含氟嵌段共聚物蜂窝状多孔膜制备与表征

采用原子转移自由基聚合(ATRP)方法,合成聚苯乙烯(PS)大分子引发剂,再引发甲基丙烯酸十二氟庚酯制备嵌段共聚物(PS-b-PDFHMA)。将嵌段共聚物与纳米二氧化钛(TiO_2)复合,利用静态呼吸图法制备抑菌性多孔膜。通过傅里叶变换红外光谱、核磁共振氢谱、凝胶渗透色谱等对嵌段共聚物结构、组成及相对分子质量进行分析和表征;利用扫描电子显微镜对多孔膜表面形貌和膜层结构进行观察;利用接触角测试仪和微生物粘附实验研究多孔膜表面润湿性及对微生物粘附的影响。结果表明,以水滴为模板的多孔膜相较于不含孔薄膜疏水性有一定改善,但细菌粘附量提高,与TiO_2复合后,多孔膜表面粗糙度上升,水接触角可达136°,其表面细菌粘附量明显下降。     

Anti-corrosive,weatherproof and self-healing polyurethane developed from hydrogenated hydroxyl-terminated polybutadiene toward surface-protective applications

Self-healing polyurethane (PU) faces aging deterioration due to active dynamic bonds, which remain a challenging predicament for practical use. In this work, a novel strategy is developed to address this predicament by leveraging the hydrophobicity and gas barrier of hydrogenated hydroxyl-terminated polybutadiene (HHPB). The dynamic oxime-carbamate bonds derived from 2, 4-pentanedione dioxime (PDO) enable the elastomer to exhibit surface self-repairability upon applied mild heat and achieve ~99.5% mechanical self-healing efficiency. The mechanical properties remained nearly intact after 30-d exposure to thermal oxidation, xenon lamp, acids, bases, and salts. Gas permeability, positron annihilation lifetime spectroscopy (PALS), and contact angle measurements reveal the pivotal role of gas barrier, free volume, and hydrophobicity in blocking undesirable molecules and ions which effectively protects the elastomer from deterioration. HHPB-PU also exhibits excellent adhesion to steel substrate. The shear strength achieves (3.02 ± 0.42) MPa after heating at 80 °C for 4 h, and (3.06 ± 0.2) MPa after heating at 130 °C for 0.5 h. Regarding its outstanding anti-corrosive and weatherproof performances, this self-healable elastomer is a promising candidate in surface-protective applications.     

埃洛石纳米管/水性聚氨酯氟化复合膜的制备及性能

利用原位聚合及表面氟化的方法制备了埃洛石纳米管/水性聚氨酯（HNTs/WPU）复合膜,并考察氨基化埃洛石纳米管（AHNTs）的含量及十七氟癸基三甲氧基硅烷（FAS）氟化对AHNTs/WPU复合膜性能的影响。结果表明:随着AHNTs与WPU的质量比增大,AHNTs/WPU复合膜的力学性能及耐热性呈先升高后降低的趋势,耐水性得到改善。当AHNTs与WPU的质量比为1.5%时,AHNTs/WPU复合膜具有较好的综合性能。AHNTs/WPU复合膜的拉伸强度、断裂伸长率及初始分解温度（T_d5）与纯WPU膜相比分别提高了50%、35%及9℃,复合膜的吸水率降低到5.8%,水接触角提高到95.1°。AHNTs/WPU复合膜经表面氟化处理后,水接触角进一步增大到114.5°,呈现出疏水性,表面氟化处理对复合膜的力学性能及吸水率也有一定的促进作用。      

Synthesis of dimethyl acetal of ketones: design of solid acid catalysts for one-pot acetalization reaction

The synthesis of dimethyl acetals of carbonyl compounds such as cyclohexanone, acetophenone, and benzophenone has successfully been carried out by the reaction between ketones and methanol using different solid acid catalysts. The strong influence of the textural properties of the catalysts such as acid amount and adsorption properties (surface area and pore volume) determine the catalytic activity. The molecular size of the reactants and products determine the acetalization ability of a particular ketone. The hydrophobicity of the various rare earth exchanged Mg–Y zeolites, K-10 montmorillonite clay, and cerium exchanged montmorillonite (which shows maximum activity) is more determinant than the number of active sites present on the catalyst. The optimum number of acidic sites as well as dehydrating ability of Ce³⁺-montmorillonite and K-10 montmorillonite clays and various rare earth exchanged Mg–Y zeolites seem to work well in shifting the equilibrium to the product side.     

聚合物接枝对脂肪酶活性及稳定性的影响

酶的稳定性和活性一直是困扰其工业应用的主要瓶颈，因此改造酶分子以提升其催化性能是当前研究的重要课题。本工作引入甲基丙烯酸异丁酯(IBMA)和甲基丙烯酸乙酯(EMA)两种疏水性不同的单体分子，通过原子转移自由基聚合分别接枝于褶皱假丝酵母脂肪酶(CRL)表面，合成聚合物接枝脂肪酶pIBMA-g-CRL和pEMA-g-CRL。酶学实验结果显示，聚合物接枝脂肪酶的催化活性和稳定性显著提升。pIBMA-g-CRL和pEMA-g-CRL的催化效率分别达到了野生型CRL的4.39倍和4.68倍。在50℃条件下孵育6 h后，pIBMA-g-CRL和pEMA-g-CRL仍分别保留51%和92%的活性，而野生型CRL的活性则仅剩14%。同样，在pH=9条件下孵育3 h后pIBMA-g-CRL和pEMA-g-CRL能够分别保留52%和83%的活性，并在pH=4~9范围内显示出更好的耐受性。光谱学实验进一步证实了聚合物接枝脂肪酶催化性能的提升与其二级结构和三级结构的变化密切相关。本研究表明，IBMA和EMA的接枝对脂肪酶的稳定性和活性的提升效果显著，是改造脂肪酶的优良材料。     

Synthesis and characterization of polyurethane foam matrices for the support of granular adsorbent materials

Polyurethane foams with different formulations were synthesized and characterized for use as supporting matrices of granular solid adsorbents. The open cell content, specific gravity, thermal stability, and hydrophobicity were determined and related to the formulation composition. The synthesized foams had open cell contents of 88.1–98.5% and specific gravity values of 120–28 kg m^?3. The thermal stability of the prepared foams was influenced mainly by the water content and the type of isocyanate used. The hydrophobicity was assessed by an analysis of the water adsorption isotherms determined on selected foams, and a correlation between these results and the formulation of the foams was attempted. Two types of activated carbons were supported in a polyurethane matrix. The adsorption characteristics evaluated before and after the supporting procedure, by nitrogen adsorption, revealed that there was only a moderate surface area reduction of 15–20%. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2045–2053, 2004     

Physicomechanical and hydrophobic properties of starch foams extruded with different biodegradable polymers

Blends of hydroxypropylated high amylose starch and various functional aids listed below were extruded into foams using a twin‐screw extruder ZSK ‐ 30. In this study, the hydrophobic character and mechanical properties of starch foams were improved by using other biodegradable polymers, such as poly‐caprolactone (PCL), poly (butylene adipate‐co‐terephthalate) (PBAT), cellulose acetate (CA), methylated pectin (MP), and polyvinyl alcohol (PVA), and crosslinkers like glyoxal. The hydrophobic character was improved in terms of a reduction in steady state weight gain, and an increase in dimensional stability (reduction in loss of radial and longitudinal dimensions) on moisture sorption. At the same time, efforts were made to maximize the expansion ratios by reduction of unit densities. Formulations of these foams (in terms of additive content and other processing parameters) were optimized. Particular formulations with PVA, polyesters like PCL and PBAT, and glyoxal with PVA gave foams with unit densities lower than 25 kg/m³. The dimensional stability increased with an increase in the polyester content, but the density increased beyond an optimum polyester content, too. The loss in radial and longitudinal dimensions under steady state conditions was 12–20% with polyesters as compared to about 50–55% for control starch. Addition of these processing aids did decrease the water sensitivity of the starch foams. Foams with CA and methylated pectin, in the presence/absence of glyoxal, had marginally lower unit densities and slightly higher expansion ratios, as compared to those of control starch. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 58–68, 2006     

基于改进克隆选择算法的蛋白质关联图预测

针对蛋白质关联图预测问题,提出一种克隆选择算法与蛋白质折叠规律相结合的预测方法,综合使用蛋白质序列疏水性质、残基的二级结构倾向、关联图总点数等信息,构造了基于限制规则的克隆选择算法适应度函数,设计了符合关联图生物学特性的变异操作。算法不需要使用额外蛋白质作为训练集,不需要从现有蛋白质数据库中提取模板,因此不受现有蛋白质结构数据的局限,可以由序列信息直接进行预测。对200个非同源蛋白质的测试验证了算法的有效性。     

介质阻挡放电对RTV涂料憎水性的影响

室温硫化硅橡胶（RTV）材料的憎水性消失与恢复性能是表征该材料特性的重要指标,传统方法是利用长时间水浸泡或电晕放电使RTV材料的憎水性消失,此试验利用介质阻挡放电设备,分析了介质阻挡放电对RTV材料性能的影响。傅氏转换红外线（FTIR）图谱等分析结果表明：介质阻挡放电使RTV憎水性消失的本质是放电破坏涂料内部的有机官能团,产生亲水性基团。试验研究表明：放电处理时间越长,放电输出电压越大,放电输出频率越高,涂料憎水性消失越快。在此基础上,使用介质阻挡放电处理不同配方的RTV试品,然后观测其憎水性恢复过程,测量结果表明RTV涂料配方中生胶的分子基团越小,甲基硅油的质量分数越大,其憎水恢复性越好。     

Role of mineral flotation technology in improving bitumen extraction from mined Athabasca oil sands: I. Flotation chemistry of water‐based oil sand extraction

The role of surface hydrophobicity in water‐based oil sand extraction is examined from the perspective of mineral flotation separation. Although anionic carboxylates (sulphonates) released from bitumen are helpful for charging bitumen and liberating bitumen from sand grains, their presence in oil sand slurries tends to make bitumen and bubbles less hydrophobic. In addition, solid hydrophobization under oil sand extraction conditions can occur through different mechanisms of carboxylate adsorption. It is the hydrophobized fine solids that present challenges for achieving a high bitumen recovery with a good froth quality, due to their competition with bitumen for attachment to bubbles. While chemisorption of carboxylates contributes to hydrophobization of heavy minerals present in oil sands, carboxylate adsorption activated by hydrolyzed metal cations alters silica and clays from hydrophilic to hydrophobic. Different adsorption mechanisms of calcium on silica, clays, and other minerals are analyzed to explain why fine solids of varying mineralogy in combination with calcium affect bitumen extraction differently. Metal ions that activate solid hydrophobization under oil sand extraction conditions are identified from dynamic attachment of solids from mature fine tailings (MFT) to bitumen. To mitigate the effect of fines on oil sand extraction, selective flocculation of fine solids is recognized as especially feasible for bitumen flotation recovery from oil sand middling streams. Future research in reducing or eliminating caustic addition, understanding the role of inorganic anions, and searching for feasible techniques for treating MFT based on different mineralogy and surface properties, are briefly discussed.