Modified Carothers equations
1. Polymerization can be stopped at a specific DP with slight excess of one
reactant.
a. Define monomer ratio r of [A] to [B] as a number always less than one.
p = 1; r = 0.98
2. Reaction can be stopped with a specific amount of monofunctional
monomer.
a. Define functionality factor f as the number average of functional
groups per monomer.
Example: Let a mixture have 0.02 mol
of alcohol and 0.98 mol of diol.
If p = 1,
Q1)
Calculate the average degree of polymerisation, after an extent of
reaction of p = 0,99, in a linear polycondensation of two pure
difunctional monomers with an equal number of reactive sites.
Q2)
This polypropylene has a number average molecular weight of
100,000 and a polydispersity of 5. What is the weight average
molecular weight?
A) 20,000 B) 100,000 C) 500,000 D) 100,005 E) 5,000,000
Q3)
polyester is made from diol monomer and adipic acid. In each batch
equimolar reactants are used and the conversion is 97.0%.
a) Calculate the number-average molecular weight.
b) If 98% conversion used. What will be the Mn of this batch?
c) If 2% more of adipic acid was used and the reaction went to
the usual conversion, what was its number-average molecular
weight?
d) How should these batches are mixede to obtain the Mn of the
usual product. What will be Mw?
Q4)
A sample of atactic polystyrene is separated into 5 fractions;
Fraction Number of Moles Molecular Weight
1 20 10000
2 20 20000
3 20 30000
4 20 40000
5 20 50000
What is the number average molecular weight?
A) 2.33 x 104 B) 3.0 x 104 C) 3.66 x 104 D) 4.33 x 104
1- What is the weight average?
A) 2.33 x 104 B) 3.0 x 104 C) 3.66 x 104 D) 4.33 x 104
2- What is the polydispersity?
A) 1 B) 2 C) 1.22 D) 1.44
Q5)
Consider the properties of the following two polyethylene samples.
Sample 1 was produced by a high pressure process while sample 2
was synthesized using a catalyst
Polyethylene 1 Polyethylene 2
Mol wt. 200,000 200,000
Density (g/cm3) 0.92 0.96
Crystalline melting pt 108°C 133°C
Which of the following statements is true?
A) Sample 2 is more branched than sample 1
B) Sample 1 is more branched than sample 2
C) Sample 1 is more atactic
D) Sample 1 is more isotactic
Q6)
The initial degree of polymerization (Xn or ν) of a 5.0 M solution of
styrene in benzene initiated by di-t-butyl peroxide was found to be
7000. Determine the concentration of butanethiol (Cs or ktrs/kp = 21)
required to reduce the Xn to 200.
Q7)
Consider the isothermal solution polymerization of styrene at 60°C in
the following formulation:
100 g styrene
400 g benzene
0.5 g benzoyl peroxide
Assume that the initiator is 100% efficient and has a half-life of 44 h.
At 60°C, kp = 145 l/mol-s, kt = 0.130 l/mol-s. All ingredients have unit
density.
a. Calculate the rate of propagation at 50% conversion.
b. How long will it take to reach this conversion?
Q8)
A company is making nylon 6,6 from hexamethylenediamine and
adipic acid. One batch is made on every 8-h shift. In each batch
equimolar reactants are used and conversion is usually 98.0%. At the
end of the run the bulk product is extruded and chopped into pellets.
Calculate the number-average molecular weight.
The afternoon shift operator dumped in too much adipic acid. From
his records you calculate that the mole ratio was 2% excess adipic
acid. If the batch went to the usual conversion, what was its number-
average molecular weight?
The night shift operator weighed things correctly but fell asleep and
let the reaction run too long —99% conversion. What will be the Mn
of this batch?
How should the company engineer mix these batches to obtain the
Mn of the usual product. What will be Mw?