S1.2. Synthesis details of HBPSi-R
The synthesis of hyperbranched polysiloxanes (HBPSi-R) is
straightforward using A2+B3transesterification co-polymerization,[1-5] where
R represents their terminal groups of amino (HBPSi-NH2),
epoxy (HBPSi-EP), vinyl group (HBPSi-V). Siloxane monomers including
KH-550, A-1871 and A-151 were used as the B3 monomers with similar
molecular structure but different functional groups, and a simple diol
(PDO) was used as the B2 reactant. The feed ratio
follows in accordance from the Florey-Carothers law to avoid
over-crosslinking. Briefly, 0.16 mol of siloxanes and 0.35 mol of PDO
were put into a three-necked flask equipped with a mechanical stirrer, a
N2 inlet and a thermometer. The mixtures were heated
from 120 °C to 180 °C at a heating rate of 5 °C h-1,
then maintain stirring until no more distillate generated.
Theoretically, the distillates from all three reactions should be the
same ethanol with low-boiling point, which could be consistently
separated from the reaction system by a condenser to drive the
polymerization proceeded. The distillates were collected for IR
detection. Taking a rough purification by pressure-reduce drying to
remove the small molecules from reaction, the liquid products can be
final obtained (Figure 1 ).