梳状弱碱性树脂(MKF-D30X)对丁二酸的静态吸附

以氯乙酰化聚苯乙烯树脂为引发剂,甲基丙烯酸缩水甘油酯为单体,通过原子转移自由基聚合(ATRP)法制备梳状链环氧树脂,再经胺化后得到一种新型、高担载、高自由度的梳状叔胺型弱碱性阴离子交换树脂(MKF-D30X)。考察了MKF-D30X树脂对丁二酸的静态吸附性能,如溶液pH、温度、浓度及吸附时间对吸附平衡的影响。结果表明:该树脂对丁二酸的吸附量随丁二酸浓度升高、时间延长、温度降低、pH降低而升高;吸附过程在实验浓度范围内符合Langmuir方程;丁二酸吸附在130 min达到平衡,吸附行为近似于拟二级动力学方程,并确定此离子交换过程为颗粒扩散控制;当丁二酸的浓度为20 g·L-1时,MKF-D30X树脂的最大吸附容量可高达421 mg·g-1(吸附液与吸附剂的比为200 mL·g-1),比商品级产品D301-1树脂的吸附量高40%。用1.0 mol·L-1的盐酸溶液做洗脱剂,脱附率达到98%,并可重复使用5次性能未减。该树脂吸附量高、解吸率高可归因于其柔性梳状长链的功能基团具有向四周呈星状扩散且自由度大的特点。     

梳状亲水性环氧基载体固定化Pseudomonas stutzeri LC2-8脂肪酶

以氯乙酰化聚苯乙烯微球(PS-acyl-Cl)为引发剂,亲水性丙烯酰胺(AM)和甲基丙烯酸缩水甘油酯(GMA)为单体,CuCl及联吡啶(Bipy)为催化体系,通过原子转移自由基聚合反应(ATRP)制备得到梳状亲水性环氧基柔性载体(PS-acyl-P(AM-co-GMA)),通过改变AM与GMA配比,使载体环氧基含量和亲水性得到控制.用该柔性载体固定Pseudomonas stutzeri LC2-8脂肪酶,优化了固定化条件,并对柔性固定化酶性质进行考察.结果显示,当n(AM)∶n(GMA)=20∶60,固定化时间为24 h,固定化温度为30℃,固定化pH为7.0时,固定化酶活力达到最高,为24.1U·g-1.固定化酶的最适pH为8.0,最适温度为30℃,其热稳定性比游离酶高,重复使用8次,剩余酶活力80％左右.以上表明,以ATRP法合成的载体PS-acyl-P(AM-co-GMA)可成功用于脂肪酶的固定化,有效提高脂肪酶的稳定性和实用性.     

触角状环氧链结构对固定化脂肪酶(YCJ01)酶活的影响

为了改善酶的刚性固定化对酶蛋白构象的负面影响,以原子转移自由基聚合法(ATRP)合成了亲水性、柔性、触角状环氧化酶固定化载体PS-acyl-P(AM-co-GMA),通过改变单体总量与引发剂量比例得到不同链长触角状环氧化酶固定化载体,并将其用于耐有机溶剂脂肪酶(YCJ01)的共价柔性固定化,重点考察了链长对固定化酶酶活的影响。结果表明,链长(增重率不超过3200%)越长,酶活越高。     

触角状环氧链结构对固定化脂肪酶(YCJ01)酶活的影响

为了改善酶的刚性固定化对酶蛋白构象的负面影响,以原子转移自由基聚合法（ATRP）合成了亲水性、柔性、触角状环氧化酶固定化载体PS-acyl-P（AM-co-GMA）,通过改变单体总量与引发剂量比例得到不同链长触角状环氧化酶固定化载体,并将其用于耐有机溶剂脂肪酶（YCJ01）的共价柔性固定化,重点考察了链长对固定化酶酶活的影响。结果表明,链长（增重率不超过3200%）越长,酶活越高。     

一种新型触角状聚苯乙烯磺酸树脂的合成研究

经氯乙酰聚苯乙烯微球(PS-acyl-Cl)的ATRP接枝聚合,制备了具有触角状聚苯乙烯链的聚苯乙烯树脂(PS-g-LPS),该树脂可快速、高效磺化,经磺化条件的优化,得到一新型的触角状聚苯乙烯磺酸树脂(v HP-SPS-Cat),对v HP-SPS-Cat进行了FT-IR、元素分析、光学显微镜观察及催化酯化。结果表明,v HP-SPS-Cat可克服试剂的物理扩散的阻碍,用于小分子酯或生物柴油的催化合成,而达到高效均相催化的效果。     

梳状弱碱性树脂对丁二酸高浓度循环解吸

建立了一种有效的、低能耗的从梳状弱碱性(MKF-D30X)树脂上解吸丁二酸的工艺。考察了解吸剂用量(体积)、解吸温度、分段解吸及分段循环解吸对MKF-D30X树脂解吸附丁二酸的影响。结果表明,MKF-D30X树脂对溶液中的丁二酸(25 mg·ml-1)有很好的吸附作用,吸附量高达425 mg·(g干树脂)-1。当解吸温度为50℃,每个阶段用10 ml、1.0 mol·L-1 HCl解吸剂,两阶段解吸3 g吸附饱和的树脂,第1阶段解吸得到的丁二酸浓度可高达52.4 mg·ml-1,将丁二酸浓度提高到原液浓度的209.6%;在此基础上再进行分段循环解吸,不仅可以维持第1阶段获得的高浓度丁二酸,且可同时获得第2阶段2倍收率的高浓度丁二酸,达到了高浓度、高效率解吸丁二酸的目的。另研究表明,分段循环解吸液再作为解吸剂,其中丁二酸的浓度对丁二酸解吸效果没有明显影响。     

亲水性树脂的合成与亲水性的研究

以含有-CONHCH_2OH、-CONH_2、-COOH、-COOROH、-NH_2、-OH、-SO_3H等亲水性基团的树脂为成膜物质,制备空调机热交换器的铝翅片面层保护膜。研究了各种基团树脂的亲水性,以及pH值、成膜温度、成膜时间、涂膜厚度、表面活性剂等对膜的亲水性的影响。     

树脂去除压裂液残余硼交联剂研究

采用臭氧对胍胶压裂返排液进行氧化预处理,处理液用LSC-800树脂螯合吸附除硼。考察了氧化时间对残余胍胶去除的影响,优化树脂除硼条件,树脂除硼后处理液循环配液的性能以及树脂再生循环利用的可行性。结果表明,臭氧氧化150 min时,总糖去除率达到了61.34%;较优的树脂除硼工艺参数:吸附时间5 h, pH值7～8,吸附温度15～30℃,吸附量为8.99 mg/g, Ca⁽²⁺⁾和Mg(2+)和Mg⁽²⁺⁾不影响树脂吸附;树脂再生循环使用5次,其单位吸附量略有增加;除硼后处理液配制胍胶粘度与清水配液时相当,交联后,80℃下挑挂性能相当。由此可知,树脂去除压裂液残余硼交联剂效果显著,并且不会影响后续再利用。     

氨基胍功能化树脂的制备及其对Cd~(2+)的吸附性能研究

以D301树脂为载体,通过接枝于D301树脂表面的单体甲基丙烯酸缩水甘油酯(GMA)上的环氧键与氨基胍盐酸盐发生开环反应,成功制备出一种富含氨基基团的新型吸附材料AHD301。采用傅里叶红外光谱仪对其结构进行表征,并且研究了功能吸附材料对Cd⁽²⁺⁾的吸附性能。结果表明,在298 K,pH为6.8的条件下,AHD301对Cd(2+)的吸附性能。结果表明,在298 K,pH为6.8的条件下,AHD301对Cd⁽²⁺⁾的吸附效率可达97.9%,最大吸附量为535.5 mg/g。并且,AHD301具有较好的重复使用性能。     

聚甲基丙烯酸丁酯-苯乙烯高吸油树脂的制备及其吸油性能研究

以甲基丙烯酸丁酯(BMA)和苯乙烯(St)为单体,二乙烯苯(DVB)为交联剂,偶氮二异丁腈(AIBN)为引发剂,聚乙烯醇(PVA)为分散剂,水为分散介质,运用悬浮聚合法制备了自溶胀型高吸油树脂。通过正交试验考察了单体配比、交联剂用量、引发剂用量和分散剂用量对树脂吸油性能的影响。结果表明:当m(BMA):m(St)=5:5、交联剂用量、引发剂用量和分散剂用量分别为单体总质量0.5%、2%和2%时,吸油树脂吸油倍率达到14.12 g g 1,吸附动力学研究发现此时吸油速率最大;通过热重表征和重复吸油试验,合成的高吸油树脂能够重复吸油多次,第五次的吸油倍率能够达到第一次的93%。     

亲水性涂料的研究

对亲水性涂料的配方设计、亲水性的影响因素、合成工艺及外加交联剂等进行了系统研究。     

Effect of degree of deprotonation of maleic anhydride-allyl polyethoxy carboxylic acid copolymer on calcium scale

A hydrophilic copolymer (MA-APEA) containing carboxylic acid group and ethylene oxide group is synthesized from maleic anhydride (MA) and allyloxy polyethoxy carboxylic acid (APEA) in free radical polymerization and its structure is characterized using FT-IR, ¹H nuclear magnetic resonance spectrometer and gel permeation chromatographic techniques. Seven polymer solutions with different degrees of deprotonation are prepared by adding caustic solution to the polymer solution. Effects of the degree of deprotonation of the polymer on curbing calcium scale and the corrosion inhibition of low carbon steel are studied. Influences of the operating conditions on inhibition against CaCO₃ scale by the polymer with different degrees of deprotonation are also investigated. Effects of the degree of deprotonation on CaCO₃ deposits/precipitate are analyzed using scanning electronic microscope and X-ray diffraction. The results show that different degrees of deprotonation of the polymer have different influences on different calcium scale and corrosion inhibition of low carbon steel. The performance of the polymer to withstand high alkalinity and high hardness and high temperature decreases with increase in the degree of deprotonation. The change in the degree of deprotonation influences the conversion of aragonite and vaterite to calcite, and hardly impacts the crystal morphology of CaCO₃ crystals. MA-APEA has proven to be an excellent calcium scale inhibitor.     

Hyperbranched polyglycerol/poly(acrylic acid) hydrogel for the efficient removal of methyl violet from aqueous solutions

Hydrogels were synthesized from hyperbranched polyglycerol (HPG) and acrylic acid through free‐radical polymerization with HPG as the crosslinker. The HPG/poly(acrylic acid) (PAA) hydrogel could absorb cationic dyes in aqueous solutions because of the existence of a porous structure and the large numbers of hydroxyl and carboxylic groups. With methyl violet chosen as a model compound, the HPG/PAA hydrogel reached a maximum adsorption of 394.12 mg/g at a feed concentration of 1 g/L. The highest removal ratio of 98.33% was observed at a feed concentration of 50 mg/L. The effects of the pH, contact time, and feed concentration on the dye adsorption were investigated. The dye adsorption data fit well with the pseudo‐second‐order and Langmuir models. We believe that the HPG/PAA hydrogels could perform well in appropriate applications in the removal of cationic dyes from aqueous solutions because of their high adsorption capacity and environmental friendliness. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42951.     

Metal‐chelating properties of poly(2‐hydroxyethyl methacrylate–methacryloylamidohistidine) membranes

Metal‐chelating membranes have advantages as adsorbents in comparison with conventional beads because they are not compressible and they eliminate internal diffusion limitations. The aim of this study was to explore in detail the performance of poly(2‐hydroxyethyl methacrylate–methacryloylamidohistidine) [poly(HEMA–MAH)] membranes for the removal of three toxic heavy‐metal ions—Cd(II), Pb(II), and Hg(II)—from aquatic systems. The poly(HEMA–MAH) membranes were characterized with scanning electron microscopy and ¹H‐NMR spectroscopy. The adsorption capacity of the poly(HEMA–MAH) membranes for the selected heavy‐metal ions from aqueous media containing different amounts of these ions (30–500 mg/L) and at different pH values (3.0–7.0) was investigated. The adsorption capacity of the membranes increased with time during the first 60 min and then leveled off toward the equilibrium adsorption. The maximum amounts of the heavy‐metal ions adsorbed were 8.2, 31.5, and 23.2 mg/g for Cd(II), Pb(II), and Hg(II), respectively. The competitive adsorption of the metal ions was also studied. When the metal ions competed, the adsorbed amounts were 2.9 mg of Cd(II)/g, 14.8 mg of Pb(II)/g, and 9.4 mg of Hg(II)/g. The poly(HEMA–MAH) membranes could be regenerated via washing with a solution of nitric acid (0.01M). The desorption ratio was as high as 97%. These membranes were suitable for repeated use for more than three adsorption/desorption cycles with negligible loss in the adsorption capacity. The stability constants for the metal‐ion/2‐methacryloylamidohistidine complexes were calculated to be 3.47 × 10⁶, 7.75 × 10⁷, and 2.01 × 10⁷ L/mol for Cd(II), Pb(II), and Hg(II) ions, respectively, with the Ruzic method. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1213–1219, 2005     

Polymeric hydrogels obtained using a redox initiator: Application in Cu(II) ions removal from aqueous solutions

Poly(acrylic acid‐co‐acrylamide) hydrogels were prepared via free‐radical solution polymerization, crosslinked with ethylene‐glycol‐dimethacrylate, potassium persulfate/ammonium bisulfite as the initiator, and applied in the removal of Cu(II) ions from aqueous solutions. Molar ratios of acrylamide/acrylic acid moieties and the amount of crosslinking agent were varied to determine the swelling capacities of hydrogels and maximum metal uptake. Polymerization kinetics was investigated by ¹H‐NMR. Hydrogel physicochemical properties were characterized by nitrogen sorption measurements, elemental analysis, FTIR, and X‐ray photoelectron spectroscopy (XPS). Swelling results indicated that hydrogels were swollen up to 27,500%. Hydrogels showed equilibrium Cu(II) adsorption capacities of 211.7 mg g^?1 and fast kinetics (～20 min). Langmuir isotherm fitted adsorption equilibrium data. FTIR and XPS results helped in elucidating the presence of monodentate copper complex on the surface of hydrogels. A simple synthesis route of hydrogels using the redox initiator suggests the potential application in the removal of toxic metals from aqueous streams. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39933.     

Binding of several heavy metal ions by polyaspartyl polymers and their application to some Chinese herbal medicines

Water‐insoluble polyaspartyl polymers were synthesized by using water as medium instead of organic medium. Taking Ca²⁺ as a reference, the binding of several heavy‐metal ions, including Pb²⁺, Cd²⁺, Hg²⁺, Cr³⁺, Cu²⁺, and Mn²⁺, by polyaspartyl polymers was studied. The experimental results revealed that polyaspartate is an excellent binding agent for the investigated heavy‐metal ions. These cation ions were bound to polyaspartate polymer by the same mechanism as Pb²⁺, which can be explained by ion exchange model. Since polyaspartate has a protein‐resembling structure that is sensitive to trace heavy metal, it was used to remove some trace heavy‐metal elements in Chinese herbal medicines. It was found that polyaspartate material was an effective agent for the removal of Pb²⁺, Cd²⁺, and Hg²⁺ ions from glycyrrhizin, angelica, and gynostemma pentaphyllum. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Pb2+ binding by polyaspartyl polymers and their application to Pb2+ removal from glycyrrhizin

Polyaspartate is an excellent Pb²⁺‐binding agent in comparison with some polyaspartamide derivatives with different side chains, in that it possesses a higher Pb²⁺ uptake and a lower Pb²⁺ equilibrium concentration. Equilibrium sorption data for Pb²⁺ on polyaspartate can be well fitted with the Freundlich and Langmuir models. Experimental results show that a crosslinked polyaspartate hydrogel is superior to poly(acrylic acid)‐based resins and polystyrene‐based chelating resins. IR spectra and X‐ray photoelectron spectra reveal that the polyaspartate hydrogel binds Pb²⁺ by both an ion‐exchange mechanism and a chelating mechanism. The polyaspartate hydrogel is also an effective agent for the removal of Pb²⁺ from glycyrrhizin. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2215–2220, 2005     

亲水疏油型含氟环氧树脂的制备和表征

以含氟表面活性剂(FSN)、聚乙二醇(PEG)、异佛尔酮二异氰酸酯(IPDI)和环氧树脂(EP)制备亲水疏油型的含氟环氧树脂。利用X射线光电子能谱仪(XPS)、接触角测定仪(CA)和原子力显微镜(AFM)表征了薄膜的表面物理化学性质。所制备的材料表面是一种对水和油具有特殊响应的智能表面,通过表面链段重构表现出亲水性和疏油性。其在FSN含量为6%时达到最佳效果,此时水的接触角为17°,十六烷的接触角为82°。     

Preparation and anti-evaporation properties of organic–inorganic superabsorbent based on Tragacanth gum and clay

In this study, the application of superabsorbent resin (SAP) in inhibiting the soil moisture evaporation (or slowing down the water outflow) was studied. The clay-SAP composites were fabricated by grafting of poly (acrylic acid-N-hydroxymethyl acrylamide/clay) (GT-g-P [AA-co-NHA]/clay) on Tragacanth gum (GT), using solution polymerization. The structure, morphology and stability of the clay-SAP composites were investigated by Fourier transform infrared, scanning electron microscope and TGA. The maximum swelling ratio of Attapulgite (3%)-, Kaolin (3%)- and Montmorillonite (3%)-SAP composite in deionized water reached 1180, 819 and 525 g/g respectively, and the maximum swelling ratio in tap water reached up to 206, 192 and 170 g/g respectively. Meanwhile, the maximum swelling ratio in 0.9% NaCl solution was 95, 82 and 62 g/g respectively. The water retention of clay-SAP composites was also analyzed as a function of temperature. In addition, by simulating the desertification area, the effect of the APT (3%)-SAP composite on the anti-evaporation performance was studied. The obtained results revealed that the water retention of APT (3%)-SAP composite was 36% at 45°C for 12 h. Under natural conditions, the evaporation rate of the anti-evaporation material was inversely proportional to the amount of APT (3%)-SAP composite added.