Tulane Center for Polymer Reaction Monitoring and Characterization Tulane University New Orleans, Louisiana 70118 Phone: (504)862-3185 http://www.polyrmc.tulane.edu/

PolyRMC celebrates its first anniversary,

August 22, 2008

PolyRMC was founded after Hurricane Katrina devastated New Orleans. We are proud to be part of the rebirth and rebuilding of Tulane and New Orleans.

Motto: Value andbased on stechnical eintegrity, arelevance

Highlights:

A New Orleans Innovator of the year Award. Strong flow of advances, publications, and presentations. Louisiana Initiatives with local industries launchedMarch, 2008: First plenary meeting of the PolyRMC Advisory Board

impact cientific and

Mission statement: To be the world’s premier center for polymerization reaction monitoringR&D

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xcellence, nd

PolyRMC nears its first anniversary with a diverse cast of participants and range of efforts and activities. The Advisory Board was hand-crafted this year and is composed of an unusual group of distinguished members of far flung academic, industrial, and business expertise. The March 2008 meeting set into motion a flurry of initiatives and missions, and demonstrated the strong support and vote of confidence PolyRMC has from the Tulane Administration.

Research efforts concentrated on breaking ground in monitoring and characterization of emulsion polymerization and ‘living’ type reactions, predictive control of reactions and processes, and exploring fundamental properties of polyelectrolytes. Numerous publications and presentations flowed from PolyRMC this year, and more novel instrumentation was brought online. A strong component of Louisiana Initiatives - building relationships with the vast local industry- was launched, along with the development of a business plan for a potential New Orleans based spin-off enterprise. Research collaborations spanned the globe, including a new natural products effort beginning with Brazil and Uzbekistan, and strong industrial collaborations continuing in North America and Europe. Support from NSF, the Louisiana Board of Regents, NASA via TIMES, and several of our private sector sponsors continued. We especially acknowledge Arkema Inc., Brookhaven Instruments Corp., Total S.A., and Polymer Laboratories Ltd. (now part of Varian, Inc.). PolyRMC members, colleagues and supporters look forward to a very intense upcoming year, complete with inevitable growing pains, and unbounded enthusiasm.

Alina M. Alb, Associate Director for Research Michael F. Drenski, Associate Director for Instrumentation

Founded August 2007 Wayne F. Reed, Founding Director

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Postdoctoral Associates Dr. Daniel Elizarrarás Dr. Rilton Alves de Freitas

• Graduate Students Tomasz Kreft, Colin McFaul Zheng Li Pascal Enohnyaket (Ph.D. 2007)

• Undergraduate Students

ex

To

pertise, versatility, reliability, expanding horizons

Alex Reed Megan Sullivan Gerard Lakin

Prof. Alina Alb – ACOMP exp.

Prof. Wayne Reed

masz Kreft – ACOMP exp.

Michael Drenski and Colin McFaul-SMSLS exp.

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Dr. Daniel Elizarrarás - ACOMP exp.

Zheng Li – FTIR exp. Alex Reed – SEC org. exp.

Prof. Rilton Alves de Freitas – SEC aq. exp.

Recent Personnel and Visitors

R. Inoubli, G. Gonzáles, S. Hokenek, A. Paril, E. Mignard, G. Sorci, F. Florenzano, J.L.Brousseau, H. Gao, K. Min, A. Heidenreich, R. Graves, B. Grassl, F. Chauvin, T. Leblanc, J.F. Lutz, A. Head, J. F. Craymer, T. Eren, A. Öncül-Koç, R. Shunmugam, J.S. Ganter, E. Bayly, S. Moyses, C. Bertelo, J. Ness, N. Sahiner, D. Norwood, D. Mountz

S. Grayson, V. T. John, G. L. McPherson, D. Mullin Tulane U.; J. Puskas, U.Akron; A. Serelis, Australia K. Matyjaszewski, Carnegie Mellon U.; A. Giz, H. Çatal-Gil Giz, Turkey; G. Tew, D. Hoagland, B. Coughlin,T. Emrick, M. Santore, UMass; J. M. Asúa, Carlos de la Cal, Spain; T. Mandal, Xavier U., New Orleans; D. Bertin, P. Tordo, O. Guerret, U. Marseille ; R. Farinato, J. Calbick, Cytec, CT; A. Parker, Firmenich S.A. Switzerland

Collaborators coming soon to PolyRMC: Dr. F. Bentrem, NRL; Dr. N.Normakhamatov, Uzbekistan; Prof. F. H. Florenzano, Brazil

Academic Collaborators

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• A major advance in ACOMP

capabilities has been the development of a ‘dual detection stream’ that permits simultaneous characterization of both the colloids (e.g. monomer droplets and latex particles) and the polymer/monomer components involved in emulsion-based polymerization reactions.

A. M. Alb, W. F. Reed, “Simultaneous monitoring of polymer and particle characteristics during emulsion polymerization”, Macromolecules 2008, 41, 2406-2414.

Our Arkema colleagues provided expertise in redox coupled initiation in emulsion polymerization and joined in the following ACS presentation:

A. M. Alb, S. Moyses, J. Ness, C. A. Bertelo, W. F. Reed, “Online monitoring of free radical polymerization in emulsions.” 235th American Chemical Society Meeting, New Orleans, April 2008.

• ACOMP was applied for the first time to monitoring RAFT (reversible addition

fragmentation chain transfer) reactions, and was used to follow the transition between controlled and uncontrolled free radical polymerization. ACOMP has now been adapted to the major types of controlled radical polymerization: NMP, ATRP, and RAFT. Our Australian colleague on this was Dr. Algirdas Serelis from Dulux Australia.

A. M. Alb, A. Serelis, W. F. Reed, “Kinetic trends in RAFT homopolymerization from online monitoring”, Macromolecules 2008, 41, 332-338.

Discoveries and Advances/ Publications/Presentations

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• First series of gradient and diblock copolymers by RAFT were monitored by ACOMP

A. M. Alb, W. F. Reed, “Online monitoring of block and gradient copolymerization by RAFT”, 235th American Chemical Society Meeting, New Orleans, April 2008.

• An unusual but practical mathematical formalism was developed to solve the classically difficult problem of determining absolute copolymer molecular weight. The formalism was immediately adapted to ACOMP and experimentally tested:

P. Enohnyaket, T. Kreft, A. M. Alb, M. Drenski, W. F. Reed, “Determination of molecular mass during online monitoring of copolymerization reactions”, Macromolecules 2007, 40, 8040-8049.

• The complex kinetic events involved in copolymeric polyelectrolyte synthesis were monitored for the first time. In this case, an unexpected blend of copolyelectrolytes and homopolymers resulted under certain reaction conditions.

A. M. Alb, A. Paril, H. Çatalgil-Giz, A. Giz, W. F. Reed, “Evolution of composition, molar mass, and conductivity during the free radical copolymerization of polyelectrolytes”, J. Phys. Chem. B 2007, 111, 8560-8566.

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• As a sequel to the first monitoring of copolyelectrolyte synthesis, deployment of a robust conductivity probe within the ACOMP platform has yielded, for the first time,

quantitative measurements of counterion condensation during synthesis. This paves the way towards a wide variety of possible fundamental studies on polyelectrolyte properties as they develop during synthesis.

G. González Garcia, T. Kreft, A. M. Alb, J. Carlos de la Cal, J. M. Asúa, W. F. Reed, “Monitoring the synthesis and properties of copolymeric polycations”, J. Phys. Chem. B, in press.

• Monitoring changes in polymer characteristics while they are being modified by post-

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A. , W. F. Reed, “Online

• The first predictive control of molecular

T. Kreft, G. González García, A. M. Alb, J.

polymerization reactions, which is an important alternate route to functional polymers, is an area of strong PolyRMC interest. In this first study, the changes in polymer scattering, viscosity, and conductivity were monitored as polyacrylamide was base- hydrolyzed into a polyelectrolyte. Paril, A. M. Alb

Monitoring of the Evolution of Polyelectrolyte Characteristics during Post-polymerization Modification Processes”, Macromolecules 2007, 40, 4409-4413.

weight in free radical homopolymers reactions was achieved.

Carlos de la Cal, J. M. Asúa, W. F. Reed, “Predictive control and online monitoring of average molar mass and composition distributions in free radical polymerization”, 235th American Chemical Society Meeting, New Orleans, April 2008.

• It was found that polybutadiene chain

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R. Inoubli, D. Elizarrarás, S. Cooper, J. Sosa, A.

• PolyRMC staff were invited to write a review article about ACOMP’s ten year old

A. M. Alb, M. F. Drenski, W. F. Reed, “Automatic continuous online monitoring of

• Highlights of recent ACOMP advances, focusing on emulsion polymerization

A. M. Alb, W. F. Reed, “Recent advances in ACOMP”, Macromolecular Symposia, in press

s online

• In a continuation of the Tulane/U Mass collaboration that was fortuitously

B. Zdyrko, P. Bar-Yosef Ofir, A. M. Alb, W. F. Reed,

scission and crosslinking in solution by free radical initiators occurs. The scission kinetics were quantified using ACOMP. Our Total S. A. colleagues on this were Drs. Scott Cooper and José Sosa.

M. Alb, M. F. Drenski, W. F. Reed, “Online monitoring of polybutadiene chain scission and crosslinking in solution by free radical initiators”. 235th American Chemical Society Meeting, New Orleans, April 2008.

history of accomplishments in the polymerization monitoring field.

polymerization reactions (ACOMP)”, Polymer International (invited) 2008, 57, 390-396

monitoring and RAFT were the subject of invited articles and presentations at congresses.

in Automatic Continuous Online Monitoring ofW. F. Reed, A. M. Alb, “Recent Advances

Polymerization Reactions”, Modeling, Monitoring and Control of Polymer Properties, Vingtièmes Entretiens du Centre Jacques Cartier, ESCPE, Lyon, France, Dec. 2007.

nski, A. M. Alb, “Recent advances in automatic continuouW. F. Reed, M. F. Dremonitoring of polymerization reactions (ACOMP)”. ISPAC, Univ. of Delaware, June 2008.

engendered by Hurricane Katrina, this collaboration with Maria Santore’s group brought our ACM (Automatic Continuous Mixing) methods to bear on Maria’s efforts in surface deposition of polymeric micelles.

M. M. Santore, “Adsorption of Copolymers Micelles and Aggregates: From Kinetics to Adsorbed Layer Structure”, J. Colloid & Interface Sci. 2008, 322, 365-374.

An area of intense interest at PolyRMC is to develop online methods for quantifying

processes involving natural products, such as extractions, enzymatic and chemical modifications, encapsulation of other agents, and the formation of nanostructures. These have wide applications in the pharmaceutical, food, agricultural, cosmetic, and materials industries.

National Science Foundation (CBET 0623531) has provided funds to help spur

r gave a series of talks in Brazil to launch the new initiative:

• The this collaboration, aiding in travel and activities of PolyRMC in Brazil, while the Brazilian government and other organizations provide for Brazilian students and scientists to spend time at PolyRMC.

The PolyRMC Directo

Universidade Federal do Río Grande do Sul, Porto

ra, D. Samios U Catarina, Florianopolis,

E. Minatti, F. Nome, D. Zanetti U 7

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s de Freitas, T. Bresolin

Other collab), R. Michel

aulo, São Carlos).

Prof. Rilton Alves de Freitas, sponsored

Métodos novos para a caracterização das solucões de polímeros

Alegre, 11/5/07 Profs. N. Silveiniversidade Federal de Sta.

11/6/07 Profs. niversidade Federal de Paraná, Curitiba, 11/7/0Profs. J. Silveira, M. R. Sierakowski, L. Akcelrud ongresso Brasileiro/Argentino de Bionanotecnolog

Itajai, 11/9/07 Profs. R. Alve

orating Brazilian faculty: Profs. F. H. Florenzano (Pouso Alegreand J. C. Pinto (Río de Janeiro), E. Frollini (U. São P

•

by CNPq is spending a six month sabbatical at PolyRMC, investigating the derivitization of chitosan using reaction monitoring and other characterization methods.

Natural Products Efforts Launched with Brazilian Colleagues

Profs. W. Reed, J. Silveira, R. Alves de Freitas, T. Bresolin

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• Another line of investigation in Natural Products opens; US/Uzbekistan

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Patents. Two new patent applications were filed this year; one provisional, one complete.

New Instrumentation. PolyRMC received the first commercial ACOMP unit from Polymer

PC instrumentation.

pdate on Louisiana Initiatives

with Louisiana industry forged

PolyRMC’s Louisiana Initia

Business plans

Under the guidance of the PolyRMC Advisory Board, and John Christie

help develop the

Collaboration. Through a grant by the U.S. Civilian Research & Development Foundation, PolyRMC has begun a collaboration with Prof. A. Boymirzaev and his colleagues of the Tashkent State Technical University.

Laboratories Ltd., produced under license from Tulane, and is actively collaborating to optimize its performance and expand its capabilities. PolyRMC is also developing new monitoring and G

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First links Dan Borné disseminated word of tives to the Louisiana Chemical Association. That sparked four

immediate respondents, with three meetings already concluded, and plans to move forward in each case on industrial problem solving and characterization issues.

and Jake Maczuga from the Tulane Technology Transfer and Business Development Office, PolyRMC undergraduate Alex Reed has been working with interns Shreya Biswas and Justin Peno, as well as NewOrleans BioInnovation Center Commercialization Coordinator Steven Ceulemans to develop a business plan for PolyRMC characterization and industrial problem solving services. The plan will efficiency, organization, and marketability of PolyRMC to enable it to reach out more effectively to businesses in the polymer and polymer pre-cursor manufacturing industry.

PolyRMC gratefully acknowledges funding f National Science Foundation CBET 0623531,Dr. Maria Burka, Program Manager

…………………………………………………

Louisiana Board of Regents

…………………………………………………

NASA via Tulane Institute for MacromolecuEngineering and Science (TIMES) Prof. Daniel DeKee, TIMES Director Dr. Michael Meador, NASA PI

………………………………………………… Arkema, Inc. Dr. Chris Roger, Arkema Project Director

…………………………………………………

Total S.A. Dr. Philippe Tanguy

Jean-Francois Minster …………………………………………………

Polymer Laboratories (now a part of Varian, IDr. John McConville Dr. Steven O’Donahue

………………………………………………… PolyRMC also acknowledges other collabo

Fun

ding

rom the following sources over the past year:

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rations on instrumentation with:

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The Advisory Board was slowly hand-craftedof a distinguished group of members of astoni

Mr. Dan Borné, President, Louisiana Chemic

Dr. Bill Bottoms, Chairman and CEO of Nano

Mr. Ronald J. Evans, Owner, International P Dr. Raymond S. Farinato, Research Fellow, Dr. John McConville, Polymer LaboratorieAnalytical, Global Business Dev., Process Mo Dr. Chris Roger, Arkema, Inc., Director of CPA) Dr. Walther Tscharnuter, President, Brookha

Dr. Hyuk Yu, Walter H. Stockmayer ProfEmeritus of Chemistry at the University of W

Dr. José Carlos Pinto, Professor Titular of thFederal University of Rio de Janeiro, Brazil. (

PolyRMC A

dvisory Board

during PolyRMC’s first year and is comprised shingly diverse backgrounds and expertise.

al Association, (Baton Rouge, LA)

Nexus Inc. (San Jose, CA)

ackaging Co., (New Orleans, LA)

Kemira Water Solutions, Inc. (Stamford, Ct).

s Ltd. (Varian Inc.), Head of N. Am. Sales, nitoring and Control (Amherst, MA)

orporate and External Research (Philadelphia,

ven Instruments Corp. (Holtsville, NY)

essor Emeritus & Eastman Kodak Professor isconsin-Madison. (Madison, Wisconsin)

e Chemical Engineering Program/COPPE at the Rio De Janeiro, Brazil).

Most of the PolyRMC Advisory Board: Mr. Dan Borné, Mr. Ronald Evans, Prof. Hyuk Yu, Dr. William Bottoms, Prof. Alina Alb, Dr. Walther Tscharnuter, Prof. Wayne Reed, Dr. John McConville, Mr. Michael Drenski

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International Collabor

ations and Participants

USA Romania France Mexico

Brazil Spain Cameroon Poland

China Turkey Uzbekistan Korea

Switzerland Britain Canada Australia

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