高取代度淀粉醋酸酯的制备

改善淀粉热塑性的方法主要是用塑化剂对其进行处理和用化学方法制备淀粉衍生物,使羟基被长链取代,减弱淀粉分子间的氢键,大分子可在较低温度下运动,从而达到降低熔融温度的目的。近年来,对高取代度淀粉醋酸酯已有报道^[1-5],Sagar等^[2]认为,粉酯的取代度越高,侧链越长,热塑性和亲水性的改变就越明显,而且酯基可起到内增塑作用,可塑性的提高反映在材料的流变学,热学及力学性能的改变上,Maheras等^[3]用高取代度的淀粉醋酸酯和纤维素醋酸酯共混,制成了纤维和塑料制品,由于高取代度淀粉醋酸酯熔点较高,Brochers等^[4]提出通过加入分子量为100－1000的增塑剂,如甘油三醋酯等,可使熔融温度降到150℃左右,Tanaka等^[6]将淀粉和乙烯类化合物在酯化催化剂的作用下反应,得到的淀粉酯性能较为理想,分子量高,具有相当好的机械性能和耐水性,国外专利报道了以甲磺酸（MSA）为催化剂制备淀粉醋酸酯的方法^[7},但对其结构和性能尚未作系统的研究,本文以冰醋酸和醋酸酐为混合酸,MSA为催化剂,制得了具有较高取代度的高直链淀粉醋酸酯,并系统研究了反应温度,反应时间,反应物比例等不同反应条件对取代度的影响,通过红外分析,特性粘度测试,溶解性等分析手段,表征了高直链淀粉醋酸酯的结构与性能。     

新型血浆代用品羧甲基糖淀粉的研究--Ⅰ.化学部分

本文报导了新型血浆代用品羧甲基糖淀粉钠及其原料糖淀粉的化学性质.从玉蜀黍淀粉经适度的酸水解,丁醇络合,分离得适当分子量和直链纯度的糖淀粉,再进行有控制的羧甲基化而制得有一定取代度的羧甲基糖淀粉钠.我们测定了糖淀粉的特性粘数和碘吸附量,并由此选择了作为血浆代用品原料所需要的平均分子量和直链纯度的糖淀粉的分离条件.     

改性PPO的溶解性能和溶度参数的初步估计

研究了聚苯醚PPO、羧化PPO、苯酰化PPO、苯磺酰化PPO和磺化PPO在不同溶剂中的溶解能力,分别讨论了各种取代基以及取代度对聚合物溶解性能的影响,由PPO衍生物的特性粘数估算了它们的溶度参数。     

三种烯丙基取代的β-环糊精作为毛细管气相色谱固定相的研究

本文通过将β-环糊精的2,6-羟基取代为烯丙基,3-羟基用3种不同链长的酰基(戊酰基、庚酰基、辛酰基)酰化合成了3种新的环糊精衍生物,并研究其作为CGC手性固定相的色谱性能和手性分离性能.色谱分离测试结果表明,此固定相不仅对一些苯的二取代位置异构体具有良好的分离能力,还具有一定的对映体分离能力,可以将反式-二氯菊酸甲酯、顺式-菊酸甲酯、丙烯醇酮乙酸酯、丙炔醇酮乙酸酯、顺式-2,3-环氧-1-己醇乙酸酯和顺式-2,3-环氧-1-戊醇乙酸酯等手性药物很好地分开.     

多糖类氨基甲酸酯衍生物的区域选择性合成及其手性识别

通过糖单元6-位羟基的保护和去保护,运用区域选择性方法合成了6种新型多糖类氨基甲酸酯衍生物,分别为纤维素/直链淀粉-[2,3-二(3,5-二甲基苯基)-6-环己基]氨基甲酸酯、[2,3-二(3,5-二氯苯基)-6-环己基]氨基甲酸酯及[2,3-二(4-氯苯基)-6-环己基]氨基甲酸酯,并将其涂敷在氨丙基硅胶的表面制备HPLC手性固定相.利用1H-NMR与FTIR光谱技术对所合成衍生物进行结构表征和分析,并应用HPLC法评价其对于9种手性化合物的手性识别能力.通过与以手性识别能力高而著称且含有单一取代基的纤维素/直链淀粉-三(3,5-二甲基苯基氨基甲酸酯)等手性固定相的对比分析表明,所合成新型手性固定相对于某些对映体显示出更优的手性识别能力.由进一步分析表明,糖单元2-、3-和6-位取代基的性能对于纤维素和直链淀粉氨基甲酸酯类衍生物的手性识别能力均具有较大影响.     

淀粉磷酸酯结合磷的测定

１引言 淀粉磷酸酯是含磷酸基团的一种变性淀粉,广泛应用于造纸、纺织和食品等工业中。在食品工业中应用的淀粉磷酸酯因取代度的不同其应用范围和用量等均不相同,所以,在淀粉磷酸酯的质量指标中,取代度（ＤＳ）是主要分析数据之一。而取代度是淀粉磷酸酯中结合磷的摩尔数与淀粉摩尔数之比,所以,只要测出结合磷即可计算出淀粉磷酸酯的取代度。 淀粉磷酸酯的结合磷含量的测定,通常采用湿灰化法或干灰化法,但均有一定的缺点,如温灰化法产生有害的酸雾及氢氧化物,对所用的器具有特殊的要求且要专门制作;干灰化法步骤较繁且费时间。这…     

新型直链淀粉类手性固定相的制备与手性拆分性能

通过对糖单元2-位进行选择性酯化以及6-位保护与去保护,运用区域选择性方法合成了5种新型直链淀粉类衍生物,分别为直链淀粉-2-苯甲酸酯-3-(4-氯苯基氨基甲酸酯)-6-(3,5-二甲基苯基氨基甲酸酯)、直链淀粉-2-苯甲酸酯-3-(4-氯苯基氨基甲酸酯)-6-(3,5-二氯苯基氨基甲酸酯)、直链淀粉-2-苯甲酸酯-3,6-二(4-氯苯基氨基甲酸酯)、直链淀粉-2-(4-氯苯甲酸酯)-3,6-二(3,5-二氯苯基氨基甲酸酯)和直链淀粉-2-(4-氯苯甲酸酯)-3,6-二(环己基氨基甲酸酯),并将其涂覆在氨丙基硅胶表面制备了HPLC手性固定相。利用核磁共振-氢谱(¹H-NMR)和傅里叶变换红外光谱(FT-IR)技术对所合成衍生物的结构进行了表征和分析,并用HPLC法评价所合成衍生物的手性识别能力。与具有单一取代基直链淀粉类手性固定相的对比分析表明,所合成的新型直链淀粉类手性固定相对于某些对映体具有更为优异的拆分结果。进一步分析表明,2-、3-和6-位取代基的性能和引入位置对直链淀粉衍生物的手性识别能力均有较大的影响。     

改性PPO的溶解性能研究

研究了 PPO、羧化 PPO(C-PPO)、苯酰化 PPO(BA-PPO)、苯磺酰化 PPO(BS-PPO)和磺化 PPO(S-PPO)在不同溶剂中的溶解能力,分别讨论了各种取代基以及取代度对溶解性能的影响,测定了各种改性 PPO 在溶剂中的特性粘数,估计了它们的溶度参数。发现,在 PPO 的溶解过程中,色散力起重要作用,S-PPO 样品的溶解过程则是极性力和氢键起主导作用,而 BA-PPO 和 BS-PPO 的溶解过程则是三种力相互作用的结果。对于不同取代度的 C-PPO,随取代度增加,在极性和形成氢键的溶剂中的溶解能力增加。     

淀粉乙酸酯的阴离子接枝己内酯聚合研究

将淀粉在二甲基甲酰胺、吡啶存在下 ,以乙酸酐进行部分乙酰化 ,制备取代度为 0 7～ 1 9的淀粉乙酸酯 (St Ac) .以萘钠与淀粉乙酸酯中残余的羟基反应 ,将羟基转化为醇盐 (ONa) ,引发己内酯进行阴离子开环接枝聚合 ,合成了淀粉 聚己内酯接枝共聚物 (St g PCL) .采用凝胶渗透色谱法 (GPC)研究了接枝前后聚合物分子量的变化情况 ,并以接枝率、单体转化率对接枝反应进行了表征 .研究了接枝条件如温度、溶剂、引发剂和单体的用量对接枝率及单体转化率的影响 .研究发现随着反应温度升高 ,接枝率、单体转化率呈S曲线变化 ,单体浓度、引发剂浓度的增大有利于接枝反应的进行 .     

交联阳离子淀粉(DS=0.95)的干法制备及其脱色性能

在碱催化剂BZ-1存在下,以N-(2,3-环氧丙基)三甲基氯化铵(GTA)为阳离子化试剂,干法制备了交联高取代度季铵型阳离子淀粉。对制得阳离子淀粉的脱色性能研究结果表明,交联高取代度阳离子淀粉对活性染料具有优异的脱色效果。     

Study on the morphology, crystalline structure and thermal properties of yellow ginger starch acetates with different degrees of substitution

Yellow ginger starch acetates with different degrees of substitution (DS) were prepared by reacting native starch with glacial acetic acid/acetic anhydride using sulfuric acid as catalyst. X-ray diffraction (XRD) of acetylated starch revealed that the crystal structure of native starch was disappeared and new crystalline regions were formed. Their formation was confirmed by the presence of the carbonyl signal around 1750 cm⁻¹, as well as the reduced hydroxyl groups, in the Fourier transform infrared spectroscopy (FT-IR). The scanning electron microscopy (SEM) suggested most of the starch granules disintegrated with many visible fragments along with the increasing DS. The thermal behavior of the native starch and starch acetate were investigated using thermogravimetric analysis (TGA) and differential thermal analysis (DTA), it was observed that the thermal stability of acetylated starch depends on the degree of substitution. Thermal stability of high DS acetylated starch is much better than that of the original starch when DS reached to 2.67.     

Study on the morphology, crystalline structure and thermal properties of yam starch acetates with different degrees of substitution

This study was carried out to understand and establish the changes in physicochemical properties of starch extracted from Chinese yam (Dioscorea opposita Thunb.) after acetylation. Yam starch acetates with different degrees of substitution (DS) were prepared by the reaction of yam starch with glacial acetic acid/acetic anhydride using sulfuric acid as the catalyst. Their formation was confirmed by the presence of the carbonyl signal around 1750 cm-1 in the Fourier transform infrared (FT-IR) spectra. The thermal behavior of the native starch and starch acetate were investigated using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results reveal that the starch acetates are more thermally stable than the native starch. The starch esters showed 50% weight loss at tem- peratures from 328℃ to 372 ℃ , while the native starch underwent 50% weight loss at 325℃ . The glass transition temperature (Tg) of the starch decreased from 273℃ to 226℃. The X-ray diffraction (XRD) patterns could be classified as typical of the C-type for yam starch. X-ray diffraction also showed the loss of the ordered C-type starch crystalline structure and the degree of crystallinity of starch de- creased from 36.10% to 10.96% with the increasing DS. The scanning electron microscopy (SEM) sug- gested that the most of the starch granules disintegrated with many visible fragments with the in- creasing DS.     

低取代醋酸纤维素的均相合成及其水溶性

本文在离子液体中进行低取代度CA的均相合成, 得到了一系列CMA, 部分合成的CMA在水中具有良好的溶解性.     

羧甲基木薯淀粉的取代方式研究

采用高效液相色谱(HPLC)和核磁共振波谱(^1HNMR)分析了混水/有机介质中合成羧甲基木薯淀粉的取代方式。发现HPLC是一种测定不同条件下合成的羧甲基木薯淀粉取代度(DS)的可靠方法。在测量的范围内,未取代、一取代、二取代和三取代无水葡萄糖单元的摩尔分数分布和Spurlin模型非常吻合。用高分辨率500MHz^1HNMR分析了木薯淀粉羧甲基过程的取代度和反应顺序。依据淀粉和羧甲基淀粉(CMS)的结构确定了各个峰位置。比较所得数据发现：依据HPLC计算的DSHPLC小于从500MHz^1HNMR计算所得的DSNMR。无水葡萄糖单元中C2、C3和C6的羧甲基化反应顺序为C6＞C2＞C3。     

醋酸酯淀粉高取代度的测定

淀粉的乙酰化改性是扩大其应用的一个重要手段。测定醋酸酯淀粉取代度 (DegreeofSubstitution ,简称DS)的方法通常有酸碱滴定法、紫外法、核磁共振法及衰减全反射法[1 ] 等 ,后 3种方法需建立标准曲线 ,要求有一系列取代度的样品 ,实验操作较困难。所以实验室更多采用酸碱滴定法。实验室多采用乙醇为溶剂进行醋酸酯淀粉高取代度的测定[1～3] 。这种方法的缺点是皂化时间需 48～ 72h ,并且高取代度醋酸酯淀粉的溶解性不理想。本文对酸碱滴定法测定醋酸酯淀粉高取代度溶剂选择进行了探讨 ,以期建立一种快速、准确地测定醋酸酯淀粉高取代度的…     

草酸淀粉酯制备及其性能研究

本文以草酸和玉米淀粉为原料,通过改变原料的摩尔比反应制备了不同取代度(0.1到0.9)的草酸淀粉酯,采用滴定法测定产物的取代度,利用红外光谱和核磁共振表征产物(取代度为0.41)的化学结构,产物中含有羰基的结果表明成功制备了草酸淀粉酯.详细考察了草酸淀粉酯的物理化学性质,利用粘度测定、热重分析、广角X衍射(WXRD)以及湿度吸收等研究不同取代度的草酸淀粉酯的分子量、热稳定性,结晶形态以及吸水性能.结果说明,与玉米淀粉相比,草酸淀粉酯的吸水率随着取代度的提高而增加,其分子量、热稳定性以及结晶性能则呈下降趋势.     

PREPARATION OF STARCH SUCCINATE WITH INTERMEDIATE DS BY AQUEOUS SLURRY REACTION

The succinylation of cornstarch by slurry reaction has been studied using sodium hydroxide as catalyst.Several reaction parameters affecting the succinylation were investigated including the concentration of starch in water,the ratio of succinic anhydride to starch,the reaction time and the reaction temperature,The favorable conditions for an intermediate degree of substitution(DS) and reasonably high reaction efficiency(RE) are pH 8.5-9.0,50% starch by weight to water.succinic anhydride to starch 1/1(w/w),reaction time 4h,reaction temperature 30℃ .Under these conditions,the DS of 0.45 and RE of 28% were achieved.The addition of an adequate amount of crosslinking agent imparted starch succinate water absorbency.     

Preparation of 6-chloro-6-desoxy- and 6-iodo-6-desoxycellulose

Conclusions The reaction of 2,3-di-O-acetylcellulose with N-chloro- or N-iodosuccinimide and triphenylphosphine gave the 6-chloro-6-desoxy- and 6-iodo-6-desoxycellulose acetates with a respective degree of substitution (DS) in halogen of 0.8–1.0 and 0.7. The deacetylation of these compounds gave 6-chloro-6-desoxycellulose (DS 0.8) and 6-iodo-6-desoxycellulose (DS 0.6).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2158–2160, September, 1977.     

水溶性N-(2-羧基苯甲酰基)化壳聚糖的合成

壳聚糖(β-(1,4)-2-氨基-2-脱氧-D-葡聚糖)是甲壳素脱乙酰化反应生成的一种线性聚合物,无毒、可生物降解、并有良好的成膜性和生物相容性,近年来已在水处理、医药、食品、化妆品、农业等领域显示了其独特的应用价值。但是,因分子内和分子间氢键的作用,壳聚糖只能溶于酸和酸     

Preparation of LDPE-acetylated/butyrylated starch blend blow films and characterization

Development of modified plastics has been studied through the LDPE-acylated starch blend films to examine the effect of different acyl groups and degrees of substitution(DS) on properties of films.Corn starch was modified with acetyl and butyryl groups and films were prepared by blending acylated starch with low density polyethylene(LDPE).Systematic studies were done to observe the effect of acyl groups,DS and starch concentration on the properties and biodegradability of the blend films.It was observed that blend films containing 5% acetylated and butyrylated starches of high DS(2.5,1.7) maintained 75% and 83% of tensile strength of LDPE films.Thermal analysis results indicated that acetylated and butyrylated starch blend films decomposed at 370 °C and 389 °C which were higher than the decomposition temperature of native starch film(349 °C).Scanning electron micrographs of blend films containing high DS acylated starch showed well dispersed starch particles due to improvement in dispersion between starch and LDPE.Water absorption capacity of high DS acetylated and butyrylated starch blend films(4.18% and 3.76%,respectively) was lower than that of native starch films(5%).This study has an advantage because of blown films prepared can be integrated with the present manufacturing systems without any other requirement.