2013 on King's online shop.
The Fleecing of Christianity
THE FLEECING OF CHRISTIANITY takes a fresh and fascinating look at the tactics some use to misuse the Gospel for personal power and gain. FLEECING shows the place "Christian" television plays in the spread of the Great Apostasy as prophesied in the Bible and documents the formation of the unified one-world church as it happens. Jackie Alnor is known worldwide for tireless research and well-documented facts, which shed light on the sometimes murky depths of cult religions. Jill Martin Rische of Walter Martin Ministries calls FLEECING, "A reader-friendly style, sharp analysis and a strong Scriptural foundation [which] combine to make this book an intriguing and enlightening read."
Jackie Alnor is a veteran researcher, writer, activist, teacher and defender of the faith who has been monitoring and taping Christian television for over twenty years; produced the highly acclaimed 1999 documentary, "The Great Apostasy: The Lost Sign"; and is a lecturer of news writing at a Christian university.
Place your order here.
The Roman Catholic Church and the Sexual Abuse of Children
The Beginning of Roman Catholicism
A booklet published by Moriel Ministries answering the question, "What is Roman Catholicism and where did it originate? Place your order here.
The Table of Contents:
Babylon and Rome
Historical Backtround: Pagan Rome
The New Covenant vs Replacement Theology
State Religions: Old and New
Augustinian Theology
The Errors of Ignatius of Antioch
Pagan Emperors/Catholic Popes
Recontextualization vs Redefinition
Influences of Gnosticism
Sempre Aidin: Always the Same
The Effects of Greek Dualism
Undermining the Humanity of Christ: The Root of Mary Worship
The Middle Ages
The Rock: Peter or Christ?
The Origin of the Papacy
The Dark Ages: Catholicism;s Gift to Europe
Aristotelianism & Humanism Are Born From the Renaissance
The Counter_Reformation and Further Corruption
The Council of Trent: The Final Insult
The Goals of Modern-Day Roman Catholicism
It Could Take Faith To ...
Lost in Faith. It could take faith to...
The UnusualSuspects
Richard compassionately writes about 25 Jews who have found spiritual fulfilment in Jesus.
About the author: Richard Gibson is a Christian minister. He was brought up in a home in which Israel and the Jewish people were respected and loved, and for a number of years he lived and worked in Israel. Richard speaks modern Hebrew fluently, is an ardent defender of the Jewish state and is married with one son.
To order, please click here.
For Zion's Sake
This book by Paul Wilkinson is a study of Christian Zionism and dispensationalism. It is a researched and readable book of theological and historical fresh air.
This book can be purchased directly from Amazon.com by clicking here.
As a lecturer at King;'s Evangelical Divinity School (formerly Midlands Bible College and Divinity Scholl), Jacob Prasch recommends the school as a place of study for those wishing a more in-depth understanding of God's Word. King's is a leading provider of open and distance-e-learning biblical and theological courses ranging from beginner through to fully accredited undergraduate and Ph.D. levels.
King's Evangelical Divinity School (formerly Midlands Bible College and Divinity School) www.kingsdivinity.org Tel. 08700 421 704 (Overseas +44 8700 421 704
HAVHA and the Black Stone
"I could not put it down… a thriller with a solid and important message." Gail, Hampshire.
"This needs to be spoken, written, brought into the open." Peter, UK.
Vartan was born in the Armenian Refugee Camp in Lebanon in about 1948. Orphaned at four, he then spent four years at the Danish Birds' Nest Orphanage until he ran away and lived on the streets of Beirut. He has made his way as a musician, with no formal education. This is a 3-D thriller—you feel as if you were there just as he was.
Hardback, First Edition, signed copies,
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of not less than £11 to
"Melkonian Books Childrens Fund"
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Mention Moriel. £2 will go to Moriel from every book sold. All remaining profits from this edition will go to the Birds' Nest Orphanage in Byblos.
Moriel publishes a FREE newsletter quarterly. This is a hard copy edition which includes at least one of Jacob's writings, complete CD, DVD and books list, prayer requests and featured writers you will not want to miss.
For information about subscribing from your particular country or to download past issues, please go here for futher information. Please note that your name will never be used to solicit a donation and will never be given to another ministry.
Moriel Ministries new email News Alert is a publication which is sent directly to your inbox regularly, warning the body of Christ to Be Alert! for the present signs of the soon-to-be Returning King of kings and Lord of lords, our Saviour, Jesus Christ.
Our Moriel correspondent, Scott Brisk, is the editor of Be Alert! whose job as watchman is to scan for all news items having a Biblical significance and to alert the body of Christ in these last days.
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This invention relates to the bromination of styrenic polymers by contacting same with a brominating agent in the presence of a bromination catalyst and, as a reaction solvent, bromochloromethane.
1. A process which comprises contacting styrenic polymer with a brominating agent in the presence of Lewis acid catalyst and solvent quantities of bromochloromethane.
2. The process of claim 1 wherein the brominating agent is bromine, bromine chloride or a mixture thereof.
3. The process of claim 1 wherein the styrenic polymer is polystyrene.
4. The process of claim 1 wherein the Lewis acid catalyst is aluminum halide.
5. The process of claim 1 wherein the Lewis acid catalyst is AlCl3, AlBr3 or a mixture thereof.
6. The process of claim 1 wherein the brominating agent is bromine, bromine chloride or a mixture thereof, the styrenic polymer is polystyrene and the Lewis acid catalyst is AlCl3, AlBr3 or a mixture thereof.
This application is a continuation of U.S. Ser. No. 08/721,389 filed Sep. 26, 1996, now abandoned, which application is incorporated herein by reference in its entirety.
This invention relates to the discovery of a highly beneficial solvent for use in the bromination of a styrenic polymer.
Brominated styrenic polymers, e.g., brominated polystyrene, are well recognized flame retardants for use in engineering thermoplastics, e.g., nylon, polyethylene terephthalate, polybutylene terephthalate, etc. These flame retardants are prepared by reacting a brominating agent, e.g., bromine or bromine chloride, with a polystyrene in the presence of a Lewis acid catalyst. Since the styrenic polymer is usually very viscous or a solid, it has been deemed necessary to provide it to the reaction as a solute in a lower viscosity solution. The art generally describes the solvent as being a halogenated hydrocarbon, and, more specifically, a chlorinated hydrocarbon. Methylene chloride and dichloroethane are universally considered to be the solvents of choice. Despite their apparent attractiveness, these two solvents are not without disadvantage.
Methylene chloride is favored as it is relatively inert in the process. However, it is disadvantaged because it has a low boiling point and is challenged as being potentially depletive of the global ozone layer.
In distinction, dichloroethane has an acceptable boiling point and, in use, is more environmentally desirable than methylene chloride. It is not, however, a panacea as it reacts in the process to a significant extent and its use is not associated with an exceptionably low color brominated polystyrene product.
It is, therefore, an object of this invention to provide a solvent for use in the bromination of styrenic polymers which is environmentally beneficial, has a boiling point in the range of 80°-95° C., is relatively inert in the bromination process, and is associated with a near-white brominated styrenic polymer product.
The Invention
This invention relates to a process for brominating styrenic polymers, which process comprises: brominating styrenic polymer in the presence of Lewis acid catalyst and solvent quantities of bromochloromethane.
The bromination of the styrenic polymer is preferably effected by either (1) adding a brominating agent to a reactor containing styrenic polymer, bromochloromethane and a Lewis acid catalyst; (2) adding, to a Lewis acid catalyst, (i) a styrenic polymer stream which is comprised of a solution of styrenic polymer and bromochloromethane and (ii) a brominating agent stream, the streams being added separately but substantially concurrently; or (3) adding a mixture which includes a brominating agent, styrenic polymer and bromochloromethane to a Lewis acid catalyst. Besides these preferred modes of addition, it is contemplated that any addition mode which effects reactive contact between the brominating agent, catalyst and styrenic polymer will be benefited by the use of bromochloromethane as the process solvent. The first-described addition mode is conventional and is illustrated in U.S. Pat. No. 4,200,703 and U.S. Pat. No. 4,352,909. Both of these patents are incorporated herein by reference for all of their teachings except for that teaching which refers to the identity of the process solvent. (Thus, in the '703 patent, column 3, lines 3-16, the Examples and the Claims are excluded, while in the '909 patent, the paragraph bridging columns 7 and 8, the Examples and the Claims are also excluded.) The second-described addition mode is illustrated by U.S. Pat. No. 4,975,496 which is also incorporated herein by reference for all of its teachings except for that teaching which refers to the process solvent.
For addition mode (2), it is a feature that there be a dispersion of at least a portion of the brominating agent substantially throughout the catalyst before there is any substantial complexing (cross-linking) of the styrenic polymer. When the brominating catalyst is AlCl3, there is generally a need to pre-add a portion of the bromine to the catalyst prior to introduction of the styrenic polymer. In such cases, at least 5 mole percent of the brominating agent is pre-added. See incorporated U.S. Pat. No. 4,975,496 for further details concerning the pre-addition of the brominating agent.
For mode (3), it is preferred that the mixture be formed via mixing of the components in a device which is outside or inside of the reactor and feeding the resultant mix to the reactor. In addition, a stream from the reactor can also be fed to the mixing device to contribute to the total resultant mix being sent back to the reactor. Also, for addition mode (3), it is preferred that the bromochloromethane, styrenic polymer and the brominating agent be substantially free of brominating catalyst at least prior to their being mixed. The phrase, "substantially free of a bromination catalyst", is to be taken to mean less than a catalytically effective amount of catalyst. With such low amounts, little or no catalyzed bromination or cross-linking should occur. Generally, such amounts will be less than 500 ppm (weight basis) of styrenic polymer present.
The amount of bromochloromethane solvent used is that amount which can dissolve the styrenic polymer and any of the brominated styrenic polymer species produced. Also, it is preferred that the amount of bromochloromethane used will result in an easily-stirred reaction mass. Generally, the total solvent used will be that amount which is needed to dissolve the styrenic polymer to yield an easy-flowing solution and that amount which may be initially present in the reactor and associated with reaction components other than styrenic polymer. In most cases, the amount of bromochloromethane used to form the styrenic polymer solution will provide a solution which contains 3 to 30 wt % styrenic polymer, based upon the total weight of the solution.
The presence or absence of water in the bromochloromethane will be in accordance with the water requirements of the particular process chosen. For example, anhydrous processes, such as that described in U.S. Pat. No. 4,352,909, will be sensitive to the solvent water content. Other processes, such as that disclosed in U.S. Pat. No. 4,200,702, require a certain level of water and, thus, are not as sensitive to the solvent water content. Still other processes, which are substantially independent of water content, can be somewhat indifferent about the solvent water content. Unless the solvent is being used as a major contributor of water to the process, most practitioners will choose bromochloromethane having less than about 100 ppm (weight basis) water.
Preferred Embodiments
Styrenic polymers which are brominated in accordance with the present invention are homopolymers and copolymers of vinyl aromatic monomers, that is, monomers having an unsaturated moiety and an aromatic moiety. The preferred vinyl aromatic monomers have the formula:
H2 C═CR--Ar
wherein R is hydrogen or an alkyl group having from 1 to 4 carbon atoms and Ar is an aromatic radical (including various alkyl and halo-ring-substituted aromatic units) of from 6 to 10 carbon atoms. Examples of such vinyl aromatic monomers are styrene, alpha-methylstyrene, orthomethylstyrene, meta-methylstyrene, para-methylstyrene, para-ethylstyrene, isopropenyltoluene, isopropenylnaphthalene, vinyl toluene, vinyl naphthalene, vinyl biphenyl, vinyl anthracene, the dimethylstyrenes, t-butylstyrene, the several chlorostyrenes (such as the mono- and dichloro-variants), the several bromostyrenes (such as the mono-, dibromo- and tribromo- variants). Polystyrene is the currently preferred styrenic polymer and, when the styrenic polymer being brominated is a copolymer of two or more vinyl aromatic monomers, it is preferred that styrene be one of the monomers and that styrene comprise at least 50 weight percent of the copolymerizable vinyl aromatic monomers.
The styrenic polymers, which are brominated in accordance with the present invention, are readily prepared by bulk or mass, solution, suspension or emulsion polymerization techniques comparable to those employed in the polymerization of styrene. Polymerization can be effected in the presence of free radical, cationic or anionic initiators, such as di-t-butyl peroxide, azo-bis(isobutyronitrile), di-benzoyl peroxide, t-butyl perbenzoate, dicumyl peroxide, potassium persulfate, aluminum trichloride, boron trifluoride, etherate complexes, titanium tetrachloride, n-butyllithium, t-butyllithium, cumylpotassium, 1,3-trilithiocyclohexane, and the like. The polymerization of styrene, alone or in the presence of one or more monomers copolymerizable with styrene, is well known and it is considered unnecessary to further discuss the polymerization process. The styrenic polymers having a molecular weight of at least 1,000, preferably at least 50,000 and most preferably 150,000 to 500,000, are brominated in accordance with the present invention. Although styrenic polymers outside these molecular weight ranges can be brominated in accordance with the present invention, there is typically no economic advantage in so doing.
The catalyst used in the processes of this invention can be any bromination catalyst, provided that the catalyst does not act to frustrate the efficient and safe production of a high quality brominated polystyrenic product. The favored catalysts are the Lewis acid catalysts which are typified by AlCl3, FeCl3, AlBr3, FeBr3, SbCl5, ZrCl4, and the like. Fe, Al and Sb2 O3 may be used to form Lewis acid catalysts by simply adding them to the reaction system. Mixtures of catalyst can also be used. Once the catalyst has been added to the reaction system, it may undergo some reaction without significant loss of catalytic activity, e.g., AlCl3 may convert to some extent to AlBr3. The more preferred catalysts are the aluminum and iron-based catalysts. Of these, the most preferred are the aluminum and iron halides, especially the bromides and chlorides. AlCl3 and FeCl3 are most highly preferred, with AlCl3 being the catalyst of choice.
The catalyst is used in an amount which is sufficient to obtain the catalytic effect sought. These catalytic amounts will depend on the activity of the catalyst, but will generally fall within the range of from about 0.2 to about 20 weight percent and preferably within the range of from about 0.2 to about 15 weight percent, based on the weight of the styrenic polymer being brominated. The most active catalysts will be used in the lower amounts while the less active catalysts will be used in the higher amounts. For the preferred aluminum and iron-based catalysts, it is preferred that they be used in amounts within the range of from about 0.5 to about 5 weight percent. AlCl3 and FeCl3 are useful in amounts within the range of from about 0.5 to about 10 weight percent. When AlCl3 is the catalyst, amounts within the range of from about 0.5 to about 3 weight percent are preferred.
The brominating agents useful in the processes of this invention can be any of those which can brominate aromatic carbons in the polymer's vinyl aromatic units (hereinafter also referred to as styrenic monomer units). The art recognizes Br2 and BrCl as good brominating agents, with the former being most preferred. Bromine can be obtained commercially in the diatomic form or can be generated by the oxidation of HBr. Br2 can be supplied either as a liquid or a gas. The amount of brominating agent used in the process should provide an overall mole ratio of total brominating agent to total styrenic polymer fed, which will provide from 1 to 3 bromine substitutions per styrenic monomer unit in the polymer. Generally, it is desired that the brominated styrenic polymer products of this invention contain at least 30 wt % bromine, based upon the total weight of the brominated polymer. It is preferred that the brominated polymer contain above about 50 wt % bromine and most preferably above about 60 wt % bromine. For any particular styrenic polymer, the amount of brominating agent used in the process will be determined by the bromine content desired considering the highest bromine content which is obtainable with the process parameters chosen. The higher bromine contents will require the most brominating agent. It is pointed out that as perbromination is approached, it becomes more difficult to substitute the last bromines. Adding ever larger amounts of a brominating agent does not always attenuate this difficulty. However, it is helpful, in attempting to maximize the bromine content, to provide a small stoichiometric excess of brominating agent. Stoichiometric excesses up to about 10% are preferred. The stoichiometry is easily determined as it requires one mole of Br2 or BrCl per substitution sought. In practice, the practitioner will determine the bromine content sought on a weight basis and then will calculate, on an idealized basis, the number of moles of brominating agent needed to obtain the same. For example, if the styrenic polymer is polystyrene and the bromine content sought is 68 wt %, at least 2.7 moles of bromine or BrCl per styrenic monomer unit will be required, not including any desired stoichiometric excess. For brominated polystyrene, a bromine content of from about 40 to about 70+ wt % bromine is desirable. This range can be theoretically obtained with a mole ratio of bromine to styrenic monomer unit of from about 0.9:1 to about 3.0:1 Preferred for brominated polystyrene is a bromine content of from about 60 to about 70+ wt %, which can be obtained with a theoretical mole ratio of from about 1.9:1 to about 3.0:1 for bromine or BrCl. The processes of this invention can, with facility, provide up to 70 wt %, say 67-68 wt %, bromine. For addition modes (2) and (3), the amount of brominating agent used in the process is that amount of brominating agent in the feed mixture and any brominating agent pre-added to the catalyst. As pointed out herein, for addition mode (3), it is not necessary to pre-add a brominating agent to the catalyst and, thus, all of the process brominating agent requirements can be supplied via the feed of the mixture. If, however, the practitioner chooses to pre-add a brominating agent to the reactor, it can be done and that amount of brominating agent is part of the overall amount of brominating agent used.
While the foregoing describes the overall quantitative relationship between the brominating agent and styrenic polymer, the quantitative relationship between these two reactants in the feed mixture for addition mode (3) has not been fully discussed. Generally, the mixture which is to be fed will contain from about 1 to about 8 moles of brominating agent per mole of styrenic monomer units at any time during the feed period. During the feed, the quantitative relationship can be constant or can vary within the above-mentioned range. (It is within the scope of this invention to allow for some excursions outside of the range so long as such does not do significant harm to the process efficiency or to product quality.) A preferred range is from about 2.5 to about 5 moles of brominating agent per mole of styrenic monomer units in the feed mixture. As can be appreciated, the use of an amount of brominating agent in the feed mixture which gives a mole ratio of brominating agent to styrenic monomer units which is less than or greater than the selected overall mole ratio of brominating agent to styrenic monomer units, will result in exhaustion of either the brominating agent or the styrenic polymer as a mixture constituent before exhaustion of the other constituent. For example, if the practitioner chooses to produce brominated polystyrene with a 70 wt % bromine content, an overall molar ratio of bromine to styrenic monomer units of 3.0:1, and any excess if desired, would be suitable. If the practitioner chooses to form a feed mixture in which the molar ratio of bromine to styrenic monomer units is 1:1, it can be seen that the amount of polystyrene to be fed will be completed before obtaining the needed overall amount of bromine. In this case, the practitioner first uses the 1:1 mixture and then continues on with just a bromine feed after the polystyrene feed has been exhausted. If, on the other hand, the molar ratio in the feed mixture is chosen to be 5:1, then the bromine will first become exhausted and the feed will have to be finished with the polystyrene alone. Generally, it is preferred to have the overall molar ratio and the feed mixture ratio at least somewhat similar. In all cases though, the initial feed should preferably contain at least a molar ratio of bromine to styrenic monomer units of 1:1.
It is preferred that the bromine used in the processes of this invention be essentially anhydrous, i.e., contain less than 100 ppm (weight basis) water and contain no more than 10 ppm organic impurities, e.g., oil, grease, carbonyl containing hydrocarbons, iron, and the like. Available, commercial grade bromine may have such purity. If, however, such is not available, the organic impurities and water content of the bromine can be conveniently reduced by mixing together a 3 to 1 volume ratio of bromine and concentrated (94-98 percent) sulfuric acid. A two-phase mix is formed which is stirred for 10-16 hours. After stirring and settling, the sulfuric acid phase, along with the impurities and water, is separated from the bromine phase. To further enhance the purity of the bromine, the recovered bromine phase can be subjected to distillation.
By forming a solution of bromochloromethane and styrenic polymer, the polymer becomes easy to handle and mix with bromine. The solutions of this invention, e.g., the reactor contents for addition mode (1) and the polystyrene streams for addition modes (2) and (3), will generally contain from about 5 to about 50 wt % polymer. More highly preferred are those which contain from about 5 to about 30 wt % polymer. When considering the total bromochloromethane in the process, which total would include that amount of bromochloromethane used to render the catalyst stirrable in addition modes (2) and (3), typically there will be 5 to 40 wt % styrenic polymer. Preferably, this range will have an upper limit of from 20 to 35 wt % styrenic polymer, the wt % being based on the total weight of bromochloromethane and styrenic polymer used in the process.
It is preferred to have the bromination catalyst associated with an amount of bromochloromethane so that the catalyst can be in a solution, slurry, dispersion or suspension as it is being contacted with the brominating agent and styrenic polymer. Such will enhance reaction mass mixing and mass transfer qualities. This association is best when considered to be a suspension. It is suitable to use from about 95 to about 99.9 wt % bromochloromethane and preferably from about 99 to about 99.8 wt %, based on the total weight of bromochloromethane and catalyst.
The feeds used in the processes of this invention should occur expeditiously, with consideration being given to the ability of the process equipment to handle the heat load from the exothermic process, the evolving HBr, and other process concerns. In short, the feeds can occur over the shortest time period that will be allowed by the equipment without excursion outside of critical process parameters. Generally, it is anticipated that the feed period will be from 0.5 to 3 hours for a commercial-size plant. Shorter feed periods are expected for smaller scale processes.
The processes of this invention occur at a temperature within the range of from about -20° to about 60° C. and preferably within the range of from about 0° to about 10° C. The pressure can be atmospheric, subatmospheric or superatmospheric.
To carry out a process of this invention, a bromination catalyst, say AlCl3, is suspended in essentially anhydrous bromochloromethane, to give an easily stirrable suspension. The suspension is prepared in a glass-lined, stirred reactor and brought to a temperature within the range of from about -5° to about 10° C. The mix is kept under an inert, dry atmosphere in the reactor. A solution of a styrenic polymer and bromochloromethane is prepared and intimately mixed with a bromine stream to yield a homogenous mixture. The cool mixture is fed into the stirred bromination catalyst suspension in the reactor. The intimate mixing of the styrenic polymer solution and brominating agent can be accomplished in a number of ways. For example, the solution and a brominating agent can be fed to a mixing device, e.g., a mixing nozzle, at the lower end of the dip tube in the reactor which extends to a point below the suspension level. The mixing device is designed to obtain the intimate mixing of the solution and brominating agent. Also, the mixing device acts to impart mixing energy, at the point of feed, to the intimate mixture and catalyst suspension. Another technique for obtaining intimate mixing of the styrenic polymer solution and brominating agent, is to use an exterior reactor loop having an in-line mixer, say an impingement mixer. Generally, the use of an exterior reactor loop includes first charging the reactor with a bromination catalyst slurry, suspension, etc., and then withdrawing from the reactor a stream which is then fed to a mixer external of the reactor. A mixture formed from at least bromine and styrenic polymer is also fed to the mixer to yield a second mixture which is formed from the two feeds to the mixer. The second mixture is subsequently fed back to the reactor. The stream withdrawn from the reactor will initially comprise the catalyst. After the second mixture is fed to the reactor and the process runs, the withdrawn stream will begin to comprise brominated polystyrene along with catalyst. As the process continues, the degree of bromination of the polystyrene will increase.
Exemplifying the use of an exterior reactor loop, reference is made to FIG. 1 wherein there is shown a reactor, generally designated by the numeral 1. Reactor 1 is a stirred reactor and initially contains a suspension comprising catalyst and bromochloromethane. Reactor discharge conduit 4 provides a stream from reactor 1 which is fed to pump 5. Pump 5 pressurizes the stream so that it is fed with force via conduit 7 to impingement mixer 10. Bromine is fed via conduit 20 to pump P1 while, at the same time, a solution of polystyrene and bromochloromethane is fed via conduit 22 to pump P2. Pumps P1 and P2 feed in-line mixer 11 to obtain an intimate mixture of bromine, polystyrene, and bromochloromethane solvent. This intimate mixture is fed to impingement mixer 10, wherein it is intimately mixed with the stream from reactor 1. The discharge from impingement mixer 10 is fed via conduit 33 to reactor 1 through feed port 3. The removal of contents from reactor 1 and their feed to impingement mixer 10 continues to occur until at least substantially all of the bromine and polystyrene/bromochloromethane solution have been fed.
As can be appreciated, the contents of reactor 1 change in composition during the bromine and polystyrene/bromochloromethane solution feeds. Initially, the contents of reactor 1 comprise catalyst and bromochloromethane. As the process runs, the reactor contents comprise and begin to become more rich in brominated polystyrene, some of which is underbrominated and some of which is of the degree of bromination sought. During a cook period, the final bromination occurs. Removal of the reactor contents can continue to occur during the cook period to aid in mixing.
As pointed out earlier, the bromination of styrenic polymers is a substitution reaction. The main by-product from this reaction is HBr. The HBr formed in the process is usually found in the head space above the reactor contents. It is preferred that the HBr be removed and passed to a water scrubber or stored as dry HBr. A dry, inert gas, say nitrogen, can be used as a pad over the reactor contents to minimize the presence of water therein.
The reactor is kept at a low temperature, e.g., from about 0° to about 10° C., during the feed of styrenic polymer and/or brominating agent feed, as the case may be, and preferably from about 4° to about 8° C.
After the feed is accomplished, the reactor is preferably maintained for a cook period of from about 0.5 to about 6 hours and preferably from about 1 to about 3 hours. The cook temperature is within the range of from about 0° to about 10° C. and preferably within the range of from about 2° to about 5° C. The cook period serves to continue the bromination until the sought degree of bromination is obtained. It may be for a long period if the reaction parameters provide for mild bromination conditions during the brominating agent and styrenic polymer feeds or it may be for a short period if the parameters chosen provide for more severe bromination conditions. The cook period can occur in the reactor.
After the cook period, the reaction mass can be treated with water, sodium sulfite, sodium gluconate and sodium hydroxide to deactivate the catalyst, kill any remaining brominating agent and to adjust the reaction mass pH. After these treatments, the reaction mass is settled to obtain a two-phase reaction mass containing an organic phase, which contains, as a solute, the brominated styrenic polymer product, and an aqueous phase. The aqueous phase is decanted and the remaining organic phase is stripped of its bromochloromethane component. It is most convenient to accomplish this strip by pouring the organic phase into boiling water. As the solvent is stripped, the brominated styrenic polymer product forms a precipitate. The precipitate can be recovered by any liquid-solid separation technique, e.g., filtration, centrifugation, etc. The recovered precipitate is then dried.
It is preferred that the bromochloromethane solvent be dry, that is it contains less than about 200 ppm (weight basis) water and more preferably less than about 150 or 100 ppm water.
The following Examples illustrate features of processes of this invention. The Delta E values, along with the L, a and b values from which it is derived, were obtained by transmission measurements made with a HunterLab Color Quest Spectrocolorimeter. The transmission cell provided a 20 mm path length. The software was set to report the color in units of "Delta E-lab". The standardization/calibration was based upon chlorobenzene and obtained by use of the instrument's black and white standard tiles. The brominated polystyrene sample to be tested was prepared by measuring 5 grams of the sample into a 50 ml centrifuge tube. Then, 45 grams of chlorobenzene was placed in the tube. The tube is shaken for 1 hour on a wrist-action shaker. If, after the shaking period has lapsed, the solution is not clear it is centrifuged for 10 minutes, at 4,000 rpm. If the solution is still not clear, it is then centrifuged another 10 minutes. If the solution is still not clear, then it cannot be analyzed. Assuming a clear solution, the solution is poured to fill the 20 mm cell for placement in the colorimeter. The calibrated instrument is set to report color as "Delta E-lab".
Bromine (683.5 g, 4.277 mole) was added over 75 minutes to a cooled (5° C.) solution of 165.0 g (1.585 mole) of polystyrene (PS) dissolved in 1,188 ml (2,364 g) of anhydrous bromochloromethane (BCM) in the presence of 3.3 g (2.9 wt % based on PS) of aluminum chloride. Evolved HBr was scrubbed by a caustic solution during the reaction. A cook period of 2 hours at 5° C. with nitrogen purge was effected. The reactor contents were diluted with 2,444 ml (4,863 g) BCM, washed with 2,000 ml water, aqueous sodium sulfite (30 g in 2,000 ml water) and then with 2,000 ml water. The aqueous and organic layers were separated. The organic layer was added batchwise into 7,000 ml of 90° C. water with agitation. BCM was removed with a Dean-Stark trap from the return distillate. The mixture was cooled and the solid product was filtered, washed (with water) and dried at 150° C. to obtain 477 g (95% yield) of brominated PS. The results of analysis are shown in the Table.
The bromination of PS was repeated as in Example I except as indicated in the Table. The amount of ethylene dichloride, EDC, used was in the same volume proportion as the BCM used in each step. The analytical results for the product are in the Table.
A Y-shaped mixing apparatus having a cooling jacket was equipped with 2 feed lines, each connected to a pump. One of the feed lines was for delivering bromine and the other was for delivering a PS and BCM solution. Bromine (93.3 g, 31.3 ml or 0.583 mole), delivered at a rate of 1 ml/min (19.4 mmol/min), and a PS/BCM solution (22.4 g PS, 0.215 mole and 97 ml or 194 g of anhydrous BCM), delivered at 4 ml/min (7.17 mmol/min), were fed simultaneously from their respective feed lines into the cooled (5° C.) Y-mixing apparatus. The resultant intimate mixture from the mixing apparatus was then fed into a cooled (5° C.) suspension of 0.45 g (2 wt % based on PS) of aluminum chloride in 49 ml (98 g) of anhydrous BCM. Evolved HBr was scrubbed by a caustic solution during the reaction. The feeds were complete in 35 minutes and the mixture was cooked for 2 hours at 5° C. After water and sodium sulfite washes, solid BrPS was isolated by precipitating from 500 ml of hot (90° C.) water as described above. A total of 66 g of BrPS (97%, yield) was obtained. The results of analysis are shown in the Table.
The bromination of PS was repeated as in Example III except as indicated in the Table. The amount of EDC used was the same volume proportion as the BCM used in each step. The analytical results are in the Table.
Aluminum chloride (3.54 g, 2 wt % based on PS) was suspended in 379 ml (754 g) of anhydrous BCM. After cooling to 3° C., a 10-ml portion of bromine was added. A solution of PS/BCM (175 g or 1.681 mole of PS dissolved in 791 ml or 1,574 g of anhydrous BCM) was pumped into the suspension at a rate of 15 ml/min (25.47 mmol/min), while bromine (total of 725 g, 230 ml, 4.537 moles, 2.7 equivalents) was added from an addition funnel at a rate of 3 ml/min (58 mmol/min). Evolved HBr was scrubbed by a caustic solution during the reaction. The mixture was held at 5° C. throughout the feed and cook period. After 3.3-hr cook, the mixture was diluted with BCM (1,068 ml or 2,127 g) and then washed with aqueous sodium sulfite and water. The product was precipitated in water and isolated as described in the previous section. A total of 522 g of BrPS (98% yield) was obtained. The results of analysis are shown in the Table.
The bromination of PS was repeated as in Example V except as is indicated in the Table. The amount of EDC used was in the same volume proportion as the BCM used in each step. The analytical results are in the Table.
TABLE__________________________________________________________________________ Ex. I Ex. II Ex. III Ex. IV Ex. V Ex. VI__________________________________________________________________________Mode of Addition Batch Batch Premixed Premixed Cofeed CofeedSolvent/deg C. BCM/5 EDC/5 BCM/5 EDC/5 BCM/5 EDC/5AlCl3 Load (wt % of PS) 2 2.7 2 2.1 2 2Avg Feed Mole Ratio Br/PS -- -- 2.7 2.7 2.3 2.2Total Eq. Br2 2.7 2.8 2.7 2.7 2.7 2.7Feed Times Br2/PS (min/min) 75/0 67/0 35/35 30/30 76/66 76/62Cook Time (min) 240 140 120 120 200 200BrPS Yield (%) 95 97 97 98 97Total Br (wt %) 66.8 68.2 68.4 67.6 68.0 67.0Hydro. Br (ppm) 2,868 7,138 2,827 3,778 1,695 2,680Solution Color (10% PhCl)L 93.21 88.97 96.74 87.10 96.94 96.45a -2.86 -3.34 -1.90 -1.68 -1.12 -2.51b 22.24 36.65 15.99 34.80 7.89 13.80Delta E 23.43 38.42 16.44 37.15 8.54 14.48GC Analysis of Solvent (Area %)Before Reaction 99.44 99.97 99.44 99.97 99.44 99.97After Reaction 99.49 99.70 99.28 99.06 99.35 98.64New Impurities in Recov. SolventEthylene Dibromide -- 0.18 -- 0.90 -- 1.28Dibromobenzene 0.02 0.10 -- -- -- --__________________________________________________________________________
As can be seen from the Table, the use of bromochloromethane provides a brominate product having superior color and Delta E values with little or no degradation of the process solvent.
A 0.910 g (6.82 mmol) portion of aluminum chloride was suspended (stirred at 250 rpm) in 190 g of dry (13 ppm water) bromochloromethane (BCM) in 1-L jacketed flask cooled to 0° C. by circulating glycol bath. A 419.86 g portion of a 10.00 wt % solution of polystyrene (403.1/n mmol) in dry B CM was pumped at a constant rate of 8.46 g/min (8.13 mmol/min) to a jacketed, glycol-cooled mixing tee mounted on the reaction flask. At the same time, bromine was pumped at a constant rate of 6.09 g/min (38.1 mmol/min) to the same mixing tee where it combined with the polystyrene solution (feed mol ratio Br2 /PS is 4.69) before dropping into the stirred catalyst suspension in the reaction flask. The bromine feed was stopped after 30.0 min (1143.5 mmol) and the polystyrene solution feed was stopped after 49.6 min (overall mol ratio of Br2 /PS is 2.84). A rinse of 160 g of dry BCM was used for the polystyrene solution feed system to assure complete transfer of the polymer to the reaction flask. The reaction temperature was maintained at 0°-5° C. throughout the addition and subsequent 2 hr cook period. The catalyst was deactivated by addition of 16.4 g of 10 wt % aqueous solution of sodium gluconate, and pH was adjusted to 14 by addition of 60.7 g of 10 wt % aqueous NaOH. The reaction mixture was washed with 10 wt % aqueous sodium sulfite followed by a water wash. The product was recovered from the organic phase by addition to vigorously stirred hot (90° C.) water. The solvent distilled from the hot water leaving a slurry of the brominated polystyrene product in water. After filtering, the powdery solid was rinsed with water and dried to constant weight in a vacuum oven (150° C./2 torr/5 hr). The dry solid weighed 127.08 g (95% yield). The product contained 68.7 wt % total Br and 3600 ppm hydrolyzable Br. The HunterLab solution color (10 wt % in chlorobenzene) values were L=94.58, a=-2.79, b=17.29 Delta E=18.34.
The brominated styrenic polymers of this invention are suitable for use as flame retardants in thermoplastics, especially engineering thermoplastics, e.g., polybutylene terephthalate, polyethylene terephthalate, nylon and the like. These brominated polymers are used in flame retarding quantities, say from about 5 to about 20 wt % brominated polymer per hundred weight of thermoplastic. Conventional blending techniques can be used as taught in the prior art. In addition, conventional additives, such as UV stabilizers, impact modifiers, flame retardant synergists, dyes, pigments, fillers, plasticizers, flow aids, antioxidants, free radical initiators, and the like may be used as the need requires.
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