PAMANTASAN NG LUNGSOD NG MAYNILA

University of the City of Manila

College of Engineering and Technology

MOLECULAR ORIGIN OF POLYMER PROPERTIES

 Chain Entanglement

Polymers can be described as materials with the

capacity to assume an enormous array of thermally
equilibrated structural configurations. Under the
heading of polymers we can define a subclass of
materials, plastics, which generally have molecular
weights above 10 kDa and which are generally based
on covalently bonded linear chains with simple
chemical structures.

For the most part plastics have moderate to low chain persistence (chain rigidity), so
display sufficient flexibility that at some point in increasing molecular weight, different
chains can physically interact with each other so that a mechanical stress can be
transferred from one chain to another.

The structural conformation that leads to transfer of a mechanical stress from one
chain to another is termed an entanglement.

If the quiescent (structurally undeformed) mechanical properties of a polymer melt

are plotted as a function of molecular weight in a log/log plot we find an initial weak or linear
dependence followed, at approximately 10 kDa) by a strong dependence on molecular
weight. The transition molecular weight is termed the entanglement molecular
weight. Polymers above the entanglement molecular weight are useful as plastics while
those below the entanglement molecular weight display features of low molecular weight
materials, generally brittle powders.

For example, candle wax is low molecular weight polyolefins of the same molecular
structure as polyethylene, then compare the mechanical properties of a candle compared

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 PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila
College of Engineering and Technology

with a milk jug. Both materials are hydrophobic and can be molded into a desirable shape,
however, candle wax is useless as a bottle and cannot be processed in a blow molding
operation to form a milk jug because it displays no melt strength and no resistance to
tearing. Both of these properties are associated with the entanglement of polymer chains in
polyethylene.

Difference between Cross Links and Entanglement

The main difference is that cross-linking has a permanent effect on the motion of the
chains whereas entanglements may be formed and disrupted.

Industrial polymers or plastics then can be defined as materials possessing chain

structure with thermally equilibrated configurational freedom that display chain
entanglements. Elastomers and thermoset polymers are subclasses of polymers where
most entanglements are replaced by chemical bonds that link different polymer chains in a
permanent network structure. These links between chains are termed crosslinks.

Generally, the polymer chains between crosslinks for an elastomer or thermoset is

somewhat below or close to the entanglement molecular weight for the uncrosslinked
polymer. This is for several reasons. Firstly, thermosets and elastomers are processed in
the liquid state so that flow and mold filling ability are enhanced with lower molecular weight
prepolymers and secondly lower molecular weights between entanglements lead to higher
modulus and tougher rubbers and thermosets.

Shear Thinning

The main feature that is responsible for the shear thinning effect observed in polymer
melts is the presence of entanglements. Because of the presence of molecular
entanglements, the motion of a polymer should be restricted. Entanglements act as a sort of
physical constraint to the molecular motion, producing a slowing down of the motion which
is similar to the effect of the chemical cross-links between chains.

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 PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila
College of Engineering and Technology

At sufficiently low shear rate, when molecular motion is fast compared to the rate of
shear, entanglements are lost due to shearing but there is sufficient time for them to reform
(since molecular motion is fast). The fluid retains its entangled character i.e. entanglements
are continuously lost and reformed.

As shear rate increases, a stage will be reached when the rate of disruption is faster
compared to the rate of formation of entanglements. Thus, the entanglement density
decreases and the resistance to flow, i.e. the viscosity is lower than at low shear rate.

In Layman’s term:

Most polymers are linear polymers; that is, they are molecules whose atoms are
joined in a long line to form a huge chain. Most of the time, but not always, this chain is not
stiff and straight, but is flexible. It twists and bends around to form a tangled mess. The
chains tend to twist and wrap around each other, so the polymer molecules collectively will
form one huge tangled mess.

When a polymer is molten, the chains will act like spaghetti tangled up on a plate. If you try
to pull out any one strand of spaghetti, it slides right out with no problem. But when
polymers are cold and in the solid state, they act more like a ball of string. Solid polymers
are like this. The chains are all tangled up in each other and it is difficult to untangle them.
This is what makes so many polymers so strong in materials like plastics, paint, elastomers,
and composites.

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 PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila
College of Engineering and Technology

 Chain Interactions

The intermolecular forces for polymers are the same as for small molecules. Because
polymer molecules are so large, though, the magnitude of their intermolecular forces can
vastly exceed those between small molecules. The presence of strong intermolecular forces
is one of the main factors leading to the unique physical properties of polymers.

Forces in nature are often divided into primary forces (typically greater than 200
kJ=mol) and secondary forces (typically less than 40 kJ=mol).

A. DISPERSION FORCES (LONDON)

Dispersion forces are due to instantaneous dipoles that form as the charge clouds in
the molecules fluctuate. Dispersion forces, the weakest of the intermolecular forces, are
present in all polymers. This force is independent of temperature and is the major force
between chains in largely nonpolar polymers, for example, those in classical elastomers and
soft plastics such as PE.

It is interesting to note that methane, ethane, and ethylene are all gases; hexane,
octane, and nonane are all liquids (at room conditions); while low molecular weight PE is a
waxy solid. This trend is primarily due to an increase in the mass per molecule and to an
increase in the London forces per polymer chain. The London force interaction between
methylene units is about 8 kcal/mol. Thus, for methane molecules the attractive forces are
8 kJ/mol; for octane it is 64 kJ/mol; and for PE with 1000 ethylene (or 2000 methylenes) it
is 2000 methylene units’ x 8kJ/mol per methylene unit 16,000 kJ/mol, which is well
sufficient to make PE a solid and to break backbone bonds before it boils. (Polymers do not
boil because the energy necessary to make a chain volatile is greater than the primary
backbone bond energy.)

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 PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila
College of Engineering and Technology

B. DIPOLE – DIPOLE FORCES

Dipole-dipole forces result from the attraction between polar groups, such as those
in polyesters and vinyl polymers with chlorine pendant groups. The magnitude of these
interactions depends on the electronegativity difference of the two atoms involved in the
polar bond. These are weaker than hydrogen bonds, typically only about 5 kJ/mole, but
again add up so that PVC has a Tg of 81oC, whereas that of polyethylene is -125oC.

In polyesters, permanent dipole permanent dipole interactions can also occur, which
holds the polymer chains together more firmly.

C. HYDROGEN BONDING

Hydrogen bonding can take place when the polymer molecule contains -OH or -NH
groups. Hydrogen bonding is the strongest of the intermolecular forces. Polymers such
as poly (vinyl alcohol) and polyamides are hydrogen bonded.

It involves a positively charged hydrogen interacting with an electronegative

element. Only hydrogen that is bonded to nitrogen, oxygen, or fluorine can do it, e.g.
in OH...O, OH...N, NH...O, OH...F, etc. interactions.

Take, for example, the nylon polymer. There are NH groups that can make hydrogen
bonds to the C=O groups of another chain. Each of these hydrogen bonds is worth only

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 PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila
College of Engineering and Technology

about 15-20 kJ/mole, compared to 300-400 kJ/mole for a covalent bond. Nevertheless, lots
of interchain hydrogen bonds add up, making the nylon polymer rather stiff and giving it a
Tg of 57oC. The corresponding polyester, which cannot make hydrogen bonds, has a T g of -
40oC.

In Kevlar, a combination of the benzene ring (which is hard to rotate) and the
presence of hydrogen bonds make its structure very strong. Kevlar is fireproof, and
forms very strong fibres (its fibres are 20 times stronger than the equivalent weight in
steel).

 Tacticity

Tacticity is simply the way pendant groups are arranged along the backbone
chain of a polymer. And when talking about tacticity, it deals a lot with vinyl polymers.
To further discuss tacticity, polystyrene will be used for illustration.

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 PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila
College of Engineering and Technology

But polymers aren’t really flat like that. The carbon atoms aren’t really in a straight
line like that, nor are the hydrogen and phenyl groups all placed at perfect right angles. The
carbon chains are more a zigzag like this:

The pendant groups tend to be point away from the chain, like this:

If all chiral centers is in the same side of arrangement of the side groups is
called isotactic, and if every other chiral center has the same arrangement, it is
called syndiotactic, whereas a random arrangement of the side groups is
called atactic or heterotactic.

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 PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila
College of Engineering and Technology

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 PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila
College of Engineering and Technology

When polymers have a regular arrangement of their atoms, like in isotactic and
syndiotactic polystyrene, it is very from them to pack together into crystals and fibers. But if
there is no order, as is the case with atactic polystyrene, packing can’t occur. This is
because molecules pack best with other molecules of the same shape.

Tacticity makes a big difference in polystyrene. Free radical vinyl polymerization

normally can only produce atactic polymers. Atactic polymers is a hard plastic, and
completely amorphous. It can’t crystallize at all. Then metallocene catalysis vinyl
polymerization was inventes, and with it, syndiotactic polystyrene became possible. It’s not
only crystalline, but it doesn’t melt until 270oC.

Another vinyl polymer, polypropylene, is a good example of the effects of tacticity. At

first, there was only atactic polypropylene. It’s kind of soft and sticky, not very strong, and
not much good for anything. Then Robert L. Banks and J. Paul Higan invented a new type of
vinyl polymerization which ended up being Ziegler – Natta polymerization. This process could
make isotactic polypropylene. This polypropylene could crystallize and could be used to
make fibers for things like carpeting.

EFFECT OF TG

Polymers with different arrangements of side groups have noticeable different

properties. For example, the difference of the glass transition temperature (Tg) of syndiotatic
and isotatic polymethacrylates lies in the range of 112 K. This has been confirmed by a
theoretical derivation based on the Gibbs–Di Marzio (1958) theory of the glass transition.
For polymers with only one substituent group other than hydrogen, the effect of tacticity on
the glass transition temperature is much less pronounced.

Also, the greater order in syndio and atactic chains favors crystallization, that is,
tactic polymers are often (partially) crystalline. The table below gives glass temperatures for
some syndiotactic, isotactic and atactic (meth) acrylate polymers.

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 PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila
College of Engineering and Technology

EFFECT OF TACTICITY ON THE GLASS TRANSITION TEMPERATURE

(K)
Polymer Tg(atactic) Tg(isotactic) Tg(syndiotactic)

Poly(methyl acrylate) 281 272 (283) 299

Poly(ethyl acrylate) 249 253 (248) 263

Poly(methyl methacrylate) 378 319 (317) 433 (432)

Poly(n-butyl methacrylate) 293 249 (250) 361 (361)

Poly(isopropyl acrylate) 267 264 (262) 285 (278)

Poly(methyl α-chloroacrylate) 416 353 (358) 452 (450)

Poly(isopropyl α-chloroacrylate) 363 321 (341) 392 (409)

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