Synthesis and application of 2‐acrylamido‐2‐methyl propane sulfonic acid/acrylamide/N,N‐dimethyl acrylamide/maleic anhydride as a fluid loss control additive in oil well cementing

Using 2‐acrylamido‐2‐methyl propane sulfonic acid (AMPS), acrylamide (AM), N,N‐dimethyl acrylamide (NNDMA), and maleic anhydride (MA), a new dispersive type fluid loss control additive (FLCA) AMPS/AM/NNDMA/MA (PANM) was synthesized by free radical aqueous solution copolymerization, and the new FLCA could be used without dispersant existing in the cement. The optimal PANM (OPANM) was obtained under the optimum reaction conditions: mole ratio of AMPS/AM/NNDMA/MA = 4/2.5/2.5/1, monomer concentration = 32.5%, amount of (by weight of monomer) ammonium persulfate/sodium bisulfate = 1.0%, pH value = 4, and temperature = 40°C. The synthesized copolymer OPANM was identified by FTIR analysis. The evaluation results show the OPANM has excellent dispersing power, fluid loss control ability, thermal resistant, and salt tolerant ability. The OPANM was even stable when the temperature was below 300°C proved by TG analysis. The thickening time of the slurry containing the synthesized additive reduces as the temperature increases. The copolymer OPANM is expected to be an excellent FLCA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

AM/AMPS/DMAM三元共聚物的合成及性能研究

为提高驱油用聚合物的耐温抗盐性,采用N,N-二甲基丙烯酰胺(DMAM)与2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酰胺(AM)通过氧化还原引发剂体系聚合方法合成了AM/AMPS/DMAM三元共聚物,用正交实验法确定了最佳合成方案为:温度40℃,pH值为11,引发剂浓度为0.18%,单体浓度为13%,DMAM加量为2%。对共聚物的耐盐性及热稳定性进行测试,在标准盐水中共聚物为2500 mg/L,温度为30℃时,粘度可达到35.3 mPa.s;温度为90℃时,粘度为9.70 mPa.s。结果表明,AM/AMPS/DMAM三元共聚物具有较好的抗盐性能和增粘性能,但抗温效果并不明显,有待进一步改进。     

Preparation,characterization, and investigation of poly(AMPS/AM/SSS) on application performance of water‐based drilling fluid

Based on the requirement of the synthesized polymer resistant to higher temperature and lower cost demand of water‐based drilling fluid system, a novel polymer, which named poly(AMPS/AM/SSS), was synthesized using acrylamide (AM), 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS), and p‐styrenesulfonate (SSS). At first, the molecular structure was investigated through Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance hydrogen spectroscopy (¹H‐NMR) and element analysis. Simultaneously, the molecular weight and distribution was obtained by gel chromatography method. Moreover, the thermal stability was produced by thermal analysis (TG). Secondly, the poly(AMPS/AM/SSS) was introduced into water‐based drilling fluid system. As a result, it was shown that the use of poly(AMPS/AM/SSS) significantly improved the filtration performance of drilling fluid system. When the adding amount is 1.2 wt %, the FL_API of drilling fluid system is 9.20 mL. Moreover, it was found that the flow curve of water‐based drilling fluid systems are more fitted to the Herschel–Bulkley flow model. Besides, the temperature resistance of water‐based drilling fluid system was obviously improved. Furthermore, it was confirmed that the cost of water‐based drilling fluid system was significantly reduced. During this study, the filtration mechanism of the synthesized poly(AMPS/AM/SSS) was studied by adsorption analysis, Zeta potential method, and morphology analysis. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46510.     

聚氧乙烯基型降滤失剂SJ-1的合成与性能评价

采用2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酰胺(AM)与具有大分子侧链聚氧乙烯基(C2H4O)n的烯丙基聚氧乙烯醚(APEG)三元共聚得到钻井液用降滤失剂SJ-1,并对其进行了性能评价。通过单因素实验优化得到最佳合成方案为:单体质量分数为15%,反应温度控制在60℃,引发剂质量分数为0.2%,n(AM)∶n(AMPS)∶n(APEG)=14∶5∶1。通过红外光谱表征可知,所合成的聚合物结构和预计的结构一致。性能评价表明,所合成的聚合物具有较好的抗温能力(200℃),在盐质量分数为30%的盐水泥浆中仍具有较好的降失水能力。     

马来酸酐水溶液共聚体系的研究

选择不同配比和用量的 2 丙烯酰胺基 2 甲基丙基磺酸 (AMPS)、2 丙烯酰胺基 2 甲基丙基膦酸 (AMPP)、丙烯酸 (AA)、丙烯酰胺 (AM)、丙烯酸甲酯等 5种聚合单体和过硫酸盐 -Fe2 + 、过氧化氢 -Fe2 + 、过硫酸盐 -次磷酸盐、过氧化氢 -次磷酸盐等 4组引发体系与马来酸酐共聚合成一系列共聚物 ,并对其性能进行分析比较。结果表明 ,AMPS可作为此共聚体系第二单体 ,在所考察的第三单体、引发体系中 ,以AMPP、过氧化氢 次磷酸盐为最佳。当引发剂用量为单体总质量的 10 % [以次磷酸盐的质量计 ,m(过氧化氢 )∶m(次磷酸盐 ) =1.0∶1.2 ],m(MA)∶m(AMPS) =8∶6时合成的共聚物聚合率达 93.41% ,在加药质量浓度分别为 12mg/L和 18mg/L条件下 ,该共聚物对CaCO3 和Ca3(PO4 ) 2 垢的阻垢率分别为 6 6 .2 9%和 10 0 % ;在相同引发剂用量和加药质量浓度下 ,m(MA)∶m(AMPS)∶m(AMPP) =10∶4∶1时合成的三元共聚物的聚合率为 92 80 % ,对CaCO3和Ca3(PO4 ) 2 垢的阻垢率分别为 97.6 1%和 95 .92 %     

Properties of high‐temperature‐resistant drilling fluids incorporating acrylamide/(acrylic acid)/(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) terpolymer and aluminum citrate as filtration control agents

A terpolymer of acrylamide (AM), acrylic acid (AA), and 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid (AMPS) was synthesized by a free‐radical solution polymerization technique, characterized by FTIR methods, and applied together with aluminum citrate in oilfield drilling as a high‐temperature‐resistant filtration control agent. Before and after thermal aging for 16 h at 180°C, the combined effect of the terpolymer and aluminum citrate on the Bingham‐type rheological and fluid‐loss properties of the corresponding fresh‐water and salt‐water muds was further investigated. The results showed that before the thermal aging, there was a similar changing trend in the rheological and fluid‐loss properties of the muds with terpolymer concentration, regardless of the presence of aluminum citrate. After the thermal aging, some hydrophilic polycomplexes of AM‐AA‐AMPS terpolymer with aluminum citrate may have been formed and consequently inhibited viscosity loss of the muds, thereby improving the fluid‐loss properties. A possible mechanism is proposed to explain the improvement. J. VINYL ADDIT. TECHNOL, 2010. © 2009 Society of Plastics Engineers     

Synthesis,characterization, and performance evaluation of the AM/AMPS/DMDAAC/SSS quadripolymer as a fluid loss additive for water‐based drilling fluid

According to the molecular structure design requirements of the fluid loss additive resistant to high temperature, 2‐acrylamide‐2‐methyl propane sulfonic acid (AMPS), acrylamide (AM), dimethyl diallyl ammonium chloride (DMDAAC) and sodium styrene sulfonate (SSS) are selected as the structure monomers. Using ammonium persulfate as initiator, a new quadripolymer is synthesized through free radical aqueous solution polymerization. According to the minimum filtration loss of the fresh water‐based drilling fluid with 0.5 wt % quadripolymer, The synthesis conditions are optimized by orthogonal test: the mole ratio of AMPS/AM/DMDAAC/SSS is 5/7/2/1, the monomer concentration is 30 wt %, the initiator concentration is 0.8 wt %, the reaction temperature is 75°C and the pH is 10. The structure of the quadripolymer is characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance hydrogen spectroscopy. The results show that the quadripolymer contains all the designed functional groups. The thermal stability of the quadripolymer is tested by thermogravimetry, differential thermogravimetry, and differential scanning calorimetry. The results show that the thermal degradation of the quadripolymer is not obvious before 272.3°C. The rheological performance and filtration loss of the quadripolymer are evaluated. The results indicate that the filtration loss decreases with the increasing dosage of the quadripolymer before and after thermal aging test at 180°C for 16 h, and the filtration loss before the thermal aging test is smaller than that after the thermal aging test. The high temperature high pressure filtration loss (FL_(HTHP)) experiment results also show that the quadripolymer fluid loss additive has excellent temperature‐resistant performance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41762.     

一种抗盐抗温降滤失剂的合成及性能研究

采用丙烯酰胺（AM）、2-丙烯酰胺基-2-甲基丙磺酸（AMPS）、丙烯酸（AA）等单体共聚合成了一种抗温抗盐降滤失剂,分析了影响合成产品的各种因素,优选了反应条件,评价了合成共聚物在淡水钻井液、盐水钻井液、饱和盐水钻井液中的降滤失效果,研究了合成共聚物的抗盐效果、抗温能力、抗钙能力和黏土膨胀抑制性。结果表明：合成共聚物具有良好的降滤失作用和抗温抗盐抗钙性能,增强了钻井液抑制泥页岩水化的能力。     

Comb‐shaped copolymer as filtrate loss reducer for water‐based drilling fluid

A new comb‐shaped copolymer was synthesized by free radical copolymerization of 2‐acrylamide‐2‐methyl propane sulfonic acid, acrylamide, N‐vinyl‐2‐pyrrolidone, and allyl polyoxyethylene ether (APEG) monomers. The copolymer was evaluated as a filtrate loss reducer in water‐based drilling fluid at 180 °C environment, and found to work well without causing high viscosity effect. Composition of the copolymer was determined by Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy, and gel permeation chromatography. FTIR, X‐ray diffraction,, and environmental scanning electron microscopy characterizations were used to probe the filtrate loss mechanism of the comb‐shaped copolymer. Thermogravimetry and differential scanning calorimetry results showed that thermal degradation of the copolymer is not obvious before 293.6 °C. The copolymer is found to be superior to its commercially available counterparts for controlling filtrate loss volume and maintaining a steady viscosity after 180 °C aging. Higher content of APEG in the copolymer helps maintain rheological properties of the drilling fluid after aging and reduces filtrate loss volume. The morphology of the copolymer in aqueous solution displays a comb‐shaped 3D structure and shows clear adsorption onto clay particles. The working mechanism for copolymer is that anchoring groups bind the copolymer onto clay particles through different binding mechanisms, while colloidal suspension stability is achieved by steric hindrance and electrostatic repulsion, as well as through PEG segment intercalation into clay lamellae. The copolymer is able to cover and seal the micro‐holes in the mud cake even at high temperature to reduce permeability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45989.     

Synthesis and Swelling Behavior of Superabsorbents Cross-Linked with N-Maleyl Chitosan

A kind of superabsorbent based on the monomers maleic anhydride (MA) and acrylic acid (AA) was prepared by solution polymerization using ammonium peroxodisulfate (AP) and sodium bisulfite (NaHSO₃) as initiator, and N-maleyl chitosan (N-MACH) as cross-linker. Effects of process parameters such as the amount of cross-linker, mass ratio of MA to AA, and neutralization degree of AA on the water absorbency of superabsorbents are discussed. The results indicated the water absorbency of superabsorbents increased and then decreased with the increase of MA content, the amount of the N-MACH cross-linker, and the neutralization degree of AA. Under the optimal conditions, the water absorbency of superabsorbents could reach l560.42 g/g and 83.7 g/g in distilled water and in 0.9% NaCl solution, respectively. In addition, to enhance the water absorbency of superabsorbents in 0.9% NaCl solution, polyvinyl alcohol (PVA) was introduced as interpenetrating polymer in the network and 2-acrylamido-2-methyl propane sulfonic acid (AMPS) was introduced as comonomer. It was proved that PVA and AMPS could effectively improve the water absorbency of superabsorbents both in distilled water and 0.9% NaCl solution.     

AM/AMPS/腐植酸接枝共聚物的合成

采用腐植酸与AM和AMPS接枝共聚合成了一种腐植酸接枝共聚物,并对其性能进行了室内初步评价。结果表明,AM/AMPS/腐植酸接枝共聚物用作泥浆降滤失剂,在淡水泥浆、盐水泥浆、饱和盐水泥浆和人工海水泥浆中具有较好的降滤失和耐温抗盐能力。     

一种改性淀粉钻井液降滤失剂的合成与性能评价

以可溶性玉米淀粉、AMPS、DMDAAC、AM四元共聚,制得一种两性离子改性淀粉钻井液降滤失剂。结果表明,该聚合物降滤失剂在淡水基浆、盐水基浆、人工海水基浆中均具有较好的降失水性能,1.0%的产品加量,淡水基浆中API失水为6 mL,饱和盐水基浆中API失水为8 mL,人工海水基浆中API失水为8.4 mL;0.6%的产品加量的淡水基浆在150℃、3.5 MPa下的失水量为24.2 mL,基浆在180℃下热滚16 h后性能无明显变化,页岩滚动回收1次、2次,回收率均在90%以上。     

Application of a new family of organosilicon quadripolymer as a fluid loss additive for drilling fluid at high temperature

An organosilicon quadripolymer of acrylamide (AM), 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid (AMPS), N‐vinylpyrrolidone (NVP) and a kind of organosilicon monomer was synthesized by solution free radical polymerization. The chemical structure of organosilicon quadripolymer was characterized by Fourier transform infrared (FTIR) spectroscopy, and molecular weight distribution was determinate by gel permeation chromatography (GPC) under the best optimum synthesis conditions, which were identified by orthogonal test according to filtrate volume of fresh water‐based drilling fluid. The colloidal properties of the organosilicon quadripolymer drilling fluid were investigated in various media such as fresh‐water, 4.0% salt‐water, and saturated brine based fluid. The results showed that the filtrate volume decreased with the increase of the organosilicon quadripolymer concentration before and after the thermal aging test at 180°C for 16 h, and the filtrate volume after the thermal aging test was larger than that before the thermal aging test, but was smaller than the base fluid. The colloidal properties and the filtrate volume could be controlled effectively at aging temperatures not exceeding 200°C. The organosilicon quadripolymer drilling fluid performance was better than corresponding terpolymer without organosilicon group and shows favorable inhibitive property and was an excellent fluid loss additive for drilling fluid resisting high temperature in deep wells. A possible mechanism is proposed to explain the improvement according to the comparative adsorption experiment. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polymeric absorbent for water sorption based on chemically crosslinked poly (acrylamide/2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt) hydrogels

Summary Swelling equilibrium of polyelectrolyte copolymer gels containing of acrylamide (AAm) and 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt (AMPS) have been studied as a function of copolymer composition. AAm/AMPS hydrogels were prepared by free radical solution polymerization in aqueous solution of AAm with AMPS as anionic comonomer and two multifunctional crosslinkers such as ethylene glycol dimethacrylate (EGDMA) and trimethylolpropane triacrylate (TMPTA). Swelling experiments were performed in water at 25 °C, gravimetrically. The influence of AMPS content in hydrogels was examined. Swelling of AAm/AMPS hydrogels was increased up to 1018% (for containing 2% AMPS and crosslinked by EGDMA) 15246% (for containing 8% AMPS and crosslinked by TMPTA), while AAm hydrogels swelled up to 804% (crosslinked by TMPTA)–770% (crosslinked by EGDMA). The values of equilibrium water content of the hydrogels are 0.8851–0.9935. Diffusion behavior was investigated. Water diffusion into hydrogels was found to be non-Fickian in character.     

Clinical Evaluation of Extracellular ADMA Concentrations in Human Blood and Adipose Tissue

Circulating asymmetrical dimethylarginine (ADMA), an endogenous inhibitor of nitric oxide synthesis, has been proposed as a biomarker for clinical outcome. Dimethylarginine dimethylaminohydrolase (DDAH) is the main enzyme responsible for ADMA metabolism and elimination. Adipose tissue ADMA concentrations and DDAH activity and their role in diabetes and obesity have not yet been investigated. In this study, we evaluated clinical microdialysis in combination with a sensitive analytical method (GC-MS/MS) to measure ADMA concentrations in extracellular fluid. Adipose tissue ADMA concentrations were assessed before and during an oral glucose tolerance test in lean healthy subjects and subjects with diabetes (n = 4 each), and in morbidly obese subjects before and after weight loss of 30 kg (n = 7). DDAH activity was determined in subcutaneous and visceral adipose tissue obtained during laparoscopic surgery (n = 5 paired samples). Mean interstitial ADMA concentrations did not differ between study populations (healthy 0.17 ± 0.03 μM; diabetic 0.21 ± 0.03 μM; morbidly obese 0.16 ± 0.01 and 0.17 ± 0.01 μM before and after weight loss, respectively). We did not observe any response of interstitial ADMA concentrations to the oral glucose challenge. Adipose tissue DDAH activity was negligible compared to liver tissue. Thus, adipose tissue ADMA plays a minor role in NO-dependent regulation of adipose tissue blood flow and metabolism.     

Fluorescent‐tagged maleic anhydride‐allylpolyethoxy carboxylate copolymer as an environmentally benign inhibitor for calcium phosphate in industrial cooling systems

Allyloxy polyethoxy ether (APEG) and succinic anhydride were used to prepare allyloxy polyethoxy carboxylate (APEL). 8‐hydroxy‐1,3,6‐pyrene trisulfonic acid trisodium salt (PY) was reacted with allyl chloride to produce fluorescent monomer 8‐allyloxy‐1,3,6‐pyrene trisulfonic acid trisodium salt (PA). APEL and PA were copolymerized with maleic anhydride (MA) to synthesize PA tagged no phosphate and nitrogen‐free calcium phosphate inhibitor POLY(MA–APEL–PA). Structures of PA, APEG, APEL, and POLY(MA–APEL–PA) were carried out by FTIR and ¹H‐NMR. Different MA : APEL mole ratios were employed for the manufacture of POLY(MA–APEL–PA) to study the effect of mole ratio on performance of POLY(MA–APEL–PA). Relationship between POLY(MA–APEL–PA)'s fluorescent intensity and its dosage was studied. The results indicate that capability of POLY(MA–APEL–PA) is heavily depended on the mole ratio of MA : APEL. Correlation coefficient r of POLY(MA–APEL–PA)'s fluorescent intensity and its dosage is 0.9999, and detection limit of POLY(MA–APEL–PA) is 0.86 mg/L. POLY(MA–APEL–PA) can be used to accurately measure polymer consumption on line besides providing excellent calcium phosphate inhibition. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Preparation of acrylic acid and AMPS cointercalated layered double hydroxide and its application for superabsorbent

This article reports the cointercalation of acrylic acid (AA) and 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS) in the interlayer region of Mg₂Al layered double hydroxide (LDH) and the application of this inorganic–organic composite material in the field of water superabsorbent. The monomers of AA and AMPS were cointercalated into galleries of Mg₂Al−LDH (denoted as AA−AMPS/LDH) with various molar ratios by ion‐exchange method, which was confirmed by powder X‐ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), and elemental analysis. The polymer‐based superabsorbent was prepared through in situ free‐radical aqueous copolymerization of AA and AMPS, with AA−AMPS/LDH as additive, N,N′‐methylenebisacrylamide (NMBA) as crosslinker and potassium persulfate (KPS) as initiator. The composition of this poly(AA‐co‐AMPS)/LDH was demonstrated as a good water superabsorbent. The LDH content, water absorbency, thermal stability, and swelling rate of this superabsorbent were also investigated in detail. Results showed that the incorporation of a 5 wt % AA−AMPS/LDH into polymer matrix increased its water absorbency significantly by 27.7% (in water) and by 51.5% (in 0.9 wt % NaCl solution). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

MA/SAS/AMPS共聚物耐高温钻井液降粘剂的研制

合成了耐240℃高温的水基钻井液降粘剂马来酸酐/丙烯磺酸钠/2-丙烯酰胺基-甲基丙磺酸(MA/SAS/AMPS)三元共聚物。优选反应条件为:水溶液聚合,n(MA)∶n(SAS)∶n(AMPS)=5∶4∶4,引发剂w(过硫酸铵)=3.0%,w(单体)=45%,共聚反应温度为85℃,反应时间为4h,得到MA/SAS/AMPS共聚物。室内实验证明,加入0.5%该共聚物使淡水基浆在常温下表观粘度由45mPa·s降至30mPa·s,降粘率为80.2%,加入0.5%使淡水基浆在240℃老化16h后的表观粘度由50mPa·s降至34mPa·s,降粘率为65%。     

Starch‐poly(acrylamide‐co‐2‐acrylamido‐2‐methylpropanesulfonic acid) graft copolymers prepared by reactive extrusion

Graft copolymers of starch with acrylamide and 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS) were prepared by reactive extrusion in a twin‐screw extruder. The weight ratio of total monomer to starch was fixed at 1 : 3, while the molar fraction of AMPS in the monomer feed ranged from 0 to 0.119. Monomer to polymer conversions were 85% or greater, with grafting efficiencies of 68% (highest AMPS content) to 85% (no AMPS). Absorbency in distilled water at pH 7 increased linearly with the mole fraction AMPS in the grafted polymer, while absorbencies in 0.9% NaCl were independent of AMPS content. When swollen in water/ethanol mixtures, swelling decreased gradually with increasing ethanol volume fraction, followed by a large decrease over a narrow ethanol concentration. This behavior is similar to that observed for AMPS‐acrylamide gels. The swelling properties suggest these graft copolymers may have applications as responsive materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42405.     

Preparation and property of 2‐acrylamide‐2‐methylpropanesulfonic acid/acrylamide/sodium styrene sulfonate as fluid loss agent for oil well cement

A novel terpolymer 2‐acrylamide‐2‐methylpropanesulfonic acid/acrylamide/sodium styrene sulfonate (AMPS/AM/SSS), used as fluid loss agent for oil well cement under high temperature, was prepared with initiator of azobisisobutryamide chloride. The optimum reaction conditions of polymerization were obtained from the orthogonal experiments, reaction temperature 40°C, initiator 0.1 wt%, molar ratio of monomers AMPS/AM/SSS 20/5/1. The structure and performance of terpolymer was characterized with Fourier transform infrared spectrometer, nuclear magnetic resonance hydrogen spectrum, thermogravimetric and simultaneous differential thermal analysis, high‐temperature and high‐pressure water loss meter, and rotational viscometer, indicating that the terpolymer was perfectly synthesized and started to decompose at 350°C and showed good performance of fluid loss control up to 160°C. The ζ‐potential instrument and scanning electron microscopy were used to investigate the mechanisms of fluid loss control, indicating that the terpolymer can prevent the generation of flocculated structure in the cement and reduce the porosity of the filter cake. These results have important referential value for developing new high‐temperature‐resisting fluid loss agents. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers