S1 Supporting information Functional polyesters with pendant double bonds prepared by coordination-insertion and cationic ring-opening copolymerizations of ε-caprolactone with renewable Tulipalin A Martin Danko 1,, Malgorzata Basko 2,, *, Slávka Ďurkáčová 1, Andrzej Duda 2, and Jaroslav Mosnáček 1, * 1 Polymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 841 45 Bratislava, Slovakia; e- mail: martin.danko@savba.sk (M. Danko), jaroslav.mosnacek@savba.sk (J. Mosnacek) 2 Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland; e-mail: baskomeg@cbmm.lodz.pl (M. Basko) equally contributed authors; deceased April 2016; * corresponding authors Table of content: Materials Analytical methods Figure SI1: 1 H NMR spectra (CDCl 3 ) of reaction mixture of MBL/Al(OiPr) 3 after 3 hours of reaction at 20 C. Additional description of NMR spectra. Figure SI2: A) 1 H and B) 13 C NMR spectra (CDCl 3 ) of P(MBL-co-CL) precipitated polymer with 7 mol% MBL content (Table 1 9A). Figure SI3: FTIR spectra of of P(MBL-co-CL) with 25 mol% MBL content prepared by ROP using MBL/CL/Al(OiPr) 3 with molar ratio 9/0.9/0.002 after 48 hours at 0 C and after precipitation to MeOH (Table 1 14A). Figure SI4: The GPC traces of purified products obtained in cationic ROP of CL and MBL in the presence of isopropanol as initiator and TfA as catalyst conducted in two stages. (Table 2, Entry 2C). Copolymer B (M n (GPC) = 7.73 kg mol -1 ) obtained by chain extension from precursor A (M n (GPC) = 3.28 kg mol -1 ).
S2 Figure SI5: 1 H NMR spectra of purified product derived from the copolymerization of CL and MBL in the presence of isopropanol as initiator and DPP as catalyst, in CDCl 3 (top) and DMSO-d 6 (bottom), (F BML = 0.11). The asterisk indicates region characteristic for -CH 2 - groups formed by vinyl addition. Figure SI6: 1 H NMR spectra of purified product derived from the copolymerization of CL and MBL in the presence of ethylene glycol as initiator and DPP as catalyst. Figure SI7: 1 H NMR spectra of purified product derived from the copolymerization of CL and MBL in the presence of di(trimetylol)propane as initiator and DPP as catalyst. Figure SI8: MALDI-TOF spectrum of P(MBL-co-CL) copolymer prepared with multihydroxyl initiators and DPP as catalyst. Figure SI9: GPC traces and UV-Vis spectra of purified product derivate from AIBN/thermos-initiated thiolene post-functionalization of P(MBL-co-CL) with 3 mol% of tio-linkers with fluorescent benzotioxanthene fluorophore. Figure SI10: A) 1 H NMR spectra of purified product derived from the photo-initiated tiolene postfunctionalization of P(MBL-co-CL) copolyester with 3 mol% of functional methylene double bonds an B) enlarged chemical shift region with comparison with original unmodified P(MBL-co-CL) copolyester.
S3 Materials. During the first distillation, the metallic initiator aluminum tris(isopropoxide) (Al(O i Pr) 3, 98 %, Sigma- Aldrich) was distilled under reduced pressure into a small flask, and during the second distillation it was distilled into small glass bubbles and sealed in a vacuum. A trimer of Al(O i Pr) 3 (A 3 ) was obtained as described elsewhere. 41 Tin octoate (Sn(Oct) 2, 98 %, Sigma-Aldrich) was twice distilled under reduced pressure and was stored in a Schlenk flask in a vacuum. ε-caprolactone (CL, 98 %, Sigma- Aldrich) and α-methylene-γ-butyrolactone (MBL, 98 %, TCI Europe) were stirred over CaH 2 and were transferred to breakseals by distillation under reduced pressure and were sealed in a vacuum. Trifluoromethanesulfonic acid (TfA, triflic acid; Sigma-Aldrich) was purified by distillation. Diphenyl phosphate (DPP) (Sigma-Aldrich) was used as received. Propanol and butanol (98 %, anhydrous, Sigma-Aldrich) were dried with sodium wires (a few molar percent), were distilled and were stored in an ampoule in a vacuum. Ethylene glycol (99.8 %, Sigma-Aldrich), di(trimethylolpropane) (DTMP, 97 %, Sigma-Aldrich) and N-acetyl cysteine ( 99 %, Sigma-Aldrich) were used as received. 2-(2- Mercaptoethyl)thioxantheno[2,1,9-dej]-isoquinoline-1,3-dione (BTXI-SH) was synthetized from benzothioxanthone 3,4-dicarboxylic anhydride (BTXA) and cysteamine hydrochloride (98 %, Sigma- Aldrich) in dimethylformamide (DMF) as a solvent. Free amine was reacted first with 1 M NaOH in DMF solution followed by addition of BTXA. Evolved water that formed during condensation was distilled off by refluxing with DMF over 16 hours. After evaporation of the remaining DMF, the crude product was chromatographed on short silica gel column availing lower solubility of BTXA in chloroform used as eluent. 2,2 -Azobis(2-methylpropionitrile) (AIBN, 98 % Sigma-Aldrich) and 2,2- dimethoxy-2-phenylacetophenone (DMPA, 99 %, Sigma-Aldrich) were used as received. Tetrahydrofuran (THF, 99 %, POCh, Gliwice, Poland) was kept for several days over KOH pellets, was filtered off and was refluxed and distilled over sodium wires, then was degassed and distributed to an ampoule and was stored over small pieces of sodium. Toluene (analytical grade, Central Chem, Slovakia) was refluxed over sodium wires and was distilled into a round-bottomed flask equipped with freshly prepared sodium wires and was then degassed and distributed to an ampoule and was stored
S4 over small pieces of sodium. Dichloromethane (DCM, 99 %, POCh, Gliwice, Poland), after preliminary drying with CaCl 2 for 24 h, was refluxed in the presence of CaH 2 for 6 h and was distilled off. All other commercial solvents were of purity per analyses and were used as received. Analytical Methods NMR spectroscopy. Monomer conversion and the content of co-monomers in synthesized polyesters were determined by 1 H NMR using a 400 MHz VNMRS Varian NMR spectrometer equipped with a 5- mm 1H-19F/15N-31P PFG AutoX DB NB probe at 25 C or on Bruker DRX500 instrument operating at 500 MHz using CDCl 3 or d 6 -DMSO as solvents. 13 C NMR was measured using the same instruments operated at 100 MHz or 125 MHz. Gel permeation chromatography. The molar mass and dispersity of the polymers were determined using gel permeation chromatography (GPC) on three systems. The GPC of copolyesters prepared by coordination-insertion ROP was performed using an Agilent Technology 1260 Infinity system that consisted of a degasser, an autosampler, and a thermostatic box for columns and was equipped with a PSS SDV 10 µm precolumn and three PPS SDV 5-µm columns (d = 8 mm, l = 300 mm; 100 Å + 1000 Å + 10 5 Å) thermostated at 30 C. A refractive index detector with THF as an eluent at a flow rate of 1.0 ml min -1 was used. Copolyesters prepared by cationic ROP were characterized using an Agilent 1100 system consisting of a degasser, an autosampler, a thermostatic box for columns and an Optilab Rex differential refractometer. Two PLGel 5-mm MIXED-C columns thermostated at 27 C were used for separation. DCM was used as a mobile phase at a flow rate of 0.8 ml min -1. The ASTRA 4.90.07 software package (Wyatt Technology Corporation) was used for data collection and processing. The GPC of PMBL VA formed through vinyl addition was performed using a system consisting of a Shimadzu LC-20AT pump, PSS GRAM 10 µm precolumn and three PPS GRAM 5-µm columns (d = 8 mm, l = 300 mm; 100 Å + 1000 Å + 10 5 Å) as well as a refractive index detector Shimadzu RID-10A with dimethylacetamide (DMAc) / lithium bromide (LiBr, 0.1 M) as an eluent at a flow rate of 1.0
S5 ml min -1. The same system was also used for GPC of fluorescently labeled polyesters prepared by post-functionalization of vinyl groups of P(MBL-co-CL) employing fluorescence detector Shimadzu RF-10A XL. The final system, used for polyesters prepared by cationic polymerization, was equipped with a Wyatt Optilab Rex interferometric refractometer as a detector. Dichloromethane was used as an eluent at a flow rate of 0.8 ml min -1 at room temperature. Molar masses were determined using polystyrene standards and anisole as an internal standard in all systems. Matrix-assisted laser desorption/ionization time-of-flight (MALDI TOF). Measurements were performed with the Voyager Elite (PerSeptive Biosystems, Framingham, MA) time-of-flight instrument equipped with a pulsed N 2 laser (337 nm) and time-delayed extraction source. An accelerating voltage of 20 kv was used. Dithranol was used as a matrix, CF 3 COO - K + was used as a cationating agent and THF was used as a solvent. Differential scanning calorimetry (DSC). DSC analysis was performed on a Mettler-Toledo DSC 821 e differential scanning calorimeter under a nitrogen atmosphere at a heating rate of 10 C min -1. Indium was used for the calibration of temperature and heat of fusion. The glass transition temperatures were determined from midpoints in the second heating using the STARe software of Mettler-Toledo. Thermogravimetric analysis (TGA). TGA of polymers was performed using a TGA Perkin-Elmer instrument at a heating rate of 20 C/min, from 0 to 600 C, under a nitrogen purge. FTIR and UV-Vis spectroscopy. FTIR spectra were obtained on a Nicolet 8700 spectrophotometer (Thermo, USA) in ATR mode using Ge crystals. UV-Vis spectra were obtained on a Shimadzu 1650PC spectrophotometer using a 1 1 cm quartz cuvette.
Figure SI1: S6
S7 Additional description of NMR spectra and assignments of signals from simple 1 H and 13 C NMR. Next, to MBL proton triplet signal 3, an additional proton triplet signal a appeared. Integrals of signals 3 and a are the same for all prepared copolyesters, and thus they could be attributed to oxomethylene protons of adjacent MBL and CL units in MBL-CL and/or CL-MBL hetero-sequences. In addition, a proton signal at 4.29 ppm (unlike the signal for monomeric triplet centered at 4.37 ppm) appeared in copolyesters with higher MBL content, and thus could be assigned to oxo-methylene protons in MBL-MBL homo-sequences. This observation was also confirmed by the appearance of signals 3 and a in the 13 C NMR in the region of 62 to 65 ppm attributed to carbons from oxomethylene moieties (Figure 2 in the main text). The similar intensity (visually, the integration was not performed) of both signals could again suggest their mutual relationship, similar to proton signals 3 and a in 1 H NMR. Moreover, a small signal 3 also appeared in this region in 13 C NMR for copolyesters with higher contents of MBL units. The carbonyl group of the CL units exhibited two signals, which can be attributed to homo- CL-CL and hetero- MBL-CL sequences at 173.5 and 173.3 ppm, respectively. Additionally, in the carbonyl region, a signal at 166.5 ppm from carbon of the MBL unit in the CL-MBL hetero-sequence was for copolyesters with higher MBL content accompanied another side signal at 166.3 ppm, which could be attributed to the MBL-MBL homo-sequence (Figure 2 in the main text). Figure S2 shows copolyester with lower MBL content where signals from expected MBL-MBL homo-sequences were not visible either in 1 H or 13 C NMR spectra.
Figure SI2: S8
S9 Figure SI3: Figure SI4:
Figure SI5: S10
S11 Figure SI6: Figure SI7:
S12 Figure SI8: Figure SI9:
Figure SI10: S13