含膦酸酯结构单元的磺胺衍生物合成与抗菌活性

为了寻找抗菌候选化合物,采用基于片段的药物发现方法,以氨基膦酸酯和磺酰氯为原料,设计合成了15个含膦酸酯结构单元的磺胺衍生物,经IR、1HNMR和13CNMR确认结构。采用两倍稀释法测定目标化合物的MIC(最小抑菌浓度)。结果表明:部分目标化合物呈潜在的抗菌活性,对所测试标准菌和耐药菌均有抑制活性。其中,化合物Ⅱf〔N-[(二乙氧基膦酰基)-4-氟苯甲基]-4-甲氧基苯磺酰胺〕对金黄色葡萄球菌(S. aureus)、大肠埃希菌(E. coli)、耐甲氧西林金黄色葡萄球菌(MRSA)及耐氟喹诺酮类大肠杆菌(MREC)的MIC分别为32、64、128和128μg/mL,化合物Ⅱl〔N-[(二乙氧基膦酰基)-4-氟苯甲基]-4-氟苯磺酰胺〕对S. aureus、E. coli、MRSA及MREC的MIC分别为32、32、64和64μg/mL,抗菌活性优于对照药磺胺嘧啶。     

模拟3种有机膦系阻垢剂与方解石(104)面的相互作用

通过pH曲线实验研究了乙二胺四亚甲基膦酸(EDTMP),己二胺四亚甲基膦酸(HDTMP)和二乙烯三胺五亚甲基膦酸(DTPMP)对碳酸钙垢的阻垢性能,在相同的加药浓度下阻垢性能强弱顺序为:DTPMPEDTMPHDTPM。同时采用周期性边界条件下的分子动力学方法,模拟研究了在水分子存在条件下各阻垢剂与方解石(104)面的相互作用,得到了相应的结合能和原子间距离等参数。结果表明:阻垢分子膦酸基团中的双键氧与碳酸钙中的Ca~(2+)形成的强静电相互作用力对吸附起了主导作用,同时膦酸基团中的氢与晶面中的氧形成了氢键,加强了吸附效果。综合考虑各分子在晶面(104)上的吸附效果,其结果与实验相符合;从分子中膦酸基团作用个数也可看出,HDTMP只有一个膦酸基团靠近晶面,因此作用力也是最弱的。     

Synthesis and performance of three flame retardant additives containing diethyl phosphite/phenyl phosphonic moieties

Three novel intumescent flame retardants (IFRs) containing phosphorus and nitrogen based on Schiff bases, poly(phosphonate ester(s)) (designated as PAB, PEB, and PPB), were synthesized and characterized. Thermal stability and flammability properties of ethylene-vinyl acetate copolymer (EVA)/30% IFRs blends were investigated by thermogravimetric analysis (TGA), limited oxygen index (LOI), vertical burning test (UL-94) and microscale combustion calorimetry (MCC). The results from UL-94 showed that EVA/IFRs blends all could reach V-2 rating. The addition of PAB into EVA reduced the PHRR value by 31%, and the LOI value increased from 19 to 24. Scanning electron microscope (SEM) observation results indicated that the existence of the cohesive charred layer on the surface of the residue was responsible for the improvement of the flame retardancy of EVA.     

Thermal and flame resistance properties of natural rubber‐g‐poly‐(dimethyl(methacryloyloxymethyl)phosphonate)

Natural rubber grafted with poly(dimethyl(methacryloyloxymethyl)phosphonate) (i.e., NR‐g‐PDMMMP) was prepared in latex medium via photopolymerization. Thermal and flame resistance properties of the NR‐g‐PDMMMP prepared with various levels of grafted PDMMMP or grafting rate (GR) were investigated. Thermal behaviors were investigated by thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC). It was found that the graft copolymer exhibited phase separation with double T_g values. A shift of T_gs toward each other was observed with increasing GR, which indicated tendency to become a single phase material. Increasing GRs also caused increasing heat and flame resistance with increasing degradation temperature and level of char residue. Furthermore, increasing level of limited oxygen index (LOI) and decreasing burning rate were observed with increasing the GR. This is attributed to increasing content of char residue of the phosphorus compound, which acted as the thermal insulation and a barrier of oxygen to transfer to the burning materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

甲基膦酸二甲庚酯对硝酸介质中Pu(Ⅳ)的萃取

研究了 HNO3介质中甲基膦酸二甲庚酯(DMHMP) 对Pu(Ⅳ)的萃取性能,考察了DMHMP浓度、NO-3浓度、HNO3浓度以及温度对Pu(Ⅳ)分配比的影响。确定了DMHMP萃取Pu(Ⅳ)的萃合物的组成为Pu(NO₃)₄·2DMHMP,其萃取反应方程式为： Pu⁴⁺_(a)+2DMHMP_(o)+4NO^-_3(a) Pu(NO₃)₄·2DMHMP_(o) 其中Pu(Ⅳ)与NO^-₃形成中性分子,再与DMHMP结合成为中性配合物进入有机相。在实验范围内Pu(Ⅳ)分配比与DMHMP浓度的平方、NO^-₃浓度的四次方成正比,萃取过程为放热反应,反应的焓变为-34.46 kJ/mol。     

活性氧杀菌剂的合成及与常用阻垢缓蚀剂的相容性研究

对活性氧杀菌剂制造技术和现行工业循环水常用水处理药剂有机磷和共聚物的相容性进行了研究．并和强氯精杀菌剂进行了比较。实验结果表明,活性氧杀菌剂在常温下对有机磷药剂分解很小;通过共聚物、有机磷的阻垢实验可知,活性氧杀菌剂的加入对聚环氧琥珀酸、聚丙烯酸、HPA、PBTCA的阻垢效果影响不大;在缓蚀配方实验中均能达到防腐要求。     

Biobased Poly-phosphonate Additives from Methyl Linoleates‡

Poly-dialkyl phosphonates were synthesized by reacting methyl linoleate with dimethyl, diethyl, and di-n-butyl phosphites in the presence of free radical initiator and positively identified and characterized using gas chromatography–mass spectrometry (GC-MS), nuclear magnetic resonance (NMR; ¹H, ¹³C, ³¹P), and Fourier transform infrared (FTIR). Neat poly-dialkyl phosphonates and their blends in high-oleic sunflower oil (HOSuO) and polyalphaolefin (PAO-6) base oils were investigated for their physical, chemical, and tribological properties. At room temperature, the poly-dialkyl phosphonates displayed much better solubility in HOSuO than in PAO-6. Solubility in the base oils increased in the order dimethyl?<?diethyl?<?di-n-butyl. Relative to methyl linoleate, the neat poly-dialkyl phosphonates displayed higher density, higher kinematic viscosity, higher oxidation stability, and better cold flow (lower pour point and cloud point) properties. As an additive (0–10% w/w) in HOSuO, increasing concentration of poly-di-n-butyl phosphonate resulted in increasing onset and peak oxidation temperatures and decreasing cloud point. Poly-di-n-butyl phosphonate blends in HOSuO also showed lower four-ball antiwear (AW) coefficient of friction (COF) and wear scar diameter (WSD) than corresponding blends with zinc dialkyl dithiophosphate (ZDDP). As an additive (0–10% w/w) in PAO-6 base oil, poly-di-n-butyl phosphonate displayed lower four-ball antiwear COF and comparable WSD relative to similar blends of ZDDP in PAO-6. The results indicate that poly-dialkyl phosphonates are promising biobased AW additives with comparable or better performance than current petroleum-based commercial AW additives such as ZDDP.     

Ring‐opening bulk polymerization of five‐ and six‐membered cyclic phosphonates using maghnite,a nontoxic proton exchanged montmorillonite clay

A new method of preparation of poly(alkylene H‐phosphonate)s by ring‐opening bulk polymerization of the five‐ and six‐membered cyclic phosphonates monomers using the nontoxic Maghnite‐H⁺ as the initiator is described. Cyclic phosphonate monomers have been first synthesized. In particular, a new one‐step synthesis of 2‐hydro‐2‐oxo‐1,3,2‐dioxaphospholane is reported with a yield of 70%. The efficiency of the montmorillonite sheet silicate clay which exchanged with protons, called Maghnite‐H⁺, as cationic initiator has been proved and the resulting biomimetic poly(alkylene H‐phosphonate)s have been characterized. The Maghnite‐H⁺ regenerated after one turn‐over has showed to be still efficient as initiator for the ring‐opening polymerization. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Evaluation of inhibitors and biocide on the corrosion control of copper in neutral aqueous environment

Polarisation and impedance measurements were performed on copper in neutral aqueous solution with and without inhibitors and biocide. The inhibitors used were 3-benzylidene amino 1,2,4-triazole phosphonate (BATP), 3-cinnamalidene amino 1,2,4-triazole phosphonate (CATP), 3-salicylalidene amino 1,2,4-triazole phosphonate (SATP) and 3-paranitro benzylidene amino 1,2,4-triazole phosphonate (PBATP). Effect of inhibitors and biocide against the corrosion of copper in neutral aqueous solution has been studied. Results elucidate the minimal interference between biocide and inhibitors system. Surface evaluation techniques like FT-IR, XRD and EDXA were used to determine the nature of the protective film formed on the metal surface.     

Corrosion inhibition of mild steel in neutral aqueous solution by new triazole derivatives

Selected triazole derivatives have been synthesised and evaluated as corrosion inhibitors for mild steel in natural aqueous environment by weight loss, potentiodynamic polarisation and ac impedance methods. All the condensed products showed good inhibition efficiency (IE). The effect of changing functional groups of some triazole derivatives on their inhibition efficiency was also reported using weight loss and potentiodynamic technique. 3-Salicylalidene amino-1,2,4-triazole phosphonate (SATP) was found to be the best corrosion inhibitor compare to the other compounds. Surface analysis was carried out to establish the mechanism of corrosion inhibition of mild steel in neutral aqueous media.