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Announcing the
Emulsion Polymers Institute's 2012 Annual Short Course: "Advances in Emulsion Polymerization
and Latex Technology"
This is a One-Week Short Course that will be offered
by the Emulsion Polymers Institute (EPI) at Lehigh University in
Bethlehem, Pennsylvania USA on June 11-15, 2012. Details of the
course are given below.
Please note that there are no space limitations on
the number of participants that can register and attend the course
since the lectures are held in a large lecture hall.
COURSE ORGANIZER:
Dr. Mohamed S. El-Aasser
Professor,
Department of Chemical Engineering
Vice President for International Affairs, Lehigh University
For more information, or to request a printed course brochure and
registration form, please contact:
Dr. Eric Daniels, Emulsion Polymers Institute
E-Mail: Eric.Daniels@Lehigh.edu
Phone: (610) 758-3602; Fax: (610) 758-5880
Note: You may also download a registration form
using the links given below to reserve your space in the 2012 Lehigh Short Course.
Credit cards (Visa, MasterCard or American
Express ONLY) can be used to charge the
course registration fee and University housing fees.
Click
here to download a 2012 Short Course Registration Form in Word (Windows)
format
Click
here to download a 2012 Short Course Registration Form in Rich Text Format (RTF)
(Windows) format
Click
here to download a 2012 Short Course Registration Form in Adobe PDF format
COURSE DESIGN:
The course is an in-depth study of the synthesis, characterization, and properties of
high polymer latexes. The subject matter includes a balance of theory and applications as
well as a balance between chemical and physical problems. Lectures will be given by
leading academic and industrial workers. Lectures will begin with introductory material
and reviews, and will progress through recent research results.
LOCATION AND TIME:
Sinclair Laboratory
Auditorium
Lehigh University
7 Asa Drive
Bethlehem, Pennsylvania 18015
Lectures will start at 8:30 A.M. Monday to Thursday.
Lectures on Friday will start at 8:00 A.M. and will end by 1:00 P.M.
All Lectures will be held in
the Sinclair Laboratory Auditorium
LECTURE/COURSE
SCHEDULE FOR
2012 SHORT COURSE
MONDAY, JUNE 11, 2012
|
7:00 AM-8:15 AM |
Continental Breakfast |
To be determined |
|
8:30 AM-10:00 AM |
Lecture 1 |
Kinetics of Free Radical-Initiated
Polymerization (F. Joseph Schork)
|
|
10:00 AM-10:30
AM |
Coffee Break |
Sinclair Lab
Auditorium Lobby (tentative) |
|
10:30 AM-12:00
PM |
Lecture 2 |
Emulsion Polymerization Mechanisms and
Kinetics
(Gary W. Poehlein)
|
|
12:00 PM-1:30 PM |
Lunch
|
To be determined |
|
1:30 PM-3:00 PM |
Lecture 3 |
The Role of Surfactants in Emulsion
Polymerization Processes (Mohamed S. El-Aasser)
|
|
3:00 PM-3:30 PM
|
Coffee
Break |
Sinclair Lab
Auditorium Lobby (tentative) |
|
3:30 PM-5:00
PM |
Lecture
4 |
Semi-Continuous Emulsion Polymerization and
Structured Latexes (Michael F. Cunningham) |
|
7:00 PM-9:30 PM |
Mixer |
Campus Pizza |
TUESDAY, JUNE 12, 2012
|
7:00 AM-8:15 AM |
Continental Breakfast |
To be determined |
|
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 |
Sinclair Lab
Auditorium Lobby (tentative) |
|
10:30 AM-12:00
PM |
Lecture 6 |
Sensors and Control of Emulsion Polymerization
Reactors (F. Joseph Schork)
|
|
12:00 PM-1:30 PM |
Lunch
|
To be determined |
|
1:30 PM-3:00 PM |
Lecture 7 |
Glass Transition
Evolution of Plasticized Latex Films: An Important Process in the
Application of Everyday Paints (James W. Taylor)
|
|
3:00 PM-3:30 PM
|
Coffee
Break |
Sinclair Lab
Auditorium Lobby (tentative) |
|
3:30 PM-5:00
PM |
Lecture
8 |
Film Formation and Cohesive Strength Development from Latex
Systems (Andrew Klein)
|
|
7:00 PM-8:30 PM |
Lecture 9: Question and
Answer Session with Speakers |
Sinclair
Lab Auditorium (tentative) |
WEDNESDAY, JUNE 13, 2012
|
7:00 AM-8:15 AM |
Continental Breakfast |
To be determined |
|
8:30 AM-10:00 AM |
Lecture 10 |
Advances in
Miniemulsion Polymerization (Mohamed S. El-Aasser)
|
|
10:00 AM-10:30
AM |
Coffee Break |
Sinclair Lab Auditorium Lobby
(tentative) |
|
10:30 AM-12:00
PM |
Lecture 11 |
Engineering of Emulsion Polymerization Reactors
(Gary W. Poehlein)
|
|
12:00 PM-1:30 PM |
Lunch
|
To be determined |
|
1:30 PM-3:00 PM |
Lecture 12 |
Branching and Grafting in
Emulsion Polymerizations (Peter Lovell) |
|
3:00 PM-3:30 PM
|
Coffee
Break |
Sinclair Lab Auditorium Lobby
(tentative) |
|
3:30 PM-5:00
PM |
Lecture
13 |
Experimental Methods for the Characterization of
Latex Particle
Size and Particle Size Distribution (Cesar A. Silebi)
|
|
5:15 PM-7:00 PM |
Mixer and No. 14- Evening
Poster Session |
Iacocca
Hall, Wood Dining Room, Mountaintop Campus |
| 7:00 PM to
8:30 PM |
Banquet |
Wood Dining Room |
THURSDAY JUNE 14, 2012
|
7:00 AM-8:15 AM |
Continental Breakfast |
To be determined |
|
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 |
Sinclair Lab Auditorium Lobby
(tentative) |
|
10:30 AM-12:00
PM |
Lecture 16 |
Latex Rheology (Cesar Silebi) |
|
12:00 PM-1:30 PM |
Picnic Lunch
|
Campus Square
Courtyard |
|
1:30 PM-3:00 PM |
Lecture 17 |
High Solids Latex Technology (Do Ik Lee)
|
|
3:00 PM-3:30 PM
|
Coffee
Break |
Sinclair Lab Auditorium Lobby
(tentative) |
|
3:30 PM-5:00
PM |
Lecture
18 |
Multi-Phase/Multi-Component
Latex Particles (Peter Lovell)
|
FRIDAY, JUNE 15, 2012
|
6:30 AM-7:45 AM |
Continental Breakfast |
To be determined |
|
8:00 AM-9:30 AM |
Lecture 19 |
Water-Borne
Pressure-Sensitive Adhesives (Peter Lovell) |
|
9:30 AM-9:45 AM |
Coffee Break |
Sinclair Lab Auditorium Lobby
(tentative) |
|
9:45
AM-11:15 AM |
Lecture 20 |
Biopolymer-Based
Nanoparticle Latexes for Industrial Applications: I. Development of
New Starch-Based Nanoparticle Latex Binders for Paper Coating
Applications |
|
11:15
AM-11:30 AM |
Coffee Break |
Sinclair Lab Auditorium Lobby (tentaive) |
|
11:30 AM-1:00 PM |
Lecture 21 |
Mixing Scale-Up in Emulsion Polymerization (Andrew Klein)
|
FEES
The fee structure for the 2012 course includes a variety of
possible discounts as described below (note that discounts cannot be combined).
|
Standard Course Tuition
|
$ 1550 |
|
"Early Bird" Discount (prior to
February 15, 2011) |
$ 1475 |
|
Multiple Participants Discount
(2 or more participants from the same company) |
$ 1400 Each |
|
EPI Industrial Liaison Member
(1st approved participant free) |
$ 0 |
| EPI Liaison Member-
2nd or Subsequent Participants |
$ 1225 Each |
| Graduate Student (needs approval) |
$ 775 |
| 1 Day Registration |
$ 700 |
| 2 Day Registration |
$ 1400 |
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, 2012 will be
honored in full. A processing charge of $650 will be deducted for cancellations after
April 16, 2012.
Click
here to download a 2012 Short Course Registration Form in Word (Windows)
format
Click
here to download a 2012 Short Course Registration Form in Rich Text Format (RTF)
(Windows) format
Click
here to download a 2012 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://www4.lehigh.edu/housing/residencehalls/az/campussquare.aspx
A processing charge of one night will be deducted for housing
cancellations after April 16, 2012.
A continental breakfast will be available to course participants at
Brodhead House
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
-
Hilton Garden
Inn at ABE Airport, 1787-B Airport Road, Allentown, PA;
610-443-1400
-
Sands Casino Resort Bethlehem, 77
Sands Boulevard
(Please use 901 Daly Ave on GPS devices)
Bethlehem, Pennsylvania 18015
* Only hotel within walking distance of the university.
ABSTRACTS OF COURSE
LECTURES:
MONDAY, JUNE 11 2012
1. Kinetics of Free Radical-Initiated Polymerization--
F. Joseph Schork (Professor Emeritus, School of Chemical & Biomolecular
Engineering, Georgia Institute of Technology )
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.
Semi-Continuous Emulsion Polymerization and Structured Latexes--
Michael F. Cunningham (Queen's University, Canada)
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.
TUESDAY, JUNE 12, 2012
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. Sensors and Control of Emulsion Polymerization Reactors--
F. Joseph Schork (Professor
Emeritus, School of Chemical & Biomolecular Engineering, Georgia
Institute of Technology)
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.
7. Glass Transition Evolution of Plasticized Latex Films: An
Important Process in the Application of Everyday Latex Paints--
James W. Taylor
(BASF Corporation)
(co-author:
Dr. Timothy Klots, BASF)
Water-borne
latex paints are used in everyday life as decorative and as
protective coatings. The application of these paints is often taken
for granted, but the drying process of latex paints involves the
evaporation of water, solvents, and the coalescence of latex
particles to a polymeric film that contains pigments, dispersants
and surfactants. A model has been developed to better under the
drying and coalescence of latex films. The temporary plasticization
of latex particles by filming aids and co-solvents is well known. A
lowering of the glass-transition (Tg) below the cure temperature is
necessary for the interdiffusion of polymer chains between
particles. The Tg evolution with time of latex films plasticized
with filming aids is modeled using fundamental equations. Both the
wet-stage and dry-stage are modeled. Fundamental equations for the
wet-film stage contain the evaporation rates, the distribution
coefficients of solvents, and wet-stage activity coefficients. The
activity coefficients of the solvents during the wet-film
evaporation are determined by measuring the minimum filming
temperature of the plasticized latex film. Solvent loss is also
modeled during the subsequent dry-stage. Activity coefficients of
solvent loss from latex films can be determined either
gravimetrically or by measuring the Tg evolution of the film as a
function of time. The influence of temperature, humidity, and
air-speed on drying is also incorporated.
The Tg
evolution of latexes formulated with Butyl CARBITOL is studied in
detail. During the dry-stage, the hardening of the film initially
follows an evaporation controlled model for solvent loss, but then
switches to a diffusion model as Tg of the film approaches ambient
temperature. Although the Tg evolution of a latex film is complex,
it will be shown that the initial Tg suppression produced by a
solvent or solvents plays an important role in selecting the optimum
solvent or solvent combination for corrosion resistance.
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 Short Course Lecturers and Participants
WEDNESDAY, JUNE 13, 2012
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. Engineering of Emulsion Polymerization Reactors--
Gary W. Poehlein (Professor Emeritus of Chemical Engineering, 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.
12. Branching and Grafting in Emulsion Polymerizations --
Peter A. Lovell (University of Manchester, UK)
Branching in polymers produced by
free-radical polymerization arises from chain transfer to polymer
and has important effects on polymer properties. In emulsion
polymerization, intermolecular chain transfer to polymer can lead to
grafting of water-soluble polymers to latex particles, facilitating
control of colloidal stability and latex rheology. Such branching
and grafting is used to good effect in the emulsion polymer industry
to control the end-use performance of latexes and emulsion
polymers. This lecture will begin with an overview of the chemistry
of
branching and grafting.
Case studies of branching in acrylate and vinyl acetate
homopolymerizations and synergistic effects in copolymerization will
then be presented , together with strategies for controlling the
level of branching. This will provide the basis for considering
grafting of water-soluble polymers used as colloid stabilizers in
emulsion polymerizations. The chemical processes which the most
commonly-used water-soluble polymers may undergo during emulsion
polymerization will be illustrated through case studies that
highlight the key principles for their control.
13. 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.
14. Advanced Research Topics in Emulsion Polymerization and Latexes: An Evening
Poster Session-- Graduate
Students in the Emulsion Polymers Institute, Lehigh University.
THURSDAY, JUNE 14, 2012
15.
Living-Controlled Radical Polymerization in Bulk, Emulsion, and
Miniemulsion--
Michael
F. Cunningham (Queen's University, Canada)
“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. 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.
18.
Multi-Phase/Multi-Component Latex Particles --
Peter A. Lovell (University of Manchester, UK)
Latex particles that
comprise two or more phases/components are important both academically and
industrially. They are used in a diverse range of applications, for example:
toughening of plastics; adhesives;
architectural coatings;
inks; controlled-release of actives; and diagnostics. This lecture will build
upon the "Semi-Continuous Emulsion Polymerization and Structured Latexes"
lecture by describing in greater detail the parameters which control the
development of particle morphology when attempting to prepare, and control the
morphology of, multi-phase latex particles in which there are two or more
polymer phases. The importance of thermodynamic versus kinetic control will be
emphasized and strategies for achieving control of morphology will be described
together with their limitations. Some examples will be given to illustrate the
principles. The focus will then switch to preparation of multi-component latex
particles in which there are both polymeric and non-polymeric materials
present. Different approaches to preparation of multi-component latex particles
will be described through examples of encapsulating non-polymeric materials,
templating of particle morphology, and synthesis of surface-functionalized
particles.
FRIDAY, JUNE 15, 2012
19. Water-Borne
Pressure-Sensitive Adhesives--
Peter A. Lovell (University of
Manchester, UK)
Pressure
sensitive adhesives (PSAs) are viscoelastic materials which adhere
to substrates on the application of slight pressure over short
periods of time. They are ubiquitous in everyday life as
self-adhesive tapes and labels used in a wide variety of
applications (e.g., bonding, signing and marking, healthcare,
automotive, electronics, furniture, security, food packaging and
retailing). Over the past few decades, water-borne PSAs based on
latexes prepared by emulsion polymerization have gained market share
at the expense of flammable, environmentally-unfriendly
solvent-borne PSAs and now comprise the largest proportion of the
overall PSA market. The growth has arisen not only because they
replace solvents with water, but also because the latexes have low
viscosity at high solids contents which brings benefits in
formulation, handling, transport and coating. This lecture will
describe the different types of PSAs before focusing on the
principle components used in preparation of acrylic water-borne PSAs
and their roles in controlling latex properties and adhesive
performance. Effects of latex particle composition/morphology,
polymer properties and branching on the performance of PSA films
will be discussed. A case study will presented to demonstrate
principles for control of adhesive performance through careful
design of structured latex particles that
determine the sub-micron and nanoscale morphology of PSA films as a
consequence of the mechanism of film formation from latexes.
20.
Biopolymer-Based Nanoparticle Latexes for Industrial Applications:
I. Development of New Starch-Based Nanoparticle Latex Binders for
Paper Coatings Applications -- Do Ik Lee (Formerly with The Dow
Chemical Company) (Co-Authors:
Steven Bloembergen,
EcoSynthetix Inc.,
Michigan, Ian J.
McLennan and John van Leeuwen,
EcoSynthetix Inc.,
Ontario, Canada)
Biobased latex
binders adopted in the paper industry in 2008 were the first use of
biopolymer-based microgels and nanogels for large-scale industrial
applications [1-12], although they had been explored and used for
drug delivery and other bio-medical applications for a long time
[13]. Both biobased latex binders and biopolymer-based microgels
and nanogels can be broadly classified as a special type of latexes
whose particles are made up of water-swollen crosslinked hydrophilic
polymers. Since the biobased latex binders currently used in the
paper industry are water-swollen crosslinked starch nanoparticles,
their wet and dry properties depend mainly on their particle size
and crosslink density. The crosslink density of starch molecules
forming the nanoparticles is especially important because it
controls the extent of water swelling (swell ratio) [3,4], that is,
as the crosslink density increases, the swell ratio of crosslinked
starch nanoparticles decreases. Varying swell ratios of the
water-swollen starch nanoparticles not only set them apart from
conventional starches and synthetic latexes in their rheological
behavior, but also differentiate themselves in paper coating
performance. Their unique rheological behavior and paper coating
performance will be discussed based on theoretical considerations as
well as some laboratory testing, pilot coater and mill trial
results.
Starch-based
biopolymer nanoparticle latexes were developed in the early 2000s
for industrial applications by two patented processes: Continuous
Reactive Extrusion Process [14] and Inverse Emulsion Process [15].
The current biobased latex binders are manufactured by a continuous
reactive extrusion process comprising of solubilizing starch
granules, i.e. converting the very high-solids starch paste into a
thermoplastic melt phase, and then crosslinking and sizing the
solubilized starch molecules into nanoparticles [14]. The resulting
product from the extruder is nearly dry agglomerates of crosslinked
starch nanoparticles which are subsequently pulverized as a final
powder product. This process was thought to be a good way to
disperse TiO2 particles uniformly and associate them with
starch nanoparticles. This is how we have developed a new
brightness grade of biobased latex binders. The performance of this
new biobased latex binder grade will be discussed in terms of the
brightness and opacity of paper coatings [8, 11-12].
The current biobased
latex binders are cured by using glyoxal-type curing agents (starch
insolubilizers) to improve their wet strength in coated paper and
paperboard applications. Although such curing agents have been
found to be adequate up to about 35% replacement of synthetic
latexes for paper coatings, it was thought that polymeric curing
agents could be more effective for particulate binders such as our
biobased latex binders that consist of crosslinked biopolymer
nanoparticles. Preliminary results will be discussed in terms of
the substitution levels of synthetic latexes in base and top
coatings as well as in single coatings [11].
Finally, the
reduction in carbon footprint and green house gas emissions that
results from the use of biobased latex binders will be discussed by
comparing starch-based latex binders with petroleum-based synthetic
latex binders [8, 11, 16-18].
REFERENCES
-
van Leeuwen, J., “Paper
Coating - SBR Latex Replacement Technology”, 2006 TAPPI Coating
and Graphic Arts Conference, Atlanta, GA., April 2006.
-
Klass, C. P., “New
Nanoparticle Latex offers Natural Advantage”,
Paper360°Magazine, p. 30-31, January 2007.
-
van Leeuwen, J.,
“Update on Biopolymer Nanoparticle Latex Development and
Applications”, 2007 TAPPI Coating and Graphic Arts Conference,
Miami, FL., April 22-25, 2007.
-
Bloembergen, S.,
McLennan, I., Lee, D. I., and van Leeuwen, J., “Paper Binder
Performance with Nanoparticle Biolatex™:
EcoSynthetix
develops EcoSphere®
biolatex for replacement of petroleum based latex binders”, ACFS,
Montreal, June 11-13, 2008.
-
Bloembergen, S., McLennan, I. J., Lee, D. I., and van Leeuwen,
J., “Paper binder performance with biobased nanoparticles. A
starch-based biolatex can replace petroleum-based latex binders
in papermaking”, Paper360ºMagazine, 46-48, Sept. 2008.
-
Figliolino, F.C., Rosso, F., van Leeuwen, J. and Klass, C.P.,
“Mill Experiences with Biolatex in Brazil”, 2009 TAPPI PaperCon
Proceedings, Section 19-1, 2009.
-
Figliolino, F.C. and Rosso, F., “Reducing Carbon Footprint with
Biolatex”, Paper360ºMagazine, 25-28, Aug. 2009.
-
Bloembergen, S.,
VanEgdom, E., Wildi, R., McLennan, I.J., Lee, D.I. Klass, C.P.,
and van Leeuwen, J., "Biolatex Binders for Paper and Paperboard
Applications", presented at 7th International Paper and Coating
Chemistry Symposium, McMaster, June 2009; Accepted for
publication in Journal of Pulp and Paper Science (JPPS)
on Nov. 26, 2010 to appear in Volume 36, No 3-4, 2011.
-
Bloembergen, S.,
VanEgdom, E., Wildi, R., McLennan, I. J., Lee, D.I., Klass, C.
P. and van Leeuwen, J., "New Biolatex Binders Based on
Biopolymer Nanoparticles" presented by D. I. Lee, 2009 PTS
Nanotechnology Seminar in Munich, Germany, April 21-22, 2009.
-
Lee, D. I.,
Bloembergen, S., and van Leeuwen, J., “Starch-Based Biopolymer
Nanoparticle Latexes for Industrial Applications,” The 3rd Asian
Symposium on Emulsion Polymerization and Functional Polymeric
Microspheres, September 20-23, 2009, Jeju Grand Hotel, Jeju,
South Korea.
-
Lee, D. I.,
Bloembergen, S., and van Leeuwen, J., “Development of New
Biobased Emulsion Binders,”
Presented at PaperCon 2010, “Talent, Technology
and Transformation,” Atlanta, GA, May 2-5, 2010.
-
12.
Lee, D. I., Bloembergen, S.,
McLennan, I. J., and van Leeuwen, S., “Biopolymer-Based
Nanoparticle Latexes for Industrial Applications: I. Development
of New Starch-Based Nanoparticle Latex Binders for Paper Coating
Applications”, Chapter 1 in a book (in press) entitled “Emulsion
Polymerization and Functional Polymeric Microspheres – Science
and Technology” based on “The
3rd Asian Symposium on Emulsion Polymerization and Functional
Polymeric Microspheres (ASEPFPM)” held in September
20-23, 2009, Jeju Grand Hotel, Jeju, South Korea.
-
Oh, J. K.,
Lee, D. I.,
and Park, J. M., “Biopolymer-based microgels/nanogels for
drug delivery applications”, Progress in Polymer Science
34, 1261–1282, 2009.
-
Giezen, F., Jongboom, R. O. J., Feil, H., Gotlieb, R .O. F. and
Boersma, A., “Biopolymer Nanoparticles”, U.S. Patent 6,677,386,
2004; Wildi, R. H., VanEgdom, E., and Bloembergen, S.,
“Process for Producing Biopolymer Nanoparticles”, U.S. Patent
Application 60/837,669, 2006.
-
Van Soest, J. J. G., Stappers, F. H. M., Van Schijndel, R. J.
G., Gottlieb, K. F., and Feil, H., “Method for the preparation
of starch particles,” US Patent No. 6,755,915, June 29, 2004.
-
Narayan, R. “Biobased and Biodegradable Materials, Rationale,
Drivers, & Technology Exemplars”, ACS (An American Chemical
Society Publication) Symposium Ser 939, Ch. 18, pg 282, 2006.
-
Narayan, R. “The Promise of Biobased and Biodegradable Polymer
Materials in Paper & Paperboard Products - Reducing Carbon
Footprint and Improving Environmental Performance”TAPPI
(Technical association of the Pulp & Paper Industry) Conference
Proceedings PaperCon09, 2009.
-
International Standards Organization, ISO 14064-2:2006,
Greenhouse Gases - Part 2: Specification with guidance at the
project level for quantification, monitoring and reporting of
greenhouse gas emission reductions or removal enhancements.
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.
LECTURERS:
Michael F. Cunningham--
Associate Professor within the
Department of Chemical Engineering, Queen’s University, Kingston, Ontario,
Canada. He received his Ph.D. in
1990 from the University of Waterloo where he studied chemical engineering with
Prof. K.F. O’Driscoll. Prior to his joining Queen’s University, he was with
the Xerox Research Centre of Canada for six years.
While there he conducted research into the design of composite polymer
particles. He was co-inventor of a
novel composite particle that is now a critical component of the xerographic
developer in Xerox copiers and printers. This work has led to 25 U.S. patents.
Among his research interests are the areas of polymer reaction
engineering, emulsion/miniemulsion polymerization, and living radical
polymerization.
Mohamed S. El-Aasser--Vice
President for International Affairs, Lehigh University, and formerly Provost,
Lehigh University; Professor of Chemical Engineering. Ph.D. from
McGill University and Pulp and Paper Research Institute in 1972. Research interests
include emulsion polymerization, emulsification, surface and colloidal properties of
latexes, latex film formation, adsorption from solutions, and stabilization of
colloids.
Andrew Klein-- Professor of Chemical Engineering, Lehigh University. Ph.D. in
Chemical Engineering from North Carolina State University at Raleigh. Industrial
experience in emulsion polymers with GAF and National Starch and Chemical Company.
Research interests include colloid and surface chemical aspects of heterogeneous
polymerization kinetics, related thermodynamics, engineering and applications.
Do Ik Lee--
B.
S. degree in Chemical Engineering from
Seoul
National
University
in 1959 and both M. S. and doctoral degrees in Chemical Engineering from
Columbia
University
in 1964 and 1967, respectively. Currently, Adjunct Professor in the Department
of Paper and Printing Science Engineering at Western Michigan University and a TAPPI Fellow. Formerly, Senior
Scientist in Emulsion Polymers R&D at The Dow Chemical Company for 35 years.
His research interests are latex technology, emulsion polymerization, structured
latex polymerization, controlled free-radical emulsion polymerization, solid and
hollow plastic pigments, paper coating technology, paper chemistry, colloid
science, particle packing, dispersion rheology, and associative alkali-soluble
latexes. He holds 28
U.S.
patents.
Peter A. Lovell--Professor
of Polymer Science in the School of Materials at The University of
Manchester in the United Kingdom. He was founding Chairman of the UK
Polymer Colloids Forum, which was established in 1993, and was
Chairman of Macro Group UK from 2004-2007. His research focuses
mainly around aspects of emulsion polymerization and related
processes. Prominent in this research has been synthesis of
core-shell and multi-layer particles (for applications in toughening
plastics and as soft adhesives) and studies of the chemistry (and
extent) of branching and grafting, including grafting to
water-soluble polymeric colloid stabilizers. Recent research
includes a novel chemistry for room-temperature crosslinking during
latex film formation, synthesis of new nitroxides for use in
controlled miniemulsion polymerization, development of click
chemistry for latex particle functionalization and the lead role in
a European collaborative research programme for development of
high-performance water-borne pressure-sensitive adhesives.
Gary W. Poehlein--
Professor Emeritus of Chemical Engineering, Georgia
Institute of Technology. Ph.D. in Chemical Engineering from
Purdue
University. Industrial experience with the Procter and Gamble
Company. Research interests include kinetics of emulsion polymerization and
continuous reactor systems.
F. Joseph Schork--
Professor and Chair, Department of Chemical and Biomolecular
Engineering, University of Maryland. Ph.D. in Chemical Engineering from the University of Wisconsin working in the
field of emulsion polymerization reactor dynamics. Industrial experience with E.I. DuPont
de Nemours & Company in the areas of emulsion polymerization and digital process
control. Research interests in polymerization reaction engineering, digital control of
polymerization reactors, system dynamics and nonlinear control. Consultant to various
companies in the area of polymerization reaction engineering.
Cesar A. Silebi-- Professor of Chemical Engineering at Lehigh
University. Ph.D. from Lehigh University. Research interests include particle
separation processes, rheological and colloidal properties of latexes,
multi-component transport in emulsions, and stability of colloidal systems.
James W. Taylor--received
his Ph.D. Degree in Chemistry from the University of Tennessee in
1982, after which he joined Union Carbide Corporation. He was
appointed principal Scientist 2011 and currently serves as the
senior research scientist in the Emulsion Research group for BASF
located in Wyandotte, MI. Dr. Taylor’s current interests include
crosslinking technology, emulsion design, and film formation.
List of companies/Universities who have
participated in the short course over the past 5 years
| Arkema Inc |
Ashland Inc. |
| Asian Paints |
|
| Avery Dennison |
Baker Petrolite |
|
Bangkok Synthetics |
Bangs Labs |
|
Barrday Inc. |
BASF Corporation |
| Benjamin Moore & Co. |
Bioarray Solutions |
| Casco Adhesives AB |
Celanese |
| Centro de Inestigacion en Polimeros |
Cheil Industries |
| Chemicals Research Institute |
Cognis Corporation |
| Colorquimica SA |
Commercial Mexicana de Pinturas
SA |
|
ConocoPhillips |
Corporacion Peruana de
Productos Quimicos |
| Cytec |
CoatingSys |
|
Coopervision Inv. |
|
| Dai-Ichi Kogyo Seiyaku |
Dade Behring |
| Dai Nippon Toryo Co. |
Denver Resins |
|
DOW Chemical |
Dow Reichold Specialty Latex |
| DuPont |
Dynalene Heat Transfer |
|
Emerald Performance Materials |
Essential Industries |
|
454 Life Sciences |
Formosa Plastics Corp. |
|
Franklin International |
Gelie Co. Ltd. |
|
General Electric Co. |
Gorilla Glue Co. |
|
Grain Processing Corp. |
H.B. Fuller |
|
Hanwha Chemical |
Hansol Chemical |
|
Henkel |
Hercules |
|
Hewlett Packard Co. |
Hexion Specialty Chemicals |
|
Isolatek International |
James Hardie Building
Products |
| Kemtec |
E. Kerwin Kolinek Consulting |
| Kumho Petrochemical |
Lanxess |
|
LG Chemical Ltd. |
Lexmark
International |
| Lintec Corp. |
Lubrizol Corp |
| Luminex Corp. |
Mapei |
| Mica Corporation |
|
| 3M |
Momentive Specialty Chemicals |
| NanoMR |
|
| NASA |
Nipsea Technologies |
| Nitto Denko Japan |
Noveon |
| Omnova Solutions |
Pegatex |
| Pidilite Industries |
|
| PPG Industries |
Queen's University |
| Reichold Inc. |
Rhodia |
|
Samsung |
|
|
Renner
Sayerlack |
Rohm
and Haas Co. |
|
Samsung Cheil |
Samsung Fine Chemicals |
|
Sealy |
Seradyn
Inc. |
| Siemen's Healthcare Diagnostics |
Solucor |
|
Stanchem Inc. |
Starquim |
| Teknoquimica SA |
ThermoFisher Scientific |
| University of Hamburg |
University of Maryland |
| University of Toronto |
The Valvoline Co. |
| Wacker Polymer Systems |
Xerox Corporation |
| Yonsei University |
Zeon Chemicals |
| |
|
|
|
|
|
 |
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