Supporting Information. Stability of Star-shaped RAFT Polystyrenes under Mechanical and Thermal Stress

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1 Eletroni Supplementary aterial (ESI) for Polymer Chemistry. This journal is The Royal Soiety of Chemistry 214 Supporting Information for Stability of Star-shaped RAFT Polystyrenes under ehanial and Thermal Stress Ozan Altintas, 1,2,3 ahdi Abbasi, 2 Kamran Riazi, 2 Anja S. Goldman, 1,3 Nio Dingenouts, 2 anfred Wilhelm 2 * and Christopher Barner-Koollik 1,3 * 1 Preparative aromoleular Chemistry, Institut für Tehnishe Chemie und Polymerhemie, Karlsruhe Institute of Tehnology (KIT), Engesserstr. 18, Karlsruhe, Germany. 2 Polymeri aterials, Institut für Tehnishe Chemie und Polymerhemie, Karlsruhe Institute of Tehnology (KIT), Engesserstr. 18, Karlsruhe, Germany. 3 Institut für Biologishe Grenzflähen, Karlsruhe Institute of Tehnology (KIT), Hermann-von- Helmholtz Platz 1, Eggenstein-Leopoldshafen, Germany. *To hom orrespondene should be addressed manfred.ilhelm@kit.edu hristopher.barner-koollik@kit.edu S1

2 Sheme S1. Synthesis of star polymers via the RAFT proess folloing a R- or Z-group approah. Note that the Z-group approah is generally preferred being unique to the RAFT proess as it avoids the formation star-star oupling, as the ore never arries the radial funtion. S2

3 Figure S1. SEC traes of trithioarbonate ore-funtional 3-arm star-shaped polystyrene 3 and 4- arm star-shaped polystyrene 4 in THF employed in the degradation and extrusion experiments prior to any stress (ALLS detetion) determined via viso detetion. S3

4 Figure S2. Weight-average moleular eight, (t), as a funtion of time at variable temperatures for the degradation of trithioarbonate ore funtional 3-arm star polystyrene 3. The satter in the starting moleular eights is due their individual SEC reanalysis for eah temperature run (featuring an error of lose to 12%). The time starts at 1 s as this period represents the sampling time of the experiment. S4

5 Figure S3. Weight-average moleular eight, (t), as a funtion of time at variable temperatures for the degradation of trithioarbonate ore funtional 4-arm star polystyrene 4. The satter in the starting moleular eights is due their individual SEC reanalysis for eah temperature run (featuring an error of lose to 12%). The time starts at 1 s as this period represents the sampling time of the experiment. S5

6 Figure S4. Arrhenius plots of the rate oeffiient for the leavage of Z-type RAFT based 3-arm star-shaped polystyrenes (3) and 4-arm star-shaped polystyrenes (4) based on n (filled symbols) and (open symbols) featuring trithioarbonate ore-funtionalities in an argon atmosphere. S6

7 Figure S5. SEC trae of the trithioarbonate ore-funtional 3-arm star-shaped polystyrene (3) before and after 8 hours applying osillatory shear ith /2 =.5 Hz and γ =.25 strain amplitude at 18 C in a nitrogen atmosphere via DRI detetor. S7

8 Figure S6. SEC trae of the trithioarbonate ore-funtional 4-arm star-shaped polystyrene (4) before and after applying osillatory shear ith /2 =.5 Hz and γ =.25 strain amplitude at 18 C in a nitrogen atmosphere. S8

9 Figure S7. Dynami frequeny seep test of star polystyrenes at the end of dynami time seep test after 8 hours (refer to Figure 8 in the main text) in rheometer. S9

10 Appendix I Weight-average moleular eight dependeny of zero shear visosity during the leavage proess Zero shear visosity and eight average moleular eight of designed star polystyrenes sho an exponential time dependene during the ore leavage proess in the folloing form: kd, () t t e (I1) (I2) D 1 D1 () t e k t k t e Negleting the effet of arm degradation, seond part in the right hand of Eq. I2, and rearrangement of these equations result in: t () kd, t e (I3) () t D e, k t (I4) A natural logarithm of both sides results: () t ln k d, t (I5) () t ln, k t D (I6) Dividing Eq. (I6) to Eq. (I5) results in: () t () t k ln, D / ln kd, (I7) Consequently: () t () t, kd kd, (I8) S1

11 The poer la dependeny of the zero shear visosity, η, of the eight average moleular eight, k, and its poer exponent, α, is of signifiant importane for rheologial properties. The exponent α reads 3.4 for linear polymers above the ritial moleular eight, 3e. With respet to these riteria, a rearrangement of Eq. (I8) and analytial moleular eight derivative of zero shear visosity is developed: kd k d, () t, () t (I9) k () t D ()/ () kd, d t d t kd kd, 1 (I1) On the other hand: d () t d ln ( t) () t (I11) d ln ( t) d () t () t (I12) Combining the Eq. (I1) (I12) results in: d ln () t kd () t () t d ln () t kd, () t kd kd, 1 (I13) Rearrangement of Eq. (I13) results in: k D k d, ln () D () () () / d, d t k t t t d ln () t k () t (I14) Finally, inserting the Eq. (I8) in Eq. (I14) gives:, d ln () t kd () t () t () t / d ln ( t) kd, ( t) (I15), d ln () t kd () t () t d ln () t kd, () t () t (I16) S11