Synthetic Polymers: Paula Yurkanis Bruice University of California, Santa Barbara

Chapter 27
Synthetic
Polymers
Paula Yurkanis Bruice

University of California,
Santa Barbara
© 2014 Pearson Education, Inc.

Polymerization
A polymer is a large molecule made by linking together repeating

units of small molecules called monomers.

A Chain-Growth Polymer
(polystyrene)
Chain-growth polymers (also known as addition polymers),

are made by chain reactions.

Step-Growth Polymer
(Dacron)
Step-growth polymers (also called condensation polymers), are made by

combining two molecules while removing a small molecule.

Chain-Growth Polymers
Chain-growth polymers are formed by one of three mechanisms.
• Radical polymerization
• Cationic polymerization
• Anionic polymerization

Radical Polymerization
The initiator is a radical.

Propagation Steps

Termination Steps

Chain Transfer
The molecular weight of the polymer can be controlled

by a process known as chain transfer.

Head-to-Tail Linkage
Chain-growth polymerization of monosubstituted ethylenes exhibits

a marked preference for head-to-tail addition.

Poly(vinyl chloride)
Head-to-tail addition forms a polymer with a substituent on every other carbon.

Stabilization of the Propagating Site
Head-to-tail addition is favored for steric reasons.
Head-to-tail addition is favored by groups that stabilize radicals.

Alkenes Used in
Radical Polymerization

Radical Initiators

Branching of the Polymer Chain

Branched Polymers are More Flexible

Recycling Symbols

Cationic Polymerization
The initiator is an electrophile.

Propagating Steps

Three Ways to Terminate the Chain

A Carbocation Monomer Can Undergo
Carbocation Rearrangement

Alkenes Used in
Cationic Polymerization
Monomers with electron-donating substituents undergo cationic polymerization.

Anionic Polymerization
The initiator is a nucleophile.

Propagating Steps
Nonterminated chains are called “living polymers” and

remain active until they are “killed.”

Alkenes Used in
Anionic Polymerization
Monomers with electron-withdrawing substituents

undergo anionic polymerization.
Super Glue
(an example of anionic polymerization)

What Determines the Mechanism?
Alkenes with substituents that can stabilize radicals undergo radical

polymerization.
Alkenes with electron-donating substituents that can stabilize cations

undergo cationic polymerization.
Alkenes with electron-withdrawing substituents that can stabilize

anions undergo anionic polymerization.
Some alkenes undergo polymerization by more than one mechanism.

Ring-Opening Polymerization
(anionic)

Ring-Opening Polymerization
(cationic)

Stereochemistry of Polymerization
Long, unbranched polymers with either isotactic or the syndiotactic

configuration can be prepared using an aluminum–titanium initiator (a Ziegler–
Natta catalyst).
Mechanism for
Ziegler–Natta-Catalyzed Polymerization

Polymerization of Dienes
These rubbers have cis double bonds.

Neoprene
(a synthetic rubber)
Neoprene has trans double bonds.

Disulfide Bonds in Rubber
The more sulfur used in vulcanization, the more rigid the polymer.

Four Types of Copolymers

Step-Growth Polymers
The monomer can have two different functional groups.
The monomer can be two different bifunctional compounds.

Step-Growth Polymerization Requires
High Yields for Long Chains

Nylon is a Polyamide
Nylon 6 is an example of a step-growth polymer formed by a

monomer with two different functional groups.

Commercial Synthesis of Nylon 6

Nylon is a Polyamide
Nylon 66 is an example of a step-growth polymer formed by two

different bifunctional monomers.

Aromatic Polyamides are Called Aramides
The incorporation of aromatic rings into polymers improves the

physical strength of the polymers.

Kevlar

Dacron is a Polyester
Polyesters are step-growth polymers in which

the monomer units are joined together by ester
groups.

Kodel is a Polyester

Lexan is a Polycarbonate
Polycarbonates have two ester groups bonded to the same carbon.

An Epoxy Resin is a Cross-Linked Polymer
(it is the strongest adhesive known)

A Urethane
A urethane has an OR and an NHR bonded to the same carbonyl carbon.

A Polyurethane

Crystallites are Highly Ordered Regions

The More Crystalline the Polymer is, the Denser,
Harder, and More Resistant it is to Heat

A Thermosetting Polymer
Thermosetting polymers are cross-linked.
The greater the degree of cross-linking, the more rigid the polymer.

An Oriented Polymer
These polymers are stronger than steel and can conduct electricity.

A Plasticizer
A plasticizer is an organic compound that is added to a polymer to

make it more flexible.
Recycling a Polymer
This is the reverse of the transesterification reaction that formed the polymer.

Biodegradable Polymers
Polylactic Acid (PLA)
Biodegradable polymers can be broken into small

molecules by microorganisms.

PLA Cannot Be Used for Hot Drinks

Biodegradable Polymers
(polyhydroxyalkanoates)
Polyhydroxyalkanoates (PHAs) are condensation

polymers of 3-hydroxycarboxylic acids.

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Chapter 27

Paula Yurkanis Bruice

© 2014 Pearson Education, Inc.

A polymer is a large molecule made by linking together repeating

© 2014 Pearson Education, Inc.

Chain-growth polymers (also known as addition polymers),

© 2014 Pearson Education, Inc.

Step-growth polymers (also called condensation polymers), are made by

© 2014 Pearson Education, Inc.

Chain-growth polymers are formed by one of three mechanisms.

© 2014 Pearson Education, Inc.

The initiator is a radical.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

The molecular weight of the polymer can be controlled

© 2014 Pearson Education, Inc.

Chain-growth polymerization of monosubstituted ethylenes exhibits

© 2014 Pearson Education, Inc.

Head-to-tail addition forms a polymer with a substituent on every other carbon.

© 2014 Pearson Education, Inc.

Head-to-tail addition is favored for steric reasons.

Head-to-tail addition is favored by groups that stabilize radicals.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

The initiator is an electrophile.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

Monomers with electron-donating substituents undergo cationic polymerization.

© 2014 Pearson Education, Inc.

The initiator is a nucleophile.

© 2014 Pearson Education, Inc.

Nonterminated chains are called “living polymers” and

© 2014 Pearson Education, Inc.

Monomers with electron-withdrawing substituents

© 2014 Pearson Education, Inc.

Alkenes with substituents that can stabilize radicals undergo radical

Alkenes with electron-donating substituents that can stabilize cations

Alkenes with electron-withdrawing substituents that can stabilize

Some alkenes undergo polymerization by more than one mechanism.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

Long, unbranched polymers with either isotactic or the syndiotactic

© 2014 Pearson Education, Inc.

These rubbers have cis double bonds.

Neoprene has trans double bonds.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

The monomer can have two different functional groups.

The monomer can be two different bifunctional compounds.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.