Lecture Plan: Teacher-2

Lecture Topics
L1 General introduction
L2 Polymer: Classification and polymerizations
L3 Polymer: Mechanism of polymerization
L4 Polymer: Processing of polymer.
L5 Plastics: Fundamental characteristics, classifications
L6 Plastics: Raw materials and manufacture of plastics
L7 Plastics: Some typical examples of plastics and uses.
L8 Class Test-1
L9 Fibers: Types of fibers, raw materials, applications
L10 Fibers: manufacturing processes of synthetic fibres.
L11 Rubber: Sources of natural rubber
L12 Rubber: chemical treatment of latex
Rubber: synthetic reactions and properties of synthetic
L13
rubber.
L14 Class Test- 2
Mechanism of Polymerization and polymer processing

 Coordination polymerization: Zeigler Natta Catalyst

 Step growth polymerization
 High and low density polyethylene
 Teflon
 Thermal transition in Polymer
 Crystalline melting temperature and glass transition
temperature

Book: Robert Ebewele, Chapter 2.

 Coordination Polymerization
Ziegler–Natta catalysts.
These are complex catalyst systems derived from a transition
metal compound from groups IVB to VIIIB of the periodic table
and an organometallic compound usually from a group IA or IIIA
metal.
A typical catalyst complex is that formed by trialkyl aluminum
and titanium trichloride as shown below:
 Ziegler-Natta Catalyst: Discovery
 A major development in polymer chemistry was the
development in 1953 of new catalysts leading to the formation
of polymer with exceptional structural regularity. The first
catalysts were described by Karl Ziegler for the low-pressure
polymerization of ethylene.
 These were modified by Giulio Natta and his associates and
used for the highly stereospecific polymerization of α-olefins,
diolefins, and other monomers.
 Ziegler and Natta were awarded the Nobel prize in
chemistry in 1963 for their work in this area. These catalysts
are usually referred to as Ziegler–Natta catalysts, and since
polymerization processes utilizing these catalysts result in
stereoregular structures, they are sometimes called
stereospecific or stereoregular polymerization.
 However, the term coordination polymerization is used here to
reflect the mechanism which, as we shall see presently, is
believed to govern the reaction involving these catalysts.
 Coordination Polymerization: Ziegler-Natta Catalyst

A Ziegler-Natta catalyst may be defined as a combination of:

(1) A halide or other salt of transition metals of group IV-VIII

(e.g. Ti, V, Cr, Mo, Rh, Rn, Co, and Ni) (Catalyst) and

(2) A light element of group I–III of the periodic table (e.g., Li,
Be, Mg, Al), present as organometallic compound (Cocatalyst)
 Coordination Polymerization: Ziegler-Natta Catalyst
Activation of Z-N Catalyst:

This chemical has a crystal structure because titanium atoms are

coupled with six chlorine atoms. It receives one ethyl group from
AlEt3 when it interacts with it. Aluminium bonds with a chlorine
atom. In titanium compounds, one chlorine atom is eliminated. As
a result, the catalyst now has an empty orbital on its surface. The
coordination of AlEt3 with titanium now activates the catalyst.
Initiation
The pair of electrons from the carbon-carbon pi-bond transfer to
produce the Ti-carbon bond, while the pair of electrons from the
Ti-AIEt3′ ethyl group shift to form a bond between the ethyl group
and the methyl-substituted carbon of propylene. Ti now has an
empty orbital due to electron shuffling and requires electrons to
fill it.
Propagation
The reaction’s propagation is dependent on the availability of
free propylene molecules. As more propylene molecules enter
the system, the process is repeated, resulting in linear
polypropylene.
Termination
Termination is the ultimate stage in the chain-growth
polymerization process, resulting in desired products. Several
termination strategies have been developed with the help of co-
catalyst AIEt3.
 Coordination Polymerization: Ziegler-Natta Catalyst
Uses:
 Coordination polymerization mechanism orients and inserts each
incoming monomer into the growing polymer chain according to a
particular steric configuration. The surface of the crystalline salts of
the transition metals that constitute part of the catalyst system is thought
to play a vital role in this function.
 With Ziegler–Natta catalysts, ethylene is polymerized to a highly linear
chain compared with the branched products from the radical
polymerization.
 By a convenient choice of catalyst system, isotactic and syndiotactic
polypropylene can be obtained. Higher α-olefins yield isotactic polymers
with heterogeneous catalyst systems.
 The versatility and selectivity of Ziegler–Natta catalysts are
demonstrated even more sharply in the polymerization of conjugated
dienes. By a suitable choice of catalyst system and reaction conditions,
conjugated dienes like butadiene and isoprene can be made to
polymerize into any of their isomers almost exclusively: trans-1,4; cis-1,4;
or isotactic or syndiotactic 1,2.
Condensation polymerization (Step growth polymerization)
Condensation polymerization is the process in which many
monomer molecules unite together to form a big macromolecule
with the loss of some simple molecules, usually water,
carbon dioxide etc. The most common example of
condensation polymerization is the formation of nylon 6,6 from
adipic acid and hexamethylene diamine.
In step-growth polymerization, the stepwise reaction occurs
between pairs of chemically reactive or functional groups on the
reacting molecules.
 Basic features of Condensation polymerization
 The terms “step polymerization” and “condensation
polymerization” are often used synonymously.
 Step polymerization occurs by stepwise reaction between
functional groups of reactants.
 The reaction leads successively from monomer to dimer,
trimer, tetramer, pentamer, and so on, until finally a
polymer molecule with large DP is formed.
 However, that reactions occur at random between the
intermediates (e.g., dimers, trimers, etc.) and the monomer
as well as among the intermediates themselves.
 In other words, reactions of both types, namely, occur equally.

 Thus, at any stage the product consists of molecules of

varying sizes, giving a range of molecular weights.
 Basic features of Condensation polymerization, continued

 The average molecular weight builds up slowly in the

step polymerization process, and a high-molecular-weight
product is formed only after a sufficiently long reaction
time when the conversion is more than 98%.

 Consider, for example, the synthesis of a polyamide, i.e., a

polymer with amide (–CONH–) as the characteristic linkage.
If we start with, say, hexamethylenediamine and adipic acid
as reactants, the first step in the formation of the polymer
(nylon) is the following reaction producing a monoamide.
 Basic features of Condensation polymerization, continued

The reaction continues step-by-step to give the polyamide

nylon-6,6. The overall reaction may thus be represented as
Q. Distinguishing Features of Chain and Step Polymerization
Mechanisms. R. Ebewele Chap 2 Table 2.3
Example 2.2:
Unsaturated polyester resins, which are used as the matrix
component of glass–fiber composites, may be obtained by the
copolymerization of maleic anhydride and diethylene glycol.
The low-molecular-weight product is soluble in styrene.
Describe, with the aid of equations, the possible structures of
the prepolymer and that of the polymer resulting from benzoyl
peroxide-initiated polymerization of a solution of the prepolymer
in styrene.
Solution: R Ebewele Chap 2 page 51
So, this is used in electricity carrying wires, squeeze bottles, toys, flexible
pipes etc.
 Triethyl aluminium
and titanium
tetrachloride (Ziglar-
Nata) catalyst
Chemically inert and non-corrosive
 Thermal transitions in polymer
 Crystalline melting Temperature, Tm
 Glass Transition Temperature, Tg

Heating up a solid crystal???

Turn to Liquid state

Heating up a polymer???
Turn to rubbery state
Thermal behavior of water and polymer
Thermal transition of polymers
 Melting (normal solid):

 A change from the crystalline solid state into the

liquid form
 A thermodynamic transition characterize by
thermodynamic variable such as heat capacity
 The change in free energy is zero
 An equilibrium between solid and liquid phase

Gm = Hm  TmSm =0 Tm = Hm/Sm

Hm = Enthalpy change during melting, cohesive energy

change
Sm = Entropy change during melting, change in order
Transition in polymer is different and complex, why?

 Polymer molecules are large enough and do not exist in

the gaseous state.
 At high temperature they decompose rather than boil
because their boiling point are higher than decomposition
temperature.
 Polymer sample has a distribution of molecular weights.
 Melting in crystalline polymeric material, Tm

 The macromolecular nature and molecular weight

distribution lead to broadening of Tm.
 The process of crystallization in polymers
involves chain folding and creates defects in the
crystals. Therefore, the actual melting point is
lower than the ideal thermodynamic melting point.
 The process of melting in polymer is more
sensitive than the simple molecules.
(Macromolecular nature and conformational
changes during melting)
 No polymer is 100% crystalline.
 Crystalline melting temperature for polymer, Tm

Not a solid-liquid phase transition

A transition from a crystalline or semi-
crystalline phase to a solid amorphous phase.
Abbreviated as simply Tm
The property is called the crystalline melting
temperature
 The crystalline melting temperature, Tm
 For a crystalline/semi-crystalline polymer, the
transformation occurs in the crystalline zone when heated.
At a certain temperature, the crystalline domains of a
polymer start to melt.
 The crystalline melting temperature is defined as the
temperature at which last crystalline domain starts to melt
and form an amorphous viscous fluid.
 A transition from a crystalline or semi-crystalline phase
(glassy or rubbery state, tough) to an amorphous liquid
phase (soft and viscous).
 Tm depends on the degree of crystallinity and the size
distribution of the crystalline domains.
 Features of thermal transition in polymer
 The transition between solid and liquid forms of a polymer
occurs over a wide temperature range (2-10ºC, depending
on the polydispersity).
 On melting, polymers become very viscous (viscoelastic)
fluids and do not have the flow behavior as in case of low
molecular weight materials.
 The thermal transition is opposed by the cohesive forces
between structural segments along the chain and between
neighboring chains. These cohesive forces or thermal
transitions depend on the structure of polymer.
 The glass transition temperature, Tg
 For an amorphous polymer, the solid-to-liquid transition
occurs gradually through an intermediate rubbery state
without a phase transformation.
 The transition from the hard and brittle glass into a softer,
rubbery state occurs over a narrow temperature range is
called the glass transition temperature.
 In case of semi-crystalline polymer, the transformation
occurs only in the amorphous region. The crystalline
zones remain unchanged and act as reinforcing element.
 If heating is continued, the crystalline zones start to melt
at a certain temperature.
https://www.youtube.com/watch?v=_-i_0_h4BF8
 Thermal transition in polymers

Rigid, tough
Soft, rubbery

Hard, brittle, Viscous

Semi-crystalline =
glassy solid liquid
Amorphous + crystalline

Rigid, tough,
Soft, rubbery

Tg Tm
Thermal transition in polymers

H
 Importance of thermal transition of polymer

 Selection of proper processing and fabrication conditions

 Characterization of physical and mechanical properties of
polymer material
 Determination of appropriate end uses.
 Example: Rubber, hard rubber (tyre, Tg>100C) to soft
rubber (band, Tg < 0C)
 Polystyrene: Tg ~ 100C
 PET: Tg ~ 80C
 PVC: Tg ~ 85C
 Polycarbonate~ 150C
 Polyether sulphone~ 220C
Measurement of crystalline melting temp.
The properties, whose values are different for
the crystalline and amorphous states.

1. Dilatometry
2. Differential Scanning Calorimetry (DSC)
3. Dynamic Mechanical Analysis
4. Stress Relaxation
5. Creep
 Next Class

 Thermal transition in Polymer

 Crystalline melting temperature and glass transition
temperature

Processing of polymers (Ebewele chap 9)

 Plasticizers
 Additives and reinforcement
 Flame retardants
 Molecular motion and glass transition

Hard, brittle, Semi-crystalline = Viscous

glassy solid Amorphous + crystalline liquid

Rigid, tough,
Soft, rubbery

Tg Tm
 Below Tg: Chain segments are frozen, undergo low
amplitude vibration.
 Near Tg: Amplitude of these vibrations becomes greater
and reduces the secondary intermolecular bond forces.
 At Tg: Chain segments acquire sufficient energy
overcome the secondary intermolecular bond forces and
undergo rotational and translational motion.
 Molecular motion and glass transition

 Rotational and translational motion play the role of energy

absorption.
 Conformational freedoms with increase in free volume
 Theories of glass transition temperature

1. Kinetic theory: Tg depends on the rate of heating or cooling

2. Equilibrium theory: Tg depends on conformational entropy

3. Free volume theory: Tg decreases with the increase of free

volume
 Determination of glass transition temperature, Tg

1. Dilatometry: By measuring free volume

2. Refractometry: By measuring refractive index
3. Calorimetry (DSC): By measuring specific heat
4. Dynamic mechanical analysis (DMA): By measuring
dynamic modulus, storage and loss modulus
5. Creep or stress relaxation: By measuring elastic modulus
Factors affecting glass transition temperature, Tg

1. Chain flexibility, stiffness and steric hindrance

2. Geometric factors
3. Intermolecular forces
4. Copolymerization
5. Molecular weights
6. Cross-linking and branching
7. Crystallinity
8. Plasticization
1. Chain flexibility, stiffness and steric hindrance
Free rotation along C-C bong or the polymer main chain

 Rigid group or cyclic structure reduces the chain flexibility

 1. Chain flexibility, stiffness and steric hindrance

Steric hindrance enhances Tg

 Bulky side group that are stiff and close to the backbone
enhances steric hindrance and reduces the chain flexibility
 2. Geometrical factors

Why polyisobutylene has low Tg than polypropylene though

polyisobutylene experiences high steric hindrance???
 Symmetrical polymer have low Tg than those of asymmetric structure.
 2. Geometrical factors

Cis-form reduces the energy barrier for rotation and increases

the free volume.
 3. Inter-chain attractive forces
Higher the cohesive energy density, higher the Tg.
 6. Cross-linking and branching

Cross-linking reduces the chain mobility, Tg increases

Branching increases the separation between chains, enhances

free volume, Tg decreases

7. Crystallinity
 Crystalline domains are regarded as physical cross-linking
 Reinforce or stiffen the structure, and decrease mobility
 Tg increases with increasing the degree of crystallinity
 8. Plasticizers
 Low molecular weight, nonpolymeric, non-volatile substances
(mostly liquid)
 Added to polymer to improve flexibility, processibility, utility
 Reduce the brittleness of amorphous polymer
 Addition of it to polymer reduces the Tg

Addition of it to polymer reduces the Tg why???

 Plasticizers are relatively small in size and can penetrate

between the polymer chains
 Establish polar attractive forces between the polymer chain
segments.
 These attractive forces reduce the cohesive forces between
the polymer chain and increase mobility
 Plasticizer
 Polymer additives and polymer blends
 Polymer reinforcement