CHE 524 - ChE ELECTIVE II

INITIATORS, POLYMER PROCESSING,

HOMOPOLYMER & COPOLYMERS

Submitted by:

MACASIL, Renzo C.

REDUBLO, Anne Paulinne P.

Submitted to:

Engr. Kim Bryan L. Duenas

 TABLE OF CONTENTS
Initiators
Introduction 3
Commonly Used Initiators 4
Initiator Efficiency 7
Polymer Processing 9
Introduction 9
Analysis of Polymer Processing 10
The Elementary Steps 11
The Shaping Steps
Thermoplastic and Thermoset Processing
Thermoplastic Processing
A. Extrusion
B. Injection Molding
C. Blow Molding
D. Thermoforming
Thermoset Procesing
A. Compression Molding
B. Transfer Molding
Homopolymer and Copolymer
References

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MACASIL, Renzo C. | REDUBLO, Anne Paulinne P. 2
 INITIATORS
Initiator is a source of any chemical species that reacts with a monomer to form an
intermediate compound capable of linking successively with a large number of other
monomers into a polymeric compound. Initiators are often used in chain-growth
polymerization such as radical polymerization to regulate initiation by heat or light.
Organic peroxides with the general formula R-O-O-R are often used as initiators because
they can split into free radicals at elevated temperatures.

Figure 1. Free Radical Mechanism

Left: Organic peroxide; Right: Free Radicals Generation at High Temperatures

A free radical is a molecule that has no charge, but, is highly reactive because it has
an unpaired valence electron. Usually, free radical monomer attacks double bond of
another monomer to form bond and propagate the free radical.

Figure 2. Free Radical pairing with another monomer

Typical initiators include peroxides, azo compounds, Lewis acids, and

organometallic reagents. However, while initiators trigger initiation of the chain and
exert an accelerating influence on polymerization rate, they are not exactly catalysts
since they are changed chemically in the course of polymerization.

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 COMMONLY USED INITIATORS:
Benzoyl peroxide

The thermal decomposition of benzoyl peroxide, which takes place between 60 and
90°C, involves the homolytic cleavage of the O–O bond to yield benzoyl free radicals that
may react to yield phenyl radicals and carbon dioxide.

Azobisisobutyronitrile

An example of photochemically induced free-radical formation is the decomposition

of azo-bisisobutyronitrile by short-wavelength visible light or near-ultraviolet radiation at
temperatures as low as 0°C, where no thermal initiation occurs.

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 di-t-butylperoxide

Initiator is a relatively unstable molecule that decomposes into a free radical. The
stability of a radical refers to the molecule's tendency to react with other compounds. An
unstable radical will readily combine with many different molecules. However a
stable radical will not easily interact with other chemical substances.

Example: The addition polymerization of chloroethene to produce poly(chloroethene)

proceeds by a free-radical mechanism.

organic peroxide → alkoxy free radical

R-O-O-R → 2R-O

The alkoxy free radical combines with a molecule of chloroethene to form a new free
radical:

This new free radical can then combine with another molecule of chloroethene:

This new free radical can react with another chloroethene molecule to form a new
free radical, etc, etc until a very large polyvinyl chloride molecule has been built. The
polymerization stops when two free radicals react with each other.

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 Initiators are characterized by Td and t½

a. Td – decomposition temperature
Temperature where decomposition of initiator undergoes auto acceleration.
Thermal energy released from decomposition of an initiator molecule aids the
decomposition another initiator molecule.
Temperature where the rate of enthalpy generated from the decomposition of the
peroxide serves to provide sufficient energy for further decomposition.

Table 1. Common Initiators with their Td

INITIATOR STRUCTURE Td
PEROXIDES
Each have a peroxide bond (O-O), which is readily cleaved to give two oxygen-centered
radicals

Benzoyl Peroxide 30⁰C

Diacetyl peroxide 35⁰C

Di t-butylperoxide 80⁰C

AZO COMPOUNDS
Can be the precursor of two carbon-centered radicals (R● and R’●) and nitrogen gas upon
heating and/or by irradiation

2,2-azobisisobutyronitrile
25⁰C
(AIBN)

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 b. t½ - half-life
The most important characteristic of a polymerization initiator is its rate of
decomposition expressed by its half-life
Time needed for initial amount of initiator to decrease concentration in half-life.
Related to decomposition rate constant
Very temperature sensitive

Table 2. Half-Lives of Free Radical Initiators

INITIATOR EFFICIENCY
Not all initiator radicals initiate polymerization. Due to side reactions and
inefficient synthesis of the radical species, chain initiation is not 100%. The efficiency
factor, f, is used to describe the effective radical concentration. The maximum value of f is
1.0, but values typically range from 0.3-0.8. The following is a list of reactions that
decrease the efficiency of the initiator.
Primary recombination
Other recombination pathways
Side reactions

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 Primary recombination: Two radicals re-combine before initiating a chain. This
occurs within the solvent cage, meaning that no solvent has yet come between the new
radicals

Other recombination pathways: Two radical initiators re-combine before initiating a

chain but not in the solvent cage.

Side reactions. On radical is produced instead of the three radicals that could be
produced.

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 POLYMER PROCESSING
Polymers are derived from petroleum; they have gone from being cheap
substitutes for natural products to providing high-quality options for a wide variety of
applications. Polymers are now produced in great quantity and variety. Polymers are used
as film packaging, solid molded forms for automobile body parts and TV cabinets,
composites for golf clubs and aircraft parts (airframe as well as interior), foams for coffee
cups and refrigerator insulation, fibers for clothing and carpets, adhesives for attaching
anything to anything, rubber for tires and tubing, paints and other coatings to beautify and
prolong the life of other materials, and a myriad of other uses.

It would be impossible to conceive of our modern world without the universal

presence of polymeric materials. Polymers have become an integral part of our society,
serving sophisticated functions that improve the quality of our life.
Polymer processing is defined as the ‘‘engineering activity concerned with
operations carried out on polymeric materials or systems to increase their utility’’
There are many processes for polymers. Selection of a process depends on many factors
including:
Quantity and production rate
Dimensional accuracy and surface finish
Form and detail of the product
Nature of material
Size of final product

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 ANALYSIS OF POLYMER PROCESSING IN TERMS OF ELEMENTARY STEPS AND
SHAPING METHODS

The field of polymer processing has been traditionally and consistently analyzed in
terms of the prevailing processing methods, that is, extrusion, injection molding, blow
molding, calendering, mixing and dispersion, rotational molding, and so on. In analogy
to chemical engineering, these processes have been viewed as the ‘‘unit operations’’ of
polymer processing.

Figure 3. Conceptual structural breakdown of polymer processing product fabrication

operations

Figure 3 schematically summarizes our approach to the breakdown of the study of

polymer processing. Raw material is prepared for shaping through the elementary steps.
The elementary steps may precede shaping or they may be simultaneous with it.
Structuring takes place throughout these processes, and subsequent to them. Finally,
postshaping operations for purposes other than structuring (printing, decorating, etc.) may
follow. Clearly, to be able to fully utilize the added degree of freedom for product design
provided by structuring, a full understanding and computational handling of polymer
chemistry, polymer rheology at a macromolecular level, and the physics of phase changes
under stress fields and non-isothermal conditions has to be carried out. With advances in

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 those fields and the exponential growth of available computing power, significant advances
are already being made toward achieving specific processed product properties, not
through trial and error, but process simulation.

THE ELEMENTARY STEPS

The polymer is usually supplied to the processors in a particulate form. Shaping of

the polymer takes place only subsequent to a series of preparatory operations. The nature
of these operations determines to a large extent the shape, size, complexity, choice, and
cost of the processing machinery. Hence, the significance of a thorough understanding of
these operations cannot be overemphasized. One or more such operations can be found in
all existing machinery, and we refer to them as elementary steps of polymer processing.

There are five clearly identifiable elementary steps:

1. Handling of particulate solids

Defining ‘‘handling of particulate solids’’ as an elementary step is justified,
considering the unique properties exhibited by particulate solids systems. Subjects such
as particle packing, agglomeration, consolidation, gravitational flow, arching,
compaction in hoppers, and mechanically induced flow must be well understood to
ensure sound engineering design of processing machines and processing plants.

2. Melting
Subsequent to an operation involving solids handling, the polymer must be melted
or heat softened prior to shaping. Often this is the slowest, and hence the rate-
determining step in polymer processing. Severe limitations are imposed on attainable
melting rates by the thermal and physical properties of the polymers, in particular, the
low thermal conductivity and thermal degradation. The former limits the rate of
heat transfer, and the latter places rather low upper bounds on the temperature and
time the polymer can be exposed. On the other hand, beneficial to increasing the rate of
melting is the very high polymer melt viscosity. All these factors emphasize the need
to find the best geometrical configuration for obtaining the highest possible rates of
melting, and for determining the processing equipment needed for rapid and efficient
melting.

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 3. Pressurization and pumping
The molten polymer must be pumped and pressure must be generated to bring
about shaping—for example, flow through dies or into molds. This elementary step,
called pressurization and pumping, is completely dominated by the rheological
properties of polymeric melts, and profoundly affects the physical design of processing
machinery. Pressurization and melting may be simultaneous, and the two processes do
interact with each other. Moreover, at the same time, the polymer melt is also mixed by
the prevailing laminar flow.

4. Mixing

Mixing the melt distributively to obtain uniform melt temperature or uniform

composition (when the feed consists of a mixture rather than a single-component
polymer), ‘‘working’’ the polymer for improving properties, and a broad range of mixing
operations involving dispersive mixing of incompatible polymers, breakup of
agglomerates, and fillers—all these belong to the elementary step of ‘‘mixing.’’

5. Devolatilization and stripping

The last elementary step of devolatilization and stripping is of particular importance to
postreactor compounding, blending, and reactive processing operations, although it
also occurs in commonly used processes, for example, devolatilizing in vented two-
stage SSEs. This elementary step involves mass transfer phenomena.

THE SHAPING STEPS

The first step we take in our analysis of polymer processing is to clearly define its
objective which is undoubtedly shaping polymer products. The shaping operation can be
preceded and followed by many manipulations of the polymer to prepare it for shaping,
modify its properties, and improve its appearance. Nevertheless, the essence of
polymer processing remains the shaping operation. The selection of the shaping method is
dictated by product geometries and sometimes, when alternative shaping methods are
available, by economic considerations.

Reviewing the various shaping methods practiced in the industry, we can classify them in
the following groups:

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 1. Calendering and coating
The first shaping method is a steady continuous process. It is among the oldest
methods, and is used extensively in the rubber and plastics industries. It includes the
classic calendering, as well as various continuous coating operations, such as knife and
roll coating.

2. Die forming
Die forming, which is perhaps the most important industrial shaping operation,
includes all possible shaping operations that consist of forcing a melt through a die.
Among these are fiber spinning, film and sheet forming, pipe, tube, and profile forming,
and wire and cable coating. This is also a steady continuous process, in contrast to the
last three shaping methods, which are cyclic.

3. Mold coating
The term ‘‘mold coating’’ is assigned to shaping methods such as dip coating, slush
molding, powder coating, and rotational molding. All these involve the formation of a
relatively thick coating on either the inner or the outer metal surfaces of the molds.

4. Molding and casting

The next shaping method is molding and casting, which comprises all the different
ways for stuffing molds with thermoplastics or thermosetting polymers. These include
the most widely used shaping operations of injection molding, transfer molding, and
compression molding, as well as the ordinary casting of monomers or low molecular
weight polymers, and in situ polymerization.

5. Stretch shaping
Finally, stretch shaping, as implied by the name, involves shaping of preformed
polymers by stretching. Thermoforming, blow molding, stretch blow molding, and cold
forming can be classified as secondary shaping operations. The first three are very
widely used.

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 Thermoplastic Processing

When heated thermoplastics soften and become fluid when additional heat is
applied. Due to no chemical bonding takes place in a thermoplastic material, the curing
process is completely reversible and it also allows thermoplastic to be remolded and
recycled to form other thermoplastic material without negatively affecting the material’s
physical properties.

There are a lot of process that can be used to form a specific product but in
thermoplastic processing the common methods used are extrusion, injection modeling, blow
molding, and thermoforming.

A. Extrusion

The continuous process named extrusion is the method that is used to produce films,
sheet, profiles, tubes and pipes. The mechanism for the said process is:

1. The polymer material that will be formed into a different type of product for a specific
used will be loaded into the hopper.

2. The Material will then be fed into a long heated chamber that is moved due to the action
of the continuously revolving screw. The plastic will be melted by the mechanical work of the
screw that can be either single or a dual revolving screw depending on the design, and the
heat of the extruder wall.

4. At the end of the extruder, the molten polymer will be forced out through a small opening
called a die to form the shape of the finished product.

5. The polymer that is extruded from the chamber will either undergo a different process or it
will be fed into a conveyor belt or unto a rollers or by immersion to cool the formed polymer.

Examples of extruded products include lawn edging, pipe, film, coated paper,
insulation on electrical wires, gutter and down spouting, plastic lumber, and window trim.

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 B. Injection Molding

Injection Modeling is a discontinuous process that produces intricate three-

dimensional parts of high quality and great reproducibility product. This type of method is
usually used for thermoplastics but it can also be used in some thermoset if necessary
conditions will be met. The mechanism of the said process is:

1. The plastic material either in the form of pellet or powder will be fed into the hopper.

2. An extruder screw pushes the plastic through the heating chamber in where the material
will be melted so that it will be formed to a different type of product.

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 3. At the end of extruder, the molten plastic will be feed in to a mold at high pressure, high
pressure is needed to be sure the mold is completely filled.

4. Once the product is cooled to a solid, the mold will open and the finish product will be
injected.

Injection Modeling process is usually to make items such as butter tubes, yogurt containers,
bottle caps, toys, fittings, and lawn chairs.

C. Blow Molding

Blow molding is a process used extensively for the production of bottles and other hollow
plastic items with thin walls. This process is used in conjunction with extrusion or injection
molding. Blow-molded objects may range in size from less than 1 Oz to a few hundred
gallons. The extrusion forms a continuous semi-molten tube of the thermoplastic material.
Then a chilled mold is clamped around the tube and compressed air with a pressure of
usually about 100psi is blown into the tube to form the desired product. The formed product
will be cooled until the plastic become solid then the clamp will be remove to get the blow

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 molded product. On the other hand, in an injection blow molding, the injection molding will
first pre-form a polymer then it will be heated until it softened so that it can be molded again
to form the desired product, the compressed air will be blown into the heated polymer then
it will be cooled. This process is commonly used to manufacture hollow plastic products and
its principal advantage is its ability to produce hollow shapes without having to join two or
more separately injection molded parts.

D. Thermoforming

Thermoforming is a process for forming moderately complex shaped parts that

cannot be injection molded because the part is either very large or too expensive or has very
thin walls. It consists essentially of two stages: elevation of the temperature of a
thermoplastic sheet material until it is soft and pliable and forming the material into the
desired shape using one of several techniques.
Thermoforming techniques may be grouped into three broad categories: vacuum,
mechanical, and air blowing processes.

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 Vacuum Thermoforming

The plastic sheet is clamped in place mechanically and heated. A vacuum is then
placed beneath the hot elastic sheet, and this makes atmospheric pressure push the sheet
down onto the contours of the cold mold. The plastic material cools down, and after an
appropriate time the cooled part is removed.

Mechanical Thermoforming

In this type of thermoforming the plastic sheet will be heated until its softened
enough to be molded into different type of products. In this process there will be no pressure
or air that will be used. In this Thermoforming the heated sheet will be clamped into the
female or draped over a male mold then the two will be close together and cooled until the

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 product solidifies. The resulting part has excellent dimensional accuracy and good
reproduction of the mold detail, including any lettering and grained surfaces.

Air Thermoforming

In this type of thermoforming

compressed air and vacuum pressure is
used to form the sheet. First a plastic
sheet is heated and sealed across the
female cavity. Air at controlled pressure is
introduced into the mold cavity. This blows
the sheet upward into an evenly stretched
bubble. A plug which fits roughly into the
mold cavity descends on the sheet. When
the plug reaches its lowest possible
position, a vacuum or, in some cases, air
under pressure is used to complete part
formation.

Thermoset Processing

Thermoset polymers are polymers that when heated will degrade before it reaches its
you melting point hence in processing it the monomer will be polymerized while you form
your desired product. This is done by the addition of resins or catalyst at high temperature to
speed up the reaction and the polymer will be formed. There are two common processes
used in thermoset processing namely compression molding and transfer molding.

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 A. Compression Molding

Compression molding is a forming process that is like the mechanical thermoforming

used in thermoplastic sheet the only difference is that the raw materials in this type of
process is an unpolymerized material. The unpolymerized material will be put in the heated
mold then a catalyst or a resin will be put in the unpolymerized material to initiate the
polymerization and then the mold will be closed, the thermoset polymerized product will take
the shape of the mold.

B. Transfer Molding

The mold interior surfaces may be gel-coated. If desired the mold is first pre-loaded
with a reinforcing fiber matrix or perform. Fiber content of a transfer molded composite can
be as high as 60% by volume. The fill material may be a preheated solid or a liquid. It is
loaded into a chamber known as the pot. A ram or plunger forces material from the pot into
the heated mold cavity. If feed-stock is initially solid, the forcing pressure and mold
temperature melt it. Standard mold features such as sprue channels, a flow gate and ejector
pins may be used. The heated mold ensures that the flow remains liquid for complete filling.
Once filled the mold can be cooled at a controlled rate for optimal thermoset curing.

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 Homopolymer and Copolymer
Polymers are large molecules, with repeating structural units of monomers. These
monomers are bonded to each other with covalent bonds to form the polymer. They have a
high molecular weight and consist over 10,000 atoms. In the synthesis process, which is
known as polymerization, longer polymer chains are obtained. It can be either
homopolymers or copolymers depending on the composition. Polymers composed of only
one repeating unit in the polymer molecules are known as homopolymers. Scientist have
developed ways to form polymers with different type of monomers to increase the properties
of the polymer that will be produced. Polymers composed of two different repeating units in
the polymer molecule are defined as copolymers. An example is the copolymer formed when
styrene and acrylonitrile are polymerized in the same reactor. There are 4 different ways that
copolymer can be arranged in order to form the polymer needed namely random,
alternating, block and graft copolymer.

A. Random Copolymer

In a random copolymer there is no specific order of the monomer in the polymer. If

we will represent the monomer as A and B, then it will look like this:

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 B. Alternating Copolymer

In an alternating copolymer there Is a specific alternating arrangement of the

monomer in the polymer.

C. Block Polymer

The copolymer is consisting of relatively long sequences (blocks) of each repeating

unit chemically bound together:

D. Graft Polymer

Sequences of one monomer (repeating unit) are “grafted” onto a backbone of the
another monomer type:

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production-process-of-polymers/

Tadmor, Z., & Gogos, C. G. (2006). Principles of Polymer Processing (2nd ed.). Hoboken, NJ:

Wiley.

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http://chemed.chem.purdue.edu/genchem/topicreview/bp/1polymer/te rms.html

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