Organic Chemistry Chapter 29

6th Edition
Paula Yurkanis Bruice Synthetic Polymers

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A polymer is a large molecule made by linking together
repeating units of small molecules called monomers:

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Chain-growth polymers, also known as addition
polymers, are made by chain reactions:

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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 proceed by one of three
mechanisms:

• Radical polymerization

• Cationic polymerization

• Anionic polymerization

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Radical Polymerization

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The molecular weight of the polymer can be controlled by
a process known as chain transfer:

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Chain-growth polymerization of monosubstituted
ethylenes exhibits a marked preference for head-to-tail
addition:

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Head-to-tail addition of a substituted ethylene results in a
polymer in which every other carbon bears a substituent:

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• Head-to-tail addition is favored for steric reasons.
• Groups that stabilize radicals also favor head-to-tail
addition.

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Branching of the Polymer Chain

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Branched polymers are more flexible

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Cationic Polymerization

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The carbocation intermediates formed during
polymerization can undergo rearrangement to form more
stable carbocations:

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Monomers with electron-donating substituents readily
undergo cationic polymerization:

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 Anionic Polymerization

The initiator is a nucleophile, generally a strong base

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Nonterminated chains are called “living polymers”
and remain active until they are “killed.”
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An Example of Anion Polymerization

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 What Determines the Mechanism?

• Alkenes with substituents that can stabilize radicals

readily 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

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 Stereochemistry of Polymerization
Substituents on the same side:

Substituents regularly alternate on both sides:

Substituents in an atactic polymer are randomly oriented

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Long, unbranched polymers with either isotactic or the
syndiotactic configuration can be prepared using an
aluminum–titanium initiator (Ziegler–Natta catalyst):

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Polymerization of Dienes

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Synthesis of Synthetic Rubber

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The product resulting from polymerization of different
monomers is called a copolymer:

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Four Types of Copolymers

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Progress of a Step-Growth
Polymerization

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Nylon 6 is an example of a step-growth polymer formed
by a monomer with two different functional groups:

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The incorporation of aromatic rings into polymers
improves the physical strength of the polymers:

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Polyesters are step-growth polymers in which the
monomer units are joined together by ester groups:

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Polyesters with two ester groups bonded to the same
carbon are known as polycarbonates:

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Epoxy resins are the strongest adhesive known:

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A urethane (carbamate) is a compound that has an
OR group and an NHR group bonded to the same
carbonyl compound:

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 Thermosetting Polymers
Very strong and rigid materials can be obtained by
cross-linking.

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 Oriented Polymers
These polymers are stronger than steel and can
conduct electricity

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 Biodegradable Polymers
These polymers can be broken into small
molecules by microorganisms
The cyclic dimer of lactic acid undergoes ring-opening
polymerization to afford a high-molecular-weight
polylactide:

Polyhydroxyalkanoates (PHAs) are condensation polymers

of 3-hydroxycarboxylic acids:

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 Other Polymers

• Thermoplastic polymers have both ordered

crystalline regions and amorphous, noncrystalline
regions.

• Elastomers are polymers that stretch and then

revert to the original shape.

• Plasticizer is an organic compound that is added to

a polymer to make it more flexible.

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Dental Restorative Resin Components
Photo-curable resin
used by dentists to
restore decayed
teeth

Bisphenol A linker

Bisphenol A may be
hazardous to humans

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Photo-Initiator Components

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 Photo-Initiation Process
A blue LED light is used to initiate polymerization

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Radical-Initiated Polymerization

Curing is complete in 12 seconds

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