Rude Erica, Laborie Marie-Pierre G
Washington State University, Department of Civil and Environmental Engineering, Wood Materials and Engineering Laboratory, PO Box 641806, Pullman, Washington 99164-1806, USA.
Appl Spectrosc. 2008 May;62(5):563-8. doi: 10.1366/000370208784344442.
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 CPMAS NMR) spectroscopy. MAPP was synthesized with 100% (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 CPMAS 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.
采用固态碳 - 13交叉极化魔角旋转核磁共振((13)C CPMAS NMR)光谱研究了马来酸酐接枝聚丙烯(MAPP)与木材之间的化学相互作用。MAPP在C(1)和C(4)碳处采用100% (13)C富集合成,以便检测[1,4-(13)C(2)]MAPP官能团,并与纤维素、木质素和枫木进行熔融共混。在纤维素/MAPP共混物中,酸酐和二羧酸马来酸官能团的(13)C CPMAS NMR校正信号强度变化表明,酯化反应可能主要发生在数量较多的二酸碳上。共混物中MAPP和纤维素碳的单质子旋转框架纵向弛豫时间((H)T(1rho))表明它们自旋耦合,即在10 - 200埃尺度上是均匀的。木质素/MAPP共混物中也表明发生了酯化反应。此外,羰基信号强度和(H)T(1rho)值的更显著变化表明木质素对MAPP的反应性可能比纤维素更高。最后,当枫木与MAPP熔融共混时,观察到的(13)C CP - MAS NMR光谱和(H)T(1rho)行为趋势与MAPP与纤维素或木质素共混时相同。因此,本研究阐明了在木材与MAPP熔融共混过程中,木材聚合物会发生酯化反应,优先与木质素反应。了解MAPP与木材的相互作用对于天然纤维增强热塑性复合材料的开发具有重要意义。