Seung Yeob Lee

MSE580
09/17/2015
Problem 2
1.
i.

fA = m + 4

ii.

Functionality fB of Epoxy resin is 2

pc =

( fA 1)( fB 1)

1
1
=
( m + 3)( 2 1) 3
1
1
=
m+3 9
m=6
iii.

If m = 6, then fA = m + 4 = 10
MWA = 2 (14.01) + 2 (12.01) + 8 (1.01) + m 14.01+ 3(12.01) + 7 (1.01)
= 60.12 + m ( 57.11)
= 60.12 + 6 ( 57.11)
= 402.78g / mol

Calculate equivalent mass:

402.78 402.78
MassA =
=
= 40.28g
fA
10
331 331
MassB =
=
= 165.5g
fB
2
MassA + MassB = 40.28 + 165.5 = 205.78g

205.78g :100g = 40.28g : A

A = 19.57g
B = 100 19.57 = 80.43g
19.57 g of amine and 80.43 g of epoxy resin

2.
Calculate the critical extents of reaction using Statistical Theory of Flory:
r = 1, = 0.500 and f = 3
1
pc =
=
r 1+ ( f 2 )

(1.00 ) 1+ ( 0.500 )( 3 2 )

= 0.816

Calculate the critical extents of reaction using Carotheres Theory:

1+ 1
= 2.18
0.5 0.5 1
+
+
3
2 2
2
2
pc =
=
= 0.92
fave 2.18

fave =

While measured value is 0.866, Carotheres Theory overestimated as 0.92 because the
quantity is assumed to tend towards infinity at the very end and Statistical Theory of Flory
underestimated as 0.816 because the intramolecular forces is not considered.
3.

N A = N B = 1 that total N i fi = 2

fi of carboxylic acid is 3, glycol is 2 and succinic acid is 2.

Calculate the critical extents of reaction using Statistical Theory of Flory:
1
pc =
r 1+ ( f 2 )
Calculate the critical extents of reaction using Carotheres Theory:
2
pc =
fave
r

0.194

0.8

0.375

fave
1+ 1
= 2.07
0.806 0.194 1
+
+
2
3
2
1+ 1
= 2.13
0.625 0.375 1
+
+
2
3
2

Carotheres

Statistical

0.968

0.915

0.938

0.953

4.
Propagation:
H3 C
H3 C

H3 C
C

H2 C

H3C

H3 C

NC

Ph

CH
NC

H3C
NC

Ph

CH

n
Ph

Ph

Combination Mode of Termination:

H3C

CH3

H3C

n
NC

Ph

CH

Ph

HC

Ph

CH3
CN

Ph

CH3

H3C
H3C

n
NC

Ph

Ph

Ph

CH3
CN

Ph

Disproportionation Mode of Termination:

H
H3C

CH3

H3C

n
NC

Ph

CH
Ph

HC
Ph

n
Ph

CH3
CN

CH3

H3C
H3C

n
NC

Ph

Ph

n
Ph

Ph

Radioactivity of Polystyrene:
1000kg 1000g
6 10 3 counts s 1 g 1

= 6 10 9 counts s 1 mol1
mol
kg
Since it is same as the AIBNs radioactivity, the mode of termination is combination mode.
5.
i.

At Steady State:
d R*
d M *
=
dt
dt
where the rate of initiation is:
d M *
d[I ]
Ri =
= kd [ I ] =
dt
dt
and the rate of radical species consumption is:
d M *
2

= 2kt M *
dt
So total radical concentration [M*] is:
k [I ]
Ri
M * =
= d
2kt
2kt
a) Increasing [M]0 four times at constant [I]0 has no effect since the total
radical concentration is not dependent on [M]0

CH3
CN

b) Increasing [I]0 four times at constant [M]0 increases the total radical
concentration by 2 because it is proportional to [I]1/2
ii.

The rate of polymerization, Rp, is equivalent to the rate of monomer consumption is:
d[M ]
k [I ]
Ri
Rp =
= k p [ M ] M * = k p [ M ]
= kp [ M ] d
dt
2kt
2kt
a) Increasing [M]0 four times at constant [I]0 increases the rate of
polymerization by 4 because it is directly proportional to [M]0
b) Increasing [I]0 four times at constant [M]0 increases the rate of
polymerization by 2 because it is proportional to [I]1/2

iii.

The number average degree of polymerization is:

kp [ M ]
Xn =
(1+ q ) fkd kt [I ]
a) Increasing [M]0 four times at constant [I]0 increases the number average
degree of polymerization by 4 because it is directly proportional to [M]0
b) Increasing [I]0 four times at constant [M]0 decrease the number average
degree of polymerization by 2 because it is proportional to [I]-1/2