Yuan Jingjing, Xu Jinbao
Department of Art and Design, Taiyuan University, Taiyuan 237016, China.
School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China.
Materials (Basel). 2024 Jan 9;17(2):330. doi: 10.3390/ma17020330.
Amphiphilic block copolymers-based aqueous color inks show great potential in the field of visual communication design. However, the conventional step-by-step chemistry employed to synthesize the amphiphilic block copolymers is intricate, with low yield and high economic and environmental costs. In this work, we present a novel method for preparing an amphiphilic AB di-block copolymer of PCL--PAA by employing a combined polymerization strategy that involves both cationic ring-opening polymerization (ROP) of the -caprolactone monomer and the reversible addition-fragmentation chain-transfer (RAFT) polymerization on the acrylic acid monomer simultaneously. The corresponding polycaprolactone (PCL) and polyacrylic acid (PAA) serve as the hydrophobic and hydrophilic units, respectively. The effectiveness of the amphiphilic AB di-block copolymer as the polymeric pigment dispersant for water-based color inks is evaluated. The amphiphilic AB di-block copolymer of PCL--PAA exhibits a molecular weight of 1400 g mol, which is consistent with the theoretical value and suitable for polymeric dispersant application. The high surface excess (Γ) of the PCL--PAA in water indicates a densely packed molecular morphology at the water/air interface. Additionally, micelles can be stably formed in the aqueous PCL--PAA solution at very low concentrations by demonstrating a low CMC value of 10 wt% and a micelle dimension of approximately 30 nm. The model ink dispersion is prepared using organic dyes (Disperse Yellow 232) and the amphiphilic block copolymer of PCL--PAA. The dispersion demonstrates near-Newtonian behavior, which is highly favorable for the application as inkjet ink. Furthermore, the ink dispersion displays a low viscosity, making it particularly suitable for visual communication design and printing purposes. Moreover, the ink dispersion demonstrates an unimodal distribution of the particle size, with an average diameter of approximately 500 nm. It retains exceptional stability of dispersion and even conducts a thermal aging treatment at 60 °C for 5 days. This work presents a facile and efficient synthetic strategy and molecular design of AB di-block copolymer-based dispersants for dye dispersions.
基于两亲性嵌段共聚物的水性彩色油墨在视觉传达设计领域显示出巨大潜力。然而，用于合成两亲性嵌段共聚物的传统逐步化学方法复杂，产率低，且经济和环境成本高。在这项工作中，我们提出了一种制备聚己内酯-聚丙烯酸（PCL-PAA）两亲性AB二嵌段共聚物的新方法，该方法采用了一种组合聚合策略，同时涉及ε-己内酯单体的阳离子开环聚合（ROP）和丙烯酸单体上的可逆加成-断裂链转移（RAFT）聚合。相应的聚己内酯（PCL）和聚丙烯酸（PAA）分别作为疏水和亲水单元。评估了两亲性AB二嵌段共聚物作为水性彩色油墨的聚合物颜料分散剂的有效性。PCL-PAA两亲性AB二嵌段共聚物的分子量为1400 g/mol，与理论值一致，适用于聚合物分散剂应用。PCL-PAA在水中的高表面过剩（Γ）表明在水/空气界面处分子形态紧密堆积。此外，通过显示低至10 wt%的临界胶束浓度（CMC）值和约30 nm的胶束尺寸，在非常低的浓度下，PCL-PAA水溶液中可以稳定地形成胶束。使用有机染料（分散黄232）和PCL-PAA两亲性嵌段共聚物制备了模型油墨分散体。该分散体表现出近牛顿行为，这对于作为喷墨油墨的应用非常有利。此外，油墨分散体显示出低粘度，使其特别适用于视觉传达设计和印刷目的。此外，油墨分散体表现出单峰粒度分布，平均直径约为500 nm。它保持了优异的分散稳定性，甚至在60°C下进行了5天的热老化处理。这项工作提出了一种简便有效的合成策略以及基于AB二嵌段共聚物的染料分散剂的分子设计。
