Fundamentals Of Solid State Polymerization

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FUNDAMENTALS OF SOLID STATE
POLYMERIZATION
C. D. Papaspyrides and S. N. Vouyiouka
School of Chemical Engineering, National Technical University of Athens,
Athens, Greece
1.1. Introduction 2
1.1.1. Polymers and plastics 2
1.1.2. Polymerization processes 3
1.1.3. Introduction to solid state polymerization 10
1.2. Solid state polymerization of chain-growth polymers (solid statepolyaddition) 11
1.3. Solid state polymerization of step-growth polymers (solid state
polycondensation) 14
1.3.1. Monomer solid state polymerization (direct SSP) 16
1.3.2. Prepolymer solid state polymerization (post-SSP, solid state
finishing) 21
1.4. Solid state polymerization apparatus and assemblies 26
1.5. Solid state applications in the polymer industry 28
1.5.1. Solid state polymerizationadvantages 28
1.5.2. Post–solid state polymerization application in polyamides 28
1.6. Conclusions 30
Solid State Polymerization, Edited by Constantine D. Papaspyrides and Stamatina N. Vouyiouka
Copyright © 2009 John Wiley & Sons, Inc.
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COPYRIGHTED MATERIAL
2 FUNDAMENTALS OF SOLID STATE POLYMERIZATION
1.1. INTRODUCTION
1.1.1. Polymers and Plastics
Plastics are indispensable contemporarymaterials used in nearly all areas of
daily life, and their production and fabrication are major worldwide industries.
The key word related to plastics is polymers, organic substances that are built
up by small molecules (monomers) joined together with covalent bonds and
forming long carbon or heteroatom chains (macromolecules). There may be hundreds,
thousands, ten thousands, or more monomerslinked together in a polymer
molecule, as noted by the Greek root of the word polymer, meaning “many
parts.” Plastics are highly modified polymeric materials that have been or can
readily be formed or molded into useful shapes, and a typical commercial plastic
resin may contain one or more polymers in addition to various additives and
fillers.
Although humankind has used natural polymers,such as animal skins, silk,
cellulose, and natural rubber since prehistoric times, the birth of plastics may
be traced back to the mid-nineteenth century. More specifically, the true nature
of polymer molecules was elucidated in 1920 by the pioneering work of Herman
Staudinger, who proposed and defended the macromolecular structure of
polymers, differing from the then- prevailing theory thatpolymers are colloids.
Distinct milestones in plastics history (Fig. 1.1) include development of the
vulcanization process by Charles Goodyear, transforming the latex of natural
rubber to a useful elastomer for tire use; the invention of celluloid, the first
1880 1900 1920 1940
Addition polymers:
e.g. PVC, PMMA,
PS, PE
1934: Nylon and Teflon TM
were produced
1960
Condensation polymers:PET, unsaturated polyesters
Ziegler Natta catalysts
• Development of new manufacturing methods
• Expansion of additives, new catalysts
• Development of new sophisticated structures, e.g.
nanocomposite, biodegradable materials
1907: The first synthetic
polymer: Bakelite was
invented
1839: C.Goodyear developed
the vulcanization process
1860: Birth of plastics industry:
Celluloid, thefirst man-made
thermoplastic, was prepared.
2009 1970
Development of
high-performance polymers,
e.g. composite materials
Fig. 1.1. Major milestones in plastics history.
INTRODUCTION 3
humanmade thermoplastic, created from nitrocellulose and camphor by JohnWesley
Hyatt; the invention by Leo Baekeland of Bakelite (phenol–formaldehyde
resin), which is used due to its excellent thermal andelectric insulating properties;
the preparation of nylon, an exotic polymer at that time, by Wallace
Carothers, who was working at Du Pont during the 1920s and 1930s; and the
development of low-pressure catalysts by Ziegler and Natta, which led to the
commercialization of polypropylene as a major commodity plastic [1,2]. The
last 30 years of plastics development involve progress in polymer...