聚羧酸盐侧链长度对水煤浆分散性能的影响及其作用机理

合成了一系列具有不同侧链长度的梳型聚羧酸盐(PC),研究了PC侧链长度对水煤浆的分散和流变性能的影响,使用X射线光电子能谱(XPS)分析了PC在煤水界面的吸附,并结合水煤浆Zeta电位及PC对煤颗粒的润湿性探讨了PC的分散作用机理,为设计制得高效的聚羧酸盐水煤浆分散剂提供依据。结果表明:长主链、短侧链和高阴离子基团含量的PC500(侧链聚合度)具有优良的分散性,所制水煤浆属假塑性流体。PC在煤表面呈单分子层吸附,其中PC500的吸附密度和吸附厚度均最大,分别为0.638 mg·m^-2和4.20 nm,其对煤粒润湿性也较好,所制水煤浆Zeta电位绝对值最高。侧链长度适中的PC500通过平衡吸附层厚度与Zeta电位发挥空间位阻和静电斥力作用分散水煤浆,其可有效地降低水煤浆Gibbs能,使煤粒间“团聚”减弱,浆体分散性提高。     

pH对含长支链聚羧酸减水剂水泥浆体性能的影响

探讨了pH对含长支链PCE(聚羧酸减水剂)水泥净浆流动度和减水率的影响,并对该水泥试块的压缩强度和凝结时间进行了研究。结果表明:pH对含长支链PCE水泥净浆流动度和减水率的影响较小;随着龄期的延长,pH对水泥试块的压缩强度由积极影响变为消极影响;随着pH的不断增加,水泥的初疑时间和终凝时间均呈先长后短态势,并且均在pH为9时相对最长,不同配浆水的pH均会使含长支链PCE水泥浆体出现缓凝现象;当配浆水的pH为13时,含长支链PCE水泥试块的微观结构相对较差,不利于增强水泥试块的压缩强度。     

高分子分散剂结构对分散性的影响

选用PAA，PMAA，P(AA／BA)，P(AA／AMPS)，P(AA／AM)5种结构不同的内烯酸糸分散刑，以去离子水为分散介质，考查了不同情况下对Ti02粉体的分散性。通过ξ电位，红外光谱和吸附实验结果表明：同等条件下分子结构中的易吸附或易电离的强极性基团对分散性的影响很大，共聚物的分散性明显好于均聚物。分子量的大小影响颗粒表面的吸附形态，同等情况下分子量越大吸附量越大。AMPS分子中含有高电子密度的氧原子和高极性的-SO2OH，吸附和静电斥力都很高，共聚物P(AA／AMPS)的分散性最好。     

二元醇对分散荧光染料墨水性能的研究

采用纳米粒径分析仪对分散荧光染料色浆的主体颗粒大小进行了研究,分析了二元醇对墨水的黏度、表面张力、保湿性、热储存稳定性、离心稳定性、墨水转移率以及喷墨转移印花后涤纶织物荧光反射率的影响。实验结果表明,采用湿磨法研磨后的染料色浆分散稳定性好,粒径为125.5 nm。二元醇质量分数低于15%时,墨水黏度变化不大;当其质量分数超过15%后,墨水黏度的增幅明显。由于氢键作用力的存在,墨水的保湿性随二元醇质量分数的增加不断提高,其中乙二醇的保湿效果最好。添加15%(质量分数)二元醇的墨水具有较好的热储存稳定性和离心稳定性。二元醇用量的增加有利于墨水转移率和涤纶织物荧光反射率的提高;但其用量过多,也会使转移率和荧光反射率降低。     

SAS/MAA/MPEGMAA聚羧酸盐分散剂的制备与性能

以甲基丙烯酸（MAA）和 4 种不同侧链长度的甲氧基聚乙二醇（MPEG相对分子质量分别为350,500,750,1000）先聚合得到酯化大单体（MPEGMAA）,再以甲基丙烯酸,烯丙基磺酸钠（SAS）为单体,在引发剂过硫酸钾,阻聚剂对苯二酚作用下聚合得到 4 种具有不同侧链长度的聚羧酸盐分散剂。通过红外（FT-IR）、核磁共振氢谱（¹H NMR）和凝胶渗透色谱（GPC）对聚合物的结构、相对分子质量及其分布进行了表征和分析,并将其作用于彬长煤制浆,考察了浆体的表观黏度、流变性、zeta电位、吸附性以及最大成浆浓度和稳定性,测定其与煤的接触角,并通过X射线光电子能谱（XPS）分析,得出煤粒表面吸附分散剂后的吸附层厚度为 6.12 nm。结果表明,侧链长度为SAS/MAA/MPEGMAA750的聚羧酸盐分散剂具有良好的润湿和吸附效果,对彬长煤具有更好的降黏、分散和稳定作用。     

Influence of fluorine-containing side chain on the properties of waterborne polyurethane-urea

In order to prepare waterborne polyurethane with excellent water resistance and thermodynamic properties, a series of side chain fluorinated waterborne polyurethane-urea (FWPU-UA) was synthesized with polytetramethylene ether glycol, N-(2-methyl-1,3-propanediol-2′-)-perfluoro-1-butanesulfonyl amine (NPBA), isophorone diisocyanate, and isophoronediamine. With the increase of NPBA content, the weight loss temperature, glass transition temperature, and tensile strength of FWPU-UA were all improved. Gaussian fitting analysis of infrared data and density functional theory simulation proved that the introduction of fluorine side chains increased the interaction of hydrogen bonding in the FWPU-UA. X-ray photoelectron spectroscopy analysis indicated that the aggregation of fluorine atoms on the surface of film were caused by the migration and enrichment of fluorine side chains. Furthermore, the water resistance of polyurethane-urea film could be significantly improved by adding a small amount of NPBA, and the seven-day water absorption rate of polyurethane-urea film was reduced from 30.13% to 12.55%.     

分散剂对无SiO_2微粉刚玉质浇注料性能的影响

为了优化刚玉质浇注料的性能,在以纯铝酸盐水泥结合的刚玉质浇注料中加入不同分散剂,系统研究了不同分散剂对浇注料基质浆体动电特性、流变特性以及对浇注料常规物理性能的影响。结果表明,加入4种分散剂的基质浆体的Zeta电位绝对值均较低,且加入高分子聚合物型分散剂浆体的Zeta电位绝对值比加入聚电解质型分散剂浆体的更低;4种分散剂均能显著降低基质浆体的表观黏度,其最佳加入量分别为0.2%、0.7%、0.6%和0.7%;加入分散剂FS10的刚玉质浇注料的需水量最低,且试样的各项物理性能都较优。     

Dispersion and rheological properties of concentrated kaolin suspensions with polycarboxylate copolymers bearing comb-like side chains

Comb-like polycarboxylate copolymers (PCs) were synthesized and first used as the dispersants for kaolin suspensions. The apparent viscosity, adsorption behavior, zeta potential, rheological behavior, and TEM images of concentrated kaolin slurries deflocculated with these copolymers were systematically investigated. Sodium acrylate homopolymer (SA) was selected as a reference in order to contribute to the knowledge of how the electrostatic interaction and molecular structure of these copolymers influenced the dispersion, adsorption, and rheological properties of colloidal kaolin suspensions. The results showed that the dispersion of kaolin slurries mainly depended on the synergistic effects of electrostatic interaction and steric hindrance for APEG type comb-like copolymers. PC₂ bearing proper carboxylic groups and side chains produced stable dispersion and fluidity in concentrated kaolin slurries. Based on the electrostatic and steric effect of comb-like copolymers, the kaolin slurries displayed a shear thickening behavior, and the Herschel–Bulkley model well described their rheological behaviors.     

Synthesis and properties of polyimides having alkyloxycarbonyl side chain

Summary A series of polyimides having alkyloxycarbonyl side chains were synthesized from dialkyl 2,5-bis(4-aminophenoxy)terephthalate and PMDA. The inherent viscosities of poly(amic acid)s were in the 1.42~0.63dL/g range. The polyimides exhibit typical 2-step thermal degradation, and lowered transition temperature for longer side chain. Wide-angle X-ray diffractograms revealed that all polymers are partially crystalline, and layered structures were observed for polymers with longer side chain. The pretilt angle is in the 8°~10° range, and increases as the length of the side chains increase.     

Selection of dispersants for the dispersion of carbon black in organic medium

The dispersion of the carbon black pigment in non-aqueous medium requires the use of dispersant additives. Two carboxylic dispersants of different chemical nature and molar masses have been investigated regarding this purpose. Their adsorption behavior has been evaluated by means of adsorption isotherms. The molecular interactions taking place at the surface have been inferred from IR and ¹³C RMN spectroscopies. The rheological behavior of the dispersions has considerably been improved by the presence of the copolymer dispersant of higher molar mass. It might adsorb at the surface by hydrogen bindings while taking a flat conformation with tails and possibly few loops that contributed to the steric stabilization of particles. The consequences of the deflocculation of the suspension on the colorimetric properties are an enhanced tinting strength and improved color stability.     

Effect of crosslinked polycarboxylate superplasticizers with varied structures on cement dispersion performance

In order to investigate the effect of double bond content in the crosslinkers on the performance of superplasticizers, three different crosslinked polycarboxylate superplasticizers were synthesized herein with various respective crosslinkers. Their impacts on the fluidity, absorption, and hydration behavior of cement systems were studied. The results showed that the polymer, which was synthesized using a crosslinker with four double bonds and five/six double bonds, had higher fluidity and the highest fluidity reached up to 395 mm at W/C of 0.35. Additionally, thermogravimetric analysis and hydration heat tests showed that the crosslinked polycarboxylate superplasticizers could prolong the hydration process of cement slurries. Among these three kinds of crosslinked polycarboxylate superplasticizers, the induction period of cement slurry containing the polymer with crosslinker of four double bonds was significantly extended to facilitate the processing of the concrete. The purpose of this study is to provide strategies for studying high-performance polycarboxylate superplasticizers with novel topological structure.     

不同降解方式对淀粉基水煤浆分散剂性能的影响

分别采用氧化法(H₂O₂为氧化剂)、酸解法(HCl)两种不同的方式制备降解淀粉,在相同的实验条件下,以丙烯酸(AA)、苯乙烯磺酸钠(SSS)为单体,H₂O₂-Fe²⁺为引发剂,通过自由基聚合反应制备3种淀粉基水煤浆分散剂。通过红外光谱(FTIR)、核磁共振氢谱(¹HNMR)、凝胶渗透色谱(GPC)对产物的分子结构、相对分子质量及分布进行了表征和分析。将3种分散剂应用于彬长煤制浆,考察对比了浆体的表观黏度、分散剂最佳添量、最大制浆浓度、流变性、Zeta电位、吸附特性及静态稳定性等。结果表明,经氧化降解制备的淀粉基水煤浆分散剂在最佳添加量0.4%(质量分数)时,水煤浆最大制浆浓度可达到67%,表观黏度为906mPa·s,煤粒表面的Zeta电位由–12.1mV变化到–47.3mV,相较于由玉米淀粉及酸降解淀粉制备的水煤浆分散剂对彬长煤具有更好的降黏、分散、稳定作用。     

Efficient dispersants for the dispersion of gallium zinc oxide nanopowder in aqueous suspensions

Appropriate dispersants for the dispersion of gallium zinc oxide (GZO) nanopowder in aqueous suspensions were identified in this study. The dispersion efficiencies and stabilization mechanisms of water‐based dispersants ammonium poly(acrylic acid) (PAA–NH₄), an anionic polyelectrolyte, and polyethylenimine (PEI), a cationic polyelectrolyte, were compared. The experimental analyses of rheology and sedimentation showed that both PAA–NH₄ and PEI were good dispersants for the dispersion of GZO. Theoretical calculations based on Derjaguin‐Landau‐Verwey‐Overbeek theory revealed that the stabilization mechanism of PEI was mainly related to the steric effect, and a very low molecular weight of 1800 g/mol was insufficient for powder stabilization. GZO was well dispersed by PEI with high molecular weight of 10 000 g/mol, but agglomeration occurred when too much PEI was added. Compared with PEI, PAA–NH₄ was more efficient because of its high contribution to the increase in electrostatic repulsion. Based on theoretical considerations on both steric and electrostatic effects, namely, the electrosteric stabilization mechanism, PAA–NH₄ is optimal for the dispersion of GZO nanopowder in aqueous suspensions.     

Effects of connection mode between carboxyl groups and main chains on polycarboxylate superplasticizer properties

Preparation and characterization of polycarboxylate superplasticizers of IPCs ( copolymer of itaconic acid and allyl polyoxyethylene ether) and MPCs (copolymer of maleic anhydride and allyl polyoxyethylene ether) are shown. The difference between IPCs and MPCs is that half of the carboxyl groups of IPCs indirectly connect to the main chains through methylene. The effects of the carboxyl group‐main chain connection mode on the properties of IPCs and MPCs were investigated by assessing the paste fluidity and the pore diameters and compressive strength. The interaction between IPCs (MPCs) and cement were revealed by zeta‐potential and the adsorption amount. The results indicated that the indirect connection mode favorably improved paste fluidity, decreased pore diameters, and increased the compressive strength compared with the direct connection mode. This is likely because that when carboxyl groups are connected to the main chains indirectly, more moving space allows easier adsorption on cement particles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Optical rotatory dispersion and circular dichroism studies of copolyaspartates with long alkyl side chain

Copoly(hexyl-l-aspartate-benzyl-l-aspartate), copoly(nonyl-l-aspartate-benzyl-l-aspartate) and copoly(dodecyl-l-aspartate-benzyl-l-aspartate) with various compositions were prepared by ester exchange reaction of poly(β-benzyl-l-aspartate). Copolyaspartates of low degree of alkylation were found to take a left handed α helix, similar to poly(β-benzyl-l-aspartate), and those of high degree of alkylation changed to a right handed α helix. Copoly(hexyl-l-aspartate-benzyl-l-aspartate) and copoly(dodecyl-l-aspartate-benzyl-l-aspartate) changed helix sense from left to right at 50% hexylation and 10% dodecylation, respectively. A small induced circular dichroism trough appeared around 230nm for these two copolyaspartates above 75% alkylation, indicative of a certain ordering of the carbonyl group due to the formation of an ordered structure of a long alkyl side chain. However, copoly(nonyl-l-aspartate-benzyl-l-aspartate) of 13% nonylation exhibited the induced circular dichroism spectrum and took a left handed α helix. Copoly(nonyl-l-aspartate-benzyl-l-aspartate) caused the reversal in helix sense above 70% nonylation according to a stabilizing effect of the ordered structure of the side chain.     

一种侧链型液晶聚合物与环氧树脂共混改性研究

设计并合成了一种侧链型液晶聚合物（SLCP），用红外光谱（FTIR），差示扫描量热分析（DSC）和偏光显微镜（POM）对聚合物结构和液晶性能进行表征，探讨其对环氧树脂共混物力学性能的影响，并分析共混物的微相分离结构，结果表明，用T31作固化剂时SLCP对环氧树脂有较好的增强增韧效果，在强度和玻璃化温度不降低的情况下断裂伸长度比未改性固化物最大提高2．6倍，但用三乙醇胺作固化剂时SLCP对环氧树脂改性效果不明显。     

染料共价改性石墨烯及其水分散性研究

本文以石墨粉为原料，以直接灰D为改性剂，将其重氮化后共价接枝到自制的还原氧化石墨烯（rGO）上，制备改性石墨烯（MG），以提高石墨烯在水中的分散性，使其更适用于纺织品整理。采用拉曼光谱（Raman）、傅立叶红外光谱（FTIR）、高分辨X射线光电子能谱（XPS）、热重分析（TGA）等表征手段对得到的改性石墨烯进行表征。结果表明，染料分子成功接枝到石墨烯上，接枝率达到21%左右。采用紫外-可见分光光度计（UV-vis）考察了改性石墨烯在水中的分散性。结果发现，相对rGO，MG在水中的分散性和稳定性都大大提高，其水溶液的最大饱和度达到0.185 mg/mL，静置7天后，仍可达到0.092 mg/mL。改性后的石墨烯同时具备了染料和石墨烯的性能。     

Effects on aqueous barium titanate tape properties of passivation of barium ion leaching by using dispersants

To passivate a barium titanate (BaTiO₃) ceramic powder surface from Ba²⁺ ion leaching in water, passivation agent layer (PAL) was formed by drying the slurry after adding a commercial polymeric dispersant. By following the several characteristic steps of actual MLCC production process, slip and green properties were compared for two different polymer-adding modes; one is the PAL and the other is the conventional dispersant mode. Compared to the conventional dispersant adding method, PAL mode was the only effective way in reducing the amount of Ba²⁺ leaching. However, slip viscosity and green body properties were not a function of adding mode but a function of dispersant itself, which means using PAL did not deteriorate any of slip and green properties of BaTiO₃.     

两种不同羧酸单体的两性聚羧酸盐水煤浆分散剂的制备及性能对比

以烯丙基醇聚氧乙烯醚500（APEG-500）、羧酸单体 （丙烯酸和衣康酸）、二甲基二烯丙基氯化铵（DMDAAC）等为原料,合成了具有不同羧酸单体的两性聚羧酸盐水煤浆分散剂。采用FTIR、1HNMR对分散剂的结构进行表征,并结合水煤浆黏度、XPS、Zeta电位、接触角、稳定性等测试,讨论了不同羧酸单体对分散剂的分散性能的影响,探究了分散剂与煤粒表面的作用机理。结果表明：当DMDAAC用量为单体质量之和的6.0%时 ,两性聚羧酸盐分散剂对水煤浆的表观黏度降低效果优于阴离子型的聚羧酸盐分散剂;羧酸单体为衣康酸的分散剂性能更优,使陕西榆林煤最大固体质量分数达到66.5%,Zeta电位由-20.8 mV变化到-31.9 mV,吸附膜厚度和饱和吸附量分别为2.56 nm和3.23 mg/g,对煤粒的润湿性更好,浆体的稳定性显著提高,表明双羧基比单羧基更能提高分散剂性能。     

β-环糊精侧链对聚羧酸减水剂抑制蒙脱土的影响

采用水泥净浆和混凝土试验,详细研究了β-环糊精侧链对聚羧酸减水剂抑制蒙脱土负效应的影响。试验表明,与仅含有聚氧乙烯侧链的传统聚羧酸减水剂相比,蒙脱土对掺加含有β-环糊精侧链的聚羧酸减水剂水泥净浆流动度的负作用影响明显减弱;蒙脱土（1.0%,以砂质量计）存在时,为获得与无蒙脱土时相同的混凝土坍落度,β-环糊精类聚羧酸减水剂的掺量增幅减小,掺加β-环糊精类聚羧酸减水剂的混凝土抗压强度下降幅度减小。结合吸附试验分析,β-环糊精类聚羧酸减水剂抑制蒙脱土负效应能力的增强应归功于其侧链中的β-环糊精基团,β-环糊精基团具有中空筒状的刚性结构,其显著的空间位阻效应将阻止蒙脱土颗粒继续吸附其他β-环糊精类聚羧酸分子,进而提高聚羧酸减水剂抑制蒙脱土负效应的能力。