交联-CMS的制备及其应用
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摘要
本论文主要研究了水相反应-滚筒反应、干燥结合法制备交联-羧甲基木薯淀粉(交联-CMS)的工艺,并研究了其基本性质、结构及在粘土悬浮剂和内墙腻子中的应用。
通过实验确定滚筒干燥机工作条件。通过单因素实验研究了中和度、酸碱比、碱化温度、碱化时间、醚化温度、醚化时间等对羧甲基反应取代度、反应效率、粘度、吸水性和保水性的影响。在此基础上,通过正交实验确定了制备羧甲基木薯淀粉的最佳工艺条件:淀粉乳质量分数25%(d.b),M_(淀粉):M_(一氯乙酸):M_(氢氧化钠)=1:0.2:0.4,碱化温度35℃,醚化温度60℃,醚化时间2.0h,在此最佳工艺条件下制备的产品取代度可达0.138。另外还分别以环氧氯丙烷和三氯氧磷作为交联剂,制备的交联-CMS的取代度亦可达0.138,通过实验最后确定制备交联-CMS的简化工艺。
对样品的流变学性质进行研究表明:交联-CMS具有剪切变稀现象,属假塑性流体;CMS片状产品的淀粉糊粘度随着片厚度的增加而上升,但当达到一定厚度后粘度呈下降趋势。随着样品细度增加粘度降低,且样品越细越易结团。交联剂的加入使两个或两个以上的淀粉分子之间“架桥”,呈多维空间网络结构,增加糊液及干燥状态下样品的粘度稳定,同时有助于提高CMS的吸水性等性能。
此外,对样品的结构进行了分析。红外光谱说明一氯乙酸以醚键的形式与木薯淀粉分子相连,交联后的CMS在3000～3700cm~(-1)的羟基伸缩振动的特征峰强度变小。电子显微镜证实滚筒干燥作用使淀粉颗粒结构破坏,形成带有孔洞的片状产品,交联-CMS糊液稳定性提高,片状结构更致密。分子量分布的测定进一步证实了加入交联剂有助于弥补碱和高温的降解作用,使分子量下降较少。差示扫描量热分析表明交联-羧甲基木薯淀粉中的交联键提高了玻璃化转变温度。
最后,论文对CMS作为粘土悬浮剂以及交联-CMS在内墙腻子中的应用进行了探讨。CMS作为粘土悬浮剂的最佳使用量为0.15%(W/W,DS为0.138)。交联-CMS用于内墙腻子的最佳条件为:交联-CMS(环氧氯丙烷用量占淀粉干基的0.02%;DS=0.136)的质量分数1%,水泥质量分数21%,m_(双飞粉):m_(石英砂)=1:1。制得的腻子达到相关标准,性价比优于同类产品。
It is studied in this thesis how to prepare corss-linked carboxymethyl starch.Carboxymethylstarch's properties and applications in clay suspension and inner wall dope are also researched inthis paper.
The single drum dryer's operation condition were studied. By single factor experiments, theeffects of the varieties of factors on the degree of substituent(DS), reaction efficiency(RE),viscidity, water-holding ability , and water keeping of CMS are studied, including the degree ofneutralisation , proportion of acid and alkali, basification temperature , basification time ,etherify temperature, etherify time and so on. Based on those, the perpendicular experiments areused to optimize the technology. The optimum condition is as follows, starch slurry 25%(d.b),M_(AGU):M_(chloroactic acid):M_(NaOH)=1:0.2:0.4, basification temperature 35℃ , etherify temperature 60℃ ,etherify time 2h. The DS of ether in the product is about 0.138. CMS paste is relatively instable,while corss-linking bond will make it more stable in the heating and shearing. POCl_3 andepichlorohydrin as corss-link reagent. The DS of Cross-linked CMS prepared is about 0.138.
The Cross-linked CMS paste is shear-thinning which belong to Pseudoplastic Liquid. It'spaste viscidity increase with the increase in the thickness of pieces of CMS, but decrease whenthe thickness arrive a certain value. The viscidity decrease the increase in the dimension of theCMS pieces. The smaller is the easier agglomeration of it is . Cross-link reagent make two ormore starch molecule “bridge” together and form a 3D net structure. This will increase theviscosity stability of the paste and dry pieces of the carboxymethyl tapioca starch. Moreover itcan improve the water sorption of the product. The fluid liquid characters of samples were studied.
The structure of sampels is researched. Infra-red spectrometris shows chloroactic acidlinked to Tapioca starch by aether bond . The intensity of the flexing-oscillation peak in3000~3700cm~(-1) become weak due to hydroxyl bond stretching. The result of micrograph revealthat reaction and drying demolished the starch granule and form the pieces with hole.Cross-linked CMS will be with better stability of paste and tighter structure of pieces than CMS.Molecular weight analysis shows that corss-link reagent make up the destruction of alkali andhigh tempreture. DSC analysis shows that the cross-linking of CMS results the increase in glasstransition temperature, which is good for storage stability.
The applications of samples in clay suspension and inner wall dope are investigated at last.When CMS is used as suspension reagent, the optimum content is 0.15%(w/w,DS=0.138).Whencross-linked CMS is used as felt reagent inner wall dope, the optimum formula is : 1% ofcross-linked CMS (epichlorohydrin 0.02% (v/w), DS=0.136) , 21% of cement , ms_(cale calciumcarbonate):m_(quartz grit)=1:1. The dope up to par and had better character than the contrast.
通过实验确定滚筒干燥机工作条件。通过单因素实验研究了中和度、酸碱比、碱化温度、碱化时间、醚化温度、醚化时间等对羧甲基反应取代度、反应效率、粘度、吸水性和保水性的影响。在此基础上,通过正交实验确定了制备羧甲基木薯淀粉的最佳工艺条件:淀粉乳质量分数25%(d.b),M_(淀粉):M_(一氯乙酸):M_(氢氧化钠)=1:0.2:0.4,碱化温度35℃,醚化温度60℃,醚化时间2.0h,在此最佳工艺条件下制备的产品取代度可达0.138。另外还分别以环氧氯丙烷和三氯氧磷作为交联剂,制备的交联-CMS的取代度亦可达0.138,通过实验最后确定制备交联-CMS的简化工艺。
对样品的流变学性质进行研究表明:交联-CMS具有剪切变稀现象,属假塑性流体;CMS片状产品的淀粉糊粘度随着片厚度的增加而上升,但当达到一定厚度后粘度呈下降趋势。随着样品细度增加粘度降低,且样品越细越易结团。交联剂的加入使两个或两个以上的淀粉分子之间“架桥”,呈多维空间网络结构,增加糊液及干燥状态下样品的粘度稳定,同时有助于提高CMS的吸水性等性能。
此外,对样品的结构进行了分析。红外光谱说明一氯乙酸以醚键的形式与木薯淀粉分子相连,交联后的CMS在3000～3700cm~(-1)的羟基伸缩振动的特征峰强度变小。电子显微镜证实滚筒干燥作用使淀粉颗粒结构破坏,形成带有孔洞的片状产品,交联-CMS糊液稳定性提高,片状结构更致密。分子量分布的测定进一步证实了加入交联剂有助于弥补碱和高温的降解作用,使分子量下降较少。差示扫描量热分析表明交联-羧甲基木薯淀粉中的交联键提高了玻璃化转变温度。
最后,论文对CMS作为粘土悬浮剂以及交联-CMS在内墙腻子中的应用进行了探讨。CMS作为粘土悬浮剂的最佳使用量为0.15%(W/W,DS为0.138)。交联-CMS用于内墙腻子的最佳条件为:交联-CMS(环氧氯丙烷用量占淀粉干基的0.02%;DS=0.136)的质量分数1%,水泥质量分数21%,m_(双飞粉):m_(石英砂)=1:1。制得的腻子达到相关标准,性价比优于同类产品。
It is studied in this thesis how to prepare corss-linked carboxymethyl starch.Carboxymethylstarch's properties and applications in clay suspension and inner wall dope are also researched inthis paper.
The single drum dryer's operation condition were studied. By single factor experiments, theeffects of the varieties of factors on the degree of substituent(DS), reaction efficiency(RE),viscidity, water-holding ability , and water keeping of CMS are studied, including the degree ofneutralisation , proportion of acid and alkali, basification temperature , basification time ,etherify temperature, etherify time and so on. Based on those, the perpendicular experiments areused to optimize the technology. The optimum condition is as follows, starch slurry 25%(d.b),M_(AGU):M_(chloroactic acid):M_(NaOH)=1:0.2:0.4, basification temperature 35℃ , etherify temperature 60℃ ,etherify time 2h. The DS of ether in the product is about 0.138. CMS paste is relatively instable,while corss-linking bond will make it more stable in the heating and shearing. POCl_3 andepichlorohydrin as corss-link reagent. The DS of Cross-linked CMS prepared is about 0.138.
The Cross-linked CMS paste is shear-thinning which belong to Pseudoplastic Liquid. It'spaste viscidity increase with the increase in the thickness of pieces of CMS, but decrease whenthe thickness arrive a certain value. The viscidity decrease the increase in the dimension of theCMS pieces. The smaller is the easier agglomeration of it is . Cross-link reagent make two ormore starch molecule “bridge” together and form a 3D net structure. This will increase theviscosity stability of the paste and dry pieces of the carboxymethyl tapioca starch. Moreover itcan improve the water sorption of the product. The fluid liquid characters of samples were studied.
The structure of sampels is researched. Infra-red spectrometris shows chloroactic acidlinked to Tapioca starch by aether bond . The intensity of the flexing-oscillation peak in3000~3700cm~(-1) become weak due to hydroxyl bond stretching. The result of micrograph revealthat reaction and drying demolished the starch granule and form the pieces with hole.Cross-linked CMS will be with better stability of paste and tighter structure of pieces than CMS.Molecular weight analysis shows that corss-link reagent make up the destruction of alkali andhigh tempreture. DSC analysis shows that the cross-linking of CMS results the increase in glasstransition temperature, which is good for storage stability.
The applications of samples in clay suspension and inner wall dope are investigated at last.When CMS is used as suspension reagent, the optimum content is 0.15%(w/w,DS=0.138).Whencross-linked CMS is used as felt reagent inner wall dope, the optimum formula is : 1% ofcross-linked CMS (epichlorohydrin 0.02% (v/w), DS=0.136) , 21% of cement , ms_(cale calciumcarbonate):m_(quartz grit)=1:1. The dope up to par and had better character than the contrast.
引文
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