Supporting Information for

Transcription

1 Supporting Information for Order-Disorder Transition in Supramolecular Polymers Jessalyn Cortese, Corinne Soulié-Ziakovic, Michel Cloitre, Sylvie Tencé-Girault, Ludwik Leibler* I. Synthesis of Thy-PPO-460-Thy and Thy-PPO-2200-Thy. S-2 II. 1 H and 13 C NMR of Thy-PPO-460-Thy and Thy-PPO-2200-Thy. S-4 III. DSC of Thy-PPO-460-Thy and Thy-PPO-2200-Thy. S-8 IV. Polarized Optical Microsopy of Thy-PPO-460-Thy and Thy-PPO-2200-Thy. S-9 V. X-ray Scattering of Thy-PPO-460-Thy and Thy-PPO-2200-Thy. S-10 VI. Rheology of Thy-PPO-460-Thy and Thy-PPO-2200-Thy. S-13 VII. Modelization of Correlation Hole of Thy-PPO-460-Thy and Thy-PPO-2200-Thy. S-14 VIII. PPO chain extension from the disordered to the lamellar state. S-17 IX. Complete list of authors for citations with 16 or more authors. S-17 S-1 1

2 I. Synthesis The thymine homoditopic supramolecular polymer (Thy-PPO-X-Thy, X=460, 2200) were synthesized via amidation of diamine telechelic poly(propylene oxide) (NH 2 -PPO-X-NH 2, X=460, 2200) with thymine-1-acetic acid. The reaction was carried out in bulk at 160 C under a nitrogen flow (Scheme 2a, adapted from a method by Montarnal et al.) 1 or in solution with a coupling agent (TBTU, Scheme 2b, adapted from Corradini et al.). 2 The chemical structure of the resulting materials was confirmed by 1 H and 13 C NMR. The end-groups peaks can be identified and the molecular weight (M n ) can be estimated: 800 g/mol for Thy-PPO-460-Thy and 2500 g/mol for Thy-PPO-2200-Thy. Scheme 1. Thy-PPO-Thy synthesis via amidification of diamine telechelic poly(propylene oxide) NH 2 - PPO-NH 2 by thymine-1-acetic acid carried out (a) in the bulk at 160 C under nitrogen flow, or (b) in solution with a coupling agent. 1 Montarnal, D.; Cordier, P.; Soulié-Ziakovic, C.; Tournhilhac, F., Leibler, L.; J. Polym. Sci., Part A: Polym. Chem. 2008, 46, Corradini, R.; Sforza, S.; Dossena, A.; Palla, G.; Rocchi, R.; Filira, F.; Nastri, F.; Marchelli, R. ; J. Chem. Soc., Perkin Trans , 20, S-2 2

3 1. Synthesis of Thy-PPO-460-Thy 1.93 g of thymine-1-acetic acid (10.5 mmol) was added progressively to Jeffamine D400 (5 mmol) at 160 C under a stream of nitrogen gas. The reaction stirred until completion of the reaction (followed by FT-IR). DMF was added dropwise if stiring became difficult. The product was purified by column chromatography (MeOH/CHCl 3 : 2/8 v/v), and dried under vacuum at 160 C. RMN 1 H (DMSO-d 6 /TMS) δ/ppm = 1.05 (d, J=6.44Hz, 26H, a,b) (s, 6H, A) - 3 to 4 (m, c,d,e) (m, 2H, f) (s, 4H, B) (s, 2H, C) (qdd, 2H, h) (s, 2H, D). RMN 13 C (DMSO-d 6 /TMS) δ/ppm = 12.0 (A) (a,b) et 45.0 (f) (B) - 71 to 76 (c,d,e) (E) (C) (F) (G) (H). 2. Synthesis of Thy-PPO-2200-Thy Thymine-1-acetic acid (1.93 g, 10.5 mmol) was dissolved in DMF (20 ml). Jeffamine D2000 (5 mmol), TBTU (O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyl uronium tétrafluoroborate) (12 mmol) and DIEA (30 mmol) were then added. The reaction stirred at room temperature for one day and was subsequently quenched by adding water (40 ml). The reaction mixture was extracted with toluene (2 x 60mL), washed with water (2 x 60 ml), dried over anhydrous magnesium sulfate, filtered, evaporated and dried under vacuum at 80 C. This grafting reaction was followed by 1 H NMR. The α methyl signal is deshielded as the amine (δ αcη3 = 0.91 ppm) transforms into an amide (δ αcη3 = 1.03 ppm). RMN 1 H (DMSO-d 6 /TMS) δ/ppm = 1.03 (d, J=5.9Hz, 121H, a,b) (s, 6H, A) - 3 to 4 (m, c,d,e) (m, 2H, f) (s, 4H, B) (s, 2H, C) (qdd, 2H, h) (s, 2H, D). RMN 13 C (DMSO-d 6 /TMS) δ/ppm = 11.9 (A) (a,b) and 45.0 (f) (B) - 71 to 76 (c,d,e) (E) (C) (F) (G) (H). S-3 3

4 II. NMR Figure 1. 1 H NMR in DMSO-d 6 of Thy-PPO-460-Thy. S-4 4

5 Figure C NMR in DMSO-d 6 of Thy-PPO-460-Thy. S-5 5

6 Figure 3. 1 H NMR in DMSO-d 6 of Thy-PPO-2200-Thy. S-6 6

7 Figure C NMR in DMSO-d 6 of Thy-PPO-2200-Thy. S-7 7

8 III. DSC Figure 5. DSC at 10 C/min of Thy-PPO-2200-Thy (exo down). Figure 6. DSC at 10 C/min of Thy-PPO-460-Thy (exo down). S-8 8

9 IV. Polarized Optical Microscopy Figure 7. Polarized Optical Microscopy of (A) Thy-PPO-460-Thy, (B) and (C) Thy-PPO-2200-Thy. S-9 9

10 V. X-Ray Scattering Figure 8. X-ray Scattering at room temperature of annealed Thy-PPO-2200-Thy. The value of lamellar spacing (61 Å) is comparable to the one observed in layered silicates intercalated with telechelic diamine PPO of the same molecular weight. 3 Figure 9. X-ray Scattering at room temperature of annealed Thy-PPO-460-Thy. 3 Lin, J.-J.; Cheng, I.-J.; Wang, R., Lee, R.-J.; Macromolecules 2001, 34, S-10

11 Figure 10. X-ray Scattering around ODT (T ODT = 85 C) of Thy-PPO-2200-Thy. Figure 11. X-ray Scattering above ODT (T ODT = 85 C) of Thy-PPO-2200-Thy. S-11 11

12 Figure 12. X-ray Scattering around ODT of Thy-PPO-460-Thy. Please note that in block copolymers BCC morphologies are often observed. Similarly, it should be possible to obtain a BCC structure in main-chain supramolecular polymers. Binder and his coworkers observed a BCC morphology for polyisobutylene monofunctionalized with diaminotriazine. 4 As the temperature is decreased, Thy-PPO-X-Thy (X=460, 2200) go directly from the disordered state to a lamellar structure because of thymine crystallization. However, it should be possible to obtain a BCC morphology in a main-chain telechelic supramolecular polymer whith no crystallization. 4 Herbst, F.; Schröter, K.; Gunkel, I.; Gröger, S.; Thurn-Albrecht, T.; Balbach, J., Binder, W. H.; Macromolecules 2010, 43 (23), S-12

13 VI. Rheology Figure 13. Frequency Sweep of Thy-PPO-2200-Thy at 60 and 70 C. Figure 14. Temperature Sweep of Thy-PPO-460-Thy at 0.7 C/min, from 130 C to 50 C. S-13

14 VII. Modelization of Correlation Hole The theory developed in reference 4 predicts a maximum in the correlation function S(q) of the disordered state, which is proportional to the scattering intensity. 5 Even though this theory was developed for non-associating diblock copolymers, it can be applied by virtually cutting the molecule in half, as a first approximation for our pseudo-triblock copolymers and associated species. This first approximation allows a relatively good fitting of the shape and position of the experimental peak, for both Thy-PPO-460-Thy and Thy-PPO-2200-Thy, using reasonable molecular parameters. The intensity is renormalized to fit the experimental curve. The visibility of the correlation hole peak depends on the contrast between the spacer and the stickers. The contrast between the PPO chain and the stickers is quite high, since the sticker electron density is 20% higher than the PPO electron density. Still, the correlation hole intensity is very low, lower than the nearest neighbors correlation halo intensity. Parameters : PPO monomeric size: a = 3.6 Å Thymine size: d Thy = 3 Å 5 Leibler, L.; Macromolecules 1980, 13, S-14 14

15 5,E-04 4,E-04 Correlation Hole Fit for Thy-PPO-460-Thy, 155 C Thy-PPO-460-Thy, 155 C 3,E-04 I (q) 2,E-04 1,E-04 0,E ,5 1 1,5 2 2,5 3 q (angström-1) Figure 15. Correlation Hole Modelization of Thy-PPO-460-Thy at 155 C. Parameters for Thy-PPO-460-Thy : fraction: f Thy = number of PPO monomeric unit: n = 6.6 C = 4.7 for PPO chain χn k = 1 S-15

16 8,E-04 7,E-04 6,E-04 Correlation Hole Fit for Thy-PPO-2200-Thy, 90 C Thy-PPO-2200-Thy, 90 C 5,E-04 I (q) 4,E-04 3,E-04 2,E-04 1,E-04 0,E ,5 1 1,5 2 2,5 3 q (angström-1) Figure 16. Correlation Hole Modelization of Thy-PPO-2200-Thy at 90 C. Parameters for Thy-PPO-2200-Thy : fraction: f Thy = number of PPO monomeric unit: n = 40 C = 7.4 for PPO chain χn k = 15 S-16

17 VIII. PPO chain extension from the disordered to the lamellar state The ratio L/r 0 of the average end-to-end length L of PPO in the ordered lamellar state versus the end-toend distance r 0 in the disordered melt is approximately 60 / 50 = 1.2 for Thy-PPO-2200-Thy and 27.7 / 22.4 = 1.2 for Thy-PPO-460-Thy. The volume V of one PPO chain can be estimated from the PPO density and molecular weight to be 3.7*10-27 m 3 for Thy-PPO-2200-Thy and 7.6*10-28 m 3 for Thy-PPO-460-Thy. The PPO chain extension required to accommodate the lamellar morphology is determined by the crystal packing of the 2D crystallized thymine plane. Assuming incompressibility of the system, the volume V of one PPO chain is then equal to L*Σ, where Σ is the area of the thymine plane occupied by one chain. This area is related to the distance d between two crystallized thymines by d = Σ = (V/L). The results obtained for Σ (7.9 Å for Thy-PPO-2200-Thy and 5.2 Å for Thy-PPO-460-Thy) are compatible with distances between two thymines in the crystallized state. IX. Complete list of authors for citations with 16 or more authors Deplace, F.; Wang, Z.; Lynd, N. A.; Hotta, A.; Rose, J. M.; Hustad, P. D.; Tian, J.; Ohtaki, H.; Coates, G. W.; Shimizu, F.; Hirokane, K.; Yamada, F.; Shin, Y.-W.; Rong, L.; Zhu, J.; Toki, S.; Hsiao, B. S.; Fredrickson, G. H. ; Kramer, E. J.; J. Polym. Sci. B: Polym. Phys. 2010, 48, S-17 17