Xin-Xing Deng

One-pot synthesis of polyamides with various functional side groups via Passerini reaction

Polyamides with various functional side groups were synthesized via Passerini reaction in a one-pot approach. The polymerization conditions and kinetics as well as the resulting polymer structures were thoroughly investigated. The facile introduction of various pendant groups, especially alkynyl and alkenyl groups, provides a platform for efficient post-polymerization modification by click chemistry.

Facile synthesis of multi-block copolymers containing poly(ester–amide) segments with an ordered side group sequence

We report a facile method for the synthesis of multi-block copolymers consisting of poly(ethylene glycol) (PEG) and poly(ester–amide) segments with an ordered side group sequence via multicomponent polymerization based on the Passerini reaction (PR). The technique involves the polymer supported liquid-phase synthesis of three PEG diacid macromonomers (M1–M3) via stepwise PR with tert-butyl isocyanoacetate and a functional aldehyde followed by selective hydrolysis, and the final multicomponent polymerization of M1–M3 with phenylacetaldehyde and 1,6-diisocyanohexane.

Functional highly branched polymers from multicomponent polymerization (MCP) based on the ABC type Passerini reaction

A new synthetic approach to prepare functional highly branched polymers (HBPs) is demonstrated via the multicomponent polymerization (MCP) of easily accessible hexanedioic acid (A2), hexane-1,6-dial (B2), 1,6-diisocyanohexane (C2) and 10-undecenoic acid (A). Both the degree of branching (DB) and the degree of additional functionalization (DF) were regulated by simply varying the ratio of A2 to A.

Combination of ATRA and ATRC for the synthesis of periodic vinyl copolymers.

A new approach to periodic vinyl copolymers via combination of atom transfer radical addition (ATRA) and atom transfer radical coupling (ATRC) is reported. The two examples are methyl methacrylate (MMA) and styrene (St) periodic copolymer (P(SMMS)) and acrylonitrile (AN) and St periodic copolymer (P(SAAS)). First, two monomer sequence units (MSU) with built-in sequence, SMMS and SAAS, are synthesized through the controlled ATRA of two ATRP initiators with St. Then, the ATRC of SMMS and SAAS are conducted at high radical conditions to generate two types of high-molecular-weight copolymers, P(SMMS) and P(SAAS). Though side reactions can not be totally avoided, characterizations of the polymer structure with a variety of means confirm that the main chain structures of P(SMMS) and (PSAAS) are predominantly with the periodic sequences from the MSUs. Attempts to suppress the side reactions are successful via the MNP-mediated ATRC of SMMS and SAAS.

Graft Copolymers with Polyamide Backbones via Combination of Passerini Multicomponent Polymerization and Controlled Chain-growth Polymerization

We report a facile ‘grafting from’ approach to graft copolymers with polyamide backbones and controlled vinyl polymer or polyester side chains. Two polyamides with in situ-formed pendant bromide or hydroxyl groups were obtained by Passerini-based multicomponent polymerization. They were used respectively to initiate the atom-transfer radical polymerization of vinyl monomers or the ring-opening polymerization of lactones to generate two new types of graft copolymers. One of the important features of the method is that the pendant initiators are generated in situ from non-branching monomers, and they are linked to the polymer backbone by ester bonds. Therefore, the vinyl polymer side chains could be detached from the backbones, and their structures could thus be fully characterized. Moreover, multicomponent polymerization and atom-transfer radical polymerization can even be carried out in a one-pot manner.