Supporting Information

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1 upporting Information ynthesis and elf-assembly of Amphiphilic emi-brush and Dual rush lock Copolymers. Daniel Zehm, a André Laschewsky,* a Peggy Heunemann b,c, Michael Gradzielski,* b ylvain Prévost, b,d Hua Liang, e Jürgen P. Rabe e and Jean-François Lutz f a Universität von Potsdam, Institut für Chemie, Karl-Liebknecht-tr. -5, 176 Potsdam- Golm, Germany, laschews@rz.uni-potsdam.de b Technische Universität erlin, transki-laboratorium für Physikalische und Theoretische Chemie, Institut für Chemie, traße des 17. Juni 1, ekr. TC7, 163 erlin, Germany, michael.gradzielski@tu-berlin.de c Institut Max von Laue-Paul Langevin (ILL), F-38 Grenoble Cedex 9, France d Helmholtz-Zentrum erlin für Materialien und Energie, Dept F Magnetism, Liese-Meitner Campus, Glienicker traße 1, D-119 erlin, Germany e Humboldt-Universität zu erlin, Department of Physics, Newtonstr. 15, 189 erlin, Germany f Fraunhofer Institut für Angewandte Polymerforschung IAP, Geiselbergstr. 69, 176 Potsdam-Golm, Germany 1

2 cheme 1: shape of an amphiphilic dual brush with unequal graft lengths (a) in a nonselective solvent, and (b) in a selective solvent for the shorter grafts. a) b) Table 1. Monofunctional RAFT chain transfer agents (CTA) used, and reactive macroraftagents (brush precursors) prepared. CTA3 poly(rmpaea) R Z n N H r

3 ynthesis of rmpaea. Acryloylchloride (.75 ml, 58 mmol) in dry ethyl acetate (15 ml) was added dropwise to a stirred solution of ethanolamine (3. g, 9 mmol) and NaH (.3 g in 1 ml H ) in ethylacetat (5 ml dry) at C, and subsequently stirred over night at ambient temperature. The organic phase was separated, dried over Na, and concentrated under reduced pressure. The residue was purified by column chromatography (ethyl acetate / methanol 1:1) to afford. g of the intermediate N-(-hydroxyethyl)acrylamide. To this colorless oil, dry THF ( ml) and triethylamine (. ml, 31.5 mmol) were added. After stirring for 1 min at C, as solution of -bromoisobutyryl bromide (3.1 ml, 5. mmol) in dry THF (15 ml) was added dropwise and the reaction was allowed to proceed over night. The mixture was successively extracted with acidic ice-water (.5M HCl), aq NaHC 3, and ethyl acetate. The combined organic phases were dried over Na, and concentrated under reduced pressure. The residue was purified by column chromatography (hexane / ethyl acetate 1:1, R f =.15) to afford the desired product as colorless oil. Yield: 1.67 g (13 % over two steps). Elemental analysis (C 9 H 1 rn 3, M r = 6.11 g/mol): Calc: C.93, H 5.3, N 5.3; Found: C 1.13, H.83, N 5.1. EI-M (positive ions): 65 (M+1) +. 1 H NMR (3 MHz, CDCl 3 ): δ H 1.9 (s, 6 H, -CH 3 ), 3.6 (q, J = 5.5 Hz, H, -CN-CH -),.9 (t, J = 5.5 Hz, H, -CH -C-), 5.65 (dd, J = 1.11, 1.5 Hz, 1 H, CH=C-CN- (E)), 6.1 (dd, J = 17., 1.11 Hz, 1 H, CH=C-CN- (Z)), 6.6 (dd, J = 17., 1.5 Hz, 1 H, =CH- CN-), 6.3 (s br, 1 H, NH). 13 C-NMR (75 MHz, CDCl 3 ) δ (ppm): 31. (-CH 3 ), 38.9 (NH-CH -), 6.8 (CH -), 17. (=CH), 13.9 (=CH ), (CNH), 17. (-C-). IR (Kr, selected bands, in cm -1 ): 383, 976, 173, 1657, 15, 163, 17, 1159, 116, 16, 983, 958. Table : ynthesis and characterization of RAFT-polymerized inimer (conditions: 65 C, initiated by AIN). RAFT conv. theory c) EC polymer a) agent [%]/[h] b) M n x 1-3 [g mol -1 ] M n x 1-3 [g mol -1 ] PDI spectroscopic analysis M n x 1 3 [g mol -1 Z/R h) ] 1 (rmpaea) 6 CTA3 31/ d) e) - a) Conditions for poly(rmpaea): [Monomer]/[CTA]/[Initiator] = /1/.1 in THF; b) Determined by 1 H-NMR analysis of the crude product. c) Calculated according to equation: M n,theor. = (conversion M r,monomer [M] / [CTA] ) + M r,cta. d) Eluent NMP, RI detection, calibrated by polystyrene standards. e) Calculated by end group analysis via UV band (λ= 39 nm, ε CTA3 = 1,7 L mol -1 cm -1 in CH Cl ). 3

4 A chemical shift δ (ppm) mass (%) temperature ( C), -, -,8-1, -1,6 d(m/m )/dt Fig. 1. A) 1 H NMR spectra of poly(clpea) in CDCl 3. ) TGA plot (contiuous line) of poly(clpea), and derivative DTG plot (dashed line) of poly(clpea). 1,,8 (iv) (iii) 1, A (iii),8 norm. RI,6,, norm.ri,6,,, Elution volume (ml), Elution volume (ml) Fig.. A) EC traces of: (i, continuous line) (PEGA) 858, (ii, dashed line) (PEGA) 9 -b-(clpea) 7 -b-(pega) 9, (iii, continuous line) Tri-, and (iv, dashed line) Tri-3. ) EC traces of (i, continuous line) (ClPEA) 68, (ii, dashed line) (PEGA) 375 -b-(clpea) 68 -b-(pega) 375, and (iii, continuous line) Tri- in THF as eluent.

5 heat flow (mw) A (iii) heat flow (mw) (iii) temperature ( C) temperature ( C) Fig. 3. DC traces of studied polymers: A) (ClPEA), (PEGA) 19 -b-(clpea) 7 -b-(pega) 19, (iii) Tri-1; ) (PEGA) 5 -b-(clpea) 5 -b-(pega) 5 Tri- (iii) Tri-3. A chemical shift δ (ppm) volume fraction (%) Dh of particles (nm) Fig.. A) 1 H NMR spectra of Tri-1 in D. ) Dynamic light scattering analysis of.1 wt% aqueous dispersions at 5 C of (PEGA) 19 -b-(clpea) 7 -b-(pega) 19 ; Tri-1, prepared by protocol A: Volume fraction distribution of aggregates' hydrodynamic diameter. AN Data Analysis In a first approach the data were analyzed in a model-independent way. Here we applied the Guinier approximation (eq. 1) from which we can derive the radius of gyration, R g, and the scattering intensity extrapolated to zero scattering angle, I(). ( q R / 3) I(q) = I() exp (equation 1) g 5

6 where I() is directly related to the molecular weight M w of the aggregates by: M I() = Φ ( LD ) w p LD (equation ) ρp NAv Here Φ is the volume fraction of the dispersed particles, LD p and LD the scattering length densities of particle and solvent, ρ p the particle density, and N Av the Avogadro's number. From the molecular weight one can then directly calculate the radius of a compact aggregate (neglecting any solvation) by taking into account the polymer density assumed to be 1.13 and 1.5 g/ml for the semi-brush and the dual brush copolymer, respectively. L Data Analysis precursor in D q / 1 - nm Tri-1 in D q / 1 - nm - a) b) Fig Tri-1 in D /DMF (1/1) q / 1 - nm Guinier- a), b), c) and erry-plot d) of L-data for a) precursor (PEGA) 19 -b- (ClPEA) 7 -b-(pega) 19 in D and the derived dual brush Tri-1 b) in D and c), d) in D /DMF (1/1) at 5 C; used! and neglected data-points for the fit tatic light scattering data were analysed by means of the Guinier approximation according to eq. 1. Concerning the validity of Guinier approximation fit of Tri-1 in D /DMF (1/1) was done only for low scattering angles due to its non-linear curve behavior. Repeating measurements of this sample appeared always in the same manner. sqrt(kc/r), Kc/R / 1-5 mol/g 18 Tri-1 in D /DMF (1/1) q / 1 - nm - c) d) 6

7 Table 3: Molecular weight Mw and radius of gyration Rg obtained via L-analyses of precursor (PEGA) 19 -b-(clpea) 7 -b-(pega) 19 and the derived dual brush Tri-1 Plot polymer Mw(q ) / g/mol Rg / nm Guinier (PEGA) 19 -b-(clpea) 7 -b-(pega) 19 3.E Guinier Tri-1 in D.5E Guinier Tri-1 in D /DMF (1/1).8E Guinier (larger q-range) Tri-1 in D /DMF (1/1) 3.13E erry Tri-1 in D /DMF (1/1) 3.1E Fig. 6. FM height image of the semi-brush block copolymer precursor (PEGA) 375 -b-(clpea) 68 -b-(pega) nm 7