Development of A Restorative Resins having Good Fitness by Using Noncontractive Monomer

1. 设计了一种用于差示扫描量热法的可见光辐照实验装置，并证实了该装置在评价各种单体的聚合热方面的实用性。合成了四种含环六元缩醛的乙烯基环丙烷衍生物，并在60、80、120℃的温度下进行了自由基聚合。虽然大多数单体通过高效液相色谱分离得到无色透明聚合物，但在六元缩醛取代外亚甲基的乙烯基环丙烷衍生物中得到交联聚合物。合成了一种含环碳酸酯的甲基丙烯酸酯（1,2-氧-5-甲基丙烯氧基甲基-1,3-二恶烷：CMA）。合成了两种CMA与甲基丙烯酸甲酯（MMA）共聚物。单体比（mol%）分别为44/56和55/45，数平均分子量为400000 ~ 46000。在1 mol%自由基引发剂的条件下，CMA/MMA的质量比分别为30/70和40/60，制备了BPO（过氧化苯甲酰）和CQ（樟脑醌）/胺（二甲氨基乙基甲基-晚）与单体的共聚单体，并对其进行了热聚合和光聚合。在70ºC条件下，光聚合的聚合热高于BPO的热聚合热，但在70ºC条件下20min的聚合总热加上120ºC条件下20min的聚合总热与光固化的聚合热基本相同。FTIR分析结果表明，碳酸螺酯基团和乙烯基在CMA和iG中均有聚合。CMA加速了g .6的聚合。本文研究了在自由基或阴离子引发剂下，MMA作为液体，采用粉液法聚合CMA和MMA共聚物。

1. An experimental visible light irradiation apparatus for differential scanning calorimetry was designed and its usefulness in evaluating the polymerization heat of various monomers was confirmed.2. Four vinylcyclopropane derivatives having cyclic six-membered acetal were synthesized and the radical polymerization was carried out at 60,80,120ﾟC.Although colorless transparent polymers were isolated by HPLC for the most monomers, a crosslinked polymer was obtained in the case of vinyl cyclopropane derivative having six-membered acetal substituted an exomethylene.3. A methacrylate containing cyclic-carbonate (1,2-oxo-5-methacryloyloxymethyl-1,3-dioxane : CMA) was synthesized.4. Two copolymers of CMA and methyl methacrylate (MMA) were synthesized. They were 44/56 and 55/45 for monomer ratio in mol% and 40000-46000 for number average molecular weight.5. The comonomers consist of CMA/MMA in the ratio of 30/70 and 40/60 by weight with 1 mol% of radical initiators, BPO (benzoyl peroxide) and CQ (camphorquinone) /amine (dimethylamino ethylmethacry-late) vs. monomer were prepared and thermal-and photo-polymerization of them were carried out. The heat of polymerization in the case of photo-polymerization was higher than in case of thermal polymerization with BPO at 70ﾟC,however, the total heat of polymerization at 70ﾟC for 20min plus 120ﾟC for 20min was almost as same as obtained by photo-curing. AS result of FTIR analyzes, both polymerizations of the spiro carbonate group and vinyl group in CMA and iG were observed. CMA accelerated the polymerization of 1G.6. We have been investigating the polymerization of copolymers consist of CMA and MMA with radical or anionic initiators and MMA as liquid by the powder liquid method.