POLYMERS OR MACROMOLECULES - The plastics bottles in which your milk,

juice, or shampoo come, are usually made of a

POLYMERS plastic called polyethylene.
◼ Polymers (or macromolecules) are made up of
simple molecules with low molecular masses ◼ Polymer backbone
joined together into extremely large molecules. -the long chain of atoms – usually carbon
- Polymers with molecular masses below atoms- running the length of a polymer molecule
about 20,000 u are called low polymers and those
above 20,000 u are called high polymers. ◼ The molecular model shows a portion of a
The word polymer literally means “many parts”. polyethylene molecule. If one of the two hydrogen
- All polymers are made up of very large atoms on every other carbon is replaced with a
molecules. These large molecules are made up of chlorine atom, we will have poly (vinyl chloride),
many smaller molecules linked end to end. commonly referred to as PVC.
- A typical polymer molecule might ◼ Plastic pipe made from PVC has been widely
contain hundreds or even thousands of smaller used in plumbing for many years, so you have
constituent molecules, which are called probably seen PVC pipe in either your house or
monomers. hardware store. The PVC used for pipes is much
harder and stronger than the polyethylene in soda
◼ Monomer bottles. The chemical composition and structures
- the single repeating unit of a polymer of these two materials are very similar.

Two types: Molecular Model

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) Polyethylene
➢ 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.

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, Poly(vinyl chloride) or PVC
parentheses are used.
Example ◼ Replacing the second hydrogen on every other
- Poly (vinyl chloride) carbon atom with chlorine, gives poly (vinylidene
chloride), which is the “plastic wrap” used in
➢ Most synthetic polymers are organic almost every kitchen to cover left overs.
compounds.
◼ Examples
-Nylon, poly(hexamethylene adipamide)
-Dacron, poly(ethylene terephthalate)
-Lucite or Plexiglas, poly(methyl
methacrylate)

◼ Polyethylene molecules
- are composed entirely of just two Poly(vinylidene chloride)
elements, carbon and hydrogen
Example
 - 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)
Made from high-density polyethylene
Polyamide
- another type of condensation polymer
formed when a diamine reacts with
a dicarboxylic acid

◼ Condensation continue to form a long-chain

polymer such as nylon-66, which has the structure
Made from polystyrene

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

Made from poly(vinyl chloride) Polymers of Commercial Importance

Two types of synthetic polymers

1. Addition polymers (also called chain-reaction
or chaingrowth 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.

Copolymers
 Other homopolymers that are synthesized by the
Other Monomers and Their Common Synthetic radicalmechanism:
Polymers -Teflon, polytetrafluoroethylene
- poly(vinyl chloride) - PVC

◼Depending upon the condition of

polymerization, the product may be

Linear polyethylene
- consists almost entirely of unbranched
chains
Other Monomers and Their Common Synthetic
Polymers

◼ 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.

Two forms of polyethylene differ slightly in

density
1. Linear polyethylene
Some Monomers and Their Common Synthetic - referred to in the recycling business as
Polymers 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.
Polyethylene
❖ Branched and
- the most familiar addition polymer
linear polyethylene
- a very stable polymer used in packaging
wraps
- made by joining ethylene monomers via
an additionreaction mechanism
- might be represented by the
polymerization process as where n is a very large
number, of the order of 2000

Polyethylene
◼ an example of a homopolymer, which is a
polymer made up of only one type of monomer
 A cooking utensil coated with Silverstone,
whichcontains polytetrafluoroethylene

◼ (b) Divide the molar mass of the polymer by

that of the monomer.

Stereoisomers of polymers Formation of nylon by the condensation

◼ When the R group (green sphere) is reaction between hexamethylenediamine and
CH3, the polymer is polypropene. adipic acid
a. Isotactic structure ◼ One of the best-known polymer condensation
◼ R groups are all on one side of the processes is the reaction between
chain hexamethylenediamine and adipic acid.
Final product
➢ Nylon 66
Six carbon atoms each in hexamethylenediamine
and adipic acid

b. Syndiotactic structure
◼ R groups alternate from side to side
◼ R group (green sphere) is CH3

c. Atactic structure
◼ R groups are disposed at random
◼ R group (green sphere) is CH3
◼ 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.
Problem
◼ The addition polymer polyvinyl chloride (PVC)
has the structure

(a) Draw the structure of the monomer from which

PVC is made.
(b) How many monomer units are in a PVC ◼ The –COOH group at one end of the ester
polymer that has a molar mass of 1.33 x molecule can react with another alcohol molecule.
105g/mol ? ◼ The –OH group at the other end can react with
Solution an acid molecule.
(a) Find the repeating unit from which the polymer ◼ This process can continue, leading eventually to
is constructed. a longchain polymer containing 500 or more ester
groups.
◼ General structure of the polyester flexible. The resulting material is both strong and
flexible, leading to widespread use in sports
gear and fashion.

Graft copolymer
Example
◼ ABS
◼ ABS is a material in which both butadiene and
acrylonitrile are attached to a polystyrene
Problem backbone.
(a) Show the structure of the ester formed when ◼ The resulting polymer offers a combination of
one molecule of ethylene glycol reacts with one the properties of its three constituents.
molecule of terephthalic acid. ◼ Polystyrene provides ease of processing,
(b) Draw the structure of a section of the Dacron glossiness, and rigidity.
(Mylar) polymer.
◼ Acrylonitrile adds chemical resistance and
Solution
hardness.
(a) split out H₂O between the alcohol and acid
◼ Butadiene provides impact resistance.
molecules
◼ ABS is the standard material of choice for the
(b) continue the esterification process at both ends
strong plastic cases of computers, televisions, and
of the molecule obtained in (a)
other household electronic goods and sometimes is
used as an alternative to PVC for pipes

Physical Properties
Two key reasons for the importance of
polymers as engineering materials:
Alternating copolymers 1. Polymers offer physical properties such as
- monomers are arranged in a regular, strength and elasticity that can be desirable in a
alternating series wide range of uses.
Block copolymer 2. The properties can be controlled or tailored
- has regions in the material where a to a greater degree than is usually possible in
single monomer unit is repeated 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.

Plastics
◼ Copolymers can be grown with different - are polymeric solids that can be formed
arrangements of monomers. Have the different into various shapes, usually by the application of
colored circles represent two different monomers. heat and pressure
The different monomers alternate in an alternating ◼ Types of plastics
copolymer or are randomly combined in a random - Thermoplastic
copolymer. - Thermosetting plastic
- Elastomer
Block copolymer
- each type of monomer tends to be Thermoplastic
clumped together ◼ can be reshaped
Graft copolymers ◼ melt or deform on heating
- involve side chains of one polymer ◼ they are not suitable for high
attached to a backbone of a different polymer temperature applications
Example
Spandex ◼ plastic milk containers
-an example of a block copolymer ◼ are made from the thermoplastic
- In this material, some regions of the polymer polyethylene
polymer are relatively stiff, whereas others are
◼ A great number of plastic objects, including between sites on the carbon backbone of different
children’s toys and bottles of many sorts, are molecular chains.
generally used at ambient temperatures. ◼ These links are referred to as cross-links
◼ The fact that they would melt if heated because they cross between and link individual
appreciably is not a major drawback. molecular strands of the polymer.
◼ The ability to melt the polymer at reasonable ◼ Depending on their complexity, products made
temperatures becomes a major advantage when from thermoplastic polymers are typically
making these objects of complicated shapes. extruded or formed in molds or presses.
◼ The fact that the material softens or melts when
Thermosetting plastic (also called a thermoset) heated allows shaping it into the desired form.
- is shaped through irreversible chemical ◼ Once cooled, the polymer solidifies and regains
processes and, therefore, cannot be reshaped its structural properties.
readily ◼ The different properties of thermoplastic and
- can maintain its shape and strength thermosetting polymers result from the ways in
when heated which the polymer chains interact with one
Examples another.
- Vulcanized rubber ◼ Chemically, these cross-links are additional
- Polyurethanes found in commercial covalent bonds that join the polymer chains to one
products including insulating foams and another.
mattresses ◼ Like most covalent bonds, they are strong
- Nylon and polyesters enough that they do not readily fail upon heating.
So the cross-linked polymer keeps its shape.
◼ To design an object that might need to be used
at higher temperatures, the use of thermoplastics is Elastomer
a poor choice. - another type of plastic that exhibits
◼ The name “thermosetting” comes from the fact rubbery or elastic behavior
that these polymers must be heated to set or “lock Example
in” their structures. Rubber
◼ The materials offer increased strength and do ◼ When subjected to stretching or bending, an
not lose their shape upon further heating. elastomer regains its original shape upon removal
◼ Rather than being extruded, most thermosetting of the distorting force, if it has not been distorted
polymers are molded. beyond some elastic limit.
◼ Nylon and polyesters, both of which are
thermosetting plastics, can be formed into fibers Elasticity
that, like hair, are very long relative to their cross- - another critical physical property of
sectional area. polymers
◼ These fibers can be woven into fabrics and - ability of many polymeric materials to
cords and fashioned into clothing, tire cord, and be stressed and deformed but return to their
other useful objects. original shape

◼ The molecular origin of the difference between ◼ Elastomers

thermoplastic and thermosetting polymers is - polymers that are particularly flexible
shown in the figure 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.

◼ The initial heating and setting of a Polymers and Additives

thermosetting polymer produces a number of links
 - 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.

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.