Basic Chemistry of Polystyrene

47

naphthalene is the initiator it is believed that the chains are

active on both ends since this initiator, a radical-ion, initiates

chains with a radical on one end and an anion on the other.

The radicals couple to form a chain with an anion on each end.

Ziegler catalysts, consisting of a trialkyl aluminum com-

pound and titanium tetrachloride, are insoluble; the active

end of the growing chain is believed to be an anion associated

with a metal ion bound to the surface of the catalyst particle.

Isotactic polystyrene is most easily made with Ziegler catalysts.

Cationic polymerization of styrene and alpha-methylstyrene

can be carried out at low temperatures if a Friedel-Crafts type

of initiator such as BF3, SnCl4 or A1C13 is used. These initia-

tors can accept a pair of electrons from the double bond,

forming a positive charge on one carbon atom which becomes

the active center. Because of its low molecular weight poly-

styrene prepared at room temperature with such initiators

is very brittle. Although low temperatures favor high molecu-

lar weights such a process is not used commercially.

Copolymerization

Mixtures of styrene and other vinyl monomers will form

copolymers in which both kinds of monomer units are present

in each polymer chain. This can be illustrated by the follow-

ing equation in which R, represents any growing polymer

chain:
Generated for camelia_moise@yahoo.com on 2013-04-10 16:38 GMT / http://hdl.handle.net/2027/mdp.39015016511761

R, + CH2=CH or CH2=CH

-» R—CH2—CH-

R'

R—CH2—CH, + CH2=CH

* R—CH2—CH—CH2-CH-

R'

R'
Public Domain, Google-digitized / http://www.hathitrust.org/access_use#pd-google