Aqueous dispersion polymerization of diacetone acrylamide (DAAM) by chain extension from a hydrophilic poly(N,N-dimethylacrylamide) (PDMA₃₀) macromolecular chain transfer agent (macro-CTA) to produce PDMA₃₀–PDAAM_x block copolymer nano-objects was investigated in detail by systematically varying solids content and degree of polymerization of the core-forming PDAAM, leading to the formation of pure lamellae, mixed lamellae/vesicles, and pure vesicles as revealed by dynamic light scattering (DLS), transmission electron microscopy (TEM), atomic force microscopy (AFM), and scanning electron microscopy (SEM). PDMA₃₀–PDAAM_x lamellae were found to span an unprecedented wide space in the morphology phase diagram. Moreover, in situ cross-linking of lamellae via statistical copolymerization of DAAM with an asymmetric cross-linker allyl acrylamide and the effect of cross-linking density on the colloidal and morphological stabilities were studied, representing the first report on in situ cross-linking of lamellae during polymerization-induced self-assembly (PISA). Finally, reversible, temperature-induced morphological transitions from lamellae to worms/spheres on cooling were investigated by DLS, TEM, ¹H NMR spectroscopy, and rheology. The kinetics of the temperature-dependent morphological transitions and the rheological properties could be tuned by the cross-linking density.

中文翻译：

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通过水聚合诱导自组装合成的聚（二甲基丙烯酰胺）-聚（二丙酮丙烯酰胺）嵌段共聚物薄片的温度诱导形貌转变

研究了从亲水性聚（N，N-二甲基丙烯酰胺）（PDMA ₃₀）大分子链转移剂（macro-CTA）扩链得到的双丙酮丙烯酰胺（DAAM）的水分散聚合反应，以生产PDMA ₃₀ -PDAAM _x嵌段共聚物纳米物体。通过系统地改变固体含量和形成芯的PDAAM的聚合度来进行详细分析，从而通过动态光散射（DLS），透射电子显微镜（TEM）揭示纯薄片，混合薄片/​​囊泡和纯囊泡的形成，原子力显微镜（AFM）和扫描电子显微镜（SEM）。PDMA ₃₀ –PDAAM _x在形态相图中发现薄层跨越了前所未有的广阔空间。此外，研究了通过DAAM与不对称交联剂烯丙基丙烯酰胺的统计共聚进行的层状原位交联以及交联密度对胶体和形态稳定性的影响，这是有关原位交联聚丙烯酰胺的首次报道。聚合诱导的自组装（PISA）过程中的薄层。最后，通过DLS，TEM，¹ H NMR光谱和流变学研究了冷却时可逆的，温度诱导的从薄层到蠕虫/球体的形态转变。取决于温度的形态转变和流变性质的动力学可以通过交联密度来调节。