crosslinking [2,3] and metal ion chelation processes. [4,5] Thus, up to now, great efforts have been made to incorporate DOPA or catechol groups in a broad range of designed polymers to get mussel-inspired adhesives, which showed good bonding performances both at dry and underwater conditions. These polymers were generally named as "catecholfunctionalized polymers" (CFPs).Up to now, notable accomplishments have been achieved by using CFPs for high performance adhesion at atmospheric environment. Yu and Deming and co-workers reported the synthesis of DOPA-containing copolypeptides, exhibiting a bonding strength of 4.0 MPa on aluminum. [6] Wilker et al. synthesized poly[(3,4-dihydroxystyrene)-co-styrene] via anionic polymerization method, which achieved a bonding strength of 11 MPa on aluminum by using CaCO 3 particles as reinforcing materials. [7] Subsequently, they also incorporated the CFPs with poly(lactic acid) [8][9][10] or pendant oligo(ethylene glycol) moieties [4] to produce biodegradable/biocompatible adhesives with good dry-state bonding strength. Wan et al. synthesized catechol-functionalized poly(vinyl alcohol) via esterification reactions [11] and acetal formation reactions, [12] exhibiting bonding strengths of 4.0 MPa on glass and 14.9 MPa on stainless steel, respectively. Kaneko et al. synthesized a hyperbranched CFP via thermal polycondensation reaction between 3,4-dihydroxycinnamic acid and 4-hydroxycinnamic acid, which showed a bonding strength of ≈10 MPa on steel. [13] Then, they also prepared a similar hyperbranched polymer system with the bonding strength on steel up to 15 MPa. [14] However, despite great progress, the bonding strength of most reported CFPs on metal substrates is smaller than 15 MPa. Recently, Messersmith and co-workers [15] and Detrembleur and co-workers [16] separately reported the synthesis of catechol-functionalized polybenzoxazines and polyhydroxyurethanes, which were used to prepare thermoset adhesive materials with excellent bonding strength of 20.5 MPa on aluminum and 22.1 MPa on stainless steel, respectively. To our knowledge, these two polymers represent the best adhesive materials among CFPs for dry-state adhesion on metal Marine mussels have the ability to cling to various surfaces at wet or underwater conditions, which inspires the research of catechol-functionalized polymers (CFPs) to develop high-performance adhesive materials. However, these polymeric adhesives generally face the problems of complex synthetic route, and it is still high challenging to prepare CFPs with excellent adhesive performance both at dry and underwater conditions. Herein, a mussel-inspired alternating copolymer, poly(dopamine-alt-2,2-bis(4-glycidyloxyphenyl) propane) (P (DA-a-BGOP)), is synthesized in one step by using commercially available monomers through epoxy-amino click chemistry. The incorporation of polar groups and rigid bisphenol A structures into the polymer backbone enhances the cohesion energy of polymer matrix. The alternating polymer structure endows the polymers with high...

Stereoselective polymerization can yield polymers with specific tacticity and properties, and it is an important topic throughout the polymer synthesis history. Herein, we report for the first time on a vesicular catalysis method to realize the green stereoregular polymerization of isotactic-rich poly(methyl methacrylate) (PMMA) in water and at ambient temperature and pressure, namely by conducting the polymerization of MMA monomers in the confined 5-10 nm thick hydrophobic layers of hyperbranched polymer vesicles. The isotactic degree of the as-prepared PMMAs increases from 12% to 40% with the decrease of vesicle size from 840 nm to 85 nm in hydrodynamic diameter (D h ) owing to the conformation confinement effect of MMA monomers inside the thin vesicle membranes through a curvature-dependent way. The present work has extended the scope of green chemistry, and it also represents a new application of polymer vesicles in stereoregular polymerization.

Here, we report a pH-controlled stereoregular polymerization of methyl methacrylate (MMA) inside the membrane of H20-COOH hyperbranched polymer vesicles using a common radical polymerization process. The vesicle size decreases from 745 to 214 nm with an increase of solution pH from 2.60 to 7.26, and the isotacticity of the obtained polymethyl methacrylates (PMMAs) is accordingly elevated from 9 to 35%. The obtained isotactic-rich PMMAs show a lower glass transition temperature depending on the isotacticity than the commercial random PMMAs. A mechanism study according to the in situ Fourier transform infrared measurements indicates that the control of polymer isotacticity results from the monomer conformation confined effect inside the thin vesicle membranes. The present study provides a new method to realize the preparation of isotactic polymers with the characteristics of facile synthesis, pH controllability, and a green polymerization process in aqueous solution as well as under mild reaction conditions of ambient temperature and pressure.