Overview of triblock polyesters (TBPEs) characterization data^a.

Sample	M n,NMR b (kg mol−1)	M n,SEC c (kg mol−1) [Đ]	f hard d	DPPE–DPPDL–DPPEe	N tot f	T g1, Tg2g (°C)	OTWi (°C)
TBPE-1	8–27–8	45.0 [1.05]	0.40	35–164–35	653	−49, 105	173
TBPE-2	13–34–13	61.3 [1.10]	0.44	52–209–52	890	−50, 122	192
TBPE-3	14–45–14	75.0 [1.07]	0.41	59–269–59	1088	−50, 123	193
TBPE-4	17–46–17	85.3 [1.06]	0.44	73–291–73	1238	−50, 126	195
TBPE-5	20–65–20	102 [1.09]	0.40	79–371–79	1480	−51, 138	206
TBPE-6	13–69–13	106 [1.06]	0.29	58–455–58	1538	−42, 146h	188
TBPE-7	10–68–10	89.8 [1.05]	0.24	42–406–42	1303	−41, 136h	177
TBPE-8	10–93–10	105 [1.07]	0.19	38–506–38	1524	−44, 132h	176
TBPE-9	5–91–5	108 [1.08]	0.12	24–565–24	1567	−44, 123h	167

^aReaction conditions: = 1.7 M in toluene, catalyst = [LZnMg(C₆F₅)₂] (see ESI for structure), chain transfer agent = 1,4-BDM, T = 80 °C, see Table S1 for more reaction data.

^bEstimated from the ¹H NMR spectra of the purified polymer by integration of the aromatic 1,4-BDM resonance (7.34 ppm) against those of PE (7.58 ppm) and PDL (4.85 ppm).

^cEstimated by SEC with THF eluent, RI and UV detector, calibrated using PS standards.

^dVolume fraction of hard block determined from the wt% hard block using eqn (S1) and previously reported room temperature densities for PE = 1.04 g cm⁻³ and PDL = 0.97 g cm⁻³.^21,54 The wt% hard was calculated from the ¹H NMR spectra of the purified polymers by comparison of the relative integrals (±3% error) of an aromatic resonance in PE (7.58 ppm) and the –CH resonance in PDL (4.85 ppm).

^eDegree of polymerization for PE–PDL–PE blocks calculated from M_n,SEC of the overall triblock, the wt% hard block from ¹H NMR spectroscopy and the mass of repeat unit for PE (246.3 g mol⁻¹) and PDL (170.3 g mol⁻¹).

^fTotal degree of polymerization (eqn (S2)) calculated from the sum of M_n of the component blocks and using a reference segment volume of 0.118 nm³.

^gEstimated by DSC (10 °C min⁻¹ heating rate), second heating curve.

^hDetermined from the maximum in the peak of tan(δ) by DMTA (1 Hz, 5 °C min⁻¹ heating rate).

ⁱOperating temperature window (OTW) calculated as the difference between upper and lower T_g values.