Properties of quaternized and cross-linked hydroxyethylcellulose composite films

IF 4.9 2区工程技术 Q1 MATERIALS SCIENCE, PAPER & WOOD Cellulose Pub Date : 2024-10-19 DOI:10.1007/s10570-024-06154-7

Ivan Šimkovic, Filip Gucmann, Edmund Dobročka, Jaroslav Filip, Michal Hricovíni, Viera Dujnič, Raniero Mendichi, Alberto Giacometti Schieroni, Daniele Piovani, Stefania Zappia, Miloš Hricovíni

{"title":"Properties of quaternized and cross-linked hydroxyethylcellulose composite films","authors":"Ivan Šimkovic, Filip Gucmann, Edmund Dobročka, Jaroslav Filip, Michal Hricovíni, Viera Dujnič, Raniero Mendichi, Alberto Giacometti Schieroni, Daniele Piovani, Stefania Zappia, Miloš Hricovíni","doi":"10.1007/s10570-024-06154-7","DOIUrl":null,"url":null,"abstract":"<div><p>Although trimetylammonium-2-hydroxypropyl-hydroxyethylcellulose (QHEC) is a well-known polysaccharide material, some of its properties have not been previously studied in detail. Therefore, we applied a combination of multidimensional nuclear magnetic resonance (NMR) in D<sub>2</sub>O on hydroxyethylcellulose (HEC) and HEC derivatives, and size-exclusion chromatography with multi-angle laser light scattering (SEC-MALS) in carbonate buffer at pH 10; while Fourier-transform infrared spectroscopy (FTIR), the X-ray diffraction (XRD), the thermogravimetry/differential/differential thermogravimetry (TG/DTG/DTA) and atomic force microscopy (AFM) in film form. SEC-MALS revealed various water-solubility of prepared derivatives: HEC (98%) > CHEC (72%) > QHEC (26%) > QCHEC (14%). Due to its substituents, the HEC macromolecule forms coil structures with varying gyration radii: QHEC (38–260 nm) > QCHEC (10–230 nm) > CHEC (21–100 nm) > HEC (23–50 nm). FTIR analysis of all prepared films confirmed their identical structure compared to that observed in liquid form in D<sub>2</sub>O. Onset temperatures (OT) of films degradation decreased in order: HEC (222 °C) > QCHEC (162 °C) > CHEC (142 °C) > QHEC (141 °C). The X-ray diffraction confirmed residual crystallinity of cellulose II (CII) in all four types of prepared films and was linked to ~ 2% water-insolubility of HEC derivatives revealed by SEC-MALS. Atomic force microscopy (AFM) showed significant differences in surface morphology among the four prepared films with surface roughness of: HEC (25 nm) > QCHEC (5.8 nm) > QHEC (4.2 nm) > CHEC (2.8 nm). Various spherical particles were found in case of HEC, circular depressions/holes approximately 4 μm in diameter were observed in case of QHEC. Except for the HEC, all other films showed granular surface probably due to insoluble components. Based on the mechanisms of quaternization and crosslinking and the results of analysis on water-soluble part and films we could assume that there are similarities in structures between the soluble and insoluble products of the reactions.</p></div>","PeriodicalId":511,"journal":{"name":"Cellulose","volume":"31 17","pages":"10341 - 10357"},"PeriodicalIF":4.9000,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s10570-024-06154-7.pdf","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Cellulose","FirstCategoryId":"88","ListUrlMain":"https://link.springer.com/article/10.1007/s10570-024-06154-7","RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, PAPER & WOOD","Score":null,"Total":0}

引用次数: 0

Abstract

Although trimetylammonium-2-hydroxypropyl-hydroxyethylcellulose (QHEC) is a well-known polysaccharide material, some of its properties have not been previously studied in detail. Therefore, we applied a combination of multidimensional nuclear magnetic resonance (NMR) in D₂O on hydroxyethylcellulose (HEC) and HEC derivatives, and size-exclusion chromatography with multi-angle laser light scattering (SEC-MALS) in carbonate buffer at pH 10; while Fourier-transform infrared spectroscopy (FTIR), the X-ray diffraction (XRD), the thermogravimetry/differential/differential thermogravimetry (TG/DTG/DTA) and atomic force microscopy (AFM) in film form. SEC-MALS revealed various water-solubility of prepared derivatives: HEC (98%) > CHEC (72%) > QHEC (26%) > QCHEC (14%). Due to its substituents, the HEC macromolecule forms coil structures with varying gyration radii: QHEC (38–260 nm) > QCHEC (10–230 nm) > CHEC (21–100 nm) > HEC (23–50 nm). FTIR analysis of all prepared films confirmed their identical structure compared to that observed in liquid form in D₂O. Onset temperatures (OT) of films degradation decreased in order: HEC (222 °C) > QCHEC (162 °C) > CHEC (142 °C) > QHEC (141 °C). The X-ray diffraction confirmed residual crystallinity of cellulose II (CII) in all four types of prepared films and was linked to ~ 2% water-insolubility of HEC derivatives revealed by SEC-MALS. Atomic force microscopy (AFM) showed significant differences in surface morphology among the four prepared films with surface roughness of: HEC (25 nm) > QCHEC (5.8 nm) > QHEC (4.2 nm) > CHEC (2.8 nm). Various spherical particles were found in case of HEC, circular depressions/holes approximately 4 μm in diameter were observed in case of QHEC. Except for the HEC, all other films showed granular surface probably due to insoluble components. Based on the mechanisms of quaternization and crosslinking and the results of analysis on water-soluble part and films we could assume that there are similarities in structures between the soluble and insoluble products of the reactions.

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

季铵化和交联羟乙基纤维素复合薄膜的性能

虽然三甲基铵-2-羟丙基-羟乙基纤维素（QHEC）是一种众所周知的多糖材料，但此前对其某些特性的研究并不详细。因此，我们对羟乙基纤维素（HEC）和 HEC 衍生物采用了 D2O 中的多维核磁共振（NMR）和 pH 值为 10 的碳酸盐缓冲液中的尺寸排阻色谱与多角度激光光散射（SEC-MALS）相结合的方法；傅立叶变换红外光谱（FTIR）、X 射线衍射（XRD）、热重/差重/差重热重（TG/DTG/DTA）和原子力显微镜（AFM）。SEC-MALS显示了所制备衍生物的不同水溶性：HEC (98%) > CHEC (72%) > QHEC (26%) > QCHEC (14%)。由于其取代基，HEC 大分子形成了具有不同回转半径的线圈结构：QHEC（38-260 nm）> QCHEC（10-230 nm）> CHEC（21-100 nm）> HEC（23-50 nm）。对所有制备的薄膜进行的傅立叶变换红外光谱分析证实，与在 D2O 中观察到的液态薄膜相比，它们的结构完全相同。薄膜降解的起始温度（OT）依次降低：HEC (222 °C) > QCHEC (162 °C) > CHEC (142 °C) > QHEC (141 °C)。X 射线衍射证实了所有四种制备的薄膜中纤维素 II (CII) 的残余结晶度，这与 SEC-MALS 显示的 HEC 衍生物约 2% 的水不溶性有关。原子力显微镜（AFM）显示，四种制备的薄膜在表面形态上存在显著差异，其表面粗糙度分别为HEC (25 nm) > QCHEC (5.8 nm) > QHEC (4.2 nm) > CHEC (2.8 nm)。在 HEC 中发现了各种球形颗粒，在 QHEC 中观察到了直径约为 4 μm 的圆形凹陷/孔洞。除 HEC 外，所有其他薄膜的表面都呈颗粒状，这可能是由于不溶性成分造成的。根据季铵化和交联的机理以及对水溶性部分和薄膜的分析结果，我们可以认为反应的可溶产物和不溶产物在结构上具有相似性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文去求助

来源期刊

Cellulose 工程技术-材料科学：纺织

CiteScore

10.10

自引率

10.50%

发文量

580

审稿时长

3-8 weeks

期刊介绍： Cellulose is an international journal devoted to the dissemination of research and scientific and technological progress in the field of cellulose and related naturally occurring polymers. The journal is concerned with the pure and applied science of cellulose and related materials, and also with the development of relevant new technologies. This includes the chemistry, biochemistry, physics and materials science of cellulose and its sources, including wood and other biomass resources, and their derivatives. Coverage extends to the conversion of these polymers and resources into manufactured goods, such as pulp, paper, textiles, and manufactured as well natural fibers, and to the chemistry of materials used in their processing. Cellulose publishes review articles, research papers, and technical notes.