STUDY ON SYNTHESIS OF AMPHOTERIC POLYACRYLAMIDE IN INVERSE EMULSION

Amphoteric polyacrylamide was prepared first by the copolymerization of acrylamide with sodium acrylate and then through Mannich reaction.The copolymerization was carried out with a redox initiation system using the method of inverse emulsion polymerization.In this paper the reaction conditions and factors that affect emulsion stability were studied.Experiments show that a stable latex can be obtained under the following conditions:anionic degree is five percent,the ratio among acrylamide,formaldehyde and dimethylamine is 1∶1∶1.2,reaction temperature is 45 ℃,reaction time lasts four hours,and pH equals 5.0.The amphoteric copolymer has a higher molecular weight and cationic degree,so it is an ideal filler retention and drainage aid in paper making.

PHOTOINITIATED INVERSE EMULSION POLYMERIZATION OF SODIUM ACRYLATE

Photoinitiated inverse emulsion polymerization of sodium acrylate(AANa)in kerosene was carried out at room orlower temperature,using 2,2-dimethoxy-2-phenylacetophenone(DMPA)as the initiator.Kinetic investigations indicated thatthe polymerization could be completed in about 30 min and produce polymer with high molecular weight(10~6～10~7).It wasfound that monomer droplets are the main sites for the polymerization(nucleation).With the increase of DMPAconcentration,polymerization rate(R_p)reaches a maximum value while molecular weight of the produced polymer has anadverse result,but the dependence of R_p on incident light intensity is similar.Influences of other parameters such asmonomer concentration,emulsifier content and reaction temperature,etc.were also studied.At lower pH values of waterphase,R_p depends strongly on the pH due to the electrostatic interaction between the ionized radicals and the monomer.Athigher pH,R_p shows a slight dependence on pH.

Microstructure and Properties of PET Fabric Grafted by Polyacrylic Acid with Inverse Microemulsion Polymerization

Annual production output of poly(ethylene terephthalate)(PET) fiber has been over 15 million tons in China due to its good mechanical properties and processability,but the shortage of hydrophilic group of PET has imposed many limitations to further extend its application.The PET fabrics were grafted with polyacrylic acid in inverse microemulsion after low pressure plasma treatment,and the microstructure and properties of the grafted fabrics were investigated with infrared spectroscopy,scanning electron microscope(SEM),hydrophilic and mechanical tests.The grafting yield was increased with the grafting time.The grafting polymer was in the granular form with its particle size ranging from a few micrometers to a dozen of micrometers,normally smaller than the fiber diameter.The moisture regain and water uptake increased while the air permeability of the grafted fabrics decreased with the increase of grafting yield.The bending rigidity and tensile properties show slightly complicated behaviors with grafting yield.The inverse emulsion grafting technique can be used to control the grafting polymer architecture.

Synthesis, adsorption and selectivity of inverse emulsion Cd(Ⅱ) imprinted polymers

Inverse emulsion polymerization was employed to synthesize inverse emulsion Cd（Ⅱ） imprinted polymers （IEⅡ P）. The morphology and functional groups of IEⅡP were characterized by SEM,FTIR and TG. Static adsorption experiments and competitive adsorption test were used to evaluate the adsorption ability of IEⅡP. The adsorption capacity of polymers could reach 86.7 mg·g^-1 under the optimal adsorption conditions. The pseudo second order kinetic model and Langmuir isotherm model could be used to analyze the experimental data well. The adsorption process of IEⅡP was chemical adsorption process and monomolecular type. Thermodynamic parameters showed that the adsorption process was endothermic and could occur spontaneously. The selectivity coefficients k of Cd^2＋/v, Cd^2＋/Zn^2＋ and Cd^2＋/Cu^2＋ were 2.4998, 1.2437 and 4.6882, respectively. The proposed method provides a new thought for removing Cd（Ⅱ） in water samples.

Investigation on the Inverse Emulsion Polymerization of Acrylic Acid

Polyacrylic acid particles in nano-scale were synthesized using an inverse (W/O) emulsion polymerization method. The particle size and size change of inverse micelles which solubilize a part of monomer solution was monitored by PCS (photon correlation spectroscopy) and the particles of polyacrylic acid were viewed in scanning electron microscope for the first time. It was concluded that the inverse micelles were primarily the polymerization reaction sites.

INFLUENCES OF WATER-SOLUBLE CATIONIC MONOMERS ON THE POLYMERIZATION RATE IN THE INVERSE EMULSION

This investigation deals with the free radical polymerization both of (2-methacryloyloxyethyl) trimethyl ammonium chloride (QACEMA) and of diallyldimethyl ammonium chloride (DADMAC) in inverse emulsion. The influences of some factors, such as the concentration of monomers, initiator and emulsifier are discussed. The polymerization rate equations of above two monomers can be written as follows: R(p) = k[M](1.21)[I](0.82)[E](0.57) (for QACEMA) R(p) = k'[M](1.34)[I](0.90)[E](0.62) (for DADMAC)

Investigation of the Electro-Mechanical Behavior of Hybrid Polyaniline/Graphene Nanocomposites Fabricated by Dynamic Interfacial Inverse Emulsion Polymerization

This paper describes a study on electrical resistivity under loading of polyaniline (PANI)/graphene nanocomposite powders and compacts. The composites were prepared by an in-situ interfacial dynamic inverse emulsion polymerization technique under sonication of aniline in the presence of graphene sheets in chloroform. During polymerization the graphene nanoplatelets are coated with PANI and are well dispersed both in the polymeric suspension and then in the dried polymer matrix as evidenced by cryogenic transmission electron microscopy (Cryo-TEM) and high resolution scanning microscopy (HRSEM). The presence of graphene nanoplatelets lowers the electrical resistivity of the polyaniline by two orders of magnitude for both the powder and the compact composites as demonstrated by their electrical resistance measurements conducted under loading. The lowest measured electrical resistivity values were 5 Ω·cm for 33% wt. graphene powder and 8 Ω·cm for 41% wt. graphene compacted composites. Cyclic electrical measurements under loading showed a distinct reproducible dependence of the bulk resistivity vs. applied pressure. This repetition is a key component for electro-mechanical sensors. To the authors’ best knowledge, this is the first report on polymerization of aniline in presence of graphene by the in-situ interfacial dynamic inverse emulsion polymerization technique and also the first report on cyclic electrical measurements under pressure of PANI/graphene nanocomposites.

Preparation of Chitosan-g-PAM PS in H_2O/scCO_2 Inverse Emulsion

Chitosan （CS） was successfully modified in supercritical carbon dioxide （ scCOz ） by grafting method to enhance its water solubility. In this work, a three.arm star-like fluorinated polymer was synthesized by atom transfer radical polymerization （ ATRP ） method and applied as a surfactant in supereriticul carbon dioxide （scCO2 ）. Then 2-acrylamido-2-methyl propane sulfonie acid （AMPS） was grafted onto CS （CS-g-PAMPS） in H2O/scCO2 inverse emulsion. The effects of mass ratio of water and surfactants （Rw/s ） and pressure of scCO2 on the grafting reaction were investigated. The grafting rate, partide size, and dispersity in water of CS-g-PAMPS varied greatly as Rw/s and pressure of scCO2 changed. It could be found that the value of Rw/s at 12 and the pressure of scCO2 at 30 MPa were the optimum conditions for the grafting reaction. CS-g-PAMPS prepared in this reaction system has higher grafting rate, smaller particle sizes, and better dispersity in water than those prepared via conventional methods.

THE PREPARATION OF DOXORUBICIN-POLYVINYLPYRROLIDONE-NANOPARTICLES BY INVERSE EMULSION POLYMERIZATION

Doxorubicin-loaded nanoparticles, using doxorubicin （ADM） as model drug and vinylpyrrolidone as matrix, were prepared by inverse emulsion polymerization in the paper. The nanoparticles were characterized by telescope electron microscopy （TEM）, laser light scattering technique （LLS） and infrared spectrum （IR）. LLS test showed that the optimal prepared ADM-loaded nanoparticles had an average size 18.8nm and a narrow size distribution between 15nm and 32nm, which was consistent with the result obtained by TEM. And 1R results indicated that the nanoparticles consisted of ADM and polyvinylpyrrolidone （PVP）.

DEVELOPMENT AND APPLICATION OF WATER-IN-OIL EMULSIONS FOR ZINC HOT ROLLING

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Study on Viscoelastic Behaviors of Waxy Crude Water-in-Oil Emulsion

Emulsion of waxy crude oil is one of the common states in the subsea pipeline. At low temperatures in offshore environment, waxy crude oils with water could form the crude oil emulsion gel of oil-in-water emulsion. Thus, the waxy crude oil emulsion viscoelastic behavior for deep sea transportation and restarting pipeline safety is particularly important. By means of MASIII HAAKE rheometer which is produced by German company, waxy crude oil emulsion viscoelastic behavior is explored at different volumetric water contents and different shear stresses. By analyzing the rate of change of shear rate in the initial stage, the influence rules of viscoelastic properties were summarized, with the change of volumetric water content and the applied shear stress and based on the experimental results, the law of emulsion is explained from the micro level. It is proposed that brittle fracture exists between wax crystals, and flexible fracture was found in the interaction between water droplets and wax crystals.

Tuning the membrane rejection behavior by surface wettability engineering for an effective water-in-oil emulsion separation

Membrane-based separation is a promising technology to eliminate water impurities from the oil phase.However,it remains a great challenge to separate water from highly emulsified viscous oil owing to the high stability of the water droplets in oil.Herein we report a surface wettability engineering on an alumina ceramic membrane to achieve an efficient separation of a water-in-oil(W/O)emulsion.Silanes with different carbon chain lengths and fluorinated status were introduced to endow the alumina membrane with different surface wettabilities.While all the modified membranes exhibited excellent separation of the W/O without Span 80(surfactant),the one with amphiphobic wettability and lowest surface energy failed to separate the Span 80 stabilized W/O.The presence of Span 80 reduced the interfacial tension of water droplets,making them easier to deform and penetrate the modified membrane with the lowest surface energy.It reveals that engineering proper surface wettability is the key to separating the oil and water phases.Besides,the modified membranes maintained decent separation performance and stability under long-term run separation of the emulsified W/O.

Experimental investigation of the effects of various parameters on viscosity reduction of heavy crude by oil-water emulsion

The effects of water content, shear rate, temperature, and solid particle concentration on viscosity reduction （VR） caused by forming stable emulsions were investigated using Omani heavy crude oil. The viscosity of the crude oil was initially measured with respect to shear rates at different temperatures from 20 to 70℃. The crude oil exhibited a shear thinning behavior at all the temperatures. The strongest shear thinning was observed at 20℃. A non-ionic water soluble surfactant （Triton X-100） was used to form and stabilize crude oil emulsions. The emulsification process has significantly reduced the crude oil viscosity. The degree of VR was found to increase with an increase in water content and reach its maximum value at 50 % water content. The phase inversion from oil- oil emulsion occurred at 30 in-water emulsion to water-in- % water content. The results indicated that the VR was inversely proportional to temperature and concentration of silica nanoparticles. For water-in-oil emulsions, VR increased with shear rate and eventually reached a plateau at a shear rate of around 350 s^-1. This was attributed to the thinning behavior of the continuous phase. The VR of oil-in-water emulsions remained almost constant as the shear rate increased due to the Newtonian behavior of water, the continuous phase.

Carbon dioxide/calcium oxide responsive behavior and application potential of amine emulsion

Green and low cost CO_(2) and CaO were used to stimulate amine emulsions to reveal the responsive behavior of amine emulsions.On this basis,oil-based drilling fluids responsive to CO_(2) and CaO were formulated and their properties were evaluated.The results showed that the amine emulsions inversed from water-in-oil state to oil-in-water state readily and their rheological behavior underwent transitions of decreasing,rising again and decreasing again via induction by CO_(2).These CO_(2) responsive behaviors could be reversed by CaO.Oil-based drilling fluids prepared based on the amine emulsions with oil-water volume ratios of 50:50 to 70:30,densities of 1.4-2.0 g/cm^(3) had good rheological and filtration properties at 160℃;and be readily cleaned up using CO_(2) bubbling.The useless solid phase with low density could be removed efficiently via reducing the viscosity of emulsion by CO_(2) and the residual liquid phase could be restored to the original state by CaO and reused to prepare drilling fluid.The mechanisms analysis indicated that CO_(2)/CaO induced the reversible conversion between amine emulsifiers and their salts,which enabled the reversible regulation of both the hydrophilic-lipophilic balance of amine emulsifiers and the emulsion particles’size and finally caused the controllable-reversion of the form and rheology of amine emulsion.

Effects of Water-Soluble Co-Solvent on Properties of W/O Pickering Emulsions

Effects of water-soluble co-solvents （WSCs）on the properties of water/oil Picketing emulsions were investigated. Picketing emulsions were prepared in the system of 1,2,4-trimethylbenzene （TMB）/hydrophobic sil- ica/water with varied concentrations of WSCs （ethanol, acetic acid and glycerin）. Mean droplet diameter distribu- tions of the obtained emulsions were studied to investigate the effects of WSCs types and concentrations. The results demonstrated that mean droplet diameter distributions decreased at first and then increased with the increase of WSC concentration. Moreover, the effect of WSC concentration on the phase inversion locus was further investi- gated. At the same time, infrared radiation （IR）spectrometer was used to investigate the mechanism. The results showed that the WSC attaching on hydrophobic silica changed the wettability of the particles, which facilitated the formation and phase inversion of the emulsion. The hydrogen bonds between the co-solvent groups attaching on the solid particles made a great effect on the droplet size of the emulsion and strengthened the interaction among emulsifiers. Overall, proper WSC was in favor of the stability of Picketing emulsion.

Preparation of Hollow Calcium Silicate Microparticles by Simple Emulsion

Hollow calcium silicate microparticles were prepared by mixing a water-in-oil (W/O) emulsion containing silicate ions in aqueous phase with an oil phase containing a calcium/di-2-ethylhexyl phosphoric acid (D2EHPA) complex. The inorganic precipitation reaction at the oil-water interface was accelerated by using a simple W/O emulsion. Hollow microparticles were obtained when the mole ratio of D2EHPA and calcium in the oil phase was nearly 2:1. The shell formation of the par-ticles depended on the acceleration of the precipitation reaction, which could be accomplished by controlling the concentrations of the calcium and silicate ions.

适用于LAS系统的全液体隔离液体系

固井施工过程中,在注入水泥浆前,需要先泵入一定量的隔离液,在海洋固井现场施工作业过程中,隔离液配制一般需要繁重的人工劳作,劳动强度大,作业效率低,加量不准确。为解决上述问题,用液体添加剂代替固体添加剂,通过LAS材料添加系统将材料混配作业,从传统的重体力劳动转化为智能化操作,降低作业强度,提高固井作业效率与降低人员成本。通过反相乳液聚合制备了一种液体隔离剂C-S70L,以它为主剂,构建了一套适用于液体加料系统(LAS)的隔离液体系。该体系推荐使用温度为20~120℃,适用密度为1.30~1.70 g/cm^(3);具有良好的悬浮稳定性(热滚后无沉降)、流变可调、失水可控以及相容性好的特点。

负载花色苷的抗酸性羧甲基壳聚糖凝胶微球的缓释研究

为拓宽壳聚糖基水凝胶的应用范围,构筑可食用的花色苷(ACNs)递送体系,采用反相乳液法,以玉米油为连续相,水杨醛(SA)为交联剂,制备了具有抗酸性能的载ACNs羧甲基壳聚糖(CMCS)凝胶微球(ACNs/CMCS-SA),表征了其结构和形貌,研究了其稳定性、溶胀性能和缓释性能。结果表明,ACNs/CMCSSA具有微米级粒径,表面光滑呈圆形;ACNs/CMCS-SA在酸性条件下稳定性良好,溶胀和缓释过程展现pH响应性;ACNs的释放行为符合Weibull模型,pH7和9时为扩散和骨架溶蚀复合释放机制控制,pH3和5时为菲克扩散和Case Ⅱ transport(0级-溶胀依赖性释放)联合释放机制控制。ACNs/CMCS-SA制备方法简单,过程绿色;对ACNs展现良好的胃酸保护和肠道释放性能,为环境友好型药物包封材料的开发和ACNs的应用提供了理论和实践参考。

新型低界面张力纳米微球调驱剂的合成与性能研究

聚丙烯酰胺纳米微球调驱剂作为一种新型的纳米驱油材料,在油田提高采收率方面取得了广泛应用。但是,目前使用的聚丙烯酰胺纳米微球功能主要以封堵为主,存在单体固含量低、水溶液吸水膨胀速度过快、驱油和降低表界面张力功能较差等问题。利用反相乳液聚合法,以白油为油相,2-丙烯酰胺-2-甲基丙磺酸(AMPS)、丙烯酰胺(AM)混合单体为水相,油酸/双子聚醚/OP-10混合表面活性剂为乳化剂,根据三元相图确定油相/乳化剂/水相三相的最佳配比(质量分数)为33.93%/24.87%/41.2%,以甲叉双丙烯酰胺(MBA)作为交联剂,在35℃利用氧化-还原剂聚合获得了既具有封堵功能,又具有超低表界面张力、高洗油效率的新型纳米微球调驱剂。工艺优化实验确定最佳的合成条件为单体配比m(AM)∶m(AMPS)为8∶1,交联剂质量分数为0.1%,氧化-还原剂质量分数为0.3%,搅拌速度为450 r/min。对聚合物纳米微球进行表征和性能评价,结果表明,其固含量为20.1%,粒径为54 nm,纳米微球封堵率可达95.1%,用其0.2%的水溶液测得界面张力为0.332 mN/m,洗油效率高达89.13%,为实施油田调驱提供了一种新材料。

高分子化学实验“反相乳液法制备聚丙烯酰胺微球”的设计

实验教学作为理论教学的延伸与拓展,对强化学生理论知识点、提升实验实践能力具有重大促进作用。为满足人才培养的最新要求,现对高分子化学实验内容进行优化,设计“反相乳液法制备聚丙烯酰胺微球”实验项目。实验过程通过改变单体浓度、引发剂加量等多个实验条件,引导学生思考不同实验条件对产物粒径的影响,加深学生对反相乳液聚合机理的理解。通过该实验,学生还能够掌握使用激光散射系统测定产物粒径的方法。