| Budget Amount *help |
¥6,600,000 (Direct Cost: ¥6,600,000)
Fiscal Year 2002: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 2001: ¥3,700,000 (Direct Cost: ¥3,700,000)
|
|---|
| Research Abstract |
1.(Meth)acrylates (ASOE, MASOE, CMA) having a pendant spiro ortho ester(SOE) and carbonate(SOC) moieties and the copolymer with MMA were synthesized, and the polymerizations were carried out in the presence of an ionic and a radical initiators. In addition, the characteristics of those (meth)acrylates were investigated. The ring-opening reaction of the SOE and SOC groups in the (meth)acrylates and those copolymers with MMA proceeded well during heat polymerization (HC) with the cationic (BSS and HPSS) and radical (BPO) initiators. In the combined use of cationic and radical initiators the reaction of both vinyl and spiro groups in the monomers (ASOE, MASOE and CMA) were also confirmed. However, a small amount of unreacted carbon-carbon double bond and a formation of OH group were observed in the polymers obtained from ASOE and MASOE and powder/liquid polymerizations. Forthermore, in the visible light irradiation to the comonomer (CMA/EGDMA) with CQ/amine a high polymerization heat was
… More
observed as same as that of heat polymerization in DSC study. Although their shrinkage was still very significant, an improvement of polymerization shrinkage was observed during the polymerizations of ASOE and MASOE and the copolymers (MASOE/MMA) with MMA. The obtained polymers from a part of bulk-polymerization ofMASOE and the powder/liquid polymerization (Cm/MMA=l.5) showed a hardness as same as that of PMMA.
2.Synthesis of 2-phenyl-1,6-dioxaspiro [4.6]undecane. First, 1,5-pentadiol was allowed to react with an equivalent amount of p-toluenesulfonyl chloride (p-TsCl) in the presence of triethylamine in dichloromethane to afford the monotosylated diol, whose residual hydroxyl group was protected with tetrahydropyranyl (THF) ether. Further, the product was reacted with lithiated trimethylsilyacetylene in a tetrahydrofuran-(THF-)hexamethylphosphoric triamide (HMPA) mixed solvent to afford, whose trimethylsilyl (TMS) group was deprotected by reaction with tetrabutylammonium fluoride (TBAF). Compound was prepared by reaction of lithiated and styrene oxide, and subsequently deprotected by acid treatment to form the diol. Finally, the spiroketal was prepared by tandem cyclization of with PdCl2 as catalyst. In a cationic polymerization of the spiroketal, a sticky liquid polymers with number-average molecular weights (Mn) of 2900-3700 were obtained as hexane-insoluble materials in 81-94 % yield at 50-100℃. The spiroketal showed 0.9-1.2 % of volume expansion during the polymerization. Less
|
