Microfabrication of 3D-hydrogels via two-photon polymerization of poly(2-ethyl-2-oxazoline) diacrylates
Microfabrication of 3D-hydrogels via two-photon polymerization of poly(2-ethyl-2-oxazoline) diacrylates
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DOI：
10.1016/j.eurpolymj.2019.109295
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发表时间：
2020-01
影响因子：
6
通讯作者：
Thomas Wloka;Steffen Czich;Maximilian Kleinsteuber;Elisabeth Moek;Christine Weber;M. Gottschaldt;K. Liefeith;U. Schubert
中科院分区：
文献类型：
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作者：
Thomas Wloka;Steffen Czich;Maximilian Kleinsteuber;Elisabeth Moek;Christine Weber;M. Gottschaldt;K. Liefeith;U. Schubert
双（丙烯酸酯）官能化聚（2-乙基-2-恶唑啉）（PEtOx-DA）用作使用新型水溶性光引发剂（PI）的结构化双光子聚合（2PP）的大单体和交联剂。通过反式1,4-二溴-丁-2-烯（DBB）引发的2-乙基-2-恶唑啉的阳离子开环聚合（CROP）封端获得遥爪。通过质谱、核磁共振光谱和尺寸排阻色谱对 PEtOx-DA 进行分析表明，回流乙腈中的 CROP 成功地从 10g 放大至 200g，聚合度分别为 10 和 18。基于环戊酮二亚苄基的供体-受体-供体 π 体系与丙烯酸酯官能化三芳基胺偶联的 PI 被证明适合生产结构化水凝胶。具有不同照射时间和激光强度的制造体素阵列显示体素宽度低于 20μm，显示出与高分辨率 PEtOx-DA 以及通过 2PP 的聚乙二醇二丙烯酸酯 (PEG-DA) 类似的结构化能力。所获得的结构的特性通过一系列线阵列以及设计的蜘蛛网图案来表征。与使用的 PEG-DA 相比，PEtOx-DA 显示出增强的适用性。
Bis(acrylate) functionalized poly(2-ethyl-2-oxazoline)s (PEtOx-DA) served as macromonomers as well as crosslinkers for the structured two-photon polymerization (2PP) using a novel water soluble photoinitiator (PI). The telechelics were obtainedviaend capping of thetrans-1,4-dibromo-but-2-ene (DBB) initiated cationic ring-opening polymerization (CROP) of 2-ethyl-2-oxazoline. Analysis of the PEtOx-DA by means of mass spectrometry, nuclear magnetic resonance spectroscopy and size exclusion chromatography revealed that the CROP in refluxing acetonitrile was successfully scaled-up from 10 g to 200 g for degrees of polymerization of 10 and 18, respectively. The PI based on a cyclopentanone dibenzylidene based donor-acceptor-donor π system coupled to an acrylate functionalized triaryl amine proved suitable to produce structured hydrogels. Fabricated voxel arrays with different shot times and laser intensities revealed voxel widths below 20 µm showing a similar structuring capability with high resolution of PEtOx-DA as well as for poly(ethylene glycol) diacrylate (PEG-DA) via 2PP. The properties of obtained structures were characterized by a series of line arrays as well as designed Spider-Web-patterns. PEtOx-DA revealed enhanced suitability in comparison to the used PEG-DA.