Synthesis and characterization of isosorbide-based α,ω-dihydroxyethersulfone oligomers

Figures & data

Figure 1. Synthesis of α,ω-dihydroxy-ethersulfones oligomers.

Figure 2. Potential structures of produced PES.

Table 1. Calculated masses (including Na⁺ doping) of potential structures (cyclic C; linear La’, Lb, Lc).

n	3	4	5	6	7	8
C	1104.1	1464.5	1824.9	2185.2	2545.7	2906.1
La’	1122.1	1482.5	1842.9	2203.3	2563.7	2924.1
Lb	1250.1	1610.5	1970.9	2331.3	2691.7	3052.2
Lc	1358.1	1718.5	2087.9	2439.3	2799.7	3160.1

Table 2. Synthesis of PES with variation of IS excess at a concentration of 0.3 mol L⁻¹.

Poly.N°	Monomer CC (mol L^−1)	Excess of IS (%)	Yields (%)	ηinh^a (dL g^−1)	Calculated composition^b (MALDI–TOFMS) %				Mn^c (g mol^−1)	Ð = Mw/Mn^d	Tg (°C)^e
					C	La’	Lb	Lc
PES-1^*	0.30	0	97	0.65	100	0	0	0	–	–	245
PES-4	0.30	10	92	0.15	11	45	12	32	14 485	1.55	219
PES-5	0.30	20	94	0.11	18	39	36	6	10 225	1.39	220
PES-6	0.30	30	98	0.09	16	24	60	5	8 176	1.34	213

^a Measured at 20 °C with c = 2 g L⁻¹ in DMSO containing 2 vol% of TFA.

^b C, La’, Lb, Lc are 4 structures of poly(ethersulfone)s.

^c Average-molecular weight, determined by SEC (in DMF) with polystyrene standard.

^d Polydispersity index determined by SEC.

^e Measured with a heating rate of 10 °C min⁻¹ under argon flow of (50 mL min⁻¹).

^* PES1: reference reaction (0.3 mol L⁻¹; time: 12 h; temperature: 140 °C and solvent: DMSO/Toluene) Casarano et al. [1]

Figure 3. MALDI–TOF spectra of PES-4, PES-5 and PES-6 (0.3 mol L⁻¹).

Figure 4. Effect of the variation of IS excess in the end group structure of produced oligomers at a concentration of 0. 3 mol L⁻¹.

Figure 5. ¹H NMR spectra [3.5–8.1 ppm] of oligoethersulfones at 0.15 mol L⁻¹ [DMSO-D6, 500 MHz, 20 °C].

Table 3. Synthesis of PES with variation of IS excess and monomer concentration.

	Monomer CC (mol L^−1)	Excess of IS (%)	Yields (%)	ηinh^a (dL g^−1)	Calculated composition^b (MALDI–TOFMS) %				Mn^c (g mol^−1)	Ð = Mw/Mn^d	Tg (°C)^e
					C	La’	Lb	Lc
PES-2	0.15	0	96	0.27	100	0	0	0	–	–	237
PES-7	0.15	20	86	0.10	29	34	22	15	9682	1.45	211
PES-8	0.15	30	81	0.08	23	29	43	6	6500	1.33	196
PES-9	0.15	50	84	0.07	17	22	64	1	7560	1.24	185
PES-10	0.15	100	92	0.06	0	28	72	0	5640	1.21	189
PES-11	0.075	50	84	0.08	14	3	83	0	6 900	1.35	180
PES-12	0.075	100	91	0.06	4	2	94	0	6 050	1.11	164

^a Measured at 20°C with c = 2 g L⁻¹ in DMSO containing 2.vol% of TFA.

^b C, La’, Lb, Lc are 4 structures of polyethersulfone.

^c Average-molecular weight, determined by SEC (in DMF) with polystyrene standard.

^d Polydispersity index determined by SEC.

^e Measured with a heating rate of 10 °C min^–1 under argon flow of (50 mL min⁻¹).

Figure 6. MALDI–ToF mass spectra of PES 8, 9 and 10 at 0.15 mol L^−1.

Figure 7. ¹³C-NMR spectra [68–180 ppm] of oligo-ethersulfones at 0.15 mol L⁻¹ [DMSO-D6, 500 MHz, 20 °C].

Figure 8. T_g of synthesized PES7-12 (Table 3).

Figure 9. MALDI–ToF mass spectra of PES-11, and PES-12 (0.075 mol L⁻¹).

Casarano R, Petri DFS, Jaffe M, Catalani LH. Synthesis and structural characterization of block and random low molecular weight copolymers composed of l-lactic acid and isosorbide succinate moieties. J. Braz. Chem. Soc. 2009;20:1414–1424.

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