22 Polymer

Richard F. Daley and Sally J.
Daley
www.ochem4free.com
Organic
Chemistry
Chapter 22
Polymer Chemistry
22.1 Structural Characteristics of Polymers 1138
22.2 Polymer Nomenclature 1141
22.3 Types of Polymerization Reactions 1144
22.4 Chain-Growth Polymerization 1146
Synthesis of Poly(vinyl acetate) 1155
Sidebar - Natural Rubber 1155
22.5 Controlling Stereochemistry in Vinyl Polymers 1157
22.6 Nonvinyl Chain-Growth Polymerization 1160
22.7 Step-Growth Polymerization 1163
Synthesis of Poly(ethylene terephthalate) 1165
Sidebar - Plastic Recycling 1167
22.8 Copolymers 1169
Sidebar - Plasticizers 1172
22.9 Cross-Linked Polymers 1173
Key Ideas from Chapter 22 1178
Organic Chemistry - Ch 22 1134 Daley & Daley
Copyright 1996-2001 by Richard F. Daley & Sally J. Daley

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No part of this publication may be reproduced, stored in a retrieval system, or

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www.ochem4free.com 5 July 2005

Chapter 22
Polymer Chemistry
Chapter Outline
22.1 Structural Characteristics of Polymers
A look at the various types of polymers
22.2 Polymer Nomenclature
An introduction to naming polymers
22.3 Types of Polymerization Reactions
Categories of polymer forming reactions
22.4 Chain-Growth Polymerization
The mechanism for the formation of vinyl chain-growth polymers
22.5 Controlling Stereochemistry in Vinyl Polymers
The Ziegler-Natta polymerization catalyst for vinyl polymers
22.6 Nonvinyl Chain-Growth Polymerization
Mechanisms for chain-growth polymer formation for nonvinyl
polymers
22.7 Step-Growth Polymerization
The mechanisms for the formation of some representative step-
growth polymers
22.8 Copolymers
An examination of the various types of copolymers
22.9 Cross-Linked Polymers
Types of cross-linking that occur in polymers

Objectives
✔ Recognize the various types of polymer structures

✔ Know how to name both source-based and nonvinyl polymers
✔ Recognize the monomers that produce polymers
✔ Write the mechanisms for cationic, anionic, and radical
polymerization of vinyl monomers
✔ Know the stereochemical types of vinyl polymers
✔ Write the mechanism for representative non-vinyl chain-growth
polymerizations
✔ Recognize the similarity of the step-growth polymerization
reactions to those studied in earlier chapters
✔ Know the types of copolymers
✔ Recognize how cross-linking occurs in epoxy polymers
Observation is a passive science, experimentation

an active science.
— Claude Bernard
A polymer is a molecule
made up of many
smaller units called
monomers.
A polymer is a large molecule that consists of a number
of smaller repeating units made from molecules called
monomers. Polymers are formed by some repetitive reaction that
adds these monomer units one-by-one to the growing chain of the
polymer. The process of converting the monomer units to a polymer is
A reaction forming a called polymerization.
polymer is a Polymers, sometimes called macromolecules, affect your life in
polymerization many ways. For example, plastics are synthetic polymers, and they
reaction. are all around you. Industry makes plastics into such things as fibers,
structural materials, and protective films. Except for fuels, more
plastics are manufactured in the world than any other organic
material. One-third of all industrial chemists work in the polymer
industry.
Another way that polymers affect your life is in the natural
chemistry of the life processes. Proteins and enzymes are polyamide
polymers. Proteins are an important part of the structure of all
animals, and enzymes catalyze the chemical processes that make

those bodies function. Cellulose and starches are polymers of

individual sugar molecules. Cellulose is the structural material of
plants, and starches are the energy storage medium for plants. Both
RNA and DNA are polymers of individual nucleic acids. These two
classes of molecules control the genetic make-up of your body. This
chapter focuses primarily on synthetic polymers. Chapters 24 and 25
cover some types of natural macromolecules.
Generally, the size and stereochemistry of the polymer
molecule determine the properties of that molecule. This chapter
examines how those features determine a polymer's physical
properties. This chapter also discusses polymer synthesis.
22.1 Structural Characteristics of Polymers

The composition of polymers is a sequence of repeating
monomer units that are covalently bonded together. The reactions
that connect these repeating units can involve any of the functional
groups discussed previously. The functional group on the repeating
unit provides the reactive site for the connecting reaction.
The repeating units of polymers have a variety of possible
structures. When all the repeating units in a particular polymer have
In a homopolymer, all
the same structure, that polymer is called a homopolymer.
the repeating units are
identical. nA A A A A A A A A or An
An example of a homopolymer is polyvinyl chloride.
CH2 CH CH2CHCH2CHCH2CHCH2CHCH2CH or CH2CH n
Cl Cl Cl Cl Cl Cl Cl
Polyvinyl chloride
When different repeating units make up the polymer chain, the

A copolymer contains polymer is called a copolymer. There are three types of copolymers:
more than one type of 1) alternating copolymers, 2) block copolymers, and 3) random
monomer unit. copolymers. If you designate the repeating units as A and B, the
following illustration shows representations of these three types of
copolymers.
Alternating copolymer
nA + nB A B A B A B A B

Block copolymer
mA + nB A A A A A B B B
Random copolymer
mA + nB A B B B A A B B
An example of the alternating copolymer is Nylon 66.
O O O O
n H2N(CH2)6NH2 + n ClC(CH2)4CCl NH(CH2)6NHC(CH2)4C

n
Nylon 66
A linear polymer is a All the above examples are linear polymers. Some polymers
molecule with a series contain additional covalent links to repeating units at various
of connected repeating
units with no locations on the backbone. Such polymers are called branched
branching. polymers. Linear or branched polymer chains can be connected by
some additional covalent links. These polymers are called cross-
A branched polymer linked polymers.
has bonds branching
from the backbone of a
linear polymer. Polymer End Groups
Cross-linked polymers
The structural drawings of all the polymers discussed in this chapter show a bond
are linear polymer
extending out of the brackets that enclose the repeating unit. The functional groups
molecules joined by a
on the ends of the polymer chains are left unspecified because the end groups are an
branching connection.
insignificant portion of the total chain. These groups have very little effect on the
physical properties of the polymer. In a given sample of polymer, a variety of end
groups may be present depending on how the polymer was synthesized.
The physical properties of a specific polymer are the result of

two molecular characteristics: 1) the length of the molecule and 2) the
functional group associated with the repeating units. To determine the
length of a polymer chain, chemists use the molecular weight of the
polymer. Different polymers of the same chain length have similar
physical properties regardless of the functional group present unless
the functional group can hydrogen bond or disrupt the intermolecular
van der Waals forces. These two interactions are more important in
determining the physical properties of the polymer than is the
molecular weight.
The physical properties of interest to a consumer are those that
show how well the polymer performs in response to various stresses.
Compressive, flexural,
These responses include compressive, flexural, and tensile
and tensile strength, as strength, as well as impact resistance. Compressive strength is a
well as impact measure of how much compression a sample can tolerate before it
resistance are
measures of the
mechanical strength of
a polymer. www.ochem4free.com 5 July 2005
fails. Flexural strength is a measure of resistance to breaking or

snapping when the sample is bent. Tensile strength is a measure of
resistance to stretching. Impact resistance is a measure of how well a
sample resists damage from a sudden impact.
Some polymers have the characteristics of a crystalline solid.
The molecules of a
crystalline polymer line Crystalline polymers have chains that tend to orient themselves in
up in a regular way a regular way, similar to the way the molecules in a crystalline solid
similar to the smaller orient themselves. The chains are held together in this regular
molecules in a crystal. orientation by hydrogen bonds or dipole alignments. These polymers
generally have characteristic melting points, are strong, and
nonelastic. Linear polyethylene is an example of such a crystalline
polymer.
Orientation of the chains of a crystalline polymer
The molecules in an
Amorphous polymers are similar to glassy solids.
amorphous polymer do Amorphous polymers do not have a characteristic melting point.
not have any preferred Instead, they often make an indistinct transition from the glassy solid
alignment. to a viscous liquid called the glass transition temperature. These
polymers do not have a regular orientation in the solid state.
A glassy solid is a solid Amorphous polymers are generally not particularly strong and tend to
that is often hard and
be quite elastic. Rubber is an example of an amorphous polymer.
brittle.
The glass transition

temperature is the
temperature at which a
polymer transforms
from a glass to a
viscous liquid
Orientation of the chains of an amorphous polymer
Many polymers are neither completely crystalline nor

completely amorphous. Segments of the chains lie parallel to each
Ordered regions among other in regions called crystallites. Other segments of the chains are
the amorphous regions not ordered. Such polymers are called semicrystalline polymers.
in a semicrystalline These polymers have much of the strength of a crystalline polymer
polymer are called along with much of the flexibility of an amorphous polymer. Nylon is
crystallites.
an example of a semicrystalline polymer.

Semicrystalline
Crystalline regions
polymers are polymers
(Crystallites)
with regions of
disorder and Amorphous region
crystallites.
Orientation of the chains of a semicrystalline polymer
Crystalline polymers generally are opaque, but amorphous

polymers generally are transparent. Thus, increasing the number of
crystallites in a polymer normally reduces the transparency of the
polymer. An example is polystyrene. Amorphous polystyrene is found
in a number of transparent, brittle "plastic" items, such as drinking
cups.
22.2 Polymer Nomenclature

The IUPAC has proposed some logical rules for naming
polymers, but polymer chemists seldom use them because many
polymers are so branched and cross-linked that their names are very
complex. Thus, this section is only an introduction to the
fundamentals of naming polymers. Many polymer chemists use source
based naming. They name the monomer then add the poly- prefix. A
complication with this method is that chemists use the common names
of the monomers more often than their IUPAC names. For example,
the common name for ethenylbenzene is styrene, so chemists call the
polymer of styrene polystyrene. In addition to using common names,
chemists refer to many polymers by their trade names. They use the
trade name Teflon® more frequently than the IUPAC name of
polytetrafluroethylene.
Vinyl polymers are among the easiest polymers to name when
following the common name method. Simply use the monomer's
common name with the prefix poly-. If the monomer's name includes
more than one word, or if a letter or number precedes the name,
enclose the monomer's name in parentheses. Thus, the polymer of 1-
pentene is poly(1-pentene). Table 22.1 lists a few common names for
vinyl polymers.

Monomer Monomer Name Polymer Polymer Name
CH2 CH2 Ethylene CH2CH2 Polyethylene

n
CH2 CHCH3 Propylene CH2CH Polypropylene

n
CH3
CH2 CHCN Acrylonitrile CH2CH Polyacrylonitrile

n
CN
CH3 CH3
CH2 C Methyl methacrylate
CH2C Poly(methyl methacrylate)
COOCH3 n
COOCH3
CH2 CH Vinyl acetate CH2CH Poly(vinyl acetate)

n
OCCH3 OCCH3
O O
CH2 CHCl Vinyl chloride CH2CH Poly(vinyl chloride)

n
Cl
CH2 CH Styrene CH2CH Polystyrene

n
CF2 CF2 Tetrafluoroethylene CF2CF2 Polytetrafluoroethylene

n
Table 22.1. Representative names for some vinyl polymers.
Nonvinyl polymers generally have some atom other than

carbon as a part of the backbone of the polymer. As with the vinyl
polymers, the nomenclature of these polymers is often source based or
based on their trade names. Nylon is an example of a family of
compounds that chemists call by their trade names. To name them,
use the word Nylon followed by a number for the number of carbons in
the monomer(s) for that Nylon. Nylon 6 is a polymer made from
monomers that consist of a single cyclic amide with six carbons. The
monomers in Nylon 68 are diamines with six carbons and dicarboxylic
acids with eight carbons.

O O
NHCH2CH2CH2CH2CH2CH2NHCCH2CH2CH2CH2CH2CH2C n
From a 6 carbon amine From an 8 carbon carboxylic acid
Nylon 68
Table 22.2 lists a few representative nonvinyl polymer names.
Monomer Monomer Name Polymer Polymer Name
O
CH2 CH2 Ethylene oxide CH2CH2O Poly(ethylene oxide)
n
O
O
Propiolactone OCH2CH2C n Polypropiolactone
O
HOCH2CH2OH Ethylene glycol

+ O O
+ Poly(ethylene terephthalate)
O O CH2CH2OC CO
Terephthalic acid n
HOC COH
O
O
Polycaprolactam
NH Caprolactam NH(CH2)5C
n Nylon 6
H2N(CH2)6NH2 Hexamethylenedi- O O Poly(hexamethylene

amine sebacate)
+ NH(CH2)6NHC(CH2)6C
+ n Nylon 68
HOOC(CH2)6COOH Sebacic acid
Table 22.2. Representative names for some nonvinyl polymers.
Exercise 22.1
Name the following polymers and draw structural formulas for the
monomers that form each of the polymers.
a) b) c)
CH2CH n O CH2CH n
CH2CH3 OCH2CH2CH2C OH
n

d) e) f)
CH3 O O
n
CHCH n NH(CH2)6NHC(CH2)4C
n
CH2CH3
Sample solution
b) Polybutyrolactone
O
22.3 Types of Polymerization Reactions

Chemists classify polymerization reactions in terms of their
reaction mechanisms. There are two types of polymerization reaction
Chain-growth mechanisms: 1) chain-growth polymerizations and 2) step-
polymerization adds growth polymerizations.
monomer units with A chain-growth polymerization begins when an initiator reacts
the same functional with a monomer molecule to create a reactive site. This reactive site
group to the chain.
then reacts with another monomer molecule joining the two, as well as
In step-growth creating a new reactive site. Monomer molecules continue adding to
polymerization, one the reactive site and forming a new reactive site as long as monomer
functional group at the molecules are available or until some termination reaction occurs. A
end of the chain polymer that forms via a chain-growth polymerization usually forms
requires a different
functional group to
from one monomer or group of monomers with the same reactive
react and lengthen the functional group. The formation of polyethylene from ethylene in the
chain. presence of an initiator is an example of a chain-growth
polymerization.
Initiator
CH2 CH2 CH2CH2 n
Polyethylene
The mechanism for a chain-growth polymerization is often a

radical reaction. As you read through the description of the chain-
growth polymerization above, you may have recognized the initiation,
propagation, and termination steps from the radical reaction that you
studied in Chapter 21. However, not all initiators generate radicals in
the initiation and propagation steps; instead, many generate cationic
or anionic intermediates. The important consideration is not whether
the reaction proceeds as a radical reaction or generates a cationic or

anionic intermediate, but that the initiator makes the chain reaction
possible.
A step-growth polymerization begins with a mixture of
monomers that contain different functional groups. Although the
mixture can contain numerous different functional groups, for
simplicity look at how the reaction proceeds with a mixture of
monomers that contains only two different functional groups. Each
functional group type can react with the other type in the mixture but
not with itself. The chain begins when one monomer joins with
another monomer containing the other functional group type. The first
monomer then reacts with the end of this two unit chain. Unlike the
chain-growth polymerization, a step-growth polymerization usually
does not have a radical, cation, or anion at the end of the growing
chain. Instead, the chain grows by the reaction of the functional group.
The formation of Nylon 66 is an example of a step-growth
polymerization.
O O
H2NCH2CH2CH2CH2CH2CH2NH2 + HOCCH2CH2CH2CH2COH
O O
NHCH2CH2CH2CH2CH2CH2NHCCH2CH2CH2CH2C
n
Nylon 66
The formation of Nylon 66 has two steps in the step-growth

mechanism. A monomer containing the diamine and another monomer
containing the dicarboxylic acid react joining the two. Either of the
following two reactions then occurs. The diamine reacts with the
carboxylic end of the two unit polymer, or the dicarboxylic acid reacts
with the amine end. Subsequent reactions occur with the proper
reagent reacting with the appropriate end of the growing chain.
Step 1
O O
H2NCH2CH2CH2CH2CH2CH2NH2 + HOCCH2CH2CH2CH2COH
O O
H2NCH2CH2CH2CH2CH2CH2NHCCH2CH2CH2CH2COH
Step 2

O O
H2NCH2CH2CH2CH2CH2CH2NH2
O O
H2NCH2CH2CH2CH2CH2CH2NHCCH2CH2CH2CH2CNHCH2CH2CH2CH2CH2CHNH2
OR
O O
O O
HOCCH2CH2CH2CH2COH
O O O O
HOCCH2CH2CH2CH2CNHCH2CH2CH2CH2CH2CH2NHCCH2CH2CH2CH2COH
Another possible second step that the step-growth mechanism

can follow is the reaction of the amine end of one chain with the
carboxylic acid end of another chain. When this occurs, instead of all
the polymer molecules growing steadily at the same rate, some grow
much more rapidly. This way of joining results in a wide variety of
possible molecular weights, making it more difficult to predict the
characteristics of the polymer in comparison to a reaction mixture in
which each chain grows at a similar pace.
22.4 Chain-Growth Polymerization

Chain-growth polymers form from radicals, cations, or anions.
Because a wide variety of monomers lend themselves so readily to the
formation of radicals, most chain-growth polymerization reactions
proceed via radical intermediates. Some monomers do polymerize with
ionic initiators, but that number is far fewer than those that
polymerize with a radical initiator. Chain-growth polymerization
reactions usually form vinyl polymers. One such vinyl polymer is
polystyrene. Polystyrene polymerizes under radical, cationic, and
anionic initiation. This section examines all three.
The radical polymerization of styrene uses benzoyl peroxide as
the initiator. As with the radical reactions you studied in Chapter 21,
a radical polymerization follows three steps: 1) the initiation step, 2)
the propagation step, and 3) the termination step. In the first reaction
of the initiation step, the benzoyl peroxide undergoes a homolytic
cleavage to form two benzoyloxy radicals. In the second reaction of the
initiation step, each benzoyloxy radical reacts with a molecule of
styrene to form a benzylic radical.

Initiation step
••
••
•
• O
•
• O
•• ••
•• O
•• O•
O
••
••
•
• O
••
•• ••
•
• O •
• O
•• ••
O• O •
•• ••
In the propagation step, the chain begins to grow as the

benzylic radical reacts with a molecule of styrene to add the styrene
and to form a new benzylic radical. This new benzylic radical then
reacts with another molecule of styrene adding the styrene and
forming another new radical. This process continues many times as
the polymer chain lengthens. Once started, the rate of reaction is
relatively high for a chain formation. Approximately 1500-1600
styrene monomer units add to the growing chain each second.
Propagation step
••
•• •
• O
•
• O
••
•• O •
O
••
• ••
The propagation reaction continues until it reacts in a

termination reaction or until it uses up all the monomer molecules in
the reaction mixture. The most common termination reaction
combines two radicals from two growing chains to form a longer chain.
This reaction terminates both chain reactions because the reaction
forms no new radical.
Termination step

•
n
m
m n
Another reaction that occurs in radical chain-growth

In a chain-transfer polymerization is a chain-transfer reaction. In a chain-transfer
reaction, one growing reaction, the end of a growing chain abstracts a hydrogen from the
polymer chain benzylic position of another chain. This abstraction creates a new
abstracts a hydrogen radical in the middle of the chain.
atom from another
polymer chain.
•
n
x y
H •
n x y
+
This new radical site serves as a reaction site for additional monomer
molecules to branch off the main polymer chain.

y x y
x
Exercise 22.2
A polymerization reaction involving 1,3-butadiene and a radical

initiator forms two different repeating polymer units. Account for the
formation of these two units.
CH2 CH CH CH2 CH2 CH
CH CH2
Cationic polymerization is similar to radical polymerization in

that both react with the initiator to form a reactive site on the same
carbon of the styrene. To run cationic polymerization reactions,
chemists use strong Brønsted-Lowry acids, as well as Lewis acids.
When they use a Lewis acid, they must also use some hydrogen halide
and water. The requirement for the hydrogen halide and water
suggests an involvement of a proton acid in the reaction.
Again using the polymerization of styrene as an example, look
at the mechanism of a cationic polymerization. The initiation step in a
cationic polymerization of styrene adds a proton to the double bond of
the styrene to form a carbocation.
Initiation step
H
H
In the propagation step, the carbocation reacts with a molecule of

styrene to form a new carbocation. This step repeats itself until the

reaction either runs out of reactants or until the polymers react in a

termination step.
Propagation step
H
H
Repeat
H
n
The reaction can terminate by losing a proton, by reacting with a

nucleophile, or by the carbocation removing a hydride from another
polymer molecule. All three of these steps are typical carbocation
termination reactions.
Termination step

H
n
-H Nu ••
Nu
H
H R H n
n
H
H
n
The removal of the hydride from another polymer chain can lead to
branching of the polymer chain similar to the branching in the radical
reaction.
Exercise 22.3
What product would you expect in a cationic polymerization reaction

of styrene if you added 1% 1,4-divinylbenzene to the reaction mixture?
What difference would you expect this small amount of added material
to make in the properties of the polymer?
The third type of chain-growth polymerization reaction

Anionic initiation presented in this section is an anionic initiation. Alkali metals or
requires a strong base organometallic compounds catalyze some polymerization reactions.
to initiate the polymer The reactive species in these reactions is a carbanion. Thus, the
chain growth.
reaction is called an anionic polymerization reaction. Styrene is one of
those compounds that polymerizes with an anionic initiator. To run an
anionic polymerization with styrene, the chemist usually prepares the
initiator before adding the styrene to the reaction mixture.
A common initiator in an anionic polymerization is sodium
naphthalide—the radical anion of naphthalene. Chemists prepare
sodium naphthalide by reacting sodium with naphthalene in THF
solvent.

Na •
Na
THF
After preparing the sodium naphthalide, they add the styrene. The
two rapidly react, transferring the radical electron in the sodium
naphthalide to the styrene to form a radical anion of styrene.
••
The radical anion is a very reactive species, so it immediately

combines with another radical anion to form a dianion.
Initiation step
••
•
••
•
•
•
•
•
This dianion, usually called distyryl sodium, is the starting point for
the polymer formation. As the polymer forms, the anion reacts with
additional molecules of styrene at each end of the distyryl sodium to
form a polymeric dianion.
Propagation step

• ••
•
•
•
••
Repeat
••
••
x x
Each polymer chain grows at a remarkably similar rate. Thus,

the process produces the polymeric dianions within a narrow range of
molecular weights. Their actual molecular weight depends on the ratio
of the amount of initiator and of styrene present in the reaction
mixture, as the amount of initiator determines the actual number of
polymers that form. The reaction has no important termination
reactions. The dianion is relatively stable until a source of protons is
added to the solution.

•• HCl
••
x x CH3OH
x x
H
Exercise 22.4
Predict the order of reactivity of styrene, p-chlorostyrene, and p-

methoxystyrene in radical, cationic, and anionic polymerization
reactions.
Polystyrene has a number of properties that make it a valuable

industrial material. It is an amorphous polymer. When made in a
radical polymerization reaction, polystyrene can form with molecular
A thermoplastic weights in excess of two million, although most commercial
material readily melts polystyrene has molecular weights under a million. The glass
to allow remolding into
desired shapes.
transition temperature for polystyrenes is above room temperature.
Polystyrene is also a good thermoplastic material. It can be melted
and remolded repeatedly, allowing ready recycling of the waste
A thermosetting materials from a molding or from a discarded molded object. A
material reacts when
thermoplastic material is different from a thermosetting material. A
heated, thus, it forms a
new polymer that does thermosetting material cannot be melted and remolded.
not melt and remold
again.

Uses of Polystyrene
Polystyrene is a plastic that has a number of different industrial and consumer uses.
One use involves molding it into cases for televisions and radios. In another process,
manufacturers mix a low boiling material with the polystyrene, then heat the
mixture. When the polymer softens, the low boiling compound vaporizes and produces
a foam. Because the foams do not conduct heat well, they work well when molded into
disposable cups for hot drinks and ice chests. Since the foam is quite rigid, it also
makes excellent insulation for construction.
Synthesis of Poly(vinyl acetate)
O
O
(PhCO)2
CH3COCH CH2
n
CH3CO
O
(92%)
Fit a 500 mL reaction kettle with a reflux condenser, mechanical stirrer,

thermometer, and addition funnel. Place 80 mL of freshly distilled water in the kettle.
Dissolve 80 mg of poly(styrene-co-maleic anhydride) (m.w. about 2000 with 67%
styrene content) in the minimum quantity of water and exactly neutralize with 1M
sodium hydroxide solution. Add this solution to the water. Prepare a solution of 86g of
vinyl acetate and 150 mg of benzoyl peroxide. Add 10 mL of the vinyl acetate solution
to the water and warm to 80oC. Once the exothermic polymerization reaction has
begun, maintain the reaction at 80oC by either heating or cooling as required. Add the
remaining vinyl acetate solution during a two hour period. Continue heating the
reaction mixture for an additional 2 hours. While continuing to use the mechanical
stirrer, steam distill the reaction mixture until the distillate contains no more vinyl
acetate monomer. Cool, with agitation, to 4oC. Filter the polymer beads from the
solution and wash repeatedly with water. Dry the beads at 30oC under reduced
pressure. The final product has a molecular weight of about 1,000,000. Yield of dry
polymer is 79.1 g.
Discussion Questions
1. Write a mechanism for the formation of poly(vinyl acetate).

2. This process is called suspension polymerization. What is the purpose of the
sodium salt of the poly(styrene-co-maleic anhydride) polymer in the reaction
mixture?
[Sidebar]
Natural Rubber

Rubber is the most important and widely used natural

polymer. A variety of plants in the tropical regions of the world
produce rubber, but the major source of commercial rubber is the
Hevea brasiliensis tree originally found in Brazil. The Hevea
brasiliensis tree is now mostly grown in Southeast Asia. The Mayans
also obtained rubber from this tree. They called it caoutchouc, or “the
weeping tree.” Joseph Priestly, the noted 18th century chemist, coined
the name rubber when he found that caoutchouc rubbed out pencil
marks.
Hevea rubber is obtained by tapping the rubber tree and
collecting the viscous liquid, called latex, that flows out. Quantities of
latex are obtained by tapping each tree every other day. Raw latex
contains about 32 - 35% rubber and 5% other organic compounds such
as sugars, fats, and steroids.
Rubber is a polymer made up of 2-methyl-1,3-butadiene
(isoprene) repeating units.
2-Methyl-1,3-butadiene
(Isoprene)
The polymer contains cis repeating units and has a molecular weight
ranging from 100,000 up to 1,000,000.
n
Rubber
A related polymer, called gutta percha, is found in trees of the

genus Dichopsis, which is native to Southeast Asia. Gutta percha has
a structure with trans double bonds and a much lower molecular
weight. A typical sample of gutta percha has a molecular weight of
about 7,000. Gutta percha is not widely used today, but has been used
in a variety of applications from golf ball covers to electrical
insulation.
n
Gutta percha

The cis arrangement of the double bonds in rubber prevents

the rubber molecules from fitting into an ordered structure. Thus,
rubber is an amorphous polymer. Because of the random coiling of its
polymer chains, rubber stretches easily. When stretched, the rubber
molecules are forced into a higher energy state. When the tension is
released, rubber snaps back to its original random coiled state. On the
other hand, molecules of gutta percha pack close together so it is more
crystalline than rubber. In general, gutta percha is harder and less
flexible than rubber.
Raw rubber is affected by environmental factors such as light,
temperature, and oxygen. These factors make rubber unsuitable for a
number of applications. In 1839, Charles Goodyear devised a method
of reacting rubber with sulfur to form a more durable material. This
process, which he called vulcanization, forms sulfur bonds in the
molecule. Vulcanization forms both the cyclic structure shown on the
left and the more desirable cross-linked structure shown on the right.
S
S S
Vulcanized rubber
Increasing the amount of sulfur makes the vulcanized polymer harder

and more durable. Adding 3 - 5% sulfur makes a product good for
rubber bands and inner tubes. Adding 20 - 30% sulfur makes a hard
rubber that was once widely used in ways that a hard synthetic plastic
is used today. The vulcanization process made early automobile tires
possible.
22.5 Controlling Stereochemistry in Vinyl Polymers

The substituents on a vinyl polymer arrange themselves in one
of three possible ways. Two of these possible arrangements are
stereoregular; the third arrangement is random. Which arrangement
the substituents take depends on the stereochemical relationship of
the substituents present on the polymer backbone. The arrangement
of the substituents on the backbone of the polymer is called the
tacticity of that polymer. The three possible arrangements of
substituents can be shown using polypropylene.

The tacticity of a
polymer is the
stereochemical
relationship among the
CH3 H CH3 H CH3 H CH3 H CH3 H
side groups on the
chain.
Isotactic polypropylene
CH3 H H CH3 CH3 H H CH3 CH3 H
Syndiotactic polypropylene
CH3 H H CH3 CH3 H CH3 H CH3 H
Atactic polypropylene
In the isotactic An isotactic polymer arranges all its substituents on the same
arrangement, the side of the polymer chain when you view the chain as a zig-zag
substituents are on the
same side of the carbon structure. A syndiotactic polymer has its substituents on alternating
backbone of the sides of the zig-zag structure. The atactic polymer has its
polymer. substituents arranged randomly on the chain.
The tacticity of a polymer strongly affects that polymer’s
In the syndiotactic
properties. For example, syndiotactic and isotactic polypropylene are
arrangement, the
substituents are on more crystalline than atactic polypropylene. Before the 1950s,
alternating sides. chemists produced polymers that were largely atactic because they
could not control the tacticity of the polymer. In the early 1950s,
In the atactic chemists developed new catalyst systems that selectively produced
arrangement, they are
stereoregular polymers. Having control over the stereochemistry
on random sides of the
backbone. during polymerization had important consequences in the polymer
industry. For example, atactic polypropylene is a soft, low-melting
amorphous solid, but isotactic polypropylene is highly crystalline and
melts at 170oC.
Karl Zeigler of Germany developed a series of catalysts that
polymerize ethylene at low temperatures and low pressures to give a
polyethylene with a high molecular weight and very little branching.
This polyethylene is denser, tougher, and has a higher melting point
than the polyethylene produced by the earlier high temperature, high
pressure methods. Recognizing that Zeigler's catalysts were capable of
polymerizing 1-alkenes (called α olefins in the polymer industry) to
yield stereoregular polymers, Guilio Natta of Italy developed the
methodology to do it. In 1963, Zeigler and Natta jointly received the
Nobel Prize for the discovery and development of these catalyst
systems.

A Zeigler-Natta
A typical Zeigler-Natta catalyst is a mixture of TiCl4 and
catalyst is not one Et3Al. Although chemists have extensively studied the mechanism for the
simple system but a Zeigler-Natta catalysis, they are not clear as to what happens. The
mixture of a transition evidence indicates that the mechanism begins with the formation of a
metal compound from
groups IVA to VIIIA complex between titanium and aluminum.
and an organometallic
compound from groups CH3CH2
I to III. CH2CH3
CH3 Al
CH2
Al(CH2CH3)3 Cl Cl
TiCl4 Ti
Cl
Cl
In this complex, titanium has an empty orbital available for

interaction with the π electrons in the monomer, thus allowing for the
A π complex is a formation of a π complex. The π complex orients the methyl group
structure that contains away from the titanium and towards the aluminum. The π complex
a bond between an then rapidly rearranges to form a bond between the CH2 group of
empty orbital in one propylene and the titanium and giving C2 of the propylene a positive
molecule and a pair of
charge.
π electrons from
another.
CH3CH2 CH3CH2
CH3 CH2CH3 CH3 CH2CH3
Al Al
CH2 CH2 H
Cl Cl H Cl Cl
Ti Ti C
Cl C Cl CH2 CH3
Cl CH2 CH3 Cl
Complex of Ti and alkene
The alkyl group of the aluminum transfers to the carbocation. This

transfer happens so rapidly that the carbocation formed in the
previous step does not have time to rearrange. Thus, the titanium
stereospecifically inserts the propylene group between itself and the
ethyl group.
CH3CH2 CH3 H CH3CH2

CH3 CH2CH3 CH2CH3
Al Al
CH2 H CH3CH2 CH2
Cl Cl Cl
Cl
Ti C Ti
Cl CH2 CH3 Cl
Cl Cl

The titanium complex continues to stereospecifically insert additional

propylene monomers between itself and the last ethyl group added to
the chain. This repeating reaction forms the isotactic polymer.
CH3 H CH3CH2
CH2CH3
Al
CH3CH2 CH2 n CH2 CHCH3
Cl Cl
Ti CH3 H CH3CH2
Cl CH3 H
Cl CH2CH3
Al
CH3CH2 CH2 CH2
n Cl Cl
Ti
Cl
Cl
To end the reaction, chemists destroy the complex by treating it with

methanol.
CH3 H CH3 H CH3CH2

CH2CH3 CH3 H CH3 H
Al
CH2 CH3OH
CH3CH2 CH2
n Cl Cl
CH3CH2 CH2 CH2
Ti n
Cl H
Cl
Exercise 22.5
Draw the structure for the product of the polymerization of styrene

with TiCl4 and AlEt3.
22.6 Non-Vinyl Chain-Growth Polymerization

Although many of the most common commercial polymers are
vinyl polymers, industry does make some important non-vinyl
polymers. Several of these polymers form from cyclic compounds that
undergo ring-opening reactions via chain-growth polymerization. The
cyclic monomers used to make these polymers include lactams,
lactones, and ethers. For example, the preparation of polyethylene
oxide is a non-vinyl chain-growth polymerization. Polyethylene oxide
is a water-soluble polyether that forms in a cationic polymerization
reaction. The reaction proceeds by using either a Brønsted-Lowry or a
Lewis acid initiator, but the reaction produces a much higher
molecular weight polymer with a Lewis acid initiator. Chemists are
unclear about the details of the Lewis acid mechanism. However, they

do know the mechanism for the reaction with a Brønsted-Lowry acid.

The initiation step for a Brønsted-Lowry acid involves the protonation
of the ether oxygen.
Initiation step
H
•• •• ••
O O
H
CH2 CH2 CH2 CH2
Protonation of the oxygen gives the two carbons an enhanced

reactivity that allows the protonated ether to react with a nucleophile
in an SN2 reaction. The nucleophile, which is the oxygen of another
molecule of ethylene oxide, opens the ring, and bonds to the carbon of
the protonated ethylene oxide. This reaction starts a chain and
produces a new cyclic intermediate. The new cyclic intermediate is
then ready for another ring opening reaction, thus propagating the
growth of the polymer.
Propagation step
H •
• •
•
O
••
O CH2
CH2 CH2
CH2 CH2 HOCH2CH2 O
••
CH2
•• ••
O
CH2 CH2
n CH2 CH2
HOCH2CH2 O H OCH2CH2 O
•• n ••
CH2
CH2
After the reaction has used all the ethylene oxide, water is added to
terminate the reaction. The water opens the final ring and produces
the final monomer of the polymer. This process typically produces a
polymer with a molecular weight of approximately 5,000.
CH2 ••
•
H2O•
H OCH2CH2 O H OCH2CH2 OCH2CH2OH
n •• –H n
CH2
The synthesis of Nylon 6 follows a similar synthetic pathway —

a nucleophile opens a ring to produce the polymer. The substrate for
the synthesis of Nylon 6 is the seven-membered cyclic compound ε-
caprolactam. ε-Caprolactam polymerizes rapidly under anionic

reaction conditions. The initiation step removes the proton from the
amide nitrogen to form a resonance-stabilized anion.
Initiation step
•• •• ••
O•• O•• •
• O ••
••
•
• NH2
•
• N H •
• N •• N ••
-Caprolactam
In the propagation step, the anion reacts with the carbonyl carbon of
another ε-caprolactam molecule. This reaction opens the ring and
produces another resonance-stabilized anion.
Propagation step
••
••
O ••
•
• O
••
•• •
O •• • O ••
•
• N •
• N ••
•
• N H •
• N H
••
••
•
• O
•
• O
••
HN
••
N••
n N H
O
O
N NH ••
NH
n ••
After the reaction has used all the monomer present in the reaction
mixture water is added to protonate the amide ion, thus completing
the polymer synthesis.

Exercise 22.6
One of the difficulties associated with the anionic lactam

polymerization that forms Nylon 6 is that a proton transfer sometimes
occurs within the polymer chain. This proton transfer leads to polymer
chain branching. Show this reaction.
Exercise 22.7
Tetrahydrofuran polymerizes in the presence of aluminum chloride

and acetyl chloride to produce a polymer used as an artificial leather
in shoes. Write the reaction for the initiation step. What is the
structure of the polymer?
Poly(lactic acid)
A particularly interesting polyester is poly(lactic acid). The synthesis of poly(lactic

acid) is a chain-growth polymerization of lactic acid.
O O
HOCHCOH OCHC
n
CH3 CH3
Lactic acid Poly(lactic acid)
Surgeons use poly(lactic acid) to do temporary surgical implants because the implant
allows the body's healing processes to replace the implant with normal body tissues.
Over a period of time, the body hydrolyzes the polymer to lactic acid. The lactic acid
then follows the normal metabolic pathway to carbon dioxide and water. Thus, all
traces of the surgical implant are gone from the body.
22.7 Step-Growth Polymerization

Step-growth polymerization requires the reaction of two
different difunctional monomers to form an alternating copolymer.
Each monomer type cannot react with itself; each reacts only with the
other. Thus, as the polymer molecule grows, the two different
monomers take turns reacting to bond onto the polymer chain.
Polyesters, polyamides, and polyurethanes are examples of copolymers
that form following the step-growth polymerization pathway.
Most of the step-growth polymers discussed in this section have
much lower molecular weights than do vinyl polymers due to the
increase of intermolecular interactions between the functional groups.
The functional groups interact more intermolecularly because of their

polarity. The advantage of this lower molecular weight is that it gives

the polymer a lower melting point than similar polymers with higher
molecular weight. The lower melting point makes it easier to mold
useful items from the molten polymer.
Poly(ethylene terephthalate) is a typical polyester that is
In a transesterification prepared via the transesterification of dimethyl terephthalate and
reaction, one ester ethylene glycol.
reacts with an alcohol
forming a different O O
ester. HOCH2CH2OH
CH3OC COCH3 197oC
O O
C COCH2CH2O + CH3OH
n
Poly(ethylene terephthalate)
Transesterification
A transesterification reaction usually has an equilibrium constant near one, thus, at

equilibrium the reaction mixture has similar quantities of all the possible esters.
Using the methyl ester helps with the reaction because the methyl ester forms
methanol, a low boiling point alcohol. The methanol can be boiled off from the reaction
mixture, thus driving the reaction to completion.
Synthesis of Poly(ethylene terephthalate)
O O
HOCH2CH2OH
CH3OC COCH3
197oC
Dimethyl terephthalate
O O
C COCH2CH2O + CH3OH
n
(100%)
Distill ethylene glycol from sodium metal in a nitrogen atmosphere. Place 15.5 g of
dimethyl terephthalate and 11.8 g of the freshly distilled ethylene glycol in a heavy
walled tube with a constricted upper portion and a vacuum attachment. Add 25 mg of
calcium acetate dihydrate and 6 mg of antimony trioxide. Enclose the tube in a metal
protective sleeve. Warm the reaction mixture in an oil bath to dissolve the mixture.
When dissolved, place a capillary tube with a slow stream of nitrogen in the solution.
Heat to 197oC and maintain the nitrogen flow. Heat 2-3 hours at 197oC, or until all

the methanol has been removed. Heat the tube to 225oC for 20 minutes and then at
285oC for an additional 10 minutes. Cap the top of the tube, connect the side arm to a
vacuum pump, and reduce the pressure to 0.3 mm of Hg. Heat at 285oC for 3.5 hours.
Remove the tube from the heat and cool the tube behind a safety shield. On cooling,
the polymer contracts from the walls of the tube and may cause it to shatter. The yield
of polymer is 15.3 g, m.p. about 270oC.
Discussion Questions
1. Why is the initial phase of the reaction run at 197oC?

2. What would be the effect on the molecular weight of the polymer if you stopped the
process before all the methanol is removed?
Poly(hexamethylene adipate), more commonly called Nylon 66,

is a typical example of a polyamide. In one synthetic method used to
prepare Nylon 66, as well as many other Nylons, chemists dissolve a
diacid chloride in an organic solvent and the diamine in aqueous
sodium hydroxide. Because the two solutions are not soluble in each
other, the polymer forms at the interface between the two layers in a
process called interfacial polymerization. With thorough mixing,
Interfacial the interface area of the two layers increases. After the polymer forms,
polymerization occurs the chemist filters the polymer from the reaction mixture.
when the monomers
are dissolved in
O O
immiscible solvents.
NH2CH2CH2CH2CH2CH2CH2NH2
When they thoroughly ClCCH2CH2CH2CH2CCl
mix the two solutions H2O, Cl2C CCl2
together, the polymer NaOH
forms. O O
NHCH2CH2CH2CH2CH2CH2NHCCH2CH2CH2CH2C
n
Poly(hexamethylene adipate)
If, instead of using an alkyl group with the diamine, the

chemist uses an aromatic ring, the polymerization process inserts an
aromatic ring into the polymer. The polymer that forms is much more
rigid than the polymer that forms with an alkyl group because the
aromatic ring increases the crystallinity of the polymer. As a
consequence, polymers with aromatic rings are exceptionally strong.
Kevlar™, for example, has a tensile strength much higher than steel
but is significantly lighter than steel.
O O
HN HNC C
n
Poly(p-phenylene terephthalamide)
Kevlar™

Kevlar™makes an excellent reinforcing fiber in tires. Bulletproof vests

contain up to 18 layers of cloth woven from Kevlar™ yarn.
Polyurethanes are produced by a step-growth polymerization of
a diisocyanate with a diol. For example, toluene-2,4-diisocyanate
reacts with ethylene glycol to form the polyurethane.
CH3 CH3
HOCH2CH2OH
O O
OCN NCO OCH2CH2OCNH NHC

n
The mechanism for this reaction is a nucleophilic addition to the C=N

bond of the isocyanate.
H ••
H O H O
ROH
••
••
R' N C O R' N C OR R' N C OR
H A Urethane
Polyurethanes are widely used in making foams. Their major

commercial use is in cushions for furniture and as a foam-in-place
insulating material. Industrial chemists have several ways for making
foams. Here is one of those ways. The chemist mixes a small amount
of water with the polyurethane reaction mixture. The water reacts
with some of the isocyanate groups to form an amine and carbon
dioxide.
H ••
H O H O
HOH
••
••
R N C O R N C OH R N C O H
H H
RNH2 + CO2
As the polymer forms, it traps the bubbles of carbon dioxide that are
also forming. These carbon dioxide bubbles give the polyurethane a
foamy texture as the polymer hardens. Generally, during the early
part of the polymerization process, the manufacturers vigorously stir
the polymer mixture to encourage the formation of smaller bubbles.

Then, as the foam becomes more viscous, they inject the mixture into
a mold to form the polymer into the desired object.
Exercise 22.8
What monomer(s) do the following polymers require to form?
a) b)
O n O O
O
O n
c) d)
O O O
C(CH2)6CNH NH n
S n
e)
O O
CNH CH2 NHCOCH2CH2CH2CH2CH2CH2O

n
Sample solution
a)
O n
O
[Sidebar]
Plastic Recycling
People today are very dependent on the use of plastics because
plastics are used in a wide variety of applications ranging from
throwaway packaging to high-tech materials. However, the use of
plastics has created a disposal problem. In the United States, 21% of
the volume and 8% of the weight of garbage come from plastics. Most
of this garbage is disposable packaging materials. The very durability
of plastics makes the problem of plastic garbage a serious problem.

Recycling plastics is the obvious answer to the problem of

plastic garbage. Their durability and low reactivity make plastics
ideal candidates for recycling. Then why aren’t more plastics being
recycled? The answer has more to do with consumer habits and
economics than technical obstacles. As recycling centers and curbside
pickup become more common, more plastics will be recycled. The
Society of the Plastics Industry developed a code that is now used on
many plastic materials. This code provides information about the
plastic used in the product. The code guides both consumers and
recyclers in separating various plastics. Table 22.3 shows the recycling
code numbers.
Recycling Polymer Common Typical uses for

Code Consumer Recycled Plastic
Products
1 Poly(ethylene Soft drink bottles Soft drink bottles
PET terephthalate) and household and household
chemical bottles chemical bottles
2 High-density Milk and water Bottles and
HDPE polyethylene jugs, bottles, and molded containers
grocery bags
3 Poly(vinyl Shower curtains, Plastic floor mats
V chloride), shampoo bottles,
Vinyl, or PVC vinyl siding, floor
tiles, credit cards
4 Low-density Sandwich bags, Trash and grocery
LDPE polyethylene shrink wrap, trash bags
and grocery bags,
squeeze bottles
5 Polypropylene Plastic lids, bottle Usually part of a
PP caps, toys, diaper mixed resin
linings, clothing material
fibers
6 Polystyrene Styrofoam Molded items:
PS materials, egg rulers, cafeteria
cartons, trays, Frisbees,
appliances, videocassettes
packaging.
7 All other Many Plastic “lumber”,
plastics and playground
mixed resins equipment, road
reflectors
Table 22.3. Society of the Plastic Industry recycling codes.

Most recycling involves separation of the plastic from

impurities, washing the plastic, and packaging it for sale. Only
poly(ethylene terephthalate) (PET) and high-density polyethylene
(HDPE) are currently being recycled in large quantities. Most other
plastics are recycled only in small quantities, if at all.
A typical recycling process begins with separation of the
polymer from contaminants. For example, a PET soft drink bottle
usually has a paper label, a HDPE base, adhesive for holding the base
and label in place, and a HDPE or aluminum cap. These must be
separated for effective recycling. Mixtures of materials are not very
useful for further manufacturing.
After sorting the various components of a soft drink bottle, the
PET bottles are shredded into small chips. An air cyclone is used to
remove the paper and other lightweight materials, and the chips are
subjected to a detergent wash to remove any remaining labels and
adhesives. The PET chips are then separated from any HDPE chips by
a floatation method. PET and HDPE have different densities. Thus,
choosing the correct solvent permits separation of the two materials.
The chips are dried and any remaining aluminum pieces are removed
electrostatically. The plastic chips are now nearly free from
contaminants. Over 30% of all PET soft drink bottles are recycled by
this method.
The Eastman Kodak Company has developed an alternative to
these physical methods of purification called chemical recycling.
Kodak uses large amounts of PET in making photographic film. It
recycles the scraps by a process known as methanolysis. Section 22.7
describes how PET is made by a transesterification reaction. Kodak
recycles PET by a transesterification reaction that is the reverse of the
one used to synthesize PET.
O O
CH3OH
C COCH2CH2O HOCH2CH2OH +
n
O O
CH3OC COCH3
The products, ethylene glycol and dimethyl terephthalate, are

purified. They are then ready to be used in further synthesis.
22.8 Copolymers

A polymer chain that forms in a copolymerization reaction

consists of two or more different repeating units. In a step-growth
copolymerization, the polymers generally form an alternating
An alternating copolymer.
copolymer has two
different repeating
units alternating along nA + nB A B A B A B A B
the chain.
Some chain-growth polymers also form alternating copolymers.

Styrene and acrylonitrile both polymerize readily under radical
conditions. When they are mixed under the appropriate reaction
conditions, the styrene radical prefers to react with an acrylonitrile
monomer, and the acrylonitrile radical prefers to react with a styrene
monomer. The preference for each radical to react with the other
monomer is more than 98%. Thus, the polymer that forms is mostly an
alternating copolymer.
+ CN n
CN
Styrene Acrylonitrile
Styrene-Acrylonitrile copolymer
A block copolymer has A block copolymer consists of two or more short chains of
two or more short repeating units bonded together to form a longer polymer chain.
homopolymer chains
bonded together to
form a longer chain. mA + nB A A A A A B B B
One method for the synthesis of a block copolymer is an anionic

polymerization of an alkene. For example, as discussed in Section
22.4, the anionic polymerization of styrene produces the following
dianion.

••
••
x x
In a living polymer, the This kind of polymeric dianion is called a living polymer. After a
polymer chain remains living polymer reacts with all the monomer available in the reaction
reactive until the
chemist deliberately
solution, you can add another monomer. This second monomer then
adds a reagent to stop reacts with the reactive site on the living polymer. For example, if you
the reaction. add methyl methacrylate monomer to the dianion, the methyl
methacrylate polymerizes to each end of the anionic site. This reaction
adds another block to the polymer. The reaction also produces a new
dianion at each end of the polymer, thus keeping the polymer alive.
The reagents commonly used to quench the anionic polymerization of
styrene are methanol and HCl.
••
••
x x
O
H2C CCOCH3
CH3
CH3 CH3 CH3 CH3

•
• •
•
y x+1 x+1 y
COCH3 COCH3 COCH3 COCH3
O O O O

When the reaction has used all the methyl methacrylate, you can add
more styrene or even a different monomer. The chain will continue
growing until you add methanol and HCl to protonate the dianion.
Block copolymers are useful because they have the properties
of both polymers. For example, a styrene-methyl methacrylate
copolymer has the crystallinity of polystyrene and the toughness of
poly(methyl methacrylate).
Random copolymers A third type of copolymer is the random copolymer. An
have no predictable example random copolymer is shown below.
sequence to the
repeating units in the
chain. mA + nB A B B B A A B B
Because there is no repetitive way of making the same random

copolymer twice, this type of reaction has little commercial value.
Exercise 22.9
If you synthesize a block copolymer from a reaction that starts with

sodium naphthalide and styrene at –78oC, then you add ethylene
oxide and run the reaction at +75oC, and quench it with HCl in
CH3OH, what is the structure of the copolymer you have formed?
[Sidebar]
Plasticizers
Plasticizers are the most widely used polymer additives in the
polymer industry. Their function is to increase the flexibility of a
particular polymer. A plasticizer is a nonvolatile liquid that dissolves
in the polymer. Similar to the way that an impurity decreases the
melting point of a small organic compound, adding a plasticizer to a
polymer decreases the glass transition temperature of the polymer.
The most common plasticizer is di(2-ethylhexyl) phthalate.
O
CH2CH3
O CH2CHCH2CH2CH2CH3
O CH2CHCH2CH2CH2CH3
CH2CH3
O
Di(2-ethylhexyl) phthalate

Plasticizers are selected based on several criteria: cost,

compatibility, and permanence. Permanence is how well the plasticizer
remains in the polymer. Plasticizers evaporate from the polymer and
are removed when the polymer comes in contact with solvents or
lubricants. However, if the loss of plasticizer is more rapid than the
expected life of the product, the plasticizer is not sufficiently
permanent.
The permanence of a plasticizer contributes to a problem with
recycling those plastics. Most manufacturers have proprietary
formulations for plasticizers, so no two are alike. Even similar plastic
products may have different plasticizers. The difficulty is that
different plasticizers may require different processes to remove them
from the plastic.
The frequently used, soft, flexible “vinyl” is actually poly(vinyl
chloride) with significant amounts of plasticizer. Poly(vinyl chloride) is
a hard, brittle polymer with a glass transition temperature about
80oC. Because poly(vinyl chloride) has so many useful properties, most
samples contain plasticizer. Often as much as 50% of a poly(vinyl
chloride) sample is plasticizer. Permanence is important in these
products as they become hard and brittle when the plasticizer
eventually evaporates.
Phthalate esters are used as plasticizers in many polymers in
automobile interiors. The “new car smell” enjoyed by many car owners
is the result of the plasticizer vaporizing in the interior of the
automobile. The smell actually advertises the deterioration of the
polymers in the interior of the car, particularly so with the vinyl
upholstery. If a new car is closed and left in the sun, it becomes very
hot and enough plasticizer can evaporate and condense on the
windows to leave a sticky film.
22.9 Cross-Linked Polymers

Cross-linked polymers consist of smaller polymer chains that
are bonded together. Each chain is bonded to multiple chains.
A prepolymer is a low
Generally, the reaction proceeds by first synthesizing the
molecular weight prepolymers. The prepolymers then undergo a reaction that links
polymer that has them together.
functional groups The most familiar cross-linked polymers are the two-part epoxy
available for reaction adhesives: 1) the resin and 2) the hardener. A typical resin is a
with a cross-linking
agent.
prepolymer derived from epichlorohydrin and bisphenol A. When
these two molecules react, they produce a prepolymer with hydroxyl
groups in the chain and, because epichlorohydrin is present in excess,
with epoxy groups at the ends of the chain. Typically this prepolymer
has a molecular weight of approximately 1500 — 2000.

CH3
O NaOH
Cl + HO C OH
CH3
Epichlorohydrin Bisphenol A
CH3
O
O C CH3 O
O
OCH2CHCH2 O C CH3
OH n CH3
The mechanism for the formation of the prepolymer begins

with the formation of the phenolate anion. The phenolate anion reacts
with the epichlorohydrin in a nucleophilic reaction bonding the two
together and opening the epoxide ring. A new epoxide ring then forms
by nucleophilic reaction of the resulting alkoxide with the carbon
bearing the chloride. This sequence repeats forming a prepolymer
containing 25 to 50 repeating units.

OH
R O H R O
CH3 O
Cl
R = HO C
CH3 Cl
R O O R O
O
Repeat
CH3
O
O C CH3 O
O
OCH2CHCH2 O C CH3
OH n CH3
Cross-linking takes place when the user mixes the hardener

with the prepolymer. The process is very rapid. Thus, the person using
the epoxy adhesive must mix the resin and hardener immediately
before using it. A typical hardener is tris(2-aminoethyl)amine.
H2NCH2CH2
NCH2CH2NH2
H2NCH2CH2
Tris(2-aminoethyl)amine
Because both hardener and prepolymer have a number of polar groups

that can hydrogen bond and coordinate strongly with the surfaces to
be bonded together, epoxy adhesives form very strong bonds. Below is
a schematic illustration of the cross-linking process.

H2NCH2CH2
NCH2CH2NH2
H2NCH2CH2
HNCH2CH2
NCH2CH2NH2
HNCH2CH2
Exercise 22.10
Chemists synthesize bisphenol A from two moles of phenol and one

mole of acetone. Propose a mechanism for this acid-catalyzed reaction.

The first commercially available cross-linked polymer was

synthesized by the reaction of phenol with formaldehyde. This process,
developed by Leo Hendrik Baekeland, produced a product called
Bakelite. Bakelite, patented early in the twentieth century, is a highly
cross-linked three-dimensional network molecule that is very resistant
to solvents, heat, and electricity. By the 1920s, Bakelite had found its
way into a variety of household products from handles for cooking pots
to electrical fixtures. Its wide variety of uses earned its inventor a
feature on the cover of Time.
The preparation of Bakelite is quite simple—heat a mixture of
phenol and formaldehyde with aqueous acid. This process forms the
polymer network of phenol rings connected at the ortho and para
positions with methylene groups.
OH O
+ HCH
H3O
OH OH OH
CH2 CH2 CH2 CH2
OH OH
CH2 CH2 CH2 CH2
OH
CH2 OH CH2
CH2
CH2 OH
CH2
CH2 CH2 OH CH2
CH2
CH2

Exercise 22.11
The first step in the formation of Bakelite is the formation of a

mixture of o- and p-hydroxymethylphenol. Write a mechanism that
explains the formation of these intermediates.
OH O OH OH
H3O
+ HCH +
CH2OH HOH2C
Key Ideas from Chapter 22
❑ A polymer, sometimes called a macromolecule, is a very large

molecule formed from smaller molecules called monomers.
Monomers convert to polymers in a polymerization reaction.
❑ A homopolymer is a polymer synthesized from a single kind of

monomer.
❑ The synthesis for a copolymer involves two or more different

kinds of monomers. A copolymer has one of the three following
structures: 1) alternating, 2) block, or 3) random copolymer.
The monomer molecules alternate in the polymer chain of
alternating copolymers. Blocks of homopolymers are bonded
together in block copolymers. Random copolymers arrange the
repeating units in a random order along the polymer chain.
❑ A polymer is either linear, branched, or cross-linked.
❑ Solid polymers are either crystalline, amorphous, or have

regions of both crystalline and amorphous structure. Few
polymers are completely crystalline, more are amorphous, and
still more have both crystalline and amorphous domains.
❑ Homopolymers are usually named as polymonomer. If the

monomer has a number or symbol prefix, enclose it in
parentheses as poly(monomer).
❑ Name copolymers by combining the names of both monomers.

For example, to name the polyester formed from ethylene glycol
and terephthalic acid is poly(ethylene terephthalate).

❑ Polymers form following either the chain-growth

polymerization pathway or the step-growth polymerization
pathway.
❑ In a chain-growth polymerization, one monomer reacts with

another monomer that contains the same functional groups.
❑ In a step-growth polymerization, one monomer reacts with a

repeating unit formed from a different monomer. Two or more
monomers alternately react with the growing polymer chain.
❑ Chain-growth reaction mechanisms have initiation,

propagation, and termination steps. The polymerization
reaction of vinyl monomers occurs under radical, cationic, or
anionic conditions.
❑ Many anionic chain-growth mechanisms produce living

polymers. A living polymer can react further with additional
monomers that are either the same as the original vinyl
monomer or a different vinyl monomer.
❑ Vinyl polymers have several different arrangements of

substituents on the polymer chain. Two of these arrangements
are stereoregular and the third is random. The arrangements
are called the tacticity of the polymer.
❑ Isotactic polymers have the substituents on the same side

when you draw the polymer in the zigzag form.
❑ Syndiotactic polymers have the substituents on opposite sides

❑ Atactic polymers have the substituents randomly arranged

❑ Ziegler-Natta catalysts control the stereochemistry of the

polymer.
❑ Chain-growth polymerization occurs with non-vinyl polymers.

Ring opening polymerization of cyclic lactams, ethers, lactones,
etc., form polymers with heteroatoms in the polymer chain.
❑ Step-growth polymerization requires the copolymerization of

two monomers forming an alternating copolymer.

❑ Cross-linking polymerization reactions involve forming very

high molecular weight polymers by reaction of low molecular
weight prepolymers with some cross-linking agent.

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Richard F. Daley and Sally J.

Copyright 1996-2001 by Richard F. Daley & Sally J. Daley

No part of this publication may be reproduced, stored in a retrieval system, or

www.ochem4free.com 5 July 2005

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✔ Recognize the various types of polymer structures

Observation is a passive science, experimentation

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those bodies function. Cellulose and starches are polymers of

22.1 Structural Characteristics of Polymers

An example of a homopolymer is polyvinyl chloride.

CH2 CH CH2CHCH2CHCH2CHCH2CHCH2CH or CH2CH n

When different repeating units make up the polymer chain, the

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An example of the alternating copolymer is Nylon 66.

n H2N(CH2)6NH2 + n ClC(CH2)4CCl NH(CH2)6NHC(CH2)4C

The physical properties of a specific polymer are the result of

fails. Flexural strength is a measure of resistance to breaking or

Orientation of the chains of a crystalline polymer

The glass transition

Many polymers are neither completely crystalline nor

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Orientation of the chains of a semicrystalline polymer

Crystalline polymers generally are opaque, but amorphous

22.2 Polymer Nomenclature

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Monomer Monomer Name Polymer Polymer Name

CH2 CH2 Ethylene CH2CH2 Polyethylene

CH2 CHCH3 Propylene CH2CH Polypropylene

CH2 CHCN Acrylonitrile CH2CH Polyacrylonitrile

CH2 CH Vinyl acetate CH2CH Poly(vinyl acetate)

CH2 CHCl Vinyl chloride CH2CH Poly(vinyl chloride)

CH2 CH Styrene CH2CH Polystyrene

CF2 CF2 Tetrafluoroethylene CF2CF2 Polytetrafluoroethylene

Table 22.1. Representative names for some vinyl polymers.

Nonvinyl polymers generally have some atom other than

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Table 22.2 lists a few representative nonvinyl polymer names.

Monomer Monomer Name Polymer Polymer Name

HOCH2CH2OH Ethylene glycol

H2N(CH2)6NH2 Hexamethylenedi- O O Poly(hexamethylene

Table 22.2. Representative names for some nonvinyl polymers.

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22.3 Types of Polymerization Reactions

The mechanism for a chain-growth polymerization is often a

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The formation of Nylon 66 has two steps in the step-growth

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Another possible second step that the step-growth mechanism

22.4 Chain-Growth Polymerization

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In the propagation step, the chain begins to grow as the

The propagation reaction continues until it reacts in a

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Another reaction that occurs in radical chain-growth

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A polymerization reaction involving 1,3-butadiene and a radical

CH2 CH CH CH2 CH2 CH

Cationic polymerization is similar to radical polymerization in