A novel twin-tailed hydrophobically associating copolymer: synthesis, characterization and solution properties

Novel twin-tailed hydrophobically associating copolymers (DDSPAM) were prepared by micellar copolymerization of acrylamide (AM) and sodium vinylsulfonate with N,N-didecyl-N-methyl-N-(4-vinylbenzyl)ammonium chloride in an aqueous solution. The structure and composition of DDSPAM were characterized by ¹H-NMR and elemental analysis. While the molecular weights of the copolymers were obtained via static light scattering, the hydrodynamic radius of aggregates was investigated using dynamic light scattering. The critical micellar concentration cmc and γ _cmc values of DDSPAM were measured using fluorescence and later correlated with the values obtained from surface tension measurements. In addition, the viscosity stability studies of DDSPAM and hydrolyzed polyacrylamide (HPAM) revealed that DDSPAM, with twin tails of hydrophobic groups, exhibited better salt tolerance as well as temperature resistance compared to HPAM.     

AM/AA/AMPS/AMQC_(12)AB四元共聚物的合成及耐温抗盐性研究

以AM、AA、AMPS、AMQC12AB为单体,VA-044为引发剂,合成了一种新型耐温抗盐的四元共聚物。考察了温度、体系pH、引发剂用量、AMPS含量、AMQC12AB含量对共聚物特性黏数的影响,并确定最佳反应条件。结果表明,比较适宜的反应条件为:聚合反应温度35℃,体系pH值7~9,引发剂用量为单体含量的0.5%,AMPS含量为单体总含量的10%,加入AMQC12AB含量为单体总含量的0.5%。聚合物测试表明,该聚合物具有良好的耐温抗盐性能。     

单体N,N-双烯丙基十二胺的合成及其疏水缔合水溶性聚合物的性能

以双烯丙基胺和1-溴代十二烷为原料合成了疏水单体N,N-双烯丙基十二胺(DiAC12),采用前加碱二元单体胶束共聚-后水解法制备三元共聚物丙烯酰胺/丙烯酸钠/N,N-双烯丙基十二胺[P(AM/NaAA/DiAC12)],以芘为荧光探针,利用荧光光谱研究了P(AM/NaAA/DiAC12)在水溶液、1.000 mol/L NaCl水溶液中的缔合行为。结果表明,当疏水单元摩尔分数x(DiAC12)=0.10%～0.40%时,随聚合物浓度、疏水单体用量的增加,芘的I1/I3值减少,缔合作用增加。     

疏水缔合水溶性聚合物P(AM/NaAA/DiAC14)的合成与性能

以双烯丙基胺和1-溴代十四烷为原料成了疏水单体N,N-双烯丙基-N-十四烷基胺(DiAC14);采取前加碱二元胶束共聚-共水解法合成了疏水缔合丙烯酰胺/丙烯酸钠/N,N-双烯丙基-N-十四烷基胺共聚物[P(AM/NaAA/DiAC14)],研究了其在水溶液中的缔合行为.结果表明P(AM/NaAA/DiAC14)缔合行为取决于其Mη的大小、疏水单体摩尔分数及其嵌段长度和分布.     

A double‐tailed acrylamide hydrophobically associating polymer: Synthesis,characterization, and solution properties

In order to improve the salt resistant, temperature tolerance, and stability of the acrylamide‐based copolymer, the double‐tailed hydrophobically associating copolymer (DTHAP) was synthesized. The chemical and spatial network structures of the copolymer were characterized by Fourier transform infrared spectroscopy (FT‐IR), nuclear magnetic resonance spectroscopy (NMR), and environmental scanning electron microscope (ESEM). The salt, temperature, aging resistance, and rheological behavior of the copolymer were investigated in detail. The experimental results showed that the performance of DTHAP were influenced by the amount of AA, PETMAM, SDS, and NaCl in the reaction system. Compared with HPAM, DTHAP solution showed excellent temperature resistance and salt tolerance. No matter in the solution varying NaCl or CaCl₂ concentration from 8 to 80 and 1 to 1.8 g/L, respectively, DTHAP behaved an obvious salt‐thickening phenomenon. The simulative tertiary oil recovery tests at 80°C indicated that DTHAP can remarkably enhance 16.9% of the oil recovery ratio. Even at 100 g/L salt solution, DTHAP exhibited an excellent performance which can also enhance 9.9% of oil recovery ratio. The experiment results indicated that DTHAP was superior to HPAM as a kind of oil displacement agent for enhanced oil recovery, especially in high‐temperature and high‐mineralization oil fields. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42569.     

AM/AMPS/DMC聚两性电解质的合成、表征与溶液性能

以丙烯酰胺(AM)、2-丙烯酰胺-2-甲基丙磺酸(AMPS)和甲基丙烯酰氧乙基三甲基氯化铵(DMC)为原料,在0.5 mol/L NaC l溶液中,以2,2-偶氮二[2-(2-咪唑啉-2-代)丙烷]二氢氯化物(VA-044)为引发剂,合成了AM/AMPS/DMC系列聚两性电解质。利用13C NMR对共聚产物结构进行表征,结果表明,在高转化率情况下,共聚物组分与投料比基本一致。考察外加小分子电解质和温度对聚两性电解质溶液性能的影响,结果显示,阴、阳离子数量相近的聚两性电解质溶液的粘度随外加盐浓度增大而增大,在温度升高时,其表观粘度保留率高于聚丙烯酰胺,说明AM/AMPS/DMC系列聚两性电解质具有一定的抗温、耐盐能力。     

Synthesis,characterization, and properties of novel hydrophobically associating fluorinated copolymers for DNA delivery

Novel fluorinated associative copolymers poly(ethylene glycol)-b-poly(2-(perfluorohexyl)ethyl methacrylate (PFHEMA)-co-3-[N-(2-methacroyloylethyl)-N,N-dimethylammonio]-propane sulfonate (DMAPS)) (PEG-b-PPFHEMA/PDMAPS) were prepared as a type of non-viral gene vector. The series of PEG-b-PFHEMA/DMAPS with different molecular weights and compositions were characterized by gel permeation chromatography–multi-angle light scattering, ¹H NMR, ¹⁹F NMR, and elemental analysis. The interactions of the copolymers with calf thymus DNA and the morphologies of the resulting complexes were studied by fluorescence spectroscopy, dynamic light scattering, and transmission electron microscopy. In addition, the DNA–polymer interaction, as determined by the gel retardation assay, and the low cytotoxicity of PEG-b-PPFHEMA/PDMAPS demonstrated that these copolymers have good DNA binding capacity and potential for high performance in the practical application of DNA delivery.     

Synthesis,characterization, and solution properties of a surface‐active hydrophobically associating polymer

A nonionic surfmer (MAA‐EO₂₃C₁₂) was prepared and reacted with acrylamide, acrylic acid, and a double tailed hydrophobic monomer (BTMAM) to synthesize a surface‐active hydrophobically associating copolymer (SHAP) through photoinitiated free radical copolymerization in aqueous solution. Fourier transform infrared and ¹H‐nuclear magnetic resonance spectroscopy were used to characterize the functional monomer and the SHAP. Several performance evaluations, such as viscosification property, temperature resistance, salt tolerance, and shear resistance, were also conducted. Experiment results demonstrated that the introduced nonionic surfmer and hydrophobic monomer could endow the copolymer with excellent temperature resistance, salt tolerance, and shear resistance capability at low concentration. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46569.     

孪尾疏水缔合丙烯酰胺/丙烯酸钠/N,N-二己基丙烯酰胺共聚物制备条件的研究

采取先加碱共聚-共水解的方法合成了孪尾疏水缔合丙烯酰胺/丙烯酸钠/N,N-二己基丙烯酰胺共聚物[P(AM/NaAA/DiC6AM)],用傅里叶变换光谱、1H-核磁共振及容量分析法对其结构进行了表征.反应10 h转化率可达92%,之后增加缓慢.水解度主要受水解时间的影响,受疏水单元摩尔分数的影响较小.还研究了疏水单元摩尔分数、总单体质量浓度、DM质量浓度、(NH4)2S2O8质量浓度、温度、SMR对P(AM/NaAA/DiC6AM)水溶液的表观黏度的影响.     

Study on preparation and solution properties of hydrophobically associating polyacrylamide by emulsifier-free ultrasonic assisted radical polymerization

Removal of heavy metals from aqueous solutions has attracted much attention worldwide. Many processes and technologies have been developed to remove heavy metals ions. In our previous study, a silica-poly acrylic amphoteric hybrid hydrogel was successfully prepared with double-network (DN) structure using ??-aminoporpyltriethoxysilane as precursor through a two-step sequential network formation technique. In the present research, the absorption behavior of this hydrogel was investigated carefully using Cu²⁺ ions and Cr₂O ₇ ^2? ions as representatives of negative and positive ions respectively. Under different adsorption conditions, the adsorption behaviors of the hydrogel were studied in detail, including initial concentration of the adsorbed ions, adsorption time, pH and ionic strength. The results showed the absorption capacity to Cu²⁺ can reach 700?mg/g with an initial Cu²⁺ concentration of 1,200?mg/L within 2?h. The experimental results show that the Freundlich adsorption law is applicable to the adsorption of Cu²⁺ and Cr₂O ₇ ^2? on the hydrogel.     

Dilute solution properties of hydrophobically associating polyacrylamide: fitted by different equations

In this paper six different equations were used to fit the data of dilute solution of both nonionic (PBAM3) and ionic (PBAMS) hydrophobically associating polyacrylamide with and without the addition of NaCl. The results showed that Fedors equation was the most accurate equation to describe the dilute solution properties of these kinds of polymers. The lower value of the polymer concentration parameter (C_m) in Fedors equation was corresponded to the higher value of the constant k in Schulz-Blaschke equation for PBAM3 system. Two types of polymers had anti-polyelectrolyte effect. In dilute solution the PBAMS polymer chains had a more extended conformation than those of PBAM3 due to the existence of ionic groups.     

聚甜菜碱型疏水聚合物的合成及性能评价

以苯甲酰氯、丙烯酸、N,N-二甲基-1,3-丙二胺和氯乙酸为主要原料,合成了一种甜菜碱型功能单体丙烯酰胺丙基甜菜碱。丙烯酰胺丙基甜菜碱单体、丙烯酰胺、疏水单体进行三元共聚,得到聚甜菜碱型疏水聚合物,对聚合物溶液的抗盐性能进行了评价。结果表明,新型聚甜菜碱型疏水聚合物溶液具有优良的盐增稠性能。     

Synthesis, structure and properties of hydrophobically associating polymers

Hydrophobically modified water-soluble polymers have recently become the subject of extensive research because of their use as aqueous viscosity modifiers in oil recovery and latex paint systems. In this study, poly(acrylamide) samples modified with small amounts of a hydrophobic monomer (ethylphenylacrylamide) have been prepared by free radical copolymerization using an aqueous micellar process in which the use of a surfactant ensures the solubilization of the hydrophobe. The copolymers exhibit improved thickening properties with respect to homopoly(acrylamide) analogs due to intennolecular hydrophobic associations. The aqueous solution-copolymer properties strongly depend on the amount of surfactant used in the synthesis. The differences observed between the samples are directly related to the copolymer microstructure, that is to a more or less block distribution of the hydrophobic units. The interactions in aqueous solution of a surfactant (sodium dodecylsulfate (SDS)) with these copolymers have been examined. A strong increase in viscosity is observed upon the addition of SDS below its critical micelle concentration, owing to the formation of mixed micelles of SDS and hydrophobic monomers. The complex rheological behavior observed is explained in terms of the balance between inter and intrachain liaisons. The effects of hydrolysis on the hydrophobic interactions are also discussed.     

A water‐soluble acrylamide hydrophobically associating polymer: Synthesis,characterization, and properties as EOR chemical

A water‐soluble acrylamide hydrophobically associating terpolymer for polymer flooding was successfully synthesized via free radical polymerization using acrylamide (AM), acrylic acid (AA), and N,N‐divinylnonadeca‐1,10‐dien‐2‐amine (DNDA) as raw materials. The terpolymer was characterized by IR spectroscopy and fluorescence spectra. Compared with partially hydrolyzed polyacryamide (HPAM), the terpolymer showed a stronger link and better dimensional network structure under the environmental scanning electron microscope (ESEM). The results of rheology indicated that the terpolymer (AM‐NaAA‐DNDA) showed an excellent shear‐resistance in high shear rate (1000 s^?1) and remarkable temperature‐tolerance (above 110°C). The salt‐resisting experiment revealed that this terpolymer had a better anti‐salt ability. According to the core flooding test, it could be obtained that oil recovery was enhanced more than 15% under conditions of 2000 mg/L terpolymer in the mineralization of 8000 mg/L at 60°C. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

疏水缔合型阳离子聚丙烯酰胺的溶液性能与应用研究

以丙烯酰胺(AM)、二甲基二烯丙基氯化铵(DMDAAC)、丙烯酸十八酯(OA)为单体,用氧化-还原引发体系,通过自由基胶束共聚法制得疏水缔合型阳离子共聚物PADO。研究了共聚物组成对PADO溶液性能的影响,以及PADO对造纸中段废水的絮凝效果。结果表明,PADO水溶液中存在强烈的分子间缔合作用,在处理造纸中段废水时,其应用效果优于聚合硫酸铁、聚合氯化铝和非离子PAM。     

疏水缔合聚合物的合成、表征及其溶液性能研究

采用自由基胶束聚合法,合成了一种疏水缔合型丙烯酰胺-烷基丙烯酸酯共聚物。用1HNMR谱和TEM对该共聚物进行了表征。用旋转黏度计测定了不同疏水基含量的聚合物的溶液性能,考察了温度对聚合物溶液性能的影响,同时研究了外加盐对聚合物溶液形貌的影响。     

Synthesis and aqueous solution characterization of novel diblock polyampholytes containing imidazole

A series of diblock copolymers of 2-(1-imidazolyl)ethyl methacrylate and tetrahydropyranyl methacrylate (THPMA) were synthesized by group transfer polymerization using propylene carbonate rather than tetrahydrofuran as the solvent to ensure homogeneous polymerizations. The resulting copolymers were characterized by gel permeation chromatography and proton nuclear magnetic resonance spectroscopy (¹H NMR) to determine their molecular weights and compositions, respectively. The THPMA units of the copolymers were subsequently converted to methacrylic acid units by acid hydrolysis. The resulting polyampholytes were characterized in terms of their composition and solubility characteristics using ¹H NMR and hydrogen ion titration. Moreover, dynamic light scattering in alkaline water (pH 9.3) indicated the presence of large non-micellar aggregates of the block polyampholytes.     

Synthesis and solution properties of hydrophobically associating ionic polymers made from diallylammonium salts/sulfur dioxide cyclocopolymerization

Sulfur dioxide, N,N-diallyl-N-carboethoxymethylammonium chloride and the hydrophobic monomers N,N-diallyl-N-dodecylammonium chloride or N,N-diallyl-N-octadecylammonium chloride were cyclocopolymerized in dimethyl sulfoxide using azobisisobutyronitrile (AIBN) as the initiator to afford water-soluble cationic polyelectrolyte (CPE) having five-membered cyclic structure on the polymeric backbone. The CPE on acidic (HCl) hydrolysis of the pendent ester groups gave the corresponding cationic acid salt (CAS) which was converted to the anionic polyelectrolyte (APE) by treatment with sodium hydroxide. The solution properties of the CPE and APE containing varying amount of the hydrophobic monomers in the range 0-10 mol% were investigated by viscometric techniques. The polymers showed that concentration (C^∗_HA) of less than 1 wt% was required for the manifestation of hydrophobic association, and displayed significant hydrophobic association in salt (NaCl)-free as well as salt-added solutions.     

Synthesis and characterization of hydrophobically modified poly(vinyl alcohol)

Summary Two different routes for the preparation of hydrophobically modified poly(vinyl alcohol), PVA are reported. The first method involves the formation of the polymeric alcoholate. An alkylhalide and propanesultone are coupled with the polymer in two subsequent steps of the Williamson ether synthesis. The product is a hydrophobically modified polymer with anionic functionality. The other method proceeds via a 1,4 addition of acrylamide and the Hoffman degradation of the amide to an amine. In the next step, the amine is alkylated with an alkylhalide. The polymers are characterised by quantitative ¹HNMR spectroscopy and titration. Received: 14 January 1999/Revised version: 19 April 1999/Accepted: 19 April 1999     

Synthesis,characterization, and properties of novel poly(ether urea)s

Two diamines, 2,6‐bis(4‐aminophenoxy)pyridine and 2,6‐bis(5‐amino‐1‐naphenoxy)pyridine, were prepared through the nucleophilic aromatic substitution reaction of 4‐aminophenol and 5‐amino‐1‐naphthol, respectively, with 2,6‐dichloropyridine. Poly(ether urea)s were synthesized through the polyaddition reactions of these diamines with aromatic, semiaromatic, and cycloaliphatic diisocyanates. All the monomers and polymers were fully characterized, and physical properties of the polymers, including the thermal behavior, thermal stability, solubility, and solution viscosity, were studied. The polyureas showed improved thermal stability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 961–965, 2004