巯基-烯点击反应合成聚酯型紫外线吸收剂及其在EVA中的应用
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摘要
以2,4-二羟基二苯甲酮(UV-0)为紫外线吸收剂母体,采用巯基-烯点击化学反应方法,制备了一种侧基含有UV-0的新型聚酯型紫外线吸收剂(PEG-b-PEUV-0)。通过FT-IR、1H-NMR、UV对产物结构进行了表征。紫外吸收性能测试表明PEG-b-PEUV-0在UV-A区具有较好的紫外吸收。将该大分子紫外线吸收剂应用到EVA (乙烯-醋酸乙烯共聚物,polyethylene-co-vinylacetate)胶膜中以提高其抗紫外老化性能。通过测试材料老化前后的衰减全反射红外光谱、拉伸强度、羰基指数、扫描电镜、光电子能谱等手段对紫外线吸收剂的应用性能进行了研究,并与添加中间体2,4-二羟基-3-(N,N-二羟乙基-氨甲基)二苯甲酮(HAHBP)的应用性能做了对比研究。结果表明添加PEG-b-PEUV-0的EVA材料在老化40 d后羰基指数增加的幅度仅为0.89%,约为空白EVA增加量的1/5;表面含氧量仅增加了1.22%,而空白EVA含氧量增加了16.1%;添加大分子紫外线吸收剂PEG-b-PEUV-0的EVA的拉伸强度保持率明显大于空白EVA材料与添加中间体HAHBP的EVA材料。所合成的大分子紫外线吸收剂PEG-b-PEUV-0对EVA材料具有良好的抗紫外光老化效果。
A novel polyester UV absorber( PEG-b-PEUV-0) with 2,4-dihydroxybenzophenone(UV-0) at the side chain was prepared via thiol-ene click reaction and its structure was confirmed by FT-IR, 1 H-NMR and UV. UV results show that PEG-b-PEUV-0 has good UV-A absorption. This PEG-b-PEUV-0 was applied in EVA to improve UV aging resistance which was studied by total reflection infrared spectra, tensile strength retention rate, weight loss rate, carbonyl index, scanning electron microscopy(SEM) and photoelectron spectroscopy(XPS) before and after UV aging. The results was compared with those of 2,4-dihydroxy-3-(N,N-dihydroxyethyl-aminomethyl) benzophenone(HAHBP) added EVA. The carbonyl index of the PEG-b-PEUV-0 added EVA is increased by only 0.89%, which is 1/5 of that of blank EVA after aging for 40 days. XPS results show that surface oxygen content of the PEG-b-PEUV-0 added EVA is increased by only 1.22%(16.1% for blank EVA). Tensile strength retention rate of the modified EVA is significantly greater than that of blank EVA and EVA with HAHBP. It is confirmed that PEG-b-PE UV-0 exhibits good anti-UV aging effect to EVA.
A novel polyester UV absorber( PEG-b-PEUV-0) with 2,4-dihydroxybenzophenone(UV-0) at the side chain was prepared via thiol-ene click reaction and its structure was confirmed by FT-IR, 1 H-NMR and UV. UV results show that PEG-b-PEUV-0 has good UV-A absorption. This PEG-b-PEUV-0 was applied in EVA to improve UV aging resistance which was studied by total reflection infrared spectra, tensile strength retention rate, weight loss rate, carbonyl index, scanning electron microscopy(SEM) and photoelectron spectroscopy(XPS) before and after UV aging. The results was compared with those of 2,4-dihydroxy-3-(N,N-dihydroxyethyl-aminomethyl) benzophenone(HAHBP) added EVA. The carbonyl index of the PEG-b-PEUV-0 added EVA is increased by only 0.89%, which is 1/5 of that of blank EVA after aging for 40 days. XPS results show that surface oxygen content of the PEG-b-PEUV-0 added EVA is increased by only 1.22%(16.1% for blank EVA). Tensile strength retention rate of the modified EVA is significantly greater than that of blank EVA and EVA with HAHBP. It is confirmed that PEG-b-PE UV-0 exhibits good anti-UV aging effect to EVA.
引文
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[12]YU Shu-juan(于淑娟),WEI De-lin(韦德麟),ZHENG Guang-jian(郑广俭),et al.Synthesis of co-polymerized light stabilizers and their application in PVC/SF composite naterials(复合型高分子光稳定剂的合成及在PVC/剑麻纤维复合材料中的应用)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2016,30(4):978-984.
[13]Butylina S,Hyvarinen M,Karki T.Accelerated weathering of wood-polypropylene composites containing minerals[J].Composites Part A:Applied Science and Manufaturing,2012,43(11):2087-2094.
[14]Hu S L,Trinchi A,Atkin P,et al.Tunable photoluminescence across the entire visible spectrum from carbon dots excited by white light[J].Angewandte Chemie,International Edition,2015,54:2970-2974.
[15]YAO Pei-pei(姚培培),LI Chen(李琛),XIAO Sheng-ling(肖生苓).Effect of ultraviolet aging on properties and structure of polystyrene(紫外老化对聚苯乙烯泡沫性能的影响)[J].CIESE Journal(化工学报),2014,65(11):4620-4626.
[2]Boguski J,Przybytniak G,?yczko K.New monitoring by thermogravimetry for radiation degradation of EVA[J].Radiation Physics and Chemistry,2014,100:49-53.
[3]LarchéJ F,Gallot G,Boudiaf-Lomri L,et al.Evidence of surface accumulation of fillers during the photo-oxidation of flame retardant ATH filled EVA used for cable applications[J].Polymer Degradation and Stability,2014,103:63-68.
[4]Czanderna A W,Pern F J.Encapsulation of PV modules using ethylene vinyl acetate copolymer as a pottant:a critical review[J].Solar Energy Materials and Solar Cells,1996,43:101-108.
[5]Allen N S,Edge M,Rodriguez M,et al.Aspects of thermal oxidation of ethylene vinyl acetate copolymer[J].Polymer Degradation and Stability,2000,68:363-371.
[6]Jentsch A,Eichhorn K J,Voit B.Influence of typical stabilizers on the aging behavior of EVA foils for photovoltaic applications during artificial UV-weathering[J].Polymer Testing,2015,44:242-247.
[7]Liang Y P,Xiang B,Liu C,et al.Ultraviolet light absorber with low surface energy:synthesis and characterization[J].Tetrahedron,2014,70:6585-6593.
[8]GAO Peng-fei(高鹏飞),TANG Yan-feng(汤艳峰),ZHU Jin-li(朱金丽),et al.Synthesis and properties of saccharide-based polymeric ultraviolet absorber containing benzophenone groups(一种糖基二苯甲酮类聚合物紫外线吸收剂的合成与性能)[J].Fine chemicals(精细化工),2014,31(7):829-833.
[9]DING Yang(丁阳),YANG Yi(杨義),REN Xue-hong(任学宏),et al.Synthesis and characterizations of water-soluble glycosylated UV-absorber(含糖基水溶性紫外吸收剂的合成与表征)[J].Chemistry Bulletin(化学通报),2016,79(12):1161-1165.
[10]Pounder R J,Stanford M J,Brooks P,et al.Metal free thiol-maleimide‘Click’reaction as a mild functionalization strategy for degradable polymers[J].Chemical Communications,2008,7(41):5158-5160.
[11]Stanford M J,Dove A P.One-pot synthesis of alpha,omega-chain end functional,stereoregular,star-shaped poly(lactide)[J].Macromolecules,2009,42:141-147.
[12]YU Shu-juan(于淑娟),WEI De-lin(韦德麟),ZHENG Guang-jian(郑广俭),et al.Synthesis of co-polymerized light stabilizers and their application in PVC/SF composite naterials(复合型高分子光稳定剂的合成及在PVC/剑麻纤维复合材料中的应用)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2016,30(4):978-984.
[13]Butylina S,Hyvarinen M,Karki T.Accelerated weathering of wood-polypropylene composites containing minerals[J].Composites Part A:Applied Science and Manufaturing,2012,43(11):2087-2094.
[14]Hu S L,Trinchi A,Atkin P,et al.Tunable photoluminescence across the entire visible spectrum from carbon dots excited by white light[J].Angewandte Chemie,International Edition,2015,54:2970-2974.
[15]YAO Pei-pei(姚培培),LI Chen(李琛),XIAO Sheng-ling(肖生苓).Effect of ultraviolet aging on properties and structure of polystyrene(紫外老化对聚苯乙烯泡沫性能的影响)[J].CIESE Journal(化工学报),2014,65(11):4620-4626.