Karpov Sergei V, Iakunkov Artem, Chernyaev Dmitry A, Kurbatov Vladimir G, Malkov Georgiy V, Badamshina Elmira R
Department of Polymers and Composites, Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry of Russian Academy of Sciences, 1 Academician Semenov Avenue, Chernogolovka 142432, Russia.
School of Engineering Sciences in Chemistry, Biotechnology and Health, KTH Royal Institute of Technology, SE-100 44 Stockholm, Sweden.
Polymers (Basel). 2024 Feb 3;16(3):426. doi: 10.3390/polym16030426.
Hyperbranched polymers (HBPs) are widely applied nowadays as functional materials for biomedicine needs, nonlinear optics, organic semiconductors, etc. One of the effective and promising ways to synthesize HBPs is a polyaddition of AB+A+B monomers that is generated in the A+CB, AA'+B, A+B'B, and A+C+B systems or using other approaches. It is clear that all the foundational features of HBPs that are manufactured by a polyaddition reaction are defined by the component composition of the monomer mixture. For this reason, we have designed a structural kinetic model of AB+A+B monomer mixture polyaddition which makes it possible to predict the impact of the monomer mixture's composition on the molecular weight characteristics of hyperbranched polymers (number average (DP) and weight average (DP) degree of polymerization), as well as the degree of branching (DB) and gel point (p). The suggested model also considers the possibility of a positive or negative substitution effect during polyaddition. The change in the macromolecule parameters of HBPs formed by polyaddition of AB+A+B monomers is described as an infinite system of kinetic equations. The solution for the equation system was found using the method of generating functions. The impact of both the component's composition and the substitution effect during the polyaddition of AB+A+B monomers on structural and molecular weight HBP characteristics was investigated. The suggested model is fairly versatile; it makes it possible to describe every possible case of polyaddition with various monomer combinations, such as A+AB, AB+B, AB, or A+B. The influence of each monomer type on the main characteristics of hyperbranched polymers that are obtained by the polyaddition of AB+A+B monomers has been investigated. Based on the results obtained, an empirical formula was proposed to estimate the p = p during the polyaddition of an AB+A+B monomer mixture: p = p = (-0.53([B]/[A]) + 0.78)υAB + (1/3)([B]/[A]), where (1/3)([B]/[A]) is the Flory equation for the A+B polyaddition, [A] and [B] are the A and B group concentration from A and B, respectively, and υAB is the mole fraction of the AB monomer in the mixture. The equation obtained allows us to accurately predict the p value, with an AB monomer content of up to 80%.
如今，超支化聚合物（HBPs）作为满足生物医学需求、非线性光学、有机半导体等领域的功能材料被广泛应用。合成超支化聚合物的一种有效且有前景的方法是AB+A+B单体的逐步加成反应，该反应在A+CB、AA'+B、A+B'B和A+C+B体系中发生，或者采用其他方法。显然，通过逐步加成反应制备的超支化聚合物的所有基本特征都由单体混合物的组成成分决定。因此，我们设计了AB+A+B单体混合物逐步加成的结构动力学模型，该模型能够预测单体混合物组成对超支化聚合物分子量特征（数均聚合度（DP）和重均聚合度（DP））、支化度（DB）和凝胶点（p）的影响。所提出的模型还考虑了逐步加成过程中可能存在的正或负取代效应。通过AB+A+B单体逐步加成形成的超支化聚合物大分子参数的变化被描述为一个无穷的动力学方程组。使用生成函数法求解该方程组。研究了AB+A+B单体逐步加成过程中组分组成和取代效应对超支化聚合物结构和分子量特征的影响。所提出的模型具有相当的通用性；它能够描述使用各种单体组合（如A+AB、AB+B、AB或A+B）进行逐步加成的每种可能情况。研究了每种单体类型对通过AB+A+B单体逐步加成得到的超支化聚合物主要特征的影响。基于所得结果，提出了一个经验公式来估算AB+A+B单体混合物逐步加成过程中的p = p：p = p = (-0.53([B]/[A]) + 0.78)υAB + (1/3)([B]/[A])，其中(1/3)([B]/[A])是A+B逐步加成的弗洛里方程，[A]和[B]分别是A和B中A基团和B基团的浓度，υAB是混合物中AB单体的摩尔分数。得到的方程使我们能够准确预测p值，AB单体含量高达80%。
