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.

1

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. Nature often does better than people do. 3 . not all molecules will be the same. Polydisperse Monodisperse Paucidisperse # # # size size size Even in a pure sample.

Addition Condensation Chain growth Step growth Example Polystyrene Nylon Empirical formula No change from Changes as byproduct monomer. time hexamer + octadecamer. etc. How grows One monomer at a Monomer + dimer. (often water) is given off. Polydispersity Can be paucidisperse “Most probable” Molecular weight Wide range: can be Low (except very high biopolymers) Synonym Chain growth Step growth polymerization polymerization 4 .

5 . Addition: one monomer at a time Also called chain growth. Condensation: anything goes! Also called step growth.

g.000 g/mol Addition: can be quite high (e. The molecular weight of condensation (step growth) polymers is limited to fairly low values. 6 but they are usually made in chain growth fashion! . 46 x 106 for polystyrene) Convert that to tons/mol Nature makes huge polycondensates. Why? Condensations: usually < 50..

many colloids (colloids are close relatives of polymers) 7 . poly(phthalocyanines). Not sure if it still is. Others: POSS. R’ --[P=N]-- x R R used to be a secret.There are such things as inorganic polymers.

This remains one of the hottest areas of macromolecular science. (McCarley. Russo) Newkome @ LSU Tomalia @ Dow Future Nobelists? Tomalia: now at MMI 8 Newkome: now at U. Warner. Daly. Akron . Cascade polymers are also known as dendrimers. it is still practiced here. Co-invented at LSU.

and we still make this one at LSU. The arborol dendrimer below was made by Newkome at LSU…. 9 .The poly(phenylene) dendrimer at left has actually been crystallized (Mullen).

example: Poly(styrene-ran-butadiene) Graft copolymer. 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)-graft- poly(butadiene)10 .

Some chemists really care about nomenclature. poly(A- stat-B) random -ran. Type Connective Example unspecified -co. polyA- graft- polyB From the Chemistry at U. polyA- block- polyB James Traynham—LSU. poly(A- co-B) statistical -stat. Missouri Rolla website 11 . poly(A- ran-B) alternating -alt. 2003 graft -graft. poly(A- alt-B) periodic -per. poly(A- per-B- per-C) block -block.

What does that mean? Star polymers have the ability to act a little bit like spheres and you can get higher M’s. Star rods would be fun. 12 . 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”.

From the Mays website In Hartford. “My Fair Lady” 13 . Tennessee (home of Jimmy Mays) they do. H’s Hardly Happen* •In Knoxville. Hereford and Hampshire. *Adapted from the musical.Letter polymers are synthetically challenging and useful for testing theories. •Matters in polyolefins—makes for better processing? Regular letter polymers help manufacturers defend billion dollar patents.

brushes and ladders give you ways to stiffen a polymer. Think “bottle brush” 14 .Combs.

Rodlike polymers are used for very high strength. liquid crystals. Rodlike because of helix 15 . Rodlike because of linear backbone N N * n * S S Used in stealth bomber? Maybe. photonics. efficient viscosification and control of phase relations.

yet behavior depends on added salt Monomer: SO3Na CH3 Weak polyelectrolytes (e. salts of strong polyacids or polybases) Angstroms? Sodium polystyrene sulfonate: fully charged. Polyelectrolytes: strange things happen when you try to separate charges by a few Angstroms.. with charged groups closely separated. Opposites may repel! . Do they still Strong polyelectrolytes tell you about (e. Concentration of charge along a backbone. 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. produces 16 some weird distortions in the molecules…and in the surrounding solution.g.g..

R group varies one unit to the next H O N n H R 17 .You are made of biopolymers.

In particular. 18 . They have 4 levels of structure. They can change their shape—the original “smart molecule”. Proteins are the most amazing molecules on Earth.efficiently compared to most human-designed combustion devices! It’s the proteins that do this. which can confer enormously high function. they make excellent catalysts—you are all “burning” fuel now…at 37oC…. large or small. They also give structure and strength and resilience.Proteins can do almost anything.

including – S-S.bridges • Quaternary: how the blobs assemble 19 . coil or random sheet (and a few others) • Tertiary: folding of the unit. The 4 levels of structure • Primary: the sequence of the amino acids • Secondary: helix.

gif Alpha helix Beta sheet http://www.uk/SC/biochemicals/bsheet. Structure = Function More Structure = More Function http://www.sciencecollege.ohio-state.com/reference/Alpha_helix Protein Normal synthetic polymer Subunit  Subunit  http://www.search.co.gif -Helical secondary structure S-S link 20 -sheet secondary structure .edu/~prg/protein1.biosci.

There are 20 common.genome.iastate.edu/edu/gene/genetic-code.html#Amino21 Acids . http://www. naturally occurring amino acids.

edu/cell/nucleic. 22 .html An interesting sub-section of the nanotech community tries to use nucleic acids as structural materials.tamuk. nucleic acids.Another type of biopolymer. contains the information needed to make proteins. Borrowed from Natural Toxins Research Center Webpage: http://ntri.

...... O CH3 O O CH2 OH O P O N A OH NH O N .. H N O H H2C O C O N N O O P O O P O O O OH 5' RNA DNA 23 . 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 ..........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 .. OH H N G N OH N N O 3' NH2 H2C O ... 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 ..... 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 .................

genome.T. in the same sense that auto factories are less prevalent than automobiles.C). a molecular “build sheet” • Nucleic acids are how we get (or “code”) proteins.edu/edu/gene/genetic- code. Nucleic acids are much less prevalent than proteins. They make interesting model polymers for a variety of studies—from better understanding of polymer flexibility to liquid crystal behavior. Three of these in a row gives a "codon" which tells the cellular machinery to add a particular amino acid.G. There are 4 bases (called A. • You can get a list of the codons for the various amino acids at: http://www. Nucleic acids code proteins.html#Amino Acids 24 .iastate.

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. Keep on branching. 25 . 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.Networks (Gels) combine the properties of liquids and solids.

Thermoplastic/Thermoset is another big distinction. They tend to divide the polymer world into thermoplastic and thermoset “resins”. have very little use for a molecular point of view. it flows (e. styrene monomer) 26 .. physicists.g.. The engineers. epoxy glue.g. it “sets up” into a solid (e. polystyrene) • Thermoset: when you heat it. just like average citizens. polyethylene. and various engineers. • Thermoplastic: when you heat it. Macromolecular chemistry involves chemists. biologists.

This year. we have focused on vetting the thousands of questions it takes to operate Challenge. Barely visible in the background is Hayden’s we had a gashed tire made from vulcanized Mom. Hayden’s father. a rubber. works at a molecular level. To give Challenge a more “hands-on” and “real-world” flavor. a school teacher. Louisiana YBTC Playbook. DMR-Award #1005707 We assist the Chemical Educational Foundation’s You Be the Chemist Challenge program. a middle school “quiz bowl” that impacts ~16. Silica-Polypeptide Composite Particles Paul S. Dad studied every day with his son. The sequence of pictures at left shows the repair of the polymeric skin of an automobile bumper which was torn during a wreck. repair the tire? and Hayden acquitted himself well in the Question 3: Explain how polymer welding national competition in Philadelphia in June. is looking on too. about titrations. studied from a new Louisiana Playbook we are designing (see sample question below and figure at left). the Louisiana champion. . Hayden Day. ↑Grad student Javoris Hollingsworth teaches 8th-grader Hayden Day. Problem #25. and “welding” them on the inside (black) side using a soldering iron.000 students in 22 states. Russo (Louisiana State University). Would heating a vulcanized rubber chemical plant technician. the 2012 Question 1: Is the bumper a thermoset or a Louisiana state champion in the Chemical thermoplastic? Educational Foundation’s You Be the Question 2: Suppose instead of a torn bumper Chemist Challenge. holding them with tape on the outside (red) part. The repair consists of pushing the parts together closely.

These are called glasses.Polymers can be amorphous. Polymers can be crystalline (amazing). crystalline. or a bit of both—corresponding to brittle. Polymers can be solid without crystalline structures. Most useful polymers a little bit of both—regions in the material have crystalline inclusions and other regions are amorphous. These materials are often tough—the amorphous regions absorb shock. 28 . gooey and tough (oversimplified!).

Transitions We deal with this later. Melting transition is the temperature ABOVE which the crystalline regions of a sample start to act like fluids. Either way. but even from the outset you should know a little bit. These molecular transitions. these are oversimplifications—big molecules have a number of transitions that describe the chain mobility. in turn. impact the physical properties—from “feel” to “stickiness” (tack) to elongation and breakage. Glass transition is the temperature BELOW which the amorphous regions of a sample start to act like solids. 29 .