Estimation of water absorption state within ionized carboxylated polymer particles with high sensitive differential scanning calorimetry

Glass transition temperature (Tg) of submicron-sized, carboxylated polymer particles dispersed in aqueous media, which were prepared by emulsion copolymerization of styrene, iso-butyl methacrylate, or methyl methacrylate with methacrylic acid, was measured at alkali or acidic pH region with a power compensation-type high sensitive differential scanning calorimeter. The Tg of relatively hydrophilic polymer particles was obviously decreased by the neutralization of the carboxyl groups with KOH, whereas that of hydrophobic polymer particles was not changed though water was absorbed therein. These results indicate that water absorption state, which means not only the amount of water absorption but also the heterogeneity of the ionized carboxylated polymer particles, markedly depends on the hydrophilicity of their base polymers. This strongly supports the formation mechanism of multihollow particles by the stepwise alkali/acid or the alkali/cooling treatments of carboxylated polymer particles proposed by the authors.Part CCLXIX of the series, “Studies on Suspension and Emulsion.”     

Curing characteristics of carboxyl functionalized glucose resin and epoxy resin

The curing characteristics of carboxylic functionalized glucose resin (glucose maleic acid ester vinyl resin: GMAEV) and epoxy resin have been studied using DSC and FTIR methods. Exothermic reactions attributed to esterification and etherification reactions of the hydroxyl and carboxyl functionalities of GMAEV with the epoxy groups were identified. Exothermic reactions showed very different patterns according to the degree of carboxyl group substituent of GMAEV. The results showed that esterification reaction occurs in the early stage of cure and then etherification followed after completion of the esterification. A cured matrix containing epoxy resin and 50 wt.% of GMAEV was prepared and characterized. The cured matrix showed thermal stability up to 300 °C. The average glass transition temperature and storage modulus of the matrix were as high as 95 °C and 2700 MPa, respectively. The cured matrix of epoxy resin and GMAEV with higher degree of carboxyl group was found to have a lower density due to the formation of bulky groups in the crosslinks.     

Behavior of nonionic emulsifier molecules on the preparation of nanoparticles from submicron-sized ionized styrene–methacrylic acid copolymer particles by the particle dissolution method

 Submicron-sized styrene–methacrylic acid copolymer (92/8 molar ratio) particles dissolved in the presence of polyoxyethylene nonylphenylether nonionic emulsifier under alkaline conditions at 90 °C, resulting in nanoparticles with diameters of about 30 nm. In order to clarify the role of the emulsifier molecules in the dissolution process, ¹H NMR measurements were carried out. As the particles swelled, the NMR integrals due to the emulsifier decreased markedly. This indicates that the emulsifier molecules permeated into the inside of the alkali-swelling particles and were adsorbed on the polymer molecules, which supports the formation mechanism of nanoparticles by the particle dissolution method proposed in a previous article. Received: 10 December 1998 Accepted in revised form: 1 April 1999     

二氧化碳和环氧丙烷共聚用的双金属催化体系

锌盐、三乙基铝、含活泼氢化合物三组份体系可以催化二氧化碳与环氧丙烷共聚,生成聚丙撑碳酸酯.实验发现,高分子羧酸是比水更好的助催化剂.体系的催化活性依赖于其中锌盐和聚合物载体的种类、体系各组份的摩尔比以及混合次序,说明反应中两种金属存在某种协同作用。本文提出了催化活性中心可能的结构.     

Electrocatalytic Oxidation of Calcium Folinate on Carboxyl Graphene Modified CuxO/Cu Electrode

Carboxyl graphene modified Cu_xO/Cu electrode was fabricated. The bare copper electrode was firstly anodic polarized in 1.0 mol/L NaOH solution in order to get Cu_xO nanoparticles, then the carboxyl graphene (CG) was electrodeposited on the Cu_xO/Cu electrode by cyclic potential sweeping. The electrocatalytic oxidation behaviors of calcium folinate (CF) at the graphene modified Cu_xO/Cu electrode were investigated by cyclic voltammetry. A positive scan polarization reverse catalytic voltammetry was used to obtain the pure catalytic oxidation current. The graphene modified Cu_xO/Cu electrode was served as the electrochemical sensor of CF, a highly sensitivity of 22.0 μA·(μmol/μL)^-1cm^-2 was achieved, and the current response was linear with increasing CF concentration in the range of 2.0×10^-7 mol/L to 2.0×10^-5 mol/L, which crossed three orders of magnitude, and the detection limit was found 7.6×10^-8 mol/L (S/N=3). In addition, the proposed sensor was successfully applied in determination of CF in drug sample.     

木质素磺酸钠在氧化铁表面的吸附驱动力

研究吸附介质的pH值、 尿素及盐类对木质素磺酸钠(SL)在氧化铁表面吸附性能的影响规律, 结果表明, 络合能力较强的柠檬酸钠使SL的吸附量几乎减少至零, 较弱络合能力的亚硫酸钠使SL的吸附量具有一定程度的降低, 而无络合能力的硫酸钠增大了SL的吸附量. 说明SL的羧基与氧化铁之间的络合吸附驱动力对吸附起主导作用, 磺酸基对其在氧化铁上吸附的影响很弱. 采用氯化锂屏蔽部分羧基后SL在氧化铁上的吸附量也有所降低, 进一步证明了羧基与氧化铁表面的络合作用是其吸附的主要驱动力.     

The Synthesis of Carboxyl Calcium Lignosulfonate and Its Applications as Water Reducer

p‐Aminobenzoic acid and calcium lignosulfonate (CL) are used as main raw materials in the synthesis of carboxyl calcium lignosulfonate (CCL). The surface activity of CCL is measured, and the properties of cement particles with CCL are investigated such as adsorption quantity and Zeta potential. Test results show that CCL has higher surface tension, lower adsorption quantity on cement than CL, the Zeta potential of cement particles with CCL is similar to that of cement particles with CL, the dispersing ability of CCL is stronger than that of CL, the viscosity loss of cement paste with CCL is less than that with CL, and the compressive and flexural strength of mortars with CCL are higher than that with CL.     

Simple approach to carboxyl-rich materials through low-temperature heat treatment of hydrothermal carbon in air

It was found that a large number of oxygen-containing functional groups (OFGs) could be created on the surface of hydrothermal carbon (HTC) by simply heating at lower temperature in air during the course of our preliminary experiments which focused on oxidation pre-treatment of pristine HTC for the purpose of grafting functionalization. Especially carboxyl groups on HTC would increase significantly, from 0.53 to 3.70 mmol/g after heat treatment at 300 °C. So, effects of heat-treatment on the OFGs on the carbon microsphere were deeply studied to confirm and explain the findings. Experiments involving different materials (HTC, activated carbon and glucose) were performed under varying conditions (heating temperature and time, in air or in Ar atmosphere). A reaction mechanism for newly generating carboxyl groups on HTC surface during heat-treatment process was supposed based on the results from the sample characterization using Boehm titrations, infrared spectra, X-ray photoelectron spectroscopy, energy dispersive spectrometry and elemental analysis. In addition, the as heat-treated product has excellent sorption capability for Pb²⁺ and Cd²⁺ ions.     

分散聚合制备羧基化单分散聚苯乙烯交联微球

以苯乙烯(St)、丙烯酸(AA)为单体,二乙烯基苯(DVB)为交联剂,偶氮二异丁腈(AIBN)为引发剂,采用分散聚合和交联剂后滴加法合成了单分散羧基化交联聚苯乙烯微球。通过傅立叶红外光谱(FT-TR),扫描电子显微镜(SEM),激光粒度及Zeta电位分析仪等对微球结构进行了表征。结果表明,引发剂、分散剂用量和交联剂的加入方式对微球粒径及单分散性影响显著,当St用量为15%(wt)、DVB用量为1%(wt)、AA用量为1%(wt)、AIBN用量为2%(wt)、PVP用量为6%(wt)时所制备的微球具有良好的单分散性和球形形貌,粒径达到4μm,且微球表面带负电荷。     

碳纳米管担载CuCoCe催化剂催化合成气制低碳醇的性能

以碳纳米管为载体,采用等体积浸渍法制备了一系列Cu Co Ce催化剂,考察了碳纳米管长度及羧基官能团对该系列催化剂催化合成气制低碳醇反应性能的影响;采用X射线衍射(XRD)、氮气吸附-脱附、透射电子显微镜(TEM)和X射线光电子能谱(XPS)等手段对催化剂进行了结构和性能表征.实验结果表明,以含有羧基官能团的、长度为0.5~2μm的碳纳米管为载体时,催化剂的低碳醇时空收率最高,达到783.72mg·gcat-1·h-1,醇产物中C2+醇选择性达到82.71%.研究结果表明,短纳米管有利于活性金属进入碳纳米管内部,并促使活性组分分散均匀,这对CO转化率和低碳醇时空收率的提高有显著作用;碳纳米管上羧基官能团的存在促进了金属与金属、金属与载体之间的相互作用,从而使醇产物中C2+醇选择性明显提高.