POLYMER CHEMISTRY

EXAM 1 Study Guide

Test Date Sept. 22, 2016
Dr. Dale Teeters

You are responsible for lecture notes, all homework, Text: Sections listed in handout.

Know the repeating unit and proper chemical name (as discussed in class) for the following
polymers. Also know their major uses.

nylon 66

nylon 610

Mylar

Teflon (not Teflon FEP)

PVC
silicone rubber

Lucite or Plexiglass

1. What are the differences between monomers, oligomers, and polymers? How do their
physical properties vary?

*Monomers: A molecule that is able to bond in long chains. (small molecules that get
together to form larger molecule)

*Polymers: many monomers. They are chains of an unspecified number of monomeric

units.

*Oligomers: Really low molecular weight species. They are not big enough to be
polymers.

- As the MW increases, the physical status changes from gas to liquid to gas because of the
sum of intermolecular forces increases. So from gas -> liquid(pentane) -> solid (wax at
29C) as we are moving from few monomers to heaps of monomers.

2. Of what importance is molecular weight when one is concerned with the physical properties
of polymers?

As the molecular weight increases, the polymer changes from gas to liquid to solid. This is
due to increasing the sum of the intermolecular forces.

3. What gives a polymer different physical properties than its constituent monomers?

- The molecular weight. ……

 -
4. Know and understand the three broad classifications of polymerization based on the
chemistry involved.

1- Condensation:
It is when molecules join together while losing small molecules by-products (Water or
methanol). This types includes: polyamides, polyesters, polyacetals, polyurethanes.
2- Addition Polymerization. (most common)
It is when molecules join together by rearranging of bonds, without losing any small
molecules.
3- Ring opening polymerization.
It is a form of chain-growth polymerization. The terminal end of the polymer chain acts
as a reactive center. It reacts with a ring that opens up to form a longer polymer chain.

5. Be able to list the polymers that we have discussed in class whose polymerization chemistry
fits each of the classifications in number 4.

6. What is characteristic of a condensation reaction?

- It forms more slowly than addition polymers, often requiring heat, and they are usually
lower in MW.
- The monomers have functional groups instead of double bonds.
- Each monomer has at least 2 reactive sites (2 functional groups).

7. What are the steps in a free radical polymerization?

1- Initiation: Makes the reactive site
2- Propogation: Make the long polymer chain.
3- Termination: Stops polymerization and completes the polymer molecule.

8. What type of polymers are formed by the following reactions: bifunctional alcohol (diol)
and a dicarboxylic acid, diol and a bifunctional acid chloride, dicarboxylic acid and a
diamine, and a diol and a diisocyanate?

 Bifunctional alcohol (diol) and a dicarboxyic acid: Polyesters.

 Diol and a bifunctional acid chloride: Polyester and gives off HCl (-C-O2-Cl)
 Dicarboxylic acid and a diamine: Polyamides
 Diol and diisocyanate: Polyurethanes (doesn’t give off a small molecule).

9. Be able to write the general chemical equations for each of the reactions listed in number 8
above. (Three equations in notes.)

10. Given a hypothetical fractionation of a polymer, be able to calculate M w, M n, and M z.

(Equations.)

11. Be familiar with molecular weight distributions.

  Physical property Vs MW
 Probability of certain MW Vs. DP
 Wr fraction of the species Vs. MWi

12. Be able to describe the various ways of determining molecular weight. Know their
limitations.
1- Membrane osmometry.
 Limits : 30,000 to 1,000,000 MW. Why? Because at higher molecular weight, the solute
would be too dilute and we will not be able to measure the MW. When it is below 30,000,
the solute permeates through the membrane and the MW we obtain will be inaccurate.
 Equation: π/C = RT/Mn. Plot π/C Vs. C and when it gets to C=0, value = RT/Mn

2- Boiling point elevation.

Ebuilliometry:
Up to 30000 MW

3- Freezing point depression.

Cryoscopy: Used in clinical chemistry.

4- Vapor pressure lowering.

5- Light scattering.
I(theta)/Io=R(theta)
Kc/R(theta)= 1/Mw + 2A2C+3A3C^2+…
K = [2*π*n(dn/dr)^2] / [(Avogadro)*(wavelength^4)], n = refractive index.

6- Viscosity:
n= C * t (n= viscosity, c= calibration constant, t=time flow)
n/n0 = nrel=t/t o (Where n= solvent viscosity, n0= solution viscosity)
nsp = (n-no)/no = n/no – 1
[n] = [nsp/C]=[1/C * LN(n/no)] = y

Plot y Vs. Concentration, and see where they move toward zero, that will be [n]
Then,
N=k*Mra where k and a are constants for a polymer and solvent combination.

7- Gel Permeation Chromatography (GPC)

- Form of high pressure liquid chromatography (HPLC)
- Widely used in industry. [large molecules flow faster.]

13. Be able to calculate molecular weights ( M n, M w, and M v) given data from the
experiments mentioned in number 12 above.

14. Know the relative ordering based on magnitude for M n, M v, M w, and M z. How do
high and low molecular weight fractions in polymers affect the various molecular weights?
Mn < Mv < Mw < Mz
15. What are the major characteristics of chain-growth and step-growth
polymerizations?

Step­growth
1. Growth occurs by a step wise intermolecular reaction. Only one reaction type.
2. Monomers can react with each other or polymers of any size. Polymer molecules grow
over the course of the whole reactions in “fits” and “starts.”
3. All functional groups on monomers or polymers are assumed to react equally.
4. High conversion of functional groups is required for high molecular weight. Average
molecular weight rises steadily during the course of the polymerization.
5. Many step-growth polymerizations involve equilibrium between reactants and
macromolecular products.
6. Condensation polymers, by this definition are usually produced by a step-growth
mechanism, but not all step-growth polymerizatons are condensation.

Chain­growth
1. Each polymer molecule increases in size at a rapid rate once started. When it stops the
reaction usually cannot start again.
2. Growth of polymer molecules is caused by a kinetic chain of reactions.
3. Involves the reaction of monomers with active centers: free radicals, ions etc.
4. In chain-growth mechanism, rates of reactions that initiate, continue, and terminate are
different.
5. Usually initiated by some external source: energy, highly reactive compound, or catalysts.
6. Often addition polymers have only carbon-carbon links in their backbone.

16. Be able to derive the Carother's equation.

fav = [Sum of (Ni*fi)]/[Sum of (Ni)]

If A-A is the limiting reagent,
= [2*NA + NA*2]/[NA+NB]
nA = equivalents, nA = 2 NA  nA/2 = NA
Therefore,
fav = [2*nA]/[NA+NB]

We define p = extent of reaction: between 0 and 1.

N = total number of moles.
No*fav = total # of useful equivalents of functional groups of all kinds.
# of linkages = No – N
p = # of functional groups used/ # of useful functional groups
= 2(No – N) / (No * fav)
Solve for N,
N= ½ * (2No-N0*Pfav)
Xn = # of initial moles/ # of remaining moles
= No / [½ * (2No-N0*Pfav)]

Xn = 2/2-pfav

17. Be able to work all types of problems associated with average functionality, the Carothers
equation, crosslinking, etc.

HW and problems.

18. Know what Xi and Wi as a function of i look like, be able to explain the significance in
these curves, and be able to work with the concepts involved.

19. What is the most widely used mechanism for polymer synthesis, i.e. what mechanism is
responsible for the most pounds of polymer every year?

Addition.

20. Again, what are the major characteristics of chain-growth polymerizations?

Step­growth
1. Growth occurs by a step wise intermolecular reaction. Only one reaction type.
2. Monomers can react with each other or polymers of any size. Polymer molecules grow
over the course of the whole reactions in “fits” and “starts.”
3. All functional groups on monomers or polymers are assumed to react equally.
4. High conversion of functional groups is required for high molecular weight. Average
molecular weight rises steadily during the course of the polymerization.
5. Many step-growth polymerizations involve equilibrium between reactants and
macromolecular products.
6. Condensation polymers, by this definition are usually produced by a step-growth
mechanism, but not all step-growth polymerizatons are condensation.

21. Be able to discuss, without using any equations, the three important steps in chain-growth
polymerization, i.e. what each step is and what it is responsible for in the polymerization
process.
1. (1) Initiation: A compound that serves as an initiator is broken apart by heat, light, etc. to
make an initial free radicals. These free radicals react with monomer molecule to make the
primary free radical where the free radical site has been moved to the end of the monomer
attached to the initiator. The system is now ready to start the process where large
molecules are made, propagation.
2. (2) Propagation: The primary free radicals react with monomer molecules. Each time a
reaction occurs, the free radical site is moved to the end of the chain. This makes chains of
monomer ended free radicals of various length. This is the step where the “bulk” of the
polymer molecules is made. The molecule is considered to be a polymer molecule when
 the reactivity of the molecule is stop by not having a free radical at the end of the
molecular chain. This is done by termination.
3. (3) Termination: The free radical on the monomer ended free radical is involved in a
chemical reaction where the free radical is used to make a bond. These reactions, at least
at this point in the class, are combination or disproportionation reactions. This stops the
propagation reaction and makes a completed polymer molecule.