Polymer chemistry of α-substituted acrylates designed for functional-group synergy

Effect of amino group modification at allyl position of methacrylamides on polymerization and polymer pH-/thermo-responsiveness

“…Although various functional polymers have been reported for α-functionalized acrylates, 34 acrylamides have hardly been studied. As shown here, modification at the α-position does not simply reflect the properties of the functional group, such as hydrophilicity and hydrophobicity, in the polymer.…”

Unsaturated polyurethanes degradable by conjugate substitution reactions with amines and carboxylate anions

“…Methacrylates carrying a leaving group, such as a halogen atom at the allylic position, undergo nucleophilic conjugated substitution reaction via an addition-elimination (S N 2 ′ ) mechanism. 17,18 Recently, we applied conjugate substitution reaction to prepare PCEs. [19][20][21] The polycondensation using dicarboxylic acid, bisphenols, and dithiols was employed under 25 °C, resulting in a variety of PCEs with high molecular weight (M n > 10 4 ).…”

Synthesis of differentiated sulfur-containing polymers by regiodivergent polymerization of Morita–Baylis–Hillman acetates and thiols

“…1 However, to date, most catalytic methods have predominantly been exercised to achieve one type of polymer in a highly regioselective manner, with relatively little attention devoted to making use of regioselectivity to synthesize differentiated polymers starting from identical monomers (Scheme 1A). 2 Yet, the latter is highly desirable in modern polymer chemistry, which could grant quick access to various structurally differentiated polymers starting from a common precursor by minorly adjusting the reaction conditions. For clarity, here we describe this strategy as “regiodivergent polymerization” according to the definition of “regiodivergent reaction” in organic chemistry, 2 a , b in which two or more regioisomeric polymers could be synthesized starting from identical monomers by controlling the regioselectivity of polymerization.…”

“…The major challenge for this vision is to find a suitable catalyst/substrate combination and identify the critical parameter to switch the regioselectivity of the polymerization. 2 Thanks to multiple reactive sites in their structures, Morita–Baylis–Hillman (MBH) adducts have been used as versatile building blocks for various nucleophilic transformations in organic chemistry. 5 Among these transformations, the nucleophile could directly attach to the α-carbon of the MBH adduct via an S N 2′ (addition−elimination) pathway in the presence of a basic catalyst, allowing the direct formation of an α-substituted product.…”