On the characterization of grafted and ungrafted starch,amylose, and amylopectin

Graft copolymers of polyacrylamide with starch, amylose, and amylopectin have been synthesized using ceric-ion-induced redox initiation technique. The polymers were characterized using different instrumental techniques like thermal, XRD, SEM, IR, NMR, and elemental analysis. The results indicated that there is a substantial amount of grafting with minimum formation of homopolyacrylamide. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1795–1810, 1998     

Synthesis,characterization, and biodegradability of fatty‐acid esters of amylose and starch

A series of starch and amylose esters with different degrees of substitution and side‐chain length were prepared and studied. The esters were prepared by acylation of the polysaccharide with the appropriate acid chlorides, such as octanoic, dodecanoic, and octadecanoic. The degrees of substitution were 0.54, 1.8, and 2.7. After preparation, the resulting esters were characterized by elemental analysis, ¹H nuclear magnetic resonance (¹H‐NMR), Fourier transform infrared (FTIR), differential scanning (DSC), thermogravimetric analysis (TGA), contact angle, and water uptake measurements. Their mechanical properties and, in particular, the tensile strength and elongation at break depend on the side‐chain length and on the degree of substitution. The extent of their biodegradability, after exposure to activated sludge, was assessed by weight loss measurements and scanning electron microscopy (SEM). It was found that these new materials are biodegradable, and the biodegradation rate decreases with increasing degree of esterification. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1440–1451, 1999     

Thermal behavior and surface morphology studies on polystyrene grafted sago starch

Polystyrene grafting onto sago starch was carried out by using ceric ammonium nitrate as a redox initiator. The grafted copolymers were characterized by FTIR, thermogravimetry (TGA), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). FTIR spectra analysis of the grafted chain and commercial polystyrene was identical, indicating that styrene was successfully grafted onto sago starch. TGA thermograms and analysis of DSC curves showed that the thermal stability of starch increases as a result of grafting. SEM micrographs showed the deformed prolate ellipsoidal shape of sago starch particles and this shape disappeared in polystyrene grafted sago starch being replaced with a spongy surface with pores. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2053–2058, 2003     

淀粉接枝衣康酸/丙烯酸高吸水材料制备与性能

旨在为降低吸水材料成本、拓宽原料来源、提高生物降解性、减少对石油化工产品的依赖提供指导,以水溶液接枝共聚法制备了淀粉接枝衣康酸/丙烯酸高吸水材料（S/IA/AA）,讨论了淀粉糊化条件、中和度、单体含量、反应温度等因素对材料吸水性能的影响,采用FTIR、SEM、EDX等对吸水材料进行表征。研究表明：淀粉糊化最佳条件为糊化温度80℃,糊化比为10 g•g^-1,糊化时间30 min;吸水材料合成最佳条件为中和度50%,衣康酸40%,淀粉20%,引发剂为4×10^-3 mol•L^-1,交联剂0.075%,反应温度50℃;利用40％衣康酸替代丙烯酸所制S/IA/AA同S/AA相比,其吸水性能有一定提高且保水性能优良。     

The effect of amylose content from differing botanical sources on the nonlinear viscoelastic properties of semidilute solutions of maize starches*

The effect of the addition of potato or maize on the shear-thickening behavior of semidilute solutions of maize was examined. The experiments were conducted at 25°C using 90/10 weight–weight dimethyl sulfoxide (DMSO)–water as the solvent. The addition of amylose to maize amylopectin reduced and eventually eliminated the observed shear-thickening behavior of maize amylopectin. When potato amylose was combined with maize amylopectin, the shear-thickening phenomenon was observed up to a total amylose content of 10% by weight. For maize amylose, the shear-thickening behavior was eliminated at an amylose content of 5%. Maize amylose is thus more effective in inhibiting the formation of the structure formed after the shear-thickening region than potato amylose. This result indicates that the amylose obtained from potatoes interacts differently, or entangles differently, with maize amylopectin than does the amylose obtained from maize. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2429–2436, 1999     

Biodegradation of starch and acrylic‐grafted starch by Aspergillus niger

The biodegradation of starch and grafted starch by Aspergillus niger was examined. The grafted polymers were poly(methyl methacrylate) (PMMA) and poly(butyl acrylate) (PBA). Thermogravimetric analysis, Fourier transform infrared, and scanning electron microscopy were used to determine the morphology and degradation degree of each material. The temperature of maximum decomposition for starch decreased as enzymatic degradation proceeded, and it was completed on the 8th day of culturing in a liquid medium. Grafted samples with PMMA and PBA achieved degradation of their starch moiety. PBA in starch‐g‐PBA samples hindered the accessibility of the enzymes to the degradable material, and this resulted in a longer degradation time. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2764–2770, 2003     

星形聚丙烯酰胺接枝淀粉的合成及应用

介绍了应用水溶液聚合方法合成了星形聚丙烯酰胺（SPAM）的方法。采用正交实验方法研究了不同的引发剂用量、相对分子质量调节剂用量、聚合体系温度对SPAM特性黏数的影响,从中优化出最佳反应条件为单体质量分数为15%,聚合温度为35 ℃,引发剂质量分数为（相对单体质量,下同）0.04%,螯合剂为0.005%,抗交联剂为0.015%,聚合体系pH值为5,得到的星形聚丙烯酰胺特性黏数为989.2 mL/g。星形聚丙烯酰胺在35℃进行氯胺化反应并加到糊化好的淀粉溶液中,在40～50 ℃下反应40 min,即得到星形聚丙烯酰胺接枝淀粉絮凝剂。结果说明,星形聚丙烯酰胺接枝淀粉絮凝剂溶解性好、絮凝能力强,具有良好的絮凝效果。     

Enzyme hydrolysis of grafted amylopectin

Previous methods of proof of grafting are based on separation of homopolymers from crude reaction products and further characterization of extracted component. This article reports the proof of grafting by a combined use of viscometry and enzyme hydrolysis that, to our knowledge, has not been reported so far. Two series of graft copolymers of amylopectin with polyacrylamide were synthesized using ceric ion-induced redox initiation technique. In the first series, a variation of ceric ion concentration at fixed acrylamide concentration and in the second series, a variation of acrylamide concentration at fixed ceric ion concentration were undertaken to effect a variation in the number and length of polyacrylamide chains. Qualitatively, it has been observed that there may be some homopolymers formed at a very high acrylamide concentration. The products may at best be a mixture of graft copolymer and homopolymer, but it contradicts the view that the products are purely physical mixtures of polysaccharide and polyacrylamide. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2627–2633, 1998     

淀粉与丙烯酰胺接枝共聚物的合成及絮凝助留性能

采用乳液聚合技术 ,以水为分散介质 ,十二烷基苯磺酸钠为乳化剂和分散稳定剂 ,用过硫酸钾引发丙烯酰胺 (AM)对淀粉 (St)的接枝共聚。接枝共聚物 (St -PAM)在 16 5 0、16 16和 1416cm-1(聚丙烯酰胺PAM的特征吸收 )处的红外光谱表明 ,在淀粉链上引入了酰胺基。控制接枝共聚条件 ,可使丙烯酰胺的接枝效率 (共聚单体占全部聚合单体的质量分数 )达到 90 .0 % ,共聚物中丙烯酰胺的接枝百分率 (St-PAM中PAM的质量分数 )达到 6 0 .9%。显著地改善了淀粉的糊化特性 ,减弱了直链淀粉的凝沉和胶凝倾向 ,使其在冷水中就具有良好的分散性。研究了淀粉与丙烯酰胺接枝共聚的特点 ,考察了单体用量、反应温度、引发剂等因素对接枝共聚的影响 ,以及接枝共聚物对纸浆的絮凝和助留效果的影响。共聚物中丙烯酰胺的接枝百分率愈高 ,纸浆的絮凝速度和留着率愈大 ,接枝百分率为 6 0 .9%的共聚物可使纸浆的网上留着率提高 12 .3%。     

Shear and extensional investigations in solutions of grafted/ungrafted amylopectin and polyacrylamide

Various polysaccharides, such as starch and its constituent amylopectin, are used as flocculants in industrial effluent treatment. Grafting them with polyacrylamide branches enhances their flocculating and turbulent drag‐reducing characteristics drastically. Aqueous solutions of the graft copolymer of amylopectin with polyacrylamide show a shear thinning non‐Newtonian behavior. It is also expected that the solutions exhibit extensional effects. When the aqueous solution at 1000 ppm was subjected to a stretching device, the formation of a thread and reduction of the thread diameter with time were observed. The extensional relaxation time was thus estimated and compared with that of polyacrylamide. The measured relaxation time indicates that the performance of the rigid branched amylopectin, when grafted with fewer and longer polyacrylamide branches, is overwhelmed by the grafted polyacrylamide chains and the reduction of rigidity by the grafting process itself. This article reports the details of the investigations that led to these conclusions. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2773–2782, 1999     

Study of cryostructuration of polymer systems. XVIII. Freeze–thaw influence on water‐solubilized artificial mixtures of amylopectin and amylose

The effects caused by cryogenic treatment (freezing–frozen storage–thawing) of 0.5–2.0 g/dL solutions of individual starch polysaccharides, namely, amylopectin (solvents: water or 0.35M NaCl aqueous solution) and amylose (solvent: 0.35M NaCl aqueous solution), and also of 0.5 g/dL solutions of their artificial mixtures with various amylopectin/amylose ratios were studied. Freezing of these systems at temperatures from −6 to −24°C for 18 h and subsequent thawing resulted in the formation of cryogelled or cryoprecipitated matter whose morphology and yield depended on the type of polysaccharide, initial polymer concentration, portion of each macromolecular component in the mixed systems, and conditions of cryogenic treatment. Comparison of the process efficiency in the mixed systems during the formation of precipitates (from storage at room temperature) and cryoprecipitates (as a result of cryogenic treatment) revealed the promoting effects of the freezing–thawing influence on polymer–polymer association and showed the presence of some synergism in the mutual interaction of these polysaccharides. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 371–381, 2000     

Preparation and characterization of amphiphilic starch nanocrystals

In this article, amphiphilic starch nanocrystals were synthesized by graft copolymerization of starch nanocrystals with styrene in aqueous emulsion system. The starch nanocrystals of size around 50 nm were used, which were prepared by acid hydrolysis of corn starch. The structure of starch‐g‐polystyrene nanocrystals was characterized by Fourier transform infrared and ¹H nuclear magnetic resonance (¹H NMR). The crystalline structure as well as its particle morphology was studied by X‐ray diffraction and scanning electron microscopy, respectively. The results indicated that the amphiphilic starch nanocrystals obtained exhibit the size around 80–100 nm. Its crystalline structure is basically not changed after grafting polystyrene suggested that the polystyrene was essentially grafted on the surface of starch nanocrystals. Wettability experiments indicated that the prepared starch‐g‐polystyrene nanocrystals can be uniformly dispersed both in water phase and oil phase revealing excellent amphiphilicity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Molecular weight and chain conformation of amylopectin from rice starch

By using laser light scattering (LS) and size exclusion chromatography combined LS, we have investigated the molecular weight and chain conformation of amylopectin from rice of India (II‐b), japonica (IJ‐b), and glutinous (IG‐b) in dimethyl sulfoxide (DMSO) solution. The weight‐average molecular weight (M_w) and radius of gyration (〈S²〉^½) of amylopectin were determined to be 4.06 × 10⁷ and 128.5 nm for India rice, 7.41 × 10⁷ and 169.6 nm for japonica rice, 2.72 × 10⁸ and 252.3 nm for glutinous rice, respectively. The 〈S²〉^½ values were much lower than that of normal polymers, indicating a small molecular volume of amylopectin, as a result of highly branched structure. Ignoring the difference of degree of branching, approximated dependences of 〈S²〉^½ and intrinsic viscosity ([η]) on M_w for amylopectin in DMSO at 25°C were estimated to be 〈S²〉^½ = 0.30M_w^0.35 (nm) and [η] = 0.331M_w^0.41 (mL g^?1) in the M_w range studied. Moreover, from the 〈S²〉^½ values of numberless fractions obtained from many experimental points in the SEC chromatogram detected with LS, the dependence of 〈S²〉^½ on M_w for the II‐b sample was estimated also to be 〈S²〉^½ = 0.34 M_w^0.347, coinciding with the above results. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

Synthesis and characterization of butyl acrylate graft sodium salt of partially carboxymethylated starch

Graft copolymers were synthesized by graft copolymerization of butyl acrylate (BA) onto sodium salt of partially carboxymethylated starch (Na‐PCMS). Ceric ammonium nitrate (CAN), a redox initiator, was used for initiation of graft copolymerization reaction. All the experiments were run with Na‐PCMS having degree of substitution, DS = 0.35. The grafting reaction was characterized by parameters such as % total conversion (%Ct), % grafting (%G), % grafting efficiency (%GE), and % add‐on. Graft copolymers were characterized by infrared spectral analysis and scanning electron microscopy. Variables affecting graft copolymerization reaction such as nitric acid concentration, reaction time, reaction temperature, and ceric ion concentration were investigated. The results revealed that 0.3M CAN as initiator, 0.3M HNO₃, with reaction time 4–4.5 h at 25–30°C were found as suitable parameters for maximum yield of graft copolymerization reaction. © 2006 Wiley Periodicals, Inc. JAppl Polym Sci 102: 3334–3340, 2006     

淀粉-聚丙烯酰胺接枝共聚物的工艺优化与性能研究

通过玉米淀粉接枝聚丙烯酰胺(PAM)制成了新型复合絮凝剂S-g-PAM,进行了影响接枝共聚物合成的单因素实验和正交实验,以对高岭土悬浊液的絮凝性能为评价指标。结果表明,最佳合成条件为,m(玉米淀粉)∶m(PAM)=3∶0.001(质量比),NaOH∶NaOCl=2∶3(体积比),反应时间40 min,反应温度30℃,对高岭土溶液(110NTU)最佳去浊度效果为97%,投加量为30 mg/L。S-g-PAM使用的pH值范围为8~10,最佳温度范围20~40℃,与其它絮凝剂相比,其絮凝效果较好。     

An investigation of the flocculation characteristics of polyacrylamide‐grafted chitosan

To investigate the flocculation characteristics of polyacrylamide (PAM)‐grafted chitosan, a series of PAM‐grafted chitosan copolymer (Chito‐g‐PAM1 to Chito‐g‐PAM4) have been synthesized by ceric ammonium nitrate‐induced solution polymerization technique in nitrogen atmosphere. The flocculation characteristics of the polymer samples (PAM, grafted and ungrafted chitosan) were studied by settling test and jar test methods in the colloidal suspensions of kaolin, iron ore, silica, and bentonite powder. It was found that the settling performance of Chito‐g‐PAM3 is best among the polymer samples. The jar test results indicate that the ungrafted chitosan has better water clarifying performance than both the PAM and grafted chitosan. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of polyethylene‐graft‐poly(styrene‐co‐maleic anhydride) and its compatibilizing effects on polyethylene/starch blends

Low density polyethylene (LDPE) was reacted with benzoyl peroxide (BPO) and 2,2,6,6‐tetramethyl‐l‐piperidinyloxy (TEMPO) to prepare a latent macroinitiator, PE–TEMPO. Little polymer was synthesized when maleic anhydride (MAH) was bulk polymerized in the presence of the PE–TEMPO. However, addition of styrene accelerated the polymerization rate and PE‐grafted‐poly(styrene‐co‐maleic anhyride) [PE‐g‐P(ST‐co‐MAH)] was produced to a high yield. Chemical reaction between MAH units and hydroxyl groups of starch was nearly undetectable in the PE/PE‐g‐P(ST‐co‐MAH)/starch blend system, and the tensile properties of the blend were not enhanced significantly. However, addition of tetrabutyl titanate (TNBT) during the blending procedure improved the tensile properties significantly through an increased interfacial adhesion between the components in the blend system. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2434–2438, 2003     

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     

水溶性壳聚糖季铵盐的制备工艺及絮凝性能研究

采用壳聚糖（CTS）为原料,NaOH为催化剂,与3-氯-2-羟丙基三甲基氯化铵（CTA）进行季铵化反应,得到了取代度较高的壳聚糖接枝物,确定最佳反应工艺条件为：n（NaOH）／n（CTA）=1．1：1,n（CTA）／n（CTS）=5：1,反应时间为8h,反应温度为78℃。合成的产物能完全溶于水,并将产物对马铃薯淀粉厂废水进行了絮凝性能测试,结果表明水溶性壳聚糖季铵盐对污水的絮凝效果良好。