Q & A : Polimer

Semester Ganjil
November 2014

1. Compounds like styrene, PhCH=CH2, are unstable as pure liquids. Such olefins tend
to explode, even in the absence of oxygen. Particles of a sticky solid, which is soluble
in benzene, can be found in debris resulting from the explosion.
A. Explain the origin of the explosive decomposition of styrene and of the heat which
is given off. You may find it useful to refer to the table of bond energies below.
Bond

Bond dissociation energy (kcal/mol)

Olefin C-H

102.7

Alkane C-H

98.8

C-C

82.6

C=C

145.8

H-H

104

B. Write a plausible structure of the sticky solid which results from styrene
decomposition. Very briefly describe the structural possibilities.

A. The olefin polymerization breaks a pi bond (the energy of which is 145.8 - 82.6
Kcal/mol) and forms a single bond (the energy of which is 82.6 Kcal/mol) for each
reacting mol of styrene. The net enthalpy change of this reaction is computed by
subtracting the enthalpy of bonds formed from the enthalpy of bonds destroyed,
because you have to put in energy to break bonds and energy is released when bonds
form. Thus DH = (145.8 - 82.6 - 82.6)Kcal/mol = 19.4 Kcal/mol, which means that the
reaction is highly exothermic; hence the explosion.
B. Structural possibilities: atactic, syndiotactic, isotactic
Structure: (-CH2-CHPh-CH2-CHPh-CH2-CHPh-) Its stickiness is your clue that its atactic.

2. Discuss the structural features of a polymer which would make it a useful

elastomer; specifically describe the underlying thermodynamic property which
causes a stretched elastomer to return to its unstretched state. Mention the
effect of molecular stereoisomers. Discuss the role of inter (between) chain
interactions and mention those factors which determine the temperature range
over which the elastomer is usefulfor example what happens on a molecular
level at low temperatures. Illustrate your discussion with an actual example,
using molecular formulas.

What makes a useful elastomer:

A useful elastomer has enough crosslinking (via vulcanization, hydrogen
bonding, dipole-dipole interaction,etc.) between polymer chains to
provide a restoring force, but not so much crosslinking that it is
crystalline. A useful elastomer also has a low Tg (glass transition
temperature: the temperature below which it goes into the glass state
and becomes brittle).
Thermodynamics:
The underlying thermodynamic property which provides the restoring
force is entropy DS.DS > 0 if you go from stretched to unstretched
because there are more conformations available in the relaxes state, so
there is more disorder.

Stereoisomerism:
stereoregular/isotactic: higher intermolecular interactions, better
packing, more crystalline.
stereoirregular/atactic: lower intermolecular interactions, less
crystalline, more "gooey" and inefficiently packed.
double bonds: cis bonds tend to make for less efficient packing
forces. The presence of such bonds cause the polymer to be less
crystalline, more rubbery. On the other hand, trans bonds enforce a
more rodlike structure.
Interchain forces:
The stronger the forces (covalent crosslinks, hydrogen bonds, dipoledipole interactions, etc) the more crystalline and rigid. Polymers with
very little interchain interaction are viscous and gooey.

Temperature:
Polymers have a glass transition temperature Tg, below which the
polymer is hard and crystalline. Above Tg, thermal energy overcomes
some intermolecular forces and the polymer is either elastomeric or
gooey. Some polymers are so rigid that heating leads to
decomposition before approaching Tg.
Useful Elastomers:
Vulcanized rubber is a great elastomer. 0% vulcanized is gooey, 2%
vulcanized is elastomeric, and 5% vulcanized is hard.
Non-useful elastomers:
Nylon has too many hydrogen bonds, so its interchain forces are too
strong.
Any polymer with a lot of crosslinking fails to be a good elastomer.

3. Write in turn the stereochemical structures of isotactic, syndiotactic, and atactic

polypropylene. Indicate which form is the most stable in solution (has the lowest
free energy) and which would have the lowest melting point. Briefly explain your
answer.

On the far left is isotactic polypropylene. Notice that all of the methyl groups are on
the same side of the chain. This is the most ordered and therefore the most
crystalline of the three polymers. It will have the highest melting point, which also
indicates that it will have the lowest DG of solvation because it's stable to begin
with.
The atactic extreme will have the lowest melting point and highest DG of solvation.

Give an example of any useful elastomer

Polyisoprene (natural rubber) once vulcanized (cross-linked a little bit) is

a great elastomer.

Below are structures for stereoisomers of polystyrene.

A. Draw a structure for the monomer from which polystyrene is

prepared.
B. Write down the tacticity of each of the numbered polymers:
C. Which structure do you expect to exhibit the highest melting
point and which would have the lowest melting point?
D. What physical methods might you use to distinguish these
stereoisomers? Suggest two and explain.
Checking the melting point and density will verify which one is
isotactic; the isotactic one will have both the highest mp and the
highest density.
E. Under what conditions does polystyrene exhibit elastic
properties? Why is polystyrene not used as an elastomer?

A. Draw a structure for the monomer from which polystyrene is

prepared.

B. Write down the tacticity of each of the numbered polymers:

#1 is syndiotactic, #2 is isotactic, and #3 is actactic
C. Which structure do you expect to exhibit the highest melting point
and which would have the lowest melting point?
The isotactic polymer will have the highest melting point due to its
packing efficiency and high interchain forces.

D. What physical methods might you use to distinguish these stereoisomers? Suggest
two and explain.

X-ray crystallography can be used to elucidate the structures and look for different
degrees of crystallinity.
1H or 13C NMR can be used to assign tacticity.
Checking the melting point and density will verify which one is isotactic; the isotactic
one will have both the highest mp and the highest density.
E. Under what conditions does polystyrene exhibit elastic properties? Why is
polystyrene not used as an elastomer?
Polystyrene exhibits elastic properties above its glass transition temperature (Tg is
about 100oC.) It is not used as an elastomer because its glass transition temperature is
too high above room temperature to be practical.

Polystyrene is stretchy above 1000C but brittle below that temperature. Why?
Polystyrene exhibits elastomeric properties above room temperature. More
specifically, the glass transition temperature of polystyrene is above 100oC, so it
does not exhibit elastomeric properties until this temperature is reached.

A. What is the monomer from which polyisobutylene is made?

B. Draw a structure for polyisobutylene.

C. What is vulcanization? Why cant polyisobutylene be vulcanized?

Vulcanization is a process in which sulfur forms sulfide or disulfide bridges
between polymer chains by reacting with double bonds. Polyisobutylene has no
double bonds, so it cannot be vulcanized or hydrogenated.

Consider a polymer X with empirical formula (CH)n. It is a gummy polymer that

becomes a more brittle polymer (Y) when hydrogenated. Deduce the structure
of X and Y from these data.
X's empirical formula leads us to conclude that each carbon is bonded to one H
and 2 other carbons. Because X can be hydrogenated, it must have double bonds.
Each carbon in X, therefore, has one C=C bond, one C-C bond, and one C-H bond.

X can have double bonds that are cis or trans. Because X is gummy, it can be deduced
that it's the cis isomer, which is likely to form coils as opposed to the rigid rods formed
by the trans isomer.
Y is the hydrogenated form of X. Each carbon is bonded to 2 hydrogens and two
carbons.