A new synthetic strategy for the preparation of methacrylic monomers and polymers carrying acyl β‐amino groups is presented. The approach is based on the Michael addition of aliphatic amines onto asymmetric acrylic/methacrylic compounds, reacting the amine highly selectively with the acrylic unit while leaving the methacrylic moiety unreacted. The corresponding polymers are then obtained by conventional radical polymerization. The use of N,N,N′,N′‐tetraethyldiethylenetriamine (TEDETA) as the secondary amine leads to TEDETA moieties supported on polymeric chains. The new aminopolymers are sensitive to pH and to temperature exhibiting a lower critical solution temperature of between 50 and 90 °C. A further interesting feature of the new approach is that the stability toward hydrolysis of the side β‐amino acyl compounds was found to be dependent on whether an acrylamide or an acrylate is employed as the acrylic group of the asymmetric starting material. The esters exhibit an enhanced sensitivity to hydrolysis, compared to standard aliphatic esters, and decompose releasing a derivative of the amine precursor, within hours or weeks, depending on the pH and temperature conditions. The use of the amides leads to stable polymers when the same experimental conditions are applied. The novel dendronic polyamines have been proven to interact with DNA and to transfect cells with efficiency close to that obtained with polyethyleneimine vectors used as positive controls. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2297–2305

中文翻译：

---

稳定或不稳定的甲基丙烯酸酯中的烯丙基多胺，可通过将迈克尔选择性加成到不对称的二丙烯酸化合物上而制得

提出了一种新的合成策略，用于制备甲基丙烯酸单体和带有酰基β-氨基的聚合物。该方法基于脂肪族胺在不对称丙烯酸/甲基丙烯酸化合物上的迈克尔加成，使胺与丙烯酸单元高度选择性地反应，而甲基丙烯酸部分未反应。然后通过常规的自由基聚合获得相应的聚合物。使用Ñ，Ñ，Ñ '，Ñε-四乙基二亚乙基三胺（TEDETA）作为仲胺可导致TEDETA部分负载在聚合物链上。新的氨基聚合物对pH值和温度敏感，在50至90°C之间显示出较低的临界溶液温度。这种新方法的另一个有趣特征是，发现侧链β-氨基酰基化合物水解的稳定性取决于是否使用丙烯酰胺或丙烯酸酯作为不对称原料的丙烯酸基团。与标准脂族酯相比，这些酯对水解表现出增强的敏感性，并在数小时或数周内分解释放出胺前体的衍生物，具体取决于pH和温度条件。当应用相同的实验条件时，酰胺的使用可产生稳定的聚合物。新型树突状多胺已被证明可与DNA相互作用，并以与用作阳性对照的聚乙烯亚胺载体相近的效率转染细胞。©2014 Wiley Periodicals，Inc. J. Polym。科学，A部分：Polym。化学2014，52，2297年至2305年