Synthesis of High Molecular Weight Biobased Aliphatic Polyesters Exhibiting Tensile Properties Beyond Polyethylene

Abstract

Synthesis of high molecular weight polyesters prepared by acyclic diene metathesis (ADMET) polymerization of bis(undec-10-enoate) with isosorbide (M1), isomannide (M2), and 1,3propanediol (M3) and the subsequent hydrogenation have been achieved by using a molybdenum-alkylidene catalyst. The resultant polymers (P1) prepared by the ADMET polymerization of M1 (in toluene at 25 °C) possessed high M n values (M n = 44400−49400 g/ mol), and no significant differences in the M n values and the PDI (M w / M n ) values were observed in the samples after the hydrogenation. Both the tensile strength and the elongation at break in the hydrogenated polymers from M1 (HP1) increased upon increasing the molar mass, and the sample with an M n value of 48200 exhibited better tensile properties (tensile strength of 39.7 MPa, elongation at break of 436%) than conventional polyethylene, polypropylene, as well as polyester containing C 18 alkyl chains. The tensile properties were affected by the diol segment employed, whereas HP2 showed a similar property to HP1.

Synthesis of Polyesters Containing Long Aliphatic Methylene Units by ADMET Polymerization and Synthesis of ABA-Triblock Copolymers by One-Pot End Modification and Subsequent Living Ring-Opening Polymerization

“…Despite many reports for synthesis of the (aliphatic) polyesters by ADMET polymerization of α,ω-diene monomers using ruthenium-carbene catalysts ( G2 and HG2 , Scheme ), − however, reports for synthesis of high-molecular-weight polymers ( ca . M n = >30,000 g/mol considered for better mechanical properties as films) , still have been limited (Scheme ).…”

“…Despite many reports for synthesis of the (aliphatic) polyesters by ADMET polymerization of α,ω-diene monomers using ruthenium-carbene catalysts ( G2 and HG2 , Scheme ), − however, reports for synthesis of high-molecular-weight polymers ( ca . M n = >30,000 g/mol considered for better mechanical properties as films) , still have been limited (Scheme ). Indeed, in our recent study, the tensile strength of certain biobased aliphatic polyesters in films increased with increasing the molar mass in the polymers .…”

“…M n = >30,000 g/mol considered for better mechanical properties as films) 41,42 still have been limited (Scheme 1). 42 Indeed, in our recent study, the tensile strength of certain biobased aliphatic polyesters in films increased with increasing the molar mass in the polymers. 42 A possibility of catalyst decomposition can be highly considered, as demonstrated previously, 22 when the metathesis polymerizations (reactions) were conducted at high temperatures (70− 90 °C) and the subsequent isomerization and undesired side reaction caused by the formed radical species were known in this catalysis.…”

“…M n = >30,000 g/mol considered for better mechanical properties as films) , still have been limited (Scheme ). Indeed, in our recent study, the tensile strength of certain biobased aliphatic polyesters in films increased with increasing the molar mass in the polymers . A possibility of catalyst decomposition can be highly considered, as demonstrated previously, when the metathesis polymerizations (reactions) were conducted at high temperatures (70–90 °C) and the subsequent isomerization and undesired side reaction caused by the formed radical species were known in this catalysis. ,,− Recently, the synthesis of some high-molar-mass polymers was demonstrated by adopting ADMET polymerizations of α,ω-diene monomers of bis­(undec-10-enoate) with isosorbide [dianhydro- d -glucityl bis­(undec-10-enoate)], isomannide, 1,4-cyclohexanedimethanol, and 1,4-butanediol in the presence of a ruthenium-carbene catalyst in ionic liquids (ILs) such as 1- n -butyl-3-methyl imidazolium hexafluorophosphate, [Bmim]­PF 6 , and 1- n -hexyl-3-methyl imidazolium bis­(trifluoromethanesulfonyl)­imide, [Hmim]­TFSI ,− (Scheme ).…”

Synthesis of Network Biobased Aliphatic Polyesters Exhibiting Better Tensile Properties than the Linear Polymers by ADMET Polymerization in the Presence of Glycerol Tris(undec-10-enoate)

“…For example, these polyesters (including conventional polyesters) can be depolymerized by treating them with alcohols (via transesterification) in the presence of a catalyst to recover monomers exclusively (facile chemical recycling) [ 12 , 13 , 14 , 15 ]; one-pot closed-loop chemical recycling (depolymerization and repolymerization) was thus also demonstrated [ 13 ]. There have been thus many reports on the synthesis of polyesters derived from plant oil through polycondensation [ 7 , 15 , 16 , 17 , 18 , 19 ] and acyclic diene metathesis (ADMET) polymerization technique [ 7 , 17 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 ].…”