一种氨烷基膦酸型水处理剂的合成及缓蚀阻垢性能的研究

介绍了一种氨烷基膦酸型水处理剂二甲基氨基甲叉二膦酸(DMAMDP)的合成方法,并进行了缓蚀阻垢性能的研究。结果表明,DMAMDP在阻碳酸钙、硫酸钙、磷酸钙和稳定锌等方面,以及缓蚀性能均优于常用有机膦酸水处理剂HEDP和ATMP。     

钙中毒商用SCR脱硝催化剂的再生特性研究

本研究分别选用络合剂氨基三甲叉膦酸(ATMP)、2-膦酸基丁烷-1,2,4-三羧酸(PBTCA)对钙中毒商用SCR脱硝催化剂(V₂O₅-WO₃/TiO₂)开展了再生方法研究，借助BET、NH₃-TPD、H₂-TPR和XPS等分析测试方法和实验探究考察了再生前后催化剂的理化特性及再生脱硝性能。结果表明，ATMP与PBTCA具有高效的再生性能，再生催化剂的脱硝效率在400℃下分别从25.8%恢复至89.8%与88.1%。与稀H₂SO₄再生相比，ATMP与PBTCA对催化剂的再生具有更高的除钙率与更低的钒损失率(不足5%)。使用ATMP与PBTCA对催化剂再生可有效恢复催化剂表面的Br?nsted酸性位；催化剂表面的活性钒物种V⁵⁺和表面化学吸附氧O_α明显增加，催化剂整体活性达到最优水平。因此，将络合剂ATMP与PBTCA用于失活SCR脱硝催化剂的再生具有广阔的应用前景。     

ATMP(氨基三甲叉膦酸)及其顺磁性Co(Ⅱ)配合物的核磁共振研究

本文用¹H、³¹P和¹³C核磁共振谱研究了ATMP(氨基三甲叉膦酸,以简式H₆L表示)及其顺磁性Co(Ⅱ)配合物。测定了不同C_co/C_ATMP摩尔比在不同pH值下的各向同性位移。定性地讨论顺磁性Co(Ⅱ)配合物在不同pH条件下的组成、电荷和空间构型变化对化学位移的影响。运用快速交换反应中化学位移与配合物浓度的关系,确定不同pH下的条件稳定常数。     

1-氨基乙叉1,1-二膦酸的合成及其阻垢和缓蚀性能

有机多膦酸是一类多齿配体的螯合剂,能与许多金属离子形成稳定的配合物,70年代国内合成了1-羟基乙叉1,1-二膦酸(HEDP),并已应用于水质稳定,金属缓蚀和无氰电镀。Lukevico 用甲腈、三溴化磷和醋酸合成了1-氨基乙叉1,1-二膦酸 CH_3C(NH_2)(P(O)(OH)_2]_2(AEDP)后,又有人用醋酰胺、醋酸酐、亚磷酸或醋酸铵、醋酸酐、亚磷酸以及醋酸铵、醋酰胺、三氧化二磷(P_4O_6)为原料进行了合成,本文报导用尿素、冰醋酸、三氯化磷合成 AEDP 及其阻垢和缓蚀性能.     

α-氨基烃基膦酸及其衍生物的合成与反应

本文报导合成α-氨基烃基膦酸(1)及其衍生物的新方法与反应。(一)提出用苯甲酰胺(或丙烯酰胺)和醛、亚磷酸三苯酯反应,经水解合成(1);(二)在BF_3·Et_2O催化下用磷酰胺或代磷酰胺、醛和亚磷酸三苯酯或苯基亚磷酸二苯酯反应,生成α-磷胺酰氨基(或硫代磷酰胺基)取代苄膦酸二苯酯或次膦酸苯酯(2)。经选择性脱去氨基保护基生成α-氨基膦酸二苯酯溴代盐(3);(三)二苯氧基氯磷、醛和磷酰胺(或硫代磷酰胺)在 ZnCl_2等路易斯酸存在     

亚硝酰亚铁螯合物——Ⅱ.用Fourier变换红外光谱法研究一氧化氮与亚铁螯合物在水溶液中的配位反应

本文报道了用Fourier变换红外光谱法研究水溶液中一氧化氮与亚铁氨基多膦酸和氨基多羧酸的配位反应。所用的多齿配体有:氨基三甲叉膦酸(NTMP),乙二胺四甲叉膦酸(EDTMP),三乙烯四胺六乙酸(TTHA),二乙烯三胺五乙酸(DTPA),反式-1,2-二胺六环四乙酸(CyDTA),乙二醇二乙醚二胺四乙酸(EGTA)和氨基三乙酸(NTA)。根据~(15)N标记实验,确认了亚硝酰配合物中N—O的特征振动频率。与水合配合物[Fe(H_2O)_5(NO)]~(2+)相比,螯合物中的N—O伸缩振动频率均有“红移”。借助于FTIR技术,考察了亚硝酰配合物与亚硫酸盐或氧气的氧化还原反应。与亚硫酸反应的产物是氨基磺酸一类的化合物。与氧接触后,亚硝酰配合物的N—O特征吸收峰逐渐消失。本文还对不同螯合物体系与NO配位时光谱变化的趋势进行了讨论。     

三维介孔氨基三亚甲基膦酸锆的合成及其担载铁催化剂的甲醛催化氧化活性

以氧氯化锆和氨基三亚甲基膦酸(ATMP)为原料合成了一种新型介孔材料氨基三亚甲基膦酸锆(NTAZP)。使用XRD、FTIR、TG-DTA和SEM等手段对所合成的介孔材料进行了结构表征和形貌分析。然后以NTAZP为载体,用Fe(NO3)3水溶液处理,得到担载Fe3+的氨基三亚甲基膦酸锆。研究结果表明,Fe3+被吸附到载体孔道中后,NTAZP结构未被破坏,Fe3+离子与NTAZP孔壁骨架上的N发生了配位作用。铁担载NTAZP(NTAZP-Fe3+)对甲醛氧化具有良好的催化活性,催化反应条件温和,催化剂稳定性良好。以载体NTAZP担载铁还避免了Fe3+进入水体,催化剂得以回收利用,避免造成二次污染。NTAZP-Fe3+是一种高效绿色的新型小分子醛类化合物氧化催化剂。     

有机磷化合物的研究(LVII)——二苯(氧)基氯膦对肟基的自由基加成——合成1-氨基取代三烷基氧化膦及烷基膦酸酯的新途径

二苯基氯膦或二苯氧基氯膦对醛(酮)肟的反应可作为合成1-氨基烷基二苯基氧化膦或1-氨基烷基膦酸二苯酯的新方法,具有条件温和、操作方便及得率高的优点。EPR研究结果揭示了这类反应属自由基机理。     

有机磷化合物的研究——Ⅻ.α-氨基烃基膦酸的合成

本文较系统地研究了由醛、酰胺(或脲素)、亚磷酸酯反应合成α-氨基烃基膦酸的方法,并讨论了各组成的结构对反应的影响.由醛与苯甲酰胺(或丙烯酰胺)、亚磷酸三苯酯反应,然后经过水解是合成α-氨基烃基膦酸的新方法,具有操作方便、得率较高及产物易于纯化的特点.对反应机理也作了初步探讨.     

α-(2-噻唑基脲基)膦酸二苯酯的合成

报道了一种简便的合成取代脲基膦酸酯的通用的新方法。在二氯甲烷中,三乙胺为缚酸剂的条件下,α-氨基膦酸二苯酯与三聚光气反应形成α-异氰酸基膦酸酯2,2不经分离,直接与2-氨基(苯并)噻唑加成得到α-(2-噻唑基脲基)膦酸二苯酯3,产率55.0%-88.9%。     

氨基膦酸螯合树脂吸附重稀土的研究

研究了重稀土在氨基膦酸树脂的吸附行为.试验结果表明,氨基膦酸树脂对重稀土的吸附在pH=5.0的HAc-NaAc缓冲溶液时最佳;298K时静态饱和吸附容量为332mg/g干树脂;用2mol/L盐酸洗脱,洗脱率为91.2%;等温吸附服从Freundlich经验式;吸附反应中△H=10.76kJ/mol,表观速率常数k298=1.223×10-4s-1,表观活化能Ea=3.2kJ/mol.     

Studies on Adsorption Behavior and Mechanism of Copper（ Ⅱ ） onto Amino Methylene Phosphonic Acid Resin

IntroductionThe adsorption ability of the functional poly-mer used to enrich metal ions is strong and the op-eration of the functional polymer is convenient.The polymer having adsorbed metal ions can be re-covered by means of an acid or an alkaline solutionand the recovered polymeric material can bereused.The adsorption ability of the polymer withvarious functional groups is different for differentmetals.Because nucleophilic atoms such as oxy-gen,nitrogen,sulphur and phosphorous atoms cancoord…     

Investigation of thermal decomposition of phosphonic acids

The paper compares building and decomposition pathways of two phosphonic acids, amino trimethylene phosphonic acid (ATMP) and 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP).The theoretical formation reactions were composed using elementary reactions and compared to reaction routes published in literature. As result, summary reaction pathways for both phosphonic acids are proposed which only vary in the number of reaction steps required. These reaction steps include carbonyl reactions, S_N2-reactions, and ionic reactions. The synthesis of ATMP proceeds in three reaction steps, whereas HEDP is formed in one reaction. The thermal decomposition of both phosphonic acids in solid state was examined by combination of thermogravimetry coupled with infrared spectroscopy as well as pyrolysis gas chromatography coupled with mass spectrometry. Decomposition mechanisms were deduced and compared to the theoretical findings resulting in the conclusion that the decomposition processes of ATMP and HEDP follows the formation mechanism.Thus, the suitability of theoretical considerations for the understanding of thermal decomposition processes is shown.     

Enhanced dehumidification performance of PVA membranes by tuning the water state through incorporating organophosphorus acid

A novel thin film composite membrane with superior propylene dehumidification performance was prepared by coating a high hydrophilic organophosphorus acid ethylene diamine tetra(methylene phosphonic acid) (EDTMPA) doped poly(vinyl alcohol) (PVA) on polysulfone (PS) hollow fiber membranes. Experimental studies and molecular dynamics simulations were combined to probe the existing states and the transport mechanism of water in the membranes. Water vapor sorption experiments revealed that the enhanced dehumidification performance was governed by the diffusion process. Water states and water distribution were investigated by molecular dynamics simulation. At low EDTMPA content (<10 wt.%), states of the water were not obviously changed and the increase of water diffusion coefficient was mainly attributed to enlarged free volume of the membrane. At high EDTMPA content (10–30 wt.%), the increase in the water diffusion coefficient mainly arose from the variations in the water states. Strong interaction between PVA and EDTMPA reduced the amount of water that bounded to the PVA and increased the proportion of free water. The diffusion coefficients of water increased with increasing proportion of free water, since the mobility of free water was higher than that of bound water. The permeance of water reached 997.7 GPU for the PVA–EDTMPA/PS membrane with a 20 wt.% EDTMPA content when the proportion of free water was the highest, and the separation factor increased to infinity.     

Asymmetric Synthesis of α-Amino Phosphonic Acids using Stable Imino Phosphonate as a Universal Precursor

A practical method for synthesizing chiral α-amino phosphonic acid derivatives was developed. Readily available and stable N-o-nitrophenylsulfenyl (Nps) imino phosphonate was utilized as a substrate for a highly enantioselective Friedel–Crafts-type addition of indole or pyrrole nucleophiles catalyzed by chiral phosphoric acid. The resulting adduct was easily converted into N-9-fluorenylmethyloxycarbonyl (Fmoc) amino phosphonic acid, which is useful for synthesizing peptides containing an amino phosphonic acid.     

Copper(II) complexes of imino-bis(methyl phosphonic acid) with some bio-relevant ligands. Equilibrium studies and hydrolysis of glycine methyl ester through complex formation

Binary and ternary complexes of Cu(II) involving imino-bis(methyl phosphonic acid) (IdP) abbreviated as H₄A and some selected bio-ligands, amino acids, peptides and DNA constituents (L), were examined. Cu(II) forms CuA and CuAH complexes with IdP. Ternary complexes are formed in a stepwise mechanism whereby iminodiphosphonic acid binds to Cu(II), followed by coordination of amino acid, peptide or DNA. The concentration distribution of the various complex species has been evaluated. The kinetics of base hydrolysis of glycine methyl ester in the presence of Cu(II)-IdP was studied in aqueous solution at different temperatures, and in dioxane-water solutions of different compositions at 25°C. The activation parameters are evaluated and discussed.     

SORPTION BEHAVIOR AND MECHANISM OF SAMARIUM(III) ON AMINO METHYLENE PHOSPHONIC ACID RESIN

Sm(III) was quantitatively adsorbed by amino methylene phasphonic acid resin (APAR)in the medium of pH=5.0. The statically saturated sorption capacity is 251mg/g @ resin. Sm(III)adsorbed on APAR can be reductively eluted by 2.0mol/L HCl. The sorption rate constant is k2gs=1.35 ×1O-Ss-1. The sorption behavior of APAR for Sm(I) obeys the Freundlich isotherm. The enthalpy change △H° of sorption is 24.9k J/mol. The apparent activation energy is Ea= ll. 7kJ/mol.The sorption mechanism shows that the nitrogen and oxygen atoms of the functional group of APAR coordinated with Sm(Ⅲ) to form coordination bond.     

Synthesis of Novel 2‐Vinylcyclopropane Phosphonic Acids

2‐Vinylcyclopropane‐1‐phosphonic acid diesters 1a–d were synthesized by the reaction of trans‐1,4‐dibromo‐2‐butene with α‐substituted phosphonic acid diesters. Esterification of 1‐ethoxycarbonyl‐2‐vinylcyclopropane‐1‐carboxylic acid with dimethyl 2‐hydroxyethyl‐phosphonate gave the 2‐vinylcyclopropane phosphonic acid dimethylester 1e. The silylation of phosphonic acid diesters 1a–e by halotrimethylsilanes followed by solvolysis with methanol or water resulted in the formation of phosphonic acids 2a–e. In the case of steric hinderance of the phosphoryl group, monoesters 3c,d were also formed. Furthermore, ethyl carboxylate 1b could be chemoselectively cleaved by aqueous potassium hydroxide to carboxylic acid 4.     

Synthesis of a Novel Perfluorinated Vinyl Ether Containing Sulfonimide and Phosphonic Acid Functionalities

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