Supporting information
Controlled Synthesis of Hyperbranched Polythioether Polyols
and Their Use for the Fabrication of Porous Anatase
Nanospheres
Xinhua Huang,1,2 Trinh Thi Kim Hoang,2 Hye Ri Lee,2 Huiju Park,2 Jin Ku Cho,3
Yongjin Kim,3 and Il Kim2
1
School of Materials Science and Engineering, Anhui University of Science and
Technology, Huainan 232001, China.
2
BK 21 PLUS Centre for Advanced Chemical Technology, Department of Polymer
Science and Engineering, Pusan National University, Pusan 609-735, Republic of
Korea. Correspondence to: I. Kim (E-mail: ilkim@pusan.ac.kr)
3
Green Process and Materials R&D Group, Korea Institution of Industrial
Technology, 89 Yangdaegiro-gil, Ipjang-myeon, Cheonan 331-822, Republic of
Korea.
Contents
page
Experimental
II–IV
1
H- and
13
C-NMR, IR, GPC, viscosity measurement, DSC, TEM, XRD, XPS, and
nitrogen sorption isotherm
V – XIII
I
EXPERIMENTAL
Materials. TMP (97%, Sigma-Aldrich), VCHO (98%, Sigma-Aldrich), 1-thioglycerol
(> 95%, Tokyo Chemical Industry Co., LTD), azobisisobutyronitrile (AIBN, 98%,
Junsei Chemical Co., Ltd), potassium hydride (KH, 30 wt% dispersion in mineral oil,
Sigma-Aldrich), Titanium (IV) isopropoxide (TTIP, purum, Sigma-Aldrich), methanol
(extra pure, moisture < 0.3%, Daejung). Anhydrous DMSO was obtained from
Sigma-Aldrich and used as received.
Synthesis of sulfur containing epoxide monomer. A solution of AIBN (130 mg, 0.8
mmol) in degassed methanol (40 mL) was added drop-wise over 4 h to a refluxing
solution of VCHO (5.0 g, 40 mmol) and 1-thioglycerol (6.5 g, 60 mmol) in degassed
methanol (7.0 mL) under an N2 atmosphere. The solution was refluxed for a further 16
h. The reaction mixture was then concentrated in vacuo to 1/3 of its initial volume.
The concentrated solution was then precipitated in diethyl ether 3 times. Finally, the
resulting product, 3-[2-(7-oxa-bicyclo[4.1.0]hept-3-yl)-ethylsulfanyl]-propane-1,2diol (CESPO), was dried in vacuo at 70 ºC for 8 h as a yellow liquid (yield 95 %).1H
NMR (400 MHz, D2O): δ = 3.71 (m, 2H, epoxy VCHO), 3.55-3.41 (m, 2H), 3.22 (s,
1H), 2.70-2.51 (m, 4H), 1.49-1.56 (m, 5H).FAB-MS m/z (%) 215.11 (100) [M-OH]+
Polymerization of CESPO. A typical polymerization procedure is as follows: A
suspension of KH in mineral oil (30% in weight) was introduced to a dry,
pre-weighed 100 mL three-neck round-bottom flask in a nitrogenous atmosphere. The
mineral oil was then removed by three extractions with THF, and the residual THF
was removed by vacuum. When the apparatus was completely dried, the flask was
weighed again to determine the amount of KH (typically 10 mg, 0.25 mmol). Then
DMSO (10 mL) and TMP (335 mg, 1.25 mmol) were introduced to the flask. The
solution was stirred for 30 min to form the potassium alcoholate. Subsequently,
II
CESPO(5.8 g, 25.0 mmol) in 20 mL DMSO was added by syringe over 10 h, and the
solution was heated to 80 °C for a further 48 h. Upon completion of the
polymerization, the mixture was precipitated in an acetone/diethyl ether mixture (500
mL, v/v = 1/4). The product was re-dissolved in methanol and neutralized by filtration
over cation-exchange resin. The obtained HPTE was precipitated twice from methanol
solution in cold diethyl ether and then dried invacuo at 60 °C for 8 h. Using the same
process, a series of HPTEs with different molecular weights were synthesized by
varying the TMP/CESPO molar ratio (see Table 1). The resultant purified products
were highly viscous. 1H NMR (400 MHz, DMSO-d6): δ = 4.5-5.6 (OH); 5.2-4.4 (OH);
2.1-3.0 (CH2 in the linear chains); 3.4-3.8 (CH); 2.0-0.9 (CH2 in the cyclohexane and
CH3 in TMP).
Synthesis of TiO2. In a typical synthesis, 50 mg of HPTE was dissolved in 10 mL
methanol. 10 μL of TTIP was then slowly added to the solution with vigorous stirring
for 2 h at room temperature, forming a white suspension. This was then centrifuged at
6000 rpm for 30 min to obtain the product as a white solid. The solid was then washed
three times with methanol and dried at 60 ˚C in vacuo. The dried solid was sintered at
350 ˚C to obtain TiO2 nanocrystals.
Characterization. 1H and
13
C NMR spectra of the polymers were recorded using a
400 MHz 1H (100 MHz 13C)spectrometer (Varian Unity Plus)with D2O and DMSO-d6
as solvent, respectively. The fast-atom bombardment mass spectra (FAB-MS) were
recorded on a JEOL JMS DX300 apparatus (JEOL, Tokyo, Japan). Gel permeation
chromatography (GPC) was performed on a Waters 2410 system equipped with a
refractive index detector, using poly(methylmethacrylate) as the calibrant. Dimethyl
formamide containing 0.01 mol/L lithium bromide was used as the mobile phase at a
flow rate of 1 mL/min at 40 °C. Small drops of the HPTEs liquid were spread on a dry
III
KBr disc and were vacuum dried at 80 ºC for 6 h to reduce the levels of adsorbed
water in the samples prior to recording their Fourier transform infrared (FTIR) spectra
under ambient conditions on a Shimadzu IR Prestige-21 (Kyoto, Japan)
spectrophotometer. Each sample was scanned 50 times with a resolution setting of 4
cm-1over the range of 4000-400 cm−1.A TA Instruments Q-1000differential scanning
calorimeter (DSC) was used from -100 to 20 °C at a heating rate of 10 °C/min with a
2 min isotherm at the maximum and minimum temperatures. The glass transition
temperature (Tg) was measured in a second heating scan.The thermogravimetric
analysis (TGA, Scinco, TGAN-1000) was performed over the range of 30 to 800 ˚C in
steps of 10 ˚C min-1 under a high-purity N2 flow (10 cm3 min-1).Viscosimetry
measurements were performed on a Schott AVS/6 Ubbelohde dilution viscosimeter at
25 ˚C using a capillary with a diameter of 0.46 mm and using methanol as the solvent.
The structures of the TiO2 species were examined using X-ray diffraction (XRD)
using an automatic Philips powder diffractometer with nickel-filtered Cu Kα radiation.
The diffraction pattern was collected over a 2θ range of 10-80° in steps of 0.02° with
counting times of 2 s step−1. The surface characteristics were analyzed using a PHI
5400 X-ray photoelectron spectroscope (XPS, Physical Electronics, Mg Kα source).
The microstructures of the samples were investigated using an S-4800 scanning
electron microscope (SEM; Hitachi, Japan), and a JEM-2100F HR transmission
electron microscope (TEM).
IV
Figure S1. NMR spectra of polythioether HPTE-1, obtained by OROP initiated with
TMP: (A) 1H NMR spectrum in DMSO-d6; (B)
13
C NMR spectrum in DMSO-d6
showing carbons corresponding to the T, DE, DT, L13, and L14 units.
V
Figure S2.1H NMR spectra of different HPTEs in D2O.
Figure S3.13C NMR spectra of different HPTEs in DMSO-d6.
VI
Figure S4. FT-IR spectra of different HPTEs: (a) HPTE-1, (b) HPTE-2, (c) HPTE-3,
(d)HPTE-4, and (e) HPTE-5.
Figure S5. GPC curves of different HPTEs: (a) HPTE-1, (b) HPTE-2, (c) HPTE-3,
(d)HPTE-4, and (e) HPTE-5.
VII
Figure S6. Specfic viscosity (ηsp) of HPTEs as a function of concentration in
methanol at 25 ˚C.
Figure S7.DSC thermograms of HPTEs synthesized viaslowmonomer addition
method in DMSO solvent.
VIII
Figure S8. TEM images of TiO2 samples taken at different times of reaction. The
scale bar is 100 nm.
IX
Figure S9. TEM images of the titanic nanostructure with different HPTEs (10 mg/mL
in methanol) as template:(A) HPTE-1,(B) HPTE-2,(C) HPTE-3, (D) HPTE-4, and (E)
HPTE-5. The scale bar is 100 nm.
X
Figure S10. Wide angle XRD patterns of TiO2templateed by different by HPTEs: (a)
HPTE-1, (b) HPTE-2, (c) HPTE-3, and (d) HPTE-4.
Figure S11. (a) Wide XPS spectrum of the TiO2 porous particles templated by
HPTE-5, the reference C1s is at 284.6eV; (b) the corresponding high resolution XPS
spectra of Ti 2p.
XI
Figure S12. TEM images of the titanic nanostructure with different concentrations of
HPTE-3 as template in methanol solution: A) 5 mg/mL, B) 10 mg/mL, C) 15 mg/mL,
D) 20 mg/mL, and E) 30 mg/mL. The scale bar is 200 nm.
XII
Figure S13.Nitrogen sorption isotherms (inset: BJH pore size distribution) of TiO2
templated by (A) HPTE-1, (B) HPTE-2, (C) HPTE-3, (D) HPTE-4, and (E) HPTE-5.
XIII