Midterm 2016

Problem 1 ​Polymerization Approaches

(a) Estimate the molecular weight of a poly(butadiene) rubber tire that weighs approximately 8
kg. (5 pts)

We can assume that the whole tire is composed of one molecule. The molecular weight is the
mass per molecule multiplied by the number of molecules per mole.
M​n​ = 8 kg/molecule×N​A
M​n​ = 4.8 × 10​27​ g/mol

(b) Draw a 10-mer of poly(propylene) polymerized using titanium tetrachloride TiCl​4​ and
triethylaluminum ​Al(C​2​H​5​)​3​. (5 pts)

(c) Zeigler-Natta catalysts often employ transition metal salts and an organometallic compound.
Could ​n​-butyllithium serve as the organometallic compound? Why or why not? (5 pts)

No, because it is too reactive and will not provide enough control over sterio-specificity in the
polymerization process.
(d) Consider the copolymerization of styrene and butadiene by anionic synthesis. What is the
mole fraction of styrene in a polymer made from a feed composed of 85% styrene with reactivity
ratios rb = 14 for butadiene and rs = 0.03 for styrene. (5 pts)

(e) Approximate the radius of gyration Rg of a 10,000 g/mol poly(methyl methacrylate)

molecule in acetone, a theta solvent, given that a 1,000 g/mol PMMA has a Rg = 1.07 nm . (5
pts)

Note: scaling should be l​2​ instead of l​0.5​, but I’m too lazy to fix it above because it cancels
off so just keep that in mind
Problem 2 ​Step Growth Polymerization

Industrial synthesis of poly(dimethyl siloxane) (PDMS), a common silicone elastomer, is

performed via the following pathway

n​ Si(CH​3​)​2​Cl​2​ + ​n+1​ H​2​O → HO[-Si(CH​3​)​2​O-]​n​ H + 2​n​ HCl

The monomer Si(CH​3​)​2​Cl​2​ serves to stabilize reaction intermediates to catalyze the reaction.
Consider the initial concentrations of monomers [Si(CH 3 )2 Cl2 ]0 = 0.2 M and [H 2 O]0 = 1 M ,
and a reaction rate constant k = 1×10−3 s−1 . Note that n is large so n≈n + 1 . The molar mass of
the PDMS monomer unit M 0 = 74 g/mol.

(a) Derive an expression relating the concentration of ​Si(CH​3​)​2​Cl​2​ to​ time, t, and the initial
reactant concentrations [Si(CH 3 )2 Cl2 ]0 and [H 2 O]0 . You do not need to simplify the
expression. (15 pts)
(b) Derive an expression relating the number-averaged degree of polymerization to time, t, and
the initial reactant concentrations [Si(CH 3 )2 Cl2 ]0 and [H 2 O]0 . ​You do not need to simplify
the expression. ​(10 pts)
(c) How long would you have to run the reaction to produce a molecular weight M n of 1000
g/mol? (5 pts)
Problem 3 ​Chain Growth Polymerization

The manufacture of rubber used in commercial applications is a very precisely controlled

process. Consider the radical polymerization of a 0.4 M solution of isoprene, M 0 = 68 g/mol , in
tetrahydrofuran (THF) initiated by 0.003 M ​2​-azobisisobutyronitrile. The reaction rate constants
f k d = 1.3×10−9 s−1 and k p /k1/2 −2 1/2
t = 7.1×10 L mol−1/2 s−1/2 .

(a) Calculate the initial rates of initiation and propagation. (4 pts)

(b) Assuming no chain transfer, calculate the resulting molecular weight and dispersity of the
initial polymer assuming termination by disproportionation. (8 pts)
(c) In reality chain transfer occurs to both the monomer and to the solvent with chain transfer
constants C M = 3×10−5 for the monomer and C S = 5×10−7 for the solvent. What is the change
in molecular weight due to chain transfer? By how much did molecular weight decrease from
(b)? (8 pts)
Bonus problems

1. In the following table, draw the monomer structure, and select a polymerization mechanism
from the list below that could be used to prepare the polymer directly.
Possible mechanisms: Self-condensation, free radical, anionic, cationic, ring-opening,
Ziegler-Natta, ATRP, RAFT, ROMP

Polymer Monomer structure(s) Polymerization Mechanism

Low density polyethylene

Radical

Poly(vinyl acetate)
Radical

Isotactic polypropylene
Ziegler-Natta

Poly(styrene-block-isoprene-
block-styrene) Anionic (RAFT, ATRP)

Poly(lactic acid)
Self-condensation or ring

Poly(ethylene oxide)
Ring opening (anionic)

Poly(isobutylene)
Cationic
2. 116 g of hexamethylene diamine (C​6​H​16​N​2​) are mixed with 144 g of adipic acid (C​6​H​10​O​4​), and
allowed to react to 98% conversion.

(a) Draw the repeat unit structure.

(b) What will the vast majority of end groups be?

The moles for each species is

116 g/(116 g/mol) = 1 mol DA

144 g/(146 g/mol) = 0.986 mol AA

Thus, as DA is the majority species, it will be the majority of the end groups

(c) What will be the value of M​n​?

N​n​ = (1+r)/(1+r-2pr) = 1.986/(1.986-2*0.98*0.986) = 37

M​0​ = (116+146-2*18)/2 = 113 g/mol

M​n​ = M​0​N​n​ = 4180

(d) What will be the value of M​W​?

M​w​ = 2 M​n​ = 8360

3. Methyl methacrylate was polymerized in benzene at 60 °C, with a concentration of 0.2 g/mL,
and AIBN at 0.16 mg/mL. Assume termination is exclusively by disproportionation; transfer to
solvent is negligible in this case.

(a) Polymer formed during the initial stages of polymerization was found to have M​w​ = 320,000.
What was the ratio of the rate of polymerization to termination, R​p​/R​t​?

For disproportionation, M​n​ = M​w​/2 = 160,000. The molecular weight of methyl methacrylate is
100 g/mol. Thus, the kinetic chain length v = 1600, and as R​p​/R​t​ = v = 1600

(b) Given that the radical lifetime was 0.75 s, what is the propagation rate constant, k​p​ (with
correct units)?

As the radical lifetime t = v/k​p​[M], k​p​ = 1600/(0.75 s *0.2 g/mL*1000 mL/1 L * 1 g/100 mol) =
1.1*10​3​ L/mol s

(c) The same polymerization was conducted under otherwise identical conditions in toluene
(assume 9 mol/L), where C​SX​ = 3 ×10​-5​. What would M​w​ be?

1/N​n​ = 1/1600 + 3*10​-5​*9/2 = 7.6*10​-4

M​n​ = N​n​*100 = 130,000

M​w​ = 2*M​n​ = 260,000

4. Living anionic polymerization is used to prepare a sample of polydimethylsiloxane (PDMS),
using “D​3​” (the cyclic trimer of dimethylsiloxane, C​6​H​18​O​3​Si​3​, M = 222 g/mol) as the monomer
and n-butyl lithium (M = 64 g/mol) as the initiator.

(a) Draw the structures of the monomer and the polymer repeat unit.

(b) Chromatographic analysis reveals that Đ = 1.01; what is M​n​, assuming the polymerization
approached the ideal case?

As Đ = 1+1/v, v = 100. Thus as the molar mass of dimethylsiloxane is 222 g/mol

M​n​ = 100*222 g/mol = 22,000 g/mol

(c) The polymerization produced 20 g of polymer; how many g of initiator were used?

20 g/(222 g/mol) = 0.09 mol of polymer

0.09 mol of polymer/(100 monomers/polymer)*64 g/mol = 0.06 g

(d) Given the result in (a), what can be inferred about the relative rates of initiation (R​i​) and
propagation (R​p​)? Circle the best answer.

(i) R​i​ >> R​p​ (ii) R​i​ ≥ R​p​ (iii) R​i​ ≈ R​p​ (iv) R​i​ ≤ R​p​ (v) R​i​ << R​p

R​i​ >> R​p

5. Experimentally determined chain dimension for poly(ethylene oxide) at 80 °C are given by
<h​0​2​>/M = 0.805 Å​2​ mol/g and for poly(dimethyl siloxane) at 25 °C are given by <h​0​2​>/M =
0.422 Å​2​ mol/g.

C-C bond: 1.54 Å

C-O bond: 1.43 Å

Si-O bond: ​1.64 ​Å

(a) Calculate the characteristic ratio C​∞​, the statistical segment length, and the persistence length
for the polymers.

Approximate monomer contour length: 2×1.43 Å + 1.54 Å = 4.4 Å

4.4
Average bond length: l = 3
= 1.47 Å

M 0 = 44 g/mol , n = 3N

〈h2 〉0 C ∞ n l2 3 C ∞ l2
M
= M
= M0
= 0.805 Å2 mol/g

C ∞ = 5.5

C ∞l
lp = 2
= 4.0 Å

〈h2 〉0
b= √M0 M = 6.0 Å

PDMS

Approximate monomer contour length: 2×1.64 Å = 3.28 Å

3.28
Average bond length: l = 2
= 1.64 Å

M 0 = 74 g/mol , n = 2N
〈h2 〉0 C ∞ n l2 2 C ∞ l2
M
= M
= M0
= 0.422 Å2 mol/g

C ∞ = 5.9

C ∞l
lp = 2
= 4.8 Å

〈h2 〉0
b= √M0 M = 5.6 Å

(b) What is the contour length of a chain of molecular weight M = 70,000 g/mol for each of these
polymers? Note that you will need the bond length for a C-O and a S-O bond.

The contour length can be calculated:

〈h2 〉0 = Llk = 2Llp

〈h2 〉0
L= 2lp

PEO M = 70, 000

〈h2 〉0 = 56, 350

L = 7044 Å = 0.7μm

PDMS M = 70, 000

〈h2 〉0 = 29, 540

L = 3077 Å = 0.3μm

(c) Based on this information, are these flexible polymers?

PDMS is more rigid than PEO, but both are relatively flexible polymers.