Supporting Information for:

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1 Supporting Information for: Self-assembled blends of AB/BAB block copolymers prepared through dispersion RAFT polymerization Chengqiang Gao, Jiaping Wu, Heng Zhou, Yaqing Qu, Baohui Li,*,, and Wangqing Zhang*,, Key Laboratory of Functional Polymer Materials of the Ministry of Education, Institute of Polymer Chemistry, Nankai University, Tianjin , China. School of Physics, Nankai University, Tianjin , China. Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin , China. *To whom correspondence should be addressed. (B. L.); (W. Z.), Tel: , Fax: The GPC traces of the PEG 45 -b-ps/ps-b-peg 45 -b-ps blends synthesized at different PEG 45 -TTC/TTC-PEG 45 -TTC molar ratio Figure S1 shows the GPC traces (left part) of the PEG 45 -b-ps/ps-b-peg 45 -b-ps blends syntheszied under [St] 0 :[RAFT] 0 :[AIBN] 0 = 300:1:1/3 with different PEG 45 -TTC/TTC-PEG 45 -TTC molar ratio ranging from 6/0 to 6/4. In the case of the PEG 45 -TTC/TTC-PEG 45 -TTC molar ratio at 6/0, that is, the individual PEG 45 -TTC macro-raft agent was employed in the dispersion RAFT polymerization, and therefore just the PEG 45 -b-ps diblock copolymers were prepared. In the case of 6/1 to 6/3, two peaks, the left one is asigned to the low molecular weight copolymer of PEG 45 -b-ps, and the right one is asigned to the high molecular weight copolymer of PS-b-PEG 45 -b-ps. In the case of 6/4, just one broad peak is observed, and the molecular weight of PEG 45 -b-ps and PS-b-PEG 45 -b-ps cannot be determined, and just the theoretical molecular weight M n,th based on the monomer conversion is afforded. Based on the GPC analysis, the peak top molecular weight, M p,gpc, for the PEG 45 -b-ps diblock copolymers and the PS-b-PEG 45 -b-ps triblock copolymers is obtained, which is summrized in Figure S1 (right part). It is found that M p,gpc is close to M n,th. S1

2 Figure S1. The GPC traces of the PEG-b-PS/PS-b-PEG-b-PS blends synthesized under [St] 0 :[RAFT] 0 :[AIBN] 0 = 300:1:1/3 with the PEG 45 -TTC/TTC-PEG 45 -TTC molar ratio at 6/0, 6/1, 6/1.5, 6/2, 6/3 and 6/4. 2. The GPC traces of the PEG 45 -b-ps/ps-b-peg 45- b-ps blends synthesized at different polymerization time Figure S2. The GPC traces of the PEG 45 -b-ps/ps-b-peg 45 -b-ps blends synthesized [St] 0 :[PEG 45 -TTC]:[TTC-PEG 45 -TTC] 0 :[AIBN] 0 = 300:3/4:1/4:1/3 at different polymerization time. S2

3 Figure S2 shows the GPC traces of the PEG 45 -b-ps/ps-b-peg 45 -b-ps blends synthesized under [St] 0 :[PEG 45 -TTC] 0 :[TTC-PEG 45 -TTC] 0 :[AIBN] 0 = 300:3/4:1/4:1/3 at different polymerization time. Based on GPC analysis, the peak top molecular weight, M p,gpc, for the PEG 45 -b-ps diblock copolymers and the PS-b-PEG 45 -b-ps triblock copolymers is obtained, which is summrized in Figure S2 (right part). It is found that M p,gpc is close to M n,th, and therefore M p,gpc is used as M n,gpc in the present study. 3. The characterization of the PEG 45 -b-ps 288 /PS 288 -b-peg 45 -b-ps 288 blends and the separated PEG 45 -b-ps 288 and PS 288 -b-peg 45 -b-ps 288 Since PEG 45 -b-ps 288 has a slightly higher solubility in the acetone/methanol mixture (88:12 w/w) than PS 288 -b-peg 45 -b-ps 288, and therefore the separation through the extraction with the acetone/methanol mixture (88:12 w/w) was made. Typically, the PEG 45 -b-ps 288 /PS 288 -b-peg 45 -b-ps 288 mixture (0.100 g) was added into a Soxhlet extractor and then extracted with acetone/methanol mixture (88:12 w/w) at 60 o C. In the initial extraction in 0.5 h, about 10 mg PEG 45 -b-ps 288 dissolved in the solvent was obtained. The solvent was removed, the obtained polymer was dried under reduced pressure at room temperature, and then the composition of the obtained polymer was checked by GPC and 1 H NMR analysis. The left polymer was continuously extracted with acetone for about 12 h at 60 o C, till about 8 mg PS 288 -b-peg 45 -b-ps 288 was remained. The extracted PS 288 -b-peg 45 -b-ps 288 was dried under reduced pressure at room temperature, and then characterized by 1 H NMR analysis (Figure S3A) and GPC analysis (Figure S3B). The successful separation of the individual block copolymers was confirmed by GPC analysis, in which the unimodal GPC traces as shown in Figure S4B were observed. Figure S4A shows the 1 H NMR spectra of the PEG 45 -b-ps 288 /PS 288 -b-peg 45 -b-ps 288 blends and the separated individual block copolymers. Figure S3B shows the GPC traces of the PEG 45 -b-ps 288 /PS 288 -b-peg 45 -b-ps 288 blends and the separated block copolymers. Form these analysis, the similar molecular weight of M n,gpc, M n,nmr and M n,th and the low Đ values of the block copolymers synthesized by the dispersion RAFT polymerization are confirmed. S3

4 Figure S3. The 1 H NMR spectra (A) and GPC traces (B) of the PEG 45 -b-ps 288 /PS 288 -b-peg 45 -b-ps 288 blends and the separated PEG 45 -b-ps 288 and PS 288 -b-peg 45 -b-ps The low-magnification TEM images of the AB/BAB nano-objects synthesized at different polymerization times S4

5 Figure S4. The TEM images of the AB/BAB nano-objects synthesized through the two PEG 45 -TTC/TTC-PEG 45 -TTC macro-raft agent co-mediated dispersion polymerization at the polymerization time of 12 h (A), 14 h (B), 18 h (C) and 24 h (D) under [St] 0 :[RAFT] 0 :[AIBN] 0 = 300:1:1/3 with the PEG 45 -TTC/TTC-PEG 45 -TTC molar ratio at 6/2. 5. The AFM height images of the PEG 45 -b-ps 288 /PS 288 -b-peg 45 -b-ps 288 compartmentalized vesicles Figure S5 shows the AFM height images of the PEG 45 -b-ps 288 /PS 288 -b-peg 45 -b-ps 288 compartmentalized vesicles, from which the curved surface on the vesicles due to the deformation of the vesicles during the solvent evaporation is observed. S5

6 Figure S5. A) AFM height image of the PEG 45 -b-ps 288 /PS 288 -b-peg 45 -b-ps 288 compartmentalized vesicles, B) the high magnification image of a compartmentalized vesicle indicated by the square shown in Fig. A, and C) the cross-sectional height profile along the line shown in Fig. B. 6. Low magnified TEM images of the self-assembled PEG 45 -b-ps/ps-b-peg 45 -b-ps blends with different DP of PS block S6

7 Figure S6. The TEM images of self-assembled PEG 45 -b-ps/ps-b-peg 45 -b-ps blends prepared through the dispersion RAFT polymerization under [St] 0 :[PEG 45 -TTC] 0 :[TTC-PEG 45 -TTC] 0 :[AIBN] 0 = m:3/4:1/4:1/3 with the target DP (m) of the PS block in the AB/BAB block copolymers at 100 (A), 200 (B), 300 (C), 400 (D), 500 (E) and 600 (F). 7. The GPC traces of the PEG 45 -b-ps/ps-b-peg 45 -b-ps blends with the different target DP of the PS block Figure S7 shows the GPC traces of the PEG 45 -b-ps/ps-b-peg 45 -b-ps blends with different DP of the PS block. Based on GPC analysis, the peak top molecular weight, M p,gpc, for the PEG 45 -b-ps diblock copolymers and the PS-b-PEG 45 -b-ps triblock copolymers is obtained, which is summrized in Figure S6 (right part). Note: in the case of the theoretical target DP = 600, the just one peak is observed, and the molecular weight of PEG 45 -b-ps and PS-b-PEG 45 -b-ps cannot be determined, and therefore just the theoretical molecular weight M n,th is afforded. It is found that M p,gpc is close to M n,th. S7

8 Figure S7. The GPC traces of the PEG 45 -b-ps/ps-b-peg 45 -b-ps blends prepared through the dispersion RAFT polymerization under [St] 0 :[PEG 45 -TTC] 0 :[TTC-PEG 45 -TTC] 0 :[AIBN] 0 = m:3/4:1/4:1/3 with the target DP (m) of the PS block in the AB/BAB block copolymers at 100, 200, 300, 400, 500 and The GPC traces of the PEG 45 -b-ps/ps-b-peg 45 -b-ps blends synthesized at different monomer concentration Figure S8 shows the GPC traces of the PEG 45 -b-ps/ps-b-peg 45 -b-ps blends synthesized under [St] 0 :[PEG 45 -TTC] 0 :[TTC-PEG 45 -TTC] 0 :[AIBN] 0 = 300:3/4:1/4:1/3 with different monomer concentration. Based on GPC analysis, the peak top molecular weight, M p,gpc, for the PEG 45 -b-ps diblock copolymers and the PS-b-PEG 45 -b-ps triblock copolymers is obtained, which is summrized in Figure S8 (right part). Note: in the case of the 25% monomer concentration, the block copolymer colloids were not as stable as those in the low monomer concentration during the dispersion RAFT polymerization, and three peaks in the GPC traces are observed, and therefore just the theoretical molecular weight M n,th is afforded. It is found that M p,gpc is close to M n,th. S8

9 Figure S8. The GPC traces of the AB/BAB blends prepared through the dispersion RAFT polymerization under [St] 0 :[PEG 45 -TTC] 0 :[TTC-PEG 45 -TTC] 0 :[AIBN] 0 = 300:3/4:1/4:1/3 with the weight ratio of the styrene monomer to the solvent at 10% (24 h, 94.8% monomer conversion), 15% (24 h, 96.0% monomer conversion), 20% (24 h, 94.9% monomer conversion) and 25% (30 h, 94.4% monomer conversion), respectively. 9. Low magnified TEM images of the self-assembled PEG 45 -b-ps/ps-b-peg 45 -b-ps blends synthesized at different monomer concentration S9

10 Figure S9. The TEM images of the self-assembled PEG 45 -b-ps/ps-b-peg 45 -b-ps blends prepared through the dispersion RAFT polymerization under [St] 0 :[PEG 45 -TTC] 0 :[TTC-PEG 45 -TTC] 0 :[AIBN] 0 = 300:3/4:1/4:1/3 with the weight ratio of the styrene monomer to the solvent at 10% (A) and 20% (B). 10. The SEM image of the self-assembled PEG 45 -b-ps/ps-b-peg 45 -b-ps blends synthesized at 25 wt% monomer concentration To detect the morphology of the self-assembled PEG 45 -b-ps/ps-b-peg 45 -b-ps blends synthesized at 25 wt% monomer concentration, a drop of the colloidal dispersion was deposited onto a piece of silicon wafer, dried in air at ambient temperature, sprayed with a gold layer about 3 nm thickness, and finally observed by SEM. The SEM image is shown in Figure S10. S10

11 Figure S10. The SEM image of the self-assembled PEG 45 -b-ps/ps-b-peg 45 -b-ps blends prepared at 25 wt% monomer concentration. Figure S11. The chain number ratio of the inside (or outside) triblock copolymer chains out of the total inside (or outside) chains, r tri,in (or r tri,out ). A chain is defined as an outside chain if the solvophilic repeated units of the chain are distributed on the outside surface of a vesicle or a multi-compartment vesicle, and the other chains are defined as inside chains. S11

12 a b R A B S ' B B end,di B end,tri Figure S12. The radical distribution profiles (a) of the A and B repeated units and solvent, ρ A, ρ B, ρ S and (b) of the chain-end B repeated units of the diblock and triblock copolymers, B end, di and B end, tri, of the multi-compartment vesicle formed from the AB/BAB blends at α = 6:3. The horizontal axis R is the radical distance from the mass center of the corresponding multi-compartment vesicle. For comparison, the radical distribution profile of the B repeated units, ρ B in the vesicles from the AB/BAB blends at α = 6:1 is also shown in (a) with a dashed curve. S12