Abstract

Styrene, also known as vinyl benzene, is an important monomer used for production of
polystyrene resins and plastic products. Polystyrene can be synthesized through free-radical
polymerization of styrene which involves three mechanistic steps: initiation, propagation, and
termination. Two major steps were done. The first was removal of commercial styrene inhibitor,
catechol, through acid-base extraction with NaOH as solvent. The second major step was
polymerization of pure styrene initiated by addition of butyl-peroxybenzoate and heat. After
heating until decrease in temperature was observed and solidifying the liquid, a transparent,
brittle fiber-like solid with a rugby like odor was obtained. The products identity was identified to
be polystyrene based on its IR spectra; hence, free-radical polymerization is an efficient
technique in production of polystyrene.

Conclusion and recommendations

Polystyrene was synthesized through free-radical polymerization of styrene. The first step was
the removal of the free-radical scavenger that inhibits polymerization, catechol, by acid-base
extraction with NaOH. Polymerization was initiated by addition of butyl-peroxybenzoate. The
sample was then heated to allow the reaction to proceed and increase polymerization rate,
however heating above 140C causes depolymerization.
The final product was a transparent, brittle, fiber like solid that has a rugby like odor. The
product was identified as polystyrene based on its IR spectra. Successful synthesis of
polystyrene proved the efficiency of the methods done in this experiment.
For better results, it is recommended to ensure complete inhibitor removal by removing all the
trapped bubble in the extraction process. In addition to that, temperature should be strictly
monitored to prevent depolymerization. Lastly, the thermometer should not be moved to losses
of the liquid polystyrene
Guide questions
1. Differentiate Chain Polymerization from Condensation Polymerization.
In chain growth polymerization, monomers add on the active site on the end of a growing
polymer chain. This happens continuously until no more monomers can react producing high-
molecular weight polymers throughout the duration of reaction. The mechanism of this reaction
involves initiation and propagation. The reaction depends on the concentration of the initiation.
On the other hand, condensation polymerization is a step-growth process wherein all molecules
react with each other. Monomers are consumed in the early stages of the reaction producing
low molecular weight polymers, the high molecular weight polymer is obtained at the end of
reaction. The mechanism of this reaction does not involve a termination step. This reaction
proceeds rapidly at the beginning but slows down as the reaction proceeds.
2. Discuss the types of polymerization processes.
Free-radical is involves molecules that produce free radicals to initiate polymerization, which
undergoes initiation, propagation, and termination steps. Cationic chain polymerization involves
lewis acid initiators that donates a proton to a monomer. Anionic chain polymerization is initiated
by anionic species such as metal oxides and organometallic compounds wherein carbanion is
produced.
3. The use of phenols, such as tert-butyl-catechol, as free-radical scavenger are based on the
fact that phenolic hydrogens are readily abstracted by radicals, producing relatively stable
phenoxy radicals, which interrupt chain processes of oxidation and polymerization. Alcohols
such as cyclohexanol, on the other hand, do not function as radical scavengers. Explain why the
two types of molecules differ in their ability to donate a hydrogen atom to a radical, R.
Phenol dissociates into a resonance stabilized phenoxide while cyclohexanols hydrogen from
the hydroxyl group is not acidic enough to be readily abstracted.
4. Write an equation for the reaction involved in the removal of tert-butyl-catechol from styrene
by extraction with NaOH.
C10H14O2 + 2 NaOH Na2C10H12O2 + 2 H2O
5. In principle, radicals could add to styrene at the carbon atom bearing a phenyl group rather
than the other one, yet do not. Explain the basis for this selectivity.
This occurs due to stearic hindrance. Also, a tertiary radical is favored because of its stability.
6. Would you expect the polystyrene generated in this experiment to be atactic, syndioatactic or
isotactic. Explain.
The polystyrene that can be produced in this experiment could be syndioatactic or isoatactic
because the monomer could attach in the same side or alternating side of the chain, producing
crystals or fibers.
7. What are thermosetting polymers? What is the difference versus thermoplastic polymers?

Thermosetting polymers have crosslinks between it chains which prevents the chains to slide
past each other. These crosslinks disables polymers to be reformed when heated. The
difference of thermosets to thermoplastic polymers is the absence of crosslinks which enables
to be reformed when heated.