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Carbon-13 Cross-Polarization Magic-Angle-Spinning Nuclear Magnetic Resonance Investigation of the Interactions Between Maleic Anhydride Grafted Polypropylene and Wood Polymers

机译:碳13交极化魔角纺核磁共振研究马来酸酐接枝聚丙烯与木材聚合物之间相互作用的

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摘要

The chemical interactions between maleic anhydride grafted polypropylene (MAPP) and wood were studied with solid-state carbon-13 cross-polarization magic-angle-spinning nuclear magnetic resonance ~(13)C CP-MAS NMR) spectroscopy. MAPP was synthesized with 100percent ~(13)C enrichment at the C_(1) and C_(4) carbons to allow detection of the [1,4-~(13)C_(2)]MAPP functional groups and was melt blended with cellulose, lignin, and maple wood. In the cellulose/MAPP blend, changes in ~(13)C CP-MAS NMR corrected signal intensities for the anhydride and dicarboxylic maleic acid functionalities suggested that esterification may have occurred predominantly from the more numerous diacid carbons. A single proton longitudinal relaxation in the rotating frame, ~(H)T_(1rho), for the MAPP and the cellulose carbons in the blend suggested that they were spin coupled, i.e., homogeneous on a 10-200 Angstrom scale. Esterification was also suggested in the lignin/MAPP blend. Furthermore, the more significant changes in the intensities of the carbonyl signals and ~(H)T_(1rho) values suggested that lignin may be more reactive to MAPP than cellulose. Finally, when maple was melt blended with MAPP, the same trends in the ~(13)C CP-MAS NMR spectra and ~(H)T_(1rho) behavior were observed as when MAPP was blended with cellulose or lignin. This study therefore clarifies that during melt compounding of wood with MAPP, esterification occurs with wood polymers, preferentially with lignin. Understanding the interactions of MAPP with wood is of significance for the development of natural-fiber-reinforced thermoplastic composites.
机译:马来酸酐接枝聚丙烯(MAPP)与木材之间的化学相互作用用固态碳13交叉极化魔术角自旋核磁共振((13)C CP-MAS NMR)光谱进行了研究。合成了MAPP,在C_(1)和C_(4)碳处富集了100%〜(13)C,以检测[1,4-〜(13)C_(2)] MAPP官能团,并与纤维素,木质素和枫木。在纤维素/ MAPP共混物中,〜(13)C CP-MAS NMR校正的酸酐和二羧酸马来酸官能度信号强度的变化表明,酯化作用可能主要是由更多的二酸碳发生的。对于MAPP和共混物中的纤维素碳,旋转框架中的单个质子纵向弛豫为〜(H)T_(1rho),表明它们是自旋偶联的,即在10-200埃范围内均质。木质素/ MAPP混合物中也建议酯化。此外,羰基信号强度和〜(H)T_(1rho)值强度的更显着变化表明,木质素对MAPP的反应性可能比纤维素高。最后,当枫木与MAPP熔融共混时,在〜(13)C CP-MAS NMR光谱和〜(H)T_(1rho)行为中观察到与将MAPP与纤维素或木质素共混时相同的趋势。因此,这项研究澄清了在木材与MAPP熔融混合的过程中,木材聚合物(优选木质素)发生酯化反应。理解MAPP与木材的相互作用对于开发天然纤维增强的热塑性复合材料具有重要意义。

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