Poly(lactide-co-ε-caprolactone) · Electronic Supplementary Information...
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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, 132-84084 Fisciano (SA), Italy. * E-mail: [email protected] S1 Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2014
Transcript of Poly(lactide-co-ε-caprolactone) · Electronic Supplementary Information...
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
Milionea,* and Carmine Capacchionea
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, 132-84084
Fisciano (SA), Italy.* E-mail: [email protected]
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Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2014
Electronic Supplementary Information
Table of Contents
1. NMR Characterization. ................................................................................................................................3
Figure S1. Carbonyl range of 13C NMR spectra (CDCl3, 25 °C) of copolymers obtained by 1. ...................3
Figure S2. Carbonyl range of 13C NMR spectra (CDCl3, 25 °C) of copolymers obtained by 2. ...................4
Figure S3. Carbonyl range of 13C NMR spectra (CDCl3, 25 °C) of copolymers obtained by 3. ...................5
2. 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)......................................................................................................................6
3. 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 Tg of CL/LA copolymers on the molar % caprolactone in
copolymers. ...................................................................................................................................................10
4. AFM Characterization. ..............................................................................................................................11
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. .............................................................................................................11
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. .......................................................................................................................11
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. .....................................................................................................................12
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1. NMR Characterization.
Figure S1. Carbonyl range of 13C NMR spectra (CDCl3, 25 °C) of copolymers obtained by 1.
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Figure S2. Carbonyl range of 13C NMR spectra (CDCl3, 25 °C) of copolymers obtained by 2.
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Figure S3. Carbonyl range of 13C NMR spectra (CDCl3, 25 °C) of copolymers obtained by 3.
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2. Evaluation of average block lengths.
The average block lengths of L-lactide (LLA) and ε-caprolactone (LCL) units in the copolymers were calculated using the following equations (P.Vanhoorne, P.Dubois, R. Jeromeand P.Teyssie, Macromolecules, 2012, 25, 37-44):
𝐿𝐶𝐿 = ( 𝐼𝐶𝐶𝐶 + 𝐼𝐿𝐿𝐶𝐶
𝐼𝐶𝐶𝐿𝐿 + 𝐼𝐿𝐿𝐶𝐿𝐿) + 1
𝐿𝐿𝐴 =(𝐼𝐿𝐿𝐿𝐿𝐿𝐿 + (𝐼𝐿𝐿𝐿𝐿𝐶 + 𝐶𝐿𝐿𝐿𝐿
2 ))((𝐼𝐿𝐿𝐿𝐿𝐶 + 𝐶𝐿𝐿𝐿𝐿
2 ) + 𝐼𝐶𝐿𝐶) + 1
∗12
in which I indicates the integral of the signals attributed to triad sequence in the carbonyl range of 13C 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 rLA = rCL = 1 (Lm1 = rm2 + rm1 [m1]/[m2]).
0,0 0,2 0,4 0,6 0,8 1,00
5
10
15
20
25
30 Theoretical value LCL by 1
L CL
CL in the feed (%)
0,0 0,2 0,4 0,6 0,8 1,00
5
10
15
20 Theoretical valueLLA by 1
L LA
CL in the feed (%)
0,0 0,2 0,4 0,6 0,8 1,00
5
10
15 Theoretical value LCL by 2
L CL
CL in the feed (%)
0,0 0,2 0,4 0,6 0,8 1,00
5
10
15
20 Theoretical value LLA by 2
L LA
CL in the feed (%)
0,0 0,2 0,4 0,6 0,8 1,00
5
10
Theoretical value LCL by 3
L CL
CL in the feed (%)
0,0 0,2 0,4 0,6 0,8 1,00
5
10
Theoretical value LLA by 3
L LA
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).
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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).
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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).
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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).
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0 20 40 60 80 100-60,0
-40,0
-20,0
0,0
20,0
40,0
60,0 Tg of copolymer by 1 theoretical value
T g (°
C)
CL in the copolymer (%)0 20 40 60 80 100
-60,0
-40,0
-20,0
0,0
20,0
40,0
60,0 Tg of copolymer by 2 theoretical value
T g (°
C)
CL in the copolymer (%)0 20 40 60 80 100
-60,0
-40,0
-20,0
0,0
20,0
40,0
60,0 Tg of copolymer by 3 theoretical value
T g (°
C)
CL in the copolymer (%)
Figure S8. Plots of the dependence of Tg of CL/LA copolymers on the molar % caprolactone in copolymers.
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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.
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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.
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