Influence of polymers on the stability of Gudao crude oil emulsions

The influence of different types and concentrations of polymers on the stability of Gudao crude oil emulsion was investigated by measuring the volume of water separated from the emulsions and the interfacial shear viscosity of the oil/water interfacial film. Experimental results indicate that the simulated water-in-oil emulsion with 40 mg/L of partially hydrolyzed polyacrylamide （HPAM） 3530S could be easily broken by adding demulsifier C and was readily separated into two layers. However, HPAM AX-74H and hydrophobically associating water-soluble polymer （HAP） could stabilize the crude oil emulsion. With increasing concentration of AX-74H and HAP, crude oil emulsions became more stable. Water droplets were loosely packed in the water-in model oil emulsion containing HPAM 3530S, but water droplets were smaller and more closely packed in the emulsion containing AX-74H or HAP. The polymers could be adsorbed on the oil/water interface, thereby increasing the strength of the interracial film and enhancing the emulsion stability.

Preparation of Organic/Inorganic Hybrid Polymer Emulsions with High Silicon Content and Sol-gel-derived Thin Films

A novel polymer/SiO2 hybrid emulsion(PAES)was prepared by directly mixing colloidal silica with polyacrylate emulsion(PAE)modified by a saline coupling agent.The sol-gel-derived thin films were obtained by addition of co-solvents into the PAES.The effects ofγ-methacryloxypropyltrimethoxysilane(KH-570)content and co-solvent on the properties of PAES films were investigated.Dynamic laser scattering(DLS)data indicate that the average diameter of PAES(96 nm)is slightly larger than that of PAE(89 nm).Transmission electron microscopy (TEM)photo discloses that colloidal silica particles are dispersed uniformly around polyacrylate particles and some of the colloidal silica particles are adsorbed on the surface of PAE particles.The crosslinking degree data and Fourier transform infrared(FT-IR)spectra confirm that the chemical structure of the PAES is changed to form Si-O-Si-polymer crosslinking networks during the film formation.Atomic force microscope(AFM)photos show the solvent induced sol-gel process of colloidal silica and the Si-based polymer distribution on the film surface of the dried PAES.Thermogravimetric analysis(TGA)curves demonstrate that the PAES films display much better thermal stability than PAE.

Preparation of Self-crosslinked Fluorocarbon Polymer Emulsion with Core-shell Structure by the Method of Soap-free Emulsion Polymerization

Using methyl methacrylate （MMA）, butyl acrylate（BA） and hexafluorobutyl acrylate（HFBA） as main raw materials, we prepared self-crosslinked fluorocarbon polymer emulsion with core-shell structure via soap-free emulsion polymerization when the conception of particle design and polymer morphology was adopted. Moreover, the influence of mole ratio of BA to MAA, pH value on the oligomer was studied. And the effects of the added amount of oligomer, self-crosslinked monomer and HFBA, mass ratio of BA to MMA, reaction temperature and the initiator on the polymerization technology and the performance of the product, were investigated and optimized. The structure and performance of the fluorocarbon polymer emulsion were characterized and tested with FTIR, TEM, MFT and contact angle and water absorption of the latex film. The experimental results show that the optimal conditions for preparing fluorocarbon polymer emulsion are as follows： for preparing the oligomer, tool ratio of BA to MAA is equal to 1.0 ： 1.60, and pH value is controlled within the range of 8.0 and 9.0; for preparing fluorocarbon polymer emulsion, the added amount of oligmer[P（BA/MANa）] is 6%; mass ratio of BA to MMA is 40 ＂ 60; the added amount of self-crosslinked monomer is 2%, the added amount of HFBA is 15 %; reaction temperature is 80 ℃; the mixture of potassium persulfate and sodium bisulfite is used as the initiator. The film-forming stability of the fluorocarbon polymer emul- sion and the performance of the latex film, which is prepared with the soap-free emulsion polymerization, are better than that prepared with the conventional emulsion polymerization.

Properties and Microstructure of Polymer Emulsions Modifi ed Fibers Reinforced Cementitious Composites

The synthesis and characterization of a new class of cementitious composites filled with polymer emulsions were investigated, and their superior mechanical strength and durability properties compared to composites devoid of fi llers were reported. Polymer emulsions were utilized to mechanically reinforce the composite and bridge the cement, fly ash, aggregate and fibers. The results reveal that the epoxy emulsion and poly（ethylene-co-vinyl acetate） emulsion markedly enhance the mechanical and durability properties of cemetitious composites. The fi bers can be pulled out in the form of slip-hardening and the abrasion phenomenon can be observed clearly on the surface of the fibers. The hydration extent of cement is higher than that of the pristine composites. The polymer modified cementitious composites designed on micromechanics, have fl exibility and plasticity which could be applied for a novel form of multifunctional materials with a range of pipeline coatings applications.

Grafting Methyl Methacrylate onto Silk via Emulsion Graft Copolymerization Using a Diethylzinc Complex Initiator

Methyl methacrylate (MMA) was grafted onto silk fiber in a one-step emulsion system using a diethylzinc and 1,10-phenanthroline complex. The reaction conditions were investigated by varying temperature and initiator to monomer ratio. Fourier transform infrared (FTIR) spectrum, thermogravimetric analysis (TGA), and scanning electron microscopy (SEC) techniques were used to characterize the structure, thermal stability, and surface morphology of the obtained product, respectively. Grafting of MMA onto silk increased the thermal stability of silk. The FTIR spectrum and SEM images provided further evidence that MMA has been successfully grafted onto the silk fiber. A peak ascribed to the C=O stretching vibration of MMA was detected in the FTIR spectrum of grafted silk fiber, which was not present in the spectrum of pure silk fiber. Moreover, the SEM images illustrated the increase in diameter and surface roughness of grafted silk compared with pure silk. Lastly, the dyeing performance of the modified silk was significantly increased.

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.

Rheological behavior of alkali-surfactant-polymer/oil emulsion in porous media

Based on deep analysis of ASP/oil emulsions flow behavior characteristic,a mathematical description of non-Newtonian emulsion was developed,and variation of rheological behaviors along the percolation flow direction was given.The effects of emulsions rheological behavior on oil recovery were quantity researched by a 2-D positive rhythm profile geological model.The result shows that the high viscosity and reduction of water phase permeability by emulsification can improve low-middle layer flow rate and enhance sweep efficiency,and the enhancement degree is related with emulsification degree.The study result can be used as reference for scheme design and production performance forecast during ASP flooding.

Emulsion Polymerization of P (MMA-AA-EA) and Its Demulsifying Performance in Water/Oil Emulsion

Stable water-in-oil emulsions are produced in oil exploitation and cause many environmental and operational issues.In this paper,a co-polymer demulsifier is reported in detail;an emulsion polymerization method is used to prepare nano-P(MMA-AA-EA)with MMA,AA and EA as the monomers,DVB as the cross-linker and APS as the initiator.The resulting products are characterized by FT-IR.Furthermore,the surface tension and particles size analysis is investigated.The results show that the surface tension reduction is 10.66 mN/m at 20?C when the concentration of co-polymer is 1000 ppm and the average size is 76.99 nm.Moreover,the HLB of polymer is discussed specifically by changing the amount of AA.With the increase of AA,the HLB value of the polymer is increased accordingly.Besides,the demulsification performance of the co-polymer is also evaluated at different synthesis and demulsification conditions.It is showed that the maximum demulsification efficiency is 96%at 70?C for 60 min.The optimum concentration of demulsifier is 400 ppm when the amounts of AA and DVB are 1.4 g and 0.1 g,respectively.At last,the process of demulsification is showed under a microscope;the coalescence process of water droplets is indicated under the action of the demulsifier.

钻井液用两性离子P(AM-AMPS-DAC)共聚物反相乳液的制备与性能评价

作为钻井液处理剂．反相乳液聚合物与粉状聚合物相比．能够减少聚合物在烘干、粉碎过程中由于降解、交联等反应造成的不利影响，产品可以直接加入钻井液并快速分散，在达到同样效果的前提下，可减少用量，降低钻井液处理费用，且更容易实现绿色环保生产。以丙烯酰胺、2-丙烯酰胺-2-甲基丙磺酸、丙烯酰氧乙基三甲基氯化铵为原料，采用氧化还原引发剂体系，通过反相乳液聚合．制备了两性离子P（AM-AMPS-DACl反相乳液聚合物。研究了复合乳化剂的HLB、乳化剂用量、引发剂用量、油水体积比、AMPS和DAC用量对共聚物的水溶液表观黏度及所处理钻井液的流变性和滤失量的影响，测定了聚合物的红外光谱和TG曲线。结果表明，当油水体积比为1．0，单体质量分数为30％，复合乳化剂质量分数为5％～6％，复合乳化剂HI。B值为7．1，引发剂用量为0．2％，n（AM）n（AMPS）：n（DAC）=0．59：0．35：0．06时，能够制得热稳定性好的反相乳液聚合物，且在淡水、盐水、饱和盐水和复合盐水基浆中具有较好的增黏、降滤失能力，抗温、抗盐能力强，同时具有较强的润滑和防塌能力。

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.

Influence of hydroxypropyl methylcellulose,methylcellulose, gelatin, poloxamer 407 and poloxamer 188 on the formation and stability of soybean oil-in-water emulsions

Macromolecules of polysaccharides, proteins and poloxamers have a hydrophobic portion and a hydrophilic one that can be used as emulsifiers. Parts of these emulsifiers are safe pharmaceutical excipients, which can replace the irritant low molecular weight surfactants to formulate emulsions for the pharmaceutical field. This project focused on preparing O/W emulsions stabilized with polymers for pharmaceuticals such as polysaccharides, proteins and poloxamers, including hydroxypropyl methylcellulose (HPMC), methylcellulose (MC),gelatin, poloxamer 407 (F127) and poloxamer 188 (F68). Emulsion physical stability was assessed by centrifugation, autoclaving sterilization and droplet size measurements. The stabilization mechanisms of emulsions were determined by interfacial tension and rheological measurements. Results stated that the efficacy of these polymers for pharmaceuticals stabilized emulsions was sorted in the order: F127 > F68 > HPMC > MC > Gelatin.

A novel approach to study the interactions between polymeric stabilized micron-sized oil droplets by optical tweezers

The well understanding of interaction forces between single dispersed droplets is crucial to the understanding of emulsion stabilization mechanism.Recently,many studies have reported the direct quantitative measurements of interaction forces between 20-200μm single droplet coated polymers by atomic force microscope(AFM).These studies have revealed many important results about the relationship of the interaction forces and the droplet deformation.However,these studies of the quantitative relationship between the measured interaction forces and the separation distance of the front end of the droplet have rarely been reported.Optical tweezer instrument can make it possible to establish the quantitative relationship between the measured force and the separation distance of the front end of the droplet,which will make better understanding of the interaction mechanisms between droplets.Due to the differences of the measuring mechanism between atomic force microscopy(AFM)and optical tweezers,the theory model of AFM measurements cannot be fitted with the force measurement by optical tweezers.We have made an exhaustive comparison of the measuring differences between AFM and optical tweezer instrument in this work.Moreover,we built a numerical model to derive the repulsive pressure through the measured force curve in order to quantify the measured force of two micron-sized oil droplet coated polymers by optical tweezers.Furthermore,the novel method can be extended to other micron-sized emulsion systems,and these findings will be a vital progress on quantitative force measurements between micron-sized droplets.

Facile synthesis of metal-organic frameworks embedded in interconnected macroporous polymer as a dual acid-base bifunctional catalyst for efficient conversion of cellulose to 5-hydroxymethylfurfural

5-Hydroxymethylfurfural(5-HMF),as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels,has been attracted extensive attention.In this research,using Pickering high internal phase emulsions(Pickering HIPEs)as template and functional metal-organic frameworks(MOFs,UiO-66-SO;H and UiO-66-NH;)/Tween 85 as co-stabilizers to synthesis the dual acid-base bifunctional macroporous polymer catalyst by one-pot process,which has excellent catalytic activity in the cascade reaction of converting cellulose to 5-HMF.The effects of the emulsion parameters including the amount of surfactant(ranging from 0.5%to 2.0%(mass)),the internal phase volume fraction(ranging from 75%to 90%)and the acid/base Pickering particles mass ratio(ranging from 0:6 to 6:0)on the morphology and catalytic performance of solid catalyst were systematically researched.The results of catalytic experiments suggested that the connected large pore size of catalyst can effectively improve the cellulose conversion,and the synergistic effect of acid and base active sites can effectively improve the 5-HMF yield.The highest 5-HMF yield,about 40.5%,can be obtained by using polymer/MOFs composite as catalyst(Poly-P12,the pore size of(53.3±11.3)μm,the acid density of 1.99 mmol·g^(-1)and the base density of 1.13 mol·g^(-1))under the optimal reaction conditions(130℃,3 h).Herein,the polymer/MOFs composite with open-cell structure was prepared by the Pickering HIPEs templating method,which provided a favorable experimental basis and theoretical reference for achieving efficient production of high addedvalue product from abundant biomass.

POLYMER SCIENCE AND TECHNOLOGY IN THE PAST AND THE FUTURE:HEROISM,EXPLORATION AND ENLIGHTENMENT

The scientific and technical history of polymerization can be divided into three periods, which will be illustratedfor emulsion polymerization. The first period was when emulsion polymers were originally produced, and was developed asan attempt to copy natural rubber latex. Indeed, the natural process is quite different from the synthetic process of emulsionpolymerization, which in fact does not even need an emulsion to be present: the term is a misnomer! The results werefunctional but limited. In the second period, the first theories appeared, and a huge range of products was madefor surface coatings, adhesives, commodity polymers such as SBR, neoprene, etc. The work of the outstanding pioneers wasbased on limited types of experimental data, and some suppositions are now seen to be incorrect. Nevertheless, manyexcellent products were made and have evolved to many materials currently in everyday use. The third period of emulsionpolymerization is now dawning. The scientific efforts of many teams over previous decades, aided by the advent of newphysical techniques for investigation, have resulted in better understanding of the fundamentals of emulsion polymerizations.Some examples from the author's group involve creating novel materials using controlled seeded emulsion polymerizationfrom natural rubber latex and other polyenes. Latex topology and controlled free-radical chemistry can be combined toproduce a) a comb polymer with hydrophobic backbone and hydrophilic 'teeth', or b) with sufficient in situ compatibilizerbetween two otherwise incompatible polymers to yield a spatially uniform material down to the nanostructure level, and c) toproduce controlled nanostructures.

Effect of stirring on preparation of hollow copolymer particles by alkali/cooling method

Hollow particles were prepared by the treatment of styrene-metbacrylic acid copolymer particles with alkali/cooling method. The influences of stirring position （in aqueous phase or at the interface of O/W） and stirring speed （90, 110 and 240 r/min） on the formation of hollow particles were investigated. It is found that the soft stirring in aqueous phase at 90 r/min leads to the formation of monohollow particles, while the violent stirring at the interface of O/W and 240 r/min gives non-hollow products. In contrast, the weak stirring in aqueous phase at 110 r/min results in sterically heterogeneous dispersion of methacrylic acid-rich regions within the original particles, and hence the formation of multihollow particles. Further investigation indicates that the change of stirring efficiency provides a way to tune the diffusion behavior of monomer styrene, and therefore influences the distribution of methacrylic acid units in the original particles as well as the morphology of the treated particles.

“SERGEANTS AND SOLDIERS RULE” IN HELICAL SUBSTITUTED- ACETYLENE COPOLYMER EMULSIONS

The ＂sergeants and soldiers rule＂ occurring in helical copolymer emulsions derived from an achiral monomer （M1） and a chiral monomer （M2） was observed. TEM, GPC, and 1H-NMR techniques in combination demonstrate the formation of nanoparticles constituted by the copolymers. CD and UV-Vis spectra show the （co）polymer chains in the nanoparticles adopt helical structures of a predominant helicity, and the copolymers follow the ＂sergeants and soldiers rule＂ in forming helical structure.

PREPARATION OF MICRON-SIZED NONSPHERICAL POLYSTYRENE/POLY(STYRENE-co-ETHYLENEGLYCOL DIMETHACRYLATE) PARTICLES BY SEEDED SOAP-FREE EMULSION POLYMERIZATION

Micron-sized nonspherical polymer particles having different morphologies were synthesized by seeded soap-free emulsion polymerization of styrene （St） and ethyleneglycol dimethacrylate （EGDMA, used as a crosslinker） on spherical, linear polystyrene （PS） seed particles. The morphology of the resulting PS/poly（St-co-EGDMA） particles was dependent on the crosslinker concentration and polymerization temperature.

Synthesis of Star Polymeric Ionic Liquids and Use as the Stabilizers for High Internal Phase Emulsions

A series of well-defined core cross-linked star （CCS） polymeric ionic liquids （PILs） were synthesized via a three- step approach. First, the styrenic imidazole-based CCS polymer （S-PVBnIm） was prepared by the RAFT-mediated heterogeneous polymerization in a water/ethanol solution, followed by the quaternization of S-PVBnIm with bromoalkanes and anion exchange. The CCS polymers were characterized by gel permeation chromatography （GPC）, nuclear magnetic resonance （NMR） spectroscopy, Fourier transform infrared spectroscopy （FTIR）, thermal gravimetric analysis （TGA）, and differential scanning calorimetry （DSC）. The obtained CCS polymers were used as the effective emulsifiers for oil-in-water high internal phase emulsions （HIPEs）. Multiple oils with different polarity including n-dodecane, undecanol, toluene and octanol were emulsified using 0.5 wt% S-PVBnIm aqueous solution under the acidic condition to form HIPEs with long-term stabilities. The excellent emulsification properties of CCS PILs were demonstrated by HIPE formation for a variety of oils. The properties of HIPEs in terms of emulsion type and oil droplet size were characterized by the confocal laser scanning microscopy （CLSM）. The intriguing capability of CCS PILs to stabilize HIPEs of various oils holds great potentials for the practical applications.

Double Emulsion Droplets as Microreactors for Synthesis of Magnetic Macroporous Polymer Beads

An easy method is presented to fabricate monodisperse magnetic macroporous polymer beads（MMPBs）. Waterin-oil high internal phase emulsion（HIPE） is prepared by emulsifying aqueous iron ions solution in an oil phase containing monomers. The HIPE is introduced into a simple microfluidic device to fabricate monodisperse（water-in-oil）-in-water double emulsion droplets. The droplets serve as microreactors to synthesize Fe3O4 nanoparticles and are on-line polymerized to form MMPBs. The prepared MMPBs display uniform size, interconnected porous structure, superparamagnetic behavior and uniform distribution of Fe3O4 in polymer matrix. The MMPBs are characterized by scanning electron microscopy（SEM）, Fourier transform infrared spectroscopy（FTIR）, X-ray diffraction（XRD）, transmission electron microscopy（TEM）, vibrating sample magnetometry（VSM）. We believe that this method is a universal technique in preparing macroporous nanocomposite beads.