高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (11): 2404-2411.doi: 10.7503/cjcu20190362

• 高分子化学 • 上一篇    下一篇

蓝光引发丙烯酸水凝胶的聚合交联动力学

孙广东,潘小鹏,钟宇浩,陈恩宇,黄益(),邵建中   

  1. 浙江理工大学先进纺织材料与制备技术教育部重点实验室, 杭州 310018
  • 收稿日期:2019-06-27 出版日期:2019-11-10 发布日期:2019-09-11
  • 通讯作者: 黄益 E-mail:yihuang@zstu.edu
  • 基金资助:
    国家自然科学基金(51273180);浙江省基础公益研究计划项目(LGG18E030008);先进纺织材料与制备技术教育部重点实验室(浙江理工大学)开放基金资助(2017QN03)

Photopolymerization Kinetics of Poly(Acrylate Acid) Hydrogels Induced by Blue Light

SUN Guangdong,PAN Xiaopeng,ZHONG Yuhao,CHEN Enyu,HUANG Yi(),SHAO Jianzhong   

  1. Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, China
  • Received:2019-06-27 Online:2019-11-10 Published:2019-09-11
  • Contact: HUANG Yi E-mail:yihuang@zstu.edu
  • Supported by:
    ? Supported by the National Natural Science Foundation of China(51273180);The Public Projects of Zhejiang Province, China(LGG18E030008);The Key Laboratory of Advanced Textile Materials and Manufacturing Technology(Zhejiang Sci-Tech University), Ministry of Education, China(2017QN03)

摘要:

研究了聚丙烯酸(PAAc)水凝胶的蓝光聚合性能及实时光流变行为, 并提出了力学性能相关的经验模型. 以樟脑醌/二苯基碘鎓六氟磷酸盐(CQ/DPI)为蓝光引发体系, 丙烯酸(AA)为单体, 聚乙二醇二丙烯酸酯(PEGDA)为交联剂, 450 nm蓝光为辐照光源, 通过光差示扫描量热法(Photo-DSC)和实时光流变法(Photo-rheology)对不同CQ, DPI, AA浓度及光照强度(I)条件下水凝胶聚合前驱液的蓝光聚合性能及交联特性进行了研究. 结果表明, 水凝胶聚合前驱液的聚合速率(Rp)与CQ, DPI和AA的质量分数(wCQ, wDPIwAA)以及光照强度(I)的平方根均呈线性关系, 由于量子产率的下降及自由体积效应, 在高浓度CQ及DPI条件下, 聚合速率和双键转化率均出现偏离线性的现象. 通过光流变系统对水凝胶前驱液光聚合交联过程中的凝胶特性及交联动力学进行了研究. 经数据拟合发现, 凝胶时间(tgel)和弹性模量(G')与相关影响因素(wCQ, wDPIwAA)分别呈现指数和幂律函数关系, 延迟时间(td)及交联速率(Rc)与wCQ, wDPI, IwAA均呈线性函数关系. 根据上述函数关系提出了描述蓝光聚合交联丙烯酸水凝胶力学性能的经验模型.

关键词: 蓝光聚合, 聚丙烯酸水凝胶, 聚合动力学, 交联结构, 弹性模量

Abstract:

In order to establish the photopolymerization kinetics model of the blue light induced photo-polymerization and crosslinking of hydrogels, camphorquinone/ diphenyl iodonium hexafluorophosphate(CQ/DPI) were chosen as initiator, and acrylic acid(AA), polyethylene glycol diacrylate(PEGDA, M ? n =1000) were chosen as monomer and crosslinker, respectively. Such hydrogel precursor was examined by photo-DSC and photo-rheology analysis under ca. 450 nm blue light to gain insight into the polymerization mechanism and evaluate the polymerization process. CQ/DPI photoinitiator exhibited a high efficiency which was advantageous to photopolymerization in aqueous solution. The maximum polymerization rate was found to be proportional to the square root of the initiator system wCQ, wDPI and illumination intensity(I), and the quantum yield and free volume effect played an important role in the polymerization rate and double bond conversion. The elastic modulus G', gel point time, delay time and cross-linking rate have different functional relationships with the initiator system(wCQ, wDPI and I). Based on the power law relationship between elastic modulus G' and I , wCQ and wDPI, the linear relationship between delay time and w CQ 0.5 , w 0.5 DPI and I 0.5, the linear relationship between crosslinking rate and w CQ 0.5 , w DPI 0.5 , I 0.5 and monomer concentrations(wAA), an empirical model describing the mechanical properties of blue-light initiate photopolymerization of PAAc hydrogels was proposed. Such model provides an approach to predicating the gelation process which was advantageous to developing and constructing new hydrogel structures.

Key words: Blue light polymerization, Poly(acrylic acid) hydrogel, Polymerization kinetics, Crosslinking structure, Elastic modulus

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