Synthesis and Performance Evaluation of Temperature-controlled Viscous Acid

A temperature-controlled viscous acid thickener was obtained by copolymerizing acrylamide, 2-acrylamido-2-methylpropane sulfonic acid, diallyl dimethyl ammonium chloride, and N-vinyl-2-pyrrolidinone, four monomers by aqueous solution polymerization, the mass ratio of the four monomers was 6: 2: 1: 1, the reaction temperature was 45°C and the reaction time was 6 h. The total mass concentration of the monomer was 25% and the oxidation-reduction system of ammonium persulphate and sodium hydrogen sulfite (mass ratio 1: 1) was used as the initiator, the amount was 0.9% of the total mass of the monomer, and the pH of the reaction solution was 6–8. Selecting glutaric dialdehyde and zirconium(IV) acetylacetonate as cross-linking agents, and compounding the synthesized quaternary copolymer after the mass ratio of the two reagents was 1: 1 to achieve acid temperature control viscous properties, were carried out. At 90°C, the quadripolymer and the cross-linking agent were mixed at a mass ratio of 5: 3, and then cross-linked at 60, 80, and 90°C, respectively, as time increased. The apparent viscosity increased sharply, and the apparent viscosity reached a maximum after 20, 15, and 10 min, and the maximum values were 680, 690, and 750 mPa s, respectively. The reaction of marble with thickening acid (20% hydrochloric acid + 1% thickener) and temperature-controlled viscous acid (20% hydrochloric acid + 1% thickener + 0.6 cross-linking agent) was performed at 90°C. The mass loss of marble was 58 and 42% of that of 20% pure hydrochloric acid, respectively. The performance evaluation results show that the temperature-controlled viscous acid has a good compatibility, and the retarding performance is greatly improved compared with the conventional thickened acid. It has good cross-linking and gel breaking performance under high temperature conditions and is suitable for high temperature formations with temperatures above 90°C. Between its excellent compatibility, it can be selected according to the corresponding formation conditions and construction purposes, and other types of acid working fluid or oilfield additives can be used together to achieve better construction results.

     

弱凝胶钻井液成胶剂AM/AMPS/OA_8的合成与表征

针对水平井、大斜度井钻井过程中井眼润滑性、岩屑携带以及钻井速度的影响等问题,通过合理的分子设计,以丙烯酰胺(AM)、2-丙烯酰胺-2-甲基丙磺酸(AMPS)和实验室自制疏水单体丙烯酸正辛醇OA_8为原料,利用胶束聚合法,制备了一种弱凝胶成胶剂AMAMPSOA_8,其结构经1H NMR和IR表征。以AMAMPSOA_8在低剪切速率下的表观粘度为指标设计正交试验,确定最优反应条件为:AM与AMPS摩尔配比为4.8∶1,引发剂用量为单体总质量的0.04%,疏水单体浓度为0.75%,于70℃反应9 h。该条件下,0.5%AMAMPS0A_8聚合物溶液在低剪切速率3 r·min~(-1)下表观粘度可达23 680 mPa·s。利用热分析仪、高温滚子炉、高温高压流变仪对产物性能进行了研究。研究表明:AMAMPSOA_8的抗温性能可达160℃;聚合物溶液体系有明显的触变性,在40 min后溶液切力增加幅度变缓。     

离子液体中AM/AMPS/N8AM三元共聚物的合成及溶液性能

以丙烯酰胺(AM)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为亲水单体, 以N-辛基丙烯酰胺(N8AM)为疏水单体, 在离子液体[bmim]BF4中实现了疏水缔合丙烯酰胺三元共聚物的合成.     

Contribution of monomer functionality and additives to polymerization kinetics and liquid crystal phase separation in acrylate-based polymer-dispersed liquid crystals (PDLCs)

Fundamental control of the polymerization behaviour of polymer-dispersed liquid crystals (PDLCs) is critical to the formation of high-performance devices by polymer-induced phase separation (PIPS). Previous PDLC research has shown that monomer functionality and additives such as surfactants or reactive diluents can impart significant changes to the electro-optical behaviour of a system, especially in acrylate-based materials. The influence of monomer functionality and additives on the polymerization kinetics and LC phase separation were examined in the formation of acrylate-based PDLCs. Real-time infrared (RTIR) spectroscopy was utilized to simultaneously monitor polymerization rate, double bond conversion and LC phase separation. In the formation of PDLCs by PIPS, increasing acrylate monomer functionality reduces the polymerization rate, overall double bond conversion and the extent of LC phase separation. Interestingly, the additives octanoic acid and N-vinylpyrrolidone (NVP) increase the polymerization rate but suppress LC phase separation. During PDLC formation, both octanoic acid and NVP enhance the solubility of the LC in the growing polymer matrix, reducing the rate of liquid-gel demixing and decreasing nematic fraction in PDLCs. As a non-reactive component, octanoic acid increases the polymerization rate by plasticizing the crosslinked polymerization. NVP, a reactive diluent added to decrease viscosity, increases polymerization rate through favourable copolymerization with acrylate monomer.     

SYNTHESIS AND CHARACTERIZATION OF WATER-SOLUBLE BLOCK COPOLYMERS WITH AN END-TAGGED NAPHTHALENE PROBE

Water-soluble A-B block copolymers of 2-perfluoroethyl-2-oxazoline or 2-pentyl-2-oxazoline as hydrophobic monomers and 2-methyl-2-oxazoline as hydrophilic monomer were prepared by means of the living cationic ring-opening polymerization. The polymerization was initiated with N-methyl-2-(1-naphthyl)-2-oxazolinium trifluoromethanesulfonate as fluorescence label followed by sequential addition of the hydrophobic and the hydrophilic monomer. The polymerization was monitored by ¹H NMR spectroscopy and gel permeation chromatography (GPC) measurements. The results revealed that fluorophilic block copolymers can be prepared by this method while lipohilic block copolymers are not accessible by this monomer sequence. Micelle formation of the fluorophilic block copolymers in aqueous solution was studied by means of steady-state fluorescence spectroscopy which confirmed strong intermolecular excimer formation of the terminal bounded naphthalene moiety. In chloroform as a good solvent for both blocks, only monomer fluorescence could be observed.     

Formation of inhomogeneities in polyacrylamide gel in the course of frontal polymerization

The deformation of gas bubbles in the course of photoinduced polymerization of polyacrylamide gel in monomer solution under microgravity conditions has been studied experimentally. The use of optical methods allows one to identify the specific features of changes in the shape of gas bubbles and to correlate these changes with different stages of polymerization. At the initial stage of the polymerization reaction, the development of gel inhomogeneities is caused by reflection and scattering of the initiating light and, correspondingly, by different rates of gel formation near the surface of a gas bubble. After its contact with the polymerization front, further deformation of the bubble is caused by the inhomogeneous development of the reaction in the formed gel. Using the interference method, the characteristic dimensions of structural inhomogeneities in the formed gel induced in the vicinity of the transparent inclusion are measured.     

Self-assembly of hydrophobic associating polyacrylamide prepared by aqueous dispersion polymerization

Abstract

Hydrophobic associating polyacrylamide (PDH) was prepared via aqueous dispersion polymerization in the presence of ammonium sulfate. In order to dissolve the polymer at high salt solution concentration, a hydrophobic precursor monomer with two cationic heads was synthesized. Upon polymerization, spherical PDH polymer particles were obtained with an average size of about 9.1?µm. The PDH was fully dispersed in water in twenty seconds, leading to a transparent gel. PDH demonstrated superior properties compared to the partially hydrolyzed polyacrylamide, for instance, regarding salt tolerance and shear resistance. Addition of a small amount of an anionic surfactant significantly affected the PDH dispersion viscosity due to the formation of mixed micelles. The viscosity slightly decreased after strong shearing (>500?s^?1), showing excellent shear resistance. These features indicate that the synthesized PDH offers a great potential for application in hydraulic fracturing and enhanced oil recovery.     

Degradation of Poly(2-hydroxyethyl methacrylate) Obtained by Radiation in Aqueous Solution

The degradation of poly(hydroxyethyl methacrylate), PHEMA obtained by γ -radiation induced polymerization of HEMA in aqueous solution, was studied. The polymer was a gel type and insoluble in common organic solvents. The DSC thermogram of the polymer gave a Tg value at 88.2°C and an endothermic peak showed further polymerization or crosslinking at 110–160°C. The degradation observed in TGA was a depolymerization type. However, the FT-IR of TGA fragments showed no monomer, which was degraded further. The degradation of monomer was studied by the GC-MS method. Similar results were also observed.     

Polymerization of micelles under irradiation with UV light

Micelle formation behavior of sodium salts of fatty acids containing double bond at the chain end, sodium 10-undecenoate (Na-10-U) and sodium 8-nonenoate (Na-8-N), was examined with measurement of electric conductivity of their aqueous solutions, and the plot of the electric conductivity against the concentration for each fatty acid was found to show two break points; at 0,044 and 0,12mol/1 for Na-10-U and at 0,16 and 0,44 mol/1 for Na-8-N. The similar behaviors of the aqueous solutions were also found with the measurements of the maximum amount of solubilized benzene into the aqueous solution and of the solution viscosity, and the concentrations corresponding to the break points were assumed to be first and second critical micelle concentrations (CMC's), respectively. Polymerization of the sodium salts under irradiation with UV light was investigated. For each fatty acid, the amount of the obtained polymer was very small at very low concentrations of the fatty acid, but it increased rapidly with increasing concentration of the monomer at concentrations higher than the first CMC and then mildly at the concentrations higher than the second CMC. Number-average degrees of polymerization of the polymers obtained were measured with a gel permeation chromatography technique and found to be up to 13 for Na-10-U and 8,5 for Na-8-N.     

Switchable supramolecular polymers from the self-assembly of a small monomer with two orthogonal binding interactions

The low molecular weight heteroditopic monomer 1 forms supramolecular polymers in polar solution as shown, for example, by infrared laser-based dynamic light scattering (DLS), small-angle neutron scattering (SANS), electron microscopy (TEM, cryo-TEM), and viscosity measurements. Self-assembly of 1 is based on two orthogonal binding interactions, the formation of a Fe(II)-terpyridine 1:2 metal-ligand complex and the dimerization of a self-complementary guanidiniocarbonyl pyrrole carboxylate zwitterion. Both binding interactions have a sufficient stability in polar (DMSO) and even aqueous solutions to ensure formation of linear polymers of considerable length (up to 100 nm). The supramolecular polymerization follows a ring-chain mechanism causing a significant increase in the viscosity of the solutions at millimolar concentrations and above. The linear polymers then further aggregate in solution into larger globular aggregates with a densely packed core and a loose shell. Both binding interactions can be furthermore switched on and off either by adding a competing ligand to remove the metal ion and subsequent readdition of Fe(II) or by reversible protonation and deprotonation of the zwitterion upon addition of acid or base. The self-assembly of 1 can therefore be switched back and forth between four different states, the monomer, a metal-complexed dimer or an ion paired dimer, and finally the polymer.     

丙烯酰胺双水相聚合体系稳定性研究

通过浊点滴定法测定了不同温度下PAAmPEGH2O双水相体系相图,发现分相浓度随着温度的升高先增后降,55℃时分相浓度最低.双水相聚合体系微观结构显示,分散相以砾状液滴形式均匀分散在连续相中.研究了聚合过程中聚合体系粘度的变化,以及聚合温度、分散介质、单体、引发剂及乳化剂等对聚合体系最终粘度的影响,聚合体系最终粘度在一定范围内随分散介质和单体浓度增加变化不大,但是超过某一浓度后聚合体系粘度急剧增加;聚合体系中加入少量乳化剂对体系粘度影响不大,但加入大量乳化剂后体系稳定性变差,聚合体系粘度急剧增加;聚合体系最终粘度随着聚合温度升高先降后增,与相图的预测结果一致.     

Cyclopolycondensation. XII. Polymerization mechanism of polybenzoxazinones in polyphosphoric acid medium

The polymerization mechanism of polyphosphoric acid (PPA) solution polymerization of an aromatic diaminodicarboxylic acid with aromatic dicarboxylic acid derivatives was studied. By means of NMR methods, the initiation process for the polymerization of polybenzoxazinone in PPA medium was elucidated. The NMR spectra of a series of compounds were taken, and the salt formation of amino groups of monomer with PPA and the equilibrium between the salt and the free amino group were determined. It was established that the polymerization proceeded through the formation of phosphorylated intermediates to give the salt of amino groups of monomer with PPA. In the second step, the amine–PPA salt dissociates into the free amino group and PPA at the polymerization temperature above 140°C. Polymerization proceeds through the attack of “free” amino on phosphorylated carbonyl compounds to form polyamide acid of high molecular weight, and on subsequently being heated in PPA at higher temperatures, it undergoes an intramolecular cyclodehydration along the polymer chain to form polybenzoxazinones.     

Facile synthesis and characterization of hyperbranched poly(ether amide)s generated from Michael addition polymerization of in situ created AB2 monomers

A new straightforward strategy for synthesis of novel hyperbranched poly (ether amide)s from readily available monomers has been developed. By optimizing the reaction conditions, the AB₂‐type monomers were formed dominantly during the initial reaction stage. Without any purification, the AB₂ intermediate was subjected to further polymerization in the presence (or absence) of an initiator, to prepare the hyperbranched polymer‐bearing multihydroxyl end‐groups. The influence of monomer, initiator, and solvent on polymerization and the molecular weight (MW) of the resultant polymers was studied thoroughly. The MALDI–TOF MS of the polymers indicated that the polymerization proceeded in the proposed way. Analyses of ¹H NMR and ¹³C NMR spectra revealed the branched structures of the polymers obtained. These polymers exhibit high‐moderate MWs and broad MW distributions determined by gel permeation chromatography (GPC) in combination with triple detectors, including refractive index, light scattering, and viscosity detectors. In addition, the examination of the solution behavior of these polymers showed that the values of intrinsic viscosity [η] and the Mark–Houwink exponent α were remarkably lower compared with their linear analogs, because of their branched nature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4309–4321, 2007     

Synthesis and properties of processable conducting copolymers from N‐ethylaniline with aniline

Copolymers were synthesized through the chemically oxidative polymerization of N‐ethylaniline (EA) and aniline (AN) in five acid aqueous media. The polymerization yield, intrinsic viscosity, molecular weight, solubility, solvatochromism, electrical conductivity, and mechanical properties of the copolymer films were systematically studied through changes in the comonomer ratio, polymerization temperature, oxidant, oxidant/monomer ratio, and acid medium. Open‐circuit‐potential and temperature measurements of the polymerization solutions showed that the polymerization rate depended on the EA content, and the polymerization was an exothermic reaction. The resultant copolymers were characterized in detail with IR, ultraviolet–visible, and ¹H NMR spectroscopy, gel permeation chromatography, wide‐angle X‐ray diffractometry, and scanning electron microscopy. The reactivity ratios of the monomer pair were calculated from the ¹H NMR spectra of the copolymers formed at a low conversion. The polymers exhibited good solubility and interesting solvatochromism in most of the solvents and variable conductivity with the EA/AN ratio and doping state. The conductivity of the HCl‐doped copolymers increased monotonically from 5.61 × 10^?7 to 2.55 × 10^?1 S/cm with decreasing EA content from 100 to 0 mol % and showed a percolation transition between EA concentrations of 20 and 30 mol %. The EA/AN copolymers also had excellent film formability and flexibility together with high mechanical and oxygen‐enriching properties. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6109–6124, 2004     

丙烯酰胺在聚乙二醇水溶液中聚合产品的微观形态

采用偶氮类水溶性引发剂2,2′-偶氮二异丙基咪唑啉二盐酸盐(VA044)引发丙烯酰胺(AM)在聚乙二醇(PEG)水溶液中的双水相聚合;研究了引发剂、单体、聚乙二醇浓度及温度对最终产品中聚丙烯酰胺(PAM)液滴形态、尺寸的影响.随着引发剂浓度的增加,液滴由球状变为细长条状;随着温度的上升,球状液滴逐渐趋于条状,然后又重新趋于球状;在初始单体浓度较低时,PAM液滴滴径分布较窄,当其浓度增加后,滴径呈多峰分布;随着PEG浓度的增加,聚合物液滴趋于球状。     

Vinyl polymerization by metal complexes. III. Vinyl polymerization initiated by oligoamide and cupric ion system

Polymerization of methyl methacrylate and other vinyl monomers was studied in the presence of oligoamide (?-aminocaproic acid, its dimer, trimer, tetramer, and pentamer) and cupric ion in aqueous media. The polymerization was found to be of free-radical character and selective for the type of vinyl monomer. Carbon tetrachloride can accelerate the polymerization. The initiation mechanism of the polymerization is discussed. Spectroscopic measurements were indicative of formation of 1:1 complex between oligoamides and cupric ion in aqueous NaClO₄ solution. Some chemical and physical properties of the resulting polymers were measured.     

Controlled Radical Polymerization of Furfuryl Methacrylate

Atom transfer radical polymerization provides a new method of controlled radical polymerization. The most important advantage of ATRP is that it is tolerant to the different functional groups present in the initiator as well as in the monomer. Furfuryl Methacrylate (FMA) is a specialty monomer, which has applications in coatings, adhesives and in biomedicals. Conventional radical polymerization of FMA leads to excessive gel formation, which limits its applications. In this investigation homo and co-polymerization of FMA has been carried out via ATRP. ATRP of FMA was carried out using CuBr as catalyst and 1, 1, 4, 7, 10, 10 hexamethyltriethylenetetramine (HMTETA) as ligand. There was no gel formation during the polymerization. ATRP of FMA was well controlled with a linear increase of molecular weight (Mn) with monomer conversion. The polymers were characterized by using ¹HNMR, FT-IR and GPC analysis. Interestingly, it was observed that the furfuryl ring was not affected during polymerization.     

表面引发接枝聚合法制备高接枝度的接枝微粒SiO2-g-PMAA

将偶联剂γ-氨丙基三甲氧基硅烷(AMPS)键合在硅胶微粒表面,得到改性微粒AMPS-SiO2;使改性微粒表面的氨基与溶液中的过硫酸铵构成氧化-还原引发体系,实现了甲基丙烯酸(MAA)在硅胶微粒的表面引发接枝聚合,制得了高接枝度(0.30 g/g)的接枝微粒SiO2-g-PMAA;研究了影响表面引发接枝聚合的主要因素。 结果表明,适宜的温度为40 ℃。 已接枝到硅胶表面的聚合物层对后续的接枝聚合产生阻隔作用。 适宜的引发剂用量为单体质量的1.1%,适宜的单体质量分数为5%左右。     

Polymerization kinetics in highly viscous media

The influence of the viscosity of the reaction medium on the rate of polymerization of styrene has been examined by adding different amounts of inert polystyrene to pure monomer and its solutions in benzene. Azobisisobutyronitrile was decomposed photochemically (λ = 365 mμ) at 25°C. or thermally at 70°C.; its rate of decomposition was followed by ultraviolet spectrometry. The rate of formation of dimethyl-N-cyanoisopropylketenimine (DKI) was followed by infrared spectrometry (2020 cm.^?1). The initiation efficiency was determined by the scintillation method with the use of a ¹⁴Clabeled initiator. The rate of polymerization was followed dilatometrically. An increase of viscosity does not affect the rate of decomposition of the initiator; on the contrary, during the photochemical decomposition, it causes an increase of DKI concentration and an appreciable decrease of efficiency (from 0.51 to 0.30). From the point of view of the rate of photopolymerization, an increase of viscosity causes a decrease in the order of the reaction with respect to the initiator (from 0.5 to 0.3) and an increase with respect to monomer from 1.5 to 2. These results are interpreted on the basis of a decrease of termination rate constant between two growing chains in favor of a termination reaction between a growing chain and a primary radical. These effects, due to an increase of the viscosity of the solution, on the initiation and termination reactions influence the rate of polymerization in opposite direction and compensate each other to approximatively 25%.     

Minimization of spatial inhomogeneity in polystyrene gels formed by free-radical mechanism

The spatial inhomogeneity in polystyrene (PS) gels has been investigated with the static light scattering technique. PS gels were prepared starting from styrene monomer and ethylene glycol dimethacrylate crosslinker in a homogeneous solution. The gel synthesis parameters varied were the crosslinker concentration, the primary chains length and the quality of the polymerization solvent. The gels were characterized by elasticity tests as well as by light scattering measurements at a gel state just after their preparation. The degree of spatial gel inhomogeneity decreased with decreasing crosslinker content, with decreasing primary chain length or, with increasing quality of the polymerization solvent. It was shown that the gel synthesis parameters varied mainly affect the distance between the pendant vinyl groups locating on the same macromolecule during the gel formation process. Increasing the distance between the pendant vinyl groups reduces the rate of the multiple crosslinking reactions so that the resulting PS gels exhibit a lesser degree of inhomogeneity.