南京林业大学学报(自然科学版) ›› 2015, Vol. 58 ›› Issue (03): 113-118.doi: 10.3969/j.issn.1000-2006.2015.03.021

• 研究论文 • 上一篇    下一篇

钛酸正丁酯催化纤维素纤维接枝聚己内酯

李韵卒,杨益琴*,杨勤武,顾俐慧,王志国   

  1. 南京林业大学轻工科学与工程学院,江苏省制浆造纸科学与技术重点实验室,江苏 南京 210037
  • 出版日期:2015-05-30 发布日期:2015-05-30
  • 基金资助:
    收稿日期:2014-10-13 修回日期:2015-03-02
    基金项目:国家林业公益性行业科研专项项目(201404510); 国家自然科学基金青年科学基金项目(31200444)
    第一作者:李韵卒,硕士生。*通信作者:杨益琴,副教授。E-mail: wsfyyq@163.com。
    引文格式:李韵卒,杨益琴,杨勤武,等. 钛酸正丁酯催化纤维素纤维接枝聚己内酯[J]. 南京林业大学学报:自然科学版,2015,39(3):113-118.

Catalytic grafting of cellulose fibers with polycaprolactone by tetrabutyl titanate

LI Yunzu, YANG Yiqin*, YANG Qinwu, GU Lihui, WANG Zhiguo   

  1. Jiangsu Provincial Key Lab of Pulp and Paper Science and Technology,College of Light Industry Science and Engineering, Nanjing Forestry University,Nanjing 210037,China
  • Online:2015-05-30 Published:2015-05-30

摘要: 以棉浆粕为原料,通过钛酸正丁酯(Ti(O-n-Bu)4)催化己内酯开环聚合接枝纤维素制备纤维素聚己内酯。通过单因素实验和正交试验研究了反应温度、反应时间、催化剂用量及己内酯用量对纤维素接枝率和己内酯转化率的影响。结果表明:反应温度是影响接枝率的主要因素,其次是己内酯用量,反应时间的影响最小。当反应温度为130 ℃、己内酯与纤维素的质量比为30、催化剂质量分数为2%(聚己内酯理论聚合度为37)、反应时间25 h时,己内酯的转化率和纤维素-聚己内酯的接枝率最高,分别为97.46%、70.44%。采用FTIR、1H-NMR、XRD对产物进行了结构和性能表征,红外光谱分析表明,纤维素与聚己内酯发生了接枝共聚反应; 1H-NMR分析表明,己内酯已基本转化为聚己内酯,根据计算可知己内酯转化率与重量法测定结果一致; X-射线衍射图谱显示纤维素共聚物中纤维素的结晶结构特征减弱,出现了聚己内酯的结晶特征峰。

Abstract: Cellulose polycaprolactone was prepared by grafting of cotton linter pulp with caprolactone(CL)catalyzed by Ti(O-n-Bu)4 via ring-opening polymerization. Effects of reaction temperature, reaction time, Ti(O-n-Bu)4 amount, and caprolactone(CL)on monomer conversion and graft rate were investigated through single factor experiments and orthogonal test. The results showed that the significance sequence of the factors affecting the grafting rate was reaction temperature, mass ratio of CL to cellulose, and reaction time. The optimal reaction conditions were as follows: the amount of catalyst was 2%(PCL theory degree of polymerization was 37), the mass ratio of CL to cellulose was 30, and the graft polymerization was carried out at 130 ℃for 25 h. At aforesaid conditions, conversion of CL reached 97.46% and graft rate of cellulose was 70.44%. Structure and properties were characterized by FTIR, 1H-NMR, XRD. The FTIR result confirmed cellulose has been grafted with PCL. The 1H-NMR analysis showed that most of the CL had transformed into PCL, and the calculated CL conversion according to 1H-NMR was consistent with the result of weight measurement method. The XRD results showed that cellulose crystalline structure in cellulose-PCL has decreased, instead crystalline characteristic peaks of PCL was appeared.

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