可聚合型紫外吸收剂及其聚合物的合成、表征和耐老化性能
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摘要
为了解决涂层耐老化性能差和传统小分子紫外吸收剂迁移、挥发的问题,以对羟基苯乙酮、4-羟基二苯甲酮、2,4-二羟基二苯甲酮3种苯酮类化合物和N-羟甲基丙烯酰胺为原料,经Friedel-Crafts反应合成3种具有可交联特性的聚合型紫外吸收剂(3-丙烯酰胺甲基-4-羟基苯乙酮(A)、3-丙烯酰胺甲基-4-羟基二苯甲酮(B)和3,5-二丙稀酰胺甲基-2,4-二羟基二苯甲酮(C))。通过紫外吸收光谱分析,表明其对紫外线均具有较强的吸收能力。后采用溶液聚合法,将A、B和C分别与丙烯酸树脂聚合,得到3种具有紫外吸收特性的丙烯酸树脂。采用红外光谱和QUV紫外加速老化分析研究了其结构和性能。结果表明,紫外吸收剂成功接枝到丙烯酸树脂中,且接枝后丙烯酸树脂的耐老化性能得到了显著提高,耐老化时间比纯丙烯酸树脂增强300 h以上。
Traditional low-molecular-weight ultraviolet(UV) absorbers have problems of poor aging resistance, adsorption migration and volatilization. Three crosslinkable polymerized UV absorbers(3-acrylamidomethyl-4-hydroxyacetophenone(A), 3-acrylamidomethyl-4-hydroxybenzophenone(B) and 3,5-dipropionamidemethyl-2,4-dihydroxybenzophenone(C)) were prepared with benzene ketone compounds(4-hydroxyacetopheone, 4-hydroxybenzophenone and 2,4-dihydroxybenzopheone) and cross-linking agent(N-methylolacrylamide) via Friedel-Crafts reaction. UV adsorption results indicate that the three polymerized absorbers have strong absorption capacity. Moreover, A, B and C were polymerized with acrylic resin by solution polymerization to obtain three acrylic resins with UV absorption characteristics. The structure and properties of the products were studied by IR and QUV accelerated aging tests, and the results show that UV absorbers are successfully grafted onto the acrylic resin. The aging resistance of the acrylic resins is significantly improved, which is increased by more than 300 hours.
Traditional low-molecular-weight ultraviolet(UV) absorbers have problems of poor aging resistance, adsorption migration and volatilization. Three crosslinkable polymerized UV absorbers(3-acrylamidomethyl-4-hydroxyacetophenone(A), 3-acrylamidomethyl-4-hydroxybenzophenone(B) and 3,5-dipropionamidemethyl-2,4-dihydroxybenzophenone(C)) were prepared with benzene ketone compounds(4-hydroxyacetopheone, 4-hydroxybenzophenone and 2,4-dihydroxybenzopheone) and cross-linking agent(N-methylolacrylamide) via Friedel-Crafts reaction. UV adsorption results indicate that the three polymerized absorbers have strong absorption capacity. Moreover, A, B and C were polymerized with acrylic resin by solution polymerization to obtain three acrylic resins with UV absorption characteristics. The structure and properties of the products were studied by IR and QUV accelerated aging tests, and the results show that UV absorbers are successfully grafted onto the acrylic resin. The aging resistance of the acrylic resins is significantly improved, which is increased by more than 300 hours.
引文
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[18]李健民.用高温连续自由基聚合工艺制备丙烯酸树脂--聚合机理、产品性能及应用[J].粘接,2015(6):90-93.LI J M.Application to the adhesive and the sealants of the acrylic polymer using high temperature radical polymerization technology[J].Adhesion,2015(6):90-93.
[19]张云,王崇武,陈金爱.涂料的耐老化性及其试验方法[J].涂料工业,2003,33(11):51-53.ZHANG Y,WANG C W,CHEN J A.Aging resistance and test method of coatings[J].Paint&Coatings Industry,2003,33(11):51-53.
[20]宁培森,王克昌,丁著明.二苯甲酮类紫外线吸收剂的发展趋势[J].塑料助剂,2008(2):7-12.NING P S,WANG K C,DING Z M.The situation and developing trend of benzophenone derivatives ultraviolent absorber[J].Plastic Additives,2008(2):7-12.
[21]KOSTROMINE S,KUHLMANN T,OSER R.Special UV absorbers for curable UV-protective coatings:US,US9273213[P].2016-03-01.
[2]徐永祥,严川伟,丁杰,等.紫外光对涂层的老化作用[J].中国腐蚀与防护学报,2004,24(3):168-173.XU Y X,YAN C W,Ding J,et al.UV photo-degradation of coatings[J].Journal of Chinese Society for Corrosion and Protection,2004,24(3):168-173.
[3]王志远.浅谈紫外线吸收剂在防火涂料中的应用[J].山东师范大学学报(自然科学版),2013,28(4):142-144.WANG Z Y.The application of UV absorbers in fire retardant coatings[J].Journal of Shandong Normal University(Natural Science Edition),2013,28(4):142-144.
[4]PICKETT J E.Permanence of UV absorbers in plastics and coatings[J].ACS Symposium Series,2001,805:250-265.
[5]汪铮,王玉民,丁著明.反应型紫外线吸收剂的研究进展[J].甘肃石油和化工,2012,26(1):8-19.WANG Z,WANG Y M,DING Z M.Research progress of UV absorber[J].Gansu Petroleum and Chemical Industry,2012,26(1):8-19.
[6]KOSTROMINE S,KüHN F.Method for producing a polymerizable UV absorber:US,9593088[P].2017-03-14.
[7]李宇.可聚合型苯并三唑类紫外线吸收剂的合成[D].大连:大连理工大学,2007.LI Y.Synthesis of polymerizable benzotriazole ultraviolet stabilizers[D].Dalian:Dalian University of Technology,2007.
[8]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 Chemical,2014,31(7):829-833.
[9]丁阳,杨義,任学宏,等.含糖基水溶性紫外吸收剂的合成与表征[J].化学通报,2016,79(12):1161-1165.DING Y,YANG Y,REN X H,et al.Synthesis and characterization of water-soluble glycosylated UV-absorber[J].Chemistry,2016,79(12):1161-1165.
[10]朱宇翔,丰枫,郑红朝,等.催化加氢合成苯并三氮唑类紫外吸收剂[J].高校化学工程学报,2015,29(6):1356-1363.ZHU Y X,FENG F,ZHENG H Z,et al.Synthesis of benzotriazole ultraviolet absorbers via catalytic hydrogenation[J].Journal of Chemical Engineering of Chinese Universities,2015,29(6):1356-1363.
[11]王洪宇.高效可聚合和高分子型二苯甲酮光引发剂的研究[D].上海:上海交通大学,2006.WANG H Y.Studies on highly efficient polymerizable and polymeric benzophenone photoinitiators[D].Shanghai:Shanghai Jiao Tong University,2006.
[12]SHEN Y,ZHU J H,CHEN H X,et al.Synthesis,characterization,and crystal structure of modified benzophenone UV-absorber containing reactive group[J].Research on Chemical Intermediates,2016,42(4):2909-2918.
[13]朱晓丹,路健,韩银峰,等.可聚合二苯甲酮类光引发剂的合成及其光聚合性能研究[J].影像科学与光化学,2013,31(2):140-149.ZHU X D,LU J,HAN Y F,et al.Synthesis and photopolymerization properties of curable benzophenone derivative photoinitiator[J].Journal of Image Science and Photochemistry,2013,31(2):140-149.
[14]PINTUS V,SCHREINER M.Characterization and identification of acrylic binding media:influence of UV light on the ageing process[J].Analytical and Bioanalytical Chemistry,2011,399(9):2961-2976.
[15]王潇霜,徐桂龙,王宜,等.含磷丙烯酸树脂的制备及其阻燃性能研究[J].高校化学工程学报,2017,31(1):186-190.WANG X S,XU G L,WANG Y,et al.Preparation of phosphorus-containing poly-acrylate resins and their flame resistant properties[J].Journal of Chemical Engineering of Chinese Universities,2017,31(1):186-190.
[16]TOCHá?EK J,VRáTNí?KOVáZ.Polymer life-time prediction:The role of temperature in UV accelerated ageing of polypropylene and its copolymers[J].Polymer Testing,2014,36(6):82-87.
[17]刘付胜聪,肖汉宁,李玉平,等.纳米TiO2和紫外线吸收剂对丙烯酸酯涂层抗光氧化性能的影响[J].功能材料,2004,35(4):495-497.LIU F S C,XIAO H N,LI Y P,et al.Effects of nanoparticle titanium dioxide and ultraviolet absorbers on anti-photooxidation of acrylic coatings[J].Functional materials,2004,35(4):495-497.
[18]李健民.用高温连续自由基聚合工艺制备丙烯酸树脂--聚合机理、产品性能及应用[J].粘接,2015(6):90-93.LI J M.Application to the adhesive and the sealants of the acrylic polymer using high temperature radical polymerization technology[J].Adhesion,2015(6):90-93.
[19]张云,王崇武,陈金爱.涂料的耐老化性及其试验方法[J].涂料工业,2003,33(11):51-53.ZHANG Y,WANG C W,CHEN J A.Aging resistance and test method of coatings[J].Paint&Coatings Industry,2003,33(11):51-53.
[20]宁培森,王克昌,丁著明.二苯甲酮类紫外线吸收剂的发展趋势[J].塑料助剂,2008(2):7-12.NING P S,WANG K C,DING Z M.The situation and developing trend of benzophenone derivatives ultraviolent absorber[J].Plastic Additives,2008(2):7-12.
[21]KOSTROMINE S,KUHLMANN T,OSER R.Special UV absorbers for curable UV-protective coatings:US,US9273213[P].2016-03-01.