1. Polymer Research
Presenters:
Ben Gau
Kelsey Fajilan
Emily Jeter
National Taiwan University
of Science and Technology
Department of Chemical Engineering
Polymer Research Laboratory
Chair Professor Liaw Der-Jang
2. Introduction to the Lab
National Taiwan University of Science and Technology
Chair Professor Liaw Der-Jang
Polymer research:
Polymer Synthesis
Solar cells
Nanotubes
Electrochromism 2
3. Polymer Research
Synthesis of Monomers
MOI-PY Polymerization
Spectroscopy and Characterization
3
120ºC / 24h
AIBN
DMF
4. New Aromatic Diol Synthesis
m-Toluidine-H
(Not available on market)
3,3'-Dimethyl-4,4'-biphenol
4
15. Polymerizing MOI-PY
MOI-PY monomer MOI-PY polymer
15
120℃
24 hrs
Substances
Used
Fw
(g/mol)
Mass
(vol.)
Molar
Ratio
MOI-PY
(monomer)
340.16 0.27 g 100
AIBN
(initiator)
164.2 0.0015 g 1
DMF
(solvent)
73.09 3 mL
YIELD: 40.5% (0.11 g)
16. Emissions of Compounds in NMP (UV 365nm)
Pyrene Nitropyrene
16
Aminopyrene MOI-PY
monomer
MOI-PY
polymer
● UV emissions of solute (compound) to solvent (NMP) concentrations of 10-5 M
● Weaker emission = less pyrene present or less compound
● Difference in color between monomer and polymer due to aggregation of pyrene
18. Polymer Research
Synthesis of Monomers
MOI-PY Polymerization
Spectroscopy and Characterization
18
120ºC / 24h
AIBN
DMF
19. TLC : Thin Layer Chromatography
Used to separate non-volatile
mixtures
Stationary phase (silica) on a sheet
aluminum foil
Use UV light to check separation
19
Product:
1:1 EA:Hexane
UV 365nm
20. NMR : Nuclear Magnetic Resonance Spectroscopy
Determines the physical and
chemical properties of
atoms or molecules
Commonly used to confirm
the identity of a substance
Sample should have a 15-
20% concentration of
polymer to maximize
effectiveness of NMR
results
20
4cm
25. FTIR : Fourier Transform Infrared Spectroscopy
The absorption peaks
correspond to the
frequencies of vibrations
between the bonds of the
atoms making up the material
Size of peaks is a direct
indication of the amount of
material present
Uses a dry sample
25
26. VNIR : Absorbance Spectroscopy
Absorbance Spectroscopy
in the Visible and Near IR
spectral region
Pi electrons or n-electrons
absorb energy and are
excited to higher anti-
bonding molecular
orbitals
Nanotubes in DMF does not show any
chirality but the polymer wrapped
nanotubes exhibits chiralities
26
MOI-PY/HiPCO shows higher absorption intensity indicating high
concentration of nanotubes dispersion by π-π interaction with pyrene
27. 27
MOI-PY/CoMoCAT shows
high selectivity of (8,3)
(10.2) (7,5) (6,5) chiralities
indicating high
concentration of
nanotubes dispersion by
π-π stacking with pyrene
27
28. PL : Photoluminescence spectroscopy
Uses principles of photo-excitation and
photoluminescence to analyse the
electronic structure of the material
28
http://www.renishaw.com/en/photoluminescence-explained--25809
A maximum emission was observed at 410nm
(blue light).
410 nm353 nm
29. CV : Cyclic Voltammetry
Used to study
electrochemical
properties of an
analyte
Two nitrogens results in
two reduction and
oxidation steps
29
30. DSC : Differential scanning calorimetry
Measures the energy
required to keep both
the reference and the
sample during
transitions at the
same temperature
30
31. TGA: Thermogravimetric Analysis
Changes in physical and
chemical properties of
materials are measured
as a function of
increasing temperature or
time
Common applications of
this technique include
analysis of
decomposition patterns
31
MOI-PY with pyrene moiety shows high 10% weight loss at about
265ºC. MOI-PY polymer was not completely isolated from remaining
MOI-PY monomer and other low molecular weight compounds, so the
graph exhibits a lower degradation temperature than expected
32. PLE : Photoluminescence Excitation
Useful to investigate the
electronic structure of
materials with low absorption
MOI-PY/HiPCO shows selectivity for (9,4). (7,6), (8,4), (8,6),
(9,5) chiralities. MOI-PY can disperse semiconducting single
walled carbon nanotubes
32
33. 33
MOI-PY/CoMoCAT shows a very high selectivity for the (6,5)
chirality. MOI-PY can disperse semiconducting single walled
carbon nanotube with high purity and selectivity.
34. 34
Acknowledgements
NTUST Chemical Engineering Department
Chair Professor Liaw Der-Jang
講座教授 廖德章
PhD Students:
Huang Ying-Chi 黃英治
Zhang Qiang 章強
Masters Students:
Paul Wang 王柏翊
Joe Tsai 蔡周益
Wang Yi-Ze 王翼澤
First step: create nitropyrene
Combine pyrene and copper nitrate with acetate; stir overnight
Distill; keep solids; dissolve in DCM, vacuum filter; mix with methanol; funnel filter and bake
Second step: aminopyrene
Nitropyrene with palladium and ethanol; mix and heat
Filter and crystallization in liquid
UV emission of compounds at different stages of polymerization process
