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.     

Novel biodegradable flocculating agents prepared by grafting polyacrylamide to Konjac

Grafting copolymers of polyacrylamide (PAM) with Konjac gum (KGM) have been synthesized using ceric‐ion‐induced initiation technique. The copolymers were characterized using several instrumental techniques, including infrared (IR) spectroscopy, elementary analysis, scanning electron microscopy (SEM), size exclusion chromatography (SEC) analysis, and intrinsic viscosity to confirm the success of grafting. The flocculation performance of graft copolymers was characterized by two methods. One was to study the relationship between the flocculants doses in kaolin suspension and the supernatant transmittance, and the other is to examine the time dependence of sediment height of kaolin suspensions. It was found that the graft copolymer is better than KGM and pure PAM. Biodegradation behavior was testified by monitoring the decay of relative viscosities, and approved by KGM ether bonds breaking in IR spectra and the molecule weight reduction in SEC analysis. The results indicate that the grafted KGM copolymers have improved both, flocculation performance and better biodegradable properties than the unmodified parent KGM and pure PAM. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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。     

Flocculation behavior of cationic pea starch prepared by the graft copolymerization of acrylamide for wastewater treatment

To improve the flocculation efficiency of coal mine wastewater treatment, we synthesized a cationic flocculant by grafting acrylamide (AM) onto pea starch, and we performed the characterization with elemental analysis, Fourier transform infrared spectrometry, scanning electron microscopy, thermogravimetric analysis, and NMR. The effects of the synthesis conditions were also investigated, and the optimal synthesis parameters of the cationic flocculant were obtained. The mass ratio between pea starch and AM was 0.5 with a reaction temperature of 65 °C. The dosages of ceric ammonium nitrate and 3‐chloro‐2‐hydroxypropyl‐trimethylammonium chloride were 0.02 and 0.11 mol/L, respectively. Application experiments for wastewater treatment were carried out consequently, and the optimal dosage of cationic pea starch was 40 mg/L within the pH range 6–8. Compared with other traditional flocculation products, the cationic pea starch showed the best flocculation behavior for coal mine wastewater. Therefore, the cationic pea‐starch‐grafted AM may be applicable as a novel flocculant in wastewater treatment and has already demonstrated outstanding features. It is bound to replace other traditional flocculants in the future. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43922.     

Lipase‐catalyzed acylation of konjac glucomannan in ionic liquids

A comparative study was made of lipase‐catalyzed acylation of konjac glucomannan (KGM) with vinyl acetate as the acyl donor in five ionic liquids (ILs) and also in the presence of the organic solvent tert‐butanol (t‐BuOH). An obvious enhancement in enzyme activity and stability was observed using ILs as the reaction media when compared with t‐BuOH. The maximum degree of substitution (DS) of the modified KGM in ILs and t‐BuOH under the conditions employed is 0.71 and 0.54, respectively. The water activity (a_w) of the reaction system affected the acylation of KGM to some extent. 1‐Butyl‐3‐methylimidazolium tetrafluoroborate (C₄MIm.BF₄) was the best IL medium for the reaction, and an a_w of 0.75 was optimum. It was also found that the nature of both the cation and the anion of ILs had an effect on the reaction. Candida antarctica lipase B immobilized on an acrylic resin (Novozym 435) displayed no acylation activity to KGM in 1‐butyl‐3‐methylimidazolium chloride (C₄MIm.Cl). The optimum reaction temperature for enzymatic acylation in ILs was shown to be 45‐55 °C. Enzymatic acylation of KGM in IL‐t‐BuOH co‐solvent systems was also investigated. When an appropriate amount of t‐BuOH was added to ILs, the DS of the modified KGM was enhanced. Additionally, the enzymatic acylation of KGM in all the media examined was shown to be regioselective, with acylation occurring predominantly at the C‐6‐OH. Copyright © 2006 Society of Chemical Industry     

有机高分子絮凝剂的合成及其应用

通过阳离子改性聚丙烯酰胺(MPAM)和聚多胺(PPA)的合成工艺的研究,探讨了反应温度及时间、反应物浓度及配比、产品的最佳投放量及最适合的pH值等因素对印染废水絮凝效果的影响。结果表明MPAM对印染废水COD的降低具有显著效果,并且可使污泥沉降的平均速率增加,PPA对印染废水色度的降低效果显著。     

阳离子魔芋葡甘聚糖的制备与表征

以3-氯-2-羟丙基三甲基氯化铵(HAT)为阳离子醚化剂,天然魔芋精粉为原料,异丙醇为分散剂制得系列季铵盐阳离子魔芋葡甘聚糖(CKGM)。研究了HAT、催化剂NaOH、反应温度和反应时间对阳离子取代度(DS)的影响,用元素分析仪测定了CKGM的取代度。确定较佳反应条件为:反应温度50℃,反应时间2 h,n(HAT)∶n(魔芋葡甘聚糖)∶n(NaOH)=1.5∶1∶2,DS为0.361,反应率为24.1%,并用FTIR1、HNMR和13CNMR进行了表征。     

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     

绿色可降解淀粉接枝改性阳离子化絮凝剂

以淀粉和丙烯酰胺为原料,加入醚化剂OMTAM进行接枝共聚反应,得到淀粉接枝改性阳离子化絮凝剂。首先对OMTMA投加量、碱的投加量和反应温度进行了单因素实验研究,并依据单因素实验结果,利用正交实验考察OMTMA的投加量、反应温度、反应时间、及碱的用量对絮凝性能的影响规律。结果表明：当最佳碱的投加量为3mL、OMTMA的投加量为0．05md、反应温度50℃、反应时间60mins时,絮凝剂对人工合成污水的去除率最佳。利用红外光谱对接枝前后的淀粉、以及接枝阳离子化以后的淀粉进行了结构表征。通过红外图谱对比分析表明,实验成功地对淀粉进行了接枝阳离子化。     

魔芋粉-丙烯酸-丙烯酰胺接枝共聚合成高吸水树脂

以魔芋粉,丙烯酸和丙烯酰胺等为原料,经接枝聚合合成了魔芋粉－丙烯酸－丙烯酰胺类超强吸水性树脂。讨论了引发剂,交联剂,丙烯酸,丙烯酰胺等用量以及反应时间和反应温度等因素对树脂吸水性能的影响。结果表明: 在魔芋粉与单体质量比为1:4,引发剂用量为0.35%（占单体的质量）,丙烯酸/丙烯酰胺（质量）为1:1,丙烯酸中和度为80% ,反应温度为55～65℃,交联剂用量为0.75%（占单体的质量）的条件下,制得的SAP吸去离子水可达720g/g,吸0.9%的NaCl溶液为110g/g。     

天然瓜尔胶改性研究

研究了阳离子瓜尔胶的制备方法、影响因素。通过对反应时间,反应温度,反应中氢氧化钠用量及溶剂等各因素的研究,得出最佳工艺条件:当瓜尔胶的用量为10.0 g时,CTA用量为1.50 g,氢氧化钠与CTA摩尔比为2.3左右,反应温度控制在80℃,反应时间为9.0 h,所得产物的取代度为0.062,反应效率为41.5%。     

聚硅酸/聚丙烯酰胺复合絮凝剂的研究

以硅酸钠为前驱体,制备得到硅溶胶,然后采用原位聚合法一步合成了聚硅酸/聚丙烯酰胺复合絮凝剂,通过红外光谱对合成产物的结构进行了表征。采用透光率、化学需氧量去除率对絮凝剂的絮凝效果进行了表征,并探讨了聚硅酸pH值、老化时间、聚合反应温度和时间等合成条件对絮凝效果的影响。结果表明,当硅酸钠浓度为0.5 mol/L、聚硅酸pH=5、老化时间为24 h、丙烯酰胺为5 g、引发剂用量为0.3 g,聚合反应温度为70 ℃、时间为90 min时,得到的聚硅酸/聚丙烯酰胺絮凝剂的絮凝效果最佳。     

季铵型低取代度阳离子淀粉的合成

以玉米淀粉及3-氯-2-羟丙基三甲基氯化铵(CTA)为原料,采用水法制备低取代度季铵型阳离子淀粉,讨论了醚化剂用量、NaOH用量、反应温度、反应时间等对取代度的影响。结果表明,最佳合成条件为:淀粉50 g,醚化剂用量3 g,NaOH用量为0.77 g,反应温度40℃,反应时间2 h,制备的阳离子淀粉取代度可达0.079。     

季铵化单宁的合成及其絮凝试验

单宁酸分子中含有大量的活泼氢原子,其与甲醛、丙烯酰胺发生曼尼西反应,获得阳离子单宁,并进一步和交联剂环氧氯丙烷反应得到季胺化单宁。通过对各种原料的配比、反应温度、反应时间等条件的优化最终获得纯度达70%的季胺化单宁。产物进行丁氰废水的絮凝试验,当原水pH为9.3、投加量为2 mg/L时,浊度去除率达98%以上,COD去除率为45%。     

Influence of Cationic Starch Adsorption on Fiber Flocculation

The adsorption of cationic starch on hardwood fibers and its influence on flocculation were studied in relation to the dosage of cationic starch, the effect of shear forces and the presence of different concentrations of inorganic salts in the paper stock. Flocculation was monitored by means of a focused beam reflectance measurement (FBRM) probe. It was established that floc size at low shear rates depends on adsorption efficiency. At high shear forces, flocs were irreversibly decomposed despite the presence of a higher amount of adsorbed cationic starch on the fibers. Therefore, flocculation was produced by a bridging mechanism. The results show a significant effect of inorganic salts on the adsorption of cationic starch on fibers. Low concentrations of inorganic salts usually improved the adsorption process while higher concentrations (> 0.01 mol/L) reduced the adsorption and limited the flocculation process.     

Synthesis and characterization of konjac glucomannan/poly(vinyl alcohol) interpenetrating polymer networks

Novel interpenetrating polymer networks (IPNs) coded as KP were synthesized successfully from poly(vinyl alcohol) (PVA) and konjac glucomannan (KGM) in the presence of glutaraldehyde as a crosslink agent. The transparent IPN films that were 40 μm thick were prepared by means of conventional solvent‐casting technique and dried at room temperature for 2 days. The structure and miscibility of the KP films were studied by Fourier transformed infrared spectra, scanning electron microscopy, differential scanning calorimetry, wide‐angle X‐ray diffraction, and ultraviolet visible spectroscopy (UV–Vis). The results indicated that strong intermolecular interaction caused by crosslink bonding between PVA and KGM occurred in the IPN films, resulting in wonderful miscibility when the reaction time is 4 h. The tensile strength, elongation at break, and moisture uptake was much higher than that of the pure PVA film, KGM film, and uncrosslinked blend films. In other words, the structure of IPN endowed the films with excellent performance, so the new material has promising applications to food package film and agricultural film because of its biodegradability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2775–2780, 2004     

疏水改性阳离子高分子絮凝剂的合成及其絮凝性能

以甲基丙烯酰氧乙基三甲基氯化铵(DMC)和甲基丙烯酸甲酯(MMA)为原料,通过无皂乳液聚合制备了流动性好的疏水改性阳离子型高分子絮凝剂P(DMC-MMA),并考察了不同因素对P(DMC-MMA)除油效果的影响。结果表明:在单体总质量分数为30%、n(DMC)∶n(MMA)=7∶3、反应温度75℃、引发剂用量为0.5%、反应时间8 h条件下制备的P(DMC-MMA)具有良好的絮凝效果,最高除油率可达96%,且絮体不黏壁。     

有机阳离子絮凝剂的制备及用于含油污泥脱油效果研究

针对大庆油田含油污泥特点,采用热洗法进行处理。为了增强脱油效果,投加有机阳离子絮凝剂对其进行有效调质。本文以环氧氯丙烷、三乙醇胺、三乙烯四胺（作为交联剂）为原料,采用水溶液聚合法制备有机阳离子絮凝剂,考察环氧氯丙烷与三乙醇胺摩尔比、三乙烯四胺用量、聚合温度、聚合时间对脱油率的影响。确定了聚合物最佳合成条件,并将其应用于含油污泥热洗法处理中,同时确定最佳使用条件。结果表明：聚合物加量为160mg/L,pH值为7时,与现场破乳剂同时加入,含油污泥脱油率可达82.83%,高于其他现场絮凝剂与破乳剂的联合加入,是一种有效的絮凝剂。SEM电镜分析表明：加入絮凝剂后,污泥絮体排列紧密,有利于污泥絮凝脱油。     

Graft copolymerization of 4‐vinyl pyridine onto konjac glucomannan initiated by ammonium persulfate

The grafting of 4‐vinyl pyridine (4‐VP) onto konjac glucomannan (KGM) by ammonium persulfate (APS) as the initiator was studied in an acid aqueous solution under an inert atmosphere. The grafting ratio (G%) and grafting efficiency (E%) were evaluated comparatively. The dependence of these parameters on the initiator concentration, sulfuric acid concentration, ratio of monomer to KGM, temperature, and reaction time was also investigated. Under conditions of [KGM] = 1.00 g/L, [APS] = 1.00 × 10^?2 mol/L, [4‐VP] = 9.32 × 10^?2 mol/L, [H⁺] = 5.00 × 10^?2 mol/L, temperature = 35°C, and time = 120 min, the optimum G% and E% were 307.27 and 52.75%, respectively. The proof of grafting was obtained from thermogravimetric analysis and infrared spectra. Preliminary research of the graft's adsorption capacity for heavy‐metal ions [Cr(VI), Cu(II), Pb(II), and Cd(II)] was done. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

絮凝技术在香波中的研究及应用

通过实验和絮凝图片比较分析,研究了絮凝的形成及其护发原理。实验结果表明,阳离子聚合物的絮凝效果随着分子量和电荷密度的增大而提升,而氢化钠的添加量对絮凝的形成具有极为关键的作用。通过筛选不同的阳离子聚合物,得出具有理想絮凝效果的阳离子聚合物为决明胶羟丙基三甲基氯化铵与瓜儿胶羟丙基三甲基氯化铵,而具有较高电荷密度的决明胶羟丙基三甲基氯化铵具有更好的絮凝效果。