RAFT法制备的含PEG链段和丙烯酰胺基嵌段烷基侧链的三嵌段共聚物的热性能和自组装行为,Macromolecules

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RAFT法制备的含PEG链段和丙烯酰胺基嵌段烷基侧链的三嵌段共聚物的热性能和自组装行为
Macromolecules ( IF 5.1 ) Pub Date : 2021-01-05 , DOI: 10.1021/acs.macromol.0c02229
Athmen Zenati _{1,

2} , Ismail Kada ₃ , Gherici-Kaddour Zaouia ₄

Affiliation

通过使用大分子引发剂聚（乙二醇）（PEG）大分子链转移剂（macro-CTA）可逆加成-断裂链转移（RAFT）聚合反应，合成了一系列基于硬-软-硬链段的杂化三嵌段共聚物（TBC）系列）和单体对-十二烷基苯基-N-丙烯酰胺（DOPAM）。通过¹ H NMR，凝胶渗透色谱和差示扫描量热法对所得的TBC进行表征和评估。上的三嵌段共聚的动力学研究表明，分子量的良好分布（RAFT聚合的可控/活性特征中号_瓦特/中号_Ñ ≤1.39）。所有TBC均表现出两个熔融温度（T_m）在50和240°C下与PEG macro-CTA不同，后者在50°C下显示单个T _m。但是，与TBC-1，TBC-2和TBC-3相比，TBC-4和TBC-5表现出较强的T _m（PDOPAM）峰，这主要是由于PDOPAM体积分数的增加。通过原子力显微镜和掠入射小角X射线散射研究了TBC的形态。具有不同嵌段比率（f _PDOPAM ≠ f _PEG的TBC（TBC-2，TBC-4和TBC-5））形成圆柱形相，特别是包含较高PDOPAM比（72％）的TBC-5产生了高度有序的圆柱形纳米结构。相反，具有几乎相同长度的PDOPAM（49％）和PEG（51％）的TBC-3自组装成层状相。

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Thermal Properties and Self-Assembly Behaviors of Triblock Copolymers Consisting of PEG Segment and Acrylamide-Based Block Bearing Alkyl Side Chains Prepared by RAFT Method

A new series of hybrid triblock copolymers (TBCs) based on hard–soft–hard segments are synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization using a macroinitiator poly(ethylene glycol) (PEG) macromolecular chain transfer agent (macro-CTA) and monomer p-dodecylphenyl-N-acrylamide (DOPAM). The resulting TBCs are characterized and evaluated by ¹H NMR, gel permeation chromatography, and differential scanning calorimetry. Kinetic studies on triblock copolymerization indicated the controlled/living characteristic of RAFT polymerization with good distribution of molecular weight (M_w/M_n ≤ 1.39). All TBCs exhibited two melting temperatures (T_m) at 50 and 240 °C unlike PEG macro-CTA, which revealed a single T_m at 50 °C. However, TBC-4 and TBC-5 showed strong T_m (PDOPAM) peaks compared to TBC-1, TBC-2, and TBC-3, mainly due to the increase in the volume fraction of PDOPAM. Morphologies of TBCs are studied by atomic force microscopy and grazing incidence small-angle X-ray scattering. TBCs (TBC-2, TBC-4, and TBC-5) with different blocks ratios (f_PDOPAM ≠ f_PEG) formed cylindrical phases, in particular TBC-5 containing a higher PDOPAM ratio (72%) generated a highly ordered cylindrical nanostructure. Contrastingly, TBC-3 with nearly the same length of PDOPAM (49%) and PEG (51%) self-assembled into the lamellar phase.

更新日期：2021-01-26

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