POLYMERS

OR
MACROMOLECULES
LEARNING OUTCOMES
 At the end of the discussion, the students should be
able to:
 discuss the properties of polymers;
 differentiate between addition and condensation polymers;
 distinguish between a block copolymer and a graft copolymer;
 explain the key physical property that characterizes a thermoplastic
polymer; and
 explore how both molecular shape and interactions between
polymer chains affect the physical properties of polymers.
 POLYMERS
 Polymers (or macromolecules) are made up of simple molecules
with low molecular masses joined together into extremely large
molecules.
 Polymers with molecular masses below about 20,000 u are called low polymers
and those above 20,000 u are called high polymers.
The word polymer literally means “many parts”.
 All polymers are made up of very large molecules. These large molecules are made up of
many smaller molecules linked end to end.
 A typical polymer molecule might contain hundreds or even thousands of smaller
constituent molecules, which are called monomers.
 Monomer
 the single repeating unit of a polymer
 POLYMERS cont.
Two types
 1. Natural polymers (or biopolymers)
 created by chemical reactions within organisms
 the stuff of life -- proteins, nucleic acids, and polysaccharides
 2. Synthetic (or man-made polymers)
 created by chemical reactions in the laboratory, i.e., by
joining monomers together, one at a time, by means of
addition reactions and condensation reactions
 POLYMERS cont.
 How to name a polymer
 Just add the prefix poly- to the monomer name
 Examples
 Polyethylene, polystyrene
 When the monomer has a two-word name,
parentheses are used.
 Example
 Poly (vinyl chloride)
 POLYMERS cont.
 Most synthetic polymers are organic compounds.
 Examples
 Nylon, poly(hexamethylene adipamide)
 Dacron, poly(ethylene terephthalate)
 Lucite or Plexiglas, poly(methyl methacrylate)
 POLYMERS cont.
 Polyethylene molecules
 are composed entirely of just two elements, carbon and hydrogen
Example
 The plastics bottles in which your milk, juice, or shampoo come, are usually made of

a plastic called polyethylene.

 Polymer backbone
 the long chain of atoms – usually carbon atoms- running the length of a polymer
molecule
 POLYMERS cont.
 The molecular model (next slide) shows a portion of a polyethylene
molecule. If one of the two hydrogen atoms on every other carbon is
replaced with a chlorine atom, we will have poly (vinyl chloride),
commonly referred to as PVC.
 Plastic pipe made from PVC has been widely used in plumbing for many
years, so you have probably seen PVC pipe in either your house or
hardware store. The PVC used for pipes is much harder and stronger
than the polyethylene in soda bottles. The chemical composition and
structures of these two materials are very similar.
Molecular Model

Polyethylene
Molecular Model cont.

Poly(vinyl chloride) or PVC

 POLYMERS cont.
 Replacing the second hydrogen on every other carbon atom
with chlorine, gives poly (vinylidene chloride), which is the
“plastic wrap” used in almost every kitchen to cover left
overs.
Molecular Model cont.

Poly(vinylidene chloride)
 POLYMERS cont.

Made from high-density polyethylene

POLYMERS cont.

Made from polystyrene

POLYMERS cont.

Made from poly(vinyl chloride)

 POLYMERS cont.
 Two types of synthetic polymers
 1. Addition polymers (also called chain-reaction or chain-
growth polymers)
 form when monomers undergo an addition reaction with one another
 typically, only one kind of monomer is involved
 2. Condensation polymers
 monomer units combine by splitting out (condensing) a simple molecule such as
H₂O
 typically, two or more different monomers react with one another to form a
condensation polymer
 Many condensation polymers are copolymers.
 POLYMERS cont.
 Copolymers
 consist of two or more different repeat units
 Two major types
 1. Polyamides (or nylons)
 formed from the condensation of carboxylic acid and amine
monomers
 Nylon 66
 one of the most common polyamides, manufactured by mixing equimolar
amounts of a six-C diamine (1, 6-diamino hexane) and a six-C diacid (1, 6-
hexanedioic acid)
 POLYMERS cont.
 Polyamide
 another type of condensation polymer formed when a diamine reacts with
a dicarboxylic acid
 POLYMERS cont.
 Condensation continue to form a long-chain
polymer such as nylon-66, which has the structure
 POLYMERS cont.
 2. Polyesters
 formed from the condensation of carboxylic acid and alcohol
monomers
 Dacron
 a popular polyester fiber, is woven from polymer strands formed
when equimolar amounts of 1,4-benzenedicarboxylic acid and
1,2-ethanediol react
Polymers of Commercial Importance
Polymers of Commercial Importance cont.
Other Monomers and Their Common Synthetic Polymers
Other Monomers and Their Common Synthetic Polymers
Some Monomers and Their Common Synthetic Polymers
 POLYMERS cont.
 Polyethylene
 the most familiar addition polymer
 a very stable polymer used in packaging wraps
 made by joining ethylene monomers via an addition-
reaction mechanism
 might be represented by the polymerization process as
where n is a very large
number, of the order of 2000
 POLYMERS cont.
 Polyethylene
an example of a homopolymer, which is a polymer made up
of only one type of monomer
Other homopolymers that are synthesized by the radical
mechanism
 Teflon, polytetrafluoroethylene
 poly(vinyl chloride) - PVC
 POLYMERS cont.
 Depending upon the condition of polymerization, the
product may be
 POLYMERS cont.
 Linear polyethylene
 consists almost entirely of unbranched chains
 POLYMERS cont.
 Neighboring chains in linear polyethylene line up
nearby parallel to each other.
 This gives a polymer that approaches a crystalline
material.
 It is used for bottles, toys, and other semirigid
objects.
 POLYMERS cont.
 Two forms of polyethylene differ slightly in density
 Linear polyethylene
 referred to in the recycling business as high-density
polyethylene, represented by the symbol “HDPE #2” on the
bottom of a plastic bottle
 Branched polyethylene
 corresponding symbol for branched polyethylene is “LDPE #4,” indicating
low-density polyethylene
 Note
 The smaller the number, the easier it is to recycle.
 POLYMERS cont.
 Branched and
linear polyethylene
 POLYMERS cont.
 A cooking utensil coated with Silverstone, which
contains polytetrafluoroethylene
 POLYMERS cont.
 Stereoisomers of polymers
 When the R group (green sphere) is CH3, the polymer is
polypropene.
 a. Isotactic structure
 R groups are all on one side of the chain
 POLYMERS cont.
 b. Syndiotactic structure
 R groups alternate from side to side
 R group (green sphere) is CH3
 POLYMERS cont.
 c. Atactic structure
 R groups are disposed at random
 R group (green sphere) is CH3
 POLYMERS cont.
 Problem
 The addition polymer polyvinyl chloride (PVC) has the structure
H H H H H H

C C C C C C

H Cl H Cl H Cl
 (a) Draw the structure of the monomer from which PVC is made.
 (b) How many monomer units are in a PVC polymer that has a molar
mass of 1.33 x
 POLYMERS cont.
 Solution
 (a) Find the repeating unit from which the polymer is
constructed. H H

H C C Cl
 (b) Divide the molar mass of the polymer by that of
the monomer.
 No. of monomer units = = 2.00 x
 Formation of nylon by the condensation reaction
between hexamethylenediamine and adipic acid
 One of the best-known polymer
condensation processes is the
reaction between
hexamethylenediamine and
adipic acid.
Final product
 Nylon 66

Six carbon atoms each in

hexamethylenediamine and
adipic acid
 POLYMERS cont.
 Polyester is formed when an alcohol with two –OH groups, HO-R-OH,
reacts with a dicarboxylic acid, HOOC-R’-COOH. The first step in the
process is the formation of a simple ester that has a reactive group at
both ends of the molecule.
 POLYMERS cont.
 The –COOH group at one end of the ester molecule can
react with another alcohol molecule.
 The –OH group at the other end can react with an acid
molecule.
 This process can continue, leading eventually to a long-
chain polymer containing 500 or more ester groups.
 POLYMERS cont.
 General structure of the polyester
 POLYMERS cont.
Problem
 (a) Show the structure of the ester formed when one molecule of
ethylene glycol reacts with one molecule of terephthalic acid.
 (b) Draw the structure of a section of the Dacron (Mylar) polymer.
Solution
(a) split out H₂O between the alcohol and acid molecules
(b) continue the esterification process at both ends of the
molecule obtained in (a)
Solution
 POLYMERS cont.
 Alternating copolymers
 monomers are arranged in a regular, alternating series
 Block copolymer
 has regions in the material where a single monomer unit is repeated
POLYMERS cont.
 POLYMERS cont.
 Copolymers can be grown with different arrangements of
monomers. Have the different colored circles represent two
different monomers. The different monomers alternate in an
alternating copolymer or are randomly combined in a random
copolymer.
 Block copolymer
 each type of monomer tends to be clumped together
 Graft copolymers
 involve side chains of one polymer attached to a backbone of a different
polymer
 POLYMERS cont.
 Spandex
 an example of a block copolymer

 In this material, some regions of the polymer are relatively

stiff, whereas others are flexible. The resulting material is
both strong and flexible, leading to widespread use in sports
gear and fashion.
 POLYMERS cont.
 Graft copolymer
 Example
 ABS

 ABS is a material in which both butadiene and acrylonitrile are attached to a polystyrene
backbone.
 The resulting polymer offers a combination of the properties of its three constituents.
 Polystyrene provides ease of processing, glossiness, and rigidity.
 Acrylonitrile adds chemical resistance and hardness.
 Butadiene provides impact resistance.
 ABS is the standard material of choice for the strong plastic cases of computers,
televisions, and other household electronic goods and sometimes is used as an
alternative to PVC for pipes.
 POLYMERS cont.
 Physical Properties
 Two key reasons for the importance of polymers as engineering
materials
 1. Polymers offer physical properties such as strength and elasticity that can be
desirable in a wide range of uses.
 2. The properties can be controlled or tailored to a greater degree than is usually
possible in metals or other classes of materials.
 Through the choice of a particular polymer and the details of its
synthesis and processing, materials engineers can choose the
properties they need with striking degree of specificity.
 POLYMERS cont.
 Plastics
 are polymeric solids that can be formed into various
shapes, usually by the application of heat and pressure
 Types of plastics
 Thermoplastic
 Thermosetting plastic
 Elastomer
 POLYMERS cont.
 Thermoplastic
 can be reshaped
 melt or deform on heating
 they are not suitable for high temperature applications
 Example
 plastic milk containers
 are made from the thermoplastic polymer polyethylene
 POLYMERS cont.
 A great number of plastic objects, including children’s toys and
bottles of many sorts, are generally used at ambient
temperatures.
 The fact that they would melt if heated appreciably is not a
major drawback.
 The ability to melt the polymer at reasonable temperatures
becomes a major advantage when making these objects of
complicated shapes.
 POLYMERS cont.
 Thermosetting plastic (also called a thermoset)
 is shaped through irreversible chemical processes and,
therefore, cannot be reshaped readily
 can maintain its shape and strength when heated
 Examples
 Vulcanized rubber
 Polyurethanes found in commercial products including insulating
foams and mattresses
 Nylon and polyesters
 POLYMERS cont.
 To design an object that might need to be used at higher
temperatures, the use of thermoplastics is a poor choice.
 The name “thermosetting” comes from the fact that these
polymers must be heated to set or “lock in” their
structures.
 The materials offer increased strength and do not lose
their shape upon further heating.
 Rather than being extruded, most thermosetting polymers
are molded.
 POLYMERS cont.
 Nylon and polyesters, both of which are thermosetting
plastics, can be formed into fibers that, like hair, are
very long relative to their cross-sectional area.
 These fibers can be woven into fabrics and cords and
fashioned into clothing, tire cord, and other useful
objects.
 POLYMERS cont.
 The molecular origin of the difference between thermoplastic
and thermosetting polymers is shown in the figure (next
slide).
 The initial heating and setting of a thermosetting polymer
produces a number of links between sites on the carbon
backbone of different molecular chains.
 These links are referred to as cross-links because they cross
between and link individual molecular strands of the polymer.
POLYMERS cont.
 POLYMERS cont.
 Depending on their complexity, products made from
thermoplastic polymers are typically extruded or formed
in molds or presses.
 The fact that the material softens or melts when heated
allows shaping it into the desired form.
 Once cooled, the polymer solidifies and regains its
structural properties.
 POLYMERS cont.
 The different properties of thermoplastic and
thermosetting polymers result from the ways in which the
polymer chains interact with one another.
 Chemically, these cross-links are additional covalent bonds
that join the polymer chains to one another.
 Like most covalent bonds, they are strong enough that
they do not readily fail upon heating. So the cross-linked
polymer keeps its shape.
 POLYMERS cont.
 Elastomer
 another type of plastic that exhibits rubbery or elastic
behavior
 Example
 Rubber
 When subjected to stretching or bending, an elastomer
regains its original shape upon removal of the distorting force,
if it has not been distorted beyond some elastic limit.
 POLYMERS cont.
 Elasticity
 another critical physical property of polymers
 ability of many polymeric materials to be stressed and deformed but return to their
original shape
 Elastomers
 polymers that are particularly flexible and elastic

 The geometry of the carbon backbone is often such that the elastomer forms an
amorphous solid rather than a crystalline one. The forces between polymer
molecules in an amorphous solid are not as strong as those in a more crystalline
system, so they can be deformed and restored with less force.
 POLYMERS cont.
 Polymers and Additives
 Despite their wide range of useful properties, polymers alone often do
not have the characteristics needed for a particular design.
 Additives can be included in the material to control polymer properties.
 Some additives have only modest mechanical effects.
 Pigments, for example, can be added solely to change the color of the
material and don’t influence the underlying molecular structure of a
polymer.
 PVC alone, is too brittle for many applications. To rectify this, relatively
small molecules called plasticizers are added to improve its flexibility.
 POLYMERS cont.
 Several critical features of a plasticizer
 It must be capable of being incorporated into the solid polymer, so its structure
should resemble the polymer being used.
 It must be nonvolatile, or it will escape from the solid too quickly and no longer
impart the desired flexibility.
 Plasticizers do escape slowly, and often the smell associated with
plastic materials arises from the release of trace amounts of these
additives.
 Other additives that find regular use include antistatic agents, fillers,
fire retardants, and light and heat stabilizers.
 POLYMERS cont.
 Exercises
 1. Define the following terms:
 a. Polymer
 b. Monomer
 c. Addition polymers
 d. Condensation polymers
 POLYMERS cont.
 2. Name at least three common polymers and give examples of
their uses.
 3. Distinguish between a block copolymer and a graft copolymer.
 4. What is the key physical property that characterizes a
thermoplastic polymer?
 5. What conditions would prohibit the use of a thermoplastic
polymer?
 6. What happens molecularly in a thermosetting polymer when it
is heated?
 REFERENCES
 Brown et al. (2012). Chemistry: The Central Science
(12th ed.). Glenview: Pearson Education, Inc.
 Chang, R. & Goldsby, K.A. (2016). Chemistry (12th
ed.). New York: McGraw-Hill Education.
 Silberberg, M.S. (2013). Principles of general
chemistry (3rd ed.). New York: The McGraw-Hill
Companies, Inc.