丙烯酸功能化纳米氧化石墨烯/丙烯酸酯复合乳液的制备及性能
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摘要
以烯丙基磺酸钠(ALS)为可聚合乳化剂,采用种子乳液聚合法制备丙烯酸功能化纳米氧化石墨烯(FAGO)/丙烯酸酯复合乳液。通过红外光谱、XRD表征GO、FAGO的结构,通过SEM和TEM观察GO、FAGO、纳米FAGO/丙烯酸酯复合乳液的形貌。结果表明,丙烯酸上的羧基与GO羟基反应生成了酯键;FAGO的边缘发生扭曲变形,局部产生较多褶皱,体系的不规整度显著增加;纳米FAGO/丙烯酸酯乳胶粒子呈规则的球形。纳米粒径电位分析表明,纳米FAGO/丙烯酸酯复合乳液粒径大小均一,分散性良好,随着ALS加入量的增加,纳米FAGO/丙烯酸酯乳胶粒子的粒径逐渐减小,其分散性指数(PDI)先减小后增大,相应的Zeta电位逐渐升高,乳液的黏度逐渐增大,乳胶膜耐水性变差,当ALS用量为0.8wt%时,纳米FAGO/丙烯酸酯复合乳液综合性能最佳。
Acrylic acid functionalized nano graphene oxide(FAGO)/acrylate composite emulsion was prepared by seed emulsion polymerization via using sodium allyl sulfonate(ALS)as polymerizable emulsifier.The structure of GO and FAGO were confirmed by FTIR and XRD,the morphology of GO,FAGO and nano FAGO/acrylate composite emulsions were observed by SEM and TEM.The results show that the carboxyl group on acrylic acid reacts with GO hydroxyl to form ester bond.The edge of FAGO is distorted and has more local folds,the system of irregularities increase significantly compared to GO.And the nano FAGO/acrylate composite latex particles are regularly spherical.The nano particle size potential analyzer test results show that the nano FAGO/acrylate composite emulsion size is uniform,well-disperse.With the increases of the amount of ALS,the particle size of the latex particles gradually decreases,its dispersion index(PDI)first decreases and then increases,the corresponding Zeta potential gradually increases,the viscosity of the emulsion gradually increases,and the water resistance of latex film becomes worse.When the amount of ALS is 0.8 wt%,the nano FAGO/acrylate composite emulsion obtains the best overall performance.
Acrylic acid functionalized nano graphene oxide(FAGO)/acrylate composite emulsion was prepared by seed emulsion polymerization via using sodium allyl sulfonate(ALS)as polymerizable emulsifier.The structure of GO and FAGO were confirmed by FTIR and XRD,the morphology of GO,FAGO and nano FAGO/acrylate composite emulsions were observed by SEM and TEM.The results show that the carboxyl group on acrylic acid reacts with GO hydroxyl to form ester bond.The edge of FAGO is distorted and has more local folds,the system of irregularities increase significantly compared to GO.And the nano FAGO/acrylate composite latex particles are regularly spherical.The nano particle size potential analyzer test results show that the nano FAGO/acrylate composite emulsion size is uniform,well-disperse.With the increases of the amount of ALS,the particle size of the latex particles gradually decreases,its dispersion index(PDI)first decreases and then increases,the corresponding Zeta potential gradually increases,the viscosity of the emulsion gradually increases,and the water resistance of latex film becomes worse.When the amount of ALS is 0.8 wt%,the nano FAGO/acrylate composite emulsion obtains the best overall performance.
引文
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[2]黄洪,傅和青,邓艳文,等.环氧树脂与丙烯酸酯复合改性水性聚氨酯的合成研究[J].高校化学工程学报,2006,20(4):583-587.HUANG H,FU H Q,DENG Y W,et al.Study on the synthesis of aqueous polyurethane modified by epoxy resin and acrylate[J].Journal of Chemical Engineering of Chinese Universities,2006,20(4):583-587(in Chinese).
[3] ATHAWALE V D,KULKARNI M A.Preparation and properties of urethane/acrylate composite by emulsion polymerization technique[J].Progress in Organic Coatings,2009,65(3):392-400.
[4]陈师,吉静.高SiO2含量硅溶胶/聚丙烯酸酯复合乳液的制备[J].北京化工大学学报(自然科学版),2005,32(3):57-60.CHEN S,JI J.Preparation of compound emulsion of high SiO2sol/polyacrylate[J].Journal of Beijing University of Chemical Technology(Natural Science Edition),2005,32(3):57-60(in Chinese).
[5] OKUTSU R,ANDO S,UEDA M.Sulfur-containing poly(meth)acrylates with high refractive indices and high abbe’s numbers[J].Chemistry of Materials,2008,20(12):4017-4023.
[6]任姗姗,陆海林,董光能.氧化石墨烯/聚乙二醇复合材料在人工关节材料上的润滑性能[J].复合材料学报,2017,34(11):2598-2604.REN S S,LU H L,DONG G N.Tribological properties of graphene oxide/polyethylene glycol composites applied on artificial joint[J].Acta Materiae Compositae Sinica,2017,34(11):2598-2604(in Chinese).
[7]白静静,尹建宇,高雄.异氰酸酯功能化氧化石墨烯/热塑性聚氨酯弹性体复合材料的制备与性能[J].复合材料学报,2018,35(7):1683-1690.BAI J J,YIN J Y,GAO X.Preparation and characterization of isocyanate functionalized graphene oxide/thermoplastic polyurethane elastomer composites[J].Acta Materiae Compositae Sinica,2018,35(7):1683-1690(in Chinese).
[8] ZHU Y,MURALI S,CAI W,et al.Graphene and graphene oxide:Synthesis,properties,and applications[J].Advanced Materials,2010,22(35):3906-3924.
[9] COMPTON O C,DIKIN D A,PUTZ K W,et al.Electrically conductive “alkylated”graphene paper via chemical reduction of amine-functionalized graphene oxide paper[J].Advanced Materials,2010,22(8):892-896.
[10] YANG X,WANG Y,HUANG X,et al.Multi-functionalized graphene oxide based anticancer drug-carrier with dualtargeting function and pH-sensitivity[J].Journal of Materials Chemistry,2011,21(10):3448-3454.
[11] SUN X,LIU Z,WELSHER K,et al.Nano-graphene oxide for cellular imaging and drug delivery[J].Nano Research,2008,1(3):203-212.
[12]王欢欢,胡祥龙.两亲性高分子功能化氧化石墨烯的制备与生物相容性评价[J].激光生物学报,2017,26(6):540-543.WANG H H,HU X L.Preparation and biocompatibility evaluation of amphiphilic polymer functionalized graphene oxide[J].Journal of Laser Biology,2017,26(6):540-543(in Chinese).
[13] CHEN Z H,YU F,ZENG X R,et al.Preparation,characterization and thermal properties of nanocapsules containing phase change material n-dodecanol by miniemulsion polymerization with polymerizable emulsifier[J].Applied Energy,2012,91(1):7-12.
[14] KIM N H,LEE T H,CHOI J S.Swelling equilibria of polymeric hydrogels containing poly(acrylamidesodiumallylsulfonate-acrylic acid)[J].Korean Journal of Chemical Engineering,2000,17(5):534-540.
[15] CHEN P,XU S,WU R,et al.A transparent Laponite polymer nanocomposite hydrogel synthesis via in-situ copolymerization of two ionic monomers[J].Applied Clay Science,2013,72:196-200.
[16] XU Z N,XIAO G M,ZHOU J N.Kinetics of carboxylic acid terpolymer high performance water-reducing agent[J].Polymer Materials Science&Engineering,2010,26(1):26-28.
[17]傅玲,刘洪波,邹艳红,等.Hummers法制备氧化石墨时影响氧化程度的工艺因素研究[J].炭素,2005(4):10-14.FU L,LIU H B,ZOU Y H,et al.Technology research on oxidative degree of graphite oxide prepared by Hummers method[J].Carbon,2005(4):10-14(in Chinese).
[18]中国国家标准化管理委员会.胶黏剂黏度的测定单圆筒旋转黏度计法:GB/T 2794—2013[S].北京:中国标准出版社,2013.Standardization Administration of the People’s Republic of China.Determination for viscosity of adhesives:Single cylinder rotational viscometer method:GB/T 2794—2013[S].Beijing:China Standards Press,2013(in Chinese).
[19] DREYER D R,TODD A D,BIELAWSKI C W.Harnessing the chemistry of graphene oxide[J].Chemical Society Reviews,2014,43(15):5288-5301.
[20]佘广为,徐瑞芬.乳化剂对有机硅酸酯乳改性丙烯液性能的影响[J].有机硅材料,2004,18(4):1-5.SHE G W,XU R F.Infection of emulsifiers on properties of silicone modified acrylate emulsion[J].Silicone Materials,2004,18(4):1-5(in Chinese).
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[22] NGAN C L,BASRI M,LYE F F,et al.Comparison of BoxBehnken and central composite designs in optimization of fullerene loaded palm-based nano-emulsions for cosmeceutical application[J].Industrial Crops and Products,N2014,59:309-317.
[23] KABIRI K,AZIZI A,ZOHURIAAN-MEHR M J,et al.Alcohophilic gels:Polymeric organogels composing carboxylic and sulfonic acid groups[J].Journal of Applied Polymer Science,2011,120(6):3350-3356.