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

1.设计了一套示差扫描量热法可见光辐照实验装置，验证了该装置在测定各种单体聚合热方面的有效性。合成了四种具有环状六元缩醛的乙烯基环丙烷衍生物，并在60、80、120ﾟC下进行了自由基聚合反应。虽然大多数单体都是无色透明聚合物，但以六元缩醛取代外亚甲基的乙烯基环丙烷衍生物得到了一种交联型聚合物。合成了含环碳酸酯的甲基丙烯酸酯(1，2-氧代-5-甲基丙烯酰氧甲基-1，3-二氧六环：CMA)。合成了甲基丙烯酸甲酯(MMA)与甲基丙烯酸甲酯(MMA)的共聚物。单体摩尔比为44/56和55/45，数均相对分子质量为40000-46000。共聚单体为CMA/MMA(质量比)为30/70和40/60，自由基引发剂用量为1%，合成了BPO(过氧化苯甲酰)和CQ(樟脑酚)/胺(二甲氨基乙基甲基丙烯酸乙酯)单体，并进行了热聚合和光聚合。在70ﾟC下，光聚合的聚合热高于BPO热聚合的聚合热，而在70ﾟC下聚合20min+120ﾟC下聚合20min的总聚合热与光固化的聚合热几乎相同。FTIR分析结果表明，CMA和IG中同时存在螺环碳酸酯基团和乙烯基团的聚合反应。CMA加速了1G.6的聚合。我们用粉液法研究了CMA和MMA在自由基或阴离子引发剂作用下，以MMA为液体的共聚反应。

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.