Polymer Chemistry Mid-term Total points: 115

Symbols carry usual meanings!

1 (35%) Explain the following terms. Use graph if necessary.

(a) For an acid catalyzed step polymerization (e.g. A − A + B − B ⎯⎯⎯ k

+ acid
→

−( A − B )n − +byproduct ), write down the relation between rate constant, k , extent reaction,

p , and the degree of polymerization, xn , of the polymers thus synthesized.

(b) Most condensation polymerization fall into a category known as carbonyl addition
elimination reaction. Explain the reason why most of these reactions require metal catalyst
for their polymerization. (Hint: Use transition-state theory to explain the reason.)
(c) Step-growth polymers containing active end-groups may undergo molecular weight
change at elevated temperatures. Give an example to explain why such a scrambling reaction
may occur.

(d) In class, we developed a theory to estimate the critical extent of reaction, pc , to predict

gelation point which is based on the Carothers theory of gelation. Explain the short comings
of the theories for the prediction of gelation.
(e) Explain the reason why auto-acceleration reaction arises during the free radical
polymerization.
(f) Explain the effect of temperature on the rate of polymerization and the molecular weight
of the polymers thus synthesized in free radical polymerizations.
(g) Based on polymerization thermodynamics (starting from the Gibbs free energy
expression), explain the reason why there exists a ceiling temperature for free radical
polymerizations.

Ans:

(a)

1  A0
 A0 k t = 1 − p − 1 = − 1 = xn − 1
 A
(b) Mechanism:
Most condensation Polymerizations fall into a category known as carbonyl-addition-
elimination reactions.

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Polymer Chemistry Mid-term Total points: 115

O O O

R C X + Y R C Y R C Y + X

intermediate-
transition state

The rate of the overall reaction depend on the ease of elimination of X − .

Hence, catalysts such metal oxides are added, antimony trioxide ( Sb2O3 ) and calcium
acetate ( (CH3COO)2 Ca ).

(c) Step-growth polymers containing active end-groups may undergo molecular weight
change at elevated temperatures.

O H O H

C N C N

+ +
O C O C

H O H O

(d) The theory is flawed. Molecules with degrees of polymerization both larger and smaller

than xn are present, and it is the largest molecules that undergo gelation first. Therefore,

the theory overestimate the critical extent of reaction when gelation occurs. pc

(e) Auto-acceleration arises as a consequence of the increase in viscosity, which greatly

reduces the possibility of termination of the growing chains.

12
 f kd k p2 
I   M 
1 2
Therefore, smaller k t , larger increase in Rp =   and larger
 k t 
12
1 k 
2

I   M 
−1 2
xn   =  p  which gives a large increase in viscosity.
2  f kd kt 
The initiation and propagation are not affected because the monomers are small and have
high mobility even in media of high viscosity.

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Polymer Chemistry Mid-term Total points: 115

d ln ( Rp )
(f)  0 → Rp increases with increasing temperature.
dT

d ln xn( ) 0 → xn decreases with increasing temperature.

dT
(g)

Gp = Hp − T Sp

1. Gp  0 in order for polymerization to occur.

2. Hp  0 which favors polymerization for most vinyl monomers.

3. However, −T Sp  0 which disfavors polymerization.

At equilibrium between polymerization and depolymerization, G p = 0 , we have

Hp
Tc =
Sp

where Tc is called the ceiling temperature, which is the upper limit in temperature in order

for the polymerization to occur.

2. (20%)
Draw the structural formula (one repeating unit) for each of the following polymers:
a. polyethylene; b. polypropylene; c. polyvinyl alcohol;
d. poly(methyl methacrylate); e. 1,4-poly(1,3-butadiene) f. a polyamide;
g. a polyimide; h. a polyurethane; i. a polycarbonate;
j. poly(ethylene terephthalate);

Ans:

a. ; b. ; c. ;

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Polymer Chemistry Mid-term Total points: 115

d. ; e. ; f. ;

g. ; h. ; i. ;

j. ;

3. (15%) What feed ratio of hexamethylene diamine (己二胺) and adipic acid (己二酸) should

be employed in order to obtain a polyamide (nylon 6,6) of 5,000g mol at 99% conversion?

Identify the end groups of this product?

(hints: ; )

Ans:

Formula weight of repeating unit = 226.

(由於高分子有兩種不同的單體所組成，所以我想就把兩種不同的單體質量做平均，用這個平
均分子量的單體來計算高分子的聚合度。)

226
M0 = = 113 ; (平均單體的分子量)
2

Mn 5,000
xn = = = 44.25 ;
M0 113

From Eq. (3), the modified Carothers equation, we have

1+ r 1+ r
xn = = = 44.25
1 + r − 2rp 1 + r − 2r  0.99

Solving, r = 0.9749 .

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Polymer Chemistry Mid-term Total points: 115

The polymerization is carried out with either COOH NH2 or NH2 COOH =0.9749. For

COOH NH2 =0.9749, all end groups will be NH2 ; for NH2 COOH =0.9749, all end groups

will be COOH . #

4. (15%) Can the following recipe for making polyesters be reacted to complete conversion
of the limiting reactant without gelation?

Component Moles Functionality Equivalents

Phthalic anhydride 2.0 2 4.0
Glycerol 0.3 3 0.9
Pentaerythritol 0.6 4 2.4
Total 2.9 7.3
where the term “equivalent” stands for the mole number of the corresponding functional
group.

Phthalic anhydride Glycerol Pentaerythritol

( C6H4 (CO)2 O ) ( C H2 (OH )(OH )C H2 (OH ) ) ( C(CH2OH )4 )

Ans:
Total acid equivalents = 4.0 and total OH equivalents: = (0.9+2.4) = 3.3
Since the OH equivalents are in deficient supply (limited reagent),

2NA0 2  3.3
The effective fav = = = 2.2759
 Ni 0 2.9
Note that this represents the average useful functionality of the reaction mixture, while
7.3
the overall average functionality is = 2.5172 .
2.9
2 2
From Eq. (5), the critical extent of reaction is pc = = = 0.88
fav 2.2759

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Polymer Chemistry Mid-term Total points: 115

5. (15%) Consider a radical polymerization process,

(a) initiation: (1) I ⎯⎯→2

kd
R • - slow, (2) R • + M ⎯⎯
ki
→ RM1• - fast.

•
(b) propagation: M1 + M ⎯⎯→ M2• ; M2• + M ⎯⎯→ M3• ; ….; Mi • + M ⎯⎯→ Mi •+1
p pk p k k

(c) termination by combination: Mi • + M j• ⎯⎯

kt
→ Mi + j

where k d , k p , and kt are the rate constant for initiation, propagation, and termination.

We also assume that f is the initiator efficiency and k p is not affected by the chain

d R 
length. We also define the rate of initiation as Ri = , the rate of polymerization as
dt
d M  d M 
Rp = − , the rate of termination as Rt = − and the average kinetic chain length
dt dt

Rp
as  = .
Ri

Based on the steady-state approximation for radicals, derive the corresponding rate equation

for Rp and the degree of polymerization, x n of the polymers thus synthesized.

Ans:

d R • 
Ri = = 2kd f I 
dt
d M 
Rp = − = k p M  M • 
dt

d M •  2
Rt = − = 2kt M • 
dt

Since the radicals are high reactive, a steady-state can then be reached such that Ri = Rt

or M •  = const .

d M • 
= Ri − Rt = 0
dt

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Polymer Chemistry Mid-term Total points: 115

We have
12 12
R   k 
M  =  i 
•
=  f d I  
 2kt   kt 
Therefore,
12
 f kd k p2 
12
f k 
Rp = k p M   d  I  I   M 
1 2 1 2
=
 k 
 kt   t 
1 2
1  kp 
2
Rp 1
I  M 
−
and  = =   2
Rt 2  f kd kt 
Since termination is based on radical combinations, the degree of polymerization,
𝑥𝑛 = 2𝜈. #
6. (15%) Discuss the key features of emulation polymerization .
(a) What is the main ingredient for emulsion polymerization?
(b) Depict the morphology for emulsion solution before polymerization.
(c) Describe the three main stages occurring in emulsion polymerization.
(d) Describe the three nucleation mechanisms in emulsion polymerization.
(e) Explain the reason why the rate of polymerization and degree of polymerization of
synthesized polymer by emulsion polymerization can be simultaneously high.

Ans:
(a)
A. Essential ingredients:
1. monomer
2. surfactant (or emulsifying agent e.g. soap)
3. water
4. water-soluble initiator – the only different ingredient from the suspension polymerization.

(b)

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Polymer Chemistry Mid-term Total points: 115

a few um

5-10nm

4nm

monomer droplet
micelle

monomer

monomer loaded micelle initiator

with 100 monomer

surfactant
# of micelles: # of droplets ~108: 1
total surface area of micelles: total surface area of droplets ~103: 1

(c)

Rp , reaction rate  , surface tension

I II III

0 0
time

(d)

Mechanism 1: nucleation in monomer micelles

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Polymer Chemistry Mid-term Total points: 115

or

micellar nucleation

Mechanism 2: nucleation of homopolymer radicals

homogeneous nucleation

Mechanism 3: droplet nucleation

oligomer monomer droplet

droplet nucleation

(e)

Both the rate of polymerization, Rp , and the degree of polymerization, xn , is proportional to

the number of particles, Np , being generation in emulsion polymerization and Np can be

easily increased by the addition of surfactant. Therefore, typically in emulsion polymerization,

the rate of polymerization and the degree of polymerization of the synthesized are usually
high.