7:00 AM -8:15 AM     Continental Breakfast – Rauch Business Center   

8:30 AM-10:00 AM    Lecture 5 – Stabilization Mechanisms in Aqueous and Non-Aqueous Latexes  (Mohamed S. El-Aasser)

10:00 AM-10:30 AM    Coffee Break 

10:30 AM-12:00 PM   Lecture 6 – Engineering of Emulsion Polymerization Reactors  (Gary W. Poehlein)

12:00-1:30 PM     Lunch – Rauch Business Center 

1:30 PM- 3:00 PM    Lecture 7 – Semi-Continuous Emulsion Polymerization and Structured Latexes (Michael F. Cunningham) 

3:00-3:30 PM     Coffee Break

3:30-5:00 PM   Lecture 8 – Film Formation and Cohesive Strength Development from Latex Systems  (Andrew Klein)  

7:00-8:30 PM  Lecture 9 – Question & Answer Session with Short Course Lecturers and Participants (with most Short Course Speakers)
 


WEDNESDAY, JUNE 9, 2010

7:00 AM -8:15 AM     Continental Breakfast – Rauch Business Center   

8:30-10:00 AM    Lecture 10 – Advances in Miniemulsion Polymerization (Mohamed S. El-Aasser)

10:00-10:30 AM   Coffee Break

10:30 AM to 12:00 PM   Lecture 11 – Experimental Methods for the Characterization of Latex Particle Size and Particle Size Distribution (Cesar A. Silebi)   

12:00 PM-1:30 PM   Lunch – Rauch Business Center  

1:30-3:00 PM     Lecture 12 –  Polyurethane Dispersions (Bedri Erdem) 

3:00 PM-3:30 PM    Coffee Break

3:30 PM-5:00 PM    Lecture 13 – High Solids Latex Technology (Do Ik Lee)

5:15 PM-7:00 PM:   MIXER and Number 14 – Evening Poster Session – Iacocca Hall, Wood Dining Room, Mountaintop Campus  

7:00 PM-8:30 PM     Banquet Iacocca Hall, Wood Dining Room, Mountaintop Campus  

THURSDAY JUNE 10, 2010

7:00 AM-8:15 PM    Continental Breakfast – Rauch Business Center 

8:30 AM -10:00 AM   Lecture 15 – Living-Controlled Radical Polymerization in Bulk, Emulsion, and Miniemulsion (Michael F. Cunningham)  

10:00 AM-10:30 AM    Coffee Break

10:30 AM - 12:00 PM  Lecture 16  – Latex Rheology (Cesar Silebi)

12:00-1:30 PM     Picnic Lunch- Rauch Business Center Courtyard

1:30 PM-3:00 PM   Lecture 17 – Sensors and Control of Emulsion Polymerization Reactors (F. Joseph Schork)  

3:00-3:30 PM   Coffee Break

3:30-5:00 PM  Lecture 18 – The Structure of Latex-Bound Pigment Coatings (Do Ik Lee)

FRIDAY, JUNE 11, 2010

6:30 AM -7:45 AM  Continental Breakfast – Rauch Business Center   

8:00 AM-9:30 AM    Lecture 19 – Basic Concepts for Morphology Control in Core-Shell Latex Particles (Donald C. Sundberg)

9:30 AM-9:45 AM  Coffee Break

9:45 AM -11:15 AM  Lecture 20 – Mechanisms and Examples of Crosslinking in Latex Systems  (Eric S. Daniels) 

11:15 AM-11:30 AM   Coffee Break

11:30-1:00 PM  Lecture 21 – Mixing Scale-Up in Emulsion Polymerization (Andrew Klein)

FEES:

The fee structure for the 2010 course includes a variety of possible discounts as described below (note that discounts cannot be combined).  
       
 

 Fees cover registration, a set of notes, five (5) days of continental breakfast, four (4) days luncheon, all breaks, a Pizza Party/Mixer on Monday evening, and a Banquet on Wednesday evening. Checks payable to Lehigh University/ Emulsion Polymers Course should accompany applications OR you may use the downloadable registration forms (links below) to e-mail or Fax your registration in. An invoice can then be sent to you OR you may use a credit card to pay for registration and University housing (Visa, MasterCard or American Express ONLY).   Please use the downloadable registration form if you would like to charge the course registration and University housing fees to a credit card. Refund requests received before April 16, 2010 will be honored in full. A processing charge of $650 will be deducted for cancellations after April 16, 2010.

Click here to download a 2010 Short Course Registration Form in Word (Windows) format

Click here to download a 2010 Short Course Registration Form in Rich Text Format (RTF) (Windows) format

Click here to download a 2010 Short Course Registration Form in Adobe PDF format

PARTICIPANTS:

The course is designed for engineers and scientists who are actively involved in emulsion work as well as for those who wish to develop expertise in the area. A basic background in chemistry will be assumed. More advanced and experienced participants may elect to attend only those days in which material of specific interest is being presented. All participants will receive a printed set of course notes as well as a CD containing supplementary course materials in PDF format.

TRANSPORTATION AND LOCALE:

Bethlehem is located in the heart of the Lehigh Valley about 50 miles north of Philadelphia and 80 miles west of New York City. It is easily accessible by plane via the Lehigh Valley International Airport (formerly known as the ABE, Allentown-Bethlehem-Easton Airport), by car via the east-west Route 78 (22) and the north-south Northeast Turnpike Extension (I-476) and Routes 309 and 378, or by bus from New York City (Port Authority Terminal). 

ACCOMMODATIONS:

Modern air-conditioned University dormitories are available within several blocks of the conference site.  Linens are provided. Single occupants will share a suite (living room and bathroom) with two (2) other course participants. Each person will have a private bedroom. Please see the following site for a description of the Campus Square dormitories:

http://www3.lehigh.edu/studentlife/housing/campussq.asp

 A processing charge of one night will be deducted for housing cancellations after April 16, 2010. Telephones are available in every suite for your added convenience. Direct-dial local service is available at no charge to you. AT&T, MCI, and SPRINT long distance calling cards, or major credit cards are required to make toll calls.

A continental breakfast will be available to course participants at Rauch Business Center each morning. Lunches from Monday to Thursday are also included, as is a Pizza Party on Monday evening and a Banquet on Wednesday evening.

Hotels/motels are for the most part far from campus and will require transportation. Hotel/motel reservations should be made by contacting the hotel/motel directly.

• Comfort Suites (*) 120 West Third Street, Bethlehem, PA; 610-882-9700
• Holiday Inn Express Hotel & Suites  2201 Cherry Lane, Bethlehem, PA; 610-838-6110
• Hampton Inn & Suites at the Gateway Conference Center, 200 Gateway Drive, Bethlehem, PA;  610-868-2442
• Best Western Lehigh Valley Hotel and Conference Center, 300 Gateway Drive, Bethlehem, PA;  610-866-5800
• Historic Hotel Bethlehem, 437 Main Street, Bethlehem, PA; 610-625-5000
• Hyatt Place, 45 West North Street, Bethlehem, PA 18018; 610-625-0500
• Marriott (Residence Inn, Courtyard or Fairfield Inn; Motel Drive, Bethlehem; 800-321-2211
• Homewood Suites by Hilton Allentown/Bethlehem Airport
  2031 Avenue C, Bethlehem, PA 18017, 610-264-7500

  * Only hotel within walking distance of the university.

ABSTRACTS OF COURSE LECTURES:

MONDAY, JUNE 7, 2010

1. Kinetics of Free Radical-Initiated Polymerization--
F. Joseph Schork (University of Maryland)

        A review of the principles of free radical-initiated polymerization, including the four basic reactions of initiation, propagation, termination and transfer, inhibition, molecular weight and molecular weight distribution, effect of temperature and pressure, autoacceleration and diffusion control of termination and propagation, and copolymerization including copolymerization reactivity ratios and copolymer sequence distribution.


2. Emulsion Polymerization Mechanisms and Kinetics--
Gary W. Poehlein (Professor Emeritus of Chemical Engineering, Georgia Institute of Technology)

        Reaction mechanisms and kinetics of free radical polymerization will be reviewed. The unique features of emulsion polymerization will be outlined and the influence of the colloidal size of the reaction sites discussed. Kinetic theories due to Smith & Ewart, Stockmayer, O'Toole, Roe, Fitch, Ugelstad, and Gilbert will be discussed.

3. The Role of Surfactants in Emulsion Polymerization Processes--
Mohamed S. El-Aasser (Lehigh University)

        Surfactants play major roles during the particle nucleation and growth stages, with direct impact on latex particle size, size distribution, polymerization rate, molecular weight, and particle morphology. Surfactants are also essential during post-polymerization processes: stripping, storage, shipping, and formulation for several applications. The general characteristics of surfactants and their adsorption profiles on latex particles will be reviewed. The specific role of surfactants in determining the particle number according to the various nucleation mechanisms will be described. Three alternatives to conventional surfactants will be reviewed.


4. Industrial Uses of Latexes and Preparation of VOC-Free Latexes --
Do Ik Lee (Formerly Senior Scientist in Emulsion Polymers R&D with The DOW Chemical Company)

    This talk will have two parts: “Industrial Uses of Latexes” and “Preparation of VOC-Free Latexes.”

 Industrial Uses of Latexes: About 10 million metric tons (~20 billion pounds) of dry latex polymers are being consumed annually in a very large number of industrial applications, including paints and coatings (~26% of the total annual latex consumption), paper and paperboard applications (~24%), adhesives (~23%), carpet backsizing (~10%), etc. This part of the talk will review the major industrial applications and types of latexes, and then the important latex variables affecting the properties of latexes for various applications will be discussed. Furthermore, industrial latexes will be grouped in terms of their T_g ranges for various applications which are in turn grouped in terms of filler levels. Finally, some specific applications will be highlighted and their latex requirements and future needs will be discussed.

 Preparation of VOC-Free Latexes: Historically, butadiene-containing copolymer latexes, such as gel-free SBR (styrene butadiene rubber) and crosslinked S/B latexes, have been steam stripped to remove their residual monomers, whereas the residual monomers of non-gel forming polymer latexes, such as acrylic latexes, have been burned out (i.e., cooked down) in their post-polymerization steps by using organic peroxides and reducing agents known as “chaser catalysts” in the industry. However, public demands and government regulations for ever lower amounts of residual monomers and VOC’s contained in latexes and latex-containing coating formulations may require the industry to consider many different approaches to meet the challenges. For example, in some cases where the post-polymerization burnout alone may not be sufficient to meet the demands, the burnout approach must be either combined with or entirely switched to steam stripping or other approaches. This part of talk will discuss the mechanisms for both batch and continuous steam stripping processes, the post-polymerization burnout mechanisms, various initiator systems for the burnout, and other considerations.

TUESDAY, JUNE 8, 2010

5. Stabilization Mechanisms in Aqueous and Non-Aqueous Latexes--
Mohamed S. El-Aasser (Lehigh University)

      The basic concepts and terminology of colloid science will be introduced. The principles of electrostatic and steric stabilization mechanisms will then be reviewed. The inverse problem of coagulating and flocculating latexes will also be discussed.
 

6. Engineering of Emulsion Polymerization Reactors--
Gary W. Poehlein (Formerly with Georgia Institute of Technology)

      The various types of reactors: batch, semi-batch and continuous, used to produce synthetic latexes, will be reviewed. Pros and cons of various types of processes will be discussed and theoretical reactor models will be presented where appropriate. Reactor design and operating factors that influence product properties will also be reviewed.

7. Semi-Continuous Emulsion Polymerization and Structured Latexes--
Michael F. Cunningham (Queen's University)

       Semi-continuous (or semi-batch) polymerizations in which the monomer is added incrementally during the course of reaction are commonly used in industrial processes because they allow control of the polymerization rate, and because they can be used to control the particle morphology. “Structured latexes” are emulsion polymer particles in which the internal morphology and/or composition vary through the particle. Examples include core-shell particles, and particles with radial composition gradients between the particle core and surface. The discussion will describe how semi-continuous processes are run, the unique features of operating an emulsion polymerization in semi-continuous mode, and how structured latexes can be synthesized.

8. Film Formation and Cohesive Strength Development from Latex Systems--
Andrew Klein (Lehigh University)

      The cohesive properties of polymer films from latexes are dependent on the film formation mechanism. Polymer film formation from latex occurs either when: (a) the molecules from the individual polymer particles interdiffuse and entangle as the particle boundaries gradually disappear; or, when (b) the molecules partially interpenetrate and cross-link, forming interparticle "spotwelds"; or when (c) water-soluble molecules react or interact with functional groups on the particle surface. In the last two cases, the particle boundaries remain distinct. The role of interpenetration depth and the diffusion rate on cohesive strength development will be discussed, using model latex systems.
 

9. Evening Session: Question and Answer Session with Most of the Short Course Lecturers and Participants

WEDNESDAY, JUNE 9, 2010

10. Advances in Miniemulsion Polymerization--
Mohamed S. El-Aasser (Lehigh University)

      Despite the fact that the first miniemulsion polymerization was carried out at Lehigh University in 1972, the term "miniemulsion" was first coined only in 1981. The number of publications on miniemulsions has been increasing exponentially over the past decade, including a few patents.        

      Miniemulsions are relatively stable oil-in-water emulsions with average droplet diameters ranging from 50 to 500 nm. These are typically prepared using a mixture of a surfactant and a  low molecular weight, highly water-insoluble costabilizer (sometimes referred to as cosurfactant). In miniemulsion polymerization, the submicron monomer droplets are the main sites for particle nucleation and growth via free radical initiation using oil-soluble or water-soluble initiators. The stability behavior of miniemulsions has been explained theoretically based on the well know concepts of Ostwald ripening and thermodynamics. Miniemulsions have been exploited in making new types of polymer colloids (latexes) that were difficult and sometimes impossible to make using conventional emulsification or emulsion polymerization processes. These include preparation of artificial latexes and hybrid latexes, high solids latexes, polymerization of highly water-insoluble monomers and macromonomers, controlled polymer microstructure and morphology, encapsulation of pigments and dyes, and controlled molecular weight via living free radical polymerization. In this lecture both the theory and practice of miniemulsions will be discussed.
 

11. Experimental Methods for the Characterization of Latex Particle Size and Particle Size Distribution --
Cesar A. Silebi (Lehigh University)

            The application of fractionation and non-fractionation methods for the determination of  particle size distribution, the range of applicability, and advantages and disadvantages and their on-line measurement capability will be discussed.  Among the methods examined are: classical and dynamic light scattering, sedimentation, disc centrifugation, electrozone sensing, sedimentation field flow fractionation, capillary hydrodynamic fractionation, and recent advances in hybrid methods of analysis.  Comparisons of several of these methods will be used to illustrate problems often encountered in the particle size distribution determination of latexes.  
 

12. Polyurethane Dispersions--
Bedri Erdem (The Dow Chemical Company)     

      Waterborne polymer systems such as acrylates and urethanes have emerged to replace solvent-based products in many demanding applications such as coatings, elastomers, sealants and adhesives. Not only do these systems result in the preparation of products with mitigated EH&S issues (solvents, monomers, etc.), but the products produced have also improved properties and performance.

      Aqueous polyurethane dispersions are heterogeneous compositions where polyurethane/urea particles are colloidally dispersed in the aqueous phase by the aid of surface active moieties. The formation and colloidal stability of submicron size polyurethane particles (~50-500 nm in diameter) can be obtained by the incorporation of ionic or nonionic groups into a polymer backbone. Ionic groups such as carboxylates, sulfonates, or quarternary ammonium salts are commonly used to incorporate ionic character into polyurethane polymer backbone.[i] These functionalities impart water-dispersibility to the ionomeric resin and help minimize the requirement for shear which is very critical in the preparation of PUDs in the batch process. The majority of PUDs produced commercially (~95%) are from prepolymers having an ionic backbone, which is attained by incorporating a molecule capable of bearing ionic (anionic or cationic) charge. Dimethylolpropionic acid (DMPA) is the most commonly used material to incorporate an internal ionic moiety for the preparation of anionic prepolymers. The chemistry of preparing ionic prepolymers is often complex and requires a fundamental understanding of the process. Several papers have been  published on the preparation of PUDs, but no report was found describing the details of the prepolymer synthesis.

      PUDs based on prepolymers capable of bearing nonionic and ionic moieties have been produced for a variety of applications. Therefore, the effects of various parameters on the kinetics and process of preparing ionic prepolymers were investigated. The kinetics of the prepolymer synthesis with emphasis on the disappearance of the acid groups (COOH) was investigated. The role of the carboxylic acid on the reactions between isocyanate and polyols were studied in the presence of various variables and conditions. The effects of the solvent type and amount, prepolymer composition, presence of different tertiary amines having different pKa values (triethyl amine, N-methyl morpholine), types of isocyanate, types of ionic molecules (DMPA, DICAP 600) and their concentrations on reaction kinetics and storage stability of prepolymers were studied. The findings enabled the preparation of anionic prepolymers and submicron size and solvent-free PUDs used for a variety of applications.  

13. High Solids Latex Technology--
Do Ik Lee (Formerly with The Dow Chemical Company)

      High-solids latex technology is based on two basic principles: the maximization of latex particle packing and the minimization of the effective volumes of latex particles from the viewpoints of dispersion rheology. With these two principles at hand, the technology is concerned with the maximization of the volume solids of latexes, while meeting their respective end-use property requirements for a variety of applications. For this reason, although the technology is capable of achieving 70% or higher volume solids latexes, its objective is to increase the volume solids of the existing latexes by 5% to 15% by considering only a bimodal approach for the packing efficiency. This talk will describe the basic principles involved in the high-solids dispersion technology, and then discuss blending (i.e., large and small particle size latex blends) and in-situ (i.e., by either surfactant or seed addition during polymerization) methods of preparation for high-solids bimodal latexes.

14. Advanced Research Topics in Emulsion Polymerization and Latexes: An Evening Poster Session-- Graduate Students in the Emulsion Polymers Institute, Lehigh University.



THURSDAY, JUNE 10, 2010
 

15. Living-Controlled Radical Polymerization in Bulk, Emulsion, and Miniemulsion--
Michael F. Cunningham (Queen's University)

      “Living” (or “controlled”) radical polymerizations provide a novel and potentially inexpensive route to designing polymers with controlled microstructure (e.g. block copolymers, star polymers) and narrow molecular weight distributions. While extensive research has been conducted into homogeneous bulk and solution living radical polymerizations, investigations into aqueous dispersed phase systems (emulsion and miniemulsion polymerization) have only recently appeared. Although little progress has been realized with emulsion polymerization, considerable success has been achieved using miniemulsion polymerization with living radical systems. This presentation introduces the three major living radical polymerization chemistries (nitroxide-mediated radical polymerization (NMRP), atom transfer radical polymerization (ATRP) and reversible-addition-fragmentation-transfer polymerization (RAFT)), and summarizes recent progress of these systems in bulk, miniemulsion and emulsion.  The emphasis will be on heterogeneous systems, and more specifically on those aspects of operating in a heterogeneous environment that influence the polymerization rate, the molecular weight distribution and the livingness of the system.  


16. Latex Rheology--
Cesar A. Silebi (Lehigh University)

     Review of experimental studies illustrating the various factors that influence the rheological properties of latexes. Topics to be covered include the effects of solids concentration, particle size and distribution, electrolyte content, particle aggregation, adsorbed surfactants, non-spherical particle morphology, particle swelling, and the use of water-soluble associative and non-associative polymeric thickeners. Consideration will also be given to thickened latexes and variables affecting their rheological flow curves.


17. Sensors and Control of Emulsion Polymerization Reactors--
F. Joseph Schork (University of Maryland)

        Recent developments in the area of on-line sensors, coupled with the availability of high-performance digital control systems, have opened up new opportunities for the efficient operation and control of latex reactors. Available sensors for on-line analysis will be discussed. The use of such measurements in the application of advanced control techniques to batch and continuous polymerization reactors will be reviewed, with special emphasis on controlling the undesirable process dynamics associated with continuous emulsion polymerization, and optimizing controllers for batch polymerization.


18. The Structure of Latex-Bound Pigment Coatings--
Do Ik Lee (Formerly with The Dow Chemical Company)

     The structure of model coatings based on monodisperse polystyrene latexes as spherical pigments and monodisperse, film-forming latexes as binders has been studied to learn more about the structure of latex-bound pigment coatings: paints and paper coatings. These model coatings have allowed us to study their structure both theoretically and experimentally. This study has proposed the formation of coatings as a two-step process: immobilization and consolidation. The immobilization of model coatings has been assumed to occur at the random dense packing of plastic pigment and latex particles, which can be calculated from the theory. Upon immobilization and further drying, latex particles start to deform and consolidate the wet coatings into the final dry coatings. From this proposed two-step process along with three latex shrinkage models, coating porosity, pore size, number of pores, etc. have been calculated with the knowledge of the critical pigment volume concentration (CPVC) and plastic pigment particle size. This study has been extended to latex-bound clay and calcium carbonate pigment coatings.

 

FRIDAY, JUNE 11, 2010

19. Basic Concepts for Morphology Control in Core-Shell Latex Particles -- Donald C. Sundberg (University of New Hampshire)

    Structured latex particles of all sorts of shapes and sizes have been used in a wide variety of polymer products and are known to impart special material properties to products ranging from adhesives to architectural coatings to impact modifiers for brittle plastics.  These particles are usually composed of two or more immiscible, high molecular weight polymers co-existing in some morphological arrangement within the latex particles.  While the famous “core-shell” structure is often desired, it may not always be achievable under the reaction conditions used to create the composite latex particles.  The purpose of this lecture is to address the fundamental parameters controlling the development of latex particle morphology and to discuss the effects of common latex polymerization recipe and process variables on the morphology of the particles as they emerge from the polymerization reactor.  As such we will introduce the concepts of “thermodynamic equilibrium morphology” and “kinetically controlled morphology” as distinctively different approaches to understanding the control of particle structure.  The former is directly related to the interfacial energies present in the three-phase polymer/polymer/water system and can be understood by minimizing the total free energy of the system via the appropriate interfacial tensions.  The latter is related to the competitive rates of oligomeric/polymeric diffusion within the particle and of chain propagation.  It is within the complexities of simultaneous chain diffusion and propagation that most latex particles achieve their observable morphologies.  Experimental evidence for a variety of morphologies will be presented with appropriate scientific analysis.
 

20. Mechanisms and Examples of Crosslinking in Latex Systems--
Eric S. Daniels (Lehigh University)

     The chemistry and technology of crosslinking in latex systems and their relationship to the latex film formation process and cohesive strength development in polymer films will be reviewed. Special emphasis will be placed on the crosslinking mechanisms (homogeneous, interfacial, and interstitial) which arise when a variety of functional groups such as carboxyl, N-methylolacrylamide derivatives, hydroxyl, epoxy, or isocyanate are incorporated into the latex particles. Research results on crosslinking and film formation in both conventional and miniemulsion latex systems containing dimethyl meta-isopropenyl benzyl isocyanate (TMI®) will be highlighted.
 

21. Mixing Scale-Up in Emulsion Polymerization--
Andrew Klein (Lehigh University)

      Scale-up of the mixing process in emulsion polymerization involves breaking the process down into individual but interrelated steps. The effect of mixing on the microscopic heterogeneity of the continuous phase, fluid shear rates and heat transfer allows each to be considered separately. A few of these effects will be discussed and illustrated with specific examples. The utility of bench scale experimentation, using an impeller-modified reaction calorimeter (Mettler RC1), with a view toward scale-up with some early experimental results, will also be discussed.