Topic Outline: Polymers have interesting behavior and

special properties, partly because of their size.

I. Introduction to Polymers The large molecules become entangled with
II. Types of Polymers each other, much like a single strand of cooked
III. Types of Polymer Structure spaghetti gets tangled up with other spaghetti
IV. Tacticity strands in a bowl of pasta. The long polymer
V. Molecular forces in Polymers chains intermingle with one another and
VI. Types of Plastic materials become entangled. A bowl of cooked spaghetti
VII. Types of Polymerization: Addition and (before you add the sauce) is a good way to
Condensation picture this situation. It is very difficult to
VIII. Mechanical Properties of Polymers separate one piece of spaghetti from the
IX. Thermal Properties of Polymers remaining pieces because the strands of
spaghetti are tangled together. Polymer
X. Physical Properties of Polymers
molecules are arranged in this way as well.
This structure gives polymers some unusual
Reporter: Katrina Rebekah V. Ighut
properties, including their resistance to
breakage. In contrast, small molecules like
Introduction to Polymers
water do not tend to get tangled with each
other; each molecule is separate and distinct
Molecules are compounds that are made of
more than one type of atom. An example of a from the other.
small molecule is water--it contains three
atoms--two of hydrogen and one of oxygen.
Polymers are very large molecules compared
to water. They have many more atoms than a
water molecule--from 10,000 to 100,000 atoms
per molecule. The word polymer is derived
from the Greek root poly-, meaning many, and
mer, meaning part or segment. Many of the Single polymer Entangled polymer
same units (or mers) are connected together to chain chains
form a long chain or polymer. Because they
can be extremely large, often made up of
hundreds of thousands of atoms, polymers are
Sample Chemical Structure
also referred to as macromolecules.
Chemical formula/structure of an ethylene
molecule:
To demonstrate the size scale difference,
consider one polymer chain as a piece of
cooked spaghetti; and one water molecule as
one single crystal of salt. This demonstrates
the great size difference between one molecule
of a substance like water (molecular weight of
18 grams/mole) and a polymer macromolecule or CH2=CH2 or C2H4
(molecular weight ranging from 2,000 to
millions in grams/mole). Chemical formula/structure of an ethylene
monomer:
 or —(CH2-CH2)— or C2H4
The — symbols at the ends of the formula
represent a monomer that is ready to
react/connect to another monomer.
Chemical formula/structure of a growing
polyethylene chain:
or —(CH2-CH2)x—
where x=number of monomers, usually in the
thousands.
It should be pointed out that when the
polyethylene chain is finished growing, two
Hydrogen atoms are added to 'cap' (finish) the
chain ends.
Polymer Architecture
A polymer was defined in the previous section
as a macromolecule made up of many
segments connected together. It is very
common for these segments to contain what is
called a carbon backbone. That is, Carbon
atoms form the 'spine' of the polymer chain and
other elements/molecules dangle from the
Carbon atoms. The monomers pictured below
illustrate this concept.
The process for connecting the segments
together to form a polymer is called
polymerization.
Natural vs Synthetic Polymers
There are two types of polymers: synthetic and
natural. Synthetic polymers are derived from
petroleum oil, and made by scientists and
engineers. Examples of synthetic polymers
include nylon, polyethylene, polyester, Teflon,
and epoxy. Natural polymers occur in nature
and can be extracted. They are often water-
based. Examples of naturally occurring
polymers are silk, wool, DNA, cellulose and
proteins.
In our previous section on network polymers,
we mentioned vulcanized rubber and pectin.
Vulcanized rubber is a synthetic (man-made)
polymer, while pectin is an example of a
natural polymer.
Rubber can be found in nature and harvested
as a latex (milky liquid) from several types of
trees. Natural rubber coming from tree latex is
essentially a polymer made from isoprene units
with a small percentage of impurities in it.
Rubber can also be made (synthesized) by
man. Synthetic rubber can be made from the
polymerization of a variety of monomers,
including isoprene.
Natural rubber does not handle easily (it's
sticky), nor does it have very good properties
or durability (it rots). It is usually vulcanized, a
process by which the rubber is heated in the
presence of Sulfur, to improve its resilience,
elasticity and durability. Synthetic rubber is
preferable because different monomers can be
mixed in various proportions resulting in a wide
range of physical, mechanical, and chemical
properties. The monomers can be produced
pure and addition of impurities or additives can
be controlled by design to give optimal
properties.
Vulcanization, also called curing, is the
chemical process used in the rubber industry in
which individual polyisoprene chains are linked
to other polyisoprene chains by chemical
bonds (see reaction sequence below). The
actual chemical cross-linking is usually done
with Sulfur, but there are other technologies
that can also be used. Vulcanization is an
irreversible process, like baking a cake. The
normally soft and springy rubber molecules
become locked together resulting in a harder
material with greater durability and chemical
resistance. Vulcanization changes the surface
of the material from very sticky to a smooth,
soft surface which does not adhere to metal or
plastic substrates.
Source: www.chemistrydaily.com.
Pectin is a long chain polymer composed of
pectic acid and pectinic acid molecules (see
structure below). Because these acids are
sugars, pectin is called a polysaccharide. It is
obtained from citrus peels and the remains of
apples. In the plant/fruit, pectin is the material
that joins the plant cells together.
Source: www.cybercolloids.net.
The pectin chains form a network because
some of the segments of the pectin chains join
together by crystallization to form a three-
dimensional network in which water, sugar and
other materials are held. Formation of a gel is
caused by physical or chemical changes that
tend to decrease the solubility of the pectin and
this favors the formation of small localized
crystals. The most important factor which
influences pectin's tendency to gel is
temperature.
When cooling a hot solution containing pectin,
the movement of the molecules is decreased
and their tendency to combine into a gel
network is increased. This ability makes pectin
a good thickener for many food products, like
jellies and jams. If there is sufficient sugar in
the mixture, pectin forms a firm gel.
History of Polymers
 The billiard balls, during the time of
Charles, Darwin is made up of pure
ivory carved from elephant tusks.
 Billiard balls were getting more
expensive and elephants were getting
more rare.

 The Phelan and Collender Pool Supply
Company offered $10,000 to anyone
who could come up with a substitute
material that worked as well as ivory,
but could be produced more quickly and
sustainably.
 John Wesley Hyatt took the challenge.
He used nitrocellulose, a flammable
solid, created by mixing cotton with nitric
acid to create hard, shiny, white sphere.
 The polymer that John created worked
well once it was created, but the
manufacturing process was dangerous
because nitrated cellulose can explode
in a warm breeze.
 But still, John created the industry that
made all of the polymer materials that
surround you right now.
 Replacements started coming in.
Namely: Polyvinyl Chloride (PVC),
Bakelite, Polystyrene, Polyester, and
Nylon. These are all polymers. Huge
chains or 3D networks of repeating
organic units called monomers.
 Rubber is a “miracle material”. It came
from trees in Brazil. It is called latex in
its fluid form and rubber when it
hardened. But it had a flaw; it melted in
summer and cracked during winter. In
1843, Charles Goodyear discovered that
if you removed the sulphur from rubber
then heated it, it would retain its
elasticity. This process called
vulcanization made rubber waterproof
and winter-proof.
 There are two types of polymers:
synthetic and natural. Synthetic
polymers are derived from petroleum oil,
and made by scientists and engineers.
Examples of synthetic polymers include
nylon, polyethylene, polyester, Teflon,
and epoxy. Natural polymers occur in
nature and can be extracted. They are
often water-based. Examples of
naturally occurring polymers are silk,
wool, DNA, cellulose and proteins.
Reporter: Bautista, Kyle Angelique E.
Types of Plastic Materials:
• Poyethylene terephthalate (PETE or PET
- most widely produced plastic in the
world
- used predominantly as a fiber (known by
the trade name “polyester”) and for
bottling or packaging
• High-Density Polyethylene (HDPE)
- stiff plastic used for more robust plastic
packaging like laundry detergent
containers as well as for construction
applications or trash bins
• Polyvinyl Chloride (PVC)
- most well-known for its use in residential
and commercial property construction
applications
- used for plumbing, insulation of
electrical wires, and “vinyl” siding
• Low-Density Polyethylene (LDPE)
- used for plastic bags in grocery stores
- has high ductility but low tensile strength
• Polypropylene (PP)
- used in a variety of applications to
include packaging for consumer
products, plastic parts for the
automotive industry, special devices like
living hinges, and textiles
• Polystyrene (PS)
- used widely in packaging under the
trade name “Styrofoam”
- also available as a naturally transparent
solid commonly used for consumer
products like soft drink lids or medical
devices like test tubes or petri dishes
• Polylactic acid (PS)
- derived from biomass rather than
petroleum
- environmentally friendly choice of plastic
• Polycarbonate (PC)
- transparent material known for its
particularly high impact strength relative
to other plastics
- used in greenhouses where high
transmissivity and high strength are both
required or in riot gear for police
• Acrylic (PMMA)
- best known for its use in optical devices
- extremely transparent, scratch resistant,
and much less susceptible to damaging
human skin or eye tissue if it fails (e.g.
shatters) in close proximity to sensitive
tissue
• Acetal (Polyoxymethylene, POM)
- very high tensile strength plastic with
significant creep resistant properties that
bridge the material properties gap
between most plastics and metals.
- known for high resistance to heat,
abrasion, water, and chemical
compounds.
• Nylon (PA)
- used for a variety of applications to
include clothing, reinforcement in rubber
material like car tires, for use as a rope
or thread, and for a number of injection
molded parts for vehicles and
mechanical equipment
• Acrylonitrile Butadiene Styrene (ABS)
- strong resistance to corrosive chemicals
and physical impacts. It is very easy to
machine, is readily available and has a
low melting temperature making it
particularly simple to use in injection
molding manufacturing processes or 3D
printing.
Types of Polymer Structures
• Linear
- resemble ‘spaghetti’ with long chains
- The monomers in these are linked
together to form a long chain.
- These polymers have high melting
points and are of higher density.
- PVC (Poly-vinyl chloride).
- used for making electric cables and
pipes.
• Branched
- resemble linear polymers with the
addition of shorter chains hanging from
the spaghetti backbone.
- Monomers join together to form a long
straight chain with some branched
chains of different lengths.
- polymers are not closely packed
together
- low density having low melting points
- Low-density polyethene (LDPE) used in
plastic bags and general purpose
containers is a common example
• Cross-linked
- resemble ladders
- the chains link from one backbone to
another
• Networked The letter n stands for the number of monomers
that are joined in repeated fashion to make the
- are complex polymers that are heavily polymer and can have a value in the hundreds
linked to form a complex network of or even thousands.
three-dimensional linkages.
- nearly impossible to soften when
heating without degrading the
underlying polymer structure

Types of Polymer Structures Based on

Molecular Forces

 Elastomers: BASIC STEPS

1. INItiation step produces free radicals by breaking

- rubber-like solid polymers, that are down a molecule like this organic peroxide.
elastic in nature.
- polymer can be easily stretched by
applying a little force.
- polymer chains are held by the weakest
intermolecular forces, hence allowing 2. Propagation steps
the polymer to be stretched.

 Fibres:

- class of polymers which are a thread

like in nature, and can easily be woven
- have strong inter-molecules forces
between the chains giving them less
elasticity and high tensile strength
3. Termination step (chain termination)

Reporter: Bjorn Pitogo

Polymerization

Addition Polymers

addition polymer is a polymer formed by chain

addition reactions between monomers that
contain a double bond or triple bond. Molecules
of ethene can polymerize with each other under
the right conditions to form the polymer called
polyethylene.

nCH2=CH2→−(CH2CH2)n−
Reporter: Drew Doroteo
Thermal Properties of Polymers +
Condensation Polymerization + Tacticity
Definition of Terms:
Glassy State
• State in the amorphous region of the
polymer, the molecules of the polymer
are in a frozen state, where the
molecules can vibrate slightly but are
not able to move significantly.
• Crystalline state is more favored,
greater Van der Waal interactions in
polymer chain.
• In this state, the polymer is brittle, hard
and rigid analogous to glass.
• When polymers are in temperatures
below their Tg (Glass Transition
Temperature) considered to be in its
glassy state.
• Bends to accommodate strain
Rubbery State
• In the amorphous region of the polymer,
when the polymer is heated, the
polymer chains are able to wiggle
around each other, and the polymer
becomes soft and flexible similar to
rubber due to increase in temperature.
• Viscoelastic
• Weaker Van der Waals interactions,
generally low Young's modulus and high
failure strain when compared to glassy
state.
• When polymers are in temperatures
above their Tg (Glass Transition
Temperature) considered to be in its
rubbery state.
Glass Transition Temperature (Tg)
• The temperature at which the glassy
state makes a transition to rubbery state
• The glass transition occurs only in the
amorphous region, and the crystalline
region remains unaffected during the
glass transition in the semi-crystalline
polymer.
• It is always lower than the melting
temperature (Tm) of the crystalline state
of the material
• The transition is not considered a phase
transition
Melting Point and Glass Transition
Temperature
Tg – Second Order Transition
Tm – First Order Transition
• The glass transition temperature is the
property of the amorphous region of the
polymer, whereas the crystalline region
is characterized by the melting point.
• The difference between
first and second order phase
transition is that in first order phase
transition entropy, volume and
energy of the thermodynamic system
change abruptly whereas in second
order phase transition it changes
continuously.
• The semi-crystalline polymer shows
both the transitions corresponding to
their crystalline and amorphous regions
• Thus, the semi-crystalline polymers
have true melting temperatures (Tm) at
which the ordered phase turns to
disordered phase, whereas the
amorphous regions soften over a
temperature range known as the glass
transition (Tg).
 • Amorphous polymers do not possess
the melting point, but all polymers
possess the glass transition
temperature.
Increases Melting Point: Presence of
double bonds, aromatic groups, bulky or
large side groups
(High Molecular Weight)
Decreases Melting Point: Defects caused
by branching chains
Factors Affecting the Glass Transition
Temperature
• The glass transition temperature
depends on the mobility and flexibility
(ease of the chain segment to rotate
along the chain backbone) of the
polymeric chains.
Increases Tg: Restricted mobility of polymer
chains
Decreases Tg: Free movement of polymer
chains
I. Intermolecular Forces
- Strong intermolecular forces cause
higher Tg
II. Chain Stiffness
- The presence of the stiffening groups in
the polymer chain reduces the flexibility
of the chain, leading to higher glass
transition temperature.
III. Cross-Linking
- The cross-links between chains restrict
rotational motion and raise the glass
transition temperature. Hence, higher
cross-linked molecule will show higher
Tg than that with lower cross-linked
molecule.
IV. Pendant Groups
- A "pendant" group on a polymer is a
small group of atoms (even a small
chain sometimes) that hangs off of the
main chain (that is, the backbone of the
polymer).
a.) Bulky pendant groups: the
presence of bulky pendant groups
can restrict rotational freedom,
leading to higher glass transition
temperature
b.) Flexible pendant groups: the
presence of flexible pendant groups
limits the packing of the chains and
hence increases the rotational
motion, tending to less Tg value
V. Plasticizers
- Plasticizers are low molecular weight
and non-volatile materials added to
polymers to increase their chain
flexibility. They reduce the
intermolecular cohesive forces between
the polymer chains, which in turn
decrease Tg.
VI. Molecular Weight
 - Tg is increased with the molecular polymerization of vinyl monomers
weight. The molecular weight is related (CH2CHX)
to the glass transition temperature by
the Fox–Flory Equation Isotactic

- Occurs when the monomer adds to the

• Tg ∞ is the glass transition temperature
at the molecular weight of infinity
• K is the empirical parameter called Fox–
Flory parameter related to the free
volume inside the polymer
• Mn is number-average molecular weight
( the sum of all molecular weights
divided by their total number)
Low molecular weight values result in
lower glass transition temperatures
whereas increasing values of molecular
weight result in an asymptotic approach of
the glass transition temperature to Tg,
polymer backbone with the pendant
group on the same as the previous
pendant group
Syndiotactic
- Occurs when the monomer adds where
the pendant group adds to the opposite
side of the polymer backbone
Atatic
- Occurs when there is no order to the
way the pendant group adds,
(completely random).

Tacticity

• Tacticity is a term used to describe the

way pendent groups on a polymer
chain are arranged on a polymer
backbone.

• The tacticity of a polymer is determined

by what side of the polymer chain the
Isotactic and syndiotactic polymers provide
pendant groups are on, this relative
long-range order, which leads to higher
position can have dramatic effects on
crystallinity in the polymer chain. (High
the physical properties of the polymer.
Density)
• Tacticity only arises when there is an
asymmetric carbon in the polymer chain
backbone usually in free radical
 Atactic polymers have little order in the
polymer backbone and is amorphous
causing lower crystallinity. (Low Density)
Condensation Polymerization
• A condensation polymerization is a form
of step-growth polymerization.
Functional groups react with each other
to form larger structural units while
releasing smaller molecules as a
byproduct, such as water or methanol.
• Condensation polymers form more
slowly than addition polymers, often
requiring heat, and they are generally
lower in molecular weight.
Step-Growth Polymerization
• A stepwise reaction between bi-
functional or multi-functional
monomers in which a high-molecular-
weight polymer is formed after a large
number of steps.
• Due to the nature of the polymerization
mechanism, the reaction has to proceed
for a long time to achieve high molecular
weight polymers.
• The easiest way to visualize the step-
growth mechanism is a crowd of people
reaching out to hold their hands to form
human chains — each person has two
hands (= two reactive sites).
Polyamides
- Carboxylic Acid (-COOH) + Amide
(RC(O)NR′R″) with a by-product of H2O
- Held together by Amide Link
- Amides have a carbonyl group attached
to a nitrogen atom
Polyesters
- Alcohol + Carboxylic Acid (-COOH) with
a by-product of H2O
- Held together by Ester Links
The average molecular weight and the
crosslink density will depend on the
functionality of each monomer involved in
the condensation polymerization and on its
concentration in the mixture.
Reporter: Mark Quiven Barcia
Degree of Polymerization
The degree of polymerization, or DP, is the
number of monomeric units in a
macromolecule or polymer or oligomer
molecule. In a nutshell, if we look at polymer as
a literal chain made up of connected links, the
degree of polymerization is the number of links
in that chain derived from dividing the whole
weight of the chain by the weight of a single
link similar to the links that comprises the
chain.
The degree of polymerization can be solved
through this equation:
 Molecular Mean Percentage (xi) In a nutshell, the Number Average Molecular
Weight (M) Weight (M i ) Weight sees different monomers as similar with
8,000-16,000 12,000 0.05 the use of the results from SEC or Size
16,000- 20,000 0.16 Exclusion Chromatography.
24,000
24,000- 28,000 0.24 Here’s an example:
32,000
32,000- 36,000 0.28 Polyethylene Vinyl Acetate (PEVA) is a
40,000 Copolymer. After undergoing SEC the following
40,000- 44,000 0.20 results were gathered:
48,000
48,000- 52,000 0.07
56,000
However, if we apply the concept of By multiplying the Percentage to the Mean
different types of polymerization and the weight, we are disregarding now the size of the
different types of Polymer molecules, we can monomers and looking at the monomers as
deduce that direct substitution on this formula similar:
is only possible for a Homopolymer that
underwent Addition Polymerization. A
Homopolymer that underwent addition
polymerization assures that the weight of a
single monomer is the weight of all monomers
present in the polymer, the same thing cannot
be said to monomers that underwent
condensation polymerization since such
polymerization creates byproducts, or
copolymers since the different monomers have
different weights.
Now that we have the mass of the
In any case that the Degree of Polymerization polymer, we can now do direct substitution
is asked but the given is a Copolymer or a from the previous formula by combining the
polymer that underwent condensation weight of the two monomers in the copolymer.
polymerization, the sample has to undergo With the atomic weight of PEVA 114g/mol the
SEC first or Size Exclusion Chromatography Degree of polymerization is 289.8.
before looking for the Number Average
Molecular Weight.

Number Average Molecular Weight. Reporter: Krizalane Salazar

The number average molecular weight Polymer Crystallinity

(Mn) measuring system requires counting the
Topic Outline:
total number of molecules in a unit mass of
polymer irrespective of their shape or size. This 1. Identify Amorphous polymers
means all molecules are treated equally. This
kind of measuring system is required in cases 2. Identify Crystalline polymers
where certain properties are dependent only
3. Differences between Amorphous and
upon the number of molecules or repeating
Crystalline polymers
units and not upon their weight or sizes.
4. Factors affecting polymer crystallinity Factors Affecting Crystallinity

1. Length of chain

POLYMERS - are macromolecules formed by  Longer chain = Less likely to crystallize

joining a large number of small units called
MONOMERS. 2. Structure

Polymer Crystallinity  Linear = More likely to crystallize

 Branched, cross-linked = Less likely to
- structure of a polymer crystallize
- degree of order or regularity in how the
molecules are packed together
-
3. Tacticity
Crystalline Polymer
 Atactic = Less likely to crystallize
- very ordered, which gives them strength  Syndiotactic = More likely to crystallize
and rigidity  Isotactic = More likely to crystallize
- there is no 100% crystalline polymer
fornit also contains considerable amount
of amorphous polymer, thus, it is called
SEMICRYSTALLINE.
- it shows x-ray diffraction pattern
- applying a load on a crystalline will
break it, rathen than bend it

Amorphous Polymer

- composed of amorphous regions where

molecules are randomly arranged
- can be either completely amorphous or
mixed with both crystalline and
amorphous
- possess flexibility and elasticity that it
would bend

Glass Transition Temperature (Tg)

 temperature range where the polymer

substrate changes from a glassy rigid
material to a soft material, and is
usually measured in terms of stiffness
or modulus.

Above Tg, polymers are rubbery.

Below Tg, polymers are brittle.