Fan Yunxin, Song Yan, He Na, Cheng Fei, Jiao Xiaojiao, Lai Guoqiao, Hua Xilin, Yang Xiongfa
Key Laboratory of Organosilicon Chemistry and Material Technology of Education Ministry, College of Material, Chemistry, and Chemical Engineering, Hangzhou Normal University, Hangzhou 311121, China.
Polymers (Basel). 2020 Dec 16;12(12):3005. doi: 10.3390/polym12123005.
A kind of hyperbranched silicone containing macrophotoinitiators (HBSMIs) were synthesized from 2-hydroxy-2-methyl-1-phenyl propanone (HMPP) and the UV-curing behaviors of HBSMIs were investigated in UV-cured transparent polyurethane-acrylate (PUA) coatings. HBSMIs show higher UV-initiating efficiency than HMPP. The migration of HBSMIs from the UV-cured coatings can be as low as 1.7-6.0 wt%, which is obviously lower than the migration of HMPP. There is a remarkable improvement of the tensile strength of the UV-cured materials initiated by HBSMI in comparison to that of the materials prepared with the same PUA initiated by HMPP. Especially for the UV-cured materials prepared from PUA with 20 wt% 1,1,1-tris(hydroxymethyl)propane (TMP), the tensile strength and the strain at break increased from 6.81 MPa to 12.14 MPa and from 43.0% to 71.9%, respectively. The fraction of improvement for the tensile strength and the strain at break is as high as 78.9% and 67.2%, respectively. The coatings prepared with HBSMI also have better UV resistance ability than those coatings prepared with HMPP because they turn slightly yellow when they are aged by UV for about 15 min while the coating prepared with 4 wt% of HMPP will turn yellow only aged by UV for 2 min. These results suggest that preparation hyperbranched silicone containing macrophotoinitiators will be one of the good strategies to improve the curing efficiency of the UV-curing system, reduce the migration of UV initiator from cured material, improve the mechanical and UV resistance performance of UV-cured materials.
一种含有大分子光引发剂的超支化有机硅(HBSMIs)由2-羟基-2-甲基-1-苯基丙酮(HMPP)合成,并研究了HBSMIs在紫外光固化透明聚氨酯丙烯酸酯(PUA)涂料中的紫外光固化行为。HBSMIs显示出比HMPP更高的紫外光引发效率。HBSMIs从紫外光固化涂料中的迁移率可低至1.7 - 6.0 wt%,明显低于HMPP的迁移率。与用HMPP引发的相同PUA制备的材料相比,由HBSMI引发的紫外光固化材料的拉伸强度有显著提高。特别是对于由含20 wt% 1,1,1-三(羟甲基)丙烷(TMP)的PUA制备的紫外光固化材料,拉伸强度和断裂应变分别从6.81 MPa增加到12.14 MPa,从43.0%增加到71.9%。拉伸强度和断裂应变的提高比例分别高达78.9%和67.2%。用HBSMI制备的涂料也比用HMPP制备的涂料具有更好的抗紫外光能力,因为当它们在紫外光下老化约15分钟时会轻微变黄,而用4 wt% HMPP制备的涂料在紫外光下仅老化2分钟就会变黄。这些结果表明,制备含有大分子光引发剂的超支化有机硅将是提高紫外光固化体系固化效率、减少紫外光引发剂从固化材料中迁移、改善紫外光固化材料的机械性能和抗紫外光性能的良好策略之一。