of Polystyrene 4-arm Stars Synthesized by RAFT- Mediated Miniemulsions.

Transcription

1 Supporting Information to Narrow Molecular Weight and Particle Size Distributions of Polystyrene 4-arm Stars Synthesized by RAFT- Mediated Miniemulsions. Hazit A. Zayas, Nghia P. Truong, David Valade, Zhongfan Jia and Michael J. Monteiro* Australian Institute for Bioengineering and Nanotechnology, University of Queensland, Brisbane QLD 47, Australia *author to whom correspondence should be sent:

2 Table S. Kinetics data of RAFT agent mediated polymerization of styrene in miniemulsion using SDS (.8 g) as surfactant and hexadecane (.78 ml) as hydrophobe in water (8. g). The polymerization was initiated with ammonium persulfate (APS) at 7ºC. M n,target Styrene (g) CTA (g) Time (min) Conv. c (%) M n,theory d M n, exp e PDI e D h f (nm) (PDI) f N c g 5K a (.8) 7.97E (.).7E (.79).9E (.).79E (.6).7E (.5) 6.57E (.55) 7.49E+7 K a (.8) 9.66E (.) 5.64E (.89).99E (.57).6E (.5).6E (.5) 8.6E (.55) 8.8E+7 K b (.46) 8.9E (.4) 5.67E (.) 6.4E (.8) 5.94E (.64) 6.55E (.5) 5.6E (.86).5E (.59).49E (.7).48E (.4).E (.5) 8.47E+7 4K b (.655) 6.7E (.57) 8.64E (.56).E (.584).6E (.49) 8.77E (.) 8.56E (.6) 8.7E (.).5E (.7) 8.47E (.9) 7.84E (.8) 7.78E+7 a Ratio of CTA:APS is maintained at :.. Ratio of CTA:APS is maintained at :.. c Monomer conversion was obtained by gravimetric analysis. d M n, theory was calculated using the equation [M Sty /M CTA ] x MW sty x %Conv. + MW CTA. e M n, exp and the corresponding polydispersity index (PDI) were measured by size exclusion chromatography using linear polystyrene standards. f Hydrodynamic radius (D h ) and the corresponding polydispersity index (PDI) were measured by dynamic light scattering (DLS). Seven measurements were taken for each sample at 5 C.

3 w (M) w (M) W(M) w (M) Electronic Supplementary Material (ESI) for Polymer Chemistry (A) 4 5K (B) 4 K min 4 min 6 min min 8 min 4 min 6 min min 8 min 4 min log M Log M (C) K min 4 min 45 min 5 min 6 min min 8 min log M (D) 4K 5 min min 4 min 45 min 6 min min 8 min 4 min logm Figure S. Overlaid RI SEC traces for RAFT agent -polystyrene latexes of M n targets of (A) 5K, (B) K, (C) K and (D) 4K. The polymerization was carried out in miniemulsion using SDS as surfactant and hexadecane as hydrophobe initiated with APS at 7ºC. Linear polystyrene standards were used for calibration and THF as eluent.

4 f b, c, g, h, i k H O d CDCl e a, j Figure S. H NMR spectra for RAFT agent -polystyrene latex of M n target of K with expanded view (inset) of region.-5. ppm. The sample was obtained from a Bruker DRX 5 MHz spectrometer and the solvent used was CDCl.

5 Intens. [a.u.] Intens. [a.u.] Electronic Supplementary Material (ESI) for Polymer Chemistry (A) x m/z (B) x =4 m/z m/z Figure S. MALDI-ToF mass spectrometry of RAFT agent polystyrene of M n target of 5K with Ag salt as cationization agent from a DCTB matrix in linear mode. (A) The full molecular weight distribution and (B) expanded view of peaks correspond to RAFT agent -PSTY 54. Theoretical mass of RAFT agent -PSTY 54 is (59.4), found (59.5). (Sample was run on Bruker Autoflex III Smartbeam TOF/TOF.)

6 (A) 5K (B) K (C) K (D) 4K Figure S4. Size distribution by intensity for RAFT agent Polystyrene latexes of M n targets of (A) 5K, (B) K, (C) K and (D) 4 K measured by dynamic light scattering.

7 Table S. Kinetics data of RAFT agent (R-approach) mediated polymerization of styrene in miniemulsion using SDS (.8 g) as surfactant and hexadecane (.78 ml) as hydrophobe in water (8. g). The polymerization was initiated with ammonium persulfate (APS) at 7ºC. M n,target Styrene (g) CTA (g) Time (min) Conv. c (%) M n,theory d M n, exp e PDI e D h f (nm) (PDI) f N c 5K a (.6).84E (.87).9E (.98).4E (.77).57E (.8).55E (.8).8E (.8).8E+8 K a (.96).56E (.7).67E (.66).8E (.7).7E (.99).98E (.).94E+8 K b (.47).E (.9) 5.8E (.9).69E (.6).99E (.78).E (.75).99E (.74).87E+8 4K b (.48) 5.59E (.54) 4.4E (.49) 4.7E (.).E (.66).E (.64).7E (.59).85E (.8).6E (.7).6E+8 a Ratio of CTA:APS is maintained at :.4. b Ratio of CTA:APS is maintained at :.. c Monomer conversion was obtained by gravimetric analysis. d M n, theory was calculated using the equation [M Sty /M CTA ] x MW sty x %Conv. + MW CTA. e M n, exp and the corresponding polydispersity index (PDI) were measured by size exclusion chromatography using linear polystyrene standards. f Hydrodynamic radius (D h ) and the corresponding polydispersity index (PDI) were measured by dynamic light scattering (DLS). Seven measurements were taken for each sample at 5 C.

8 W (M) w (M) w (M) W (M) Electronic Supplementary Material (ESI) for Polymer Chemistry (A) 5 5K (B) 5 K 4 4 min 4 min 6 min min 8 min 4 min min 4 min 6 min min 8 min log M Log M (C) 4 K (D) 4K 5 min min min min 8 min min Log M 5 min min 5 min min 6 min min 8 min 4 min Log M Figure S5. Overlaid RI SEC traces for RAFT agent -polystyrene latexes of M n target of (A) 5K, (B) K, (C) K and (D) 4K.The polymerization was carried out in miniemulsion using SDS as surfactant and hexadecane as hydrophobe initiated with APS at 7ºC. Linear polystyrene standards were used for calibration and THF as eluent.

9 f b, c, e, g, h, i d H O CHCl e k a, j Figure S6. H NMR spectra for RAFT agent -polystyrene latex of M n target of K with expanded view (inset) of region.-5. ppm. The sample was obtained from abruker DRX 5 MHz spectrometer and the solvent used was CDCl.

10 Intens. [a.u.] Electronic Supplementary Material (ESI) for Polymer Chemistry x4 (A) m/z (B) (57.76) ( ) =4 m/z Figure S7. MALDI-ToF mass spectrometry of RAFT agent polystyrene of M n target of 5K with Ag salt as cationization agent from a DCTB matrix in linear mode. (A) The full molecular weight distribution and (B) expanded view of peaks correspond to RAFT agent (4 arm)-psty a,b,c,d (where a+b+c+d=44). Theoretical masses of RAFT agent (4 arm)- PSTY a,b,c,d (where a+b+c+d=44) are (57.76) and ( ), found are (57.96) and ( ), respectively. (Sample was run on Bruker Autoflex III Smartbeam TOF/TOF.) m/z

11 (A) 5K (B) K (C) K (D) 4K Figure S8. Size distribution by intensity of RAFT agent Polystyrene latexes of M n targets of (A) 5K, (B) K, (C) K and (D) 4 K measured by dynamic light scattering.

12 Conversion (%) M n (x ) PDI Electronic Supplementary Material (ESI) for Polymer Chemistry Synthesis of -arm PSTY by RAFT Solution Polymerization in Toluene The molar ratios of [STY]:[RAFT]:[AIBN] were set up as ::. and 4::. to target K and 4 K molecular weight at the % conversion, respectively. Typically, for the molar ratio 4::., RAFT agent (. mg, 4.8 x -5 mol) and AIBN (.788 mg, 4.8 x -6 mol) were dissolved in g (.9 x - mol) of STY and 8 ml of toluene. The solution was purged with argon for min and then polymerization mixture immersed in a preheated oil-bath at 7 o C. Aliquots were then taken out for the analysis at regular intervals and the reaction stopped after 4 h. (A) (B) (C) 8 6 K 4K 5 9 K 4K K Mn theory 4K Mn theory.8.6 K 4K Time (h) Conversion (%) Conversion (%) Figure S9. Kinetics data for RAFT agent mediated styrene polymerization in toluene at 7 C initiated with AIBN. (A) Conversion vs time, (B) number average molecular weight (M n ) vs conversion and (C) polydispersity index (PDI MWD ) vs conversion. [STY]:[RAFT]:[AIBN] = ::. and 4::. to target K and 4 K molecular weight at the % conversion, respectively.

13 Conversion (%) M n (x ) Electronic Supplementary Material (ESI) for Polymer Chemistry Synthesis of 4-arm PSTY by RAFT Solution Polymerization in Toluene A typical RAFT-mediated polymerization of styrene in toluene in the presence of the 4-arm RAFT agent was carried out as follows. An initial [STY]:[RAFT]:[AIBN] ratio = ::. : STY ( g, 9. - mol), (97.7 mg mg, mol), AIBN (.58 mg, mol) and 8 ml of toluene were introduced in a Schlenk tube equipped with a magnetic stirrer. The solution was purged with argon for min and heated at 7 o C. Aliquots were regularly taken and analyzed by GPC (MWD) and gravimetry (conversion). After 4 h, AIBN (. eq to ) was added to the polymerization and continued for a further 4 h. (A) (B) (C) K 4K 4 k 4k K mn theory 4K Mn theory PDI MWD k 4k Time (h) Conversion (%) Conversion (%) Figure S. Kinetics data for RAFT agent (4-arm RAFT agent) mediated styrene polymerization in toluene at 7 C initiated with AIBN. (A) Conversion vs time, (B) number average molecular weight (M n ) vs conversion and (C) polydispersity index (PDI MWD ) vs conversion. [STY]:[RAFT]:[AIBN] ratio = ::. : STY ( g, 9. - mol), (97.7 mg mg, mol), AIBN (.58 mg, mol) and 8 ml of toluene. After 4 h, AIBN (. eq to ) was added to the polymerization and continued for a further 4 h.

14 Conversion (%) M n (x ) Electronic Supplementary Material (ESI) for Polymer Chemistry Synthesis of 4-arm PSTY by RAFT Solution Polymerization in bulk A typical RAFT-mediated polymerization of styrene in bulk in the presence of the 4-arm RAFT agent was carried out as follows. An initial [STY]:[RAFT]:[AIBN] ratio = ::. : STY ( g, mol), (46.6 mg, mol) and AIBN (.4 mg, mol) were introduced in a Schlenk tube equipped with a magnetic stirrer. The solution was purged with argon during min and heated at 7 o C for h. Aliquots were regularly taken and analyzed by GPC (MWD) and gravimetry (conversion). (A) K 4K (B) 4 k 4k K mn theory 4K Mn theory (C) PDI MWD k 4k.4 4 Time (h) 5 Conversion (%) Conversion (%) Figure S. Kinetics data for RAFT agent (4-arm RAFT agent) mediated styrene polymerization in bulk at 7 C initiated with AIBN. (A) Conversion vs time, (B) number average molecular weight (M n ) vs conversion and (C) polydispersity index (PDI MWD ) vs conversion. [STY]:[RAFT]:[AIBN] ratio = ::. : STY ( g, mol), (46.6 mg, mol) and AIBN (.4 mg, mol).

15 . Hart-Smith, G.; Chaffey-Millar, H.; Barner-Kowollik, C., Living Star Polymer Formation: Detailed Assessment of Poly(acrylate) Radical Reaction Pathways via ESI-MS. Macromolecules 8, 4 (9), -4.