Rotator-phase photopolymerization has been developed in the field of free-radical addition polymerization since the photopolymerization in the rotator phase was first proposed, and other mechanisms urgently need to be extended. Herein, four long-chain glycidyl ethers were synthesized, and their polymorphic behavior was studied by differential scanning calorimetry and X-ray diffraction. Among all, the octadecyl glycidyl ether (OGE) and the hexadecyl glycidyl ether (HGE) are proven existing rotator phases. The cationic ring-opening photopolymerization of the OGE in the rotator phase was achieved, and the highest conversion reached 68.6% at 30 °C, which is even higher than that of liquid-state photopolymerization at adjacent higher temperatures (27.2% at 40 °C). The mechanism was discussed and explained with the aid of a molecular dynamic simulation. In order to further develop the cationic ring-opening photopolymerization in rotator phases at relatively low temperatures, three types of long-chain compounds were chosen to separately blend with the OGE to construct binary systems. The conversion of the OGE at 20 °C (17% in the pure OGE system) could be obviously improved in all binary systems, and the maximum conversion could reach 56%. Subsequently, the interactions of different long-chain compounds on the OGE and the effect on polymerization behavior are both discussed.

中文翻译：

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旋转相中长链环氧化物的阳离子开环光聚合：证实、机理和组合

自从首次提出旋转相光聚合以来，旋转相光聚合在自由基加成聚合领域得到了发展，其他机制迫切需要扩展。本文合成了四种长链缩水甘油醚，并通过差示扫描量热法和X射线衍射研究了它们的多晶型行为。其中，十八烷基缩水甘油醚（OGE）和十六烷基缩水甘油醚（HGE）是已被证明的现有旋转相。实现了OGE在旋转相中的阳离子开环光聚合，30℃时最高转化率达到68.6%，甚至高于邻近较高温度下的液态光聚合（40℃时为27.2%） ）。借助分子动力学模拟对该机制进行了讨论和解释。为了进一步发展相对较低温度下旋转相中的阳离子开环光聚合，选择了三种类型的长链化合物分别与OGE共混构建二元体系。所有二元体系中20℃时OGE的转化率（纯OGE体系中为17%）均得到明显提高，最高转化率可达56%。随后，讨论了不同长链化合物对 OGE 的相互作用以及对聚合行为的影响。