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The NIR-sensitized cationic photopolymerization of oxetanes in combination with epoxide and acrylate monomers
Polymer Chemistry ( IF 4.6 ) Pub Date : 2021-08-31 , DOI: 10.1039/d1py00999k
Yulian Pang 1 , Hongjun Jiao 2 , Yingquan Zou 1 , Bernd Strehmel 3
Affiliation  

A study involving NIR-sensitized cationic photopolymerization focused on a series of oxetanes exhibiting remarkable reactivities. A heptamethine cyanine carrying a cyclopentene moiety at the central position and an iodonium salt containing the aluminate [(Al(O-t-C4F9)4)4] served as the initiator system, which was combined with a high-power NIR-LED as the excitation source emitting at 805 nm with an intensity of 1.2 W cm−2. Real-time FTIR analysis pursued under adiabatic conditions showed the good reactivities of the distinct oxetanes used in this study. The final conversion and reaction rates of OXT-03 depended on the concentration of the sensitizer rather than on the concentration of the iodonium salt. Moreover, hybrid photopolymerization based on free-radical and cationic photopolymerization used an oxetane monomer containing an –Si(OR)3 moiety in combination with TMPTA at different ratios. The results obtained showed that when the ratio of TMPTA : GR-Si123 was 5 : 5, the free-radical polymerization rate of TMPTA was similar compared to the cationic polymerization rate of GR-Si123. The addition of TMPTA resulted in an improvement in the solubility of the initiator components in the mixture, while dissolution in neat GR-Si123 can be seen to be more or less as poor. This mixture of monomers containing cationic and radical polymerizable groups facilitated the formation of interpenetrating polymer networks (IPNs ). In addition, the use of an epoxide and acrylate ester resulted in similar accelerations of the cationic polymerization of oxetane in both UV and NIR-sensitized photopolymerization. DMA investigations revealed the tan δ data, which provided the respective glass transition temperature (Tg) data. Here, a TMPTA : GR-Si123 ratio of 5 : 5 resulted in the lowest Tg value.

中文翻译:

氧杂环丁烷与环氧化物和丙烯酸酯单体的 NIR 敏化阳离子光聚合

一项涉及 NIR 敏化阳离子光聚合的研究侧重于一系列表现出显着反应性的氧杂环丁烷。在中心位置带有环戊烯部分的七次甲基花青和含有铝酸盐[(Al(O- t -C 4 F 9 ) 4 ) 4 ] -的碘鎓盐作为引发剂体系,与高功率NIR-LED 作为激发源,在 805 nm 处发射,强度为 1.2 W cm -2。在绝热条件下进行的实时 FTIR 分析表明,本研究中使用的不同氧杂环丁烷具有良好的反应性。OXT-03的最终转化率和反应速率取决于敏化剂的浓度而不是碘盐的浓度。此外,基于自由基和阳离子光聚合的混合光聚合使用含有 -Si(OR) 3部分的氧杂环丁烷单体与不同比例的TMPTA组合。结果表明,当TMPTA  :  GR-Si123的比例为5:5时,TMPTA的自由基聚合速率与GR-Si123的阳离子聚合速率相似。加入TMPTA导致在混合物中的引发剂组分的溶解度的提高,而溶解在纯的GR-Si123可以看出或多或少是穷人。这种含有阳离子和自由基可聚合基团的单体混合物促进了互穿聚合物网络(IPN)的形成。此外,环氧化物和丙烯酸酯的使用导致在 UV 和 NIR 敏化光聚合中氧杂环丁烷的阳离子聚合的类似加速。DMA 调查揭示了 tan  δ数据,它提供了各自的玻璃化转变温度 ( T g ) 数据。此处,5:5的TMPTA  :  GR-Si123比率导致最低的T g值。
更新日期:2021-09-15
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