Assignment 4

Question 1

a) Step growth polymer

b)

Monomer No of Moles (N) f Equivalence (N*f)

Phthalic anhydride (PA) 2.5 2 5
Ethylene glycol (EG) 0.8 2 1.6
Glycerol (GL) 1.1 3 3.3

Equivalence of acid anhydride group = 5

Equivalence of OH group = 1.6 + 3.3 = 4.9
Since the equivalence of OH group is less than the equivalence of the acid anhydride group, EG and GL
are limiting reagents. Thus, we run out of EG and GL which will react with 4.9 equivalence of PA.
4.9
A that can react = ∗ 100% = 98% 𝑜𝑟 0.98
5
∑𝑛𝑖=1 𝑁𝑖 𝐹𝑖 0.98(5) + 4.9
𝑓𝑎𝑣 = 𝑛 = = 2.227
∑𝑖=1 𝑁𝑖 (2.5 + 0.8 + 1.1)

The extent of reaction is given as 72%, i.e. p=0.72,

2
𝑁𝑢𝑚𝑏𝑒𝑟 𝑎𝑣𝑒𝑟𝑎𝑔𝑒 𝑑𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑝𝑜𝑙𝑦𝑚𝑒𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛, 𝑋̅𝑛 =
2 − 𝑝𝑓𝑎𝑣
2
=
2 − 0.72 ∗ 2.227
= 5.04
c) Estimate the gel point:
2 2
𝑝𝐺= =
𝑓𝑎𝑣 2.227
𝑝𝐺= 0.898
At gel point, the extent of reaction is 0.898. When the extent of reaction is 1% less than the gel point,

𝑝 = 𝑝𝐺 − 1%
𝑝 = 0.898 − 0.01
𝑝 = 0.888
2
𝑁𝑢𝑚𝑏𝑒𝑟 𝑎𝑣𝑒𝑟𝑎𝑔𝑒 𝑑𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑝𝑜𝑙𝑦𝑚𝑒𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛, 𝑋̅𝑛 =
2 − 𝑝𝑓𝑎𝑣
 2
=
2 − 0.888 ∗ 2.227
2
=
0.02242
𝑋̅𝑛 = 89.2

1d)

Monomer No of Moles (N) f Equivalence (N*f)

Phthalic anhydride (PA) 3.2 2 6.4
Ethylene glycol (EG) 3.2 2 6.4

𝑋̅𝑛 = 70
2𝑚𝑜𝑙
𝐶𝑃𝐴,0 =
𝐿
𝐿
𝐾 = 0.01
𝑚𝑜𝑙 − 𝑠
Since the reaction is catalyzed, it is a second order reaction.

𝑋̅𝑛 = [𝐴 − 𝐴]𝑘𝑡 + 1
2𝑚𝑜𝑙 0.01𝐿
70 = ∗ ∗𝑡+1
𝐿 𝑚𝑜𝑙 − 𝑠
69𝑠 = 0.02𝑡
69𝑠
𝑡=
0.02
𝑡 = 3450𝑠
1e)

i. Increase the reaction temperature: this provides the reactants sufficient energy to react.
ii. Add a Lewis acid as a catalyst: this stabilizes reactive intermediates thus lowering the
activation energy of the reaction.
 Question 2

2a) The difference between the line is caused by the lack of inhibitor in the monomer represented by the
solid line and presence of inhibitor in the monomer represented by the dashed line.

I would order the monomer that follows the dashed line because the inhibitor in it prevents
polymerization during shipping.

2b) Without chain transfer, the degree of polymerization is:

̅𝑛
𝑀 138,000𝑔/𝑚𝑜𝑙
𝑋̅𝑛𝑜 = = = 1326.9
𝑀𝑜 104𝑔/𝑚𝑜𝑙
With chain transfer, the degree of polymerization reduced to:
̅𝑛
𝑀 85,000𝑔/𝑚𝑜𝑙
𝑋̅𝑛 = = = 817.3
𝑀𝑜 104𝑔/𝑚𝑜𝑙
Estimate 𝑘𝑝 from the equation below:

1 1 𝑘𝑡𝑟 [𝑆𝐻]
= + ∗
̅ ̅
𝑋𝑛 𝑋𝑛𝑜 𝑘𝑝 [𝑀]
𝐿
𝑘𝑡𝑟 = 3700 , [𝑆𝐻] = 1.2 ∗ 10−4 𝑀, [𝑀] = 1.0𝑀
𝑚𝑜𝑙 − 𝑠
𝐿
3700 ( ) −4
1
=
1
+ 𝑚𝑜𝑙 − 𝑠 ∗ (1.2 ∗ 10 𝑀)
817.3 1326.9 𝑘𝑝 (1.0𝑀)
𝐿
1 1 0.444 ( )
− = 𝑚𝑜𝑙 −𝑠
817.3 1326.9 𝑘𝑝
𝐿
1 1 0.444 ( )
− = 𝑚𝑜𝑙 −𝑠
817.3 1326.9 𝑘𝑝
𝐿
0.444 ( )
4.699 ∗ 10 −4
= 𝑚𝑜𝑙 −𝑠
𝑘𝑝
𝐿
𝑘𝑝 = 944.88
𝑚𝑜𝑙 − 𝑠
Now use the equation for the degree of polymerization without chain transfer to calculate initiator
efficiency, f.
𝑘𝑝 [𝑀]
𝑋̅𝑛 = 1 1 1 1
2𝑘𝑡 2 𝑓 2 𝑘𝑑 2 [𝐼]2
 1 𝑘𝑝 [𝑀]
𝑓2 = 1 1 1
2𝑋̅𝑛 𝑘𝑡 2 𝑘𝑑 2 [𝐼]2
𝐿 𝑚𝑜𝑙
1 944.88 ∗ 1( 𝐿 )
𝑓2 = 𝑚𝑜𝑙 − 𝑠
𝐿 1 1 1 𝑚𝑜𝑙 1
2 ∗ 1326.92 ∗ (108 ) 2 ∗ (2 ∗ 10−6 𝑠 ) 2 (0.01 𝐿 )2
𝑚𝑜𝑙 − 𝑠
1
1 944.88 𝑠
𝑓2 = 1 1
𝐿2 1 𝑚𝑜𝑙 2
2 ∗ 1326.92 ∗ 104 1 1 ∗ 1.414 ∗ 10−3 1 ∗ 0.1 1
𝑚𝑜𝑙 2 − 𝑠2 𝑠2 𝐿2
1 944.88
𝑓2 =
2 ∗ 1326.92 ∗ 104 ∗ 1.414 ∗ 10−3 ∗ 0.1
1 944.88
𝑓2 = = 0.252
3752.5
𝑓 = 0.2522
𝑓 = 0.0634
So, the initiator efficiency is 6.34%.

b) Initial rate of polymerization.

𝑘𝑝 1 1
𝑅𝑝 = 1 (𝑓𝑘𝑑 ) [𝐼] [𝑀]
2 2

𝑘𝑡2
𝐿
944.88 10−6 1 𝑚𝑜𝑙 1 𝑚𝑜𝑙
𝑅𝑝 = 𝑚𝑜𝑙 − 𝑠 ∗ (0.0634 ∗ 2 ∗ )2 [0.01 ]2 [1 ]
8 𝐿 1/2 𝑠 𝐿 𝐿
(10 )
𝑚𝑜𝑙 − 𝑠
1
944.88( 𝑠 )1/2 10−6 1 1 𝑚𝑜𝑙
𝑅𝑝 = 4
∗ (0.0634 ∗ 2 ∗ )2 [0.01]2 [1 ]
10 𝑠 𝐿
1
944.88( 𝑠 )1/2 10−6 1 1 𝑚𝑜𝑙
𝑅𝑝 = ∗ (0.0634 ∗ 2 ∗ )2 [0.01]2 [1 ]
104 𝑠 𝐿
𝑚𝑜𝑙
𝑅𝑝 = 3.36 ∗ 10−6
𝐿−𝑠
2c)

Stabilized by
inductive effects

Question 3
𝐿 𝐿
3a) 𝑅𝑝 = 2 ∗ 10−5 , 𝑅𝑖 = 4.5 ∗ 10−9
𝑚𝑜𝑙−𝑠 𝑚𝑜𝑙−𝑠

At steady state, the rate of initiation is equal to the rate of termination i.e. 𝑅𝑖 = 𝑅𝑡
𝑚𝑜𝑙
𝑅𝑝 2 ∗ 10−5
𝑋̅𝑛 = = 𝐿 −𝑠
𝑅𝑡 4.5 ∗ 10−9 𝑚𝑜𝑙
𝐿−𝑠
𝑋̅𝑛 = 4444
3b)
𝑘𝑝 [𝑀]
𝑋̅𝑛 = 1 1 1 1
2𝑘𝑡 2 𝑓 2 𝑘𝑑 2 [𝐼]2
𝑘𝑝 [𝑀]
𝑋̅𝑛 = 1 ∗ 1 1 1
𝑘𝑡 2 2𝑓 2 𝑘𝑑 2 [𝐼]2
1 𝑘𝑝 [𝑀] 1
𝑘𝑑 2 = ∗ ∗
1 1 1
𝑋̅𝑛
𝑘𝑡 2 2𝑓 2 [𝐼]2
 1
1
𝐿2 𝑚𝑜𝑙 1 1
𝑘𝑑 = 0.012
2 1 1 ∗ 1.0 𝐿
* 1 1 1 1*
𝑚𝑜𝑙 2 −𝑠2 4444
2∗0.82 ∗0.012 𝑚𝑜𝑙 2 /𝐿 2

𝑘𝑑 = 2.28 ∗ 10−10 𝑠 −1

3c) For styrene, 𝑄1 = 1.0, 𝑒1 = −0.8, 𝑟1 = ?; For vinyl chloride, 𝑄2 = 0.056, 𝑒2 = 0.16, 𝑟2 = ?
𝑄1
𝑟1 = ∗ 𝑒 (−𝑒1 (𝑒1 −𝑒2 )
𝑄2
1.0
= ∗ 𝑒 −(−0.8)((−0.8)−(0.16))
0.056
1.0
= ∗ 𝑒 0.8(−0.96)
0.056
𝑟1 = 8.285

𝑄2
𝑟2 = ∗ 𝑒 (−𝑒2 (𝑒2 −𝑒1 )
𝑄1
0.056 −(0.16)((0.16)−(−0.8))
= ∗𝑒
1
0.056 −0.16(0.96)
= ∗𝑒
1
𝑟2 = 0.048

3d) 𝑟1 = 8.29, 𝑟2 = 0.05, 𝑟1 𝑟2 = 8.29 ∗ 0.05 = 0.41

From this information, 𝑟1 ≫ 1, 𝑟2 < 1, 𝑎𝑛𝑑 𝑟1 𝑟2 < 1, thus the polymer formed will mostly be a
homopolymer of styrene.