New Functional Acrylates

本研究涉及α -羟甲基丙烯酸酯（HMA）酯的化学合成、聚合和表征。对各种烷基酯（rhma）丰富化学性质的扩展和探索，将使具有卤化物、酯、醚、硅醚、聚氨酯和胺基的可聚合衍生物成为可能。其中许多还会含有硅氧烷、碳氢化合物和碳氟化合物残留物。利用新发现的RHMA醇基的成醚反应，将合成具有内部和末端基团的反应性低聚物。此外，还将提供具有超亲核催化剂基团的单体，以及能够形成可聚合胶束、囊泡、单层和液晶状态的单体。醚二聚体的环聚合产生含有羧酸基团的含吡喃聚合物，具有潜在的抗癌和抗病毒活性。RHMA的反应性卤化物和异氰酸酯的形成将单体和聚合物的功能能力扩展到许多其他衍生物。阴离子和基团转移聚合的醚和硅醚将允许等规和控制MW聚合物的形成。研究还将涉及分子内6元环氢键对聚合物溶解度和物理性质的影响，a-甲基取代基对聚合的立体抑制作用，以及利用t-丁基效应形成高分子量的环聚合物。

This research deals with the chemistry of alpha- hydroxymethylacrylate (HMA) ester synthesis, polymerization, and characterization. Extension and exploration of the rich chemistry of various alkyl esters (RHMAs) will make available polymerizable derivatives possessing halide, ester, ether, silyl ether, urethane, and amine groups. Many of these will also possess siloxane, hydrocarbon, and fluorocarbon residues. Reactive oligomers with internal and terminal groups will be synthesized using a newly- discovered ether-forming reaction of the RHMA alcohol groups. Also available will be monomers with supernucleophilic catalyst groups, and monomers capable of forming polymerizable micelles, vesicles, monolayers, and liquid crystalline states. Cyclopolymerization of the ether dimers generates pyran-containing polymers with pendent carboxylate groups with potential anticancer and antiviral activity. Formation of reactive halides and isocyanates of the RHMA's extends the functional capability of the monomers and polymers to many other derivatives. Anionic and group transfer polymerizations of ethers and silyl ethers will allow isotactic and controlled MW polymer formation. Studies will also deal with intramolecular 6-membered ring hydrogen bond effects on polymer solubility and physical properties, steric inhibition of polymerization by a-methyl substituents, and use of the t-butyl effect to form high molecular weight cyclopolymers.