干法制备高取代度高黏度羧甲基淀粉

以马铃薯淀粉和氯乙酸钠为原料,通过分阶段碱化和醚化方法,采用先进的干法工艺制备了高取代度、高黏度的羧甲基淀粉。并详细考察了氯乙酸钠用量、碱用量、反应温度及时间等条件对产品取代度和黏度的影响。实验结果表明,当淀粉、氯乙酸钠及氢氧化钠摩尔比为1:1:1．25时,在碱化和醚化反应温度、时间分别为35℃、 60 min和70℃、2．5 h条件下,可制备出取代度最高达0．73,反应效率为73％,黏度可达11 600 mPa·s的高取代度、高黏度羧甲基淀粉。     

高取代度羧甲基淀粉醚的制备研究

本文采用两次加碱法以乙醇为溶剂制备高取代度(DS=0.9)羧甲基淀粉醚,可使原料氯乙酸的利用率提高到80%以上,粘度(0.2%水溶液)高于15 MPa·s。     

羧甲基淀粉醚取代度的测定方法

本文论述了羧甲基淀粉醚取代度的测定方法,指出新开发的分光光度法与经典的灰化法和改进后的酸洗法比较,其精密度和准确度均无显著性差异。     

快速测定羧甲基淀粉的官能团及取代度

本文介绍一种快速测定羧甲基淀粉的官能团及取代度的方法——铜盐沉淀法。将硫酸铜溶液加入淀粉溶液中生成羧甲基淀粉铜沉淀,过滤除去沉淀。再用络合滴定法滴定滤液中过量铜。该法准确可靠,简便易行,适用于淀粉工业中常规的生产性检验。     

高取代度羧甲基淀粉的合成及应用研究Ⅰ.高取代度羧甲基淀粉的合成

首次研究成功了一套在甲醇存在下,在碱性介质中进行了氯乙酸与淀粉反应合成取代度１．０至３．０的羧甲基淀粉的新工艺,优化反应条件为：投料比：淀粉：一氯乙酸：氢氧化钠＝１：１：２,反应温度５０℃,反应时间５ｈ反应率为９０％以上。     

高取代度羧甲基淀粉的合成及性能研究

以木薯淀粉、氯乙酸为原料,异丙醇为溶剂,多次加碱工艺合成高取代度羧甲基淀粉(CMS).通过正交实验考察了反应温度、反应时间、反应物料浓度、水的用量对取代度的影响,对影响羧甲基淀粉醚取代度的各因素进行了优化.制备取代度DS＞1.3的木薯羧甲基淀粉的原料最佳摩尔比:力[木薯淀粉(以吡喃环单元AGU计)]:n(氯乙酸)=1:3,n(氢氧化钠):n(氯乙酸)=2.5:1,醇与水的体积比为19:1,碱化温度30℃,碱化时间60 min,醚化温度50℃,醚化时间120 min.     

高取代度羧甲基淀粉的合成及应用研究Ⅰ.高取代度羧甲基淀粉的合成

首次研究成功了一套在甲醇存在下,在碱性介质中进行氯乙酸与淀粉反应合成取代度（ＤＳ）１．０至３．０的羧甲基淀粉（ＣＭＳ）的新工艺,优化反应条件为：投料比：淀粉∶一氯乙酸∶氢氧化钠＝１∶１∶２（摩尔比）,反应温度５０℃,反应时间５ｈ,反应率为９０％以上。     

一次羧甲基化制备高取代度(DS=2.20)羧甲基玉米淀粉

通过一次羧甲基化制备了DS=2.20的高取代度羧甲基玉米淀粉(CMCS)。研究了氢氧化钠用量、反应介质、反应时间和反应温度对反应效率(RE)和取代度(DS)的影响。当n(NaOH)/n(AGU)=4时,最佳反应条件为n(NaOH)/n(ClCH2COOH)=2.5、异丙醇中φ(水)=2.4%、反应温度50℃、反应时间2h,在最佳反应条件下制得CMCS的DS=2.20,RE=55%。另外,用红外光谱证明了CMCS中存在羧甲基结构。     

甘蔗渣制备高取代度羧甲基纤维素研究

提出一种一锅法制备高取代度羧甲基纤维素的方法,选用甘蔗制糖过程中产生的副产物甘蔗渣为主要原料,经碱浸泡、碱化及醚化合成了羧甲基纤维素,经单因素实验和正交试验探究得到最大取代度为0.3,且有良好的水溶性。利用红外光谱(IR)仪、X-射线衍射(XRD)仪、扫描电镜(SEM)仪及元素分析仪等设备对其进行了表征。证明所得产品为高取代度的羧甲基纤维素。     

高取代度淀粉醋酸酯的制备研究

本文就高取代度淀粉醋酸酯的制备进行了研究 ,讨论了原料的选择处理及制备过程中各因素的影响 ,为确定最佳的合成条件提供了依据。结果表明 ,选用优质淀粉原料并进行一定的改性处理 ,以对甲苯磺酸作催化剂 ,合理选配酯化剂 ,预先糊化并控制在低温反应 ,可获得性能优良且性价比较高的高取代度淀粉醋酸酯制品     

Optimization of preparation conditions of carboxymethyl potato starch through orthogonal experimental design

To optimize the preparation conditions of carboxymethyl potato starch (CMPS), the effects of relevant factors on viscosity (η) of 2% CMPS aqueous solution and degree of substitution (DS) were investigated. These condition parameters included etherification temperature, alkalization and etherification time, water content in the mixed solvent, ratio of liquid volume to starch mass, molar ratio of sodium hydroxide to monochloroacetic acid, and molar ratio of monochloroacetic acid to anhydroglucose unit. After individual parameter influencing η and DS was researched one by one, an orthogonal experiment of L₁₈ (2 × 3⁷) was designed to identify the main factors affecting them. In light of range analysis, the comparative importance of factors impacting η and DS was obtained, separately. Results of variance analysis showed that the most effective factor to control DS was etherification temperature, whereas the influences of all factors on η were not significant. Meanwhile, η and DS of the optimized final product were found to be 12,000 mPa.s and 0.68, respectively. In addition, the structure of CMPS was characterized by Fourier transform infrared (FTIR) spectrophotometer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

高取代度酯化淀粉的制备与工艺研究

采用有机溶剂法制备高取代度淀粉琥珀酸酯。以琥珀酸酐为酯化剂,对淀粉进行酯化改性。经单因素试验法得到淀粉琥珀酸酯的制备条件,采用正交试验法研究淀粉琥珀酸酯制备的最佳工艺条件：反应温度50℃,反应时间5 h,每克活化淀粉催化剂用量1 m L,活化淀粉与酸酐分子的摩尔比为1∶3。在最佳制备条件下,制得取代度为0.40的淀粉琥珀酸酯。     

季铵型高取代度阳离子淀粉的合成

采用3-氯-2-羟丙基三甲基氯化铵(CTA)为醚化剂,通过干法对淀粉进行改性,合成季铵型高取代度阳离子淀粉。研究了体系中水的质量分数、CTA用量、CTA与NaOH的摩尔比、反应时间、反应温度对产品的取代度和黏度的影响。最佳合成条件为:淀粉100 g,体系中水的质量分数25%,n(CTA)∶n(NaOH)=1∶1.2,反应时间4 h,反应温度70℃。在此条件下制得的阳离子淀粉取代度高达0.598,质量分数0.5%糊液的黏度为0.079Pa.s。干法具有合成工艺简单、反应效率高、环境污染小、成本低等优点。对其市场前景进行了展望。     

Synthesis,characterization, and anticoagulant activity of carboxymethyl starch sulfates

To develop a renewable and compatible anticoagulant as potential heparin alternative, carboxymethyl starch sulfate (CMSS) was prepared by the reaction of carboxymethyl starch (CMS) and sulfating reagent [N(SO₃Na)₃]. The chemical structures of CMS and CMSS were characterized by Fourier transform infrared spectroscopy and ¹³C nuclear magnetic resonance. The influences of reaction parameters, including the pH of sulfating reagent, the molar ratio of sulfating reagent to CMS, reaction time, and temperature on the degree of substitution of sulfate groups (DS) of CMSS were studied. Meantime, the DS of each CMSS was determined by barium sulfate–glutin nephelometery method. Moreover, the anticoagulant activity of CMSS was investigated by the coagulation assays of activated partial thromboplastin time, thrombin time, and prothrombin time. The results revealed that the anticoagulant activity of CMSS was closely related to the DS value and concentration. The anticoagulant activity was promoted with the increasing of the DS and concentration. The molecular weight (M_w) in measured range had little impact on anticoagulant activity in contract to the DS and concentration. In this article, the CMSS with the DS of 1.91, concentration of 75 μg/mL and the M_w of 2.61 × 10⁴ had the best blood anticoagulant activities. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

尿素缓释膜材料高取代醋酸酯淀粉的研制

采用醋酸酐作为酯化剂,吡啶作为活化催化剂,液相均相催化反应技术制备尿素缓释膜材料高取代度(DS)醋酸酯淀粉。分别考察制备过程中单一影响因素对醋酸酯淀粉取代度的影响关系,并结合正交实验得出影响因素结论与最佳反应条件。醋酸酐用量是影响醋酸酯淀粉取代度的主要因素,吡啶用量、活化时间和反应时间对取代度的影响为次要因素。最佳反应条件:可溶性淀粉20g,吡啶用量30mL,活化时间1h,醋酸酐用量60mL,反应时间1h,在此条件下制得的醋酸酯淀粉的取代度DS=2.94。     

高取代度淀粉醋酸酯的合成及表征

采用活化淀粉作为原料,醋酸酐作为酯化剂,浓硫酸作为催化剂,在冰醋酸溶剂体系中合成了高取代度淀粉醋酸酯,通过正交实验探讨了各因素与取代度的关系。实验发现,淀粉活化预处理有利于高取代度淀粉醋酸酯的合成;醋酸酐用量是影响淀粉醋酸酯取代度的主要因素,反应温度和催化剂用量是次要因素;最佳反应条件:活化淀粉15.87 g,反应温度70℃,醋酸酐用量28 g,催化剂浓硫酸用量0.7 g,在此条件下制得的淀粉醋酸酯的取代度DS=2.465。通过扫描电镜对淀粉醋酸酯与淀粉的结构进行了观察,发现其聚集态与原淀粉相比发生本质改变,表面疏松多孔,比表面积增大,因此产品具有较好的溶剂溶解性能。     

己酰酯化羧甲基淀粉的制备及粘度性质研究

以羧甲基淀粉(CMS)为原料,己酰氯为酯化试剂,二甲基亚砜(DMSO)为溶剂,吡啶为有机碱合成了己酰酯化羧甲基淀粉(HCMS)。研究了反应温度、反应时间、催化剂用量、溶剂用量对己酰酯化取代度(DS)和反应效率(RE)的影响,确定了最佳反应条件为:5 g CMS,40 mL DMSO,反应温度为50℃,反应时间为30 min,有机碱用量为1.0 g。通过IR、流变仪对产物进行了结构及溶液黏度性质研究。通过对不同质量分数和己酰酯化取代度(DShexyl)的羧甲基淀粉溶液黏度性质(剪切速率0～500 s-1)的研究表明,达到临界聚集质量分数2.0%时,适当己酰基取代度(DShexyl=0.3)的HCMS,可以使羧甲基淀粉溶液的黏度由420 mPa.s提高到34 000 mPa.s(γ=5 s-1)。     

Starch derivatives with high degree of functionalization. III. Influence of reaction conditions and starting materials on molecular structure of carboxymethyl starch

Carboxymethyl starch (CMS) was prepared in a completely heterogeneous procedure in a methanol/water slurry activated with aqueous sodium hydroxide (45%, w/v) using monochloroacetic acid as the etherifying agent. The influence of the reaction conditions and the type of starting starch (amylose content and preactivation) was evaluated in regard to the formation of the main repeating units (i.e., unfunctionalized and mono‐, di‐, tri‐, and tetra‐O‐carboxymethylated) and the pattern of functionalization within the anhydroglucose units (AGU). The reproducible synthesis gave products with a maximal degree of substitution of CM groups (DS_CM) of 0.66, which was reached in a one‐step synthesis. Repeated carboxymethylation led to products with a DS_CM of 0.88. As revealed by means of HPLC analysis after complete acidic depolymerization, in any sample the mono‐O‐carboxymethylated glucose (mono‐O‐CMglc) was preferably present while the di‐O‐CMglc was formed to a very low extent only. The tri‐O‐CMglc was found in some samples while tetra‐O‐CMglc was not detected. The mole fractions determined did not follow the simple Spurlin statistic as shown for CM cellulose synthesized under comparable conditions. Within the carboxymethylated AGUs a preferred functionalization at position 2 was analyzed by means of ¹H‐NMR spectroscopy after hydrolytic chain degradation. Consequently, the CMS samples synthesized contained mainly 2‐mono‐O‐CM‐AGU. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2036–2044, 2001     

酯化淀粉的制备

本文以马铃薯淀粉为原料,醋酸乙烯酯为酯化剂,制备低取代度醋酸酯淀粉,研究了各反应因素对产品取代度的影响,并以取代度为指标,用单因素试验,确定了其最佳工艺条件,即反应体系pH值10.25,反应温度26℃,反应时间1h,酯化剂用量1g。     

高黏度、高热稳定性羧甲基淀粉己酸酯的溶液性质

以羧甲基淀粉(CMS)为原料制备了高黏度、高热稳定性的羧甲基淀粉己酸酯(CMSH)。用IR和TG对产物进行了结构和热稳定性质研究;通过Brookfield R/S-CC流变仪对羧甲基淀粉己酸酯溶液黏度性质和影响因素,如己酰基质量分数、浓度、剪切力、温度及溶液黏度的剪切恢复性质、温度敏感性质等进行了详细研究。结果表明,引入己酰基基团后,可以降低黏度对温度的敏感性,显著提高羧甲基淀粉的热稳定性和溶液的黏度值。但己酰基团的引入,不能提高CMS溶液黏度的抗剪切性和剪切恢复性。当己酰基质量分数为11.8%时,羧甲基淀粉己酸酯的初始热分解温度由260℃提高到300℃;溶液的黏度值由420 mPa·s提高到32000 mPa·s。