化学学报 ›› 2011, Vol. 69 ›› Issue (17): 2031-2038. 上一篇    下一篇

研究论文

紫外光固化超支化聚酯的合成及性能

张林雅1,2,矫庆泽*,1,赵芸1,周明吉1,冯薇2,葛艳蕊2   

  1. (1北京理工大学化工与环境学院 北京 100081)
    (2河北科技大学化学与制药工程学院 石家庄 050018)
  • 投稿日期:2011-02-01 修回日期:2011-03-31 发布日期:2011-05-03
  • 通讯作者: 张林雅 E-mail:linyazhang@sina.com

Synthesis and Properties of UV-curable Hyperbranched Polyester

Zhang Linya1,2 Jiao Qingze*,1 Zhao Yun1 Zhou Mingji1 Feng Wei2 Ge Yanrui2   

  1. (1 School of Chemical Engineering and Environment, Beijing Institute of Technology, Beijing 100081)
    (2 College of Chemical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018)
  • Received:2011-02-01 Revised:2011-03-31 Published:2011-05-03

以季戊四醇为核, 2,2-羟甲基丙酸为臂, 采用熔融缩聚法合成并表征了末端含大量羟基的超支化聚酯, 其支化度高, 黏度低, 具有良好的热稳定性. 以甲基丙烯酸酐改性超支化聚酯, 得到链末端含有C=C的超支化甲基丙烯酸酯, 在最佳反应条件下改性反应的转化率可达89%以上. 改性后的超支化聚酯表现出更低的黏度, 热失重曲线呈现为两段, 玻璃态转化温度(Tg)降低. 低黏度的超支化甲基丙烯酸酯应用于紫外光固化金属涂料, 稀释剂用量少, 成膜速率快, 固化完全. 探讨了含有不同数量C=C的超支化聚酯对光固化膜性能包括凝胶率、附着力、冲击强度、柔韧性、硬度及耐溶剂性能的影响. 随C=C含量的提高, 凝胶率增大, 膜机械性能及耐溶剂性变化明显. 实验表明, 选择具有不同活性基团数量的超支化聚酯, 有利于得到综合性能优异的紫外光固化材料.

关键词: 超支化聚酯, 甲基丙烯酸酐, 改性, 光固化, 涂层

Using the molten polycondensation, the second to fourth generation of hyperbranched polyesters with a great number of hydroxyl groups were synthesized and characterized based on the pentaerythritol as core and 2,2-bis(hydroxymethyl) propionic acid as arm. They had high branched degrees, low viscosity and good thermal stability. By methacryloyl anhydride, the hyperbranched polyesters were modified to be the hyperbranched methacrylates with C=C at the chain ends. The percent conversion could be reached above 89% under the optimum reaction conditions. The modified hyperbranched polyesters exhibited lower viscosity, two segmental thermogravimetric curve and lower glass transition temperature (Tg). When the hyperbranched methacrylates with low viscosity were applied in UV-curable coating for metals, it could take less solvent, fast coating speed and complete curing. The effects which the hyperbranched polyesters with different C=C contents took on the properties of UV-curable coating such as gel content, adhesive strength, impact strength, flexibility, hardness and the solvent resistances were studied. With the improvement of C=C contents, the gel contents were increased. Also the mechanical properties and solvent resistances of coatings were changed significantly. The experiments exhibited that it would help to gain the perfect UV-curable materials by choosing the hyperbranched polyesters with different contents of active groups.

Key words: hyperbranched polyester, methacryloyl anhydride, modified, UV-curable, coating