Microphase Separation Transformation in Bio-Based Benzoxazine/Phenolic/PEO-b-PCL Diblock Copolymer Mixtures Induced by Transesterification Reaction

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-12-20 DOI:10.1021/acs.macromol.4c02072

Yang-Chin Kao, Yi-Hsuan Ku, Mohamed Gamal Mohamed, Wei-Hung Su, Shiao-Wei Kuo

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引用次数: 0

Abstract

Herein, we synthesized a difunctionalized bio-based vanillin azine monomer (4,4′-((1E,1′E)-hydrazine-1,2-diylidenebis(methaneylylidene))bis(2-methoxyphenol), VBAZ-2OH) via a Schiff base reaction between vanillin and hydrazine monohydride. Subsequently, we successfully prepared 2,2′-(((1E,1′E)-hydrazine-1,2-diylidenebis(methaneylylidene))bis(8-methoxy-2H-benzo[e][1,3]oxazine-6,3(4H)-diyl))bis(ethan-1-ol), VBAZ-BZ-2OH), which contains oxazine units, through a Mannich condensation reaction of VBAZ-2OH with ethanolamine and paraformaldehyde in 1,4-dioxane as the solvent. The chemical structures of these two monomers (VBAZ-2OH and VBAZ-BZ-2OH) were characterized by using NMR and FTIR analyses. Our study aimed to investigate the transesterification reactions by blending different VBAZ-BZ-2OH/phenolic resin (BP) compositions with a PEO₁₁₂-b-PCL₉₉ (EC) diblock copolymer to form various BP/EC blends. These blends exhibit competitive hydrogen-bonding interaction phenomena, which were analyzed using one-dimensional and two-dimensional FTIR analyses. Interestingly, after thermal treatment of BP/EC blends at 150 °C, the ordered self-assembled lamellae or hexagonal packed cylinder structures transform into the disordered micelle or disorder structure in BP/EC blends as a result of the transesterification reaction due to EC becoming miscible with a VBAZ-BZ-2OH monomer, disrupting the ordered self-assembled structure, which was confirmed through TEM and SAXS analyses. The transesterification reaction could easily understand the order–disorder morphological transformation using BP/EC blends to replace thermogravimetric analysis (TGA) coupled with microcomputed gas chromatography (TGA-GC) analyses.

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.