NPG Asia Materials. Supporting information: Intrinsic self-healing polymers with high E-modulus based on dynamic reversible urea bonds

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1 NPG Asia Materials Supporting information: Intrinsic self-healing polymers with high E-modulus based on dynamic reversible urea bonds By S. Zechel, R. Geitner, M. Abend, M. Siegmann, M. Enke, N. Kuhl, M. Klein, J. Vitz, S. Gräfe, B. Dietzek, M. Schmitt, J. Popp, U. S. Schubert,* M. D. Hager* Scratch healing experiments NMR-spectra SEC curves DSC curves TGA curves Rheology measurements Mechanical properties IR and Raman spectra (measured and calculated) S2 S5 S7 S8 S12 S14 S23 S29 S1

2 Scratch healing experiments: a b c d e f g h i j k l 340 µm Figure S1: Self-healing studies of P1. a) Film, b) first scratch, c) first healing after 90 minutes at 90 C, d) second scratch, e) second healing after 60 minutes at 90 C, f) third scratch, g) third healing after 20 hours at 80 C, h) fourth scratch, i) fourth healing after 20 hours at 80 C, j) fifth scratch, k) partial healing after 20 hours at 70 C and l) partial healing after 40 hours at 70 C. S2

3 a b c d e f g h i j k l 340 µm Figure S2: Self-healing studies of P2. a) First scratch, b) first healing after 20 hours at 100 C, c) second scratch, d) second healing after 20 hours at 100 C, e) third scratch, f) third healing after 20 hours at 90 C, g) fourth scratch, h) fourth healing after 20 hours at 90 C, i) film, j) first scratch at the new position, k) partial healing after 20 hours at 80 C and l) partial healing after 40 hours at 80 C. S3

4 a b c d e 340 µm Figure S3: Self-healing studies of P3. a) Film, b) scratch, c) no healing after 20 hours at 100 C, d) no healing after 40 hours at 100 C and e) no healing after 60 hours at 100 C. S4

5 NMR spectra: δ [ppm] δ [ppm] Figure S4: 1 H (top) and 13 C (bottom) NMR spectra of compound 1 in CDCl 3. S5

6 δ [ppm] δ [ppm] Figure S5: 1 H (top) and 13 C (bottom) NMR spectra of compound 2 in CDCl 3. S6

7 SEC curves: Normalized RI signal intensity Elution volume [ml] Figure S6: SEC curves of P1 after heating for 48 hours in aniline at 100 C. S7

8 DSC curves: 6 4 DSC [mw/mg] Temperature [ C] Figure S7: DSC curve of compound 1. 1 st heating run (solid black line). S8

9 0.8 DSC [mw/mg] Temperature [ C] Figure S8: DSC curve of P1. 2 nd heating run (solid black line). S9

10 0.6 DSC [mw/mg] Temperature [ C] Figure S9: DSC curve of P2. 2 nd heating run (solid black line). S10

11 1.0 DSC [mw/mg] Temperature [ C] Figure S10: DSC curve of P3. 2 nd heating run (solid black line). S11

12 TGA curves: Mass loss [%] Temperature [ C] Figure S11: TGA curve of P Mass loss [%] Temperature [ C] Figure S12: TGA curve of P2. S12

13 Mass loss [%] Temperature [ C] Figure S13: TGA curve of P3. S13

14 Rheology measurements: G and G [Pa] tan d Temperature [ C] Figure S14: Temperature-dependent rheology measurement of P1 (Gˈ: Solid red line, Gˈˈ: Solid black line and tan δ solid blue line). S14

15 G and G [Pa] tan d Temperature [ C] Figure S15: Temperature-dependent rheology measurement of P2 (Gˈ: Solid red line, Gˈˈ: Solid black line and tan δ solid blue line). S15

16 6x10 7 5x10 7 G and G [Pa] 4x10 7 3x10 7 2x10 7 1x Frequency [Hz] 10 8 G and G [Pa] Frequency [Hz] Figure S16: Frequency-dependent rheology measurement of P1 at 80 C (Gˈ: Solid black line and Gˈˈ solid red line; Top: Linear plot and bottom: double logarithmic plot). S16

17 8x10 6 7x10 6 G and G [Pa] 6x10 6 5x10 6 4x10 6 3x10 6 2x10 6 1x Frequency [Hz] 10 7 G and G [Pa] Frequency [Hz] Figure S17: Frequency-dependent rheology measurement of P1 at 100 C (Gˈ: Solid black line and Gˈˈ solid red line; Top: Linear plot and bottom: double logarithmic plot). S17

18 1.8x x x10 6 G and G [Pa] 1.2x x x x x x Frequency [Hz] 10 6 G and G [Pa] Frequency [Hz] Figure S18: Frequency-dependent rheology measurement of P1 at 120 C (Gˈ: Solid black line and Gˈˈ solid red line; Top: Linear plot and bottom: double logarithmic plot). S18

19 1.2x x10 7 G and G [Pa] 8.0x x x x Frequency [Hz] 10 7 G and G [Pa] Frequency [Hz] Figure S19: Frequency-dependent rheology measurement of P2 at 80 C (Gˈ: Solid black line and Gˈˈ solid red line; Top: Linear plot and bottom: double logarithmic plot). S19

20 2.5x x10 6 G and G [Pa] 1.5x x x Frequency [Hz] 10 7 G and G [Pa] Frequency [Hz] Figure S20: Frequency-dependent rheology measurement of P2 at 100 C (Gˈ: Solid black line and Gˈˈ solid red line; Top: Linear plot and bottom: double logarithmic plot). S20

21 1.4x x10 6 G and G [Pa] 1.0x x x x x Frequency [Hz] 10 6 G and G [Pa] Frequency [Hz] Figure S21: Frequency-dependent rheology measurement of P2 at 120 C (Gˈ: Solid black line and Gˈˈ solid red line; Top: Linear plot and bottom: double logarithmic plot). S21

22 Table S1: Summary of the crossover points of Gˈ and Gˈˈ. Temperature [ C] Crossover frequency [Hz] P1 P S22

23 Mechanical properties: Figure S22: Picture of the tested dog bone specimens of P2. Original sample (top), cut sample (middle) and healed sample (bottom; change in color is presumably based on the thermal degradation of the initiator; a degradation of the polymer network can be excluded by Raman measurements). S23

24 a) Stress [MPa] Strain [%] b) Stress [MPa] Strain [%] S24

25 c) 10 8 Stress [MPa] Strain [%] Figure S23: Results of the tensile tests of P1. a) Original sample, b) sample heated to 100 C during measurement and c) healed sample. S25

26 a) Stress [MPa] Strain [%] b) 7 6 Stress [MPa] Strain [%] Figure S24: Results of the tensile tests of P2. a) Original sample and b) healed sample. S26

27 a) Stress [MPa] Strain [%] b) 4 3 Stress [MPa] Strain [%] Figure S25: Results of the tensile tests of P3. a) Original sample and b) healed sample. S27

28 a) 15 Stress [MPa] Strain [%] b) Stress [MPa] Strain [%] Figure S26: Results of the tensile tests of P4. a) Original sample and b) sample heated to 100 C during measurement. S28

29 IR and Raman spectra: Normalized Raman intensity Relative wavenumber [cm -1 ] Figure S27: Raman spectrum of hexyl isocyanate at 25 C recorded using a laser wavelength of 1064 nm. S29

30 Normalized Raman intensity Relative wavenumber [cm -1 ] Figure S28: Raman spectrum of N,N'-di-tert-butylethylenediamine at 25 C recorded using a laser wavelength of 1064 nm. S30

31 1.0 Normalized Raman intensity Relative wavenumber [cm -1 ] Figure S29: Raman spectrum of BMA at 25 C recorded using a laser wavelength of 1064 nm. S31

32 1.0 Normalized Raman intensity Relative wavenumber [cm -1 ] Figure S30: Raman spectrum of PBMA at 25 C recorded using a laser wavelength of 1064 nm. S32

33 1.0 Normalized Raman intensity Relative wavenumber [cm -1 ] Figure S31: Raman spectrum of benzoin methyl ether at 25 C recorded using a laser wavelength of 1064 nm. S33

34 Normalized Raman intensity Relative wavenumber [cm -1 ] Figure S32: Raman spectrum of compound 1 at 25 C recorded using a laser wavelength of 1064 nm. S34

35 Normalized Raman intensity Relative wavenumber [cm -1 ] Figure S33: Raman spectrum of compound 2 at 25 C recorded using a laser wavelength of 1064 nm. S35

36 6 Normalized Raman intensity Relative wavenumber [cm -1 ] Figure S34: Raman spectrum of polymer P1 at 25 C recorded using a laser wavelength of 1064 nm. S36

37 0.10 Normalized Raman intensity Relative wavenumber [cm -1 ] Figure S35: Raman spectrum of polymer P2 at 25 C recorded using a laser wavelength of 1064 nm. S37

38 Normalized IR absorbance Wavenumber [cm -1 ] Figure S36: Baseline corrected FT-IR spectrum of polymer P2 (on NaCl crystal) at 30 C. S38

39 16 Normalized IR absorbance Wavenumber [cm -1 ] Figure S37: Baseline corrected FT-IR spectrum of polymer P2 (on NaCl crystal) at 100 C. S39

40 1.0 Normalized IR absorbance Wavenumber [cm -1 ] Figure S38: Baseline corrected FT-IR spectrum of polymer P2 (on NaCl crystal) at 150 C. S40

41 1.00 Normalized peak area (C=C) x(bma) Figure S39: Determination of the detection limit of non-polymerized BMA in PBMA: The dependency of the normalized peak area of the C=C-vibration at 1641 cm -1 of BMA from the mole fraction of BMA in PBMA is depicted in order to show the suitability of this method for the determination of the residual BMA in PBMA (red solid dots) as well as pure BMA (black) and pure PBMA (blue). The pink dot represents a mixture of PBMA, BMA and 1 showing that the C=C-vibration is not suitable to monitor the polymerization if an urea is present. S41

42 0.35 Normalized peak area (C-H) x(bma) Figure S40: Determination of the detection limit of non-polymerized BMA in PBMA: The dependency of the normalized peak area of the C-H-stretching vibration at 3107 cm -1 of BMA from the mole fraction of BMA in PBMA is depicted in order to show the suitability of this method for the determination of the residual BMA in PBMA (red solid dots) as well as pure BMA (black) and pure PBMA (blue). The pink dot represents a mixture of PBMA, BMA and 1 showing that the C-H-stretching vibration is suitable to monitor the polymerization if an urea is present. S42

43 30 Normalized mean peak area (C=O) x(1) Figure S41: Determination of the detection limit of compound 1 in PBMA: The dependency of the normalized peak area of the C=O-vibration at 1631 cm -1 of 1 from the mole fraction of 1 in PBMA is depicted in order to show the suitability of this method for the determination of the urea content in PBMA (red solid dots) as well as pure PBMA (blue). Furthermore, the obtained values for polymers P1 and P2 are inserted (black). S43

44 Normalized Raman intensity Relative wavenumber [cm -1 ] Figure S42: Calculated Raman spectrum of hexyl isocyanate. 1.0 Normalized Raman intensity Relative wavenumber [cm -1 ] Figure S43: Calculated Raman spectrum of N,N'-di-tert-butylethylenediamine. S44

45 1.0 Normalized Raman intensity Relative wavenumber [cm -1 ] Figure S44: Calculated Raman spectrum of 2-isocyanatoethyl methacrylate. Normalized Raman intensity Relative wavenumber [cm -1 ] Figure S45: Calculated Raman spectrum of compound 1. S45

46 1.0 Normalized IR intensity Wavenumber [cm -1 ] Figure S46: Calculated IR spectrum of compound Normalized Raman intensity Relative wavenumber [cm -1 ] Figure S47: Calculated Raman spectrum of compound 2. S46