ChE 412-512 - Spring 2010

Polymer Materials Engineering

Homework Set #3 Ch 9,10 (80 pts)
due Tuesday, February 16

1. (15 pts) Condensation Polymerization

1 mole of hydroxybutyric acid (HO-(CH2)3-COOH) is placed in a reactor that reaches 50 %
conversion.
a. How many moles of unreacted COOH groups are left in the reactor? How many moles of
unreacted monomer are left in the reactor?
b. What are the average Mn, Mw, and PDI for the reaction mixture?

2. (10 pts) Calculate the gel point conversion (based on the limiting reactant) for reacting 3 mol
ethylene glycol (see p.21 D) with 1 mol butyl dianhydride (p.22 R - replace the ‘R’ group with
(CH2)4).

3. (10 pts) Work Rosen Chapter 9, Problem 10.

4. (20 pts) In a free radical polymerization, 1 mol of acrylic acid monomer CH2=C(H)(COOH) is
placed in a reactor with 0.001 mol of hydrogen peroxide.
In this problem, ignore volume shrinkage during polymerization, and assume no chain transfer
(no loss of radicals to anything except another monomer once a chain reaction has begun).

a. How much monomer remains at 75 % conversion?

b. If the initiator efficiency is 0.37, what is the average chain length in the reactor, including the
remaining monomer? (xn)
c. After the monomer is removed (by evaporation under vacuum), what is the average chain
length of PAA?
d. What is the number-average molecular weight of the PAA in part c?
e. How would you determine the polydispersity of PAA in part c?

5. (15 pts) Temperature-Dependence of Chain Length

For the same experiment discussed in Chapter 10, Example 3,
A. Determine the temperature required to run the free radical polymerization to obtain a polymer
with double the molecular weight of the polymer produced at 60 oC.
B. For the reaction temperature in A, find the rate of this reaction compared to 60 oC.

6. (10 pts) An initial experiment at Bausch and Lomb has produced poly(methyl methacrylate),
whose monomer is CH2=C(CH3)(COOCH3), (used in eyeglasses and hard contact lenses) with a
number average molecular weight of 143,000, by carrying out the reaction at 65 oC for 45
minutes. Since the product design group has determined that a molecular weight of 100,000 is
satisfactory, how fast can you speed up the production process and still achieve the desired
MW? The activation energies for each reaction step are: propagation = 7 kcal/mol, initiator
decomposition = 27 kcal/mol, and termination = 3 kcal/mol.