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Overview

The 3rd annual Controlled Polymer Synthesis conference will take place as scheduled.

Our deepest sympathy's go out to the people involved in the widespread tragedy of Tuesday, September 11, 2001. There are no words to describe the senselessness of this horrible act. Our thoughts are with the families at this time.

Sincerely,
Craig Wohlers
President

Novel advances on the controlled synthesis of polymers continues to evolve at an accelerated pace, however, utlizing these advances to develop various applications remains a significant challenge. This conference will examine the advantages and limitations of a variety of polymerization applications and processes, such as living radical polymerization, radical polymerization, coatings and nanopolymers.

Join our international panel of experts to hear the latest research in this exciting field within materials science, including such areas as:

Polymer Synthesis
Visualization of Individual Molecules * Cationic Polymerization * Diphenylethene, the Way to Controlled Radical Polymerization * Transition Metal Complexes * Grafting Polymer Chains from Inorganic Surfaces

Living Radical Polymerization
LRP on Solid Surfaces * Effect Polymers from Copper * Control in ATRP of methyl methacrylate * Correlating Molecular Structure with Propertied by ATRP * ATRP and Packed-Column Technology * RAFT Process * Polyolefin Elastomers

Films and Coatings
Polymeric Thin Films via HFCVD * Deposition of Fluorinated Films from Radio Frequency Glow Discharges * Exploiting Acrylic Polymer Architectures * Novel PVDF coatings

Nanopolymers
Nanostructured Materials for Drug Delivery * Biomaterial Design * Nanostructures using Well-Defined Macromolecules * Predicting Mesophases of Copolymer/Nanoparticle Composites

Don't miss this opportunity to learn of the latest R&D in polymer and controlled polymer synthesis. Register today!

Agenda

Monday, December 3, 2001

Controlled Polymer Synthesis

8:55 Session Chairperson's Opening Remarks
Krzysztof Matyjaszewski, Ph.D., J.C. Warner Professor
of Natural Sciences, Dept. of Chemistry, Carnegie
Mellon University

9:00 Visualization of Individual Molecules: An Intriguing Way to Control Polymer Synthesis
Sergei S. Sheiko, Ph.D., Assistant Professor, Department of Chemistry, University of North Carolina at Chapel Hill

The progress made in scanning force microscopy of polymers during the last 5 years will be reviewed including fundamental principles of SFM and recent developments towards visualization and probing of individual macromolecules. Complementary to spectroscopic and scattering techniques, this approach provides a wealth of information about the structure and conformation of polymer molecules. One can directly measure the contour length, the radius of gyration and the persistence length of the molecules. The possibilities and limitations of SFM techniques with respect to control of polymer synthesis will be discussed.

9:30 Controlled Polymer Synthesis by Cationic Polymerization
Rudolf Faust, Ph.D., Professor, Dept. of Chemistry, University of Massachusetts Lowell

During the last decade, living cationic polymerization evolved to a stage when the controlled synthesis of linear or star-branched (co)polymers with controlled molecular weight, molecular weight distribution, block sequence and end-functionality can be readily accomplished. Some of these technologies have recently been commercialized. These will be critically evaluated in comparison with recent advances in cationic macromolecular engineering in general and the synthesis of functional polymers and block copolymers in particular. In addition recent efforts for the determination of the rate constants of elementary reactions in cationic polymerization will be reviewed.

10:00 Controlled Polymerizations Using Transition Metal Complexes
Bruce M. Novak, Ph.D., Howard J. Schaeffer Distinguished University Professor, and Head, Dept. of Chemistry, North Carolina State University

An issue of central importance in polymer synthesis is the ability to control the reactivity of the propagating chain ends. We are interested in the general goal of promoting poorly controlled (nonliving) polymerizations to highly controlled (living) polymerizations by substituting the intrinsically reactive chain
ends with organometallic complexes. Examples discussed include the use of organometallic analogues for radical, anionic and cationic intermediates.

10:30 Refreshment Break and Poster/Exhibit Viewing

11:00 Diphenylethene, the Way to Controlled Radical Polymerization and Solvent Free Dispersions
Wolfgang Bremser, Ph.D., Project leader, BASF Coatings AG, Germany*

Unfortunately this speaker has cancelled, no replacement has been provided

11:00 Controlled Synthesis of Polypeptides Using Transition Metal Complexes
Tim Deming, Ph.D., Materials Dept., University of California at Santa Barbara

The use of low-valent metal complexes for the polymerization of alpha-amino acid-N-carboxyanhydrides (NCAs) will be presented. Details of these polymerizations will be discussed in addition to studies on the initial reactions of NCA monomers with the various metals. These reactions will be analyzed to correlate how the chemistry of different metals, and different modes of monomer additions, affect the control of polypeptide formation.

11:30 Grafting Polymer Chains from Inorganic Surfaces Using Controlled/"Living" Radical Polymerizations
Timothy E. Patten, Ph.D., Assistant Professor, Department of Chemistry, University of California at Davis

Living polymerization from surfaces offers the potential to control spatial and physical surface properties and to prepare composite materials with well-defined structures. The application of controlled /"living" polymerization methods to surface polymerization is relatively unexplored. We have studied the controlled /"living" radical polymerizations from the surface of silica nanoparticles using ATRP. We found that the polymerizations exhibited the diagnostic criteria for a controlled /"living" polymerization: an increase in the molecular weight of the pendant polymer chains with monomer conversion and a narrow molecular weight distribution for the grafted chains. This method offers the potential to prepare hybrid polymer/ inorganic nanoparticles with precise structures.

12:00 Lunch Sponsored by The Knowledge Foundation

Living Radical Polymerization

1:25 Session Chairperson's Opening Remarks
Karen L. Wooley, Ph.D., Professor, Department of Chemistry, Washington University

1:30 Living Radical Polymerization on Solid Surfaces
Takeshi Fukuda, Ph.D., Professor, Institute for Chemical Research, Kyoto University

Surface-initiated living radical polymerization is characterized by a high initiation efficiency and control of chain length, chain length distribution and chain architecture of graft polymers. This method provides a high-density polymer brush in which graft chains are highly extended, especially in a solvent, along the film-thickness direction, and for this reason, the primary structure of graft chains is reflected on the film structure. Kinetic features of this polymerization and some properties of these high-density brushes are discussed.

2:00 Effect Polymers from Copper(I) Mediated Living Radical Polymerisation
David M. Haddleton, Ph.D., Professor, Department of Chemistry, University of Warwick, United Kingdom

Specialty polymers are finding applications in areas as diverse as electronics, biomedical and more traditional adhesives and coatings/inks markets. The advent of living radical polymerisation has given us the opportunity to synthesise a plethora of block and graft molecular architectures. Many, many papers have appeared in the academic literature describing a diverse range of molecular structure. This chemistry has found its place for the preparation of new effect macromolecules. In areas where a particular effect is desired in a product can be designed into a polymer and we now have the tools to prepare these polymers for testing in sufficient quantities. At Warwick we have developed stand alone patent protected chemistry base around a series of ligands used in conjunction with copper(I). Our work is directed to a range of novel architecture polymers that are already at customer trials. It is these high-added value applications where the added cost of the chemistry and the process are not as troublesome to the market. In order to fully exploit our technology the University of Warwick has created a spin-out company "Warwick Effect Polymers" which has an exclusive license to the patent family. This presentation will describe the chemistry in detail, how it operates, the process requirements, catalyst removal, etc. A range of different molecular architectures will be presented and the types of polymers, which are close to commercialisation, described.

2:30 Maximization of the Degree of Control in the Atom Transfer Radical Polymerization of Methyl Methacrylate
Bert Klumperman, Ph.D., Professor, Lab of Polymer Chemistry, Eindhoven University of Technology, The Netherlands

Atom transfer radical polymerization is one of the most versatile techniques in living radical polymerization. Similar to all the living radical polymerization techniques it is of crucial importance to minimize the importance of chain breaking reactions. The present study is focused on the role of the copper complex in the maximization of the degree of control. The potential of two different ligand systems will be discussed.

3:00 Refreshment Break and Poster/Exhibit Viewing

3:30 Correlating Molecular Structure with Properties for Materials Made by ATRP
Krzysztof Matyjaszewski, Ph.D., J.C. Warner Professor of Natural Sciences, Dept. of Chemistry, Carnegie Mellon University

Copper-based ATRP (atom transfer radical polymerization) is among the most efficient controlled/living radical polymerization techniques. ATRP of styrenes, (meth)acrylates and other vinyl monomers provides (co)polymers with predetermined molecular weights in a large range 200>Mn>2,000,000 and with low polydispersities (1.05 less than Mw/Mn less than 1.5). Polymerization can be carried out in bulk, solution and emulsion. Block, graft, star, hyperbranched, gradient and periodic copolymers have been prepared. The presentation will focus on the next main challenge,i.e. a correlation of well-defined molecular structures prepared by ATRP with macroscopic properties, which are also affected by processing.

4:00 Supported Atom Transfer Radical Polymerization and its Continuous Packed-Column Reactor Technology
Shiping Zhu, Ph.D., Associate Professor, Department of Chemical Engineering, McMaster University, Canada

Several supporting methods including insoluble particles as well as soluble-but-recoverable polymeric systems were developed to immobilize ATRP catalysts to facilitate the catalyst recycling. Packed with the supported solid catalysts, column reactors configured in series were used to prepare block copolymers in a continuous manner. Radical mechanisms and diffusion-controlled reactions involved in ATRP particularly at high monomer conversions were also elucidated.

4:30 Recent Advances in Radical Polymerization by Reversible Addition-Fragmentation Chain Transfer (RAFT Process)
San H. Thang, CSIRO Molecular Science, Australia

A controlled radical polymerization developed at these laboratories, namely, free radical polymerization by Reversible Addition-Fragmentation Chain Transfer (RAFT process) has emerged as a robust and industry friendly route to produce living homopolymers, block and star polymers. The process involves a conventional free radical polymerization in the presence of a thiocarbonylthio compound of general structure S=C(Z)SR. This talk will present our recent advances in the RAFT process with particular emphasis on the rapid polymerization of methacrylates.

5:00 New Polyolefin Elastomers: Advances Based on Catalyst Discovery
Geoffrey W. Coates, Ph.D., Professor, Dept. of Chemistry & Chemical Biology, Cornell University

Two classes of living catalysts for polyolefin synthesis will be presented. Application of these catalysts for the synthesis of polyolefin elastomers will be discussed. First, functional polyolefins with elastomeric properties derived from inter-chain hydrogen bonding will be described. Second, the discovery of new living, stereoselective olefin polymerization catalysts will be presented. Using these catalysts, a new class of elastomeric block polyolefins was synthesized.

5:30 End of Day One

Tuesday, December 4, 2001

Films and Coatings

8:55 Session Chairperson's Opening Remarks
Craig J. Hawker, IBM Almaden Research Center

9:00 Polymeric Thin Films via Hot Filament Chemical Vapor Deposition (HFCVD)
Karen K. Gleason, Ph.D., Professor, Dept. of Chemical Engineering, MIT

Dr. Gleason is unable to attend. Dr. Hilton G. Pryce Lewis, CEO, GVD Corporation will present this talk.

Hot-filament CVD (HFCVD) can produce films containing linear polymeric chains, differing from the extensively cross-linked organic films typically produced by plasma enhanced CVD. In HFCVD, the gas thermally decomposes over a hot surface while the substrate remains cool (usually room temperature) to promote the adsorption of film precursors. HFCVD fluorocarbon and organosilicon films have potential applications ranging from replacements for silicon dioxide interlevel dielectric layers in integrated circuits to biopassivation coatings for surgically implantable devices.

9:30 Deposition of Fluorinated Films with Well-Defined Structures from Radio Frequency Glow Discharges
David G. Castner, Ph.D., Director, National ESCA and Surface Analysis Center for Biomedical Problems, Depts. of Bioengineering and Chemical Engineering, University of Washington

Radio frequency glow discharge (RFGD) was used to deposit fluorinated thin films with well-defined and highly-ordered surface structures and chemistries. The ability to vary the surface structure and chemistry of these films provide an excellent method for examining the relationship between the surface properties of a film and its performance in a given application. The surface composition, molecular structure, orientation, and topography of the RFGD films have been characterized with x-ray photoelectron spectroscopy (XPS), static time-of-flight secondary ion mass spectrometry (ToF-SIMS), near edge x-ray absorption fine structure (NEXAFS) and scanning probe microscopy (SPM).

10:00 Exploiting Acrylic Polymer Architectures in Surface Coatings Applications
Andrew T. Slark, Ph.D., National Starch and Chemical Ltd, Adhesives Division, United Kingdom

The importance of linking synthesis with architecture, basic properties and applied properties will be emphasised. Only appreciating this whole picture can direct polymer design effectively, to provide the appropriate cost/performance balance. It will be demonstrated that extreme control in polymer architecture may not be required, even for specialty applications. Conventional free-radical polymerisation of (meth)acrylate monomers is critically compared to "living" methodologies, highlighting a number of disadvantages for the latter and exposing the lack of knowledge on polymer properties. It will be shown that a more pragmatic approach to modifying free-radical polymerisation is possible. It is speculated that this will provide new architectures, which have some structural heterogeneity but may allow stronger potential
for exploitation.

10:30 Refreshment Break and Poster/Exhibit Viewing

11:00 Novel PVDF Based Coatings
Marina Despotopoulou, Ph.D., ATOFINA

Unfortunately this speaker has cancelled, no replacement has been provided

Nanopolymers

10:55 Session Chairperson's Opening Remarks
San H. Thang, CSIRO Molecular Science, Australia

11:00 Complex Nanostructured Materials Designed as Sophisticated, Yet Simple, Vessels for Drug Delivery
Karen L. Wooley, Ph.D., Professor, Department of Chemistry, Washington University

Regioselective reactivity of macromolecules, controlled over nanoscale dimensions, is providing the means to prepare unique nanostructures to advance the availability of materials for fundamental and applied studies in nanoscience and nanotechnology. This presentation will highlight the preparation and study of core-shell nanoparticles that result from segregation of the chain segments of amphiphilic block copolymers, carried-out in solution, followed by intramicellar cross linking, selectively throughout the shell layer. The crosslinking chemistry transforms the supramolecular assemblies into robust nanomaterials, and allows for them to serve as nanoscale constructs for further manipulation of the composition, structure, properties and functions. The block copolymer composition and the cross linking agents determine independently the dimensions, compositions, and thus the properties, of the nanoparticle core and shell. Therefore, a range of block copolymers have been employed, the syntheses of which most often involve living radical polymerizations. Their assembly is performed in an aqueous environment, utilizing poly(acrylic acid) as a hydrophilic chain segment, with cross linking being accomplished by amidation, upon reaction with diamino-terminated cross linking agents. Several examples of these materials will be described, with focus upon the implications of different core behaviors-from glassy (polystyrene), to fluid-like (polyisoprene or poly(methyl acrylate), to crystalline (polycaprolactone) and even hollow nanocages. Discussion will center particularly upon methodologies that are being developed to excavate the nanoparticle core material and enhance the available internal volume. Data demonstrating the partitioning of guests within the nanoparticles will be presented.

11:30 Controlled Polymer Synthesis: Biomaterials Design
Kathryn Uhrich, Ph.D., Associate Professor, Depts. of Chemistry & Chemical Biology, Rutgers University

This talk will focus on designing biodegradable,"temporary" polymers as controlled release drug delivery systems - polymers that deliver drugs at a specific rate or to a specific location. The challenges in this multidisciplinary field are to minimize the body's immune response to the polymer, maximize the drug's efficacy, and optimize drug release as a function of the polymer chemistry and structure.

12:00 Lunch on Your Own

1:30 Control of Nanostructures Using Well-Defined Macromolecules
Craig J. Hawker, IBM Almaden Research Center

The fabrication of nanoscopic devices will increasingly rely on the precise control over materials properties and function on very small size scales, typically 5 nanometers to a few microns. Recent developments in "living" free radical procedures have allowed the construction of tailor-made polymer molecules with unprecedented control, while still permitting a wide range of functional groups to be incorporated. The design and application of these materials in advanced storage devices and microelectronics for the information technology industry will be discussed. Further examples will demonstrate that these new synthetic techniques may also have application in other areas such as bio-sensors, DNA chips, etc.

2:00 Predicting the Mesophases of Copolymer/Nanoparticle Composites
Anna Balazs, Ph.D., William Kepler Whiteford Professor, University of Pittsburgh

The interactions between mesophase-forming copolymers and nanoscopic particles can lead to highly organized hybrid materials. The morphology of such composites depends not only on the characteristics of the copolymers, but also on the features of the nanoparticles. To explore this vast parameter space and predict the mesophases of the hybrids, we develop a mean field theory for mixtures of soft, flexible chains and hard spheres. Applied to diblock/nanoparticle mixtures, the theory predicts new ordered phases, where particles and diblocks self-assemble into spatially periodic structures. The method can be applied to other copolymer/particle mixtures and used to design novel composite architectures. *In collaboration with Russell B. Thompson, Valeriy V. Ginzburg*, Chemical Engineering Department, University of Pittsburgh and Mark W. Matsen, Polymer Science Centre, University of Reading, UK *Present address: Dow Chemical Company

2:30 Design of nanostructured polymers
via nitroxide mediated living radical polymerization
Denis Bertin, Ph.D., University of Marseilles, France*

The recent development in nitroxide mediated controlled radical polymerisation allow now to prepare new complex architecture polymers such as block, graft, gradient or functional (co)polymers. A new beta-phosphonylated nitroxide (SG1) and derivatives was developed and permits control of a large variety of monomers: acrylates, diences, acrylamide, stryenics, and acrylonitrile with a high efficiency in order to prepare nonstructured materials from many applications such as electronics. Many descriptions of use of SG1 will be presented for synthesis of these new materials. *In collaboration with Pr P.Tordo, University of Marseilles, France and O. Guerret, ATOFINA, GRL, France.

3:00 Panel Discussion: Evolution of Polymer Technologies

Panelists:
Krzysztof Matyjaszewski
Karen L. Wooley
Craig Hawker
San Thang

3:30 Closing Remarks and End of Conference

Call for Posters

Industry and academic scientists are encouraged to submit poster titles for this event. One-page abstracts (8 1/2” x 11” with 1-inch margins) must be submitted no later than October 17, 2001 for inclusion in conference documentation. Additional poster submissions will be accepted until November 10, 2001 but may not be included in conference documentation.

Note: If you're submitting a poster, you MUST be registered and paid in advance to ensure that a posterboard is reserved for you.

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