磷酸酯化苯丙共聚物乳液的合成及防锈性能

以甲基丙烯酸（MAA）为亲水单体、甲基丙烯酸羟丙酯（HPMA）为交联单体、苯乙烯（St）和甲基丙烯酸甲酯（MMA）为硬单体、丙烯酸丁酯（BA）为软单体、2-羟乙基甲基丙烯酸酯磷酸酯（PM-2）为功能单体、十二硫醇为链段调节剂，采用半连续种子乳液聚合法，制备了具有核壳结构的磷酸化苯丙防锈乳液（PM-2-SP）。讨论了PM-2用量对PM-2-SP乳液稳定性，胶膜耐水性及漆膜防锈性能的影响。利用激光粒径散射仪（DLS）及透射电镜（TEM）对PM-2-SP乳液的乳胶粒的大小及形貌进行了表征，通过原子力显微镜(AFM)对胶膜表面进行观测，采用盐水喷雾试验机对漆膜的防腐性进行测试。结果表明：当PM-2用量为4%（以总单体质量为基准，下同）时，PM-2-SP乳液粒径为135.7nm，PDI为0.150，且具有核壳结构，稳定性能较好；同时胶膜表面光滑、致密，且有优异的耐水性能；漆膜相比纯苯丙腐蚀电位上升率为47.16%，可达到-0.391V，腐蚀电流下降率为94.76%，可达到1.95E-7（A?cm2），耐盐雾时间达到144h。     

Theoretical kinetic study of the reaction between dimethyl disulfide and OH radicals

The potential energy profile of the reaction between dimethyl disulfide and OH^? radicals is explored by utilizing ab initio and hybrid meta density functional theory methods. Having the energies and structural data of the stationary points, statistical rate theories, such as transition state theory and variable reaction coordinate-transition state theory, are employed to compute the overall rate constants, and discuss the mechanism and product channels. On the basis of the calculations, the overall rate coefficient is predicted to be 2.49?×?10^?10?cm³?molecule^?1?s^?1 at 298?K. It is found that in the most favorable pathway, the reaction proceeds via formation of the relatively unstable intermediate CH₃S^?(OH)SCH₃ decomposing rapidly to yield CH₃S^?+CH₃SOH.     

聚苯胺颗粒对水性环氧树脂涂层防腐性能的影响

以盐酸为掺杂剂、过硫酸铵为氧化剂、咪唑类离子液体为稳定剂，采用化学氧化聚合法合成了导电聚苯胺(PANI)颗粒，将其分散到水性环氧树脂(ER)中制成聚苯胺水性环氧防腐涂层，研究了聚苯胺颗粒对涂层防腐性能和机械性能的影响。结果表明，添加聚苯胺显著提高了水性环氧涂层的阻隔性能，信号频率f=0.01 Hz时，PANI/ER涂层的阻抗(|Z|f=0.01Hz)均高于纯ER涂层。添加5.0wt% PANI时ER涂层阻隔性能最好，浸泡0~168 h时|Z|f=0.01Hz稳定在约8.0×108 Ω?cm2，浸泡168 h后|Z|f=0.01Hz=7.5×108 Ω?cm2，远高于ER和其它PANI/ER体系。中性盐雾实验结果表明，聚苯胺赋予了涂层钝化腐蚀的能力，显著提高了涂层的防腐性能，且其添加量越高，防腐性能越好。弯曲和冲击实验结果表明，涂层的机械性能随聚苯胺含量增加先上升后降低，当聚苯胺添加量不超过5.0wt%时，涂层的机械性能优异，附着力和韧性均较好；PANI添加量增至7.0wt%时，ER涂层的脆性明显变大，机械性能下降。聚苯胺在水性环氧体系中的最宜添加量为5.0wt%，此时涂层的机械性能良好，综合防腐性能最优。     

Excellent Mechanical and Transparency Properties of Cationic Waterborne Polyurethane Films Modified by Boehmite Sol

The strategies for nanosol from metal alkoxide have enabled production of ultratransparent and mechanically robust polymer nanocomposites at extremely high loading. Herein, a simple approach to fabricate high‐performance polyurethane‐based nanocomposites via unmodified boehmite nanoparticles is reported. Evaluating their physical properties, the uniform dispersion of boehmite in the matrix caused nanocomposites retains ultrahigh transparency. Hydrogen bonding and intermolecular entanglement between boehmite and polyurethane brings about the mechanical properties of the nanocomposites material enhanced, i.e., strength, stiffness, and toughness. Optimized strength, stiffness, and toughness of Boehmite/Cationic waterborne polyurethane at 40 wt% (BNC40) are up to 58.1 MPa, 1096.7 MPa, 249.5 MJ m^?3, respectively. Furthermore, the feasibility and mechanism of polymer strengthening and toughening by inorganic rigid nanoparticles is explored from the aspects of crystallinity and micromorphology.     

水性锈转化涂料的制备及性能

采用苯丙乳液与改性苯丙乳液共混作为成膜物质,以单宁酸为转锈剂,柠檬酸为配位剂,焦性没食子酸为转锈促进剂,再加入成膜助剂、有机胺类缓蚀剂、渗透剂等,制备了一种可应用于带锈钢材的水性锈转化涂料。通过正交试验和单因素试验确定了涂料的最优配方为:成膜物质65%,转锈剂5%,转锈促进剂2%,缓蚀剂0.6%,渗透剂2%,配位剂0.5%,成膜助剂1.6%,蒸馏水余量。采用塔菲尔极化曲线测量、中性盐雾试验和盐水浸泡试验考察了漆膜的耐蚀性。结果表明,所制水性锈转化涂膜可耐盐雾96 h,耐盐水浸泡168 h,且耐酸性较强,在pH为2的3.5%NaCl溶液中有保护作用。与两款市售涂料相比,该自制水性锈转化涂料具有更好的耐蚀性。     

Immobilization of surface non-affinitive protein onto a metal surface by an external electric field

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Migration analysis,antioxidant, and mechanical characterization of polypropylene-based active food packaging films loaded with BHA,BHT, and TBHQ

Polypropylene (PP) based active composite films were prepared by adding butylated hydroxy anisole (BHA), butylated hydroxytoluene (BHT), and tertiary butylated hydroquinone (TBHQ) antioxidants using the extrusion molding process. All concentrations of BHT, 2% to 3% BHA, and 3% TBHQ significantly increased the tensile strength (TS) of the composite films compared with control films. Increasing antioxidant concentration decreased TS values for BHT films, whereas an opposite trend was observed for BHA and TBHQ films. BHA at < 2%, BHT at > 2%, and TBHQ at all added concentrations significantly reduced elongation at break (E_b) of the composite films compared to control films. Water vapor permeability (WVP) of 1% BHT film was not significantly different from control. However, other antioxidants especially at increased concentrations significantly increased WVP values. TBHQ films with 300% to 662% increase had the highest WVP and BHT films with 5% to 81% increase had the lowest WVP among composite films. All three antioxidants had a negative effect on the transparency of the films; however the effect of BHA at higher concentrations was greater. The antioxidants did not change the color attributes of the films. Films containing all antioxidants showed 2,2-diphenyl-1-picrylhydrazyl radical-scavenging activity, which increased with increase in their concentration, especially for those containing 3 wt.% BHT and TBHQ. Overall, incorporating BHA and BHT into a PP matrix improved mechanical, barrier, antioxidant properties, and film appearance and consequently were proposed for the development of antioxidant active PP films. TBHQ film is not recommended for food packaging because of its weak mechanical properties (lower E_b and TS values, higher WVP, and greater migration).     

两种海藻内生菌的分离及其抗氧化活性研究

为研究不同海藻不同内生菌(细菌、真菌)的抗氧化活性差异,并筛选出抗氧化活性较好的菌株。选取广西北部湾海域绿藻门石莼(Ulva lactuca L.)与褐藻门裙带菜(Undaria pinnatifida Suringar)为研究对象,以其清除DPPH、羟基自由基与超氧阴离子的能力综合评价体外抗氧化活性,在抗氧化能力都较强的前12株菌株中进一步遴选出石莼与裙带菜内生细菌与内生真菌各3株进行深入检测。石莼与裙带菜的内生细菌、真菌对DPPH、羟基自由基与超氧阴离子的清除活性均随质量浓度增加而升高;不同藻类的石莼与裙带菜的内生菌抗氧化活性之间存在显著差异(P0.05);同种藻类内生菌间,除裙带菜内生真菌外,整体表现为,石莼与裙带菜的内生细菌对DPPH、羟基自由基与超氧阴离子的半抑制浓度IC_(50)值均显著高于内生真菌,说明石莼与裙带菜内生细菌的抗氧化活性显著低于内生真菌。其中,石莼内生真菌SZ-5菌株清除DPPH、羟基自由基与超氧阴离子的综合能力相对最强,IC_(50)依次为(0.59±0.06)、(1.30±0.36)、(1.14±0.35)mg/mL;经分子鉴定为短梗霉菌属真菌Aureobasidium spp.。     

咖啡酸的化学改性及产物抗氧化性的研究

以咖啡酸和氨基酸乙酯盐酸盐为原料,1-(3-二甲基氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC)及1-羟基苯并三唑(HOBt)为催化剂,合成咖啡酰甘氨酸乙酯、咖啡酰丙氨酸乙酯、咖啡酰丝氨酸乙酯、咖啡酰苏氨酸乙酯4种产物。利用核磁共振氢谱(~1H NMR)和高效液相色谱-质谱(HPLC-MS)对产物结构进行表征,考察了咖啡酸化学改性产物对DPPH自由基及羟基自由基活性的抑制率及对红细胞膜的刺激性,并与咖啡酸单体进行了比较。结果表明,通过在咖啡酸中引入甘氨酸乙酯、丙氨酸乙酯、丝氨酸乙酯和苏氨酸乙酯后,4种咖啡酸酰胺类产物均呈现较好的抑制DPPH自由基、羟基自由基活性的效果;咖啡酰丝氨酸乙酯清除DPPH自由基能力较强,其IC_(50)值为13.5 μmol/L;咖啡酰丙氨酸乙酯清除羟基自由基能力较强,其IC_(50)值为0.214 mmol/L。红细胞溶血试验结果表明,4种咖啡酸酰胺类衍生物的红细胞溶血率均低于咖啡酸单体。