Alkenes: Polymers

A polymer is a very large molecule consisting of

repeating units of simpler molecules (the monomer)
Ethylene is polymerized to polyethylene, for example

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 POLYMER

Polymers have been a part of life since prehistoric times.

Cellulose in wood and starches obtained from vegetables

are carbohydrate polymers made from many thousands of
glucose molecules.

Silk and wool are polymer made from amino-acids.

DNA, the molecule that carries genetic information, is a

polymer of nucleotides.
Synthetic polymers provide a wide variety of items that we use every day.
Question

This alkene makes what common products?

a. plastic bottles
b. garden hoses
c. nonstick coatings
d. coffee cups

Answer: b. Vinyl chloride makes plastic pipes and

tubing, garden hoses and garbage bags.
Question
The abbreviation PETE appears on many consumer
products. What does it stand for?

a. phenyl ether tetraethylene

b. phosphorus ethyl tertiary ethylene
c. polyethylene terephthalate
d. polyester tetramer ethene

Answer: c. PETE stands for polyethylene terephthalate.

Free Radical Polymerization
of Alkenes

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 Alkenes combine many times to give polymer
Reactivity induced by formation of free radicals

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 Free Radical Polymerization:
Initiation
Initiation - a few radicals are generated by the reaction
of a molecule that readily forms radicals from a
nonradical molecule
A bond is broken homolytically

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 Polymerization: Propagation
Radical from intiation adds to alkene to generate alkene
derived radical
This radical adds to another alkene, and so on many
times

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 Polymerization: Termination
Chain propagation ends when two radical chains
combine
Not controlled specifically but affected by reactivity and
concentration

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 Free-Radical Polymerization of Propene

H2C CHCH3

CH CH CH CH CH CH CH
H CH3 H CH3 H CH3 H

polypropylene
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 ..
RO
.. Mechanism

H2C CHCH3

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 ..
RO: Mechanism

H2C CHCH3

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 ..
RO: Mechanism

H2C CHCH3

H2C CHCH3

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 ..
RO: Mechanism

H2C CHCH3

H2C CHCH3

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 ..
RO: Mechanism

H2C CHCH3

H2C CHCH3

H2C CHCH3

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 ..
RO: Mechanism

H2C CHCH3

H2C CHCH3

H2C CHCH3

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 ..
RO: Mechanism

H2C CHCH3

H2C CHCH3

H2C CHCH3

H2C CHCH3

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 Other Polymers
Other alkenes give other common polymers

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 Unsymmetrical Monomers

If alkene is unsymmetrical, reaction is via more highly

substituted radical

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 Chain Branching During
Polymerization
During radical propagation chain can develop forks
leading to branching
One mechanism of branching is short chain branching in
which an internal hydrogen is abstracted

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 Long Chain Branching
In long chains, a hydrogen from another chain is
abstracted

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Cationic Polymerization

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 Vinyl monomers react with Brnsted or Lewis acid to produce a
reactive carbocation that adds to alkenes and propagates via
lengthening carbocations

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 Cationic Polymerization

Dimerization of 2-methylpropene

monomer (CH3)2C CH2

(C4H8)
H2SO4

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Mechanism of Cationic Polymerization

CH3
+ H2C C
H+
CH3

CH3

CH3C +

CH3 28
Mechanism of Cationic Polymerization

CH3 CH3
CH3C + + H2C C

CH3 CH3

CH3
+
CH3CCH2C CH3

CH3 CH3 29
 Mechanism of Cationic Polymerization
CH3
+
CH3CCH2C CH3

CH3 CH3

CH3 CH3
CH3CCH C(CH3)2 CH3CCH2C CH2
+
CH3 CH3 CH3
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