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林产化学与工业

林产化学与工业 ›› 2023, Vol. 43 ›› Issue (5): 8-16.doi: 10.3969/j.issn.0253-2417.2023.05.002

• 研究报告 • 上一篇    下一篇

磺化木质素基链转移剂的合成及其在水相RAFT聚合中的应用

刘婧伊1,2, 王广彬1, 王春鹏1,2, 储富祥1,2, 许玉芝1,2,*()   

  1. 1. 中国林业科学研究院 林产化学工业研究所；江苏省生物质能源与材料重点实验室；国家林业和草原局林产化学工程重点实验室；林木生物质低碳高效利用国家工程研究中心，江苏 南京 210042
    2. 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
  • 收稿日期:2022-06-29 出版日期:2023-10-28 发布日期:2023-10-27
  • 通讯作者: 许玉芝 E-mail:xuyuzhi@icifp.cn
  • 作者简介: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
    刘婧伊(1998—)，女，辽宁朝阳人，硕士生，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 of Sulfonated Lignin Based Chain Transfer Agent and Its Application in Aqueous RAFT Polymerization

Jingyi LIU1,2, Guangbin WANG1, Chunpeng WANG1,2, Fuxiang CHU1,2, Yuzhi XU1,2,*()   

  1. 1. Institute of Chemical Industry of Forest Products, CAF; Key Lab. of Biomass Energy and Material, Jiangsu Province; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; National Engineering Research Center of Low-Carbon Processing and Utilization of Forest Biomass, Nanjing 210042, China
    2. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China
  • Received:2022-06-29 Online:2023-10-28 Published:2023-10-27
  • Contact: Yuzhi XU E-mail:xuyuzhi@icifp.cn

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摘要：

以玉米秸秆木质素为原料，将木质素磺化改性，再利用二硫化碳、溴乙酸甲酯对磺化木质素(SL)进行黄原酸酯功能化改性，合成了磺化木质素基链转移剂(SL-CTA)，之后将其用于丙烯酰胺的水相RAFT聚合反应制备磺化木质素-丙烯酰胺共聚物(SL-g-PAM)，并采用多种方法对链转移剂及共聚物进行表征。研究结果表明：相比于磺甲基化改性，芳基磺化改性的效果更好，当1 g木质素与2 g氯磺酸在25 ℃下反应4 h时，改性效果最佳，此时磺化木质素含S量为1.83%，Mw/Mn为1.19，含总羟基量为4.86 mmol/g，且水溶性良好。FT-IR、13C NMR对磺化木质素基链转移剂的结构表征结果发现：红外谱图显示900 cm-1处出现C—S伸缩振动吸收峰及1 738 cm-1处出现C=O特征峰，13C NMR谱图中δ 172处出现了C=S的碳原子峰，共同证明了SL-CTA的成功合成。探究丙烯酰胺的水相RAFT聚合体系中单体/链转移剂/引发剂比例、pH值及反应温度对单体转化率的影响，结果表明：单体/链转移剂/引发剂物质的量之比为500∶4∶1、pH值5、70 ℃下反应4 h时转化率高达98.5%。该实验条件下，聚合反应一级动力学曲线呈现了较好的线性关系，所得聚合物的相对分子质量与转化率也基本呈现一次线性关系，同时其多分散系数较低且分布相对较窄(1.13~1.43)，证明了反应具有较高的可控性。

关键词: 木质素, 磺化, 丙烯酰胺, 水相, 可逆加成断裂链转移聚合(RAFT)

Abstract:

The sulfonated lignin-based chain transfer agent(SL-CTA) was synthesized using pre-sulfonated corn stover lignin, followed by the functional modification of xanthate carbon disulfide and methyl bromoacetate. The SL-CTA was used in the aqueous RAFT polymerization of acrylamide to prepare sulfonated lignin-acrylamide copolymer(SL-g-PAM). Various methods were used to characterize the chain transfer agents and copolymers. The results showed that the arylsulfonation modification was more effective than the sulfomethylation modification. The best modification effect was achieved when 1g of lignin was reacted with 2 g of chlorosulfonic acid at 25 ℃ for 4 h, where the S concentration in sulfonated lignin was 1.83%, the ratio of Mw/Mn was 1.19, the amount of total hydroxyl groups was 4.86 mmol/g, and the water solubility was good. The chemical structure of the SL-CTA was then investigated by FT-IR and 13C NMR. The results showed that the stretching vibration absorption peak of C—S bond at 900 cm-1 and the characteristic peak at 1 738 cm-1 relating to C=O group were found in the FT-IR spectrum, and the peak at δ 172 corresponding to carbon atom of the C=S appeared in the 13C NMR spectrum, proving the successful synthesis of the chain transfer agent. In addition, the effects of the ratios of monomer/chain transfer agent/initiator, pH value and reaction temperature on the monomer conversion in the aqueous RAFT polymerization system of acrylamide were investigated. The results showed that the conversion rate was as high as 98.5% when the ratio of monomer/chain transfer agent/initiator was 500∶4∶1, pH value was 5, reaction temperature was 70 ℃ and reaction time was 4 h. Under the experimental conditions, the first-order kinetic curve of the polymerization reaction showed a good linear relationship, and the relative molecular mass of the obtained polymer also presented a linear relationship with the monomer conversion rate. At the same time, its polydispersity index was low and the distribution was relatively narrow(1.13-1.43), which all indicated that the reaction had high controllability.

Key words: lignin, sulfonation, acrylamide, aqueous phase, reversible addition fragmentation chain transfer polymerization(RAFT)

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