反相乳液聚合制备阳离子改性接枝淀粉

本实验以淀粉、丙烯酰胺、阳离子单体(二甲基二烯丙基氯化铵)为原料,采用过硫酸铵--尿素氧化还原引发体系,以油酸失水山梨醇酯为乳化剂,通过反相乳液聚合技术,合成阳离子改性淀粉接枝共聚物.分析讨论了单体配比、乳化剂用量、引发剂用量及油水体积比等合成条件对共聚物性能的影响,并采用正交实验方法对合成条件进行了优化.     

Graft Copolymerization Onto Starch. 3: Grafting of Acrylamide Using Ceric Ion Initiation and Preparation of Its Hydrogels

The grafting of acrylamide (AM) onto maize starch in aqueous medium initiated by ceric ammonium nitrate (CAN) has been studied gravimetrically under nitrogen atmosphere. The effect of concentration of monomer and initiator, polymerization time and reaction temperature has been studied in terms of efficiency of grafting (%GE) and percentage Add-on (%Add-on). The %GE was found to decrease with increase in monomer concentration, but the reverse trend was obtained on increasing the polymerization time and temperature. The maximum %GE was obtained at 45°C when polymerization was carried out for 180 min using [CAN] = 0.004 mol/L and [AM] = 0.141 mol/L in 100 mL of distilled water with 2 g of starch. These graft copolymers were characterized by IR spectroscopy and thermogravimetric analysis. The graft copolymers showed enhanced thermal stability than pure starch. Hydrogels were prepared by grafting AM onto gelatinized maize starch followed by saponification of these graft copolymers with NaOH. The maximum water absorption obtained was 170 g/g.     

反相乳液聚合制备阳离子改性接枝淀粉

本实验以淀粉、丙烯酰胺、阳离子单体(二甲基二烯丙基氯化铵)为原料,采用过硫酸铵-尿素氧化还原引发体系,以油酸失水山梨醇酯为乳化剂,通过反相乳液聚合技术,合成阳离子改性淀粉接枝共聚物.分析讨论了单体配比、乳化剂用量、引发剂用量及油水体积比等合成条件对共聚物性能的影响,并采用正交实验方法对合成条件进行了优化.     

Response Surface Methodology for the Optimization and Characterization of Cassava Starch‐graft‐Poly(acrylamide)

Response surface methodology (RSM) was employed for the synthesis of cassava starch‐graft‐poly(acrylamide) using ceric ammonium nitrate as free radical initiator. Concentration of acrylamide, concentration of ceric ammonium nitrate, reaction temperature and duration of reaction were optimized using a 4‐factor 3‐level Box‐Behnken design. The dependent variables were percentage grafting (%G) and grafting efficiency (GE). Second order polynomial relationships were obtained for %G and GE, which explained the main, quadratic and interaction effects of factors. The highest%G and GE obtained were 174.8% and 90.7%, respectively. The optimum values of parameters predicted through RSM were 20 g acrylamide/10 g dry starch, 3.3 g/L ceric ammonium nitrate, 180 min reaction duration and 45ºC temperature with a %G of 190.0. For GE, the predicted levels of factors for the optimum value of 90.8% were 17.5 g acrylamide/10 g dry starch, 4.1 g/L ceric ammonium nitrate, 180 min reaction duration and 55ºC temperature. The graft reaction was confirmed by FTIR analysis, where the absorption bands corresponding to the C=O stretching and N‐H bending of the –CONH₂ group were observed. Scanning electron microscopic studies on grafted starches revealed that the granular structure of the starch was affected by the reaction. X‐ray diffraction analysis showed that the crystallinity of starch was decreased as a result of grafting and the reduction was higher for the grafted starches with higher percentage grafting.     

Synthesis and Application of New Thickerners Part I: Preparation of Poly (Acrylic Acid)-Starch Graft Copolymer

Graft polymerization of maize starch with acrylic acid using potassium persulphate as free radical initiator was investigated under different conditions. Variables studied included initiator concentration, acrylic acid concentration, starch/water ratio and polymerization temperature. The carboxyl content of the grafted starch was determined and used for calculation of the grafted yield. It was found that the graft yield increases by increasing persulphate; no significant enhancement in grafting could be observed upon using higher persulphate concentrations. Grafting increases also by increasing acrylic acid concentration up to 150% (based on wt. of starch) and tends to decrease at higher concentrations. Starch/water ratio of 1:6 constitutes the optimal for maximum grafting. Raising the polymerization temperature from 25 to 43°C enhances the polymerization rate. The apparent activation energy of the copolymerization reaction amounts to 182.17 Joule/mole.     

以季戊四醇为核分子的支化CPAM的制备及其增强效果

以季戊四醇(PETL)为聚合反应的支化剂,硝酸铈铵为引发剂,选用二甲基二烯丙基氯化铵(DADMAC)为阳离子单体,丙烯酰胺(AM)为单体,通过自由基聚合反应制备支化阳离子聚丙烯酰胺(BCPAM);利用红外光谱、13 C-NMR核磁共振谱对所合成的产物结构进行了表征;研究引发剂的用量、阳离子单体用量对产物特性黏度的影响;以BCPAM作为纸张增强剂,研究其对纸张强度性能的影响.研究结果表明,所合成的产物为BCPAM;引发剂及阳离子单体用量因影响产物相对分子质量或分子链的形态而影响其特性黏度;BCPAM对纸张增强作用显著,当其用量为0.5％时(对绝干浆),纸张的抗张指数提高了40.6％,撕裂指数提高了27.6％,耐破指数提高了12.6％.     

铝铵基阳离子淀粉的制备与应用

实验利用水溶剂法,以普通阳离子淀粉（CS）、二甲基二烯丙基氯化铵单体（DADMAC）、铝溶胶为原料,硝酸铈铵（CAN）为引发剂,制备了铝铵基阳离子淀粉（ACS）。研究了引发剂用量、单体用量、反应温度、反应时间等对接枝反应的影响。研究发现最佳的反应条件为：引发剂用量为0.54%,单体用量为50%,铝溶胶加入量为3.5%,反应温度为55℃,反应时间为3 h,m（H2O）∶m（St）=2∶1,可制得氮含量约为0.58%的ACS,高于普通的阳离子淀粉CS（0.30%）。用紫外分光光度法测定产品的铝含量并采用红外光谱对接枝共聚物进行了结构分析。将铝铵基阳离子淀粉应用于脱墨浆中,最低白水浊度为5.2 NTU;最高灰分含量为23.27%。在用量低于0.5%时,能同时提高纸张的强度和细小纤维的留着率,具有助留和增强的双重作用。通过在浆中加入相同量的ACS和CS进行比较,发现ACS的絮凝作用和助留效果均优于CS。     

Inverse Emulsion of Starch‐graft‐Polyacrylamide

An inverse emulsion of cationic starch‐graft‐polyacrylamide was prepared by inverse emulsion polymerization and a subsequent Mannich reaction. The copolymerization was carried out using potassium persulfate as initiator. The reaction conditions and factors affecting emulsion stability were studied. Experiments showed that a high solids content, a high cationic degree and a stable latex can be obtained under the following condition: A molar ratio starch/acrylamide/formaldehyde/dimethylamine of 0.11:1:1:1.2; a stable inverse emulsion system; graft copolymerization of starch and acrylamide for 2‐3 h at 50 °C; pre‐formation of an aldehyde‐amine adduct, which is subsequently dropped into an inverse emulsion of starch‐graft‐polyacrylamide. The reaction temperature was 45 °C, the reaction time was 3‐4 h, and the pH was 5.5.     

Synthesis of Vinyl Polymer-Starch Composites to Serve as Size Base Materials

Starch was polymerized independently with acrylamide, acrylic acid, methacrylic acid and acrylonitrile (AN) using potassium persulphate (K₂S₂O₈) as initiator. The products of the polymerization reaction consisted of free starch, grafted starch, homopolymer and oxidized starch. The ratios of these composite constituents were found to differ considerably depending upon the nature of monomer as evidenced by differences in viscosity curves (amylograph-viscograph) as well as sizeability of the composites and their ease of removal from cotton yarns during desizing. Also studied was the dependence of the extent of polymerization (grafting and homopolymerization) of AN to starch on K₂S₂O₈ and AN concentrations, polymerization temperature, starch/AN ratio and starch + AN/liquor ratio; and the onset of these factors on the apparent viscosity of the composite obtained thereof. Results indicated that the extent of polymerisation increased by increasing the persulphate concentration to 6 g K₂S₂O₈/100 g starch then levelled off; the same held good for apparent viscosity but the latter decreased upon using concentrations higher than 6 g K₂S₂O₈/100 g starch. While the extent of polymerization increased over a range of 8-32g AN/100 g starch, apparent viscosity decreased. Raising the polymerization temperature from 30 to 60°C caused significant enhancement in the extent of polymerization but with the certainty that maximum apparent viscosity was attained at 50°C. The extent of polymerization was much favoured at higher AN ratio, but maximum apparent viscosity was attained at starch/AN ratio of 83:17. On the other hand, the extent of polymerization decreased by increasing starch + AN/liquor ratio upto 1:75 then remained almost constant upto a ratio of 1:12.5; meanwhile maximum apparent viscosity was observed at a material/liquor ratio of 1:7.5. The results were interpreted in terms of differences in the magnitude of constituents of the poly (AN) - starch composite and their affinity for and swellability in water.     

Effects of cationization on DSC thermal profiles,pasting and emulsifying properties of sago starch

Cationic sago starches were prepared using an aqueous alkaline process with different levels of cationic reagent 3‐chloro‐2‐hydroxypropyltrimethylammonium chloride (0.01–0.10 M ), sodium hydroxide (0.03–0.86 M ) and reaction temperature (30–62 °C). The degree of substitution (DS), reaction efficiency, thermal and pasting properties of cationic sago starches were analysed. Emulsifying and fat binding properties of native sago starch, cationized sago starch and commercial chitosan were compared at two different pH values (4 and 7). Degree of substitution increased with an increase in concentration of cationic reagent or NaOH, or reaction temperature. The reaction efficiency was proportional to the concentration of NaOH and reaction temperature but inversely proportional to the cationic reagent concentration. The highest DS and reaction efficiency achieved was 0.06 and 79%, respectively. The pasting temperature and gelatinization enthalpy of cationic starch (DS 0.06) were lower compared with native sago starch. Cationization increased the peak viscosity and breakdown of the starch paste but decreased the setback. The presence of cationic groups significantly increased emulsion stability, emulsion viscosity and fat binding capacity of sago starch. However, the cationic sago starch was still inferior to chitosan, which showed the highest emulsion stability, emulsion viscosity and fat binding capacity. There was no significant difference between the surface tension values of native and cationic sago starch and chitosan. The influence of pH on emulsifying properties was not significant. The emulsion stability of the cationic sago starch improved due to an increase in viscosity and fat binding capacity but not its surface active property. Copyright © 2004 Society of Chemical Industry     

过硫酸铵引发阳离子淀粉接枝共聚物合成与表征

采用水溶液聚合方法,以过硫酸铵(APS)为引发剂,将玉米淀粉(St)与丙烯酰氧乙基三甲基氯化铵(DAC)单体接枝聚合,制备阳离子淀粉高分子聚合物。讨论单体质量比、引发剂用量、反应温度和反应时间等因素对聚合物阳离子度的影响。结果表明：当加入淀粉质量1.0%的过硫酸铵,DAC与淀粉质量比2.5:1,50℃反应8h时,接枝共聚物的阳离子度最高可达53.68%。用红外光谱、扫描电镜、热失重分析对接枝共聚物结构进行表征,表征结果均证实阳离子淀粉高分子聚合物制备成功。     

新型引发体系对淀粉接枝共聚反应的影响研究

为探讨新型引发体系对淀粉接枝共聚反应的影响,以玉米淀粉为原料,采用过硫酸铵-亚硫酸氢钠引发体系合成了淀粉接枝丙烯酸丁酯共聚物,确定了丙烯酸丁酯浓度、引发剂浓度、过硫酸铵与亚硫酸氢钠间摩尔比、反应温度、反应时间等工艺条件.并通过红外光谱、X-射线衍射仪和扫描电子显微镜对共聚产物结构进行了表征.过硫酸铵-亚硫酸氢钠引发体系可有效降低接枝共聚反应的活化能,从而降低反应温度,且该接枝淀粉的合成工艺简单,成本较低.     

衣康酸/丙烯酸与聚酯织物接枝共聚性能

研究了在水溶液中以过氧化苯甲酰为引发剂,衣康酸/丙烯酸为单体与碱处理后的三叶形聚酯(PET)平纹织物接枝共聚;对共聚条件如聚合温度、时间、引发剂浓度、单体物质的量比等进行研究,得出最佳聚合条件。电子扫描电镜照片和傅里叶红外变换光谱显示衣康酸/丙烯酸共聚到聚酯大分子上。研究结果表明随着接枝率的上升,织物吸湿快干性能提高;阳离子染料上染率大幅度提高,织物色光鲜艳。     

A Novel Copolymer: Starch‐g‐Polyvinylpyrrolidone

In this study, graft copolymerization of N‐vinylpyrrolidone (N‐VP) onto starch was carried out in an aqueous medium using azobisisobutyronitrile (AIBN) as initiator. The variables affecting the graft copolymerization, such as monomer and initiator concentrations, reaction time and temperature, were thoroughly examined. In general, grafting of N‐vinylpyrrolidone onto starch increased with the increase in time and monomer concentration up to a certain value and then leveled off. Similarly, increase both in initiator concentration and temperature first favored and than impeded the grafting reaction. Optimum conditions established for grafting were as follows: N‐VP = 0.7 M, AIBN = 1.5×10^‐3 M, T = 70°C and t = 5 h. Structural changes of the grafted starch were followed by FTIR, intrinsic viscosity and water absorption capacity studies.     

低取代度阳离子淀粉-丙烯酰胺接枝共聚物的制备及应用

以低取代度的阳离子淀粉为原料,硝酸铈铵为引发剂,制备了低取代度阳离子淀粉-丙烯酰胺接枝共聚物。研究了丙烯酰胺与阳离子淀粉质量比、反应温度、反应时间和引发剂浓度对接枝率和接枝效率的影响。结果表明:接枝率和接枝效率最高的条件为:m(丙烯酰胺)∶m(阳离子淀粉)=2.5∶1,反应温度为55℃,反应时间为3 h,c(引发剂)=2 mmol/L。将合成的聚合物用于纸张增强,当低取代度阳离子淀粉-丙烯酰胺接枝共聚物的用量为1.0%时,对纸张的增强效果最好,可使纸张抗张指数增加23.0%,撕裂指数增加12.7%,耐破指数增加63.7%,耐折度增加115.1%。     

Synthesis,characterization and swelling behaviour of superabsorbent polymers from cassava starch‐graft‐poly(acrylamide)

Superabsorbent polymers (SAPs) were prepared from cassava starch by graft copolymerization of acrylamide on to starch using ceric ammonium nitrate (CAN) as free radical initiator, followed by alkali saponification. The reaction parameters such as concentration of acrylamide, concentration of CAN, temperature, and duration of polymerization reaction were optimized for maximum water absorbency using a 4‐factor 3‐level Box‐Behnken design. The highest values of percentage grafting and absorbency obtained were 174.8% and 425.2 g/g, respectively. The polymers were characterized by determination of grafting efficiency, N‐content, acrylamide content, FTIR analysis, SEM and XRD analyses. Thermogravimetric analysis (TG) showed that the SAP has higher thermal stability. The rate of water absorbency and the swelling behaviour of the SAP under different conditions of pH, and different salts were determined. The de‐swelling pattern of the hydrogels over different time durations was also determined.     

Poly(Acrylic Acid)-Starch Composites. A Key for Improving Sizeability and Desizeability of Starch from Cotton Textiles

Maize and rice starches were independently polymerized with acrylic acid (AA) using potassium permanganate/citric acid initiation system. The dependence of total conversion (grafting and homopolymerization) on AA, potassium permanganate and citric acid concentrations, time and temperature of polymerization and rate of stirring were studied. Based on the results appropriate conditions for preparation of poly(AA)-starch composites were established. While the total conversion increased by increasing AA concentration from 10% to 30%, based on weight of starch (ows), maximum total conversion occured upon using 0,2% potassium permanganate along with 0.025% citric acid, ows, for 10 min at 40°C and stirring rate of 300 r. p. m. It was further disclosed that: (a) the total conversion for maize starch is higher than rice starch, (b) the apparent viscosity of the composite increases by increasing AA concentration from 10% to 30% and polymerization temperature from 30°C to 50°C, (c) for 10% AA concentration the composite consists of 97.67 starch and 2.33% poly-(AA) of which 1.36% is grafted whereas for 30% AA concentration the composite consists of 79.3% starch and 20.7% poly(AA) of which 3.2% is grafted, (d) the sizeability of native starches is considerably improved after polymerization with AA and (e) size removal from cotton fabric with the composites to ca. 80% while wize removal from cotton fabric sized with native starches amounts to ca. 20%.     

马铃薯淀粉与醋酸乙烯酯接枝聚合影响因素的研究

以马铃薯淀粉为接枝骨架,过硫酸铵为引发剂,醋酸乙烯酯(VAc)为接枝单体进行接枝共聚。考察了不同引发剂浓度、反应温度、反应时间、单体配比、淀粉浓度对单体转化率、接枝率及接枝效率的影响,确定最佳工艺条件为:引发剂浓度18 mmol/L,反应温度60℃,反应时间3.5 h,单体配比2.5:1,淀粉浓度5%。并通过扫描电镜,X射线衍射,傅里叶红外光谱对淀粉接枝共聚物进行分析,结果表明:淀粉接枝共聚后,淀粉的微观形貌已经改变,结晶度降低且醋酸乙烯酯成功接枝在马铃薯淀粉上。     

Effect of Pullulanase Debranching of Sago (Metroxylon sagu) Starch at Subgelatinization Temperature on the Yield of Resistant Starch

The effects of pullulanase debranching of sago (Metroxylon sagu) starch in the granular state and subsequent physical treatments on the formation and yield of type III resistant starch (RS 3) have been investigated. Sago starch was enzymatically debranched with pullulanase at 60°C and at pH 5.0 using different enzyme concentrations (24, 30, 40, 50 PUN/g dry starch) which was added to 20% (w/v) starch slurry and incubated for 0 to 48 h. Optimum enzyme concentration of 40 PUN/g dry starch and three debranching times (8, 16 and 24 h) have been selected for subsequent preparation of RS. Granule morphology and molecular weight distribution (MWD) of the debranched and resistant starch were examined. Debranched starch samples showed blurred birefringence patterns, a decrease in amylopectin fraction, an increase in low molecular weight fraction and a broadening of MWD. Debranched starch samples with a maximum RS yield of 7% were obtained at 8 h debranching time. Temperature cycling and incubation at certain temperature and storage time enhanced the formation of RS. Under the conditions used in this study, the optimum conditions to obtain the highest RS yield (11.6%) were 8 h of debranching time, followed by incubation at 80°C for seven days. The MWD analysis showed that RS consisted of material with relatively low degree of polymerization. This study showed that pullulanase treatment of starch in the granular state resulted in limited debranching of amylopectin but the subsequent physical treatments (incubation time/temperature) can be manipulated to promote crystallization and enhance formation of RS 3.     

Modification and Characterization of Leucaena glauca Seed Gum by Graft Copolymerization with Acrylonitrile

The suitable conditions for graft copolymerization of acrylonitrile on to Leucaena glauca seed gum in aqueous system were investigated using hydrogen peroxide as initiator. For the purpose, a series of reactions have been carried out at different reaction conditions which cover the range of hydrogen peroxide concentration (5–20 mmole/l), acrylonitrile concentration (0.05–0.25 mole/l), backbone concentration (0.00617–0.03086 mole AGU) and polymerization time (30–180 min). The grafting temperature was kept at 85°C for all reactions. The products have been characterized by various methods including viscometry, spectrophotometry and thermometry.