Hybrid copolymerization of cyclic and vinyl monomers

In this work, we report the hybrid copolymerization of various cyclic monomers and vinyl monomers. Our studies demonstrate that 1-tert-butyl-4,4,4-tris-（dimethylamino）-2,2-bis[tris（dimethylamino） phophoranyliden-amino]-2A5,A5-catenadi（phosphazene） （t-BuP4） can catalyze the hybrid copolymerization of caprolactone （CL）, lactide （LA） or cyclic carbonate ester with acrylate or methyl acrylate. However, the polymerization of cyclosiloxane with vinyl monomers yields two corresponding homopolymers, and the polymerization of lactone with acrylonitrile （AN） produces only polyacrylonitrile. Clearly, the extent of matching of activity between a monomer and an active center determines whether or not there is hybrid copolymerization.

Hybrid Copolymerization via the Combination of Proton Transfer and Ring-opening Polymerization

Phosphazene base,t-BuP2,was employed to catalyze the proton transfer polymerization(PTP)of 2-hydroxyethyl acrylate(HEA),and PTP was further combined with ring-opening polymerization(ROP)to exploit a new type of hybrid copolymerization.The studies on homopolymerization showed that t-BuP2 was a particularly efficient catalyst for the polymerization of HEA at room temperature,giving an excellent monomer conversion.Throughout the polymerization,transesterification reactions were unavoidable,which increased the randomness in the structures of the resulting polymers.The studies on copolymerization showed that t-BuP2 could simultaneously catalyze the hybrid copolymerization via the combination of PTP and ROP at 25°C.During copolymerization,HEA not only provided hydroxyl groups to initiate the ROP ofε-caprolactone(CL)but also participated in the polymerization as a monomer for PTP.The copolymer composition was approximately equal to the feed ratio,demonstrating the possibility to adjust the polymeric structure by simply changing the monomer feed ratio.This copolymerization reaction provides a simple method for synthesizing degradable functional copolymers from commercially available materials.Hence,it is important not only in polymer chemistry but also in environmental and biomedical engineering.

Preparation of polymer nanocomposites with enhanced mechanical properties using hybrid of graphene and partially wrapped multi-wall carbon nanotube as nanofiller

Triblock copolymer of poly（p-dioxanone） and polyethylene glycol end-capped with pyrene moieties（（Py-PPDO）_2-b-PEG） was synthesized and used as modifier for multi-wall carbon nanotubes（MWCNTs）.Nano-aggregates（（Py-PPDO）_2-b-PEG@MWCNTs） with shish-kebab like partially wrapped morphology and very good stability were obtained by incorporating the copolymer with MWCNTs.The bare MWCNT sections of（Py-PPDO）_2-b-PEG@MWCNTs were able to induce n-n interactions with graphene（GE） and resulted in a novel GE/（Py-PPDO）_2-b-PEG@MWCNTs hybrid.The dispersity of GE in solution or polymer matrix was therefore greatly improved.The PCL nanocomposite films using GE/（Py-PPDO）_2-bPEG@MWCNTs as hybrid nanofiller exhibited obviously improved mechanical properties especially at very low hybrid nanofiller content.The influence of the nanofiller content and feed ratio of GE/MWCNTs on the mechanical properties of composites films was evaluated.When the feed ratio of GE to MWCNTs is 2：8 and the total loading of nanofiller is only 0.01 wt%,the tensile strength of the composite film increased by 163%and the elongation at break increased by 17% compared to those of neat PCL These results can be attributed to fine dispersion of the nanofillers in PCL matrix and the hybrid interactions between GE and MWCNTs.Therefore,this work provides a novel method for preparing polymer nanocomposites with high mechanical performance and low nanofiller loading.

Morphology and Thermoresponsive Behavior of Hybrid Micelles of Polystyrene-b-Poly((N-isopropyl acrylamide)-co-(4-vinylbenzyl chloride)) with Prussian Blue

The hybrid micelles of polystyrene-b-poly（（N-isopropyl acrylamide）-co-（4-vinylbenzyl chloride）） block copolymer（PS-b-P（NIPAM-co-VBC）） with Prussian blue（PB） in the corona were prepared by reaction of pentacyano（4-（dimethylamino）-pyridine）ferrate（Fe-DMAP）-attached PS-b-P（NIPAM-co-VBC） with Fe Cl3. The formation of the PB framework inside the micelles was verified by UV-Vis, FTIR and TGA. The morphology of the hybrid micelles was studied by TEM and compared with that of the neat and Fe-DMAP-attached PS-b-P（NIPAM-co-VBC）. It is found that attachment of Fe-DMAP may change the short rod-like micelles of the neat PS-b-P（NIPAM-co-VBC） into spherical ones and lead to a smaller micelle size. The morphology of the hybrid micelles may be altered or remain unchanged after formation of the PB framework, depending on the chain structure of PS-b-P（NIPAM-co-VBC） and starting concentration. The thermoresponsive behavior of different micelles was studied using DLS. It is observed that attachment of Fe-DMAP can improve the hydrophilicity of the P（NIPAM-co-VBC） block, leading to weaker hysteresis of the micelle size during the heating and cooling cycle. However, the crosslinked PB framework in the micellar corona may result in a more evident hysteresis phenomenon and blur the two-stepwise change of the micellar size with temperature.

Recent progress on DNA block copolymer

DNA has gained great attention because of its unique structure,excellent molecular recognition property,and biological functions.When married with versatile synthetic polymers,the DNA conjugated polymer hybrids,known as DNA block copolymers（DBCs）,have been launched and well developed for the syntheses of new materials and nanostructures with different functions in the past several decades.Compared to conventional synthetic block copolymers,using DNA as a building block provides several advantages over other polymer candidates,such as molecular recognition,programmable self-assembly,biocompatibility,and sequence-encoded information.In this review,recent developments in this area will be summarized and meaningful breakthroughs will be highlighted.We will discuss representative examples of recent progress in the syntheses,structure manipulations,and applications of DBCs.