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Student: Vu Hai Nam

Lecturer: Xiaohua Ma
School of Material Science and Engineering
Tianjin Polytechnic University

Homework 1. The sodium naphthalene polymerization of methyl methacrylate is


carried out in benzene and tetrahydrofuran solutions. Which solution will yield the
highest polymerization rate? Discuss the effect of solvent on the relative
concentrations of the different types of propagating centers.
Solution:
The dielectric constants of benzene and tetrahydrofuran (THF) are 2.3 and 7.6
respectively. It means that the THF solvent is more polar than the benzene solvent. In
anionic polymerization with alkali metal compounds, the high reaction rate is observed
in a more polar solvent such as ethers, or THF in this case. Thus THF solution will yield
the highest polymerization rate.
In anionic polymerization, there is a variety of basic initiator including covalent or ionic
metal amides and organometallic compounds. Among them, alkyl-lithium compounds
are the most used in commercial polymerization due to their solubility in a hydrocarbon
solvent. Alkyl-lithium is poorly soluble in a hydrocarbon solvent such as benzene due to
its polar structure. In addition, these compounds are soluble in a more polar solvent
such as ethers.
Homework 2. Assume that 1.0* 103 mol of sodium naphthalene is dissolved in
tetrahydrofuran and then 2.0 mol of styrene is introduced into the system by a rapid
injection technique. The final total volume of the solution is 1 liter. Assume that the
injection of styrene results in instantaneous homogeneous mixing. It is found that half
of the monomer is polymerized in 2000 s. Calculate the propagation rate constant.
Calculate the degree of polymerization at 2000 and at 4000 s of reaction time.
Summary:
n.C10H8Na = 103 Mol
n.C8H8 = 2 mol
V=1L
T1/2 = 2000 s
What is the propagation rate constant (KP)? Calculate the degree of polymerization at
2000 and 4000s
Solution:
We see that the polymerization rate is given simply by the rate of propagation:
d [ M ]
 R p =kp.[M]
dt

After integration, we have

 [M ] 
ln  0   k p  t (*)
 [M ] 

It’s found that at t=2000s, half of the monomer is polymerized, so the equation (*)
becomes
ln(2) = kp*2000s
ln  2 
 kp  = 0.347 x 10-3 s-1
2000

In addition, the number average degree of polymerization ( X n ) is defined as

N0 [M 0 ]
Xn  
N [M ]

Substitute to equation (*), we have

 [ M ]0 
ln    k pt
 [M ] 

At t = 2000
[M]0
 e p = 2 => degree of polymerization is 2
k t

[M ]

At t=4000
[M]0
 e p = 4 => degree of polymerization is 4
k t

[M ]

Homework 3. Show by equations the synthesis of the following types of block


copolymers
a. ABA
b. CABAC
where A, B, and C represent styrene, butadiene, and isoprene, respectively.
Solution:
a. Block copolymers of ABA

b. Block polymerization of CABAC


CABAC block copolymers are synthesized by addition of monomer C to the ABA living
polymer