木质素基RAFT链转移剂的合成及其聚合特性研究

doi:10.3969/j.issn.0253-2417.2018.06.010

林产化学与工业 ›› 2018, Vol. 38 ›› Issue (6): 75-80.doi: 10.3969/j.issn.0253-2417.2018.06.010

木质素基RAFT链转移剂的合成及其聚合特性研究

王广彬¹, 陈家宝¹, 谷利敏⁴, 王春鹏^1,2,3, 许玉芝^1,2,3

1. 中国林业科学研究院林产化学工业研究所;生物质化学利用国家工程实验室;国家林业局林产化学工程重点开放性实验室;江苏省生物质能源与材料重点实验室, 江苏南京 210042;
2. 中国林业科学研究院林业新技术研究所, 北京 100091;
3. 南京林业大学江苏省林业资源高效加工利用协同创新中心, 江苏南京 210037;
4. 河南省化工研究所有限责任公司, 河南郑州 450052

收稿日期:2018-04-16 出版日期:2018-12-25 发布日期:2018-12-27
通讯作者: 许玉芝,副研究员,硕士生导师,主要从事生物质材料研究;E-mail:xuyuzhi@icifp.cn。 E-mail:xuyuzhi@icifp.cn
作者简介:王广彬(1994-),男,山东济宁人,硕士生,主要从事生物质材料研究工作
基金资助:
国家自然科学基金资助项目（31770604）

Synthesis and Characterization of Lignin Based Chain Transfer Agent Used for RAFT Polymerization

WANG Guangbin¹, CHEN Jiabao¹, GU Limin⁴, WANG Chunpeng^1,2,3, XU Yuzhi^1,2,3

1. Institute of Chemical Industry of Forest Products, CAF;National Engineering Lab. for Biomass Chemical Utilization;Key and Open Lab. of Forest Chemical Engineering, SFA;Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China;
2. Research Institute of Forestry New Technology, CAF, Beijing 100091, China;
3. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China;
4. Henan Research Institute of Chemical Industry CO. LTD., Zhengzhou 450052, China

Received:2018-04-16 Online:2018-12-25 Published:2018-12-27

摘要/Abstract

摘要： 采用一锅法，以木质素为原料，经二硫化碳、2-溴丁酸甲酯进行黄原酸酯功能化改性合成木质素基大分子链转移剂（lignin-CTA），通过FT-IR、¹H NMR、¹³C NMR对其结构进行表征，并将其用于丙烯酰胺的RAFT聚合反应制备木质素-丙烯酰胺共聚物（lignin-g-PAM），考察该反应的聚合特征。木质素功能化改性前后的红外谱图显示：改性后羟基吸收峰明显减弱，并且在1148和1732 cm^-1处分别出现了-CS键振动吸收峰和酯键的羰基吸收峰，说明2-溴丁酸甲酯已成功接枝到木质素大分子上；同时lignin-CTA的¹H NMR谱图中于δ 0.90处出现了2-溴丁酸甲酯末端甲基的活泼氢质子峰，¹³C NMR谱图中于δ 162处出现了-C=S的碳原子峰，进一步印证了接枝反应的进行。丙烯酰胺的RAFT聚合反应结果显示：聚合物的相对分子质量与转化率基本呈现线性关系，同时其多分散系数较低且分布相对较窄（1.26~1.53），证明该聚合反应具有高效可控特性。

关键词: 木质素, 可逆加成裂解链转移聚合(RAFT), 链转移剂, 可控聚合

Abstract: Lignin based chain transfer agent (lignin-CTA) was synthesized by one-pot reaction with using lignin, carbon disulfide and methyl 2-bromobutyrate as raw materials and was characterized by FT-IR, ¹H NMR and ¹³C NMR spectroscopy, respectively.Then this lignin-CTA was used for performing reversible addition-fragmentation chain transfer polymerization(RAFT) of acrylamide to prepare lignin-acrylamide copolymer(lignin-g-PAM). And the polymerization characteristics of the reaction was studied. In FT-IR spectra of lignin before and after functional modification, the intensity of peak corresponding to hydroxyl group decreased obviously after modification. In addition, the peak at 1148 cm^-1 corresponding to CS bond and the peak at 1732 cm^-1 corresponding to ester carbanyl groupappeared in the spectrum of lignin-CTA, which indicated that the methyl 2-bromobutyrate was successfully grafted on the lignin. The peak at δ 0.90 in the ¹H NMR spectrum of lignin-CTA was corresponded to the protons of end methyl of methyl 2-bromobutyrate and the peak at δ162 in ¹³C NMR spectrum of lignin-CTA was attrubuted to the carbon atom of -C=S bond. These all proved that methyl 2-bromobutyrate was grafted on lignin successfully. In the RAFT polymerization of acrylamide, number-average molecular weight (M_n) and PDI values vs conversions presented linear relationship and the polydispersity index was low and distributed in a narrow range, indicating that this polymerization process was highly efficient and well controlled.

Key words: lignin, reversible addition-fragmentation chain transfer polymerization (RAFT), chain transfer agent, controlled polymerization

中图分类号:

TQ35

王广彬, 陈家宝, 谷利敏, 王春鹏, 许玉芝. 木质素基RAFT链转移剂的合成及其聚合特性研究[J]. 林产化学与工业, 2018, 38(6): 75-80.

WANG Guangbin, CHEN Jiabao, GU Limin, WANG Chunpeng, XU Yuzhi. Synthesis and Characterization of Lignin Based Chain Transfer Agent Used for RAFT Polymerization[J]. Chemistry and Industry of Forest Products, 2018, 38(6): 75-80.

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木质素基RAFT链转移剂的合成及其聚合特性研究

Synthesis and Characterization of Lignin Based Chain Transfer Agent Used for RAFT Polymerization

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