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Unit 3 – The Chemistry of Engineering

Materials

Polymers



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 the differences in behavior and molecular structure of

thermoplastic and thermosetting polymers.

• Describe the sequencing arrangements along polymer chains and

crystalline state in polymeric materials.

1.0 PROPERTIES AND CHARACTERIZATION OF POLYMERS
A 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. 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. Natural polymers have been around
since life itself began. Cellulose, starch, and other complex carbohydrates are examples of
natural polymers. Natural rubber is a polymer obtained from rubber trees and even the code
for life itself, DNA, is a natural polymer.
Because of the size polymers, we might expect that molecules containing thousands
of carbon and hydrogen atoms can form a massive number of structural and geometric
isomers (if 𝐶 = 𝐶 𝑏𝑜𝑛𝑑𝑠 𝑎𝑟𝑒 𝑝𝑟𝑒𝑠𝑒𝑛𝑡). Nevertheless, these molecules are made up of
monomers, simple repeating units, and this type of composition markedly restricts the
number of possible isomers. 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 only type of
monomer (e.g. polyethylene), then it is known as homopolymer. Other homopolymer that

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are synthesized by the radical mechanism are TeflonTM, polytetrafuoroethylene and

poly(vinyl chloride) (PVC).
Synthetic polymers can be made from many different starting materials which usually
come from crude oil (raw material). Presently, crude oil is the starting material for many
plastics, pharmaceuticals, fabrics, and other carbon-based products.

Polymer Molecules
The molecules in polymers 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, the 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:

| | | | | | |
−𝐶 − 𝐶 − 𝐶 − 𝐶 − 𝐶 − 𝐶 − 𝐶 −
| | | | | | |

Each of the two remaining valence electrons for every carbon atom may be involved
in side bonding with atoms or radicals that are positioned adjacent to the chain. Of course,
both chain and side double bonds are also possible.

2.0 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:

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Next, 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 (Figure 1).
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.



a) b)
Figure 1. For polyethylene, (a) a schematic representation of repeat unit and chain
structures, and (b) a perspective of the molecule, indicating the zigzag backbone structure
(Callister & Rethwisch, 2014).

Other chemistry of polymer structure such as tetrafluoroethylene monomer to form
polytetrafluoroethylene (PTFE) is shown below:




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

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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)
(Figure 2).


a)





b)





c)


Figure 2. Repeat unit and chain structures for (a) polytetrafluoroethylene, (b) poly(vinyl
chloride), and (c) polypropylene (Callister & Rethwisch, 2014).


3.0 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.

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Table 1. Description and schematic representations of linear, branched, crosslinked, and

network (three-dimensional) molecular structures. Circles designate individual repeat units
(Callister & Rethwisch, 2014).

Polymer Description Figure
Structure
Linear -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.
-Some of the common polymers that form with
linear structures are polyethylene, poly(vinyl
chloride), polystyrene, poly(methyl methacrylate),
nylon, and the fluorocarbons.
Branched -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 -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.

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Network -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 belong to this group.

Note that polymers may have more than one distinctive structural type, for example,
a linear polymer may have limited branching and crosslinking.

4.0 COMMON POLYMERIC MATERIALS
Presently, there are more than 60,000 synthetic polymers known, with this, six types
of polymers (Table 2) account for roughly 75% of those used in both Europe and the United
States.

Table 2. Six Common Polymers (Symbols retrieved from:
https://www.acmeplastics.com/content/your-guide-to-plastic-recycling-symbols/)
Polymer Recycle Monomer Properties of 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
LDPE and bases.
-Strong and tough.

Polyethylene Ethylene -Similar to LDPE Opaque milk, juice,
-More rigid, tougher, detergents, and
slightly more dense. shampoo bottles.
Buckets, crates, and
HDPE fencing
Polyvinyl chloride Vinyl chloride -Variable. Rigid if Rigid: Plumbing
not softened with a pipe, house siding,
plasticizer. Clear charge cards, hotel
and shiny, but often room keys.
pigmented. Softened: Garden

PVC or V Resistant to most hoses, waterproof

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chemicals, including boots, shower

oils, acids, and curtains, IV tubing.
bases.
Polystyrene -Variable. “Crystal” “Crystal” form: Food
form transparent, wrap, CD cases,
sparkling, transparent cups.
somewhat brittle. “Expandable” form:
-“Expandable” form Foam cups,
PS Styrene lightweight foam. insulated
-Both forms rigid containers, food
and degraded in packaging trays, egg
many organic cartons, packaging
solvents. peanuts.
Polypropylene Propylene -Opaque, very Bottle caps. Yogurt,
tough, good cream, and
weatherability. High margarine
melting point. containers.
PP -Resistant to oils. Carpeting, casual

furniture, luggage.
Polyethylene Ethylene glycol -Transparent, Soft-drink bottles,
terephthalate 𝐻𝑂 − 𝐶𝐻! 𝐶𝐻! − 𝑂𝐻 strong, shatter- clear food
resistant. - containers,
Terephthalic acid Impervious to acids beverage glasses,
and atmospheric fleece fabrics, carpet
gases. yarns, fiber-fill
PETE or PET -Most costly of the insulation.

six.


5.0 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.
There are 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 (Figure 3). The number-
average molecular weight is expressed as

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‡‡‡‡
𝑀* = ˆ 𝑋) 𝑀) 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1
where Mi represents the mean (middle) molecular weight of size range i, and Xi is the fraction
of the total number of chains within the corresponding size range.

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

within the various size ranges. It is calculated according to

‡‡‡‡‡
𝑀 O = ˆ 𝑊) 𝑀) 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2

where, again, Mi is the mean molecular weight within a size range, whereas Wi denotes the
weight fraction of molecules within the same size interval.
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
‡‡‡‡
𝑀*
𝐷𝑃 = 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 3
𝑚

where m is the repeat unit molecular weight.

a) b)

Figure 3. Hypothetical polymer molecule size distributions on the basis of (a) number and
(b) weight fractions of molecules (Callister & Rethwisch, 2014).

The length of polymer chains has affected many polymer properties. For example, as
molecular weight (about 100,000 g/mol) of a polymer increases, its melting or softening
temperature also increases. But for polymers with very short chains or having a molecular
weights on the order of 100 g/mol, will usually exist as liquids at room temperature. Those
with molecular weights of approximately 1000 g/mol exists as waxy solids (e.g. paraffin
wax) and soft resins. For polymers with molecular weights ranging between 10,000 and
several million g/mol exist as solid, they are sometimes termed as high polymers. Therefore,
the same polymer material can acquire various properties if it is produced with different
molecular weight.

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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) the degree of polymerization, and
(c) the weight-average molecular weight.

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

Computations in Example 1.
𝒈
Molecular Weight Mean 𝑴𝒊 𝒎𝒐𝒍 𝑿𝒊 𝑾𝒊
𝒈
Range !𝒎𝒐𝒍"

5,000 - 10,000 7,500 0.05 0.02

10,000 – 15,000 12,500 0.16 0.10
15,000 – 20,000 17,500 0.22 0.18
20,000 – 25,000 22,5000 0.27 0.29
25,000 – 30,000 27,500 0.20 0.26
30,000 – 35,000 32,5000 0.08 0.13
35,000 – 40,000 37,500 0.02 0.02

Solution:
a) Use Equation 1 for solving the number-average molecular weight
‡‡‡‡
𝑀* = ∑ 𝑋) 𝑀)
‡‡‡‡
𝑀* = 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)
𝑴𝒏 = 𝟐𝟏𝟏𝟓𝟎 𝒎𝒐𝒍
𝒈

b) Use equation 3 for solving degree of polymerization
22222
1
𝐷𝑃 3
&
; 𝑠𝑜𝑙𝑣𝑒 𝑓𝑜𝑟 𝑚 𝑤ℎ𝑖𝑐ℎ 𝑖𝑠 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑟𝑒𝑝𝑒𝑎𝑡 𝑢𝑛𝑖𝑡

𝐹𝑜𝑟 𝑃𝑉𝐶 𝑡ℎ𝑒 𝑟𝑒𝑝𝑒𝑎𝑡 𝑢𝑛𝑖𝑡 𝑖𝑠 𝐶𝐻! 𝐶𝐻𝐶𝑙
- - - -
𝑚 = 2 Ž12.01 '.2• + 3 Ž1.01 '.2• + 35.45 '.2 = 62.50 '.2

!((#0 -/'.2 𝒈
𝐷𝑃 = 5!.#0 -/'.2 = 𝟑𝟑𝟖. 𝟒 𝒎𝒐𝒍


c) Use Equation 2 for solving weight-average molecular weight

‡‡‡‡‡
𝑀 O = ∑ 𝑊) 𝑀)

‡‡‡‡‡
𝑀O = 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

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6.0 THERMOPLASTIC AND THERMOSETTING POLYMERS

Molecular structure has a great effect on how polymers react to mechanical forces at
elevated temperatures. Indeed, one classification for these materials is according to behavior
with rising temperature. Thermoplastics (or thermoplastic polymers) and thermosets (or
thermosetting polymers) are the two subdivisions.
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).
For thermosetting polymers which are 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.

7.0 COPOLYMERS
A copolymer is composed of two repeat units as represented in Table 3. 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.

Table 3. 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).

Copolymer Description Figure
Random two different units are randomly
dispersed along the chain

Alternating two repeat units alternate chain positions

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Block identical repeat units are clustered in

blocks along the chain

Graft homopolymer side branches of one type
may be grafted to homopolymer main
chains that are composed of a different

repeat unit

8.0 POLYMER CRYSTALLINITY
In crystalline state, 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. 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. Figure 4 shows the 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 as shown in Figure 4.
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. The extent of crystallinity may range from completely
amorphous to almost entirely (up to about 95%) crystalline. If compared to metal specimens
(almost always entirely crystalline) and many ceramics (either totally crystalline or totally
noncrystalline) polymeric materials behave differently.

Figure 4. Arrangement of molecular chains in a unit cell for polyethylene (Callister &
Rethwisch, 2014).

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LEARNING ENRICHMENT ACTIVITIES
Watch the video to learn more about the topic

https://www.youtube.com/watch?v=rHxxLYzJ8Sw

Refer to the link below to explore more understanding about the topic

https://chem.libretexts.org/Courses/Sacramento_City_College/SCC%3A_Chem_400_-

_General_Chemistry_I/Text/12%3A_Solids_and_Modern_Materials/12.9%3A_Polymers_and_Plastics

References:

Callister, W. D. (2014). Materials Science and Engineering: An Introduction. John Wiley & Sons,
New York

Chang, Raymond and Kenneth A. Goldsby, (2017) Chemistry, (12th International Edition), New
York: McGraw-Hill.

Fahlman, B. D., Purvis-Roberts, K. L., Kirk, J. S., Bentley, A. K., Daubenmire, P. L., Ellis, J. P., &
Mury, M. T. (2018). Chemistry in context: applying chemistry to society (No. 540 C517cc).
McGraw-Hill,.

SCI 401 –GENERAL CHEMISTRY