棉织物的反应性二苯甲酮紫外线吸收剂/液体石蜡整理

利用反应性二苯甲酮紫外线吸收剂UV-1/液体石蜡对棉织物进行抗紫外线整理,以整理后织物的均匀性和UPF值为评价指标,对织物带液率、Na_2CO_3质量浓度、整理温度及时间等因素进行优选,得到的优化工艺为:棉织物以120%带液率浸轧40 g/L Na_2CO_3溶液,先在30℃下处理40 min后升温至70℃并保温40 min。与水浴整理相比,UV-1/液体石蜡整理工艺具有更高的UPF值,且具有优良的耐水洗牢度。     

Fate of trace organics during rapid infiltration of primary wastewater at Fort Devens, Massachusetts

Transport and fate of trace organics were studied during rapid infiltration of primary wastewater at a land application facility in Fort Devens, Massachusetts. A preliminary sampling trip was made to compare trace organic concentrations in the infiltrating wastewater and in ground water samples from three monitoring wells around the site. Trace organic concentrations were reduced by the rapid infiltration process. However, significant concentrations of specific compounds could be detected in ground water down-gradient of the site.Therefore, a field study was undertaken to determine the primary region where trace organics were removed in the system. Teflon monitoring wells were installed at a depth of 1.2 m in one of the basins at the site prior to flooding. Flooding was initiated and samples of the raw wastewater, the wastewater entering the basin, the infiltrate at 1.2-m depth and the ground water down-gradient of the site were analyzed for six compounds selected for the study.Results from replicate samples during the 6-day flooding period demonstrated that most of the removal for the six compounds occurred in the top meter of the soil, although concentrations of each compound increased substantially in the basin infiltrate from two of the sample points after the fourth day of flooding. No removal of p-dichlorobenzene, p-(I,1,3,3-tetramethylbutyl)phenol and 2-(methylthio)benzothiazole was apparent in the aquifer itself, as indicated by relatively high concentrations of these compounds in the contaminated monitoring well down-gradient of the site.These data indicate that trace organic concentrations in primary effluent can be reduced by rapid infiltration and that most of the removal occurs in the top meter of the soil during the early phase of the flooding cycle. This removal capability can rapidly diminish, however, and result in ground water contamination by trace organics above background levels.     

Benzophenone vs. Copper/Benzophenone in Light‐Promoted Atom Transfer Radical Additions (ATRAs): Highly Effective Iodoperfluoroalkylation of Alkenes/Alkynes and Mechanistic Studies

Iodoperfluooralkylation of terminal alkenes and alkynes is effectively photo‐promoted by benzophenone 2 (BP) or the photoreducible copper(II) complex 1 . In particular, BP at 1 mol% in methanol upon 365 nm irradiation with a low‐pressure mercury lamp (type TLC=thin layer chromatography, 6 W) results in a fast reaction with excellent reaction yields. Complex 1 and BP 2 exhibited very similar reactivity, suggesting that the reactions involving 1 are likely to be governed by the benzophenone photoactivation processes, rather than copper(I)/(II) redox processes. Mechanistic investigations using transient absorption spectroscopy revealed that a deactivation pathway of the benzophenone triplet (³BP*) is via its reaction with the methanol solvent. We propose that the generated radicals, in particular ^.CH₂OH, play a key role in the initiation step forming R_f^. by reacting with R_fI, R_f^. then entering a radical chain cycle. ¹H NMR studies provided evidence that a substantial amount (∼7% NMR yield) of the hemiacetal CH₃OCH₂OH is formed, i.e., the possible by‐product of the reaction between ^.CH₂OH and R_fI. Finally, DFT calculations indicate that a triplet‐triplet energy transfer (TTET) process from ³BP* to perfluorooctyl iodide (C₈F₁₇I) is unlikely or should be rather slow under the reaction conditions, consistent with the transient absorption studies.

     

二苯甲酮腙合成工艺条件的研究

以二苯甲酮(BP)和水合肼为原料合成二苯甲酮腙(BPH),探讨了催化剂种类、催化剂用量、原料配比、溶剂种类等因素对产物收率及色泽的影响,并对产物进行IR和HPLC表征和成本核算。结果表明:常规低沸点溶剂更合适,高沸点溶剂会使副产物增多,影响产品质量;离子液体作催化剂能大大缩短反应时间;最佳合成条件为:离子液体催化剂用量为BP质量的2%、n(水合肼)∶n(BP)=2.8∶1、无水乙醇为溶剂、反应时间3h、温度控制在回流状态下。从工业成本角度考虑,最佳合成条件为:冰乙酸催化剂用量为BP质量的2%、n(水合肼)∶n(BP)=2.8∶1、无水甲醇为溶剂、反应时间9h、温度控制在回流状态下。     

Non-visible print set-off of photoinitiators in food packaging: detection by ambient ionisation mass spectrometry

Direct analysis in real time coupled to time-of-flight mass spectrometry (DART/TOF-MS) was used to detect the non-visible set-off of photoinitiators on the food contact surface of three different packages. The samples were intentionally under-cured to provoke set-off. Twelve commercially available photoinitiators were included in the ink formulations including α-amino-, morpholino, and α-hydroxy benzophenones, thioxanthones, aryl-phosphine oxide and three polymeric versions of these. Major colours of the packages’ prints were analysed, as well as the specific areas of the inner surface in contact with them. Larger quantities of photoinitiators were detected on the food contact areas in contact with the darker colours of the images. Speed-cure 7005 and 4-phenylbenzophenone were the compounds most susceptible to set-off in each of the samples by DART response. An identification protocol for unknown set-off compounds was tested, resulting in the set-off detection of diethylene glycol ethers, erucamide and acrylates, and confirmed by solvent extraction GC-MS analysis. Finally, DART/TOF-MS was scanned across transects of the food contact side of packages to map the presence of photoinitiators. Higher photoinitiator signals were observed in patterns corresponding to the printed image, suggesting DART/TOF-MS might “image” print set-off.     

Efficiency of 4,4′‐bis(N,N‐diethylamino) benzophenone for the polymerization of dimethacrylate resins in thick sections

The efficiency of 4,4′‐bis(N,N‐diethylamino)benzophenone (DEABP) for the polymerization of dimethacrylate monomers in thick sections ( 1 – 2 mm) was studied. DEABP (λ_max = 365 nm) represents a complete initiating system as it contains both ketone and amine functional groups. During irradiation, DEABP photobleaches at a fast rate causing deeper penetration of light through the underlying layers, but the photoinitiation efficiency (rate of polymerization per photon absorption rate) is relatively poor. As a result, irradiation of methacrylate monomers at 365 nm results in a slow average polymerization rate and a reduced monomer conversion for thick sections due to the light attenuation caused by the high absorptivity of DEABP and photolysis products. These results highlight the inherent interlinking of light attenuation and photobleaching rate in polymerization of thick sections. Copyright © 2011 Society of Chemical Industry     

Toughening of AT-Resins with a Polyphenylquinoxaline

Acetylene terminated (AT) resins are addition-curable thermoset materials which do not generate volatiles during cure and therefore can be fabricated into void-free structures. They retain good thermal and mechanical properties even after exposure to high humidity environments. Their use as composite matrix resins and adhesives has shown promise. These resins, however, are brittle. Molecular structure modifications and blending with thermoplastic modifiers have been used to improve their toughness. In this work, improvement in toughness has been sought through the use of a polyphenylquinoxaline (PPQ) modifier. The blended systems showed improvements in toughness, thermooxidative stability, and lap shear strength over the original AT-resins.     

Photochemical ECE and DISP processes. The self-inhibiting disproportionation (SID) mechanisms. Theory and experiment

Channel electrodes are used to characterize the photochemical DISP2 mechanism in respect of the photoelectro-reductions of

1. (i) 9,10-diphenylanthracene,

2. (ii) benzophenone and

3. (iii) 4-fluorobenzophenone.

Quantitative measurements show that the simple DISP2 mechanism requires extension to allow for the possibilities of first a conproportionation step acting as a back-reaction to the disproportionation, and of second quenching of the excited state which leads to reaction. Both these steps, if present, serve to inhibit the overall DISP2 process. Accordingly a general scheme of Self-Inhibiting Disproportionation (SID) Mechanisms is introduced and characterized in the channel electrode geometry by computer simulations. A general protocol is established for identifying the various possible sub-cases of the general SID mechanism and illustrated with reference to the three experimental systems of interest, in all of which both conproportionation and quenching are shown to be mechanistically significant.     

新型催化剂合成对甲氧基二苯甲酮的研究

介绍用水杨酸铁合成对甲氧基二苯甲酮的方法，并从多方面与传统催化剂无水三氯化铝进行比较，该新型催化剂具有用量少、产率高、工艺简单、无污染等优点。     

水性光引发剂(4-苯酰基)苯甲基铵-N-十二烷基-N,N-二甲基溴化物的合成

以4-甲基二苯甲酮为原料,经溴化合成4-溴甲基二苯甲酮,再与二甲基十二胺反应合成新型的光引发剂(4-苯酰基)苯甲基铵-N-十二烷基-N,N-二甲基溴化物,对新化合物结构进行了IR,MS,1HNMR表征。产品纯度大于98%,收率大于81%(以4-溴甲基二苯甲酮计)。对产品的光引发性能进行了初步研究。