基于点击反应大分子紫外线吸收剂的合成及在EVA中的应用
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摘要
以巯基-烯点击化学反应的方法,制备了一种新型大分子紫外线吸收剂PHA-b-PEUV-0。通过红外光谱、核磁共振氢谱、紫外光谱对产物的结构进行了表征。利用ATR-FT-IR、拉伸强度保持率、接触角、邵氏硬度、X射线光电子能谱以及表面形貌研究了PHA-b-PEUV-0对乙烯-醋酸乙烯(EVA)材料的抗紫外加速老化性能,并与2,4-二羟基二苯甲酮(UV-0)的应用性能进行了对比研究。结果表明,EVA材料添加PHA-b-PEUV-0与UV-0紫外线吸收剂均可以起到一定的防御紫外加速老化的作用,但PHA-b-PEUV-0在抑制EVA材料表面含氧量与羰基指数增加、拉伸强度保持率及邵氏硬度降低等方面均优于UV-0。2种紫外吸收剂对EVA材料表面接触角的影响不同,添加PHA-b-PEUV-0的EVA材料表面接触角随老化时间的延长呈先减小后增大的交替变化趋势,添加UV-0的EVA材料的接触角随老化时间的延长呈先减小后增大的现象,但添加PHA-b-PEUV-0的EVA材料的接触角波动幅度较小。扫描电镜观察到空白EVA材料在老化20 d开始有凹陷出现,随老化时间的延长,凹陷结构逐渐增多。添加UV-0的材料表面从老化20 d开始有凹陷及碎屑状物析出,老化40 d后碎屑物增多,而添加PHA-b-PEUV-0的EVA材料在老化30 d后才出现少量的凸起结构,可见PHA-b-PEUV-0具有优于UV-0的综合抗紫外加速老化性能。
A novel polyester UV absorber,PHA-b-PEUV-0,was prepared by thiol-ene click reaction. The structure of PHA-b-PEUV-0was confirmed by1H-NMR,FT-IR,and UV spectrometric analyses. The anti-UV-accelerated aging performance of PHA-b-PEUV-0added to EVA materials was studied by estimating the tensile strength retention,contact angle and Shore hardness,and by ATR-FT-IR,XPS,and SEM analyses. The obtained results were compared with those of EVA materials with added UV-0. The results show that the addition of PHA-b-PEUV-0and UV-0 to EVA materials has a protective effect against UV-accelerated aging. However,PHA-b-PEUV-0is better than UV-0 in suppressing the increase in oxygen content and carbonyl index of the surface of EVA materials,retaining the tensile strength,and decreasing the Shore hardness. The two UV absorbers have different effects on the contact angle of the EVA materials surface. The surface contact angle of the EVA materials added with PHA-b-PEUV-0shows an alternating trend of first decreasing and then increasing with the UV aging time. The contact angle of the EVA materials with added UV-0 first decreases and then increases with UV aging time. However,the contact angle of the EVA materials with added PHA-b-PEUV-0fluctuate less.SEM analysis show that blank EVA materials begins showing a depression after 20 d of UV aging. With the increase in aging time,the concave structure gradually increases. Pits and detritus appeare on the surface of the materials with added UV-0 after 20 d of UV aging,and the amount of detritus increases after 40 d of aging. However,in the EVA materials with added PHA-b-PEUV-0,only a small amount of raised structure is observed. It can be seen that PHA-b-PEUV-0has acomprehensive anti-UV-accelerated aging performance that is superior to that of UV-0.
A novel polyester UV absorber,PHA-b-PEUV-0,was prepared by thiol-ene click reaction. The structure of PHA-b-PEUV-0was confirmed by1H-NMR,FT-IR,and UV spectrometric analyses. The anti-UV-accelerated aging performance of PHA-b-PEUV-0added to EVA materials was studied by estimating the tensile strength retention,contact angle and Shore hardness,and by ATR-FT-IR,XPS,and SEM analyses. The obtained results were compared with those of EVA materials with added UV-0. The results show that the addition of PHA-b-PEUV-0and UV-0 to EVA materials has a protective effect against UV-accelerated aging. However,PHA-b-PEUV-0is better than UV-0 in suppressing the increase in oxygen content and carbonyl index of the surface of EVA materials,retaining the tensile strength,and decreasing the Shore hardness. The two UV absorbers have different effects on the contact angle of the EVA materials surface. The surface contact angle of the EVA materials added with PHA-b-PEUV-0shows an alternating trend of first decreasing and then increasing with the UV aging time. The contact angle of the EVA materials with added UV-0 first decreases and then increases with UV aging time. However,the contact angle of the EVA materials with added PHA-b-PEUV-0fluctuate less.SEM analysis show that blank EVA materials begins showing a depression after 20 d of UV aging. With the increase in aging time,the concave structure gradually increases. Pits and detritus appeare on the surface of the materials with added UV-0 after 20 d of UV aging,and the amount of detritus increases after 40 d of aging. However,in the EVA materials with added PHA-b-PEUV-0,only a small amount of raised structure is observed. It can be seen that PHA-b-PEUV-0has acomprehensive anti-UV-accelerated aging performance that is superior to that of UV-0.
引文
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[2]Li Y J,Qiao X L,Zhou C Z,et al.Photochemical transformation of sunscreen agent benzophenone-3 and its metabolite in surface freshwater and seawater[J].Chemosphere,2016,153:494-499.
[3]Zucchi S,Blüthgen N,Ieronimo A,et al.The UV-absorber benzophenone-4 alters transcripts of genes involved in hormonal pathways in zebrafish(danio rerio)eleuthero-embryos and adult males[J].Toxicol.Appl.Pharmacol.,2011,250:137-146.
[4]安秋凤,王前进,路德待,等.聚醚/二苯甲酮侧基聚硅氧烷的膜形貌及亲疏水行为[J].高分子材料科学与工程,2008,24(1):83-86.An Q F,Wang Q J,Lu D D,et al.Film morphology,hydrophilichydrophobic behavior of polysiloxane bearing ployether and benzophenone derivative side groups[J].Polymer Materials Science&Engineering,2008,24(1):83-86.
[5]Ma W,Jiang X,Liu Y,et al.Synthesis of a novel water-soluble polymeric UV-absorber for cotton[J].Chin.Chem.Lett.,2011,22:1489-1491.
[6]高鹏飞,汤艳峰,朱金丽,等.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].精细化工,2014,31(7):829-833.Gao P F,Tang Y F,Zhu J L,et al.Synthesis and properties of saccharide-based polymeric ultraviolet absorber containing benzophenone groups[J].Fine Chemicals,2014,31(7):829-833.
[7]Kristin G S,Kuestermeye B,Stanton C.Uniform polymer particles formulated with ultraviolet protective materials for the protection of UVsensitive molecules[J].Dyes Pigments,2014,105:12-22.
[8]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].Chem.Commun.,2008,7:5158-5160.
[9]于淑娟,韦德麟,陆树文,等.苯并三唑类光稳定剂的合成及在剑麻纤维基复合材料中的应用[J].高分子材料科学与工程,2016,32(8):21-27.Yu S J,Wei D L,Lu S W,et al.Synthesis of benzotriazole light stabilizers and their application in sisal fiber based composite material[J].Polymer Materials Science&Engineering,2016,32(8):21-27.
[10]Butylina S,Hyvarinen M,Karki T.Accelerated weathering of woodpolypropylene composites containing minerals[J].Composites Part A,2012,43:2087-2094.
[11]Hu S L,Trinchi A,Atkin P,et al.Tunable photoluminescence across the entire visible spectrum from carbon dots excited by white light[J].Angew.Chem.Int.Ed.,2015,54:2970-2974.
[12]Huang P,Lin J,Wang X,et al.Light-triggered theranostics based on photosensitizer-conjugated carbon dots for simultaneous enhancedfluorescence imaging and photodynamic therapy[J].Adv.Mater.,2012,24:5104-5110.
[13]姚培培,李琛,肖生苓.紫外老化对聚苯乙烯泡沫性能的影响[J].化工学报,2014,65(11):4620-4626.Yao P P,Li C,Xiao S L.Effect of ultraviolet aging on properties and structure of polystyrene[J].CIESC Journal,2014,65(11):4620-4626.
[14]吴建兵,凌丽霞,马国章,等.巯基-乙烯基点击反应在紫外光固化过程中的应用[J].高分子材料科学与工程,2013,29(10):169-174.Wu J B,Ling L X,Ma G Z,et al.The application of thiol-ene click reaction in UV curing process[J].Polymer Materials Science&Engineering,2013,29(10):169-174.