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.

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.

Synthesis of Novel Polymer-Bonded Water-Soluble Metal Porphyrins

The reaction of 5, 10, 15, 20-tetra-(4-pyridyl) porphyrin 1 with triruthenium dodecacarbonyl [Ru3(CO)12], zinc(II) acetate, copper(II) acetate, cobalt(II) acetate afforded complexes 2a?2d respectively. Treatment of 2a?2d with Merrifield’s peptide resin obtained 3a?3d. The compounds 3a?3d reacted with methyl iodide respectively gave 4a?4d. New complexes 4a?4d have been identified by IR, UV-visible spectra, and AES.

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.

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).

PREPARATION AND PHOTOSENSITIVITY OF WATER SOLUBLE PHENOLIC RESINS CONTAINING ACRYLOYL AND QUATERNARY AMMONIUM CHLORIDE GROUPS

New water soluble and photocrosslinkable prepolymers containing acrylate and quaternary ammonium salt groups were synthesized from epoxy phenolic resin via ring-opening reaction with acrylic acid and with aqueous solution of triethylamine hydrochloride successively. The second reaction needs no phase transfer catalyst to accelerate, since the product formed can act as a phase transfer catalyst. The prepolymer obtained contains both photocrosslinkable acrylate groups and hydrophilic quaternary ammonium salt groups. Optimum conditions for these reactions were studied. The photosensitivity of the prepolymer was also investigated. The effects of different photoinitiators, different crosslinkable diluent monomers and amine accelerator on the photosensitivity of the prepolymer were compared. The photoinitiator of hydrogen abstraction type is still effective without using amine or alcohol as accelerator, because the prepolymer contains a H beside the OH groups formed in the ring-opening reactions.

Change of Water-Soluble-Protein, Urea-Soluble-Protein and Membrane Intrinsic Protein in Human Senile Cataract

Purpose:To analyze the change of water-soluble-protein(WSP),urea-soluble-protein(USP)and membrane intrinsic protein(MIP)in human senile catarct.Methods:The water-soluble-fractions(WSF)were prepared basically according to the method of Kibbelear,et al.But in this study,5mmol/LB-mercaptoethanol was added to the buffer solution.The urea-soluble-fractions(USF)were pre-pared basically according to the method of Kibbelear,et al.Lens fiber cell mem-branes were purified basically according to the method of Russell,et al.SDS-PAGE were performed according to the procedure of Laemmili,et al.using re-solving gel13%and3%stacking gel.Results:The WSPwas fractionated intoHM^+α^-,β1-3^-andγ-crystallin compo-nents.In nuclear cataractous lenses HM^+α^-and B-crystallin increase,while r-crystallin decrease.The USP from clear lenses contains mainlyαβchains of22KD,whereas in cataractous lenses,especially in nuclear cataractous lenses,the relative amount of the 28-and23KDpolypeptide(the components of β-crys-tallin)increased markedly.Lens fiber cell MIP,clear lens and cataract lens con-tained the main polypeptide of 27KD(MIP)and23KD(MP23).Conclusion:The water-insolube protein,whether in quantity or in quality,plays an important role in cataract formation.Eye Science 1995,11:124-127.

Water-dispersible and soluble porous organic polymers for biomedical applications

Porous organic polymers(POPs)have become an emerging class of advanced porous organic materials owing to their structural diversity and tailored functions in solid state and organic media.Creating water-soluble and related water-dispersible POPs is still very challenging in the research area of porous organic materials.Their porosity-based functions with diverse topological architectures in aqueous media offer promising platforms in bio-related fields.This review highlights recent progress on water soluble or dispersible POPs for biomedical applications including bioimaging and biosensing,nanocarriers for drug delivery and tumor targeting,phototherapeutics,protein and gene delivery,biomacromolecule encapsulation and discrimination,and anti-microbial activity.

WSP聚合物混凝土力学性能试验研究

在相同工作条件下,通过试验研究了新一代水溶性高分子聚合物(WSP)混凝土与普通混凝土、掺加聚羧酸高效减水剂的混凝土以及掺加聚丙烯纤维的混凝土的立方体抗压强度、轴心抗压强度、轴心抗拉强度、劈拉强度、弯曲抗拉强度、弹性模量等。结果表明:WSP具有高效减水作用;WSP聚合物改性混凝土在保证抗压强度的同时,抗折强度有所提高,其综合力学性能良好,大大改善了混凝土的脆性特征;SEM照片分析显示,将WSP加入混凝土基体后,在早期生成纤维状物质,能够从根本上对混凝土进行改性。

基于油藏化学驱能耗分配原理的理想流度控制型驱油剂研究Ⅰ:聚/表二元复合驱油体系的渗流阻力调控机理及应用

针对驱油剂的深部流度控制能力与近井地带注入性之间的矛盾,提出了理想流度控制型驱油剂应满足低黏度配制/输送、近井地带低吸附量长期稳定注入和低浓度产出液的技术要求,同时,在渗流过程中能够在储层深部不同位置建立多级渗流阻力峰值,并且前缘后驱替相渗流阻力应始终保持在较低水平。基于固/液界面吸附作用与分子间相互作用的协同效应,设计了在渗流过程中具备动态改变体系组成和微观溶液结构,从而改变其渗流阻力特征的疏水缔合聚合物/阴离子型表面活性剂二元体系。相较于HP-1(1500 mg/L),表观黏度相近、组成不同的二元体系HP-1(1500 mg/L)/SDSB(150 mg/L)和HP-1(1500 mg/L)/SDSB(200 mg/L),在段塞注入及其后续水驱过程中可以在多孔介质的中、后部构建数值更高、空间分布更优的动态渗流阻力,说明二元体系具备运移增黏特征和延迟突破特征,其前缘的流度控制能力更强,并且渗流阻力在储层的空间分布更合理,从而延长了段塞整体突破时间,有利于提高波及体积和驱油效率。在相对稠油、强非均质性和水驱含水率为80%的渤海某油田油藏条件下,采用基本相同剂量、相近成本的化学剂工业产品进行的驱油实验表明:二元体系后续水驱突破之前驱油剂段塞渗流阻力的空间动态分布特征是影响驱油效率的关键因素,二元体系(AP-P4(1400 mg/L)/ZX-27(300 mg/L),黏度为6.4 mPa·s)比疏水缔合聚合物AP-P4(1750 mg/L,黏度为62.9 mPa·s)多提高10%的原油采收率。

ArF浸没式光刻胶用抗水涂层研究进展

氟化氩(ArF)浸没式光刻需在光刻胶表面形成抗水涂层,阻挡光刻胶和水之间组分交换。抗水涂层对光刻胶的分辨率、工艺窗口、低缺陷要求起着重要作用,平衡抗水涂层的疏水性和碱溶性是设计聚合物结构的重点和难点。分析了形成抗水涂层的方法和成膜机理,对比了不同方法的优缺点,根据聚合物所含官能团及其碱溶性,对抗水涂层聚合物进行了分类总结,重点阐述抗水涂层聚合物的结构和性能要求,尤其关注了聚合物侧链的位阻效应和氢键作用对涂层的疏水性影响。最后对抗水涂层的应用和发展进行了展望。

A SYNTHETIC APPROACH FOR WATER SOLUBLE HYPERBRANCHED POLY(N,N-ETHYLIDENEBIS(N-2-CHLOROACETYL ACRYLAMIDE)) WITH HIGH DEGREE OF BRANCHING VIA ATOM TRANSFER RADICAL POLYMERIZATION/SELF-CONDENSING VINYL POLYMERIZATION

A novel acrylamide A2B2＊ （A = alkene, B＊ = alkyl chlorine） type inimer was obtained from commercially available 1,2-ethylenediamine, chloroacetyl chloride and acryloyl chloride. The as-prepared monomer can form water-soluble hyperbranched poly（N,N-ethylidene bis（N-2-chloroacetyl acrylamide））s （HPECA） through atom transfer radical polymerization/self-condensing vinyl polymerization method in the presence alkyl chlorine/CuCl/2,2-bipyridine activation system which can effectively suppress the gelation formation.1H-NMR spectra and dual detector size exclusion chromatography proved the hyperbranched structure indisputably, and the degree of branching was determined by the detailed analyses of 1H-NMR spectra. The trend of the degree of branching was in consistent with the result of Mark- Houwink exponent a. The experiment results suggested that the conversion was 67%, Mw = 13.2 x 104, Mark-Houwink a = 0.282 and the degree of branching = 64% when the reaction temperature was 120 ℃, reaction time = 168 h and N,N- ethylidene bis（N-2-chloroacetyl acrylamide）：Cu（I） = 50：0.62.

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.

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.

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 Amino Grafted Silicon Nanoparticles and Their Use in Polymer Solar Cells

Stable aqueous amino-grafted silicon nanoparticles （SiNPs-NH2） were prepared via one-pot solution method. By grafting amino groups on the particle surface, the dispersion of SiNPs in water became very stable and clear aqueous solutions could be obtained. By incorporating SiNPs-NH2 into the hole transport layer of poly（3,4- ethylenedioxythiophene）/polystyrene sulfonic acid （PEDOT＇PSS）, the performance of polymer solar cells composed of poly[2-methoxy,5-（2＇-ethylhexyloxy）-1,4-phenylene vinylene] （MEH-PPV）：[6,6]-phenyl-C61-butyric acid methyl ester （PCBM） as active layer can be improved. SiNPs-NH2 are dispersed uniformly in the PEDOT：PSS solution and help form morphologies with small-sized domains in the PEDOT：PSS film. SiNPs-NH2 serve as screens between conducting polymer PEDOT and ionomer PSS to improve the phase separation and charge transport of the hole transport layer. As a result, the sheet resistance of PEDOT：PSS thin films is decreased from （93 ±5） × 10^5 to （13 ± 3） × 10^5 Ω/□. The power conversion efficiency （PCE） of polymer solar cells was thus improved by 9.8% for devices fabricated with PEDOT＇PSS containing 1 wt% of SiNPs-NH2, compared with the devices fabricated by original PEDOT：PSS.

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.

纤维-水溶性聚合物加固砂土抗剪强度特性试验研究

为了解纤维-水溶性聚合物的抗剪强度和砂土的破坏机理,通过一系列直剪试验和数值模拟,研究了不同水溶性聚合物含量和纤维含量条件下加固砂土的剪切强度特性,分析了加固砂土的抗剪强度特性及其参数变化和破坏特征。试验结果表明:加固砂土的抗剪强度特性随水溶性聚合物含量和纤维含量的增大而显著提高;水溶性聚合物和纤维的掺入提升了加固砂土的黏聚力,但对内摩擦角的影响较小;当纤维含量为0.8%时,水溶性聚合物含量从1%增大至4%,加固砂土的抗剪强度增强了55.58 kPa;当水溶性聚合物含量为4%时,纤维含量从0.2%增大至0.8%时,黏聚力增加了32.69 kPa。聚合物和纤维含量的增大促进了复合砂土各组分之间的联合,增强了加固砂土的整体性,提升了土体的稳定性。