Engr. Excel D.

De Guzman
General Chemistry
Learning Objectives
Describe the properties and structure of polymers and
know the common polymeric materials.

Determine the average molecular weights of polymers

and degree of polymerization.

Cite differences in behavior and molecular structure of

thermoplastic and thermosetting polymers.

Describe the sequencing arrangements along polymer

chains and crystalline state in polymeric materials.
 Monomers (mono meaning “one”; meros meaning “unit”)
 are the small molecules that are used for synthesizing polymers and each
monomer is analogous to a link in a chain.

Polymers (poly means “many”) can be created from one monomer, of from a
combination of two or more different monomers.
If a polymer is made up of one type of monomer (e.g. polyethylene), then it is known as
homopolymer. Other homopolymer that are synthesized by the radical mechanism are
TeflonTM, polytetrafuoroethylene and polyvinyl chloride (PVC).

POLYMER is a molecular compound that can be distinguished by a high molar

mass, ranging into thousands and even millions of mass and they are made up of many
repeating units.
PROPERTIES AND CHARACTERIZATION OF
POLYMERS

SYNTHETIC (man-made) POLYMERS

• were first developed in the early 20th century, and these polymers remarkably
transformed our world as different materials can be created with properties that are
ideal for different applications.
• Examples o Ethylcyanoacrylic
o Polytetraflouroethylene o Polyetylene terephalate
o Polystyrene o Polylactic acid
o Polyvinly acetate o kevlar
PROPERTIES AND CHARACTERIZATION OF
POLYMERS

NATURAL POLYMERS

• have been around since life itself began.

• Examples:
o Starch o Protein
o Collagen
o Cellulose
o Keratin
o Lignin
o Silk
o DNA o chitin
 Polymer Molecules

• are gigantic and because of their size they are often referred to as macromolecules.
• The backbone of each of a carbon-chain polymer is a string of carbon atoms and
within each molecule
• atoms are bound together by covalent interatomic bonds
• Many times each carbon atom singly bonds to two adjacent carbon atoms on either
side which is represented as follows:
 THE CHEMISTRY OF POLYMER MOLECULES

The hydrocarbon ethylene (C2H4) is a gas at ambient temperature and pressure which
has the following molecular structure

Under appropriate conditions, ethylene gas reacted and it will transform to polyethylene
(PE) which is a solid polymeric material. This process begins when an active center is formed
by the reaction between an initiator or catalyst species (R·) and the ethylene monomer, as
follows:
 THE CHEMISTRY OF POLYMER MOLECULES
The polymer chain forms by the sequential addition of monomer units to this actively
growing chain molecule which is represented schematically as follows:

After the addition of many ethylene monomer units, the final result is the polyethylene
molecule. Representation of polyethylene chain structure is shown below:

or alternatively as:
Here, the repeat units are
enclosed in parentheses,
and the subscript
n indicates the number
of times it repeats.
 THE CHEMISTRY OF POLYMER MOLECULES
Polyethylene

A B
a schematic representation a perspective of the molecule,
of repeat indicating the zigzag backbone
unit and chain structures structure
 Tetrafluoroethylene monomer to form polytetrafluoroethylene (PTFE)

Polytetrafluoroethylene (having the trade name

Teflon) belongs to a family of polymers called
the fluorocarbons.

The vinyl chloride monomer (CH2=CHCl) is a slight variant of that for ethylene, in which one
of the four H atoms is replaced with a Cl atom. Its polymerization is represented as:

and leads to poly(vinyl chloride) (PVC), another common polymer.

 Some polymers may be represented using the following generalized form:

where the R represents either an atom [i.e., H or Cl, for polyethylene or poly(vinyl chloride),
respectively] or an organic group such as CH3, C2H5, and C6H5 (methyl, ethyl, and phenyl)

Repeat unit and chain structures

a) b) c)
polytetrafluoroethylene poly(vinyl chloride) polypropylene

(Callister & Rethwisch, 2014)

 MOLECULAR STRUCTURE OF POLYMERS

Molecular weight and shape of a polymer is not the only basis of its physical
characteristics, the difference in the structure of the molecular chains must also
be considered.

There are four different molecular structures its includes:

1. Linear
2. Branched
3. Crosslinked
4. Network (three-dimensional)
 LINEAR MOLECULAR
STRUCTURE

DESCRIPTION

• Linear polymers are those in which the repeat units are joined
together end to end in single chains.
• These long chains are flexible where each circle represents a unit.
• There may be extensive van der Waals and hydrogen bonding
between the chains.
• polyethylene, poly(vinyl chloride), polystyrene, poly(methyl
methacrylate), nylon, and the fluorocarbons.
 BRANCHED MOLECULAR
STRUCTURE

DESCRIPTION

• The chain packing efficiency is reduced with the formation of

side branches, which results in a lowering of the polymer density.
• For example, high-density polyethylene (HDPE) is primarily a linear
polymer, whereas low-density polyethylene (LDPE) contains short-
chain branches.
 CROSSLINKED MOLECULAR
STRUCTURE

DESCRIPTION

• Adjacent linear chains are joined one to another at various

positions by covalent bonds.
• The process of crosslinking is achieved either during synthesis or
by a nonreversible chemical reaction.
• Often, this crosslinking is accomplished by additive atoms or
molecules that are covalently bonded to the chains.
• Many of the rubber elastic materials are crosslinked.
 NETWORK MOLECULAR
STRUCTURE

DESCRIPTION

• These are multifunctional monomers forming three or more active

covalent bonds make three-dimensional networks.
• A polymer that is highly crosslinked may also be classified as a
network polymer.
• These materials have distinctive mechanical and thermal
properties;
• the epoxies, polyurethanes, and phenol-formaldehyde
Common Polymeric
Materials

17
 COMMON POLYMERIC MATERIALS

Presently, there are more than 60,000 synthetic polymers known, with this, six types of
polymers account for roughly 75% of those used in both Europe and the United States.

The Six types of common polymers

Polyethylene Polyethylene Polyvinyl Polyethylene Polypropylene Polystyrene

Terephthalate chloride

PETE or PET HDPE PVC or V LDPE PP PS

 SIX COMMON POLYMERS

Polymer Recycle Properties of

Monomer Uses of Polymer
Symbol Polymer
Polyethylene Ethylene  Translucent if not Bags, films, sheets,
pigmented. bubble wrap, toys,
 Soft and flexible. wire insulation.
 Unreactive to
acids and bases.
LDPE  Strong and
tough.
Polyethylene Ethylene  Similar to LDPE Opaque milk, juice,
 More rigid, detergents, and
tougher, slightly shampoo bottles.
more dense. Buckets, crates, and
fencing
HDPE
 SIX COMMON POLYMERS

Polymer Recycle Properties of

Monomer Uses of Polymer
Symbol Polymer
 Variable. Rigid if Rigid: Plumbing
not softened with pipe, house siding,
Polyvinyl chloride Vinyl chloride a plasticizer. charge cards, hotel
Clear and shiny, room keys.
but often Softened: Garden
pigmented. hoses, waterproof
Resistant to most boots, shower
PVC or V chemicals, curtains, IV tubing.
including oils,
acids, and bases.
 SIX COMMON POLYMERS

Polymer Recycle Properties of

Monomer Uses of Polymer
Symbol Polymer
 Variable. “Crystal” form: Food
“Crystal” form wrap, CD cases,
Polystyrene Styrene transparent, transparent cups.
sparkling, “Expandable” form:
somewhat brittle. Foam cups,
 “Expandable” insulated
form lightweight containers, food
PS foam. packaging trays,
 Both forms rigid egg
and degraded in cartons, packaging
many organic peanuts.
solvents.
 SIX COMMON POLYMERS

Polymer Recycle Properties of

Monomer Uses of Polymer
Symbol Polymer
Polypropylene Propylene  Opaque, very Bottle caps. Yogurt,
tough, good cream, and
weatherability. margarine
High melting containers.
point. Carpeting, casual
 Resistant to oils. furniture, luggage.
PP
Polyethylene Ethylene glycol  Transparent, strong, Soft-drink bottles,
Terephthalate HO-CH2CH2-OH shatter resistant. clear food
 Impervious to acids containers,
and atmospheric
Terephthalic acid beverage glasses,
gases.
fleece fabrics,
 Most costly of the
six. carpet
PETE or PET yarns, fiber-fill
insulation.
Molecular Weight and Degree
of Polymerization
MOLECULAR WEIGHT AND DEGREE OF
POLYMERIZATION

• Polymers with very long chains has extremely large molecular weights but during
polymerization process, not all polymer chains will grow to the same length and this
results in a distribution of chain lengths or molecular weights.
• Usually, an average molecular weight is specified, which can be determined by the
measurement of various physical properties such as viscosity and osmotic pressure.
 SEVERAL WAYS OF DEFINING AVERAGE MOLECULAR WEIGHT

The number-average molecular weight Mn is obtained by dividing the chains into a

series of size ranges and then determining the number fraction of chains within each size
range. The number average molecular weight is expressed as

𝑀𝑛 = 𝑋𝑖 𝑀𝑖 (Equation 1)

where;

Mi- represents the mean (middle) molecular weight of size range i

Xi- the fraction of the total number of chains within the corresponding size range.
 SEVERAL WAYS OF DEFINING AVERAGE MOLECULAR WEIGHT

A weight-average molecular weight Mw is based on the weight fraction of molecules

within the various size ranges. It is calculated according to

𝑀𝑤 = 𝑊𝑖 𝑀𝑖
(Equation 2)

where;

Mi- represents the mean (middle) molecular weight of size range i

Wi- denotes the weight fraction of molecules within the same size interval.
 SEVERAL WAYS OF DEFINING AVERAGE MOLECULAR WEIGHT
Degree of Polymerization (DP) is an alternative way of expressing average chain size of a
polymer.
• DP represents the average number of repeat units in a chain and it is related to
the number-average molecular weight Mn by the equation
where;
𝑀𝑛 (Equation 3)
m- is the repeat unit
𝐷𝑃 = molecular weight.
b) 𝑚
a)

Figure 3

Hypothetical polymer molecule size distributions on the basis of (a) number and (b) weight
fractions of molecules (Callister & Rethwisch, 2014).
 EXAMPLE 1

Assume that the molecular weight distributions shown in Figure 3 are for poly(vinyl
chloride). For this material, compute
(a) the number-average molecular weight,
(b) (b) the degree of polymerization
(c) (c) the weight-average molecular weight.

Data to be used for Number/Weight-Average Molecular Weight

 SOLUTION

(a) Use equation 1 for solving the number-average molecular weight

Equation 1

𝑀𝑛 = 𝑋𝑖 𝑀𝑖

𝑀𝑛 = 7,500 0.05 + 12,500 0.16 + 17,500 0.22 + 22,500 0.27

+27,500 0.20 + 32,500 0.08 + 37,500 0.02

𝒈
𝑴𝒏 = 𝟐𝟏𝟏𝟓𝟎
𝒎𝒐𝒍
 SOLUTION

(b) use equation 3 for solving degree of polymerization

Equation 3

𝑀𝑛 ; 𝑠𝑜𝑙𝑣𝑒 𝑓𝑜𝑟 𝑚 𝑤ℎ𝑖𝑐ℎ 𝑖𝑠

𝐷𝑃 = 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡
𝑚 𝑜𝑓 𝑟𝑒𝑝𝑒𝑎𝑡 𝑢𝑛𝑖𝑡

𝐹𝑜𝑟 𝑃𝑉𝐶 𝑡ℎ𝑒 𝑟𝑒𝑝𝑒𝑎𝑡 𝑢𝑛𝑖𝑡 𝑖𝑠 𝐶𝐻2𝐶𝐻𝐶𝑙

𝑔 𝑔 𝑔 𝑔
𝑚 = 2 12.01 + 3 1.01 + 35.45 = 62.50
𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙

21150 𝑔/𝑚𝑜𝑙
𝐷𝑃 = = 𝟑𝟑𝟖. 𝟒 𝒈/𝒎𝒐𝒍
62.50 𝑔/𝑚𝑜𝑙
 SOLUTION

(c) use Equation 2 for solving weight-average molecular weight

Equation 2

𝑀𝑤 = 𝑊𝑖 𝑀𝑖

𝑀𝑤 = 7,500 0.02 + 12,500 0.10 + 17,500 0.18 + 22,500 0.29

+27,500 0.26 + 32,500 0.13 + 37,500 (0.02)
𝒈
𝑴𝒘 = 𝟐𝟑𝟐𝟎𝟎
𝒎𝒐𝒍
 THERMOPLASTIC AND
THERMOSETTING POLYMERS
 Thermoplastics Polymers

• Thermoplastics soften upon heating and later liquefy, then it hardens when cooled.
This process is reversible and can be repeated.
• As the temperature is increased, secondary bonding forces of the molecules are
decreased (through increased molecular motion) so that the relative movement of
adjacent chains is facilitated when a stress is applied.
• Exposure of a molten thermoplastic polymer to a very high temperature results to an
irreversible degradation
• Examples of common thermoplastic polymers are polyethylene, polystyrene,
poly(ethylene terephthalate), and poly(vinyl chloride).
 Thermosetting Polymers

• Thermosetting polymers is a network polymers, they do not soften upon heating and they become
permanently hard during their formation.
• Network polymers have covalent crosslinks between adjacent molecular chains.
• During heat treatment, the bonds fasten the chains together to resist the vibrational and rotational
chain motions at high temperatures. Therefore, the materials do not soften when heated. Excessive
heating temperatures will cause severance of these crosslink bonds and polymer degradation.
• As compared to thermoplastics, these thermoset polymers are generally harder and stronger and
have better dimensional stability.
• Examples of these thermosets (crosslinked and network polymers) are vulcanized rubbers, epoxies,
phenolics, and some polyester resins.
 COPOLYMERS

• composed of two repeat units.

• It is possible that there are different sequencing arrangements along the
polymer chains which depends on the polymerization process and the relative
fractions of these repeat unit types.
• Synthetic rubbers are usually copolymers.
 COPOLYMERS

Schematic representations of random, alternating, block, and graft copolymers.

The two different repeat unit types are designated by blue and red circles (Callister & Rethwisch, 2014).
 POLYMER CRYSTALLINITY

the atomic arrangement in polymer materials are more complex as compared to

metals and ceramics because in polymers it involves molecules instead of just atoms or
ions in crystalline state.

• Polymer crystallinity is the packing of molecular chains to produce an ordered

atomic array.
• Crystal structures may be specified in terms of unit cells, which are often quite
complex.

example of a unit cell for polyethylene and its

relationship to the molecular chain structure
(unit has orthorhombic geometry). Obviously,
the chain molecules also extend beyond the
unit cell
 POLYMER CRYSTALLINITY

• Molecular substances having small molecules (e.g. water and methane) are normally either
totally crystalline (as solids) or totally amorphous (as liquids).
• As an effect of their size and usual complexity, polymer molecules are often partially crystalline
(or semicrystalline), having crystalline regions dispersed within the remaining amorphous
material.
• An amorphous region is the result of any chain disorder or misalignment, a case that is quite
common, because twisting, kinking, and coiling of the chains hinder the strict ordering of every
segment of every chain.
Engr. Excel D. De Guzman
General Chemistry