Supporting information

Poly(e-caprolactone) Networks with Tunable Thermoresponsive Shape Memory via a Facile Photo-initiated Thiol-Ene Pathway

Thuy Thu Truong1, Son Hong Thai1, Ha Tran Nguyen1,2, Tam Huu Nguyen,1 Le-Thu T. Nguyen1,*

1Faculty of Materials Technology, Ho Chi Minh city University of Technology, Vietnam National University (VNU–HCM), 268 Ly Thuong Kiet, District 10, Ho Chi Minh City, Vietnam.

2Materials Technology Key Laboratory (Mtlab), Ho Chi Minh City University of Technology, Vietnam National University (VNU–HCM), 268 Ly Thuong Kiet, District 10, Ho Chi Minh City, Vietnam.

* Corresponding author. E–mail address:

Scheme S1. Synthesis of allyl-functionalized PCLs from PCL-diols by cationic polymerization of allyl glycidyl ether via the activated monomer mechanism.

Figure S1. 1H NMR spectrum in CDCl3 of an allyl-functionalized PCL (containing in average 4 allyl groups per polymer chain). The signal denoted as i’ corresponds to the protons of –(R’)–AGE–CH2(R)– groups of CL units next to AGE units.

Figure S2. Crosslinked fraction of the networks formed via the reaction between APCLs and multi-thiols as a function of irradiation time at varying DMPA contents and molar thiol-to-ene ratios.

Figure S3. Transmission FTIR spectra of (a) tetrathiol, (b) APCL1 (b), and an equimolar thiol-to-ene mixture of APCL1 and tetrathiol with 1.5 wt% of DMPA (c) before and (d) after 30 min of UV-irradiation.

Figure S4. Demonstration of the partial integration at 30 oC of the melting peak (30 oC ∆Hmelt.PCL part, Table 2) of the PCL switching segments.

Figure S5. DMTA (storage modulus) curves of networks prepared via the thiol–ene reactions between allyl-functionalized PCLs and multi-thiols. The curve numbering corresponds to the network entries in Table 1-3.

Figure S6. Shape recovery ratio (Rr) as a function of time at 50 oC (left) and as a function of temperature (right) for three cycles of PCL networks 1-7.

Figure S7. Shape recovery ratio (Rr) as a function of time at 30 oC for three cycles of PCL network 8.

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