Switchable Polymerization Catalysis Using a Tin(II) Catalyst and Commercial Monomers to Toughen Poly(l-lactide)

Abstract

Sustainable plastics sourced without virgin petrochemicals, that are easily recyclable and with potential for degradation at end of life, are urgently needed. Here, copolymersand blends meeting these criteria are efficiently prepared using a single catalyst and existing commercial monomers l -lactide, propylene oxide, and maleic anhydride. The selective, one-reactor polymerization applies an industry-relevant tin(II) catalyst. Tapered, miscible block polyesters are formed with alkene groups which are postfunctionalized to modulate the polymer glass transition temperature. The polymers are blended at desirable low weight fractions (2 wt %) with commercial poly( l -lactide) (PLLA), increasing toughness, and elongation at break without compromising the elastic modulus, tensile strength, or thermal properties. The selective polymerization catalysis, using commercial monomers and catalyst, provides a straightforward means to improve bioplastics performances.

Heterotrinuclear Ring Opening Copolymerization Catalysis: Structure–activity Relationships

“…In the PA/CHO ROCOP case, the less coordinating and more rigid aryl ester groups seem less likely to coordinate perhaps explaining why CHO homopropagation is not observed. Such a rationale bears similarity to the selectivity recently observed in Sn­(II) epoxide/anhydride ROCOP catalysts where alternating ester–ether linkages (ABB patterns) form. , …”

“…Such a rationale bears similarity to the selectivity recently observed in Sn(II) epoxide/anhydride ROCOP catalysts where alternating ester−ether linkages (ABB patterns) form. 73,74 Next, the investigation turned to the influences of changing the "exterior" metals, M, coordinated by the bis(phenoxy)diimine pockets of the ligand, H 2 L 1 . The Ni(II) 1 NiNa and Mg(II) 1 MgNa catalysts were obtained in near quantitative 58 The inclusion of the additional sodium center reduces the internuclear distance (Co−Na) to ∼3.45 Å as observed in the X-ray structure of the NaOTf complex of 1 Co , again reported by Akine and co-workers.…”

Ring‐Opening Copolymerization of Cyclic Anhydrides and Epoxides by bis(amidinate)tin(II) Complex via Binary Catalyst System

“…These unique polymer sequences possess enhanced thermal properties compared to the [AB] n polyester analogues. Commercial Sn(OMe) 2 catalyst was also reported by Williams for ROCOP of propylene oxide (PO) and maleic anhydride (MA) yielding poly(ester‐ ran‐ ether) (PE) with an average ratio of 1 : 2 for ester:ether linkages [14b] . Moreover, this catalyst was active for switchable polymerization using mixture of MA, PO, and L ‐lactide ( L‐ LA) giving tapered block polyester, PE‐ b ‐(PE‐ ran ‐PLLA)‐ b ‐PLLA.…”

Switchable Copolymerization of Maleic Anhydride/Epoxides/Lactide Mixtures: A Straightforward Approach to Block Copolymers with Unsaturated Polyester Sequences

“…For example, the poly(propylene maleate) (PPM) quasi‐block copolymers afford high‐performing plasticizers for commercial polylactide after post‐functionality. [ 25 ] The poly(propylene fumarate) (PPF) block copolymers are resorbable building scaffolds for additive manufacturing via stereolithographic printing. [ 26–28 ]…”