46

Polystyrene

the number of polymer radicals present must be limited since

they can react with each other. In the emulsion system it is

possible to have a larger number of growing polymer radicals,

since they are physically isolated and cannot react with each

other. The rate depends on the number of independent poly-

mer particles (micelles) formed by the use of increased

quantities of soap. It has been shown that at equivalent poly-

merization rates the molecular weight obtained in an emul-

sion system may be 4 to 5 times that obtained in bulk. If

equivalent molecular weights are obtained the rate in emul-

sion polymerization may be 4 to 5 times as great as that in

bulk. In some cases the differences may be more extreme.

Styrene has been polymerized experimentally in solution

(e.g. tetrahydofuran) by the use of metal alkyls such as

butyl lithium 1 and sodium naphthalene.2 These are soluble

initiators; if water, or other proton donors or acidic materials

are rigorously excluded, "living polymers" can be prepared.

All the initiator is consumed at the beginning of polymeriza-

tion, starting the growth of polymer chains. The alkyl group,

such as butyl, is on one end of the chain while the active

center is a negative ion associated with the positive metal ion.

The chains grow until all the styrene is polymerized, and re-

main active until more styrene is added. As polymerization

proceeds no new chains are initiated; those already started

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

continue to grow until a terminator such as water or carbon

dioxide is added.

On the other hand in free radical poJvmp.riTatinn pnlvmer

rjiains are continiir>"gly hf>;nf initiated during^Jhe—process,

.grow for no longer than a few seconds and are terminated by

reaction with each other, reactionwitlTrnitiatoTlree radicals,

or_chain transfer with styrene or a transfer_agenL If sodium

1 Morton, Stephens, and Hall, Am. Chem. Soc. Meeting, N. Y.,

Sept., 1957.

2 Szwarc, Levy, and Milkovich, /. Am. Chem. Soc, 78, 2656 (1956).
Public Domain, Google-digitized / http://www.hathitrust.org/access_use#pd-google