碳链接枝共聚物——Ⅲ.聚丙烯酰胺的均相氧化及其与苯乙烯接枝共聚反应

不久前我们曾报导了聚丙烯酰胺的水溶液在室温或55℃时有可能与过氧化氢发生均相氧化反应,形成聚丙烯酰胺大分子过氧化物.这种水溶性的聚丙烯酰胺大分子过氧化物可引发烯类单体的接枝共聚,得到相应的碳链接枝共聚物。利用这种简便的接枝方法不仅可以合成一系列具有综合性能的接枝共聚物新品种,而且对大分子过氧化物引发烯类单体接枝共聚反应历程的研究也具有一定意义。     

中低渗透高温高盐油藏驱油共聚物P(AM/AMPSNa/AANa)的合成及性能

在中低渗透高温高盐油藏聚合物驱技术中, 超高相对分子质量聚丙烯酰胺(HPAM)存在不易注入、剪切降粘显著和耐温抗盐性能差等问题。 本文以丙烯酰胺(AM)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为单体, 采用过硫酸胺(NH₄)₂S₂O₈和甲基丙烯酸N, N-二甲氨基乙酯(DMAEMA)作为支化结构复合引发体系, 通过共聚后水解工艺, 合成含支化结构耐温抗盐驱油共聚物P(AM/AMPSNa/AANa)。 研究了引发温度、链转移剂用量、引发剂用量对共聚物特性黏数的影响, 并通过红外光谱(IR)和¹³C NMR表征了产物结构。 筛选特性黏数1915 mL/g左右的共聚物, 进行性能评价。 实验结果表明, 共聚物具有优异的耐温抗盐性能、抗剪切性能、抗老化性、注入性和驱油性能, 可应用在中低渗透高温高盐油藏三次采油中。     

碳酸乙烯酯溶剂中丙烯腈的聚合行为

以碳酸乙烯酯为溶剂,偶氮二异丁腈（AIBN）为引发剂,采用溶液自由基聚合的方法对丙烯腈(AN)均聚合、丙烯腈/衣康酸(AN/IA)二元共聚及丙烯腈/衣康酸/丙烯酸甲酯(AN/IA/MA)三元共聚合进行了研究。 考察了反应温度对丙烯腈均聚合,以及聚合单体浓度对丙烯腈共聚合的影响,在60 ℃合成了相对分子质量高于4.5×105、单体转化率高于85%的丙烯腈均聚物及共聚物。 采用正十二烷基硫醇（DDT）和甲酰基哌啶（FP）作为链转移剂,对AN均聚物、AN/IA及AN/IA/MA共聚物的相对分子质量进行调控,考察了链转移剂浓度对聚合物相对分子质量和单体转化率的影响。 结果表明,w(DDT)为0.25%时（以单体质量计）,聚合物相对分子质量可有效调节到1×105,而单体转化率保持在80%以上。     

键合喹诺酮类药效基团的抗菌聚丙烯酰胺的制备及其抗菌性能

设计合成了两种含喹诺酮类药效基团的新型甲基丙烯酸酯单体,分别将其与丙烯酰胺通过自由基共聚合成了两种共聚物。采用1 H-NMR、13C-NMR、GPC和分光光度计等手段对大单体和共聚物的结构进行了表征。分别测定了这两种甲基丙烯酸酯单体和共聚物对大肠杆菌和金黄色葡萄球菌的最低抑菌浓度(MIC)。结果表明:这两种共聚物均具有高效的抗菌性能,并且键合环丙沙星的聚丙烯酰胺的抗菌能力明显优于键合吡哌酸的聚丙烯酰胺。     

分散聚合法制备非离子型聚丙烯酰胺“水包水”乳液

利用丙烯酰胺在硫酸铵水溶液分散介质中的分散聚合制备了聚丙烯酰胺水溶性聚合物分散体;研究了硫酸铵浓度、聚甲基丙烯酰氧乙基三甲基氯化铵(PDMC)的相对分子质量及甲酸钠用量对聚丙烯酰胺水分散体系分散稳定性的影响.结果表明,获得稳定聚丙烯酰胺分散体系的最佳合成条件为:不加甲酸钠、PDMC的相对分子质量为8.02×105、硫酸铵的质量分数为20.9%.在最佳条件下得到的聚丙烯酰胺聚合物的相对分子质量为1.12×106.     

IA/ASP/AMPS三元共聚物合成及阻垢性能

以衣康酸(IA)、天冬氨酸(ASP)和2-丙烯酰胺-2-甲基丙磺酸(AMPS)为单体,在过硫酸铵引发下采用水溶液自由基聚合方法制备了新型IA/ASP/AMPS三元共聚物阻垢剂,并利用红外光谱仪对其结构进行分析表征。通过正交实验和单因素实验考察单体摩尔配比、引发剂用量、反应温度及反应时间对共聚产物阻垢性能的影响,确定其最佳合成条件。实验结果表明:共聚单体的摩尔比nIA:nASP:nAMPS为3:1:0. 5,引发剂用量占单体总质量的10%,反应温度为85℃,反应时间为4 h时,合成三元共聚物对碳酸钙、硫酸钙及磷酸钙的阻垢性能最好,阻垢率分别达91%、95%及96%以上;此共聚物的固含量和黏均相对分子质量分别为30. 5%、1402。静态阻垢法评价温度对IA/ASP/AMPS共聚物阻垢性能的影响,结果表明,IA/ASP/AMPS共聚物适用于含碳酸钙、磷酸钙的高温循环冷却水体系。     

聚丙烯酰胺类絮凝剂专利技术综述

通过对聚丙烯酰胺类絮凝剂技术领域的专利分析发现,该领域全球重点申请人主要为三井和三菱株式会社等,中国重点申请人主要为中国石油化工股份有限公司和中国科学院,该专利技术在全球和中国的技术集中度均不明显,较为分散。分析该领域的技术发展路线后可知,丙烯酰胺单体纯化、添加特定共聚单体、改进聚合方式和聚合工艺、引发剂选择或加入方式是该领域的研究重点。还对三井株式会社、中国石油化工股份有限公司的重点专利技术进行梳理,二者都通过上述各种重点技术手段来改进聚丙烯酰胺的絮凝性能。     

三次采油耐温抗盐聚合物的合成与评价

以丙烯酰胺(AM)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和氢氧化钠(Na OH)为原料,采用过硫酸铵[(NH4)2S2O8]、亚硫酸钠(Na2SO3)和四甲基脲[N(CH3)2CON(CH3)2]作为新型复合引发体系,通过共聚后水解工艺,合成了高分子量三元共聚物(AM-AANa-AMPSNa).考察了引发剂用量、单体浓度、p H和引发温度对共聚物黏均分子量的影响.确定最优条件为:引发剂用量0.035%,单体质量浓度为25%,介质p H 7,引发温度0℃.通过红外光谱和核磁碳谱表征了其结构,并系统评价了其理化性能指标、黏弹性、注入性和驱油性能.结果表明,该共聚物较高分子量部分水解聚丙烯酰胺(HPAM)具有更优异的耐温抗盐性能.其黏均相对分子量达到3000万以上,在胜利油田III型盐水中,浓度1500 mg/L,温度85℃条件下,溶液表观黏度达到17.7 m Pa s,岩心驱油实验在水驱采收率51.8%基础上,可再提高15.8%.上述性能表明,该高分子量三元共聚物有望应用在高温高盐油藏三次采油技术中.     

水溶性聚合物和两亲聚合物：聚（丙烯酰胺－co－丙烯酸钠）－g－聚（β－胺基丙酸）接枝共聚物

合成了端丙烯酰胺基聚（β－胺基两酸）大分子单体，用端基滴定法和１Ｈ—ＮＭＲ法测定了大分子单体的分子量，用１３Ｃ—ＮＭＲ和氢氧化钠水解法测定了支化度．在水溶液中用硫酸亚铁／异丙苯过氧化氢氧化还原引发体系引发丙烯酸胺、丙烯酸钠与聚（β－胺基丙酸）大分子单体的共聚反应，合成了聚（丙烯酰胺－ｃｏ－丙烯酸钠）－ｇ－聚（β－胺基丙酸）接枝共聚物．用１Ｈ—ＮＭＲ和滴定法测定了接枝共聚物的组成．溶液性质的数据表明，与部分水解聚丙烯酰胶相比，聚（β－胺基丙酸）含量较高的接枝共聚物具有较好的耐盐性和优异的贮存稳定性．     

水溶性聚合物和两亲聚合物：聚（丙烯酰胺－co－丙烯酸钠）－g－聚（β－胺基丙酸）接枝共聚物

合成了端丙烯酰胺基聚（β－胺基丙酸）大分子单体，用端基滴定法和１Ｈ－ＮＭＲ法测定了大分子单体的分子量，用＾１＾３Ｃ－ＭＮＲ和氢氧化钠水解法测定了支化度，在水溶液中用硫酸亚铁／异丙苯过氧化氢氧化还原引发体系引发丙烯酰胺，丙烯酸钠与聚（β－胺基丙酸）大分子单体的共聚反应，合成了聚（丙烯酰胺－ｃｏ－丙烯酸钠）－ｇ－聚（β－胺基丙酸）用１Ｈ－ＮＭＲ和滴定法测定了接枝共聚物的组成。溶液性质的数据表明，与部分     

Dispersing and stabilizing silicon nanoparticles in a low-epsilon medium

One possible approach to prevent the oxidation of silicon nanoparticles during a dispersing process is to use a dispersing medium, which does not contain any oxygen atoms in its structure, e.g. toluene. However, dispersing nanoparticles in such a non-polar organic medium is a major challenge, because the particles tend to aggregate very easily. The attempt of wet-grinding non-stabilized SiNP in toluene with a stirred media mill results in μm-sized aggregates that precipitate rapidly. In order to achieve stable suspensions with regard to aggregation a suitable additive, added during the process of dispersion, is necessary. The stabilizing efficiency of several different additives, mostly oligo- and polymeric compounds, was evaluated by investigating the aggregate formation via dynamic light scattering, complemented by scanning electron micrographs. This work demonstrates that the stability of the particulate system and therefore the formation of aggregates can be adjusted selectively by the choice of the additive towards well-dispersed or densified particles. The attachment of the additives upon the surface of the SiNP was examined by diffuse reflectance infrared Fourier transform spectroscopy and the surface coverage was quantified by a combination of thermogravimetric analysis and gas sorption experiments.     

羟丙基甲基纤维素作为水泥添加剂研究(一)

以三聚氯胺甲醛树脂磺酸盐（MS）为分散剂，羟丙基甲基纤维素衍生物为粘稠剂，研究了它们的复合物对混凝土材料的分散性与粘稠性及其它性能的影响，并探索了其作用机理．     

生物农药微胶囊壁材料研究

用原位聚合法对生物农药阿维菌素进行包囊,然后制备微胶囊制剂,并对用于该制剂的两种高分子囊壁材料-三聚氰胺甲醛树脂和脲醛树脂的性能进行了研究。结果表明,两种树脂皆为较好的生物农药用微胶囊缓释剂型的囊壁材料,其制备工艺简单,具有良好的稳定性、粒径大小与分布、悬浮性、缓释性等,包封率均达80％以上。其中三聚氰胺甲醛树脂悬浮性较脲醛树脂更好,缓释性更持久。     

Antibacterial mechanism of chitosan microspheres in a solid dispersing system against E. coli

In this study, we investigated the antibacterial mechanism through the interfacial contacting inhibition behaviors of chitosan antimicrobials against Escherichia coli in solid dispersing state. Chitosan microspheres (CMs) were prepared by emulsification cross-linking reaction, and oleoyl-CMs (OCMs) were obtained by introduction of oleoyl groups to the chitosan. The CMs were with smooth surface and spherical shape of diameter of about 124 microm. The antibacterial activity was directly proportional to the concentration and the hydrophobic property of CMs. The fluorescence experiments indicated CMs had influenced the structure of membrane, especially the OCMs were speculated to interact with proteins on the cell membrane. SEM photographs showed E. coli adhered to the surface of the CMs and provided evidences for the disruption of the cells, while the bacterium conglomerated on the surface of the OCMs. The CMs changed the permeability of membrane and caused cellular leakage that correlated with the hydrophobic interaction between CMs and cytoplasmic membrane phospholipids of Gram-negative bacteria. Solid dispersing system makes the antibacterial activities of CMs counted as a sequent event-driven to study the antibacterial mechanism of chitosan originally.     

Direct facile approach to the fabrication of chitosan-gold hybrid nanospheres

Chitosan-gold hybrid nanospheres were prepared through a direct facile approach that utilized cross-linked composite nanospheres consisting of low-molecular-weight chitosan (LWCS) and ethylenediaminetetraacetic acid (EDTA) as a precursor reaction system. EDTA was employed not only to construct the counterion interaction-based composite nanospheres with the cationic chitosan but also as the reductant for subsequent in situ gold salt reduction within the LWCS-EDTA composite nanospheres. This approach elegantly ensured that each and every nanosphere was loaded with gold nanoparticles and no nonembedded free gold nanoparticles would exist in the dispersing medium. Moreover, becauseof the noncovalent interaction between LWCS and EDTA, the EDTA reductant can be easily removed from the cross-linked nanospheres, and "pure" chitosan-gold hybrid nanospheres can be obtained. The obtained chitosan-gold hybrid nanospheres were found to have a tunable size and good dispersing stability within a wide pH range. The embedded gold nanoparticles were in the range from several to several tens of nanometers, which may be useful for sensing and imaging. Morphology studies indicated that most of the loaded gold nanoparticles were located in the interior of the hybrid nanospheres. Taking into account the good biocompatibilities of LWCS, abundant functional (amino) groups in chitosan, and the mild preparation conditions, we find that the chitosan-gold hybrid nanospheres prepared here may have tremendous potential in advanced biomedical applications.     

Effect of carbon nanofibers on mechanical and electrical behaviors of acrylonitrile‐butadiene rubber composites

Recently, carbon nanofibers have become an innovative reinforcing filler that has drawn increased attention from researchers. In this work, the reinforcement of acrylonitrile butadiene rubber (NBR) with carbon nanofibers (CNFs) was studied to determine the potential of carbon nanofibers as reinforcing filler in rubber technology. Furthermore, the performance of NBR compounds filled with carbon nanofibers was compared with the composites containing carbon black characterized by spherical particle type. Filler dispersion in elastomer matrix plays an essential role in polymer reinforcement, so we also analyzed the influence of dispersing agents on the performance of NBR composites. We applied several types of dispersing agents: anionic, cationic, nonionic, and ionic liquids. The fillers were characterized by dibutylphtalate absorption analysis, aggregate size, and rheological properties of filler suspensions. The vulcanization kinetics of rubber compounds, crosslink density, mechanical properties, hysteresis, and conductive properties of vulcanizates were also investigated. Moreover, scanning electron microscopy images were used to determine the filler dispersion in the elastomer matrix. The incorporation of the carbon nanofibers has a superior influence on the tensile strength of NBR compared with the samples containing carbon black. It was observed that addition of studied dispersing agents affected the performance of NBR/CNF and NBR/carbon black materials. Especially, the application of nonylphenyl poly(ethylene glycol) ether and 1‐butyl‐3‐methylimidazolium tetrafluoroborate contributed to enhanced mechanical properties and electrical conductivity of NBR/CNF composites.     

Adsorbing behavior of polycarboxylate superplasticizer in the presence of the ester group in side chain

The effect of the ester group in side chain on adsorbing behavior and dispersion of polycarboxylate superplasticizer (PC) was studied by comparing the performance of two types of PC. The fluidity of cement paste was tested to discuss the dispersing ability and dispersing retention ability of PC. The total organic carbon analyzer was used to measure the adsorption amount, and the adsorption layer was obtained by x-ray photoelectron spectroscopy. Fourier-transform infrared spectroscopy, nuclear magnetic resonance, and pH value were used to verify the stability of the ester group, and the electrokinetic properties of cement particle were confirmed using the zeta potential measurement. The results show that the ester group in side chain reduces the initial dispersing ability while it increases the dispersing retention ability. The dispersing retention ability depends on the increase of adsorption amount and adsorption layer in 5–60 minutes, and the greater increase leads to the better dispersing retention ability. The ester group can be decomposed to release carboxyl group to enhance the adsorbing ability of PC under the condition of cement hydration, which is the main reason for the greater increase of adsorption amount and adsorption layer and the improvement in dispersing retention ability. It suggests that grafting the ester group is a good way to enhance the dispersing retention ability.     

Structural and mechanical properties of composite hydrogels composed of clay and a polyelectrolyte prepared by mixing

We investigated the structural, mechanical, and swelling properties of composite hydrogels consisting of clay, a dispersing agent (tetrasodium diphosphate), and sodium polyacrylate (PAAS) prepared by mixing. Regardless of the simple preparation method, the gel exhibits excellent properties such as mechanical toughness and high swelling ability. For production of the tough gels, it is important to disperse clay particles using the dispersing agent and to use high molecular weight PAAS for formation of bridge connecting different clay particles in a dispersed state. Synchrotron small-angle X-ray scattering experiments reveal that PAAS was adsorbed on the positively charged edge of the clay particles.     

Use of carbon black as a reinforcing nano-filler in conductivity-reversible elastomer composites

This study presents an innovative approach to the production of reinforced elastomer composites filled with carbon black Printex XE-2B, using the calendering process and ionic liquids (ILs) as dispersing agents. The effect of Printex XE-2B on the mechanical and electrical properties of acrylonitrile-butadiene rubber (NBR) composites was compared to that of conventional carbon black Humex N339. It was found that the highly structured Printex XE-2B significantly enhanced both the mechanical and electrical properties of the NBR composites, in contrast to standard Humex N339. To obtain uniform filler dispersion in the polymer matrix, several different ILs were employed as dispersing agents. The application of ILs had a considerable effect on the properties of the prepared composites, due to the improved dispersion of the filler particles in the composite matrix, which favored the formation of ‘conductive paths.’ Importantly, the prepared NBR/Printex XE-2B/IL composites were found to have reversible and repeatable electrical properties following exposure to chloroform vapors.     

Properties of various phosphatidylcholines as emulsifiers or dispersing agents in microparticle preparations for drug carriers

We investigated characteristics of various phosphatidylcholines (PCs) used as dispersing agents and emulsifiers. Six PCs with different lengths of acyl hydrocarbon chains and different degrees of unsaturated acyl hydrocarbon chains were selected to examine influences of a lipophillic part of phosphatidylcholines in emulsion and dispersion systems. Vesicles and oil-in-water emulsions were prepared by sonication under several ambient temperature conditions. Mean diameters of vesicles and oil droplets in emulsions were measured by a submicron particle sizer. In vesicles that are generated by hydration of the PCs and have a bilayer form, particle size was influenced by length and degree of unsaturation of acyl hydrocarbon chains of a PC. PCs with shorter acyl hydrocarbon chains or unsaturated bonds are considered more potent dispersing agents. Preparation temperature of the PC is also a factor affecting potency of dispersion. In O/W emulsions in which PCs were absorbed at water-oil interfaces and which have a single layer form or liquid-crystal layer form, particle size was also influenced by length and degree of unsaturation of acyl hydrocarbon chains of a PC. PCs with shorter and saturated acyl hydrocarbon chains are considered more potent emulsifiers. Unsaturation of acyl hydrocarbon chains weaken the ability of emulsification due to vulnerable double bonds. For stable emulsions, it is considered beneficial for PCs to form small oil droplets and lamellae liquid-crystal phase. From this perspective, saturated PCs with short hydrocarbon chains, i.e., DLPC and DMPC, may have advantages in preparing a stable emulsion not only by giving a smaller droplet size but also by forming lamellae liquid-crystal phase. When considering characteristics of PCs as emulsifiers, their characteristics as dispersing agents is also useful information.