Supplementary Information

Contributions of Hard and Soft Blocks in the Rheology and Self-healing of Metal-Ligand-containing Block Copolymers

Ranjita K. Bose,a Marcel Enke,b,c Antonio M. Grande,a Stefan Zechel,b,c Felix H. Schacher,b,c

Martin D. Hager,b,c Santiago J. Garcia,a,* Ulrich S. Schubert,b,c Sybrand van der Zwaaga

a Novel Aerospace Materials, Department of Aerospace Engineering, Delft University of Technology, Kluyverweg 1, Delft 2629HS, Netherlands

b Laboratory for Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Humboldtstr. 10, 07743 Jena, Germany

c Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena, Philosophenweg 7, 07743 Jena, Germany

Table SI 1: Overview of the results of size exclusion chromatography (SEC) and thermal analysis of P1 to P4. All polymers have been described in literature.[S1]

Used

polymer Composition1 Used polymer

Hard vs. soft ratio

Mn

[g/mol]Mw

[g/mol] ᴆ Tg

[°C]Td

[°C]

P1a BA/L ‒ ‒ 11,700a 17,000 1.47 ‒48 364

P1 BA/L ‒ ‒ 14,800a 17,600 1.19 ‒30 366

P2 BA/L-b-PS-b-BA/L P1a 1:1 23,600a 31,300 1.33 20 362

P3 BA/L-b-PS-b-BA/L P1 1:2 21,600a 26,900 1.24 ‒8 365

P4 PS ‒ ‒ 6,400b 8,700 1.37 72 362

1 = PS: Polystyrene; BA: n-Butyl acrylate and L: ligand

a = Poly(methyl methacrylate) as SEC standard; b = Poly(styrene) as SEC standard

Table SI 2: Summary of the thermal analysis of MP1 to MP4. All polymers have been described in literature.[S1]

Metallo-

polymer

Used

Polymer

Hard vs.

soft ratio

Metal

salt

Tg

[°C]

Td

[°C]

MP1 P1 ‒ MnCl2 11 322

MP2 P2 1:1 MnCl2 25 354

MP3 P3 1:2 MnCl2 -5 376

MP4 P3 1:2 Ni(NO3)2 16 341

Table SI 3: Overview of the sample number and their number in the previous publication.[S1]

Sample numberSample number in the

previous paper[S1]

P1a P1

P1 P3

P2 P2

P3 P4

P4 P5

MP1 ‒

MP2 MP3

MP3 MP7

MP4 ‒

Figure SI 1: 1H NMR spectrum of P2 (CDCl3, 300 MHz).[S1]

Figure SI 2: 1H NMR spectrum of P3 (CDCl3, 300 MHz).[S1]

Figure SI 3: FT-IR spectra of P2.

Figure SI 4: FT-IR spectra of P3.

Figure SI 5: TGA curve of MP1.

Figure SI 6: TGA curve of MP2.

Figure SI 7: TGA curve of MP3.

Figure SI 8: TGA curve of MP4.

Figure SI 9: G’ and G” of all polymers at Tref = 100 °C

a)

b)

Figure SI 10: Rheological TTS of (a) P2 (backbone block copolymer of MP2) and (b) P3 (backbone block copolymer of MP3 and MP4).

a)

b)

Figure SI 11: SAXS data for (a) MP2, and (b) MP3.

Table SI 4: SAXS results of the metallopolymers MP1 to MP4.

Metallopolymer SAXS signal [2Θ in °] Domain size [nm]

MP1 ‒a ‒

MP2 0.38 23.2

MP3 0.34 26.1

MP4 ‒a ‒

a = No SAXS-reflex observed

References:

[S1] M. Enke, R. K. Bose, S. Bode, J. Vitz, F. H. Schacher, S. J. Garcia, S. van der Zwaag,

M. D. Hager and U. S. Schubert, Macromolecules, 2016, 49, 8418-8429.