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Tranimit S) :: Sciincevmmokrbbig - 4K, Liersitneuvitr""1
Tranimit S) :: Sciincevmmokrbbig - 4K, Liersitneuvitr""1
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Pro j ect' i99 Cost share #: E-19-346 Rev #: 0
Center # : R6430-0A0 Center shr 11: F6430-0A0 OCA file #:
Work type : RES
Contract#: CBT-8717926 Mod #: Document : GRANT
Prime 4/: Contract entity: GTRC
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GEORGIA INSTITUTE OF TECHNOLOGY
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Gary W. 1cehlein
Associate Vice President
for Graduate Studies and Research
GWP : sd
Enclosures
admitted to:
of Thermal Engineering
submitted by:
November 9, 1988
(2) Two other doctoral students joined the program; David Lange
and Paul Thumer.
An Equal Education and Employment Opportunity institution A Unit of the University System of Georgia
Thank you for the consideration of this request. Please let me know
if you need any other information.
Sincerely,
rr
Gary W. Poehlein
Associate Vice President and
Dean of Graduate Studies
Enclosure
Lynn Boyd
Contracting Officer
ANNUAL REPORT
NATIONAL SCIENCE FOUNDATION
submitted to:
of Thermal Engineering
submitted by:
PERSONNEL:
PUBLICATIONS:
(1) Two doctoral students, Richard Mead and Zhigiang Song, com-
pleted PhD dissertations; a third, Glenn Shoaf, will complete his
PhD in December 1989.
An Equal Education and Employment Opportunity . Institution A Unit of the University System of Georgia
Of course, not all of these students were supported on my NSF grant, but it
is the keystone. Further details on the students, publications and research
results are provided in the attached annual report.
Thank you for the consideration of this request. Please let me know
if you need any other information.
Sincerely,
■••■••...
Gary W. Poehlein
Associate Vice President and
Dean of Graduate Studies
7
Lynn Boyd
Contracting Officer
Enclosure
submitted to:
of Thermal Engineering
submitted by:
PERSONNEL:
PUBLICATIONS:
12. "Free Radical Transport from Latex Particles," Richard Mead and Gary
Poehlein, J. Appl. Polym. Sci., 38, 105-122 (1989).
The most important contribution during the first two years of this
grant has been the education of students. Two students have received
PhD's and a third will complete all doctoral degree requirements in late
4
1989. Three doctoral students are in earlier stages of their graduate edu-
cation and dissertation research. Five of these six students are U.S. citi-
zens. The research group has also included three visiting scholars and one
undergraduate student. Obviously not all of these students and scholars
have been supported by funds in the Grant No. CBT-8717926. The NSF
grant, however, represents the centerpiece of my research support struc-
ture. It is the glue that holds the pieces in place.
Research progress during the first year of the grant was focussed on
the following major issues in emulsion polymerization technology.
• Particle nucleation
• Copolymerization in continuous reactor systems.
More details concerning this work was a part of the progress report sub-
mitted in November 1988 and in some of the publications listed in this
report.
The research during the current year has involved emulsion copoly-
merization with functional, water-soluble, monomers and vinyl acetate
emulsion polymerization in the presence of polyvinylalcohol. Glenn Shoaf
is in the final stages of his doctoral dissertation which is concerned with
the copolymerization of carboxylic acids and styrene. The acid monomers
are completely water soluble and hence behave very different from the
hydropholic monomers which are normally used in emulsion polymeriza-
tion reactions. Mr. Shoaf's work included:
Future work, during the next year, will continue the above projects
and increase efforts in other areas such as dispersion polymerization in
non-aqueous media and the kinetics of branching and grafting reactions.
The development of more fundamental understanding of these phenomena
will help to enhance present polymerization processes and to develop new
systems.
OMB Number 345-0058
5. Award Number
CBT - 8717926
6. Project Title
Emulsion Polymerization Kinetics
PART II
SUMMARY OF COMPLETED PROJECT / AWARD # CBT-8717926
P.I.: Gary Poehlein, Georgia Institute of Technology
Project Title: Emulsion Polymerization Kinetics
Emulsion polymerization is a major industrial process used for the production of synthetic
rubbers, plastics and environmentally desirable water-based coatings and adhesives. The primary
objective of this project was to develop a more complete understanding of the fundamental reaction
mechanisms and kinetics of emulsion copolymerization when one monomer has significant water
solubility. The research involved theoretical modeling of batch, semi-batch and continuous
reactors. The utility of these models has been demonstrated with experimental studies involving
five copolymer systems with styrene and comonomers of differing water solubilities such as
methyl acrylate and acrylic acid.
The combination of mathematical modeling and carefully designed experiments has led to a
better quantitative understanding of: (1) the distribution of various ingredients among the various
phases and interfaces in the reaction system, (2) the transfer of active free radicals between the
aqueous and organic phases, and (3) the rates of polymerization in the continuous and disperse
phases. This increased knowledge base has placed in the hands of other researchers and industrial
workers an enhanced ability to define future research and to develop commercial products and
processes.
Attachment 2
PART III
TECHNICAL INFORMATION / AWARD # CBT-8717926
P.I.: Gary Poehlein, Georgia Institute of Technology
Project Title: Emulsion Polymerization Kinetics
The results of the research conducted under CBT-8717926 have been made available to the
external community via a number of accepted mechanisms: (1) publications in the archival
literature; (2) symposium presentations; (3) seminars; (4) professional consulting and, last but not
least, (5) generation of educated professionals in an important field. Documentation of
contributions in these area are provided in the remainder of this section.
(1) Publications during Grant Period:
1. "Particle Formation in Emulsion Polymerization: Transient Particle Concentration," with Z.
Song, J. Macromol. Sci.-Chem., A25(4), 403-443 (1988).
2. "Particle Formation in Emulsion Polymerization: Particle Number at Steady State," with Z.
Song, J. Macromol. Sci-Chem., A25(12), 1587-1632 (1988).
3. "Emulsion Copolymerization of Styrene-Methyl Acrylate and Styrene-Acrylonitrile in
Continuous Stirred-Tank Reactors (I)," with Richard Mead, I&EC Research, 27(12), 2283-93
(1988).
4. "Emulsion Copolymerization of Styrene-Methyl Acrylate and Styrene-Acrylonitrile in
Continuous Stirred-Tank Reactors (II), Aqueous-Phase Polymerization and Radical Capture,"
with Richard Mead, I&EC Research, 28(1), 51-57 (1988).
5. "Emulsion Polymers/Emulsion Polymerization," with F. J. Schork, Polymer News, la, 231-
40 (1988).
6. "Batch and Continuous Emulsion Copolymerization of Ethyl Acylate and Methacrylic Acid,"
with Glenn Shoaf, Polym.-Plast. Technol. Eng., 28, No. 3, 289-327 (1989).
7. "Free Radical Transport from Latex Particles," with Richard Mead, J. Appl. Polym. Sci.,
105-122 (1989).
8. "Particle Nucleation in Emulsifier-Free Aqueous-Phase Polymerization: Stage 1," with Z.
Song, J. Coll. Interface Sci., 121, No. 2, 486-500 (1989).
9. "Particle Formation in Emulsifier-Free Aqueous-Phase Polymerization of Styrene," with Z.
Song, J. Coll. Interface Sci., 128. No. 2, 501-510 (1989).
10. "Emulsion Copolymerization in Continuous Reactors," with D. M. Lange, G. Shoaf and R.
N. Mead, Proceedings of International Conference, Polymer Latex III, London (June 1989).
11. "Kinetics of Emulsifier-Free Emulsion Polymerization of Styrene in the Presence of Chain
Transfer Agents," with Z. Song, Polym.-Plast. Technol. Eng., 29(4), 377-405 (1990).
12. "Polymerization in Non-Uniform Latex Particles II: Kinetics of Two-Phase Emulsion
Polymerization," with C.-S. Chern, J. Polym. Sci., Part A, Polym. Chem., 28, 3055-3071
(1990).
13. "Polymerization in Non-Uniform Latex Particles III: Kinetics of Grafting in Emulsion
Polymerization," with C.-S. Chern, J. Polym. Sci., Part A, Polym. Chem., 211, 3073-3099
(1990).
14. "Partition of Carboxylic Acids in an Emulsion Copolymerization System," with G. L. Shoaf,
I&EC Research 22, 1701-1709 (1990).
15. "Kinetics of Crosslinking Vinyl Polymerization," with C.-S. Chern, Polym.-Plast. Technol.
Eng., 29(5&6). 575-589 (1990).
16. "Kinetics of Emulsifier-Free Emulsion Polymerization of Styrene," with Z. Song, J. Polym.
Sci., Part A, Polym. Chem., a, 2359-2392 (1990).
17. "Kinetics of Emulsion Copolymerization with Acrylic Acids," with G. L. Shoaf, J. Appl.
Polym. Sci., 42:5, 1213-1238 (1991).
18. "Solution and Emulsion Polymerization with Partially Neutralized Methacrylic Acid," with G.
L. Shoaf, J. Appl. Polym. Sci., 42:5, 1239-1258 (1991).
19. "Kinetic Analysis of Seeded Emulsion Polymerization of Vinyl Acetate," with David M.
Lange, Sadao Hayashi, Akihiko Komatsu and Toshihiro Hirai, J. Polym. Sci., Part A,
Polym. Chem., 29, 785-792 (1991).
(5) Students:
Students listed below have received some support from Grant CBT-8716926:
(1) Richard Mead (PhD 1987) - Currently with American Cyanamid.
(2) Z. Song (PhD in 1989) - Currently with Guertin Bros. Coating and Sealant Ltd.
(Canada).
(3) Glenn Shoaf (PhD 1989) - Currently with Tennessee Eastman Co.
(4) David Lange (PhD 1991) - Accepted position with Ameripol Synpol (Uniroyal-Goodrich)
(5) Xizhen Qian (Visiting Scholar) - Currently on Faculty of Tianjin Institute of Technology,
PRC.
(6) - (12) Kevin Fontenot (PhD Cand.), Paul Thurner (PhD Cand.), Cheryl Matthews-
Gilmore (PhD Cand.) Pei Yang (PhD Cand.), 0. Badmus (PhD Cand.), Ganti
Sriniwas (MS Cand.), and Chris Durden (UG) - Currently students at Georgia
Tech.
FINAL TECHNICAL REPORT / AWARD CBT-8717926
P.I.: Gary W. Poehlein / Georgia Institute of Technology
Project Title: Emulsion Polymerization Kinetics
INTRODUCTION
The major goals of the Polymerization Engineering Research Program directed by Gary
Poehlein are:
(2) Expand the fundamental knowledge base in the general area of heterogeneous free-
radical polymerization reactions.
The remainder of this report includes a summary of progress achieved during the period of Grant
CBT-8717926 in each of these "goal" areas.
STUDENTS
The students involved in polymerization research who have received financial support of
some form from the subject grant are listed below along with degrees received and current status.
Students listed below have received some support from Grant CBT-8716926:
(2) Z. Song (PhD in 1989) - Currently with Guertin Bros. Coating and Sealant Ltd.
(Canada).
(3) Glenn Shoaf (PhD 1989) - Currently with Tennessee Eastman Co.
(4) David Lange (PhD 1991) - Accepted position with Ameripol Synpol (Uniroyal-Goodrich)
(5) Xizhen Qian (Visiting Scholar) - Currently on Faculty of Tianjin Institute of Technology,
PRC.
(6) - (12) Kevin Fontenot (PhD Cand.), Paul Thurner (PhD Cand.), Cheryl Mathews-
Gilmore (PhD Cand.) Pei Yang (PhD Cand.), 0. Badmus (PhD Cand.), Ganti
Sriniwas (MS Cand.), and Chris Durden (UG) - Currently students at Georgia
Tech.
RESEARCH RESULTS
Brief descriptions of research results are provided in the remainder of this section.
1. Kinetics in Continuous Reactors:
The study of emulsion polymerization in continuous reactors has been an active interest of
the Principal Investigator for a period of years. These studies have resulted in a better
understanding of fundamental mechanisms and kinetics and have helped industrial scientists and
engineers design more effective processes to produce commodity and innovative specialty latexes.
Recent efforts have involved copolymerization with water-soluble monomers in a reactor system
comprising a tubular prereactor followed by a series of two CSTRs. The focus of the work
involves measurement of reaction rate, particle size distribution, composition of the copolymer
formed in each reactor, and molecular weights. These measurements permit evaluation of kinetic
parameters such as radical desorption coefficients and monomer cross-transfer reaction rate
constants.
The reactor system is designed to permit variation of feed introduction location. Hence,
portions of recipe components can be added downstream of the tubular prereactor to control
copolymer composition, solids concentration, particle size distribution and particle morphology.
Past copolymerization work involved styrene-methyl acrylate and styrene-acrylonitrile systems.
Present research involves copolymerization with water-soluble monomers such as acrylic and
methacrylic acid. The results of this research will permit a more rational design of commercial
reactors and help to increase our understanding of the important relationships between reactor
design and operation and product quality parameters.
Future work with continuous reactors will involve studies of grafting reaction kinetics,
morphology of the latex particles and molecular microstructure from copolymerization reactions,
the use of functional monomers that are water soluble, and dispersion copolymerization. A more
detailed knowledge of these phenomena is important for the operation and modification of present
processes and especially for the development of new products and processes.
2. Nonuniform Latex Particles:
Reaction kinetic theories for emulsion polymerization have almost all been based on the
assumption that the various reagent species are uniformly distributed (except for stochastic
variations) within the monomer-swollen polymer particles. Grancio and Williams (.I. Polym.
Sci.:A-1, 8, 2617 (1970)) suggested a nonuniform monomer distribution with a monomer-rich
shell but their model has been challenged by other workers. In addition, the experimental results
of Grancio and Williams can be explained without resorting to arguments based on a monomer-rich
shell.
Our work has been concerned with the distribution of free radicals in latex particles. Most
emulsion polymerization systems employ water-soluble initiator which generate oligomers in the
aqueous phase. These oligomers have hydrophilic and often ionic end groups. When such free
radicals penetrate the monomer-swollen latex particles, the end groups would have a very strong
tendency to remain at or near the surface, at least during the short active life of the radical. The free
radical end of the oligomer could move into the particle by diffusion or monomer propagation.
We have made calculations of free radical distributions in a lattice model of a latex particle.
These calculations predict a significant nonuniformity in the radial distribution of free radicals.
This phenomena is quite important because it can effect polymerization kinetics, grafting reactions
and particle morphology.
We have used this concept of a nonuniform radical distribution to model grafting reactions.
Initial results are very promising and this work will continue. Future efforts will also be aimed at
studying the development of particle morphology. Being able to predict and control particle
structure is a key factor in developing new and innovative latex products.
3. Particle Nucleation:
Particle concentration and size distribution are very important latex characteristics. They
influence rheology and, in many cases, application performance. The ability to control particle
number and size characteristics is, therefore, essential for the development and manufacture of
most latex products. Work in the areas of nucleation theory and particle number control was the
subject of Dr. Song's Ph.D. dissertation and is being considered in Ms. Gilmore's work on VAc
polymerization in the presence of PVOH stabilizer.
Song's work included nucleation theory and experiments with and without added
emulsifier. The results of his work have enhanced our knowledge of particle nucleation with
conventional emulsion polymerization recipes and in emulsifier-free systems.
Future work will include studies of particle number control efforts for semi-batch systems.
Cheryl Matthews-Gilmore (Ph.D. candidate) is involved with this project which includes
collaboration with Air Products and Chemicals, Inc. Systems employing steric stabilizers are
being studied. Grafting reactions with the stabilizer can contribute to particle formation in such
systems.
4. Acid Monomers:
Functional monomers such as those with carboxyl groups are often used as minor
ingredients in emulsion polymerization. Such monomers can help stabilize the particles and
improve application performance. We have completed a process development research study with
ethyl acrylate-rnethacrylic acid comonomers in which up to 78 mole % of the water-soluble
monomer, MAA, was used. The fact that typical, nonviscous latexes with very little water-soluble
polymer were formed was somewhat surprising.
The extension of this work to styrene recipes with smaller amounts of acid monomer was
the subject of G. Shoaf's and D. Lange's Ph.D. dissertations. Their work has helped to show
how reactions in the continuous phase can contribute to the overall process. Experimental work
and reaction modeling considered the distribution of reagents in the various phases and the
corresponding reactions. The relative rates of reaction of the different monomers was studied as
was the influence of partial neutralization of the acid monomer. Future work on the nature of the
copolymer molecules formed (i.e., blockiness) represents an important extension of Shoaf's and
Lange's work. A greater understanding of what is happening in the continuous phase is needed.
TECHNOLOGY TRANSFER
Communication of the research results of others has involved the standard mechanisms of
published papers, oral presentations, consulting and the employment of graduates by industries
and universities. Documentation of these activities are included in the standard NSF Final Project
Report -- Form 98A.
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