支化结构对树枝状聚合物静态吸附特征的影响

采用浸泡法研究了不同支化程度的驱油用树枝状聚合物在石英砂上的静态吸附特征,并利用动静态激光光散射仪和环境扫描电子显微镜测定了聚合物溶液的分子尺寸和微观结构。结果表明,不同支化程度的树枝状聚合物溶液的等温吸附曲线均呈现三段式的吸附特点;在初始阶段,支化结构小的聚合物支链条数较少以及流体力学半径较小,其在固定表面积的石英砂上吸附位阻比支化结构大的聚合物小,导致吸附量较大;在吸附形式为多层吸附的Ⅱ、Ⅲ阶段,支化程度大的聚合物支化链间相互作用越强,易缠结形成网络结构,致使其在石英砂表面吸附层数多,吸附量比支化程度小的聚合物多。     

PVDF溶液流变性及影响因素研究进展

PVDF溶液流变特性研究是产品应用的关键,其流变性对于PVDF水处理膜的制作过程及锂电池电极黏接效果有着很大影响,只有弄清PVDF溶液的流变特性及影响因素,才能进一步指导产品质量控制和推广应用。概述了聚合物分子量分布、分子链结构等对溶液流变特性的影响,并探讨了分子量分布控制技术、分子链支化控制技术及支化链检测方法。     

茂金属线性低密度聚乙烯树脂的结构与性能

对国产和进口茂金属线性低密度聚乙烯树脂(mLLDPE)的分子量及分布、支化程度、基本性能与流变行为进行了对比分析,研究表明国产mLLDPE与进口同类产品相比,分子量分布宽,支化程度高,加工性能更好,可以通过流变测试的各种参数如黏流活化能、剪切变稀指数、松弛谱分布宽度对其结构进行剖析。同时对两者薄膜制品的性能进行了研究,结果表明,国产mLLDPE树脂生产的薄膜力学性能更为优异,但鱼眼稍多,外观略差。     

不同梳形支化结构聚苯乙烯熔体的流变行为

以主链长度相当、支链数目和支链长度变化的一系列梳形支化聚苯乙烯为对象,采用旋转流变仪测定其流变参数,研究了梳形支化结构对聚合物熔体流变行为的影响。结果表明,梳形支化聚苯乙烯的零剪切黏度随支化数目或支链长度的增加而增大。在支链长度低于链缠结临界分子量Me时,随支链数目增加,梳形支化聚苯乙烯的零剪切黏度与重均分子量对数曲线的斜率为2.8~2.9。在支链数目一定时,当支链长度增加到链缠结临界分子量Me之前,梳形支化聚苯乙烯的零剪切黏度与重均分子量对数曲线的斜率为3.2左右。梳形支化聚苯乙烯呈假塑性流动行为,其非牛顿指数小于1,且随支链数目或支链长度的增加有小幅下降。由于支链减轻了链缠结程度,导致梳形支化聚苯乙烯的黏流活化能低于线形聚苯乙烯,随支链数目增加,对链缠结的抑制作用增大,黏流活化能进一步下降。     

剪切力度对聚合物溶液微观粒径分布的影响研究

使用高剪切分散机及动静态光散射仪研究不同浓度的1200万、1900万及2500万聚合物溶液在不同剪切强度下的粒径分布变化。结果表明,三种分子量聚合物溶液主峰粒径均随浓度的升高而增大。经不同程度剪切后,三种分子量聚合物溶液粒径分布范围均发生裂变,剪切力度越大,双峰现象越明显。     

星型中乙烯基聚丁二烯橡胶的研制

在以 n-BuLi为引发剂,THF为结构调节剂,环己烷为溶剂的丁二烯聚合体系中,用 SiCl_4作偶合剂,研究了不同的偶合条件对聚合物的偶合效率、[η]、分子量分布、支化度、微观结构及流变行为的影响。实验结果表明,当SiCl_4/n-BuLi(当量比)为0.3左右时,偶合效率、支化度、[η]和η_a出现最大值。偶合反应对聚合物的微观结构无影响,但加宽了聚合物的分子量的分布,从而改善了聚合物的冷流性与加工性能。     

核磁共振对高聚物短链支化的研究

高聚物主链上支化的类型和数量是决定低密度聚乙烯(高压聚乙烯)和高密度聚乙烯(低压聚乙烯)物理性能差异的主要原因。短链支化影响聚合物的形态和半结晶聚合物的固态性质,而长链支化对溶液的粘度和熔体流变行为产生深远的影响。长链支化是由于分子间链转移反应产生,短链支化是分子内链转移反应引起的。在这类聚合物的结构测定中,除了分子量和分子量分布之外,支化度是一个重要的结构参数。     

微支化聚丙烯酰胺的支化结构表征及热稳定性/流变性研究

以过硫酸铵(APS)和甲基丙烯酸二甲氨基乙酯(DMAEMA)为引发体系,在水溶液中采用常规自由基聚合制备了不同支化程度的聚丙烯酰胺(b-PAM).考察了微支化结构和支化程度对聚合物热稳定性和流变性的影响.结果表明,支化结构能够明显提高聚合物的热稳定性、抗剪切性和剪切稀释性以及粘弹性,且各项性能随着支化度的增加而增强.     

长链支化聚丙烯的反应挤出制备及其流变和热力学性能研究

在过氧化引发剂和季戊四醇三丙烯酸酯(PETA)存在下,采用反应挤出法制备了长链支化聚丙烯（LCB-PP）。用旋转流变仪和差示扫描热法系统研究了纯的和改性PP的流变性能和热力学性能,并考察了不同过氧化引发剂对改性PP的性能和支化情况的影响。研究发现,单纯使用过氧化引发剂改性时,PP以降解为主;加入多功能单体PETA后,PP以接枝反应为主。流变行为研究发现,过氧化引发剂/PETA改性的PP,其流变性能呈现如低频处储能模量增大,剪切变稀行为明显,损耗角随频率变化出现平台区,零剪切黏度增大等特点,证明改性PP存在长链支化结构,通过公式计算发现改性PP的支化度较高。差士扫描量热分析表明,过氧化引发剂/PETA改性PP的结晶温度高于纯PP,这也说明改性PP存在长链支化结构。同时发现过氧化引发剂/PETA改性PP时,过氧化引发剂结构对改性PP的流变性能、热力学性能和支化度影响较小。     

温度对超高分子量抗盐型聚丙烯酰胺黏度及剪切率的影响

聚丙烯酰胺溶液具有溶质分子量高,分子链状结构长,且在水中卷曲盘绕形成网状结构的特点,导致其对环境温度具有较高的敏感性[1]。在不同季节、不同水质的情况下都会使聚合物配注过程的温度发生变化。为了研究温度对聚合物溶液物理性质的影响程度,针对采油六厂实际生产中的配注情况,本研究对利用矿化度分别为500mg/L和5000mg/L两种水质,在5℃至50℃范围内对1000mg/L和2000mg/L两个浓度的聚合物溶液进行黏度测定及剪切试验,从而总结出不同的温度对相同溶液的黏度及剪切率影响规律。     

Effect of microscopic aggregation behavior on polymer shear resistance

The study of polymer aggregation behavior effect on shear resistance shed light on the synthesis of antishear polymer for oil displacement and enhances the application effect of polymer flooding. The effects of mechanical degradation on the properties of polymer solutions were studied by using partially hydrolyzed polyacrylamide (HPAM), hydrophobically modified HPAM (HMPAM), and dendritic hydrophobic associative polymers (DHAP), which are characterized by “granular,” “chain,” and “cluster” aggregation behavior, respectively. The results show that mechanical shearing can dramatically reduce the performance of polymer solution. The shearing resistance can be effectively enhanced by improving the polymer aggregation behavior. After being strongly sheared, hydrophobically associating polymers can still partially restore its network through hydrophobic association, therefore rebuild the solution viscosity. For DHAP, the broken molecular chains distribute more evenly in solution after shearing. In addition, the strength of reconstructed network structure of DHAP is better than that of HMAPM, which implies a better shear resistance. Furthermore, the hydrophobic association of linear polymers will increase their static adsorption on quartz sand. Meanwhile, DHAP with stronger spatial structure has less static adsorption, which is beneficial to maintain a higher polymer concentration in solution. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48670.     

Concept of secondary heterogeneous structure of long-chain branched polyethylene

The mechanism of formation of surface roughness and extrusion swelling of the extrudate and the steady-shear viscous flow behavior in the region of high shear rate for branched polymers were investigated using two low-density polyethylenes and their sheared samples. These two polyethylenes varied in their degree of branching, molecular weight, and molecular weight distribution but were similar in their melt flow index. The effect of molecular parameters, especially long-chain branching, on viscoelastic properties in the molten state was also considered. Samples of various degree of shearing level were prepared by passing them repeatedly through an extruder. Results of intrinsic viscometry, gel permeation chromatography, and infrared spectroscopy of the original and the sheared samples indicate that no appreciable variation between them takes place in the molecular parameters during the process of extrusion shearing. Both surface roughness and extrusion swelling of the extrudate diminish with increase in the extent of shear. The extrusion shearing affects the surface roughness and extrusion swelling of the extrudate as well as the capillary entrance effect more markedly for the highly branched polymers with considerably higher molecular weight than for the less branched species with bell-type molecular weight distribution. These results demonstrate that heterogeneity becomes more conspicuous with the degree of long-chain branching level, and therefore the role of long-chain branching in the development of the heterogeneity is particularly important. It is suggested that the secondary heterogeneous structure arises through phase separation or from the heterogeneous formation of strongly entangled network at the branching point of the long-chain branching in the manufacturing process of the low-density polyethylene and that its presence causes the distinctive viscoelastic properties of long-chain branched polymer melts.     

Introducing four different branch structures in PET by reactive processing––A rheological investigation

Chain extension/branching by reactive processing is a well-known method to enhance the rheological properties of polymers. In this study, pyromellitic dianhydride, poly(glycolic acid), triglycidyl isocyanurate, and bisphenol A diglycidyl ether were used as chain extender/branching agents to produce branched Polyethylene terephthalate (PETs) with four different molecular structures. According to the linear rheological characterizations, the storage modulus and complex viscosity of modified PET samples enhanced significantly after branching. The shear viscosities of modified PET show a pronounced shear-thinning behavior and a remarkable increase at low frequencies, which can be an indication of the existence of long-chain branches (LCBs) in the molecular structure of polymer and broadening the molecular weight distribution. Fourier transform infrared (FTIR) and differential scanning calorimetry (DSC) analysis were used to investigate the effect of branching agents on the chemical structure and thermal properties of PET, respectively. DSC results show that higher amounts of LCBs lead to lower melting and crystallization temperatures.     

Study on properties of hydrophobic associating polymer as drag reduction agent for fracturing fluid

In the paper, the hydrophobic associating polymer ACS-210 was prepared by solution polymerization of acrylamide, acrylic acid, salt-resisting monomer and hydrophobic monomer. Chemical structure and properties of the polymer was characterized by FTIR, TGA and XRD. The rheological property of ACS-210 solution was investigated by rheometer. The frictional resistance of the ACS-210 solutions at different application condition was examined using friction testing system. Results showed that the thermal stability of polymer ACS-210 increases and crystallinity of ACS-210 declines after incorporating of hydrophobic monomer. The viscosity of ACS-210 solution of different concentration decreased with prolonging the shearing time and the retention rate of viscosity is relatively high after long shearing time. The relation curve between the viscosity of polymer solution and shear rate followed the power law model. When the concentration of ACS-210 aqueous solution was less than the critical associating concentrations, storage modulus G’ is less than loss modulus G”, the association was weaker between the molecular chains, and the effective spatial structure did not form. After increasing the concentration of the polymer solution, G’ is more than G”, the degree of association of polymer is stronger. The synthesized polymer has favorable drag reduction effect. The molecular weight is not the only factor to determine drag reduction efficiency. The hydrophobic association can also improve the drag reduction efficiency.     

The effect of degree of branching on the rheological and thermal properties of hyperbranched aliphatic polyethers

A series of hyperbranched aliphatic polyethers with different degree of branching (DB) and molecular weights have been studied with respect to their rheological and thermal properties. The DB was shown to affect the ability of the polymers to crystallize and thereby also the rheological properties of the polymers. A low DB resulted in semi-crystalline polymers with melting points between 100 and 130°C. The polymers with a higher DB were essentially amorphous and behaved as non-entangled Newtonian liquids in the molten state.     

反应性微凝胶分散液的流变性能

为了在实际应用中更好地利用反应性微凝胶分散液的流变特性,采用自稳定分散聚合的方法合成了带有环氧基或羧基的反应性微凝胶,并研究了其在不同溶剂中的流变性能。结果表明,与相应的线形聚合物相比,当相对分子质量一定时,反应性微凝胶分散液的特性黏度较低,对聚合物相对分子质量依赖性较小;随着反应性微凝胶交联度的增加,特性黏度变小。在二甲苯中,随着反应性微凝胶质量分数的增加,分散液逐渐由牛顿流体转变为非牛顿流体,且随着反应性微凝胶质量分数的增加,假塑性增加。在甲苯、苯乙烯(St)或甲基丙烯酸异冰片酯(IBOMA)稀溶液中,反应性微凝胶的官能团种类对特性黏度的影响较弱,官能团种类对高浓度溶液的流变性能有较大的影响。     

Effect of micro-aggregation behavior on the salt tolerance of polymer solutions

Polymer solution for oil displacement is mostly used in the middle and late stage of water flooding reservoir development, and reservoir groundwater conditions are often one of the main conditions restricting polymer application. Therefore, it is necessary to develop salt tolerance of polymer solutions with different aggregation behaviors, so as to facilitate the synthesis and optimization of suitable polymer systems. The differences in the micro-aggregation behavior of three polymers with different molecular structures were explored. On this basis, the effects of divalent metal cations on the properties of the polymer solutions were analyzed by assessing the micro-aggregation behavior, apparent viscosity, hydrodynamic size, and shear rheological characteristics. The results showed that the linear partially hydrolyzed polyacrylamide (HPAM) was seriously affected by divalent cations, and the viscosity decreased obviously. The aggregation behavior of the polymer changed by hydrophobic association can enhance the salt tolerance of the solution. The hydrophobically modified partially hydrolyzed polyacrylamide (HMPAM) with “chain beam” aggregation behavior has strong intermolecular connection, which enables it to withstand the content of calcium and magnesium ions of 1100 mg l⁻¹. When the content of calcium and magnesium ions exceeds 600 mg l⁻¹, dendritic hydrophobically associating polymer (DHAP) will destroy the interaction between molecular chains, resulting in the decrease of apparent viscosity and hydrodynamic size. For polymer flooding in high-salinity reservoir, salt tolerant polymer system can be constructed by optimizing molecular weight and hydrophobic group content.     

Newtonian behaviour of sheared aqueous carboxymethylcellulose solution on aging

The effects of microbiological attack on the rheological properties of sodium carboxymethylcellulose (NaCMC) solutions are described. The effect of aging on the viscosity of aqueous NaCMC solution was studied by means of a Brookfield viscometer. An aqueous NaCMC solution was allowed to age and was subjected to shearing at different time intervals. Dilatant rheological properties were observed in contrast to the usually pseudoplastic behaviour of a normal NaCMC solution. This is attributed to the effect of shear-induced recombination of NaCMC macromolecular crystallites produced as a result of chain scission of NaCMC molecules during aging. The recombination of the crystallites gives higher values of viscosity at higher shear rates. A five months aged sample when subjected to shearing for a period of 20 h exhibits different behaviour. After prolonged post-shearing of this sample, the viscosity measured at shear speeds of 10 rpm and 20 rpm at 72 h and 102h approaches a common value for post-shearing period. The approach to the Newtonian character is attributed to the shear-stress-induced breakdown of the crystalline aggregates. These studies reveal that the aging effects on NaCMC solution have a drastic influence on the rheological properties.     

High shear rheology and shear degradation of aqueous polymer solutions

We have investigated the possibility of replacing hydraulic oils with aqueous polymer solutions having the same rheological properties. We measured the low and high shear rate viscosities of polymer solutions at several moderate concentrations and compared the results to the predictions of a molecular model. We found that viscosities measured at shear rates near 1 million reciprocal seconds are in good agreement with those calculated using the model of Mochimaru.⁶ Shear degradation studies were also conducted using higher molecular weight versions of some of the polymers. Exposure of these to very high shear rate caused a permanent decrease in viscosity and a corresponding change in the molecular weight and molecular weight distribution. Taken together, these results show that very low molecular weight polymers at moderate concentrations are necessary to formulate an aqueous hydraulic fluid with approximately Newtonian behavior at shear rates near 1 million reciprocal seconds, and without long-term polymer degradation.