CHE 543

Introduction
Course Notes
Prof Alexander Penlidis
Dept of Chem Eng
Univ of Waterloo. Waterloo ON N2L 3G1
Tel: 519 888 4567 ext 36634
E-mail: [email protected]

Copyright: A. Penlidis, 2017

This copy is for individual use only in connection with this course.
It may not be resold or used to make additional copies
 Intro: Course Title/Keywords
• Polymer Production: Polymer Reaction
Engineering (PRE)

• Polymerization and Polymer Properties

• Polymer Reaction Engineering (PRE) and

Modern Polymer Production Technology

2
 Intro: PRE Overview
• Comprehensive PRE covers the following topics:
1. BASIC CONCEPTS/DEFINITIONS
2. BASIC PRINCIPLES OF POLYMER MOLECULAR WEIGHTS
Distributions/Average Molecular Weights (MW)/Moments of MW Distribution (MWD)
3. PRACTICAL ASPECTS OF MOLECULAR WEIGHT MEASUREMENTS (Polymer
Characterization) Membrane Osmometry/(Laser) Light Scattering/Solution
Viscometry/Gel Permeation Chromatography (GPC, SEC, HDC, …)
4. STEP GROWTH POLYMERIZATION (Polycondensation)

5.* CHAIN GROWTH POLYMERIZATION (Free-radical/Ionic/Controlled free-radical/…)

Homo-polymerization (polym)/Co- and Ter-polym/Rate Expressions/MW
Development/Branched and Crosslinked Systems/Reactor Design and Production
Optimization Considerations
6.* EMULSION POLYMERIZATION (Heterogeneous Multiphase/Dispersion/…)
7.* IONIC AND COORDINATED POLYMERIZATIONS (can also be covered under 5)
8.* POLYMER PROPERTIES (material interspersed in all previous parts)

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 Intro: PRE Overview
• Parts 1- 4 from slide 3 are usually studied in an
introductory course that covers the interface between
basic Polymer Science/Polymer Chemistry/ Polymer
Technology and PRE
• Parts 5-8 (the *-ed parts) of slide 3 are more hard-core
PRE (interface between Chemical Reaction (Rxn)
Engineering and polymerization reactors)
• Need PRE to produce the appropriate polymer but also
to impart the appropriate micro-molecular (micro-
structural) properties to the polymer molecule

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 Intro: PRE Overview
• Why need PRE?
• If the polymer molecule (polymeric material that
you sell to the customer) has the appropriate
micro-structure, then you can facilitate
considerably what follows
• What does follow? Polymer Engineering (a
generic term to study polymer mechanical
properties), Polymer Rheology (flow of polymer
melts), and (Reactive) Polymer Modification (e.g.,
to change properties or produce
nanocomposites)

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 Intro: PRE Overview
• The items (topics) of the last bullet from slide 5
constitute Polymer Processing and Application
Properties of Polymers (for a wealth of
applications)
• But basis?
• PRE! PRE is the ‘glue’ between different ‘sub-
disciplines’ that study polymeric materials!
• Polymeric materials? Today referred to as nano-
materials or innovative materials or advanced
materials! Rediscovery of old terms!
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 Intro: PRE Overview
• Understand the basic principles of PRE; then you
have many general tools at your disposal to tackle
a plethora of diverse problems in advanced
material design and production!
• PRE with additional tools from ‘Polymer
Characterization’ relate ‘Polymer Production’ to
‘Structure-Property Relationships’ (SPR)
• Be generalists with a strong technical
background! Only then can you be
innovative/creative! Subsequently, easier to
become specialists!

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Polymers are everywhere!

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Physical state trends with molecular weight

Polyethylene is essentially a large homologue of

methane.
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 Overall Objectives/Targets
• Bamford et al. (1958): "The ultimate aim of the
chemist (kineticist) is to deduce the absolute (?!)
values of the individual velocity coefficients, to
express them in Arrhenius form, to obtain the
activation energies and frequency factors, and to
relate these quantities to the chemical structure
of the reacting entities".
• Polymer Sci/Tech: Many advances in the last 100-
120 yrs or so (Goodyear, Mayo, Flory,
Stockmayer,…and DuPont, Dow, BASF, Bayer,
Union Carbide, Uniroyal, Exxon…)

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 Overall Objectives/Targets
• How about PRE, Polymer Characterization and
Polymer Processing?
• Relatively new (last 50 yrs)
• Chemical Reaction Engineering, Physico-Chemical
Analytical Techniques and Rheology are, of
course, not new. But their synthesis in
PRE/Polymer Processing/Reactive Modification
is!
• Subject taught in universities?
• ‘New’ jargon?

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NSF meeting on Nanotechnology (circa 2005)

“Those who are involved with this new (?) nanotechnology,

almost without exception, seem to ignore the massive
amount of fundamental knowledge about polymer
nanoparticles and how such particles can be economically
produced with controlled processes and end-product
properties . . . you might see what is happening . . . in fields
such as electronics, optics, inorganic coatings, cosmetics, etc. .
. . Maybe some of your old expertise in latexes can become
new again”!

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 PRE development?

• Revival in 1990s (materials revolution)

– New “technological” advances (physics,
microelectronics) have given us improved “probes”
(equipment) to characterize and understand “detailed
structure” and “properties”
– (Also, reduced analysis time!)

• From Process Engineering to Product Development

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 Overall Objectives/Targets
• What are the AIMS of the chemical engineer
involved with polymer reactor engineering
and polymer production technology (i.e., CHE
543)?

• To DESIGN and OPTIMIZE/CONTROL polymer

reactor systems for the ECONOMIC/ SAFE/
(‘GREEN’) production/use of polymers
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 Overall Objectives/Targets
• The two fields are largely complementary:

• POLYMER SCIENCE/TECHNOLOGY (CHE 541) and

‘POLYMER ENGINEERING’ (CHE 543)
• (Will review very quickly basic aspects of CHE 541)

• FINAL AIM:

Efficient polymer reactor/polymer process & product (in

general) Design; Troubleshooting; Optimization; Control

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 Some facts to keep in mind
• From conventional petrochemical plants to polymer
processing, important job multiplier effect

• For instance, jobs per 100 KT of ethylene (last 30 yrs):

25 (ethylene production)
700 (stage 1 derivatives; VCM, Sty, EO, …)
2000 (stage 2 derivatives; PE, PVC, PS, S(N)BR, …)
35000 (stage 3 derivatives; films, fibers, bottles, pipes,
paints, medical devices, …)

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Some facts to keep in mind (cont’d)
• Major survey within ACS (circa 1998-2000);
ACS has about 35,000+ members:

30% of all chemical engineers and chemists are

employed by polymer industry

80% of all chemical engineers and chemists will

have worked with polymers during their
professional careers
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 Research Trends
• Biology/Polymer Science/Health Science/Bio-plastics/Water
soluble polymers/Controlled drug release
• Catalysis
• CFD/Fluid mechanics
• Colloidal systems/Surfaces/Interfaces
• Conductive polymers (plastics)
• Coatings- new applications for corrosion control, composites
and fibers, films, protective coatings
• Electronics- organic chips, light emitting diodes, nanofibers,
smart materials, conductive adhesives and inks
• ‘Sensors’

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 Research Trends (cont’d)
• Controlled radical polymerizations
• Crosslinked networks/Polymer gels/Branched architectures
• High temperature polymerizations/Processing
• Microporous media
• Multicomponent systems/Membranes
• Multiphase systems (reaction + separation)
• Nano-structured polymers
 Advanced polymer coatings (incl. water-based latex) for
architectural and anti-corrosion applications
 Micro- and nano-capsules for controlled drug release
applications

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 Research Trends (cont’d)

• Nano-structured polymers (cont’d)

 Molecularly imprinted polymers
 Polymeric sensors
• Reactive modification/ Supercritical conditions
• Thin films
• Advanced mathematical tools/ Simulation/ High throughput
tools/ Neural nets (ANNs)/ Genetic algorithms

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 Shifting Research Frontiers
(Summary)
A. 1) Advanced Technology Applications
 Polymers in Health/Medicine/Biotechnology
 Polymers in Information/Communications
2) Manufacturing: Materials and Processing/
Modification
B. Enabling Science
 Polymer Synthesis
 Polymer Characterization
 Math Modelling/Computer Simulation

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 Generalized Trends

A. From PRE and emphasis on process engineering, shift towards

product engineering/design and downstream properties
(maybe we will see more patents from academia?)
Hence, PRE and Rheology/Processing
PRE experts to form partnerships with rheologists/processing
experts (e.g., adhesive technology)

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 Generalized Trends Cont’d.

B. Structure-Property Relationships for better performance of

products
– Characterization of properties/morphology
– Microscopic properties - mechanical properties -
fabricated articles - integrated modeling approaches
– Tailor-made properties (interfaces with other disciplines)
– Material characterization techniques (more expensive as
more advanced and more specialized; need more
interaction for complementarity; role of industry/
government)

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 POLYMER REACTION
ENGINEERING (and its suite of mathematical/statistical tools):
A
Bridge between
Polymer Science
and
Polymer Processing/Modification

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