Water‐soluble/dispersible cationic pressure‐sensitive adhesives. II. Adhesives from emulsion polymerization

In our previous work, we reported that cationic water‐soluble pressure‐sensitive adhesives (PSAs) could be synthesized in ethanol or methanol. These cationic water‐soluble adhesives would not cause a stickies problem during paper recycling and can be easily removed from the papermaking system by adsorbing on wood fibers. In this study we report the synthesis and application of water‐based cationic PSAs using miniemulsion polymerization. A redox initiator system of cumene hydroperoxide/tetraethylenepentamine was used to force interfacial polymerization. The end‐use properties of the PSAs were evaluated, and the repulpability of the PSAs in paper recycling was studied. It was found that the cationic PSA from miniemulsion polymerization itself was insoluble and nondispersible in water during the paper recycling process. However, if this water‐insoluble cationic PSA from miniemulsion was formulated with a water‐soluble cationic PSA made from ethanol, the solubility or dispensability of the former PSA in water was improved. The molecular weight and degree of crosslinking of the PSA polymer have significant effects on the properties and dispersability of PSA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 347–353, 2004     

DABCO催化蒽酮与二亚苄基丙酮的Michael加成反应研究

以二亚苄基丙酮类衍生物和蒽酮为原料,采用有机催化合成9种新型蒽酮衍生物,考察不同催化剂、溶剂等反应条件对产品产率的影响,筛选得到最优催化剂为三乙烯二胺(DABCO),最优溶剂为二氯甲烷,产率最高达89.9%。     

智慧控制在水厂协同消毒中的应用

针对协同消毒工艺在水厂实际应用中存在的问题和难点,通过对水厂协同消毒工艺的控制进行升级改造及模拟实验,研究了传统控制与智慧控制协同消毒在多种因素影响下的实验结果。相较传统控制,智慧控制协同消毒可将消毒剂控制指标精度提高72%左右、消毒剂投加量减少16%左右、消毒副产物的生成量减少22%左右。在水厂协同消毒应用中智慧控制较传统控制具有更好的控制效果及推广价值。     

火焰原子吸收光谱法测定1,4-丁炔二醇水溶液中二氧化硅

采用火焰原子吸收光谱法测定1,4-丁炔二醇水溶液中的二氧化硅,用标准加入法能够很好的消除基体效应,R2=0.9999,方法的加标回收率在96.5%~103.5%之间,相对标准偏差(n=9)为0.2%~5.0%。     

Synthesis of Gemini‐Like Methyl Acrylate‐Acrylic Acid‐Methyl Acrylate Triblock Copolymers Surfactants by RAFT Polymerization in Solution and Investigation of their Behavior at the Air–Water Interface

A series of methyl acrylate‐acrylic acid amphiphilic triblock copolymers (PMA‐PAA‐PMA) were prepared by solution polymerization using S,S′‐bis (α,α‐dimethy1acetic acid) trithiocarbonate (BDAT) as a reversible addition fragmentation chain transfer (RAFT) agent and methyl acrylate (MA) as the first monomer. The triblock copolymers and their common MA homopolymer precursors were characterized in terms of their compositions, molecular weights and behavior at the air–water interface using ¹H‐NMR spectroscopy, thermogravimetric analysis, gel permeation chromatography, surface tension, transmission electron microscopy (TEM) and dynamic light scattering respectively. The results indicated that PMA‐PAA‐PMA was successfully synthesized through RAFT polymerization. The polydispersity index (PDI) decreased when the molar ratio [n(MA)/n(AA)] increased, the lowest PDI was obtained at 5.23 wt% RAFT and the molecular weights were consistent with the theoretical value as the RAFT agent percentage varied. The polymer neutralized by sodium hydroxide solution shows a low critical micelle concentration (CMC), which was <10^?2 mol L^?1 in water. The A_min values increased and showed a maximum with decreased AA chain length. TEM showed that the neutralized polymer formed a special vesicle structure with large pore structure which led to a low CMC and surface tension of water.     

Effect of Nb addition on microstructure and properties of laser cladding NiCrBSi coatings

NiCrBSi coatings with different Nb additions have been prepared by laser cladding. The microstructure, phase composition, hardness, and wear resistance of the coatings were studied by scanning electron microscopy (SEM), electron probe microanalyser (EPMA), X-ray diffraction (XRD), microhardness tester and M-200 wear tester. The results show that the phases in the NiCrBSi coating without Nb addition include γ-Ni, Cr₂₃C₆, Cr₇C₃, Ni₃B, Ni₃Si₂ and CrB. The NbC phase appears in coatings after the addition of Nb element. When the addition of Nb is 2?wt-%, the NbC particles with a size of about 1.2?μm were found in the coating, and the amount of NbC is about 1.8?vol.-%. With the increase of Nb addition, the size and amount of NbC in the coatings also increased. When the addition of Nb is 6?wt-%, the size of NbC is about 2.3–6.1?μm and the morphology of NbC changed from particle to quadrangular and petaloid shaped. In addition, when the addition of Nb is 2?wt-%, the hardness and wear resistance of the coating are the best, and the wear resistance of the coating is 104% higher than that without Nb addition.     

Copper‐Catalyzed Asymmetric Conjugate Addition of Dimethylzinc to Acyl‐N‐methylimidazole Michael Acceptors: Scope,Limitations and Iterative Reactions

An efficient copper‐catalyzed enantioselective conjugate addition of dimethylzinc to unsaturated 2‐acyl‐N‐methylimidazoles has been achieved using a chiral bidentate hydroxyalkyl‐NHC ligand. The reactions proceed with excellent regioselectivity (1,4 vs. 1,6 and 1,8) in extended conjugated systems to afford the 1,4‐adducts in high enantioselectivities. This regioselectivity could be ascertained by DFT studies highlighting the crucial role of the imidazole ring. Thanks to the development of efficient protocols to regenerate the unsaturated 2‐acyl‐N‐methylimidazole moiety, an iterative process has been developed ultimately leading to 3,5,7 all‐syn or anti‐anti polydeoxypropionate stereodiads.

     

Enantioselective Copper(II)‐Catalyzed Conjugate Addition of Indoles to β‐Substituted Unsaturated Acyl Phosphonates

The first copper‐catalyzed enantioselective conjugate addition of indoles to β‐substituted unsaturated acyl phosphonates was successfully realized by using a heteroarylidene‐tethered bis(oxazoline) ligand. The reaction features high efficiency, cheap catalyst and broad generality. In the case of either β‐alkyl‐ or β‐aryl‐substituted unsaturated acyl phosphonates, the 3‐indolyl adducts were achieved in high yields with good to excellent enantioselectivities (up to 97% ee). The 3‐indolyl adducts can serve as important intermediates in the synthesis of indole alkaloids.

     

Organocatalytic Enantioselective Conjugate Addition of Malonic Acid Half Thioesters to Coumarin‐3‐carboxylic Acids Using N‐Heteroarenesulfonyl Cinchona Alkaloid Amides

We disclose herein an efficient enantioselective conjugate addition reaction between coumarin‐3‐carboxylic acids and malonic acid half thioesters (MAHTs). The reaction was catalyzed by N‐heteroarenesulfonyl Cinchona alkaloid amides to afford double‐decarboxylative conjugate addition products in good yield with high enantioselectivity. The reaction of various coumarin‐3‐carboxylic acids with MAHTs gave products in high yield with high enantioselectivity.

     

Enantioselective Construction of Cyclic Enaminone‐Based 3‐Substituted 3‐Amino‐2‐oxindole Scaffolds via Catalytic Asymmetric Additions of Isatin‐Derived Imines

The first catalytic asymmetric construction of the cyclic enaminone‐based 3‐substituted 3‐amino‐2‐oxindole scaffold with potential bioactivity has been developed via chiral phosphoric acid‐catalyzed enantioselective addition reactions of cyclic enaminones to isatin‐derived imines, which afforded a series of cyclic enaminone‐based 3‐substituted 3‐amino‐2‐oxindoles in high yields and excellent enantioselectivities (up to 99% yield, 97% ee). The investigation of the reaction mechanism suggested that it was facilitated by a dual hydrogen‐bonding activation mode between the two substrates and the chiral phosphoric acid. Besides, this method could be utilized for a large‐scale synthesis with maintained enantioselectivity. This approach will not only offer a useful method for enantioselective construction of the cyclic enaminone‐based 3‐substituted 3‐amino‐2‐oxindole scaffold, but also enrich the research on catalytic asymmetric addition reactions of isatin‐derived imines by using electron‐rich olefins as nucleophiles. More importantly, a preliminary evaluation on the cytotoxicity of some selected products revealed that two of the enantio‐pure compounds exhibited moderate to strong cytotoxicity to A549, 786‐0, ECA109 and BT474 cancer cell lines.