水性抗菌羟基丙烯酸树脂的制备及性能
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摘要
以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸(AA)、丙烯酸羟丙酯(HPA)为单体,过氧化二苯甲酰(BPO)为引发剂,乙醇为助溶剂,采用半连续溶液聚合法合成得到了水性羟基丙烯酸树脂(hs-WA),再用三乙胺(TEA)中和,最后引入季铵盐抗菌剂3-(甲氧基硅烷基)丙基二甲基十八烷基氯化铵(TSA),合成得到了水性抗菌羟基丙烯酸树脂(hs-WAT)。利用FTIR、1HNMR、接触角、SEM、TG和DSC对样品进行了分析,并采用菌落计数法和抑菌圈法对样品进行了抗菌测试。结果表明:引入TSA反应后,树脂的表面形貌没有改变;水接触角从78.5?增大至87.5?;样品的分解温度范围为299～456℃,热稳定性提高;聚合物链柔韧性增强(Tg=8.3℃)。抗菌性能分析表明:当引入TSA的质量分数为4%(以树脂的固含量计)时,hs-WAT膜对大肠杆菌(革兰氏阴性菌)以及金黄色葡萄球菌(革兰氏阳性菌)的杀灭率达99.9%以上,TSA未发生迁移,合成的聚合物为水性非渗透性接触型抗菌材料。
Waterborne hydroxyl polyacrylate(hs-WA) was synthesized by semi-continuous solution polymerization using methyl methacrylate(MMA),butyl acrylate(BA), acrylic acid(AA) and hydroxypropyl acrylate(HPA) as monomers, benzoyl peroxide(BPO) as intiator, ethanol as co-solvent and triethylamine(TEA) as neutralizer.Then, quaternary ammonium salt antibacterial agent, 3-(methoxysilyl) propyldimethyloctadecyl ammonium chloride(TSA) was introducedand reacted with hs-WA to synthesize an antibacterial waterborne hydroxy polyacrylate(hs-WAT).The samples were characterized by FTIR, 1HNMR, contact angle measurement, SEM, TG and DSC.Their antibacterial properties were tested by colony counting method and inhibition zone method.The results showed that the introduction of TSA did not change the surface morphology of hydroxyl polyacrylate, but made the water contact angle increase from 78.5? to 87.5?. The thermal properties of samples were enhanced and their decomposition temperatures were between 299 ℃ and 456 ℃. In addition, the introduction of TSA improved the polymer chain flexibility, the minimum glass transition temperature(Tg) of samples was 8.3 ℃. When the mass fraction of TSA was 4% based on the solid content of the resin, the as-prepared hs-WAT film could eliminate over 99.9% of Gram-negative bacteria(E. coli) and Gram-positive bacteria(S.aureus) and no inhibition zone formed, which indicated that TSA did not migrate and the synthesized hs-WAT was a non-permeable contact antibacterial material.
Waterborne hydroxyl polyacrylate(hs-WA) was synthesized by semi-continuous solution polymerization using methyl methacrylate(MMA),butyl acrylate(BA), acrylic acid(AA) and hydroxypropyl acrylate(HPA) as monomers, benzoyl peroxide(BPO) as intiator, ethanol as co-solvent and triethylamine(TEA) as neutralizer.Then, quaternary ammonium salt antibacterial agent, 3-(methoxysilyl) propyldimethyloctadecyl ammonium chloride(TSA) was introducedand reacted with hs-WA to synthesize an antibacterial waterborne hydroxy polyacrylate(hs-WAT).The samples were characterized by FTIR, 1HNMR, contact angle measurement, SEM, TG and DSC.Their antibacterial properties were tested by colony counting method and inhibition zone method.The results showed that the introduction of TSA did not change the surface morphology of hydroxyl polyacrylate, but made the water contact angle increase from 78.5? to 87.5?. The thermal properties of samples were enhanced and their decomposition temperatures were between 299 ℃ and 456 ℃. In addition, the introduction of TSA improved the polymer chain flexibility, the minimum glass transition temperature(Tg) of samples was 8.3 ℃. When the mass fraction of TSA was 4% based on the solid content of the resin, the as-prepared hs-WAT film could eliminate over 99.9% of Gram-negative bacteria(E. coli) and Gram-positive bacteria(S.aureus) and no inhibition zone formed, which indicated that TSA did not migrate and the synthesized hs-WAT was a non-permeable contact antibacterial material.
引文
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[2]Kugel A, Stafslien S, Chisholm B J. Antimicrobial coatings produced by“tethering”biocidestothecoatingmatrix:Acomprehensive review[J]. Progress in Organic Coatings, 2011, 72(3):222-252.
[3]LamSJ,WongEHH,BoyerC,etal.Antimicrobialpolymeric nanoparticles[J]. Progress in Polymer Science, 2018, 76(1):40-64.
[4]TillerJC,LiaoCJ,LewisK,etal.Designingsurfacesthatkill bacteriaoncontact[J].ProceedingsoftheNationalAcademyof Sciences of the United States of America, 2001, 98(11):5981-5985.
[5]Liu Haidi(刘海弟), Yue Renliang(岳仁亮), Zhang Jingkun(张婧坤),etal.Preparationoftrichlosan/SiO2compositematerialand investigation into its antibacterial peformance[J]. Fine Chemicals(精细化工), 2011, 28(11):1046-1050.
[6]MiloviNM,WangJ,LewisK,etal.ImmobilizedN-alkylated polyethylenimine avidly kills bacteria by rupturing cell membranes withnoresistancedeveloped[J].Biotechnology&Bioengineering,2005, 90(6):715-722.
[7]XueY,XiaoH,ZhangY.Antimicrobialpolymericmaterialswith quaternaryammoniumandphosphoniumsalts[J].International Journal of Molecular Sciences, 2015, 16(2):3626-3655.
[8]Tezel U, Pavlostathis S G.Role of quaternary ammonium compounds onantimicrobialresistanceintheenvironment[M].Antimicrobial ResistanceintheEnvironment.JohnWiley&Sons,Inc,2011:349-387.
[9]Kang Shaoran(康少冉), An Qiufeng(安秋凤), Ma Libo(马立博), et al.Synthesisoforgainquaternaryammoniumsaltpolymerandits application as an antibacterial fabric softener[J]. Fine Chemicals(精细化工), 2015, 32(10):1152-1156.
[10]MaWei(马威),TuoTingting(拓婷婷),ZhangShufen(张淑芬).Research development of antibacterial agent[J]. Fine Chemicals(精细化工), 2012, 29(6):521-525, 536.
[11]Zhang Faai(张发爱), Wang Yunpu(王云普), Yu Caili(余彩莉), et al.Studyofwatersolubilityofacrylicresincontaininghydroxyl group[J]. Fine Chemicals(精细化工), 2005, 22(9):717-720.
[12]JenaKK,NarayanR,AlhassanSM.Highlybranchedgraphene siloxane-polyurethaneurea(PU-urea)hybrid coatings[J]. Progress in Organic Coatings. 2017, 111(11):343-353.
[13]KaramdoustS,YuB,BonduelleCV,etal.Preparationof antibacterialsurfacesbyhyperthermalhydrogeninducedcrosslinkingofpolymerthinfilms[J].JournalofMaterialsChemistry,2012, 22(11):4881-4889.
[14]BasriH,IsmailAF,AzizM,etal.Silver-filledpolyethersulfone membranesforantibacterialapplications-effectofPVPandTAP additiononsilverdispersion.[J].Desalination,2010,261(3):264-271.
[15]Lin J, Lin W, Li S, et al. Evaluation of the antibacterial activity and biocompatibility for silver nanoparticles immobilized on nano silicate platelets[J].ACSAppliedMaterials&Interfaces,2012,5(2):433-443.
[16]HeLihong(何丽红),ZhouChao(周超),LiLi(李力),etal.Superhydrophobicity of surface-modified TiO2 with silane coupling agent[J]. Fine Chemicals(精细化工), 2014, 31(9):1061-1064.
[17]Bao Yan(鲍艳), Guo Jiajia(郭佳佳), Wang Xian(王宪). Synthesis andpropertiesofquaternaryammoniumorganicsilicongemini surfactant[J]. Fine Chemicals(精细化工), 2016, 33(6):343-346.
[18]Vasiljevi?J, Tom?i?B, Jerman I, et al. Novel multifunctional waterand oil-repellent, anti-bacterial, and flame-retardant cellulose fibres created by the sol–gel process[J]. Cellulose, 2014, 21(4):2611-2623.
[19]CuiX,ZhongS,WangH.Emulsifier-freecore–shellpolyacrylate latexnanoparticlescontainingfluorineandsiliconinshell[J].Polymer, 2007, 48(25):7241-7248.
[20]DongYaohua(董耀华),GuoNa(郭娜),LiuTao(刘涛),etal.Research on the preparation of Ag-loaded self-polishing/low surface energy coating and its antifouling ability[J]. Surface Technology(表面技术), 2015, 44(3):100-106.
[21]SunXiaoying(孙小英),SuYouquan(苏友权),JinLujiang(金鹿江), et al. Synthesis and ant-biofouling properties of fluorine/silicone synergistically modified acrylic resins[J]. Acta Polymericasinica(高分子学报), 2013,(1):134-141.
[22]Cheng Zhang(程章), Zhang Fan(张帆), Sun Xiaoying(孙小英), et al.Preparationandpropertiesofamphiphilicfluorinatedsilicone modifiedacrylicresincoatingscontainingPEGforanti-fouling applicaion[J].ActapolymericaSinica(高分子学报),2016,(8):1112-1120.
[23]YanL,XuZ,WangX.Influenceofnano-silicaontheflame retardancyandsmokesuppressionpropertiesoftransparent intumescent fire-retardant coatings[J]. Progress in Organic Coatings,2017, 112(9):319-329.
[24]WuX,LiJ,LiG,etal.Heat-triggeredpoly(siloxane-urethane)s basedondisulfidebondsforself-healingapplication[J].Journalof Applied Polymer Science, 2018. DOI:10. 1002/APP. 46532.
[25]ZhangChaoying,ZhuZhewen,GongShuling,etal.Synthesisof stable high hydroxyl content self-emusifying waterborne polyacylate emulsion[J]. Journal of Applied Polymer Science, 2017, 44844:1-11.
[26]Wang Jichang(王季昌). Tg design and selection of acrylic resin[J].China Coatings(中国涂料), 2008, 23(10):52-56.