Introduction to Polymer Materials Assignment #1
1. In your own words, please explain the difference between step-growth
polymerization and chain-growth polymerization.
For step-growth polymerization, all species grow step by step. Otherwise, for
chain-growth polymerization, successive linking of monomers to the end of a
growing chain.
For chain growth polymerization, there is no rapid loss of monomers at the
beginning. However, for step growth polymerization, a rapid loss of
monomers can be observed at beginning.
Chain growth shows no growth of polymer chain after termination while step
growth shows no termination. Also, chain growth polymerization requires
initiators to break the double bond in monomer molecule. Otherwise, step
growth polymerization does not require initiators.
2. Please explain the difference between “configuration” and “conformation”.
Configuration is the structural feature that change by only breaking chemical
bonds but, conformation can change into other part by rotating one part of a
chain around a bond. Conformation is spatial arrangement of the different parts
of a chain.
3. In general, how do the properties of network polymers differ from those of
linear or branched polymers?
In general, network polymers are insoluble in solvents because the polymer
chains are tied together by strong covalent bonds. Since crosslinks between
polymer chains are stronger than normal intermolecular attractions, the
polymer material formed from crosslinking is stable and stronger. However,
linear, and branched polymers are not.
Cross-linked polymers include thermosets and elastomers while linear polymer
include thermoplastics. The properties of cross-linked polymers mainly depend
on the degree of cross linking. if the degree of cross-linking is high, the
softening behavior of the polymer will be much harder.
The solubility parameter of the cross-linking polymers varies with the cross-
linking density. If a polymer has a low degree of cross-linking, it will tend to
swell in the liquid.
Cross linked polymer can’t tolerate repeated heating cycles. However linear
polymer can tolerate repeated heating cycles. With respect to recyclability,
cross linked polymer can’t be remolded. However, linear polymer can be
remolded.
4. Write the name and structure of monomers needed to synthesize the
following vinyl polymers.
(a) Poly (vinyl fluoride) -> monomer: vinyl fluoride
(b) monomer: pent-1-ene
(c) monomer: 2-methyl propene
(d) monomer: 1,1dicyano ethene
(e) poly(4-Vinyl-pyridine) -> monomer: 4-Vinyl-pyridine
(f) 1-chloro-3-ethenylbenzene
(g) (prop-1-en-2-yl) benzene
(h) (z)-1-chloro-2-methoxyethene
5. From the practical standpoint, is it better to use “good” solvent or “poor”
solvent when measuring molecular weight of polymer?
No, it is not better to use a poor solvent or good solvent when measuring
molecular weight of polymer.
If a solvent is “good,” interactions between polymer segments and solvent
molecules are energetically favorable and will cause polymer coils to expand.
If a solvent is “poor,” polymer-polymer self-interactions are preferred, and the
polymer coils will contract.
For example, in the case of osmotic pressure among colligative solutions,
which is a measurement method of number average molecular weight, the
equation has a term for two body interaction and three body interaction. If
measured in a power or good solvent, this terms value will be significantly
different from the existing value.
Therefore, accurate molecular weight can be measured only when measured
in theta state.
6. Calculate 𝑀𝑛 , 𝑀𝑤 and the polydispersity index for a hypothetical polymer
sample that contains equimolar amounts (and equal weight) of polymer
having molecular weights of 30,000, 60,000, and 90,000.
30000 + 60000 + 90000
𝑀𝑛 = = 60000𝑔/𝑚𝑜𝑙
3
300002 × 1 + 600002 × 1 + 900002 × 1
𝑀𝑤 = = 70000𝑔/𝑚𝑜𝑙
30000 × 1 + 60000 × 1 + 90000 × 1
𝑀𝑤 70000 7
Polydispersity index = = = = 1.16666 ⋯
𝑀𝑛 60000 6
7. Please briefly describe shear rate dependence of shear stress for various
types of fluids such as polymer, water, etc. In the due course, please explain
the effect of molecular weight and molecular weight distribution of polymer.
According to the Newton’s law of viscosity, shear stress is shear rate times
viscosity. (𝑠ℎ𝑒𝑎𝑟 𝑠𝑡𝑟𝑒𝑠𝑠 = 𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 × 𝑠ℎ𝑒𝑎𝑟 𝑟𝑎𝑡𝑒)
With respect to the power low equation, there is the relation between shear
stress and shear rate that satisfy the equation
log 𝜏 = log 𝐴 + 𝐵𝑙𝑜𝑔(𝑠ℎ𝑒𝑎𝑟 𝑟𝑎𝑡𝑒)
where A is constant, and B is the index of flow.
If we plot the graph log(𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦) 𝑣𝑒𝑟𝑠𝑢𝑠 log 𝑀𝑤 , we can identify the 𝑀𝑐
which is the critical molecular weight for entanglement to begin. The
log(𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦) has linear relation with the log 𝑀𝑤 and the slope increase right
after the 𝑀𝑐 . Therefore, a high molecular weight increases the viscosity of
the material.
If we plot the graph log(𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦) 𝑣𝑒𝑟𝑠𝑢𝑠 log(𝑠ℎ𝑒𝑎𝑟 𝑟𝑎𝑡𝑒) for broad molecular
weight distribution and narrow molecular weight distribution, we can identify
the effect of molecular weight distribution on shear thinning. For Broad
distribution, shear thinning set in earlier. And for narrow distribution, shear
thinning sets in later but once it does set in its magnitude is large.
8. Glass transition temperature (Tg) can be observed from amorphous polymer.
What are the factors to affect Tg for various types of polymers? In addition,
can we expect Tg from semi-crystalline polymer? If so, why? If not, please
provide rationale.
Tg highly influenced by the chemical structure of the repeating unit. Flexible
backbone and small substituent groups result the low Tg. And rigid backbone
(main-chain aromatic groups) results high Tg. This chain flexibility is adjusted
by the amount of aromatic composition or nonrotational (unsaturated) group
linkages in the main chain, or bulky substituent groups.
Tg increases with increasing molecular weight. But there exists a point at
moderate molecular weight where further increasing molecular weight has very
little effect of Tg.
Cross-linking, crystallization, diluents make the high Tg. For Diene Polymers,
cis or trans structure has the lower Tg depending on the polymer. In addition,
the weaker intermolecular interaction, the lower Tg. With respect to tacticity,
syndiotactic and atactic polymer have the higher Tg and isotactic one has the
lower Tg.
Answer for the question ‘Can we expect Tg from semi-crystalline polymer?’ is
yes.
Semi-crystalline polymers have a combination of random and ordered
structures. In other words, semi-crystalline polymer has amorphous region. But,
these ordered structures are crystals that restrict the movement of polymer
chains resulting in higher Tg.
9. Melting temperature (Tm) of polyethylene is in the range of 100 – 130 degree
C, and that of Nylon 66 is about 245 degree C. Please describe the reason
why they have so much difference in Tm.
Nylon 66 can form hydrogen bonding interactions due to the presence of
amide linkages. The stronger force between polymer chains, the higher the
melting point. Therefore, the presence of hydrogen bonding makes the
melting range of Nylon 66 higher than the melting range of Polyethylene
which does not have hydrogen bonding.
