Supporting Information
Control through Monomer Placement of Surface Properties and Morphology of
Fluoromethacrylate Copolymers
Ao Chen,1 Idriss Blakey,1,2 Kevin S. Jack,3 Andrew K. Whittaker1,2,4 and Hui Peng1,4*
1Australian
Institute for Bioengineering and Nanotechnology, The University of Queensland, Brisbane
Qld 4072
2Centre
for Advanced Imaging, The University of Queensland, Brisbane Qld 4072
3Centre
for Microscopy and Microanalysis, The University of Queensland, Brisbane Qld 4072
4Australian
Research Council Centre for Convergent Bio-Nano Science and Technology
Correspondence to: Dr Hui Peng (E-mail: h.peng@uq.edu.au)
1
Scheme S1. Schematic illustration of the synthesis of the statistic copolymers.
2
A
b
PMMA33
b
a
Poly(MMA33-block-F3MA22)
b
a
a
4.6
4.4
Poly(MMA33-block-F3MA39)
b
Poly(MMA33-block-F3MA49)
4.2
4.0
3.8
3.6
3.4
Chemical Shift (ppm)
2D Graph 2
B
Before
After
7.5
7.4
7.3
7.2
7.1
7.0
Chemical Shift (ppm)
Figure S1. (A) Expanded region of the 1H NMR spectra of PMMA33 and block copolymers prepared from this
macro-CTA, (B) Expanded region of the 1H NMR spectrum of poly(MMA33-block-F3MA39) before and after
removal of the RAFT end group.
3
A
PMMA33
Poly(MMA37-block-F3MA11)
Poly(MMA33-block-F3MA22)
Poly(MMA37-block-F3MA26)
Poly(MMA33-block-F3MA39)
Poly(MMA33-block-F3MA49)
15
16
17
18
19
20
Retention Time (min)
B
C
Poly(MMA82-stat-F3MA18)
Before
After
Poly(MMA69-stat-F3MA21)
Poly(MMA58-stat-F3MA20)
Poly(MMA32-stat-F3MA34)
Poly(MMA15-stat-F3MA48)
15
16
17
Retention Time (min)
18
15
16
17
18
Retention Time (min)
Figure S2. GPC traces for the (A) block copolymers, (B) statistic copolymers and (C) poly(MMA33-blcok-F3MA39
before and after removal of the RAFT end group.
4
Calculation of the SAXS lattice parameters:
The lattice parameter of poly(MMA37-block-F3MA11) could not be determined due to inability to assign the
structure, however the long period for this sample was obtained from equation (1), which is generally used for
calculating the period of lamellar phase.
The hexagonal lattice parameters for poly(MMA33-block-F3MA22) and poly(MMA37-block-F3MA26)
were obtained using equation (2).
The lattice parameters of body centered cubic (BCC) structures were calculated by plotting the reciprocal
spacing (1/dhkl) vs the m = (h2+k2+l2)1/2, where hkl is the Miller index. The hkl values of BCC structure are 110,
200, 211, 220 and 310… and the according (1/dhkl) can be calculated from the relative Bragg peak positions qhkl
at q*: √2q*: √3q*: 2q*: √5q*… using equation (3).
The value of the cubic cell lattice parameter a is the reciprocal of the slope of the line. The values of 1/dhkl were
plotted against m for poly(MMA33-block-F3MA39) and poly(MMA33-block-F3MA49) in Figure S3. From the slope,
the lattice parameters for poly(MMA33-block-F3MA39) and poly(MMA33-block-F3MA49) were obtained,
respectively 19.1 nm and 20.2 nm. The linearity and the negligible intercept values also indicate successful
assignment of the spherical phase.
5
A
B
Figure S3. Plots of the reciprocal of spacing 1/dhkl of the block copolymers poly(MMA33-block-F3MA39) and
poly(MMA33-block-F3MA49) versus the m = (h2+k2+l2)1/2. The linearity and low intercept values indicate valid
assignments of the phase separation structures. The cubic cell lattice parameters are obtained as the reciprocal
of the slopes: 19.1 nm (A, top) and 20. nm (B, below).
6