聚合漆酚-镍配合物的电化学合成与性质研究

探讨了漆酚 (EPU)的电化学聚合及其聚合漆酚 镍配合物 (EPU_Ni2 +)的制备 .采用X光电子能谱、红外光谱、动态机械热分析 (DMTA)、TG_DTA、原子发射光谱 (AES)等手段对配合物(EPU_Ni2 +进行表征 .AES结果表明 :镍含量达 7.5 % .由于存在着Ni2 +与EPU的配位作用 ,并引起进一步交联 ,从而提高了玻璃化转变温度和耐热性能     

电化学聚合漆酚铜配合物催化引发醋酸乙烯酯聚合的研究

将电化学聚合方法得到的聚合漆酚 (EPU)与氯化铜异丙醇溶液作用生成电化学聚合漆酚铜配合物(EPU Cu2 + ) .采用顺磁共振波谱 (ESR)、红外光谱 (FT IR)、XPS光电子能谱、原子发射光谱 (AES)、元素分析及AES等手段进行表征 ,确定该配合物的结构即每个铜离子与EPU分子中二个链节单元的羟基发生配位 .配合物中铜含量达 8 6 3% .实验表明 ,电化学聚合漆酚铜 (EPU Cu2 + )配合物膜在室温下的Na2 SO3水体系 (pH =7)中能催化引发醋酸乙烯酯 (VAc)按自由基加聚反应历程进行聚合 .讨论了温度、Na2 SO3浓度、VAc浓度和EPU Cu2 + 膜用量对聚合速率、诱导时间的影响 ,求得聚合速率的表达式Rp=0 0 7e- 2 82 5 RT[VAc]1 54[Na2 SO3]0 5,实验结果表明 ,EPU Cu2 + 配合物膜催化引发醋酸乙烯酯 (VAc)聚合的诱导期为 12 2s ,反应 2 4h后PVAc得率为79% , Mw =1 2 6× 10 6 , Mn=2 6 3× 10 5,多分散性系数为 4 79.     

电化学聚合漆酚铜配合物的结构及其催化性能

 将电化学聚合法得到的聚合漆酚（EPU）与氯化铜的异丙醇溶液作用制成了电化学聚合漆酚铜配合物（EPU－Cu2＋）,并用顺磁共振波谱、红外光谱、X射线光电子能谱、动态机械热分析和原子发射光谱等手段进行了表征．结果表明,该配合物中每个铜离子与EPU分子中二个链节单元的羟基发生配位,铜含量达8．63％．实验结果还表明,该配合物在Na2SO3的水体系（pH＝7）中能催化引发MMA按自由基反应历程进行聚合．     

电聚合漆酚镝配位聚合物研究

根据漆酚结构特点和稀土元素的电子结构特殊性，研究电聚合漆酚（EPU）与 氯化镝反应生成配位聚合物（EPU－Dy~(3+)）,采用FT－IR，元素分析，XPS，荧光 光谱，DMTA，DTA－TG等手段对其进行表征，探讨其结构与性质，元素分析等测定 结构证明了每个Dy~(3+)分别与EPU分子中3个链节单元的羟基发生配位，从而得到 配位聚合物的结构，证实了配合物中存在着Dy~(3+)与EPU的配位作用，并引起进一 步交联，且镝含量达13.18%，DMTQ，DTA－TG分析结果表明玻璃化转变温度和耐热 性能均有所提高，荧光光谱表明EPU对Dy~(3+)不起敏化作用，EPU与Dy~(3+)配位后 使Dy的特征荧光淬灭。     

电化学聚合漆酚钐配合物的研究

利用电化学方法合成的聚合漆酚 (EPU)与氯化钐的异丙醇溶液作用 ,得到聚合漆酚钐配合物 (EPU Sm3 + ) .采用红外光谱、紫外 可见光光谱、荧光光谱、XPS光电子能谱、动态机械热分析 (DMTA)以及差热 热重(DTA TG)等手段进行表征 ,确定其每个钐离子与EPU分子中三个链节单元的羟基发生配位 .原子发射光谱(AES)结果确定钐含量达 13 18% .配合物的电阻为 9 6× 10 1 0 Ω(EPU为 7 9× 10 1 0 Ω) .发现因配位作用而使配合物进一步交联 ,而难溶于有机溶剂 ,同时玻璃化转变温度和耐热性能得到提高     

电化学聚合漆酚-镨配合物的合成及其表征

通过电化学方法合成的聚合漆物、与氯化镨作用生成聚合漆酚－镨配合物膜。采用原子发射光谱、红外光谱、荧光光谱、差热－热重分析、Ｘ光电子能谱和动态热分析等手段进行表征。探讨其结构与耐热性质。证明了螯合物中存在Ｐｒ＾３＋和ＥＰＵ的配位作用,并引起进一步交联,因而难溶于绝大多数有机溶剂,同时玻璃化转变温度和耐热性能均得提高。     

电化学聚合漆酚钴膜配位结构与催化性能研究

电化学方法合成的聚合漆酚 (EPU)通过与氯化钴的异丙醇溶液作用 ,生成聚合漆酚钴配合物膜(EPU Co3+ ) .采用红外光谱、XPS光电子能谱、DTA TG、动态机械热分析 (DMTA)以及原子发射光谱 (AES)等手段进行表征 ,确定其配位结构 ,即每个钴离子与EPU中两个链节单元的羟基发生配位而交联 ,因此玻璃化转变温度和耐热性能均得到提高 .实验表明 ,此配合物膜在室温下的Na2 SO3水体系 (pH =7)中能催化引发VAc的聚合     

电化学聚合漆酚钴膜引发甲基丙烯酸甲酯（MMA）聚合的研究

利用电化学技术合成的聚合漆酚（EPU）与氯化钴的异丙醇溶液反应,得到电化学聚合漆酚钴配合物膜,经XPS光电子能谱、红外光谱、TG－DTA、动态机械热分析（DMTA）以及原子发射光谱（AES）等手段进行表征并确定其结构。由于每个钴离子与EPU分子中两个链节单元的羟基发生配位引进进一步交联。因此玻璃化转变温度和耐热性能均得到提高。实验表明,在常温下的Na2SO3水体系（pH值为7）中配合物膜能引发甲基丙烯酸甲酯（MMA）聚合。     

电化学聚合漆酚稀土配合物的合成与表征

采用电化学方法合成的聚合漆酚(EPU)与三异丙氧基稀土Re(Pr,Nd,Eu)反应,生成稀土金属配合物(EPU-Re3+)。利用FT-IR、荧光光谱、XPS、DMTA、AES等手段对其表征,探讨其结构与性质。证明了配合物中存在着稀土金属离子Re3+与EPU的配位作用,并引起进一步的交联,因而难溶于绝大多数有机溶剂,而且其玻璃化转变温度和耐热性能均得到提高。     

均三嗪衍生物应用于Fe3+和Cu2+的选择性识别研究

合成了2,4-二甲基-6-(4’-N,N-二甲氨基苯乙烯基)-1,3,5-均三嗪(1)和2-苯乙烯基-4,6-二甲基-1,3,5-均三嗪(2)两种化合物,并对其进行了1H NMR,MS,元素分析等表征.采用吸收光谱法研究了金属离子与化合物间的相互作用,结果显示:化合物1对Fe3+和Cu2+表现出高选择性光谱响应,其最大吸收波长由393 nm分别红移至525 nm和513 nm,溶液颜色由黄色变为粉红色.化合物1与Fe3+结合形成1∶1型配合物,其结合常数为1.8×104L mol-1;与Cu2+结合形成2∶1型配合物,其结合常数为2.6×1010L mol-1.化合物2仅对Fe3+呈现显著的光谱变化,其最大吸收波长由304nm红移至357 nm,而Cu2+的加入未引起光谱明显变化,2与Fe3+亦形成1∶1型配合物,结合常数为1.0×105L mol-1.结果表明Fe3+可能与化合物1和2中三嗪N配位,而Cu2+与化合物1中甲氨基中的N配位.同时考察了其它金属离子如Li+,K+,Mg2+,Ca2+,Co3+,Ni2+,Ag+,Cd2+,Hg2+和Zn2+等离子对化合物1和2吸收光谱的影响,结果显示两者光谱均无明显变化,据此提出了高选择性Fe3+,Cu2+的识别体系.     

分光光度法连续测定发样中铜和铁

建立了一种在表面活性剂OP存在下,用2－（5－溴－2－吡啶偶氮）－5二乙氨基酚（5－Br-PADAP)作显色剂分光光度法同时测定铜和铁含量的新方法,用该法测定铜和铁,显色络合物最大吸收波长均为558nm,PH3．5时,测得Cu-5-Br-PADAP的为9．1＊1010^4ug/10mL,铁线性范围为0－5．0ug/10mL,此法应用于人发样品分析,方法简便,快速结果,准确,满意。     

In-situ synthesis of 3D printable mono- and Bi-metallic (Cu/Ag) nanoparticles embedded polymeric structures with enhanced electromechanical properties

The interest of additive manufacturing with 3D printing increases day by day, which provides improved mechanical, electrical, magnetic and thermal properties of 3D parts. The production of 3D parts with the stereolithography (SLA) method, which allows it to be produced with high precision, resolution and complex geometries, distinguishes itself from other alternative additive manufacturing methods (FDM. SLS. LOM. LMD etc.). However, studies on the preparation of functional 3D polymer nanocomposites with the SLA method are quite limited. This study aims to produce silver (Ag) and/or copper (Cu) based 3D polymer nanocomposites for enhancing its mechanical strength, thermal stability and electrical conductivity. Mono and bimetallic (Cu/Ag) nanoparticles have been in-situ synthesized by selective irradiation of laser beam method using a commercial SLA device. In this method, metal (Cu/Ag) acrylate containing photocurable resin is not only cured but also leads to thermal decomposition of metal ions into nanoparticles to form functional 3D structures. The mechanical, electrical and thermal properties of polymer nanocomposites are characterized in detail. As a result of the analysis, the nanoparticles, with an average diameter of 25–55 nm, are well dispersed in the polymer matrix without agglomeration. The temperature at which 5% weight loss of Ag and Cu based polymer structures is measured as 179.3 °C while the glass transition temperature is found to be 223.81 °C. Most importantly, the resistance values are significantly decreased from 456.62 GΩ (Gigaohm) to 1.50 GΩ by increasing the amount of Ag addition at 3D polymeric structures. Therefore, this study allows the production of polymer nanocomposites not only in complex structures but also in desired properties especially for electrically conductive materials, capacitors and electronic applications.     

Structural and electrical properties of nickel–iron thin film on copper substrate for dynamic random access memory applications

Using pulse electrodeposition technique, nano crystalline NiFe films were deposited on conductive copper substrates, under galvanostatic mode in an ultrasonic field at different conditions such as pulse current magnitude, deposition time and ultrasonic bath temperature. As-prepared NiFe/Cu thin films were characterized for phase analysis, surface morphology, surface roughness and resistivity measurements. The results show that the use of ultrasonic bath at room temperature has reduced the surface roughness, resistivity, average grain size and crystallite size of NiFe/Cu thin films. The resistivity is reduced with increasing deposition current from 44.2 µΩ cm at 40 mA to 33.0 µΩ cm at 100 mA. On the other hand, a significant drop of the resistivity from 35.7 to 9.4 µΩ cm is observed if the deposition time was reduced from 5 to 3 min.     

Thermal treatment,spectroscopic analyses,and electrical properties of poly(copper 2,3,9,10,16,17,23,24-octacyanophthalocyanine)

Thermal treatment of novel poly(copper 2,3,9,10,16,17,23,24-octacyanophthalocyanine), PCOCP, has been carried out at different temperatures in an inert atmosphere. As polyacrylonitrile, the polymer can be thermally cyclized through the cyano groups to produce semiconductive and conductive materials. Polymeric copper octacyanophthalocyanine material with a conductivity as high as 5–8 (Ω cm)^-1 was prepared. Weight loss, electrical data, infrared, and photoacoustic results of the thermally treated copper octacyanophthalocyanine polymer are discussed.     

In situ STM imaging of bis-3-sodiumsulfopropyl-disulfide molecules adsorbed on copper film electrodeposited on Pt(111) single crystal electrode

The adsorption of bis-3-sodiumsulfopropyldi-sulfide (SPS) on metal electrodes in chloride-containing media has been intensively studied to unveil its accelerating effect on Cu electrodeposition. Molecular resolution scanning tunneling microscopy (STM) imaging technique was used in this study to explore the adsorption and decomposition of SPS molecules concurring with the electrodeposition of copper on an ordered Pt(111) electrode in 0.1 M HClO(4) + 1 mM Cu(ClO(4))(2) + 1 mM KCl. Depending on the potential of Pt(111), SPS molecules could react, adsorb, and decompose at chloride-capped Cu films. A submonolayer of Cu adatoms classified as the underpotential deposition (UPD) layer at 0.4 V (vs Ag/AgCl) was completely displaced by SPS molecules, possibly occurring via RSSR (SPS) + Cl-Cu-Pt → RS(-)-Pt(+) + RS(-) (MPS) + Cu(2+) + Cl(-), where MPS is 3-mercaptopropanesulfonate. By contrast, at 0.2 V, where a full monolayer of Cu was presumed to be deposited, SPS molecules were adsorbed in local (4 × 4) structures at the lower ends of step ledges. Bulk Cu deposition driven by a small overpotential (η < 50 mV) proceeded slowly to yield an atomically smooth Cu deposit at the very beginning (<5 layers). On a bilayer Cu deposit, the chloride adlayer was still adsorbed to afford SPS admolecules arranged in a unique 1D striped phase. SPS molecules could decompose into MPS upon further Cu deposition, as a (2 × 2)-MPS structure was observed with prolonged in situ STM imaging. It was possible to visualize either SPS admolecules in the upper plane or chloride adlayer sitting underneath upon switching the imaging conditions. Overall, this study established a MPS molecular film adsorbed to the chloride adlayer sitting atop the Cu deposit.     

Hyperbranch-polyethyleniminated functional polymers II: effect of polyethyleniminated polyoxypropylenediamines on copper nanoparticle formation in aqueous solution

Colloidal aqueous solution of zerovalent copper (Cu(0)) nanoparticles were prepared from the Cu²⁺ ions coordinated with polyethyleniminated polyoxypropylenediamines (D400(EI) _x ) followed by chemical reduction of NaBH₄. Aqueous solution of copper clusters formed in the presence of D400(EI)₈ with a loading ratio of [EI]/[Cu²⁺] = 3 were stable without precipitation for standing more than 1 month. The protective effects of D400(EI) _x and the particle size of the resulted Cu nanoparticle are regulated by the attachments of ethylenimine (EI) groups per polymer backbone and the normality ratio of [EI]/[Cu²⁺] used. It is found that the more EI-content per polymer backbone results in the smaller particle size and the narrower size dispersity of the colloidal Cu(0) particles, and the average particle size of 5.07 nm with standard deviation of 0.86 nm was obtained in the presence of D400(EI)₈ with the ratio of [EI]/[Cu²⁺] = 3. As the polymer concentration of D400(EI)₈ increases (the increase of [EI]/[Cu²⁺]), the average particle size of the prepared Cu(0) nanoparticle slightly changes, but interestingly, the size dispersity gradually decreases, where the standard deviation for the concentration at [EI]/[Cu²⁺] = 5 is 0.82 nm approaching that for monodispersed nanoparticles (0.5 nm).     

伏安法研究五元瓜环对Cu(Ⅱ)配合物的识别性能

利用伏安法研究了五元瓜环(记为Q[5])对Cu(Ⅱ)配合物的识别性能。结果表明:在pH 5.0的Na2(H2EDTA)介质中,扫描速度为100 mV.s-1时,Q[5]-[Cu(H2EDTA)H2O]配合物的电极反应为单电子准可逆氧化还原反应。摩尔比法测出Q[5]与[Cu(H2EDTA)H2O]作用比为2∶1,稳定常数为3.59×109 L2.mol-2。在所选择的实验条件下,Cu(Ⅱ)浓度在2×10-6~1.6×10-4 mol.L-1范围内,峰电流与其浓度具有较好的线性关系,方法回收率为99.4%~100.7%。     

Electrodeposition of copper on a Pt(111) electrode in sulfuric acid containing poly(ethylene glycol) and chloride ions as probed by in situ STM

This study employed real-time in situ STM imaging to examine the adsorption of PEG molecules on Pt(111) modified by a monolayer of copper adatoms and the subsequent bulk Cu deposition in 1 M H(2)SO(4) + 1 mM CuSO(4)+ 1 mM KCl + 88 μM PEG. At the end of Cu underpotential deposition (~0.35 V vs Ag/AgCl), a highly ordered Pt(111)-(√3 × √7)-Cu + HSO(4)(-) structure was observed in 1 M H(2)SO(4) + 1 mM CuSO(4). This adlattice restructured upon the introduction of poly(ethylene glycol) (PEG, molecular weight 200) and chloride anions. At the onset potential for bulk Cu deposition (~0 V), a Pt(111)-(√3 × √3)R30°-Cu + Cl(-) structure was imaged with a tunneling current of 0.5 nA and a bias voltage of 100 mV. Lowering the tunneling current to 0.2 nA yielded a (4 × 4) structure, presumably because of adsorbed PEG200 molecules. The subsequent nucleation and deposition processes of Cu in solution containing PEG and Cl(-) were examined, revealing the nucleation of 2- to 3-nm-wide CuCl clusters on an atomically smooth Pt(111) surface at overpotentials of less than 50 mV. With larger overpotential (η > 150 mV), Cu deposition seemed to bypass the production of CuCl species, leading to layered Cu deposition, starting preferentially at step defects, followed by lateral growth to cover the entire Pt electrode surface. These processes were observed with both PEG200 and 4000, although the former tended to produce more CuCl nanoclusters. Raising [H(2)SO(4)] to 1 M substantiates the suppressing effect of PEG on Cu deposition. This STM study provided atomic- or molecular-level insight into the effect of PEG additives on the deposition of Cu.     

1-(2-噻唑)-3-(8-(5-对磺酸基苯基偶氮)喹啉)-三氮烯的合成及其与铜(Ⅱ)的显色反应

合成了新试剂1-(2-噻唑)-3-(8-(5-对磺酸基苯基偶氮)喹啉-三氮烯(TCPQT),并研究了其与Cu2+的显色反应。结果表明:在pH 7.5的磷酸盐缓冲溶液中,TCPQT与Cu2+形成摩尔比为1:1的紫红色络合物,该络合物在606.5nm处有一最大吸收峰,其表观摩尔吸光系数为3.36×105L.mol-1.cm-1,Cu2+的质量浓度在0～0.4μg/mL范围内符合比尔定律,相关系数r=0.9993。方法已用于测定食品中的微量铜。     

Copper(I) stabilized on N,N′-methylene bis-acrylamide crosslinked polyvinylpyrrolidone: An efficient reusable catalyst for click synthesis of 1,2,3-triazoles in water

N,N′-methylene bis-acrylamide crosslinked N-vinyl-2-pyrrolidone (NVPMBA) polymer was prepared via suspension polymerization technique and used as a polymeric support for the reduction of Cu(II) to Cu(I). It was observed that NVPMBA matrix facilitated the stabilization of Cu(I) particles. Furthermore, the copper supported polymer catalyst (CuNVPMBA) was characterized by Fourier transform infrared, X-ray diffraction, scanning electron microscopy (SEM), energy dispersive X-ray analysis, transmission electron microscope (TEM), X-ray photoelectron spectra (XPS), inductively coupled plasma optical emission spectroscopy, and derivative thermogravimetry analysis. SEM showed that both the polymer and CuNVPMBA exhibit a spherical morphology. TEM revealed that copper nanoparticles formed on the polymer surface have an average particle size of 5.14 nm. XPS analysis confirmed the presence of Cu(I) and Cu(II) in the ratio 1:2. The copper content in CuNVPMBA was found to be 1.25 wt%. CuNVPMBA was found to be very effective in promoting the click reaction between terminal alkynes and azides in aqueous media in the absence of ascorbate or external base under mild conditions to form 1,2,3-triazoles in excellent yield with a copper loading as low as 0.2 mol%. The catalyst could be reused and recycled several times without significant loss of catalytic activity.