Chapter 27

Synthetic
Polymers

Paula Yurkanis Bruice

University of California,
Santa Barbara

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 Polymerization

A polymer is a large molecule made by linking together repeating

units of small molecules called monomers.

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 A Chain-Growth Polymer
(polystyrene)

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

are made by chain reactions.

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 Step-Growth Polymer
(Dacron)

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

combining two molecules while removing a small molecule.

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 Chain-Growth Polymers

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

• Radical polymerization

• Cationic polymerization

• Anionic polymerization

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 Radical Polymerization

The initiator is a radical.

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 Propagation Steps

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 Termination Steps

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 Chain Transfer

The molecular weight of the polymer can be controlled

by a process known as chain transfer.

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 Head-to-Tail Linkage

Chain-growth polymerization of monosubstituted ethylenes exhibits

a marked preference for head-to-tail addition.

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 Poly(vinyl chloride)

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

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 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.

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 Alkenes Used in
Radical Polymerization

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 Radical Initiators

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 Branching of the Polymer Chain

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 Branched Polymers are More Flexible

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 Recycling Symbols

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 Cationic Polymerization

The initiator is an electrophile.

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 Propagating Steps

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 Three Ways to Terminate the Chain

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 A Carbocation Monomer Can Undergo
Carbocation Rearrangement

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 Alkenes Used in
Cationic Polymerization

Monomers with electron-donating substituents undergo cationic polymerization.

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 Anionic Polymerization

The initiator is a nucleophile.

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 Propagating Steps

Nonterminated chains are called “living polymers” and

remain active until they are “killed.”

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 Alkenes Used in
Anionic Polymerization

Monomers with electron-withdrawing substituents

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

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 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.

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 Ring-Opening Polymerization
(anionic)

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 Ring-Opening Polymerization
(cationic)

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 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).
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 Mechanism for
Ziegler–Natta-Catalyzed Polymerization

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 Polymerization of Dienes

These rubbers have cis double bonds.

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 Neoprene
(a synthetic rubber)

Neoprene has trans double bonds.

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 Disulfide Bonds in Rubber

The more sulfur used in vulcanization, the more rigid the polymer.

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 Four Types of Copolymers

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 Step-Growth Polymers

The monomer can have two different functional groups.

The monomer can be two different bifunctional compounds.

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 Step-Growth Polymerization Requires
High Yields for Long Chains

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 Nylon is a Polyamide

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

monomer with two different functional groups.

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 Commercial Synthesis of Nylon 6

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 Nylon is a Polyamide

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

different bifunctional monomers.

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 Aromatic Polyamides are Called Aramides

The incorporation of aromatic rings into polymers improves the

physical strength of the polymers.

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 Kevlar

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 Dacron is a Polyester

Polyesters are step-growth polymers in which

the monomer units are joined together by ester
groups.

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 Kodel is a Polyester

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 Lexan is a Polycarbonate

Polycarbonates have two ester groups bonded to the same carbon.

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

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 A Urethane

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

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 A Polyurethane

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 Crystallites are Highly Ordered Regions

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

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 A Thermosetting Polymer

Thermosetting polymers are cross-linked.

The greater the degree of cross-linking, the more rigid the polymer.

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 An Oriented Polymer

These polymers are stronger than steel and can conduct electricity.

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 A Plasticizer

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

make it more flexible.
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 Recycling a Polymer

This is the reverse of the transesterification reaction that formed the polymer.

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 Biodegradable Polymers
Polylactic Acid (PLA)

Biodegradable polymers can be broken into small

molecules by microorganisms.

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 PLA Cannot Be Used for Hot Drinks

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 Biodegradable Polymers
(polyhydroxyalkanoates)

Polyhydroxyalkanoates (PHAs) are condensation

polymers of 3-hydroxycarboxylic acids.

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