Shengtao Zhou , Jun Xu , Zhaohui Zhang , Shiyun Zhu , Jun Li , Wei Zhang , Fengshan Zhang , Kefu Chen
{"title":"利用深共晶溶剂均相催化技术可控制备醋酸纤维素","authors":"Shengtao Zhou , Jun Xu , Zhaohui Zhang , Shiyun Zhu , Jun Li , Wei Zhang , Fengshan Zhang , Kefu Chen","doi":"10.1016/j.carbpol.2024.122964","DOIUrl":null,"url":null,"abstract":"<div><div>This work proposed a homogeneous preparation strategy of cellulose acetate by using a deep eutectic solvent consisting of zinc chloride/phosphoric acid/water (ZnCl<sub>2</sub>/PA/H<sub>2</sub>O). The results showed that the DES (the molar ratio of ZnCl<sub>2</sub>: PA: H<sub>2</sub>O = 1:1:3) had good solubility for bamboo pulp with high degree of polymerization. The dynamic dissolution behavior of cellulose in DES was also studied. Cellulose was first moistened and swollen and then dissolved. The crystalline state of cellulose changed from type I to type II after regeneration. Under the synergistic effect of acetic anhydride (Ac<sub>2</sub>O), the dissolved cellulose in DES could be uniformly acetylated. The effects of temperature, reaction time and molar ratio of Ac<sub>2</sub>O/anhydrous glucose on degree of substitution (DS) were investigated in their respective ranges (30–50 °C, 2–10 h and 4–24). Cellulose acetate with DS of 0.42–1.81 was successfully prepared. The substituent distribution of the sample was analyzed as C-6 > C-2 > C-3. Moreover, the entire process required no additional catalysts or activation steps, reducing the difficulty of solvent recovery. The insight from this study provides a new idea for the development of greener methods for the homogeneous preparation of cellulose acetate.</div></div>","PeriodicalId":261,"journal":{"name":"Carbohydrate Polymers","volume":"349 ","pages":"Article 122964"},"PeriodicalIF":10.7000,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Controlled preparation of cellulose acetate by deep eutectic solvent homogeneous catalysis\",\"authors\":\"Shengtao Zhou , Jun Xu , Zhaohui Zhang , Shiyun Zhu , Jun Li , Wei Zhang , Fengshan Zhang , Kefu Chen\",\"doi\":\"10.1016/j.carbpol.2024.122964\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>This work proposed a homogeneous preparation strategy of cellulose acetate by using a deep eutectic solvent consisting of zinc chloride/phosphoric acid/water (ZnCl<sub>2</sub>/PA/H<sub>2</sub>O). The results showed that the DES (the molar ratio of ZnCl<sub>2</sub>: PA: H<sub>2</sub>O = 1:1:3) had good solubility for bamboo pulp with high degree of polymerization. The dynamic dissolution behavior of cellulose in DES was also studied. Cellulose was first moistened and swollen and then dissolved. The crystalline state of cellulose changed from type I to type II after regeneration. Under the synergistic effect of acetic anhydride (Ac<sub>2</sub>O), the dissolved cellulose in DES could be uniformly acetylated. The effects of temperature, reaction time and molar ratio of Ac<sub>2</sub>O/anhydrous glucose on degree of substitution (DS) were investigated in their respective ranges (30–50 °C, 2–10 h and 4–24). Cellulose acetate with DS of 0.42–1.81 was successfully prepared. The substituent distribution of the sample was analyzed as C-6 > C-2 > C-3. Moreover, the entire process required no additional catalysts or activation steps, reducing the difficulty of solvent recovery. The insight from this study provides a new idea for the development of greener methods for the homogeneous preparation of cellulose acetate.</div></div>\",\"PeriodicalId\":261,\"journal\":{\"name\":\"Carbohydrate Polymers\",\"volume\":\"349 \",\"pages\":\"Article 122964\"},\"PeriodicalIF\":10.7000,\"publicationDate\":\"2024-11-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Carbohydrate Polymers\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0144861724011901\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Carbohydrate Polymers","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0144861724011901","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
引用次数: 0
摘要
本研究提出了一种使用氯化锌/磷酸/水(ZnCl2/PA/H2O)组成的深共晶溶剂均匀制备醋酸纤维素的策略。结果表明,DES(氯化锌/磷酸/水的摩尔比为 1:1:3)对高聚合度竹浆具有良好的溶解性。此外,还研究了纤维素在 DES 中的动态溶解行为。纤维素首先被湿润、膨胀,然后被溶解。再生后,纤维素的结晶状态从 I 型变为 II 型。在乙酸酐(Ac2O)的协同作用下,DES 中溶解的纤维素可被均匀乙酰化。研究了温度、反应时间和 Ac2O 与无水葡萄糖的摩尔比对取代度(DS)的影响。成功制备出 DS 为 0.42-1.81 的醋酸纤维素。样品的取代基分布分析为 C-6 > C-2 > C-3。此外,整个过程不需要额外的催化剂或活化步骤,降低了溶剂回收的难度。这项研究为开发更环保的醋酸纤维素均相制备方法提供了新思路。
Controlled preparation of cellulose acetate by deep eutectic solvent homogeneous catalysis
This work proposed a homogeneous preparation strategy of cellulose acetate by using a deep eutectic solvent consisting of zinc chloride/phosphoric acid/water (ZnCl2/PA/H2O). The results showed that the DES (the molar ratio of ZnCl2: PA: H2O = 1:1:3) had good solubility for bamboo pulp with high degree of polymerization. The dynamic dissolution behavior of cellulose in DES was also studied. Cellulose was first moistened and swollen and then dissolved. The crystalline state of cellulose changed from type I to type II after regeneration. Under the synergistic effect of acetic anhydride (Ac2O), the dissolved cellulose in DES could be uniformly acetylated. The effects of temperature, reaction time and molar ratio of Ac2O/anhydrous glucose on degree of substitution (DS) were investigated in their respective ranges (30–50 °C, 2–10 h and 4–24). Cellulose acetate with DS of 0.42–1.81 was successfully prepared. The substituent distribution of the sample was analyzed as C-6 > C-2 > C-3. Moreover, the entire process required no additional catalysts or activation steps, reducing the difficulty of solvent recovery. The insight from this study provides a new idea for the development of greener methods for the homogeneous preparation of cellulose acetate.
期刊介绍:
Carbohydrate Polymers stands as a prominent journal in the glycoscience field, dedicated to exploring and harnessing the potential of polysaccharides with applications spanning bioenergy, bioplastics, biomaterials, biorefining, chemistry, drug delivery, food, health, nanotechnology, packaging, paper, pharmaceuticals, medicine, oil recovery, textiles, tissue engineering, wood, and various aspects of glycoscience.
The journal emphasizes the central role of well-characterized carbohydrate polymers, highlighting their significance as the primary focus rather than a peripheral topic. Each paper must prominently feature at least one named carbohydrate polymer, evident in both citation and title, with a commitment to innovative research that advances scientific knowledge.