Polymeric Materials - Part II

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Types of Polymers
 Thermosets
Classification based on Processing
 Thermoplastics
 Elastomers – Classification based on mechanical
properties
 Hydrogels- Classification based on chemical
properties
 Polyelectrolytes-Classification based on chemical
properties
 Natural-Classification based on origin
 Biodegradable-Classification based on biostability

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What makes One Polymer
Different from Another?
 Strength of intermolecular forces and their sum
over long polymer chains.

 Molecular weight and entanglement, which slow

down motion of polymers.
 Crystallinity.

 Crosslinking.

All these properties determine the diverse states of

macromolecular aggregation that polymers show.
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Schematic sketch of thermosets and thermoplastics.
The latter can be amorphous or a structure similar to
thermosets but a lower crosslink density.

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Consequences of the random
coil model
 Crystallization strongly impeded by chain
entanglement-only partial crystallization or
glassy state upon cooling of a melt
 Entanglement gives rise to very high viscosity
of polymer melts
 Entropic restoring force upon stretching of a
chain- entropy elasticity of elastomers

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Binding and Structure of
Polymers
Interchain bonding: covalent
Intermolecular binding
 permanent dipole ( polar groups)
 induction forces: induced dipole
 hydrogen bonds
 repulsive forces (Pauli principle)
 Van der Waals interaction

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Intermolecular Interactions
 Forces between
permanent dipoles
 Different
electronegativity of
partners
 permanent dipole
moment
 Examples of “polar
groups“: e.g., in PVC

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 nitrite group (less polar)

 ester group (less polar)

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Dipole forces in a polymer.

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Effect of Polar Groups:
 lower solubility (except in strongly polar
solvents)
 higher softening temperature (glass
temperature Tg).

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Almost no external dipole moment for
symmetrical arrangement of dipoles!

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Hydrogen bonds
only for F, O, N as strongly electronegative partner

 Illustration of hydrogen
bonds in polyamid 6
(PA6)
 Particularly strong in
polyamides and
polyurethanes

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Thermoplastics
 thermoplastic polymers are defined as
materials that soften, melt, and flow when
heat is applied; the adhesives solidify when
cooled.
 Majority of familiar plastics
 Can be reprocessed

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Thermoplastics
Amorphous
 Random structure

 Good clarity

 Broad melt temperature

 Low mold shrinkage (<0.005 in./in.)

 Acrylic, polycarbonate, PETG,polystyrene,

PVC, TPU,

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Thermoplastics
Semi-crystalline
 Linear alignment of chains

 Harder, less flexible

 Unique melting point

 High mold shrinkage (>0.01 in./in.)

 Polyethylene (LDPE / MDPE /HDPE),

polypropylene, PTFE, Polyamide, PEK, TPU

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Schematic sketch of thermosets and thermoplastics.
The latter can be amorphous or a structure similar to
thermosets but a lower crosslink density.

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(Thermo)plastics
 Glass transition at Tg: onset of long-range
chain mobility
 If semicrystalline plastics: melting intervall of
crystallites at Tm
 - T > Tg: mouldable into any shape
 - T < Tg: range of usage
 ·Soluble

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Thermosets
 A thermosettingpolymer, as the name suggests, becomes set
into a given network, normally through the action of a catalyst—
heat, radiation, or a combination of these factors—during the
process of cross-linking.
 As the name suggests, cross-linking is the process of forming
cross-links between linear polymer molecules (curing is another
term commonly used).
 As a result of this process, thermosets become infusible and
insoluble.
 Thermosetting resins (e.g., epoxies, polyesters, and phenolics)
are the basis of many structural adhesives for load-bearing
medical applications, as well as for the precision joining of
electronic parts.

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Thermosets
 Hard, strong, rigid
 Excellent heat resistance

 Cannot be reprocessed

Crystalline
 Epoxy, phenolic, polyester,

Amorphous
 Rubber, silicone, polyurethane

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Thermosets
 Not meltable
 Not soluble
 Not swellable
 Processing generally prior to crosslinking

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Elastomers
 Not meltable
 Not soluble
 Swellable
 Used at T > Tg (Tg often reduced by
plasticizers).

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Schematic sketch of thermosets and thermoplastics.
The latter can be amorphous or a structure similar to
thermosets but a lower crosslink density.

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Polyelectrolytes

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Polyelectrolytes
 But when the polymer chain is
covered with negative charges
(which repel each other), the
polymer can't be bunched in
on itself. So the chain
stretches out, like this.
 This makes the solution
(remember we're talking about
polyelectrolytes in solution)
more viscous.
 Think about it.
 When the polyelectrolyte chain
stretches out it takes up more
space, and is more effective at
resisting the flow of the solvent
molecules around it.

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Reversibility of the Process
 If one take a solution of a
polyelectrolyte in water, and
throws in a lot of salt.
 The NaCl will separate into
Na+ and Cl- ions.
 In the case of a negatively
charged polyelectrolyte like
poly(acrylic acid), the positively
charged Na+ ions will get in
between the negative charges
on the polymer, and cancel
them out in effect. When this
happens, the polymer chain
collapses back into random
coil again.
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Polymerization
 Starts with monomers
 The Addition-Condensation System

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Addition Polymerization
 polymerization where
the entire monomer
molecule becomes part
of the polymer.
 ethylene is polymerized
to make polyethylene.

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Condensation Polymerization
 Reaction where part of the monomer molecule is
kicked out when the monomer becomes part of the
polymer.
 The part that gets kicked out is usually a small
molecule like water, or HCl gas.
 The polymerization of Nylon 6,6
 Because there is less mass in the polymer than in
the original monomers, we say that the polymer is
condensed with regard to the monomers.

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Nylon 6,6 is made from adipoyl chloride and
hexamethylene diamine

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Chain Growth Polymerizations
 monomers become part of the polymer one at
a time.

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Step Growth Polymerizations
 This is a little more complicated, whereas
chain growth polymerizations add one
monomer at a time; multiple reaction
products are possible.
 Let's take a look at the step growth
polymerization of two monomers, terephthoyl
chloride and ethylene glycol, to make a
polyester called poly(ethylene terephthalate).

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Terephthoyl chloride and ethylene
glycol react to form an ester dimer

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Molecular Weight
 Let's think about a small
molecule, say, hexane.
Hexane has a molecular
weight of 86.
 Every hexane molecule has
a molecular weight of 86.
 Now if we add another
carbon to our chain, and the
appropriate amount of
hydrogen atoms, we've
increased our molecular
weight to 100.
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Molecular Weight
 That's fine, but the molecule
is no longer hexane. It's
heptane!
 If we have a mixture of
some molecules of hexane
and some of heptane, the
mixture won't act like pure
heptane, nor will it act like
pure hexane.
 The properties of the
mixture, say its boiling point,
vapor pressure, etc., will be
neither those of pure
hexane nor pure heptane.

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Dispersity
 Consider a protein-a protein in a polymer of amino
acids linked a linear sequence, and like classic
small molecules, it has a specific molecular weight
and can be said to be monodisperse.
 However, commercial synthetic polymers, such as
HDPE, are made up of molecules of different
molecular weight.
 The numerical number for n, or the degree of
polymerization (DP).
 Thus, the average molecular weight of a
polydisperse polymer is equal to the product of the
DP and the molecular weight of the repeating unit or
mer.
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But Polymers are Different.
 Imagine polyethylene.
 If we have a sample of polyethylene, and some of
the chains have fifty thousand carbon atoms in
them, and others have fifty thousand and two
carbon atoms in them, this little difference isn't going
to amount to anything.
 If you really want to know the truth, one almost
never finds a sample of a synthetic polymer in which
all the chains have the same molecular weight.
 Instead, we usually have a bell curve, a distribution
of molecular weights.
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Molecular Weight
The Number Average Molecular
Weight, Mn
 the total weight of all the
polymer molecules in a
sample, divided by the total
number of polymer molecules
in a sample
The Weight Average Molecular
Weight, Mw

Where N is the number of moles in

the sample with mass M, and N*M is
the mass of the sample.
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Molecular Weight

1. Number Average Molecular Weight (Mn)

weight NxMx
Mn = =
molecules Nx

2. Weight Average Molecular Weight (Mw)

CxMx NxMx)(Mx)  NxMx2

Mw = = =
Cx NxMx NxMx

3. Polydispersity

Polydispersity = Mw/Mn
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Influence of Increasing Molar
Mass on Properties

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Influence of Molecular
Weight on Mechanical Properties.

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Experimental Determination of
Molecular Weight
 Gel Permeation Chromatography
 Laser Light Scattering
 Viscometry

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Branched Polymers
 Not all polymers are linear
 Some thermoplastic
polymers, like polyethylene,
can be made in linear or
branched versions.

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HDPE vs LDPE
LDPE
HDPE

The branching increases the volume and thus

reduces the density of the polymer.

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Star Polymers
 Sometimes the ends of
several polymer chains
are joined together at a
common center.
 Polymers like this are
called star polymers.
 They're often used as
additives or as coating
materials.

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Dendrimer
 Sometimes there is no
backbone chain at all.
 Sometimes a polymer is
built in such a way that
branches just keep growing
out of branches and more
branches grow out of those
branches.
 These are called
dendrimers, from the
ancient Greek word for
"tree".
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