A study of the properties of hydrophobically associating water-soluble polymers used in drilling fluids

Hydrophobically associating water-soluble polymers (HPAP) have been synthesized from acrylamide(AM), acrylate (AA), 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and hydrophobic monomer (AP) in aqueous solution by radical polymerization. New polymer drilling fluids are made up of HPAP, which is used as viscosifiers and encapsulation agents. Properties of this system are reported in this paper. Results indicate that this system has a high value of yield point to plastic viscosity (YP/PV≥0.7), high viscosity at a low-shear rate (LSRV≥30000mPa·s), excellent shear thinning behavior, good solid-carrying behavior, resistance to shear, good thermal stability (as high as 140℃) and salt resistance. The system has excellent behavior in high-density solution of NaCl and in calcium and magnesium rich saline solutions. Hence, HPAP also can be used in saltwater polymer drilling fluids.

Preparation of Ultrafine Water-soluble Polymers Nanofiber Mats via Electrospinning

A series of water-soluble polymers such as poly（ethylene oxide）（PEO）, polyacrylamide（PAM） and poly（vinyl pyrrilidone）（PVP） was successfully prepared via the electrospinning of their aqueous solutions without the use of a surfactant. The effects of solution properties on the electrospinning of PEO, PAM and PVP solutions were investigated. The viscosity of the solution, charge density carried by the jet, and the surface tension of the solution are the key factors that influence the morphology and diameter size of the fibers. The viscosity of the solution was measured on a modular compact rheometer. The morphology and the diameter size distribution of the fibers were observed under an environmental scanning electron microscope（ESEM）. The results show that the diameters of the nanofibers electro spun from the solutions of these water soluble polymers were uniform and less than 300 nm.

Application of Water-Soluble Polymer in Dewatering of Fine Coal

The addition of water-soluble polymer to a fine coal slurry to enhance dewatering process is considered to be one of the most effective ways of solving the problems of dewatering of fine coal. A series of tests are conducted with a vacuum dewatering apparatus to study the effects of various factors such as the species of polymer, polymer dosage and its ways of addition, and the pH of fine coal slurry on filtrating and dewatering of fine coal.

SCIENTIFIC PRINCIPLES FOR MODIFICATION OF WATER-SOLUBLE POLYMERS. FORMATION OF MACROMOLECULAR COMPLEXES

The study of nanosecond dynamics of macromolecules with the lumines-cent methods make it possible to investigate the formation and functioning of polymericcomplexes, polymeric conjugates and macromolecular metal complexes, which are widelyused for solving many practical tasks. The nanosecond dynamics of macromolecules are ahighly sensitive indicator of interpolymer complexes (IPC) formation. It enables us to solvethe problems of studying IPC formation and stability and to investigate the interpolymerreactions of exchange and substitution. The investigation of changes in the rotational mo-bility of globular protein molecules as a whole makes it possible to determine the complexcomposition and its stability, and to control the course of polymer-protein conjugate forma-tion reaction. The nanosecond dynamics of polymers interacting with surfacants' ions (S)are the sensitive indicator of the S-polymer complex formation. A method for determin-ing the equilibrium constants of the S-polymer complex formation was developed on thebasis of the study of polymer chains mobility. It is established that nanosecond dynamicsinfluences the course of chemical reactions in polymer chains. Moreover, the marked effectof the nanosecond dynamics is also revealed in the study of photophysical processes (theformation of excimers and energy migration of electron excitation) in polymers with pho-toactive groups. It was found that the efficiency of both processes increases with increasingthe mobility of side chains, the carriers of photoactive groups.

XPS Study on Water-Soluble Polymer Surfactant Film

By means of changing the detection angle, the molecular conformation of a new type of polymer surfactant, acrylamide-poly(oxyethykene alkyl ether)acrylate-anionic monomer random copolymer, was studied by x-ray photoelectron spectroscopy(XPS) in detail.

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.

Polymer-based nanoparticulate solid dispersions prepared by a modified electrospraying process

A modified electrospraying process is exploited to enhance the dissolution profiles of a poorly water-soluble drug. With polyvinylpyrrolidone (PVP) as a hydrophilic polymer matrix and ketoprofen (KET) as a model drug, polymer-drug composites in the form of nanoparticles were prepared and characterized. The surface morphologies, the physical status of the drug, and the drug-polymer interactions were studied using FESEM, DSC, XRD, and ATR-FTIR. FESEM observations demonstrated that the nanoparticles gradually decreased in size from 640 ± 350, to 530 ± 320, 460 ± 200 and 320 ± 160 nm as the KET content increased from 0, to 9.1%, 16.7% and 33.3% w/w, respectively. Results from DSC and XRD suggested that KET was distributed in the PVP matrix in an amorphous manner at the molecular level. This is thought to be due to their compatibility, arising through hydrogen bonding as demonstrated by ATR- FTIR spectra. In vitro dissolution tests showed that the nanoparticles released the incorporated KET within 1 min, evidencing markedly improved dissolution over pure KET and a KET-PVP physical mixture. Electrospraying can hence offer a facile route to develop new polymer composites for biomedical applications, in particular for improving dissolution rate of poorly water-soluble drugs.

STUDY ON HIGH PERFORMANCE ANTI—WEAR ADDITIVES FROM WATER—SOLUBLE POLYMERIC LUBRICANT

A series of high performance lubricants of water-soluble polymers with telechelic or star structures has been studied. Their average molecular weights (M) over bar are 1800-6000. The chemical structures of the lubricants are characterized by their hydrophilic groups (-CH2CH2O-), -COOH, -OH, -CONH2 and antiwear active elements (S,P,Zn and Mo). The results of assessing for the anti-wear property indicate that this kind of water-soluble polymeric lubricants possesses excellent watersolubility, lubricity and anti-wear property. A preliminary study on the anti-wear mechanism of the polymers is performed by means of electron probe and scanning electron microscopy (SEM).

STUDIES ON THE POLYMERIZATION OF β-CYCLODEXTRIN WITH EPICHLOROHYDRIN

Different proportions of β-cydodextrin and epichlorohydrin were used to prepare a group of β-cyclodextrin polymers. The relationship between the reaction extent and the molar ratios of reactants was discussed according to the results of ~1H-NMR, ^(13) C-NMR spectra and elemental analysis. Especially, high resolution ~1H-NMR spectra were usd for studying the reaction active sites and the extent of reaction. The solubility of oil soluble drugs in water was largely improved in the presence of water-soluble β-cyclodextrin polymer.

Polymer Coatings for Protection of Wood and Wood-Based Materials

Three major types of protective coating of wood and wood-based materials have been considered. These three types include the coatings based on carboxyl-containing water-soluble polymers which are easily cross-linked by inorganic salts or OH-containing compounds, pH-sensitive coatings and polymer multi-layer structures. First of three mentioned approaches allows affecting permeability and enhancing the prevention the loss of water from the surface of wood to its surrounding. The advantage of the second approach is its ability to vary and purposely adjust the polymer composition and the number and distribution of -COOH groups in the chain which make the originally water-soluble polymers completely insoluble. The strong feature of the third approach which includes broad use of hydrogen-bonded films produced by layer-by-layer self-assembly is the possibility of manipulation of coatings stability after construction.

ASSOCIATION BEHAVIOR OF PORPHYRIN PENDANTS IN pH-SENSITIVE WATER-SOLUBLE POLYMER

A novel tripyridylporphyrin monomer,5-[4-[2-（acryloyloxy）ethoxy]phenyl]-10,15,20-tris（4-pyridyl）porphyrin （TrPyP）,was synthesized and polymerized with acrylamide（AM） to prepare the hydrophobically associating water-soluble polymer PAM-TrPyP.The aggregation behavior of porphyrin pendants was investigated by UV-Visible and fluorescence spectra.The polymer displays a strong tendency of hydrophobic association even in dilute solutions.With increasing the concentration,the maximum absorption wavelength of Soret band changes from 416 nm to 407 nm,and the fluorescence corrected for the inner filter effect exhibits moderate concentration quenching.All the results indicate thatπ-πinteraction of porphyrin pendants plays a key role in association of PAM-TrPyP,and H-aggregates of porphyrins are mainly formed in the concentrated solution.On the other hand,dynamic light scattering（DLS） and transmission electron microscopy（TEM） were used to follow the changes in size and structure of the macromolecular assemblies with the concentration increase.The polymer aggregation conformation changes from loose ＂vesicle-like＂ morphology to solid globule accordingly.When pH value of solution decreases to 4.3,pyridine moieties on porphyrin pendants could be protonated and the H-aggregates formed in macromolecular matrix are destroyed by electrostatic repulsion interactions.

Application of amphoteric polymers in the process of leather post-tanning

With the characteristics of controllable charge and environmental friendliness,amphoteric polymers can be used in post-tanning process to solve the problems that arise during leather making and are caused by the low absorption rate of single-charge chemicals,incompatibility with new tanning methods,and complex operation process.In this review,the structure,performance,and preparation of amphoteric polymers are reported.Then,the charge change of collagen during different tanning and pH treatments is introduced.Finally,the application and development of amphoteric polymers during the post-tanning process of leather making are discussed.This review has certain guiding significance to the preparation and application of amphoteric polymers for tanning system.

Alcohol/water-soluble porphyrins as cathode interlayers in high-performance polymer solar cells

Three alcohol/water-soluble porphyrins, Zn-TPyPMeI： zinc（II） meso-tetra（N-methyl-4-pyridyl） porphyrin tetra-iodide, Zn- TPyPAdBr： zinc（II） meso-tetra[1-（1-adamantylmethyl ketone）-4-pyridyl] porphyrin tetra-bromide and MnC1-TPyPAdBr： man- ganese（III） meso-tetra[1-（1-adamantylmethyl ketone）-4-pyridyl] porphyrin tetra-bromide were employed as cathode interlayers to fabricate polymer solar cells （PSCs）. The PCvaBM （[6,6]-phenyl C71 butyric acid methyl ester） and PCDTBT （poly[N-9＂- hepta-decanyl-2,7-carbazole-alt-5,5-（4＇,7＇-di-2-thienyl-2＇,3＇-benzothiadiazole）]）-blend films were used as active layers in polymer solar cells （PSCs）. The PSCs with alcohol/water-soluble porphyrins interlayer showed obviously higher power con- version efficiency （PCE） than those without interlayers. The highest PCE, 6.86%, was achieved for the device with MnCl- TPyPAdBr as an interlayer. Ultraviolet photoemission spectroscopic （UPS）, carrier mobility, atomic force microscopy （AFM） and contact angle （0） characterizations demonstrated that the porphyrin molecules can result in the formation of interfacial dipole layer between active layer and cathode. The interfacial dipole layer can obviously improve the open-circuit voltage （Voc） and charge extraction, and sequentially lead to the increase of PCE.

Effect of cationic monomer structure on the aggregation behavior of amphoteric acrylic polymer around isoelectric point

Amphoteric polymer can be used as retanning agent in leather manufacture. It is particularly useful in chrome-free tanning systems since it can regulate the charge properties of chrome-free leather and enhance the fixation of anionic post-tanning chemicals in leather. However, the aggregation and precipitation of amphoteric polymer retanning agents around the isoelectric point (pI) hinder their wide application. Herein, we synthesized five amphoteric acrylic polymers (AAPs) by free radical copolymerization with acrylic acid and five different cationic acrylic monomers. The effect of cationic monomer structure on the aggregation behavior of AAPs was investigated. The aggregation of AAPs in aqueous solution showed pH and concentration dependence. Light scattering analysis showed that Poly (AA-co-MAPTAC) and Poly (AA-co-DMAPMA) were in the shape of coiled linear flexible chains with small particle size (Rg 7.6 nm and 14.8 nm, respectively) near the pI. However, Poly (AA-co-DAC), Poly (AA-co-DMC) and Poly (AA-co- DMAEMA) were in the shape of hollow spheres and exhibited serious aggregation. Quantum chemical calculations suggested that the amide groups in the cationic monomers MAPTAC and DMAPMA enhanced the nucleophilicity of AAPs. Thus the corresponding AAPs could carry a large number of cationic charges to slow their aggregation when the pH just climbed over the pI. The results are expected to provide theoretical reference for the synthesis and widespread application of AAPs.

A Water-soluble Conjugated Polymer for Thiol Detection Based on ＂Tu rn-off＂ Effect

We investigated a novel water-soluble conjugated polymer （WSCP） for thiol detection based on ＂turn-off＂ ef- fect. This WSCP was modified with poly（ethylene glycol） （PEG） by disulfide linkages to achieve good solubility in aqueous solution （34 mg/mL） and high quantum yield （0.47）. The separation of water-soluble PEG chains from the conjugated backbone induced by the cleavage of the disulfide linkages would lead to a significant decrease of the water solubility and a dramatical fluorescence quenching of the probe. The combined intuitive images and fluores- cence spectrophotometer further confirmed that decreased solubility produced an aggregation of the hydrophobic conjugated backbone. The fluorescence intensity of the probe showed a good linear relationship with glutathione （GSH） （1-200 nmol·L^-1）, and the detection limit was 16 nmol·L^-1. This WSCP probe was confirmed to be a good sensing material with high selectivity to thiols by testing various biological molecules. And this WSCP probe ex- hibited good detection effect to intracellular thiols by testing Hela cells. Considering the good sensitivity and selec- tivity, the probe could be further used in vivo. In conclusion, this conjugated polymer probe made up for the draw- backs of the micromolecue probes and contributed to the development of new probes based on conjugated poly- mers.

Water-soluble crosslinked β-cyclodextrin polymer inclusion complexes with C60

At present, using cyclodextrins or cyclodextrin derivatives with suitable internal annular dimension to embed C60 so as to form inclusion complexes has been one of the main ways to improve C60＇s water-solubility. In three kinds of cyclodextrins (α-, β-, γ-CD), only γ-CD has cavity large enough to include C60 whereas α-, and β-CD have not. In the case of DMβCD, the "out-stretching" methyl groups enlarge the cavity so that it can include C60. Starting from the same thought, we use epichlorohydrin crosslinked

Effect of cationic monomer structure on the aggregation behavior of amphoteric acrylic polymer around isoelectric point

Amphoteric polymer can be used as retanning agent in leather manufacture.It is particularly useful in chrome-free tanning systems since it can regulate the charge properties of chrome-free leather and enhance the fixation of anionic post-tanning chemicals in leather.However,the aggregation and precipitation of amphoteric polymer retanning agents around the isoelectric point(pl)hinder their wide application.Herein,we synthesized five amphoteric acrylic polymers(AAPs)by free radical copolymerization with acrylic acid and five different cationic acrylic monomers.The effect of cationic monomer structure on the aggregation behavior of AAPs was investigated.The aggregation of AAPs in aqueous solution showed pH and concentration dependence.Light scattering analysis showed that Poly(AAA-co-MAPTAC)and Poly(AA-co-DMAPMA)were in the shape of coiled linear flexible chains with small particle size(R_(g)7.6 nm and 14.8 nm,respectively)near the pl.However,Poly(AA-co-DAC),Poly(AA-co-DMC)and Poly(AA-co-DMAEMA)were in the shape of hollow spheres and exhibited serious aggregation.Quantum chemical calculations suggested that the amide groups in the cationic monomers MAPTAC and DMAPMA enhanced the nucleophilicity of AAPs.Thus the corresponding AAPs could carry a large number of cationic charges to slow their aggregation when the pH just climbed over the pl.The results are expected to provide theoretical reference for the synthesis and wide-spread application of AAPs.

新型两性离子粘土稳定剂的制备及其性能研究

以丙烯酰胺(AM)、二甲基二烯丙基氯化铵(DMDAAC)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和N-乙烯基吡咯烷酮(NVP)为反应单体,以过硫酸胺、亚硫酸氢钠为引发剂,制备了一种新型的两性离子粘土稳定剂,并采用红外光谱对其结构进行了表征。结果表明,在40℃下,当引发剂加量为0.55%,AM∶AMPS∶DMDAAC∶NVP物质的量比为160∶20∶13∶2,反应时间为3 h时,所制备的四元共聚物AM/AMPS/DMDAAC/NVP防膨率可达90.74%,具有良好的耐温耐盐性及耐酸碱性能,可以有效防止粘土水化膨胀、分散运移,有利于降低采油成本,在油气田领域具有良好的应用潜力。

耐温耐盐两性聚丙烯酰胺稠化剂的制备及其性能

为了提高压裂液稠化剂的耐温耐盐性能,以丙烯酰胺(AM)、丙烯酸(AA)、阴离子单体2-丙烯酰胺-2-甲基丙磺酸(AMPS)和阳离子单体丙烯酰氧乙基三甲基氯化铵(DAC)为单体,单体AM、AA、AMPS、DAC质量比为9∶1∶3∶1.5,将单体以总质量分数为30%溶于水中(水相),将质量分数为10%的乳化剂(Span-80、Tween-80质量比为9∶1)溶于白油(油相),油水相比为1∶2.5,合成了具有耐温耐盐性的油包水乳液稠化剂PAAD,其黏均相对分子质量为383×10^(4)。通过红外光谱和核磁共振氢谱表征了PAAD,测定了聚合物PAAD的耐温性、抗盐性、耐剪切和破胶性能。研究结果表明,PAAD具有良好的耐温抗剪切性能,在90℃、剪切速率为170 s^(-1)下,质量分数为1.5%的PAAD聚合物溶液剪切1.5 h后黏度保持在51.7 mPa·s。PAAD溶液在高剪切后进入低剪切区后可快速恢复黏度,可保障悬砂不沉降。PAAD具有良好的抗盐性,在矿化度为50 g/L的模拟高盐海水中,质量分数为1.5%的PAAD聚合物溶液的黏度为45 m Pa·s。在90℃下,破胶剂用量为0.2%时,质量分数为1.5%的PAAD聚合物溶液在3 h内可完成破胶,破胶液的表面张力为30 mN/m,油水界面张力为1.9 mN/m,残渣含量为220 mg/L,对岩心基质的伤害性为9%,达到行业标准要求。