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Abstract: A novel postpolymerization modification methodology is demonstrated to achieve selective functionalization of hyperbranched polymer (HBP). Terminal and internal acrylates of HBP derived from cross‐metathesis polymerization (CMP) are functionalized in a chemoselective fashion using the thiol‐Michael chemistries. Model reactions between different thiols (benzyl mercaptan and methyl thioglycolate) and acrylates (n‐hexyl acrylate and ethyl trans‐2‐decenoate) by using dimethylphenylphosphine or amylamine as the catalyst are investigated to optimize the modification protocol for HBP. High‐molecular‐weight HBP P0 is generated through CMP of AB2 monomer 2, a compound containing one α‐olefin and two acrylate metathetically polymerizable groups. CMP kinetics is monitored by NMR and gel permeation chromatography (GPC). Accordingly, microstructural analysis is conducted in detail, and CMP procedure is optimized. Postpolymerization modification of HBP P0 is performed via two distinguished strategies, namely one‐step complete modification and sequential modification, to generate terminally and/or internally functionalized HBPs P1–P3 in a chemoselective fashion by using phosphine‐initiated and/or base‐catalyzed thiol‐Michael chemistries. Finally, thermal stability and glass transition behaviors of HBPs P0–P3 are studied by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively. [ABSTRACT FROM AUTHOR]

Sequence-regulated polymerization is realized upon sequential cross-metathesis polymerization (CMP) and exhaustive hydrogenation to afford precision aliphatic polyesters with alternating sequences. This strategy is particularly suitable for the arrangement of well-known monomer units including glycolic acid, lactic acid, and caprolactic acid on polymer chain in a predetermined sequence. First of all, structurally asymmetric monomers bearing acrylate and α-olefin terminuses are generated in an efficient and straightforward fashion. Subsequently, cross-metathesis (co)polymerization of M1 and M2 using the Hoveyda-Grubbs second-generation catalyst (HG-II) furnishes P1- P3, respectively. Finally, hydrogenation yields the desired saturated polyesters HP1- HP3. It is noteworthy that the ε-caprolactone-derived unit is generated in situ rather than introduced to tailor-made monomers prior to CMP. NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) results verify the microstructural periodicity of these precision polyesters. Differential scanning calorimetry (DSC) results reflect that polyesters without methyl side groups exhibit crystallinity, and unsaturated polyester samples show higher glass transition temperatures than their hydrogenated counterparts owing to structural rigidity. [ABSTRACT FROM AUTHOR]

Sequence‐controlled polymerization is the forefront of polymer chemistry. Herein, the feasibility of sequence regulation by using organocatalyzed ring‐opening polymerization (ROP) is demonstrated. In particular, ring expansion strategy is employed to synthesize pre‐organized monomers 1 and 2. ROP is conducted by using 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene and benzyl alcohol as the catalyst and initiator, respectively. Poly(ester amide)s (PEAs) P1–P3 comprising glycolic acid, lactic acid, and 7‐aminoheptanoic acid units are obtained in high molecular weights and good yields. NMR and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry results verify the microstructural integrity of P1 and P2. Differential scanning calorimetry results show that PEA without methyl branches is crystalline. Moreover, thermal stability, surface wettability, and degradation profiles of P1–P3 are also investigated. [ABSTRACT FROM AUTHOR]