by Susana B.

Grassino

Polymers are a very special kind of compounds, which don't

behave like small molecules do. And they don't not only
because of their big molecular size. Precisely that "big size"
sets off three unique properties that are attributed only to
giant molecules.

What properties, you might ask? Surely you've seen them

before. Those properties depend on differences, and
applications depend on the properties, or better, the
combination of properties that each polymer
has.

OK, but what are those properties, anyway? In

case you haven't visited the page in which
they're explained, we can summarize them
again:

 Strength of intermolecular forces and their

sum over long polymer chains.
 Molecular weight and entanglement, which slow down
motion of polymers.
 Crystallinity.
 Crosslinking.

All these properties determine the diverse states of

macromolecular aggregation that polymers show.
For instance, could you imagine a polymer in its gaseous
state? Don't worry. There're not gaseous polymers. Such
large molecules have so strong intermolecular forces
holding them together, that you would need to heat them at
no less than 500°C to achieve evaporation. But at those high
temperatures you would no longer have polymers, but a big
mass of decomposed or carbonized monomers.

Even the liquid state is rarely observed in polymers. Most of

the time the compound exhibits a rubber-like consistency,
and becomes viscous when the temperature is gradually
increased.

Solid polymers usually exist as amorphous glasses.

However, when a certain order in their chain structure is
present, such polymers can crystallize, like fibers,
polyketones or syndiotactic polystyrene.

All solid polymers display a high state of aggregation, unlike

macromolecular solutions, particularly the dilute ones.
That's why specific studies of shape and size of each
polymer chain have been carried out.

Polymer solutions are highly viscous, but if you increase

their concentration, they become so viscous that, at a
certain point, intermolecular forces come into play again and
the liquid character vanishes. We are talking now about a
"gel" instead of a solution. Interesting, huh?

Would you like to learn more? Then let's look at each state
of aggregation separately:

 Solid Polymers
 Liquid Polymers
 Polymer Solutions
 Polymer Gels

Copyright ©2000 | Department of Polymer Science | University of Southern

Mississippi
So you want to know just how and why these polymers, these macromolecules, act
differently from small molecules. So we'll tell you. That's just the kind of nice people we
are. There are, for those of you who didn't bother to read the title, three ways in which
polymers will act differently from small molecules. And the reasons are a little bit more
complicated than just "because they're bigger". The three are usually named:

Chain entanglement
Summation of intermolecular forces
Time scale of motion
That's all well and good, these fancy names, but what do they mean in reality?

Chain Entanglement

Remember now that most polymers are linear polymers; that is, they are molecules whose
atoms are joined in a long line to form a huge chain. Now 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.

Now 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. We're not
talking about a new ball of string neatly wrapped up, either. We're talking about that
tangled up old ball of string that you've been collecting for years. Trying to pull one strand
out of this mess is a little harder. You're more likely to end up making a big knot!

Solid polymers are like this. The chains are all tangled up in each other and it is difficult to
untangle them. This is what make so many polymers so strong in materials like plastics,
paint, elastomers, and composites.

Summation of Intermolecular Forces

Remember intermolecular forces? If you don't I'll fill you in. All molecules, both small ones
and polymers, interact with each other, attracting each other through electrostatics. Some
molecules are drawn to each other more than others. Polar molecules stick together better
than nonpolar molecules. For example, water and methane have similar molecular weights.
Methane's weight is sixteen and water's is eighteen. Methane is a gas at room temperature,
and water is a liquid. This is because water is very polar, polar enough to stick together as
a liquid, while methane is very nonpolar, so it doesn't stick together very well at all.

As I said, intermolecular forces affect polymers just like small molecules. But with
polymers, these forces are greatly compounded. The bigger the molecule, the more
molecule there is to exert an intermolecular force. Even when only weak Van der Waals
forces are at play, they can be very strong in binding different polymer chains together.
This is another reason why polymers can be very strong as materials. Polyethylene, for
example is very nonpolar. It only has Van der Waals forces to play with, but it is so strong
it's used to make bullet proof vests.

Time Scale of Motion

This is a fancy way of saying polymers move more slowly than small molecules do. Imagine
you are a first grade teacher, and it's time to go to lunch. Your task is to get your kids from
the classroom to the cafeteria, without losing any of them, and to do so with minimal
damage to the territory you'll have to cover to get to the cafeteria. Keeping them in line is
going to be difficult. Little kids love to run around every which way, jumping and hollering
and bouncing this way and that. One way to put a stop to all this chaotic motion is to make
all the kids join hands when you're walking them to lunch. This won't be easy rest assured,
as there's always going to be a lot of little boys who are too macho to hold the hands of the
girls next to them in line, and some who are too insecure in their manhood to hold anyone's
hand. But once you get them to do this, their ability to run around is severely limited. Of
course, their motion will still be chaotic. The chain of kids will curve and snake this way
and that on its way to eat soybean patties disguised as who knows what. But the motion will
be a lot slower. You see, if one kid gets a notion to just bolt off in one direction, he or she
can't do it because he or she will be bogged down by the weight of all the other kids to
which he or she is bound. Sure, the kid can deviate from the straight path, and make a few
other kids do so, but the deviation will be far less than you'd bet if the kids weren't all
linked together.

It's the same way with molecules. A bunch of small molecules can move around a lot faster
and a lot more chaotically when they're not all tied to each other. Tie the molecules
together in a big long chain and they slow down, just like kids do when you join them into a
chain.

So then how does this make a polymeric material different from a material made of small
molecules? This slow speed of motion makes polymers do some very unusual things. For
one, if you dissolve a polymer in a solvent, the solution will be a lot more viscous than the
pure solvent. In fact, measuring this change in viscosity is used to estimate polymer
molecular weight. Click here to find out how.
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Copyright ©2005 Polymer Science Learning Center Department of Polymer Science

The University of Southern Mississippi