[ESR study on self-curing resin for rebasing during polymerization].

M Andoh
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Abstract

The effects of temperature, concentrations of activator (N, N-dimethyl-p-toluidine) and inhibitor (hydroquinone), atmosphere, liquid powder ratio and mixing time on polymerization process of self-curing resin for rebasing were studied by electron spin resonance. When powder and liquid were mixed at a ratio commercially recommended at a physiologic temperature of 37 degrees C, the propagating radical was first detected 5.5 minutes later, of which time interval corresponds to induction time for polymerization. After the induction time, the concentration of propagating radicals increased rapidly with time and reached the maximum level at 27 minutes. The radicals thus formed remained stable for more than 2.5 days when stored in air at 37 degrees C, though their concentration diminished gradually. With increasing temperature for curing, the maximum level of the radical concentration decreased and the propagating radicals disappeared more rapidly, indicating recombination reactions to be perferentially occurring at higher temperatures. Increase in the amount of activator of N,N-dimethyl-p-toluidine resulted in increase in the radical concentration. When powder was mixed with a liquid containing less inhibitor of hydroquinone, the radicals were found to remain stable longer. In air, propagating radical was detected faster and free radical was concentrated more rapidly than in the water and nitrogen gas. The fluidity of self-cured resin for rebasing as measured by use of spin probe TEMPO disappeared rapidly with increasing temperature for curing, decreasing the amount of liquid and shortening the mixing time. When curing temperature was raised to 37 degrees C from 22 degrees C at minutes after mixing, the fluidity disappeared 2.5 minutes later, i.e., at 5.5 minutes after mixing. To investigate the effects of the MMA-derivative radicals on growth of HeLa cells, HeLa cells were cultured on resins containing MMA-derivative radicals. The number of HeLa cells on resins containing MMA-derivative radicals was 7/10 of that of HeLa cells on resins containing no radicals.

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聚合过程中自固化树脂重基的ESR研究。
利用电子自旋共振研究了温度、活化剂(N, N-二甲基对甲苯胺)和抑制剂(对苯二酚)浓度、气氛、液粉比和混合时间对自固化树脂聚合过程的影响。在37℃的生理温度下,将粉末和液体按商业推荐的比例混合,在5.5分钟后首次检测到增殖的自由基,该时间间隔对应于聚合诱导时间。诱导时间结束后,随着时间的推移,传播自由基的浓度迅速增加,27分钟时达到最大值。这样形成的自由基在37℃的空气中贮存时,虽然浓度逐渐降低,但仍能保持2.5天以上的稳定性。随着固化温度的升高,自由基的最大浓度降低,扩散的自由基消失得更快,表明复合反应优先发生在较高的温度下。N,N-二甲基-对甲苯胺活化剂用量的增加导致自由基浓度的增加。当粉末与含有较少对苯二酚抑制剂的液体混合时,发现自由基保持稳定的时间更长。在空气中,比在水和氮气中更快地检测到传播自由基,并且自由基的浓缩速度更快。自旋探针TEMPO测定自固化树脂的流动性随固化温度的升高、液量的减少和混合时间的缩短而迅速消失。当搅拌后1分钟固化温度由22℃提高到37℃时,2.5分钟即搅拌后5.5分钟流动性消失。为了研究mma衍生物自由基对HeLa细胞生长的影响,我们将HeLa细胞培养在含有mma衍生物自由基的树脂上。含mma衍生物自由基树脂上的HeLa细胞数量是不含自由基树脂上HeLa细胞数量的7/10。
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