u4774143

Jia Xie

Summer research report

1. Acknowledgments
In the summer of 2013 - 2014, I did some research work under the supervision of Dr. Leesa
Smith. I got really great support from Professor Michelle Coote. Thanks to the financial
support I received from ANU that I could fully focused on my lab research and benefited a
great deal from this amazing opportunity.
2. Executive Summary
I investigated different Lewis acids, potassium trifluoromethanesulfonate (potassium triflate),
magnesium

trifluoromethanesulfonate

(magnesium

triflate),

indium

(III)

trifluoromethanesulfonate (indium triflate), scandium trifluoromethanesulfonate (Scandium

triflate), and different solvents, THF, ethanol, n-Hexane, toluene, which were found to have
no effect on tacticity of PMA. Besides, I learnt how to how gel permeation chromatography
(GPC) works and how to analysis data. Furthermore, I learnt how to use software to analyse
PLP data to calculate kp from molecular weight distribution.

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Jia Xie

3. Effect of Lewis Acids on Stereoregulation in Free-Radical Polymerization

Table 1. Experimental Results for the Tacticity of Poly(methyl acrylate) at 60 C in bulk
form.i
Lewis Acid

[LA]0/[MA]0ii

[ACHN]

Yield

Pm

KOTf

0.05

100mM

0%

Mg(OTf)2

0.05

100mM

0%

In(OTf)3

0.05

100mM

0%

None

N/A

100mM

0%

In(OTf)3

0.05

50mM

30%

ScOTf

0.05

50mM

0%

None

N/A

50mM

0%

Table 2. Experimental Results for the Tacticity of Poly(methyl acrylate) at 60 C in

different solvents.i
Solvent

[LA]0/[MA]0

[ACHN]

Yield

Pm

THF

0.05

50mM

36%

0.53

Ethanol

0.05

50mM

0%

N-Hexane

0.05

50mM

0%

Toluene

0.05

50mM

13%

0.49

None

N/A

50mM

0%

I was very interested in effect of Lewis acids on stereoregulation in free-radical

polymerization. Thus I continued my unfinished experiments from last semester when doing
research project with Professor Michelle. I tried polymerization of methyl acrylate (MA) in
the presence of Lewis acid initiated by ACHN at 60C. This time new LAs, potassium
trifluoromethanesulfonate

(potassium

triflate),

magnesium

trifluoromethanesulfonate

(magnesium triflate), indium (III) trifluoromethanesulfonate (indium triflate) were tested.

However, no NMR was completed since the polymers obtained were very impure and the
yields were very low. Based on the experiments I did on polymerization of MA in the
presence of Lewis acid initiated by ACHN, no stereocontrol was discovered. Thus, I tried

i Solvent: CDCl
3
Pm = [m(Ha) + m(Hb)] / [m(Ha) + r(H) + m(Hb)] -: No polymer was recovered
ii

(Initial concentration of Lewis acid) / (Initial concentration of MMA)

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Jia Xie

another approach. I did polymerization of MA in the presence of Lewis acid, indium (III)
trifluoromethanesulfonate

(Indium

triflate)

and

scandium

trifluoromethanesulfonate

(Scandium triflate), initiated by ACHN at 60C using several solvents: THF, ethanol, nHexane, toluene and in bulk form (no solvent). It was found that THF and n-Hexane samples
had a better yield in polymerization comparing with other solvents. NMR on both was carried
out, however no stereocontrol was found (Pm is about 0.5).
In these experiments, interesting findings about indium and scandium were observed. Indium
samples went brown during reaction and scandium samples went yellow. If not degased
properly, oxygen could react with the radicals and side reactions would take place, which
would cause impure polymers or even no polymer. Another experiment was carried out under
constant nitrogen flow to reduce the oxygen effect. And the samples obtained were nearly
colorless, which confirmed that oxygen did have an effect on polymerization.
4. Effect of Lewis Acids on Branching in PMA
I prepared few samples for GPC analysis. The aim of this is to get an idea on how GPC
works and polymer branching. GPC is the most widely used technique for analyzing polymer
samples in order to determine their molecular weights and weight distributions. (See Lab
book for detailed GPC data)

u4774143
Jia Xie

5. Effect of Lewis Acids on Propagation Rate constant (kp)

Table 3. Experimental Results for PLP of Poly(methyl methacrylate) at 25 C with
In(OTf)3.iii
Sample

Pulse rate

(hz)

J23_A

10

J23_B

Dark
time

[M] mol/L

logM (1)

logM(2)

M (1)

M (2)

kp (1)

kp (2)

Density

0.1

9.38

4.46

4.8

288

630

307

336

0.94

10

0.1

9.38

4.39

4.77

245

588

261

313

0.94

J23_C

2.5

0.4

9.38

5.05

5.31

1121

2039

298

272

0.94

J23_D

2.5

0.4

9.38

5.06

5.32

1147

2087

305

278

0.94

J23_E

0.2

9.38

4.76

5.08

575

1201

306

320

0.94

J23_F

0.2

9.38

4.78

5.08

602

1201

321

320

0.94

(s)

Table 4. Experimental Results for PLP of Poly(methyl methacrylate) at 25 C with

ScOTf. iii

Sample

Pulse rate

(hz)

J25_A

10

J25_B

Dark
time

[M] mol/L

logM (1)

logM(2)

M (1)

M (2)

kp (1)

kp (2)

Density

0.1

9.38

No inflection points

10

0.1

9.38

No inflection points

J25_C

2.5

0.4

9.38

5.11

5.37

1287

2341

343

312

0.94

J25_D

2.5

0.4

9.38

5.12

5.41

1317

2567

351

342

0.94

(s)

The aim of these experiments was to understand how PLP works and how to use software to
show molecular weight distribution in order to calculate kp.

iii Initiator: Benzoin
Laser Power: 20 mJ/pulse

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Jia Xie

Fig.1: PLP molecular weight distribution of J23_E

Fig. 2: PLP molecular weight distribution of J25_A

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Jia Xie

Fig.1 and 2 show the PLP molecular weight distribution of two samples, it is clear that Fig.2
doesnt show two inflection points. Thus kp cant be calculated. It is found that when
increasing the pulsing rate, the inflection points are getting less obvious. This is maybe
because the polymerization was so fast. Besides, NMR on typical samples (J23_A, J23_D,
J25_C, J25_D) was carried out and no stereocontrol was shown (Pm is about 0.2).
6. Limitation and Future work
Due to time limit, more experiments on PLP of scandium didnt complete. In the future, I
would like to do more experiments, such as how temperature change or initiator change cause
different results.
In total, I had a very rewarding summer and I believe what I learnt this summer would benefit
my future life. Thanks again for Dr. Leesa Smith and Professor Michelle Cootes patient help
and advice.