Supplementary Figure S1. SEC trace of polymerization of Methyl acrylate (MA) with a high initiator to monomer ratio (1:4) via in situ DE-ATRP (30% AA

Transcription

1 Supplementary Figure S1. SEC trace of polymerization of Methyl acrylate (MA) with a high initiator to monomer ratio (1:4) via in situ DE-ATRP (30% AA of Cu II ). The result shows a characteristic of living polymerization, which indicates that the kinetics chain length of in situ DE-ATRP can be diminished to an extremely low level.

2 Supplementary Figure S2. 1 H NMR spectrum of different periods of polymerization of 1,3-butanediol diacrylate (BDA) towards hyperbranched structure via in situ DE-ATRP (30% AA of Cu II ). The vinyl conversion is defined as the ratio of consumed vinyl groups to all the original vinyl groups, as shown in Supplementary Equation S1: Vinyl Conversion = consumed vinyl groups original vinyl groups current vinyl groups = 1 = 1 original vinyl groups integrals of a 2 integrals of n (S1)

3 Supplementary Figure S3. 1 H NMR spectroscopy of purified polymer products: (a) Hyperbranched polybda (3.5h product in Figure 2 (a)); (b) Cyclized polybda (5h product in Figure 2 (b)). The branched ratio is defined as the ratio of branched BDA units to all the BDA units, as shown in Supplementary Eq. S2: Branch ratio = branched BDA units all BDA units = 1 linear BDA units all BDA units integrals of a = 1 integrals of n (S2)

4 Supplementary Figure S4. GC for the samples from the early period of polymerization of hyperbranched polybda, showing the composition evolution within the polymerization system: (a) GC of 0h sample in Figure 2 (a); (b) GC of 0.5h sample in Figure 2 (a); (c) GC of 1h sample in Figure 2 (a).

5 Supplementary Figure S5. SEC trace evolution for polymerizations from different types of divinyl monomers: (a) Polymerization of DEGDA; (b) Polymerization of EGDMA; (c) Polymerization of DVB.

6 Supplementary Figure S6. Time dependence of the composition of the polymerization mixtures monitored by SEC equipped with a RI detector, indicating that the divinyl monomer firstly underwent a large-scale linear oligomerization (<1.5h) followed by oligomer combination (>1.5h)

7 Supplementary Figure S7. 1 H NMR spectrum of different periods of polymerization of disulfide-based diacrylate (DSDA) towards hyperbranched structure via in situ DE-ATRP (30% AA of Cu II ). The vinyl conversion is defined as the ratio of consumed vinyl groups to all the original vinyl groups, as shown in Supplementary Eq. S3: Vinyl Conversion = consumed vinyl groups original vinyl groups current vinyl groups = 1 = 1 original vinyl groups integrals of a (integrals of e)/2 (S3)

8 Supplementary Figure S8. 1 H NMR spectroscopy of purified hyperbranched polydsda (10h product in Supplementary Figure S6). The branched ratio is defined as the ratio of branched DSDA units to all the DSDA units, as shown in Supplementary Eq. S4: Branch ratio = branched DSDA units all DSDA units = 1 linear DSDA units all DSDA units = 1 integrals of a (integrals of e)/4 (S4)

9 Supplementary Figure S9. 1 H NMR spectrums before and after cleavage of the purified hyperbranched polydsda (10h product in Supplementary Figure S6). The disulfide bond was completely cleaved after 2 h, since the resonance of proton (2.9 ppm) completely disappeared. Peaks of vinyl groups also disappeared, since the vinyl groups were consumed by the newly generated -SH groups.

10 Supplementary Table S1. Polymerization conditions and molecular weight characteristics of polymerizations from different divinyl monomers: Time (hrs) M n d (Da) M w d (Da) PDI d Vinyl e conv. Branch e ratio % ~0% Hyperbranched a polydegda % ~2% % 19% % 37% % 66% Hyperbranched b polyegdma % ~0% % ~2% % 30% % ~0% Hyperbranched c polydvb % 15% % 20% % 40% a I/DEGDA/CuBr 2 /PMDETA/AA = 1 : 2 : 0.05 : 0.05 : 0.015, I: ethyl 2-bromoisobutyrate (EBriB), PMDETA: 1,1,4,7,7-pentamethyldiethylenetriamine, AA: L-Ascorbic Acid, solvent: 2-butanone, T = 60 o C; b I/EGDMA/CuBr 2 /PMDETA/AA = 1 : 2 : 0.05 : 0.05 : , solvent: 2-butanone, T = 60 o C; c I/DVB/CuBr 2 /PMDETA/AA = 1 : 2 : 0.05 : 0.05 : 0.025, solvent: toluene, T = 90 o C; d M n, M w and PDI are determined by SEC equipped with a refractive index (RI) detector. e Vinyl conversion and branch ratio were calculated by 1 H NMR analysis of original reaction mixtures and precipitated samples.