Synthesis of poly(sulfonate ester)s by ADMET polymerization

Abstract

Many hydrocarbon polymers containing heteroatom defects in the main chain have been investigated as degradable polyethylene-like materials, including aliphatic polyesters. Here, acyclic diene metathesis (ADMET) polymerization was used for the synthesis of aliphatic poly(sulfonate ester)s. The requisite sulfonate ester containing α,ω-diene monomers with varying numbers of methylene groups were synthesized, and their polymerization in the presence of ruthenium-N-heterocyclic (Ru-NHC) alkylidene catalysts was studied. A clear negative neighboring group effect (NNGE) was observed for shorter dienes , either inhibiting polymerization or resulting in low-molecular-weight oligomers. The effect was absent when undec-10-en-1-yl undec-10-ene-1-sulfonate was employed as the monomer, and its ADMET polymerization afforded polymers with appreciable number-average molecular weights of up to 37,000 g/mol and a dispersity Đ of 1.8. These polymers were hydrogenated to afford the desired polyethylene-like systems. The thermal and morphological properties of both saturated and unsaturated polymers were investigated. The incorporation of sulfonate ester groups in the polymer backbone offers an interesting alternative to other heteroatoms and helps further the understanding of the effects of these defects on the overall polymer properties.

High Melting Precision Sulfone Polyethylenes Synthesized by ADMET Chemistry

“…ADMET chemistry has produced polymers with polar functionalities such as carboxylic acids, phosphonic acids, halogens, alcohols, and many others precisely spaced along a linear polyethylene backbone. Recently, oxidized sulfur functionalities have been prepared—specifically sulfonate esters and sulfites . Here, we report the synthesis of linear aliphatic polysulfones via ADMET, wherein the sulfone group is in the polymer backbone (rather than pendent to it) in addition to being precisely spaced along the polymer chain.…”

Controlled Living Cascade Polymerization To Make Fully Degradable Sugar-Based Polymers from d-Glucose and d-Galactose

“…Acyclic diene metathesis (ADMET) polymerization, , ring-opening metathesis polymerization (ROMP), − and cyclopolymerization , are powerful polymerization techniques that have been used to prepare a wide range of functional polymers. While these techniques have been used to prepare various partially or fully backbone-degradable polymers, − they have rarely been used to prepare degradable SBPs.…”

Sugar‐Based Polymers from d‐Xylose: Living Cascade Polymerization, Tunable Degradation, and Small Molecule Release

“…[50] By decreasing the concentration and increasing the temperature,c ompared to the optimized conditions for M1 and M2 (see Table S1 in the Supporting Information for optimization), we found the polymerization of M3 to be controlled up to M/I of 125 (Figure 3C), with M n values ranging 8.9-32.2 kDa and M values ranging 1.09-1.29 (Table 1, entries 10-14). Addition of as econd methyl group (M4)l ed to ar ather significant decrease in polymerization performance.H owever, by increasing the concentration and further increasing the temperature,w ec ould achieve controlled polymerizations up to M/I of 60 (Figure 3D), with M n values ranging 7.7-25.9 kDa and M values ranging 1.15-1.28 (Table 1, entries [15][16][17][18][19]. Forboth of these monomers,kinetics studies supported first order monomer conversion (see Table S2 in the Supporting Information) albeit with slower rates (than M1 and M2), which is presumably due to the added steric hinderance of the methyl groups,w hich would slow catalyst approach to the alkyne.L ikewise,t he polymerization of M4 (with ad imethyl group) was the slowest by at least one order of magnitude.…”