Dr. D. A. Savin Electronic Handout 2008 D. A.

Savin

Techniques PSC341L/720

Experiment 5: Free-Radical Polymerization of Styrene

Key differences between step growth and chain growth polymerization reactions:
Step Growth
Reaction occurs in slow, stepwise manner Any two species can react monomer + monomer dimer dimer + monomer trimer dimer + dimer tetramer Slow increase in MW Distribution of molecular species Rapid disappearance of monomer Generally long reaction times necessary to obtain HMW polymer Only high polymer and monomer present Monomer concentration decreases steadily Long reaction times give greater yield, but not higher MW

Chain Growth
Rapid addition of monomer to growing chain end Few initiated chains, monomer adds to growing chain end High MW polymer formed at once

Polystyrene Styrene monomer, a petrochemical typically produced from benzene and ethylene, is polymerized to form polystyrene.

Polystyrene

Dr. D. A. Savin Electronic Handout 2008 D. A. Savin

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Tacticity in Polystyrene Tacticity relates to the stereochemistry of the side-chain phenyl groups:

H H H

R R R

R H R

H R H

H R

R H

H R

R H

H H H

R R R

R R

H H

isotactic

syndiotactic

atactic

Dr. D. A. Savin Electronic Handout 2008 D. A. Savin

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Atactic polystyrene, the common commercial form of polystyrene, is a commodity plastic with an estimated global consumption of 10.5 million metric tons in 2000.1 It is amorphous and transparent with a Tg of approximately 100C. Typical applications for polystyrene include food packaging, toys, appliances and CD cases. Commercial production of polystyrene began in the 1930s in Germany (BASF) and was introduced in the US by Dow Chemical in 1937. Styrofoam, trademark of Dow Chemical for foamed polystyrene, was introduced in 1957. Dow (Styron) is the leading global producer of polystyrene.2 Other major producers include BASF (Polystyrol), Chevron Phillips, Nova, Atofina, and Hunstman. Atactic polystyrene homopolymer is often referred to as crystal polystyrene to differentiate it from the many common polystyrene copolymers and blends in commercial use. Syndiotactic polystyrene is produced using metallocene catalysts, and is substantially more expensive than atactic commodity polystyrene. Dow recently introduced syndiotactic polystyrene products under the tradename QUESTRA. Syndiotactic polystyrene, in contrast to atactic polystyrene, is semi-crystalline, and exhibits enhanced chemical resistance and thermal stability.

Free-Radical Polymerization Vinyl monomers may be polymerized via free-radical polymerization, a type of chain growth reaction. Typical polymers manufactured via free-radical polymerization include low density polyethylene, poly (methyl methacrylate), polyacrylonitrile, poly (vinyl chloride), polyacrylamide, poly (acrylic acid), and polystyrene. Due to the reactivity of vinyl monomers, it is often necessary to add an inhibitor to stabilize the monomer and prevent premature radical formation and polymerization. Inhibitors scavenge any radicals formed and produce lowreactivity radicals which will not initiate polymerization of the vinyl monomer. Common inhibitors include substituted phenols and quinones, with 4-tert buylcatechol commonly used to inhibit styrene polymerization. Free-radical polymerization proceeds via multiple steps: chain initiation, chain propagation, chain transfer, and chain termination. Chain initiation involves formation of reactive radicals. Initiating radicals may be provided via thermal decomposition of added initiators. Typical initiators of this type include dialkyl peroxides, diacylperoxides, and azo compounds.

Initiator

Formula

Useful polymerization Temperature (C) 3

Benzoyl Peroxide

O O Ph C O O C Ph

40 90

Dr. D. A. Savin Electronic Handout 2008 D. A. Savin

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t-Butyl Peroxide

(CH3)3 C O O C (CH3)3 CN CN CH3 C N = N C CH3 CN CN

80 150

Azobisisobutyronitrile

25 80

Initiation: Initiator 2 R R + M R1 R = radical M = monomer

In chain propagation steps, monomer molecules add to the active chain end while forming a new active chain end. Monomer will continue to add to the chain end until chain transfer or termination occurs. Monomers may add to the growing chain via head-to-head or head-to-tail reactions.

Propagation: R1 + M R2 R2 + M R3 ... Rn + M Rn+1 ~CH2 CH + CH2 = CH Ph Ph ~ CH2 CH CH2 CH Ph Ph

Head-to-tail

~CH2 CH + CH2 = CH Ph Ph

~ CH2 CH CH CH2 Ph Ph

Head-to-head

Dr. D. A. Savin Electronic Handout 2008 D. A. Savin

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Chain transfer involves transfer of the active radical to another molecule, which stops chain propagation at the growing polymer chain. The molecule to which the active site was transferred can initiate another chain. In some cases an external chain transfer agent is added to the polymerization reaction. Butyl mercapatan is commonly added to polystyrene reactions. Additionally, chain transfer to solvent, monomer, initiator, and/or polymer may also occur.

Chain Transfer: Rn + ZY RnY + Z

ZY = chain transfer agent

In chain termination the active chain center is destroyed. Dead polymer may be formed through combination or disproportionation reactions. Polystyrene has been shown to terminate primarily by combination reaction.

Termination: Rn + Rm Pn + m Rn + Rm Pn + Pm Study Questions 1. Which is more likely, head-to-head or head-to-tail addition in the propagation step? 2. What are some reasons for addition of a chain transfer agent to a polymerization reaction? General References4,5,6,7
1 2

combination disproportionation

P = polymer

http://pardos.marketing.free.fr/37.htm http://www.dow.com/homepage/index.html 3 Bovey, F. A., Winslow, F. W. Macromolecules, Academic: Orlando, 1979, p. 31 4 http://www.cheresources.com/polystymonzz.shtml 5 http://www.huntsman.com/petrochemicals/ShowPage.cfm?PageID=1129 6 http://www.devicelink.com/mpb/archive/98/07/001.html 7 Allcock, H. R.; Lampe, R. W.; Mark, J. E. Contemporary Polymer Chemistry, Ed. 3, Pearson Education: Upper Saddle River, NJ, 2003.