two in one: use of azide functionality for controlled photo
TRANSCRIPT
—Supporting Information—
Two in One: Use of Azide Functionality for Controlled Photo-crosslinking
and Click-modification of Polymer Microspheres
Marco Albuszis,† Peter. J. Roth,‡,* Werner Pauer,†,* and Hans-Ulrich Moritz†,*
† Institute for Technical and Macromolecular Chemistry, University of Hamburg, Bundesstraße
45, 20146 Hamburg, Germany
‡ Department of Chemistry, Faculty of Engineering and Physical Sciences, University of Surrey,
Guildford, Surrey, GU2 7XH, United Kingdom
Corresponding Author Email Addresses:
P. J. Roth ([email protected])
W. Pauer ([email protected])
H.-U. Moritz ([email protected])
Electronic Supplementary Material (ESI) for Polymer Chemistry.This journal is © The Royal Society of Chemistry 2016
Synthesis of Chloromethyl-functional Microspheres
Figure S1. SEM images of 4-vinylbenzyl chloride (VBC)-functional microspheres with VBC
feed contents of (a) 10 wt-%; (b) 50 wt-%; (c) 100 wt-% showing well-defined microspheres.
Figure S2. 1H NMR spectra of microspheres (dissolved in CDCl3) containing 4-vinylbenzyl
chloride in varying amounts (20, 30, 40, 50, 100 wt-%). δ/ppm = 7.30–6.20 (Ar–H); 4.51 (–CH2Cl);
3.51 (–CH2OEt); 2.10–0.90 (backbone).
Figure S3. Degree of chlorine substitution by ethanol for different 4-vinylbenzyl chloride
contents in poly(styrene-co-4-vinylbenzyl chloride) microspheres.
8 7 6 5 4 3 2 1 0
ppm
20 %
30 %
40 %
50 %
100 %
4.8 4.4 4.0 3.6
0 20 40 60 80 1000
20
40
60
80
100
without Aliquat 336
Ch
lorin
e s
ubsitu
tio
n [%
]
Chlormethylstyrene in monomer mixture [wt%]
Azidomethyl-functional Microsphere Characterization
Figure S4. Photographs of microsphere samples MS1 (left), MS50 (middle), and MS100 (right)
showing powders of white to yellow color depending on VBA content.
Figure S5. Disc centrifuge results of samples MS1 (black), MS2 (red), MS5 (blue), and MS10
(pink) giving particle diameters around 2.5 μm.
Figure S6. IR spectra of P(S-co-VBA) microspheres with VBA feed ranging from 1–20 wt-%
with the N=N=N asymmetric stretch band inset
1 2 3 4 5
0.0
0.2
0.4
0.6
0.8
1.0
rela
tive w
eig
ht
particle diameter [m]
MS1
MS2
MS5
MS10
3500 3000 2500 2000 1500 1000
0
20
40
60
80
100
tra
nsm
issio
n [%
]
wave number [cm-1]
1%
2%
5%
10%
20%
2200 2150 2100 2050 2000
Figure S7. Thermogravimetric analysis of azide-functional microspheres showing the azide-to-
nitrene reaction around 250 °C and the decomposition of the polymer material as of ~ 350 °C.
Photo-crosslinking
0 5 10 15 20 25 30
-4.0
-3.5
-3.0
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
ln(1–conversion)
Time (min)
Figure S8. First order kinetic fit of the IR-determined azide conversion during the irradiation of
sample MS100.
200 400 600 800
0
20
40
60
80
100
incr. azide
content
weig
ht [%
]
temperature [°C]
MS1
MS2
MS5
MS10
MS20
MS30
MS40
MS50
MS75
MS100
incr. azide
content
Figure S9. 13C solid state NMR spectra of microspheres MS100 before (top) and after (bottom)
exhaustive photo-crosslinking.
200 180 160 140 120 100 80 60 40 20
200 180 160 140 120 100 80 60 40 20
ppm
b
a