Method for High Refractive Index Polymers

Transcription

1 Supporting information for Incorporating Pendent Fullerenes with High Refractive Index Backbones: A Conjunction Effect Method for High Refractive Index Polymers Shuang Chen, Dongxue Chen, Min Lu, Xin Zhang, He Li, Xiaoyan Zhang, Xiaoming Yang, Xiaohong Li,*, Yingfeng Tu*, and Christopher Y. Li Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou , China Key Laboratory of Marine Materials and Related Technologies, Ningbo Institute of Materials Technology & Engineering, CAS, Ningbo , China Department of Materials Science and Engineering, Drexel University, Philadelphia, PA 19104, United States 1

2 Quantitative 1 H NMR analysis for fullerene polyesters P1-P4 P1: 1 H NMR (600 MHz, CDCl 3 ), δ (ppm): 7.73 (1.93H, H at the 3,4-thiophene ring), 7.22 (solvent and H at the triazole ring), (3.26H, H at the benzene ring), 5.29 (3.57H, COOCH 2 -Ar), 5.05 (0.15H, OH), 4.78 (0.98H, H at the bridging C), 4.67 (0.51H, Ar-CH 2 OH), 4.45 (2.04H, COOCH 2 in the side chain), 4.31 (2.17H, CH 2 O-Ar in the side chain), 3.94 (2.00H, CH 2 linked to N in the triazole ring), 2.70 (1.89H, CH 2 linked to C in the triazole ring), (35.60H, side chain CH 2 ). For the quantitative 1 H NMR analysis, the peaks at 7.73(1.93H), 5.29 (3.57H), 4.67 (0.51H) were used. P2: 1 H NMR (600 MHz, CDCl 3 ), δ (ppm): 8.82 (1.99H, H at the 5,8-naphthalene ring), 7.97 (2.02H, H at the 2,3-naphthalene ring), 7.52 (2.10H, H at the 6,7-naphthalene ring), 7.21(solvent and H at the triazole ring), 6.93 (2.99, H at the benzene ring), 5.31 (3.85H, COOCH 2 -Ar), 5.04 (0.08H, OH), 4.73 (0.93H, H at the bridging C), 4.66 (0.20H, Ar-CH 2 OH), 4.43 (2.01H, COOCH 2 in the side chain), 4.28 (2.14H, CH 2 O-Ar in the side chain), 3.93 (2.00H, CH 2 linked to N in the triazole ring), 2.69 (2.06H, CH 2 linked to C in the triazole ring), (28.25H, side chain CH 2 ). For the quantitative 1 H NMR analysis, the peaks at 8.82(1.99H), 5.31 (3.85H), 4.66 (0.20H) were used. P3: 1 H NMR (600 MHz, CDCl 3 ), δ (ppm): 8.02 (1.76H, H at the 1,2,4,5-substituted benzene ring), 7.23(solvent and H at the triazole ring), (3.06H, H at the 1,3,5-substituted benzene ring), 5.32 (3.35, COOCH 2 -Ar), 5.04 (0.09H, OH), 4.77 (0.91H, H at the bridging C), 4.68 (0.50H, Ar-CH 2 OH), 4.44 (1.91H, COOCH 2 in the side chain), 4.31 (2.16H, CH 2 O-Ar in the side chain), 3.95 (2.00H, CH 2 linked to N in the triazole ring), 2.69 (2.03H, CH 2 linked to C 2

3 in the triazole ring), (32.65H, side chain CH 2 ). For the quantitative 1 H NMR analysis, the peaks at 8.02 (1.76H), 5.32 (3.35H), 4.68 (0.50H) were used. P4: 1 H NMR (600 MHz, CDCl 3 ), δ (ppm): 8.08 (3.78H, H at the 1,4-substituted benzene ring), 7.22 (solvent and H at the triazole ring), (1.01H, p-arh to ether), (2.00H, o- ArH to ether), 5.29 (3.57H, COOCH 2 -Ar), 5.04 (0.95H, OH), 4.76 (0.95H, H at the bridging C), 4.66 (0.29H, Ar-CH 2 OH), 4.43 (1.97H, COOCH 2 in the side chain), 4.29 (2.05H, CH 2 O-Ar in the side chain), 3.92 (2.00H, CH 2 linked to N in the triazole ring), 2.68 (1.99H, CH 2 linked to C in the triazole ring), (33.72H, side chain CH 2 ). For the quantitative 1 H NMR analysis, the peaks at 8.08 (3.78H), 5.29 (3.57H), 4.66 (0.29H) were used. 3

4 Scheme S1. The chemical structures of polyester P1 with different chain ends. Here we use polyester P1 as an example to illustrate the determination of the molecular weights of the polyesters by end-groups estimation. For the 1 H NMR spectrum of P1 (see Figure 4), I k, I k, I m represent the integral values of the resonances corresponding to k (4.67), k (5.29) and m (7.73), respectively. Since (I k + I k )/4 >I m /2, we can deduce that on average, there are coexisted polyesters with structure A as well as B, which are shown in Scheme S1. According to the following equations (1), (2), (3), we can calculate the number-average molecular weight of P1. (4n 2) x+ 4ny 2x+ 4y = I I k ' k (1) 2nx + 2ny 4nx + 4ny + 4y = I k I m + I k ' (2) x + y = 1 (3) where n is the number of repeating units, x and y are the ratios of polyesters with structure A and B, respectively. Similar calculation can be applied to P2-P4. 4

5 Diffusion Coefficient of Polymers in Solution: Typically, for a monodispersed polymer system, there is a relationship between the diffusion coefficient and the weight-average molecular weights: 1,2 α D= AM (4) where A is a constant for a given polymer system, α a negative constant. The equation leads to equation 5: lg D=α lg M + lg A (5) Thus, for a given polymer system, with the plot of different diffusion coefficient measured from different molecular weights, one can obtain the constant A and α, or vice versa, with the known constants, by the measured diffusion coefficient, one can get the molecular weights of a polymer. 5

6 Tables and Figures Table S1. Molar refraction increments R j of different polymer substructures at Sodium D line (589 nm). a No. Group R j No. Group R j 1 b H ar p-c 6 H 4 (arom) CH C 6 H 3 (arom) CH c Triazole 25 4 CO d C O (ether) d,e C 10 H 8 (naphthalene) b Br d,e C 4 H 4 S (thiophene) a Data from the reference 3 unless specially mentioned. b Data from the reference 4. c The molar refraction increment value of triazolecannot be found in any reference, and the value of benzene was used instead. d Data from the website: e Subtract the sum value of two atoms of H ar when they are used. 6

7 Chemical Shift (ppm) Figure S1. 13 C NMR spectrum of fullerene diol monomer 4. 7

8 Figure S2. 1 H DOSY NMR spectrum of fullerene polyester P2. Figure S3. 1 H DOSY NMR spectrum of fullerene polyester P3. 8

9 Figure S4. 1 H DOSY NMR spectrum of fullerene polyester P4. 9

10 P Chemical Shift (ppm) Figure S5. Quantitative 1 H NMR spectrum of fullerene polyester P2. P Chemical Shift (ppm) Figure S6. Quantitative 1 H NMR spectrum of fullerene polyester P3. 10

11 P Chemical Shift (ppm) Figure S7. Quantitative 1 H NMR spectrum of fullerene polyester P4. 11

12 -9.2 Monomer -9.4 lg D -9.6 P1 P3 P4 P lg M Figure S8. The diffusion coefficients of fullerene monomer 4 and fullerene polyesters P1-P4 vs. their corresponding molecular weights. 12

13 P1 P2 P3 P4 Endo Heat Flow (W/g) Temperature ( C) Figure S9. DSC curves of fullerene polyesters P1-P4 at heating and cooling rate of 10 C/min. 13

14 Absorbance (a.u.) monomer P1 P2 P3 P Wavelength (nm) Figure S10. UV-Vis spectra of monomer and P1-P4 polyesters (C 60 concentration normalized to 0.10 mg/ml). 14

15 Figure S11. (a) AFM image of the film of P1 on a fused silica substrate; (b) The height profile at the corresponding cross-section in (a). References 1. Chen, A.; Wu, D.; Johnson, C. S. J. Am. Chem. Soc. 1995, 117, Li, W.; Chung, H.; Daeffler, C.; Johnson, J. A.; Grubbs, R. H. Macromolecules 2012, 45, Groh, W.; Zimmermann, A. Macromolecules 1991, 24, vankrevelen, D. W. In Properties of Polymers, 4th ed.; Elsevier: Amsterdam, 2009; pp