2021_ionic polymerization and copolymer

PBL TOPIC 2: Polystyrene in our daily life

Kimi and Bella are students of chemical engineering department. They like having lunch in student
cafetaria or make delivery order from restaurant around campus. Many times they get meal packed in
a nice plastic or foam polystyrene. Even though, they have been told not to put any food inside a
styrofoam, they do not know why it is dangerous. When they are assigned to make a report on
polymer in daily lives application, they are interested to have small investigation on this type of
plastic. They found articles in the internet that state a pro and contra about polystyrene.

After reading that article, they wonder how general polystyrene and foam polystyrene are synthesized,
their characteristics and how they can have impact to the environment and human health.

Kimi and Bella also found article about syndiotactic polystyrene:

There's a new kind of polystyrene out there, called syndiotactic polystyrene. It's different
because the phenyl groups on the polymer chain are attached to alternating sides of the
polymer backbone chain. "Normal" or atactic polystyrene has no order with regard to the
side of the chain on which the phenyl groups are attached. Syndiotactic polystyrene (SPS) is a
semicrystalline polymer that exhibit performance attributes that are significantly different
from those of amorphous styrenic materials. These properties include a high melting point,
good chemical and moisture resistance, and a high degree of dimensional stability.

The concept of stereoregularity in polymer chains is illustrated in the above figure with
polystyrene. Stereoregular poly(1-alkene) can be isotactic or syndiotactic depending on the
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relative orientation of the alkyl groups in polymer chains consisting of units −[CH 2−CHR]−,
like the phenyl groups in the figure. In the isotactic polymers, all stereogenic centers CHR
share the same configuration. The stereogenic centers in syndiotactic polymers alternate
their relative configuration. A polymer that lacks any regular arrangement in the position of
its alkyl substituents (R) is called atactic. Both isotactic and syndiotactic polypropylene are
crystalline, whereas atactic polystyrene, which can also be prepared with special Ziegler–
Natta catalysts, is amorphous. The stereoregularity of the polymer is determined by the
catalyst used to prepare it.

After reading this article, they are curious to find out more about how syndiotactic
polystyrene, and about tacticity. Kimi and Bella also found article about other polymer that
contain styrene:

Butadiene-Styrene copolymers are known as material that are stronger, not as brittle, and
capable of taking harder
impacts without breaking
than regular polystyrene.
Styrene-butadiene or
styrene-butadiene rubber
(SBR) describe families
of synthetic rubbers
derived from styrene and
butadiene (the version developed by Goodyear is called Neolite. These materials have good
abrasion resistance and good aging stability when protected by additives. In 2012, more than
5.4 million tonnes of SBR were processed worldwide. About 50% of car tires are made from
various types of SBR. The styrene/butadiene ratio influences the properties of the polymer:
with high styrene content, the rubbers are harder and less rubbery

Kimi and Bella try to find more about butadiene-styrene copolymer including methods of
synthesis. Now they are starting to make a concept map to get the whole picture of this polymer.
They will use this concept map to know more about polystyrene. As they open and read the polymer
textbook on polystyrene, they found that they should learn also on some principles to give more
understanding on how it is synthesized and how it is combined with different monomers to form
copolymer. They are curious why polystyrene, which is vinyl polymer, can be made by living anionic
polymerization technique and how it is produced commercially.

Assignment:
1. Based on this article, make concept map include polystyrene, syndiotactic polystyrene
and butadiene-styrene copolymer issues
2. Answer the question based on curiosity of Kimi and Bella after reading the articles
and these pages
3. In the laboratory you plan to make anionic polymerization of styrene using
homogeneous electron transfer initiation. Electron transfer complexes formed when
sodium react with naphtalene in tetra hydro furan (THF) solvent. The complex sodium
naphthalide initiates polymerization by donation of electron to monomer styrene to
form monomeric radical anion and then rapid coupling to form dicarbanionic species.
Propagation takes place when monomer react with both ends of dicarbanionic
species.In this anionic polymerization, each initator species generates a single
carbanionic active center and polymerization ends when all the monomers are reacted.
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Total styrene reacted is 210 gram and the amount initiator used is 0.5 ml of 0.2 mol/L
solution sodium naphtalide in THF.How do you determine:
a) Initiation reaction of formation dicarbanionic species
b) Propagation reaction of dicarbanionic species with styrene monomer
c) If initiation rate constant is << kp, and propagation rate constant kp is 4.2x103 mol-1
sec-1. How do you calculate value of Rp?
d) If number average degree of polymerization (Xn) in this living polymerization is
equal to the amount of monomer consumed per moles of polymer chain produced,
how to calculate the value of Xn? (initiation by electron transfer give value of K
constant is 2) (Mo styrene is 104.15 g/mol)
e) How much is the number-average molecular weight of the polystyrene formed?
(Mn)

4. If copolymer of styrene and other monomers are synthesized by mixing : styrene

monomer (1) and other monomers (2) with monomer reactivity ratio (r) as follow:
r1=k11/k12 and r2 = k22/k21

Monomer (2) r1 r2
butadiene 0.78 1.39
methyl methacrylate 0.52 0.46
methyl acrylate 0.75 0.18
acrylonitrile 0.40 0.04
vinyl chloride 17 0.02
A. What are the copolymer compositions of all mixture if each monomer is added
equimolar. (f1=f2)
B. Are any of the mixture can form block copolymer?
C. What are the copolymer compositions of all mixture if monomer 1 added is twice as
much as monomer 2. (f1=2f2)
D. Which mixture can form azeotropic copolymerization? Azeotropic composition has
value of f1=F1, what is the composition of azeotropic copolymer ?

https://www.pslc.ws/macrog/styrene.htm