Petrochemical

industries II
Characterization and Course Code: CH408

Classification of
Lecture 9
Polymers-2
4thYear Students
Semester 8
Lecture 9 2023-2024

Dr.Tarek Abbas
Chemical and Petrochemical Engineering Department
Faculty of Engineering and Technology
 Polymers Classification (Cont.)
2- Based on polymer behavior at rising temperature
▪ Polymers are classified into three types based on its behavior at rising
temperature :
1. Thermoplastic polymer
2.Thermosetting polymer
3. Elastomer
where thermoplastic and thermosetting are plastics while elastomer is rubber.

▪ Polymer market shares : Thermoplastics are

commercially the most important of the three
▪ Thermoplastics
types, constituting around 70% of the
tonnage of all synthetic polymers produced . ▪ Thermosetting

while thermosets and elastomers share the

▪ Elastomer
remaining 30% about evenly, with a slight
edge for the former. 2
 Thermoplastic polymers

• Thermoplastics are solid materials at room

temperature but viscous liquids when
heated to temperatures of above melting
point.

• As the temperature is raised above the

melting point, the bonds weaken, making it
easier to form the plastic into any desired
shape. When polymer is cooled, it returns to
its original strength and hardness.

• Thermoplastics melt then solidify without chemical change. This characteristic

allows them to be easily and economically shaped into products.
• Thermoplastic polymers can be heating and cooling cycles repeatedly
without significant degradation.

• The reason is that they consist of linear and/or

branched macromolecules that do not cross-link
upon heating.
• By contrast, thermosets and elastomers change
chemically when heated, which cross-links their
molecules and permanently sets these polymers.
• Branches increase bond among the molecules,
which makes the polymer : Stronger in the solid
state & More viscous at a given temperature in the
plastic or liquid state.
• Examples of thermoplastic polymers are polyethylene , PVC ,
polypropylene, polystyrene , nylon. 4
 Thermosetting polymers
• A thermosetting polymer is a polymer that
is obtained by irreversibly hardening
(curing) a soft solid or viscous
liquid polymer (resin).
• Curing is induced by heat or suitable
radiation and may be promoted by high
pressure or mixing with a catalyst .

• Heat is not necessarily applied externally but is often generated by the

reaction of the resin with a curing agent (catalyst, hardener).
• Curing results in chemical reactions that create extensive cross-linking
three-dimensional between polymer chains to produce
an infusible and insoluble polymer network.
A: individual linear polymer chains
A B
B : Polymer chains which have
been cross linked to give a rigid 3D
thermoset polymer (typically, 10-50% of
repeat units are crosslinked).

▪ Thermosets can not repeated heating cycles as thermoplastics but

proceed the following:
1 . When initially heated, they soften and flow for molding.
2. Elevated temperatures produce chemical reaction that hardens the
material into an infusible solid.
3. If reheated, thermosets degrade rather than soften.
▪ Thermosets application are:
wood adhesives ,paints, printed
circuit boards , fiber reinforced
plastics.
▪ Examples of thermosets are
:Epoxy resins - Phenolic resins-
Polyester resins - Urea
formaldehyde.

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How cross-linking is done in thermosets?
Curing is accomplished at the fabrication plant rather than the
chemical plant, as the following :

1-Catalyst-Activated System
• Cross-linking occurs when small
amounts of a catalyst are added
to the polymer which is in liquid
form.
• Without the catalyst, the polymer
remains stable.
• Once combined with the catalyst it
changes into solid form

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2-Temperature-Activated System
• Curing is caused by heating during
shaping operation (e.g., moulding).
• Starting material is a linear polymer in
granular/powder form
• As heating is added, the material
softens for moulding ,but continued
heating results in cross-linking.
Crosslinked polyethylene has excellent
• It is a most common thermosets system. electrical insulation properties

3-Mixing-Activated System
• The mixing with catalyst forms a cross-linked solid polymer and elevated
temperatures are sometimes used to accelerate the reactions.

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 Comparison between thermosetting vs. thermoplastic
▪ Thermosets generally have better mechanical, thermal and chemical
properties. They also have better electrical resistance and dimensional
stability than do thermoplastics.
▪ TS have modulus of elasticity 2-3 times greater than TP.
▪ TS are Brittle, no ductility.
▪ TS are capable of higher service temperature than TP
▪ TS are Less soluble than TP in common solvents.
▪ TS can not be remelted - instead, they degrade or burn.

▪ Thermoset plastics are not as widely used as the thermoplastic.

▪ One reason is that the added curing processing increases costs and
complications . For example, phenolic resins with 6% of the total plastics
market comparing polyethylene with 35% market share.
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 Elastomers
• Elastomers exhibit extreme elastic deformation when subjected to
relatively low mechanical stress .Some elastomers can be stretched by a
factor of 10 - 500 and yet completely recover to their original shape.
• Their molecular structure are low degree of cross-linked comparing
thermosets which possessing a high degree of cross-linking.

• So, thermosets are hard and brittle, while elastomers are elastic.

• Elastic properties are due to:

- Molecules are tightly twist when unstretched.
- Degree of cross-linking is less than thermosets.
• Elastomers have two categories:
- Natural rubber : polyisoprene
- Synthetic rubbers : SBR
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• As shown in fig.a , if the elastomer contains no cross-links, the
application of a force causes deformation; after the load is removed, the
elastomer is permanently deformed.
• As shown in fig.b ,when cross-linking occurs, the elastomer still may
undergo large elastic deformation; however, when the load is removed,
the elastomer returns to its original shape.
• Vulcanization process is a chemical process for converting natural
rubber into more durable materials via the addition of sulfur .
• Cross-linking of polyisoprene chains may introduce sulfur atoms by loss
of a hydrogen of one chain and the breaking of unsaturated bond in
another chain.

Cross-linking of
polyisoprene chains
(2-methyl-1,3-butadiene)
Effect of vulcanization process on rubber stiffness
• Stiffness is the rigidity of an
object - the extent to which it
resists deformation in response
to an applied force .
• The complementary concept
is flexibility: the more flexible an

object is, the less stiff it is.

• Increasing in the stiffness as a function of strain for three grades of

rubber is as the following order:
Crude nature rubber vulcanized rubber synthetic rubber

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 3- Based on polymer and copolymer arrangement
Tacticity or Stereoisomerism: : Describes the stereo location in the polymer
chain of atom or groups in non-symmetrical monomers, For example PVC or
polypropylene.
a- isotactic polymer
The arrangement of hetero atoms in cis
direction.

b-Syndiotactic polymer
The arrangement of hetero atoms in trans
direction.

c-atactic polymer
The arrangement of hetero atoms in both
cis & trans directions.

• Polymers having regular structures as isotactic or syndiotactic will be able to

solidify into crystalline or semicrystalline networks.
In case of copolymer as EVA ,at least two different monomers
can be polymerized together by four different arrangement
cases as follows :

• Random – A and B is randomly

positioned along polymer chain
Random

• Alternating – A and B alternate in

polymer chain
Alternating
• Block – large blocks of A units
alternate with large blocks of B units
Block

• Graft – Chains of B units is grafted

onto A backbone

A– B–
Graft
▪ Acrylonitrile butadiene styrene terpolymer(ABS) is really made
up of two copolymers: BS and SAN grafted together.

▪ ABS is made by polymerizing of styrene and acrylonitrile in presence

of polybutadiene. The proportions can vary from 15 to 35% acrylonitrile, 5
to 30% butadiene and 40 to 60% styrene.
▪ It is amorphous graft thermoplastic terpolymer
 4- Based on polymer crystallinity
• Polymer crystallinity or atomic arrangement in polymer crystals is a
polymer chain layout, and it is very important to determine a lot of polymer
properties. There are two types:

Amorphous Crystalline

▪ Crystalline polymer is a two-phase system ,crystalline region dispersed

throughout an amorphous region.
▪ Degree of crystallinity is the proportion of crystallized material in the
mass.It is usually less than 100%. This means that polymers are
rarely 100% crystalline. Both amorphous and crystalline structures are
possible .
• Polymer crystallinity can be determined by different
laboratory methods as DSC , X-ray scattering , Dilatometry
and Polarized Optical Microscopy.
Microscopy
• Crystalline polymers are denser than amorphous polymers, so the
degree of crystallinity can be obtained from the measurement of
density:

% Crystallinity

Ρc : Density of perfect crystalline polymer

Ρa : Density of completely amorphous polymer
Ρs : Density of partially crystalline polymer that we are analyzing
Degree of crystallinity is control by:
• Rate of cooling during solidification : Long time is necessary for chains
to move and align into a crystal structure
• Heat treating causes crystalline regions to grow and degree of
crystallinity to increase.
• Mechanical deformation, as in the stretching of heated thermoplastic
polymer, tends to align the structure and increase crystallization.
• Plasticizers (chemicals added to a polymer to soften it) reduce the
degree of crystallinity.

Mer complexity: crystallization less likely in complex structures, simple

polymers, such as polyethylene, PVC , PP crystallize relatively easily.
Chain configuration: linear polymers crystallize relatively easily, branches
inhibit crystallization, network polymers almost completely amorphous,
crosslinked polymers can be both crystalline and amorphous.
• Isomerism: isotactic, syndiotactic polymers crystallize relatively easily -
geometrical regularity allows chains to fit together, atactic polymers is
difficult to crystallize.

• Copolymerism: easier to crystallize if mer arrangements are more

regular - alternating, block can crystallize more easily as compared to
random and graft.

▪ More crystallinity: higher density, more strength, higher

resistance to dissolution and softening by heating, because in
the crystalline phase, the intermolecular bonding is more
significant. Hence, the polymer deformation can result in the
higher strength leading to oriented chains.
5-Based on polymerization process

The synthesis of polymers can be occurred by either of three processes:

1. Addition polymerization process

• This is also called chain growth polymerization. In this, small monomer
units join to form a giant polymer. In each step, the length of the chain
increases.
• Examples of polymers which are produced by addition polymerization
Polyethylene, polypropylene, polyvinylchloride
• There are two mechanisms of addition polymerization
- Free radical addition polymerization
-Coordination addition polymerization

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2- Condensation Polymerization process
• Small molecules like H2O, NH3, CH3OH are eliminated during step growth
of monomer. Generally, organic compounds containing bifunctional groups,
such as idols, dials (dialdehyde –diketones) , diamines and dicarboxylic
acids diesters, undergo this type of polymerization reaction. For example,
preparation of nylon 6,6 & polyesters.
Example 1:

+ 2
n

During the formation of PET ,the OCH3 group and a hydrogen atom are
removed from the monomers, permitting the two monomers to join and
producing methyl alcohol as a byproduct.
Example 2

The linear nylon chain is produced when a hydrogen atom

from the hexamethylene diamine combines with an OH group
from adipic acid to form a water molecule .
3-Copolymerization process
In this process, two or more different monomers join to form a polymer.
Synthetic rubbers are prepared by this polymerization. For example,
butadiene styrene rubber (BS rubber) which is made up from the
combination of butadiene and styrene.

BS rubber
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 Some case studies
1-Comparison between some properties of low density versus high
density polyethylene (as an empirical data)
Polyethylene Linear Low density High density
Degree of crystallinity 45% 82%
Amorphous Crystalline

Specific gravity 0.92 0.96

Modulus of elasticity 240 MPa 700 MPa

Melting temperature 115oC 135oC

Greater crystallinity tend to increase the density, melting point &

improve the physical and mechanical properties at constant
other properties as MFI and Mwt.
 2-Comparison plastic deformation of various
thermoplastics polymers
Tensile Module of
Polymer strength elasticity Structure
(psi) x1000 (psi) x1000
LLD polyethylene 2000 40 little branching ,amorphous
structure with symmetrical
monomer
HD polyethylene 5500 180 nearly no branching , crystalline
structure with symmetrical
monomer
Polypropylene 6000 220 Semi-crystalline structure with
methyl side groups

polystyrene 8000 450 Amorphous structure with

benzene side groups.

PVC 9000 600 Amorphous structure with

chlorine atoms as side groups.
▪ Adding atoms other than
hydrogen to the chain
increases strength & stiffness.
▪ The methyl group in PP
provides some improvement.
▪ The benzene ring of styrene
provides higher properties .
▪ The chlorine atom in PVC
provides a large increase in
properties.
Thank YOU

Dr.Tarek Abbas