Poly(lactide-co-ε-caprolactone) Copolymers by. Bis-Thioetherphenolate Group 4 Metal Complexes: Synthesis, Characterization and Morphology

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1 Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2014 Electronic Supplementary Information Poly(lactide-co-ε-caprolactone) Copolymers by Bis-Thioetherphenolate Group 4 Metal Complexes: Synthesis, Characterization and Morphology Francesco Della Monica, a Ermanno Luciano, a Antonio Buonerba, a Alfonso Grassi, a Stefano Milione a, * and Carmine Capacchione a a Dipartimento di Chimica e Biologia and NANOMATES, Research Centre for NANOMAterials and nanotechnology at Salerno University, Università degli Studi di Salerno, via Giovanni Paolo II, Fisciano (SA), Italy. * smilione@unisa.it S1

2 Table of Contents 1. NMR Characterization...3 Figure S1. Carbonyl range of 13 C NMR spectra (CDCl 3, 25 C) of copolymers obtained by Figure S2. Carbonyl range of 13 C NMR spectra (CDCl 3, 25 C) of copolymers obtained by Figure S3. Carbonyl range of 13 C NMR spectra (CDCl 3, 25 C) of copolymers obtained by Calculation of average block lengths...6 Figure S4. Average block lengths of caprolactone (up) and lactide (down) in the copolymers obtained by 1 (left), 2 (middle) and 3 (right) Thermal Analysis....7 Figure S5. DSC thermogram of the copolymers CL/LA obtained with complex 1 (traces of the second heating cycle with a heating rate of 10 C min -1 )....7 Figure S6. DSC thermogram of the copolymers CL/LA obtained with complex 2 (traces of the second heating cycle with a heating rate of 10 C min -1 )....8 Figure S7. DSC thermogram of the copolymers CL/LA obtained with complex 3 (traces of the second heating cycle with a heating rate of 10 C min -1 )....9 Figure S8. Plots of the dependence of T g of CL/LA copolymers on the molar % caprolactone in copolymers AFM Characterization Figure S9. Height and phase contrast TM-AFM micrographs of CL/LA copolymer of run 6 of Table 1 thermal treated at 50 C for 15 min Figure S10. Height and phase contrast TM-AFM micrographs of CL/LA copolymer of run 11 of Table 1 annealed at 50 C for 15 min Figure S11. Height and phase contrast TM-AFM micrographs of CL/LA copolymer of run 8 of Table 1.12 Figure S12. Height and phase contrast TM-AFM micrographs of CL/LA copolymer of run 5 of Table 1 annealed at 100 C for 15 min S2

3 1. NMR Characterization. Electronic Supplementary Information Figure S1. Carbonyl range of 13 C NMR spectra (CDCl 3, 25 C) of copolymers obtained by 1. S3

4 Figure S2. Carbonyl range of 13 C NMR spectra (CDCl 3, 25 C) of copolymers obtained by 2. S4

5 Figure S3. Carbonyl range of 13 C NMR spectra (CDCl 3, 25 C) of copolymers obtained by 3. S5

6 2. Evaluation of average block lengths. Electronic Supplementary Information The average block lengths of L-lactide ( ) and ε-caprolactone ( ) units in the copolymers were calculated using the following equations (P.Vanhoorne, P.Dubois, R. Jeromeand P.Teyssie, Macromolecules, 2012, 25, 37-44): = ( I CCC + I LLCC I CCLL + I LLCLL ) + 1 = ( I LLLLLL + ( I LLLLC + CLLLL 2 )) (( I LLLLC + CLLLL 2 ) CLC) 1 + I in which I indicates the integral of the signals attributed to triad sequence in the carbonyl range of 13 C NMR spectrum, the subscript C stands for the caproyl unit and the subscript L stands for the lactidyl unit. The figure S4 shows the calculated values respect to the theoretical values in the case of an ideal random copolymerization with r LA = r CL = 1 (L m1 = r m2 + r m1 [m 1 ]/[m 2 ]) Theoretical value by 1 15 Theoretical value by 2 10 Theoretical value by ,0 0,2 0,4 0,6 0,8 1,0 CL in the feed (%) 0 0,0 0,2 0,4 0,6 0,8 1,0 CL in the feed (%) 0 0,0 0,2 0,4 0,6 0,8 1,0 CL in the feed (%) 20 Theoretical value by 1 20 Theoretical value by 2 Theoretical value by ,0 0,2 0,4 0,6 0,8 1,0 CL in the feed (%) 0 0,0 0,2 0,4 0,6 0,8 1,0 CL in the feed (%) 0 0,0 0,2 0,4 0,6 0,8 1,0 CL in the feed (%) Figure S4. Average block lengths of caprolactone (up) and lactide (down) in the copolymers obtained by 1 (left), 2 (middle) and 3 (right). S6

7 3. Thermal Analysis. Figure S5. DSC thermograms of the CL/LA copolymers obtained with complex 1 (profiles from second heating cycles with a heating rate of 10 C min -1 ). S7

8 Figure S6. DSC thermogram of the copolymers CL/LA obtained with complex 2 (profiles from second heating cycles with a heating rate of 10 C min -1 ). S8

9 Figure S7. DSC thermogram of the copolymers CL/LA obtained with complex 3 (traces of the second heating cycle with a heating rate of 10 C min -1 ). S9

10 60,0 40,0 T g of copolymer by 1 theoretical value 60,0 40,0 T g of copolymer by 2 theoretical value 60,0 40,0 T g of copolymer by 3 theoretical value Tg ( C) 20,0 0,0-20,0-40,0 Tg ( C) 20,0 0,0-20,0-40,0 Tg ( C) 20,0 0,0-20,0-40,0-60, CL in the copolymer (%) -60, CL in the copolymer (%) -60, CL in the copolymer (%) Figure S8. Plots of the dependence of T g of CL/LA copolymers on the molar % caprolactone in copolymers. S10

11 Electronic Supplementary Information 4. AFM Characterization. Figure S9. Height and phase contrast TM-AFM micrographs of CL/LA copolymer of run 6 of Table 1 thermal treated at 50 C for 15 min. Figure S10. Height and phase contrast TM-AFM micrographs of CL/LA copolymer of run 11 of Table 1 annealed at 50 C for 15 min. S11

12 Electronic Supplementary Information Figure S11. Height and phase contrast TM-AFM micrographs of CL/LA copolymer of run 8 of Table 1. Figure S12. Height and phase contrast TM-AFM micrographs of CL/LA copolymer of run 5 of Table 1 annealed at 100 C for 15 min. S12