Characterization of cationic polyacrylamide‐grafted starch flocculant synthesized by one‐step reaction

Cationic polyacrylamide‐grafted starch (St‐g‐CPAM) flocculant was prepared by using corn starch and acrylamide (AM) as monomers, dimethyl diallyl ammonium chloride (DMDAAC) as cationic monomer through solution polymerization. The effects of initiator, reaction temperature, and monomer concentration on flocculation, the efficiency of grafting, and the yield of grafting were investigated. The results show that the optimal conditions of the polymerization are as follows: the concentration of ceric ammonium nitrate is 0.5%, the reaction temperature is 60°C, the concentration of total monomer is 20%, and the monomer ratio between AM and DMDAAC is 7 : 3. The flocculation capability was characterized by turbidity reduction. The thermal behavior, chemical structure, and microstructure of St‐g‐CPAM were also investigated by thermal gravimetric, IR, and SEM analyses. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

β‐Cyclodextrin modified cationic acrylamide polymers for flocculating waste drilling fluids

In this article, the P(AM/A‐β‐CD/DMDAAC) is used as flocculant. The synthesis and characterization of the cationic polyacrylamide flocculant modified by β‐cyclodextrin have been studied in the early article. This article stresses its excellent flocculated performance and mechanism. In the flocculated process, the bridging flocculation played a dominant role. Through the flocculation experiments, it can be seen that the flocculating rate of the P(AM/A‐β‐CD/DMDAAC) on four solutions can go up to 93.4%, 89.7%, 85.1%, and 96.7%, respectively. As can be seen from experiment data, the flocculated property of P(AM/A‐β‐CD/DMDAAC) is superior to polyacrylamide and poly (dimethyl diallyl ammonium chloride). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40197.     

AM/DMDAAC/AA型两性聚丙烯酰胺的制备及应用研究

以丙烯酰胺(AM)、二甲基二烯丙基氯化铵(DMDAAC)、丙烯酸(AA)为单体,用溶液共聚法制备两性聚丙烯酰胺(AMPAM),研究了反应条件对两性聚丙烯酰胺分子量及絮凝性能的影响。结果表明,采用K2S2O8-NaHSO3(质量比1∶1)氧化还原复合引发体系,引发剂用量为0.88%,单体用量为24.5%,聚合温度为55℃,溶液pH值为6,单体摩尔比为n(AM)∶n(DMDAAC)∶n(AA)=1∶0.3∶0.5,聚合时间为4 h,得到的产品综合性能最佳,且具有良好的絮凝脱色效果。     

阳离子型超支化聚丙烯酰胺的合成与反应中影响产物黏度因素的探讨

以季戊四醇为支化剂,按一定的比例加入丙烯酰胺(AM)并加入阳离子单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)增加其阳离子性,合成了具有阳离子性的超支化聚丙烯酰胺。对产物进行了红外光谱(FTIR)分析,并使用旋转粘度计和一定计算测得了聚合物的增比黏度。而后探讨了反应温度、反应时间和引发剂用量对产物粘度的影响。     

Homogeneous synthesis and characterization of polyacrylamide‐grafted cationic cellulose flocculants

In this work, cationic cellulose (CC) with different degrees of substitution (DS) was successfully synthesized by the reaction between cellulose and 3‐chloro‐2‐hydroxypropyl‐trimethylammonium chloride (CHPTAC) in a 7 wt % NaOH and 12 wt % urea aqueous solution. The structure of the CC was characterized by using elemental analysis, ¹H‐NMR, and FTIR. The DS values of CC ranged between 0.18 and 0.50, which could be obtained by adjusting the reaction temperature, reaction time, and molar ratio of CHPTAC to anhydroglucose unit of cellulose. The cationic cellulose–graft–polyacrylamide flocculant (CC‐g‐PAM) based on CC and polyacrylamide (PAM) was also synthesized in a homogeneous aqueous solution. The flocculation characteristics of CC and CC‐g‐PAM were evaluated in a kaolin suspension. The results showed that CC‐g‐PAM was an effective flocculant for the kaolin suspension under acidic or neutral conditions, and the flocculation efficiency was over 90%, while the CC showed better flocculation performance under alkaline conditions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43106.     

反相乳液共聚合制备高分子絮凝剂工艺及产物性能

以丙烯酰胺（AM）和二烯丙基二甲基氯化铵（DMDAAC）为共聚单体,采用反相乳液聚合方法合成了高相对分子质量和高阳离子结构单元含量的共聚物絮凝剂（PDA）,比较了不同种类引发剂和分散剂等对聚合过程的影响,优化了聚合体系。考察了单体配比、引发剂浓度和乳化剂含量等因素对单体转化率和产物相对分子质量的影响。采用傅里叶红外光谱（FT-IR）、核磁共振氢谱（1H NMR）和紫外可见分光光度计等对所得高分子絮凝剂进行了结构和性能表征。红外光谱、核磁共振氢谱和黏度测试结果表明,丙烯酰胺和二烯丙基二甲基氯化铵进行了共聚合反应并得到了高分子产物,且产物中二烯丙基二甲基氯化铵组分含量远高于相应条件下水溶液聚合产物。当[DMDAAC]/[AM]=1∶4、引发剂浓度为30mmol/L、乳化剂含量为18%时,产物黏均相对分子质量可达2.2×105,阳离子单元含量达17%。     

Synthesis,characterization, and flocculation characteristics of hydrolyzed and unhydrolyzed polyacrylamide grafted xanthan gum

The partial hydrolysis of xanthan gum‐g‐polyacrylamide was carried out in alkaline medium. Four grades of partially hydrolyzed products were synthesized by varying the reaction parameters. The neutralization equivalents of these products were determined by titration with standard sodium hydroxide solution. The flocculation characteristics of all the hydrolyzed graft copolymers and the unhydrolyzed xanthan gum‐g‐polyacrylamide were determined in 5 wt % iron ore and kaolin suspensions. The partially hydrolyzed product with neutralization equivalent of 1000 g showed better performance than that of other partially hydrolyzed products, but all hydrolyzed products exhibited poorer performance than that of the unhydrolyzed product in flocculation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1411–1419, 2004     

琥珀酰壳聚糖季铵盐的合成及絮凝性能

壳聚糖由于水溶性差、电荷密度低等缺点,使其在絮凝应用方面受到限制。对壳聚糖进行化学改性,可以改善其水溶性和絮凝性能。本文采用苯甲醛保护壳聚糖氨基,然后与丁二酸酐反应合成琥珀酰壳聚糖（SACTS）,进一步与二甲基二烯丙基氯化铵（DMDAAC）反应合成琥珀酰壳聚糖季铵盐（SAQCS）。采用FTIR、¹H NMR、XRD、ESEM等方法对SAQCS的结构和形貌进行表征。探讨了引发剂用量、单体配比、反应温度、反应时间对SAQCS阳离子度的影响。结果表明,SAQCS较优合成工艺条件为：引发剂用量（占单体的质量分数） 2%,m（DMDAAC）/m（SACTS）=5.4,反应温度70℃,反应时间7h。此工艺条件下合成的SAQCS的阳离子度为42.26%。将SAQCS、壳聚糖、聚丙烯酰胺与配制的高岭土模拟废水进行絮凝实验,考察了pH、投加量、温度对絮凝效果的影响。结果表明,当絮凝条件为pH=2～5、投加量3~9mg/L、温度25～50℃范围内,使用SAQCS絮凝后上清液浊度去除率均在96%以上。     

High‐temperature resistance water‐soluble copolymer derived from acrylamide,DMDAAC, and functionalized sulfonamide for potential application in enhance oil recovery

A water‐soluble poly(AM‐AA‐DMDAAC‐TCAP) was prepared using acrylamide (AM), acrylic acid (AA), diallyl dimethyl ammonium chloride (DMDAAC), and N‐allyl‐4‐methylbenzenesulfonamide (TCAP), and the synthesis conditions were investigated. The obtained copolymer was characterized by FTIR, ¹H‐NMR, SEM, TG, and XRD. The temperature resistance and thickening function of the copolymer are improved significantly compared with that of partially hydrolyzed polyacrylamide. It is found that the viscosity of copolymer could achieve up to 53.3% retention rate at 120°C compared to that at 30°C. About 16.6% for enhanced oil recovery is obtained by poly(AM‐AA‐DMDAAC‐TCAP) brine solution at 65°C. In addition, the results of XRD show that 3000 mg/L copolymer combined with 10 wt % KCl solution could reduce the d‐spacing of sodium montmorillonite from 18.94 to 14.86 Å exhibiting remarkable effect on inhibiting hydration of clays. All the results demonstrate that poly(AM‐AA‐DMDAAC‐TCAP) have excellent performance for potential application in enhance oil recovery. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40727.     

低相对分子质量阳离子聚丙烯酰胺的合成研究

以丙烯酰胺(AM)、二甲基二烯丙基氯化铵(DMDAAC)为原料采用水溶液聚合法制备了一种阳离子度为50%,相对分子质量100000～200000的低相对分子质量阳离子聚丙烯酰胺水溶液,研究了单体配比、投加浓度、聚合温度、引发体系等对反应的转化率和产物相对分子质量的影响.通过加入质量分数0.5%的抗交联剂CPL和螯合剂EDTA·2Na.采用三元复合引发体系可以将聚合反应不饱和单体的转化率提高到96%以上,并且通过控制分子质量调节剂SF的用量可以得到不同相对分子质量分布范围的阳离子聚合物.该产品对高含水原油采出液有独特的预脱水性能,可提高油田采出液油水分离设备的效率和油水分离效果,与反相破乳剂、净水剂等配合使用还可以提高其对含油污水的处理效果.     

Synthesis of a novel amphoteric chelating polymer flocculant and its performance in Cu2+ removal

A novel amphoteric chelating polymer flocculant (ACPF) was synthesized. The synthesis involved the copolymerization of dimethyldiallylammonium chloride and acrylamide to prepare poly(dimethyldiallylammonium chloride‐co‐acrylamide) [P(DMDAAC‐co‐AM)], Mannich reaction of P(DMDAAC‐co‐AM) with triethylenetetramine and formaldehyde to prepare P(DMDAAC‐co‐AM)‐graft‐TETA, and xanthogenation of P(DMDAAC‐co‐AM)‐graft‐TETA with CS₂ and NaOH. The removal performance of ACPF toward Cu²⁺ was investigated, and the ACPF structure was characterized. ACPF performance considerably improved at 121–187 mL/g intrinsic viscosity, 20.78–28.32 mol % cationic degree of P(DMDAAC‐co‐AM), and 22.11–28.44% sulphur content of ACPF. The Cu²⁺ removal rate was above 99% at a 1.98 : 1 molar ratio of ‐CSS^? to Cu²⁺. This rate was 5.86% higher than that using polyacrylamide‐graft‐triethylenetetramine‐dithiocarbamate (PAM‐graft‐TETA‐DTC). The zeta potential and sedimentation rate of flocs obtained from ACPF were higher and their volume was smaller than those from sodium triethylenetetramine‐multidithiocarbamate and PAM‐graft‐TETA‐DTC at the same sulphur dosage. This result indicates that the positive charges of ACPF polymeric chains effectively neutralize excess negative charges in flocs, which benefits the bridging of flocs with negative charges to promote their formation and growth. These positive charges can also cause the flocs to become larger and tighter, thereby improving flocculation and settling performance. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Study on chain deformation of polyacrylamides in solutions and its flocculation performance during the flocculation process

Effects of external conditions, solution concentration, solvent quality, added salt, and pH on the chain conformation dimension of two kinds of polyacrylamide (PAAm) flocculants, neutral‐PAAm, and cationic‐P(AAm‐DMC) (DMC, 2‐[(methacryloyloxy)ethyl] trimethylammonium chloride), in parent solutions and their flocculation performance for Kaolin suspensions have been investigated by Ubbelohde viscometer and spectrophotometer, respectively. It was found that a negative correlation existed between the flocculation performance of PAAm flocculants and their chain sizes in parent solutions. This was attributed to the expanded chain deformation of PAAm flocculants during the flocculation process from the flocculant parent solution to the Kaolin suspension and was interpreted in term of the competitive interaction among the polymeric flocculant, solvent, and Kaolin particle in the chain deformation process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The flocculation and rheological characteristics of hydrolyzed and unhydrolyzed grafted sodium alginate in aqueous solutions

Sodium alginate is a natural anionic polysaccharide obtained from natural and microbial resources. It is also used as a flocculating agent and thickener. It is grafted with polyacrylamide, in the presence of ceric ammonium nitrate (CAN) as an initiator. The graft copolymer (SAG‐g‐PAM) is again hydrolyzed with some amount of alkali. The flocculation characteristics of hydrolyzed graft copolymer (Hyd SAG‐g‐PAM) are compared with that of the unhydrolyzed ones, in 5 wt % kaolin and 10 wt % iron ore suspensions. The flocculation characteristics of the hydrolyzed graft copolymer are also compared with those of some of the commercial flocculants. The SAG‐g‐PAM and Hyd SAG‐g‐PAM are characterized by IR and intrinsic viscosity measurements. The rheological properties of aqueous solutions of hydrolyzed and unhydrolyzed graft copolymers are measured by Advanced AR‐1000 Rheometer. There is drastic enhancement in flocculation and viscosifying characteristics on hydrolysis of the graft copolymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1480–1488, 2004     

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。     

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.     

二甲基二烯丙基氯化铵与丙烯酰胺共聚物的结构表征及应用

在引发剂过硫酸铵 (APS)的作用下 ,二甲基二烯丙基氯化铵 (DMDAAC)和丙烯酰胺 (AM)通过共聚合反应合成了一种新的阳离子型聚合物。在n(DMDAAC)∶n(AM) =2∶1、c(APS) =2 0×1 0 - 2 mol L、t=60℃、t=3h的条件下 ,所得共聚物的阳离子度 (聚合物链节中阳离子单体的链节所占摩尔分数 )为 45%、相对分子质量为 4 7× 1 0 6 、产率达 96%。用红外光谱对聚合物的结构进行了表征 ,同时对聚合物的絮凝与脱水作用也进行了实验。     

Formulation design,optimization, characterization and swelling behaviour of a cationic superabsorbent based on a copolymer of [3‐(methacryloylamino)propyl]trimethylammonium chloride and acrylamide

A series of crosslinked copolymers with cationic nature have been prepared based on acrylamide (AAm) and [3‐(methacryloylamino)propyl]trimethyl ammonium chloride (MAPTAC) using N,N′ methylene‐bis‐acrylamide (MBA) as crosslinking agent. Taguchi's method has been employed for the purpose of formulation design and optimization as well as investigating the effects of various compositional parameters, such as total monomer concentration, cationic monomer and crosslinking agent concentration. The swelling behaviour of the synthesized gels in electrolyte solutions composed of ions with different valency has been studied and compared with an anionic‐based superabsorbent. The swelling capacity and absorbency were found to be enhanced with increase of the MAPTAC moieties of the copolymer chains, and therefore increase of their cationic character. All the cationic hydrogels prepared had greater swelling capacity, with less change in their swelling behaviour, when immersed into aqueous solutions containing multivalent cations. The anionic‐based hydrogels collapsed in similar ionic solutions with moderate‐to‐high ionic strength and did not show any tendency to re‐swell. The complex modulus (G*) of the crosslinked copolymers in the equilibrium swollen state was measured by rheomechanical spectroscopy and was correlated with the chemical composition of the network. Thermogravimetric analysis of the dry cationic superabsorbent showed more bound water but similar thermal behaviour to crosslinked polyacrylamide Copyright © 2003 Society of Chemical Industry     

Dispersion copolymerization of acrylamide and dimethyl diallyl ammonium chloride in ethanol‐water solution

Poly (acrylamide‐dimethyldiallylammonium chloride) (PAM‐DMDAAC) particles have been prepared via dispersion polymerizations using poly (vinyl pyrrolidone) (PVP) as a steric stabilizer in ethanol‐water media. The monomer reactivity ratios of acrylamide (AM, r₁) and dimethyldiallylammonium chloride (DMDAAC, r₂) were determined as 6.664 and 0.120, respectively, which means that PAM‐DMDAAC is a nonideal copolymer. The effects of various polymerization parameters (e.g., concentration of monomer and initiator, medium polarity, the ratio of AM to DMDAAC, initial temperature and ethylene diamine tetraacetic acid disodium (EDTA)) on the intrinsic viscosity and conversion of copolymer have been investigated. The copolymer was characterized by FTIR and NMR. The optimum operating conditions for preparing PAM‐DMDAAC were determined as ethanol content 50%, C_monomer (wt %) 40%, n_AM: n_DMDAAC 8 : 2, C_initiator (wt %) 0.04% and initiate temperature 40°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis,characterization, and flocculation properties of poly(acrylamide‐methacryloxyethyltrimethyl ammonium chloride‐methacryloxypropyltrimethoxy silane)

A novel hydrophobically modified and cationic flocculant poly(acrylamide‐methacryloxyethyltrimethyl ammonium chloride‐methacryloxypropyltrimethoxy silane) (P(AM‐DMC‐MAPMS)) was synthesized by inverse emulsion polymerization. The molecular structure of hydrophobically cationic polyacrylamide (HCPAM) was characterized by FTIR and ¹H‐NMR. The effects of DMC and MAPMS feed ratio on intrinsic viscosity and solubility were measured. The effects of hydrophobically cationic flocculants on reactive brilliant red X‐3B solution and kaolin suspension were studied. It was found that the introduction of MAPMS could increase the intrinsic viscosities of P(AM‐DMC‐MAPMS) and enhance the flocculation properties to anionic dye solution and kaolin suspension, but reduced their water‐solubility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,characterization, flocculation,and rheological characteristics of hydrolyzed and unhydrolyzed polyacrylamide‐grafted poly(vinyl alcohol)

Graft copolymers of poly(vinyl alcohol) and polyacrylamide (PVA‐g‐PAM) were synthesized using a ceric ion–induced solution polymerization technique at 28°C. Three grades of graft copolymers were synthesized with varying acrylamide concentrations. Three grades of hydrolyzed products of PVA‐g‐PAM were synthesized with varying concentrations of sodium hydroxide solution. Hydrolyzed and unhydrolyzed PVA‐g‐PAM were characterized by viscometry, X‐ray diffractometry, infrared spectroscopy, and thermal analysis. Rheological investigation was also carried out on the aqueous solutions of various samples. The flocculation characteristics of various materials were investigated by the use of jar and settling tests in 0.25 and 5 wt %, respectively, using kaolin and iron ore suspensions. Among the series of graft copolymers, the one with fewest but longest PAM chains showed superior performance. The flocculation characteristics of the best‐performing graft copolymer were compared with those of various commercially available flocculants in the two suspensions under investigation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2109–2122, 2006