New Functional Acrylates

本研究主要研究α-羟甲基丙烯酸甲酯(HMA)酯的合成、聚合和表征。扩展和探索各种烷基酯(RHMA)的丰富化学成分将使具有卤化物、酯、醚、硅醚、氨基甲酸酯和胺基的可聚合衍生物成为可能。其中许多还将含有硅氧烷、碳氢化合物和氟碳残留物。具有内部和末端基团的反应性低聚物将使用新发现的RHMA醇基的醚化反应来合成。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、小泡、单分子层和液晶态的单体。乙醚二聚体的环聚反应生成具有潜在抗癌和抗病毒活性的含吡喃的聚合物。RHMA的活性卤化物和异氰酸酯的形成将单体和聚合物的官能化能力扩展到许多其他衍生物。醚和硅醚的阴离子和基团转移聚合将允许形成全同立构和受控的MW聚合物。研究还将涉及分子内六元环氢键对聚合物溶解性和物理性质的影响，α-甲基取代基对聚合的空间抑制，以及利用叔丁基效应形成高分子量环状聚合物。

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.