Polymer Classifications:

Foreword.
This presentation is to be used with Chapter 2
of the Virtual Book. Students can complete
their virtual book thusly:
1. Make simple sketches and write ideas
during the class when this material is
presented.
2. Improve that by making better sketches
and editing a downloaded copy of
Chapter2.

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Linear polymers can be represented by a
simple sequence such as: A-A-A-A-A .
CH CH2

Polystyrene
n

Styrene monomer

Nylon HOOC
COOH
H2N-(CH2)6-NH2
Nylon monomer

Two monomers
make one Nylon 6,6
repeating unit.* 2
*There many different kinds of nylon.
 Polydispersity is the term we use to describe the
fact that not all macromolecules in a given sample
have the same repeat number x.

Polydisperse Monodisperse Paucidisperse

# # #

size size size

Even in a pure sample, not all molecules will be the same.

Nature often does better than people do.

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 Addition Condensation
Chain growth Step growth

Example Polystyrene Nylon

Empirical formula No change from Changes as byproduct

monomer. (often water) is given off.

How grows One monomer at a Monomer + dimer,

time hexamer +
octadecamer, etc.

Polydispersity Can be paucidisperse Most probable

Molecular weight Wide range: can be Low (except

very high biopolymers)

Synonym Chain growth Step growth

polymerization polymerization
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 Addition: one monomer at a time
Also called chain growth.

Condensation: anything goes!

Also called step growth.

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 The molecular weight of condensation (step
growth) polymers is limited to fairly low values.
Why?
Condensations: usually < 50,000 g/mol
Addition: can be quite high
(e.g., 46 x 106 for polystyrene)
Convert that to tons/mol

Nature makes huge polycondensates,

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but they are usually made in chain growth fashion!
There are such things as
inorganic polymers.

R
--[P=N]--
x
R
R used to be a secret. Not sure if it still is.

Others: POSS, poly(phthalocyanines), many colloids

(colloids are close relatives of polymers) 7
 Cascade polymers are also known as dendrimers. This
remains one of the hottest areas of macromolecular
science. Co-invented at LSU, it is still practiced here.
(McCarley, Warner, Daly, Russo)

Newkome @ LSU
Tomalia @ Dow

Future Nobelists?
Tomalia: now at MMI 8
Newkome: now at U. Akron
The poly(phenylene) dendrimer at left has
actually been crystallized (Mullen).

The arborol dendrimer below was

made by Newkome at LSU.and
we still make this one at LSU.

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 Copolymers can be used to tailor functionality
or generate new phases and behaviors.

Block copolymer, example:

Poly(styrene)-block-poly(butadiene)

Random copolymer, example:

Poly(styrene-ran-butadiene)

Graft copolymer,
example:
Poly(styrene)-graft-
poly(butadiene)10
Some chemists really care about nomenclature.
Type Connective Example

unspecified -co- poly(A-

co-B)

statistical -stat- poly(A-

stat-B)

random -ran- poly(A-

ran-B)

alternating -alt- poly(A-

alt-B)

periodic -per- poly(A-

per-B-
per-C)

block -block- polyA-

block-
polyB
James TraynhamLSU, 2003
graft -graft- polyA-
graft-
polyB From the Chemistry at U. Missouri Rolla website

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 What does
that mean?

Star polymers have the

ability to act a little bit like spheres
and you can get higher Ms.
f=4
A lot of the
magic of
polymers is just
size.

Suppose each of the 4 arms is polydisperse. Are such molecules more

or less polydisperse than their linear counterparts?

Each arm of this star is a random coil. Star rods would be fun.
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Letter polymers are synthetically challenging
and useful for testing theories.

From the Mays website

In Hartford, Hereford and Hampshire, Hs Hardly Happen*

In Knoxville, Tennessee (home of Jimmy Mays) they do.

Matters in polyolefinsmakes for better processing? Regular letter
polymers help manufacturers defend billion dollar patents.

*Adapted from the musical, My Fair Lady 13

Combs, brushes and ladders give
you ways to stiffen a polymer.

Think bottle brush

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Rodlike polymers are used for very high
strength, liquid crystals, photonics, efficient
viscosification and control of phase relations.
Rodlike because of linear backbone

N N
* n *
S S

Used in
stealth
bomber?
Maybe.

Rodlike because of helix 15

 Polyelectrolytes: strange things happen when you try to

separate charges by a few Angstroms.

Do they still
Strong polyelectrolytes tell you about
(e.g., salts of strong polyacids or polybases) Angstroms?

Sodium polystyrene sulfonate: fully charged, yet behavior depends on

added salt

Monomer: SO3Na

CH3

Weak polyelectrolytes (e.g., weak polyacids or polybases)

Poly(acrylic acid)
Behavior depends on added salt and pH
Monomer: CH2=CH-COOH

One of the hottest areas of fundamental polymer research involves polyelectrolytes.

Concentration of charge along a backbone, with charged groups closely separated, produces 16
some weird distortions in the moleculesand in the surrounding solution. Opposites may repel!
You are made of biopolymers.
R group varies one
unit to the next

H O
N n
H R

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Proteins can do almost anything.
Proteins are the most amazing molecules on Earth,
large or small. They have 4 levels of structure,
which can confer enormously high function. In
particular, they make excellent catalystsyou are
all burning fuel nowat 37oC.efficiently
compared to most human-designed combustion
devices! Its the proteins that do this. They also
give structure and strength and resilience. They
can change their shapethe original smart
molecule.

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 The 4 levels of structure
Primary: the sequence of the amino acids
Secondary: helix, coil or random sheet
(and a few others)
Tertiary: folding of the unit, including
S-S- bridges
Quaternary: how the blobs assemble

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 Structure = Function
More Structure = More Function
http://www.sciencecollege.co.uk/SC/biochemicals/bsheet.gif

Alpha helix
Beta sheet

http://www.search.com/reference/Alpha_helix

Protein
Normal synthetic polymer
Subunit
Subunit

http://www.biosci.ohio-state.edu/~prg/protein1.gif

-Helical secondary structure

S-S link
20
-sheet secondary structure
There are 20 common, naturally occurring amino acids.

http://www.genome.iastate.edu/edu/gene/genetic-code.html#Amino21
Acids
Another type of biopolymer, nucleic acids, contains the
information needed to make proteins.

Borrowed from
Natural Toxins Research Center Webpage:
http://ntri.tamuk.edu/cell/nucleic.html

An interesting sub-section of the nanotech community tries

to use nucleic acids as structural materials. 22
Biopolymers: Nucleic Acids
Ribose sugar Base OH 5'
3' O
H O P O
O P O H3C O ..... H N
O N O
O P O OH CH2
T N H ...... N A O
OH N
O O O N
H2C OH
U O
O N N H O O P O
H2C O P O H O
O N
O OH O ... H N
O CH2
O P O N
N O G N H ........ N C
OH O
OH H2C N N OH
N G N NH ......... O
O O P O
CH2 O N O
NH2 O P O H
N N H ..... O CH3
O O CH2
OH
O P O N A
OH
NH O N ........ H N T OH
OH N H2C N
N
O P O
A N O O
H2C O N H O
O N O P O N H .. O N
O CH2
O P O OH C N .....
OH H N G N
OH N N
O 3'
NH2 H2C O .... H N O
H
H2C O C O
N N
O O P O
O P O O O
OH 5'

RNA DNA 23
 Nucleic acids code proteins, a
molecular build sheet
Nucleic acids are how we get (or code) proteins. There are 4
bases (called A,T,G,C). Three of these in a row gives a "codon"
which tells the cellular machinery to add a particular amino acid.
Nucleic acids are much less prevalent than proteins, in the
same sense that auto factories are less prevalent than
automobiles. They make interesting model polymers for a
variety of studiesfrom better understanding of polymer
flexibility to liquid crystal behavior.
You can get a list of the codons for the various amino acids at:
http://www.genome.iastate.edu/edu/gene/genetic-
code.html#Amino Acids

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Networks (Gels) combine the
properties of liquids and solids.
Keep on branching. The ultimate
molecule: M = The Gentrys Sing Keep on
Branching (or something like
that)
High-speed Jello Video CLICK FOR SONG!
CLICK IT!
Pathetic Cover of Keep on
High-Speed Jello Video Branching by Boy Band Bay
CLICK IT! City Rollers
CLICK FOR SONG!
High-Speed Jello Video
CLICK IT!

It only takes a little polymer (a few percent by weight) to turn the water to a
nominal solid, and the polymers in gelatin are held by noncovalent forces.

Making the network for a tire involves significantly more polymer

and covalent forces are involved. 25
 Thermoplastic/Thermoset is
another big distinction.
Macromolecular chemistry involves chemists,
biologists, physicists, and various engineers.
The engineers, just like average citizens, have
very little use for a molecular point of view.
They tend to divide the polymer world into
thermoplastic and thermoset resins.

Thermoplastic: when you heat it, it flows (e.g.,

polyethylene, polystyrene)
Thermoset: when you heat it, it sets up into a
solid (e.g., epoxy glue, styrene monomer)

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 Silica-Polypeptide Composite Particles
Paul S. Russo (Louisiana State University), DMR-Award #1005707

We assist the Chemical Educational Foundations You Be the Chemist

Challenge program, a middle school quiz bowl that impacts ~16,000
students in 22 states. This year, we have focused on vetting the
thousands of questions it takes to operate Challenge. To give
Challenge a more hands-on and real-world flavor, the Louisiana
champion, Hayden Day, studied from a new Louisiana Playbook we
are designing (see sample question below and figure at left).
Louisiana YBTC Playbook, Problem #25.
The sequence of pictures at left shows the
repair of the polymeric skin of an automobile
bumper which was torn during a wreck. The
repair consists of pushing the parts together
closely, holding them with tape on the outside
(red) part, and welding them on the inside
(black) side using a soldering iron. Grad student Javoris Hollingsworth
teaches 8th-grader Hayden Day, the 2012
Question 1: Is the bumper a thermoset or a Louisiana state champion in the Chemical
thermoplastic? Educational Foundations You Be the
Question 2: Suppose instead of a torn bumper Chemist Challenge, about titrations. Barely
visible in the background is Haydens
we had a gashed tire made from vulcanized Mom, a school teacher. Haydens father, a
rubber. Would heating a vulcanized rubber chemical plant technician, is looking on
too. Dad studied every day with his son,
repair the tire? and Hayden acquitted himself well in the
Question 3: Explain how polymer welding national competition in Philadelphia in
June.
works at a molecular level.
Polymers can be amorphous, crystalline, or
a bit of bothcorresponding to brittle,
gooey and tough (oversimplified!).
Polymers can be solid without crystalline
structures. These are called glasses.
Polymers can be crystalline (amazing).
Most useful polymers a little bit of bothregions
in the material have crystalline inclusions and
other regions are amorphous. These
materials are often toughthe amorphous
regions absorb shock.
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 Transitions
We deal with this later, but even from the outset you
should know a little bit.

Glass transition is the temperature BELOW which the

amorphous regions of a sample start to act like
solids.
Melting transition is the temperature ABOVE which the
crystalline regions of a sample start to act like fluids.
Either way, these are oversimplificationsbig molecules
have a number of transitions that describe the chain
mobility.
These molecular transitions, in turn, impact the physical
propertiesfrom feel to stickiness (tack) to
elongation and breakage.

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