增塑剂选择对淀粉基聚合物性能的影响

Mykyta Byshko, Seminskyi Oleksandr, Oleg Zubriy
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Amylose is less susceptible to the plasticizing effect than amylopectin, so plasticizer molecules interact more efficiently with starch containing more amylopectin. Therefore, a starch film with a higher amylopentin content has better flexibility and extensibility. Amylose influences the gas-protective properties of films. We compared the values of vapor permeability of films depending on different botanical origins and concluded that vapor permeability was higher for films with higher amylopectin content. \nThe type and amount of plasticizer are important in the production of thermoplastic starch (TPS). The introduction of a plasticizer breaks down hydrogen bonds and reduces the glass transition temperature of starch. At elevated temperatures and under shear forces, the starch in the presence of plasticizers turns into a liquid fluid mass that can be fed to the processes of extrusion, injection molding or blowing. TPS prepared only in an aqueous medium has low mechanical properties. Ethylene glycol, sorbitol, sucrose, fructose, glucose, urea, amides, amino acids and others are often used as plasticizers. The addition of glycerin increases the plasticity of TPS. Fillers plasticized with glycerin absorb much more moisture from the air than films plasticized with sorbitol. This is because sorbitol has the same hydrophilicity and hydroscopicity as pure starch. TPSs containing higher molecular weight plasticizers are stronger and have a higher glass transition temperature but are more brittle. \nThe mechanical properties of TPS are equally dependent on the botanical origin of the starch and plasticizer used. We determined that these values can differ up to 88 times for tensile strength, up to 25 times for tensile strain and up to 83.2 for the modulus of elasticity. The highest tensile strength and modulus of elasticity among the considered materials are achieved in rice starch, plasticized with sorbitol. 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引用次数: 0

摘要

合成塑料已广泛应用于日常生活和工业中,但也因此成为环境污染的最大因素之一。减少污染的方法之一是用天然塑料代替合成塑料。生产天然塑料最常用的原料是淀粉和纤维素。淀粉生物塑料很有趣,因为它们很容易修改,可以使用与合成塑料相同的技术和设备进行加工。从淀粉中获得生物塑料的特点是,原始淀粉是一种干燥的颗粒状材料,不能以其原始形式成型。淀粉可以用增塑剂在高温下成型。当与增塑剂一起加热时,淀粉会失去结晶度。这个过程分为两个阶段。第一个阶段的特点是膨胀,第二个阶段涉及淀粉颗粒的糊化和破坏。淀粉生物聚合物的性质直接取决于淀粉的结构、生产参数和最终添加剂的组成。不同植物来源的淀粉具有不同的“直链淀粉-支链淀粉”比例,这影响了产品的最终特性。淀粉具有良好的成膜能力,这些淀粉来自木薯和玉米。玉米淀粉薄膜含有较多的直链淀粉,因此具有较大的抗湿性,但弹性模量较低。直链淀粉含量高的淀粉具有较高的伸长率和抗拉强度,但弹性模量较低。这是由于直链淀粉和支链淀粉对增塑剂的敏感性不同。与支链淀粉相比,直链淀粉对增塑剂的影响较小,因此增塑剂分子与含有更多支链淀粉的淀粉更有效地相互作用。因此,支链淀粉蛋白含量较高的淀粉膜具有较好的柔韧性和延展性。直链淀粉影响薄膜的气体保护性能。我们比较了不同植物来源的薄膜透气性,得出支链淀粉含量高的薄膜透气性更高的结论。增塑剂的种类和用量是生产热塑性淀粉的重要因素。增塑剂的引入打破了氢键,降低了淀粉的玻璃化转变温度。在高温和剪切力的作用下,淀粉在增塑剂的存在下变成液体流体,可以用于挤出、注射成型或吹塑过程。仅在水介质中制备的TPS具有较低的机械性能。乙二醇、山梨醇、蔗糖、果糖、葡萄糖、尿素、酰胺、氨基酸等常被用作增塑剂。甘油的加入提高了TPS的可塑性。用甘油塑化的填料比用山梨醇塑化的薄膜从空气中吸收更多的水分。这是因为山梨醇具有与纯淀粉相同的亲水性和吸水性。含有更高分子量增塑剂的tps强度更高,玻璃化转变温度更高,但脆性更大。TPS的机械性能同样取决于所使用的淀粉和增塑剂的植物来源。我们确定这些值在抗拉强度上可以相差88倍,在拉伸应变上可以相差25倍,在弹性模量上可以相差83.2倍。在考虑的材料中,用山梨醇塑化的大米淀粉具有最高的拉伸强度和弹性模量。与甘油和硬脂酸组成的玉米淀粉值最低。山梨醇塑化的淀粉膜比甘油塑化的淀粉膜有更高的密闭性。与甘油相比,尿素、甲酰胺和乙醇胺作为增塑剂的效果更好,能使薄膜更坚固、更均匀。氢键强度的关系为尿素>甲酰胺>乙酰胺>多元醇。我们认为,在淀粉基热塑性材料的生产技术中,最重要的问题之一是正确选择增塑剂、增塑剂的浓度和模态参数,这些是使材料获得规定的物理和机械特性所必需的。
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Influence of plastificer selection on starch-based polymer properties
Synthetic plastics have become widely used in everyday life and industry but, thus, have become one of the biggest factors in environmental pollution. One of the ways to reduce pollution is to replace synthetic plastics with their natural counterparts. The most common raw materials for the production of natural plastics are starch and cellulose. Starch bioplastics are interesting because they are easily modified and can be processed employing techniques and the same equipment that is used for synthetic plastics. The peculiarity of obtaining bioplastics from starch is that the original starch is a dry granular material that cannot be molded in its original form. Starch can be molded at elevated temperatures using plasticizers. When heated together with the plasticizer, starch loses its crystallinity. This happens in two stages. The first stage is characterized by swelling and the second involves gelatinization and destruction of the starch granules. The properties of starch biopolymers directly depend on the starch structure, production parameters and composition of the final additives used. Starches of different botanical origins have different "amylose-amylopectin" ratio, which influences the final characteristics of the product. Good film-forming ability is inherent in starch from ahipa, cassava and corn. Corn starch films contain more amylose and, therefore, have greater moisture resistance but lower modulus of elasticity. Starch with a higher amylose content has higher values of elongation and tensile strength but lower modulus of elasticity. This is due to different sensitivities of amylose and amylopectin to plasticizers. Amylose is less susceptible to the plasticizing effect than amylopectin, so plasticizer molecules interact more efficiently with starch containing more amylopectin. Therefore, a starch film with a higher amylopentin content has better flexibility and extensibility. Amylose influences the gas-protective properties of films. We compared the values of vapor permeability of films depending on different botanical origins and concluded that vapor permeability was higher for films with higher amylopectin content. The type and amount of plasticizer are important in the production of thermoplastic starch (TPS). The introduction of a plasticizer breaks down hydrogen bonds and reduces the glass transition temperature of starch. At elevated temperatures and under shear forces, the starch in the presence of plasticizers turns into a liquid fluid mass that can be fed to the processes of extrusion, injection molding or blowing. TPS prepared only in an aqueous medium has low mechanical properties. Ethylene glycol, sorbitol, sucrose, fructose, glucose, urea, amides, amino acids and others are often used as plasticizers. The addition of glycerin increases the plasticity of TPS. Fillers plasticized with glycerin absorb much more moisture from the air than films plasticized with sorbitol. This is because sorbitol has the same hydrophilicity and hydroscopicity as pure starch. TPSs containing higher molecular weight plasticizers are stronger and have a higher glass transition temperature but are more brittle. The mechanical properties of TPS are equally dependent on the botanical origin of the starch and plasticizer used. We determined that these values can differ up to 88 times for tensile strength, up to 25 times for tensile strain and up to 83.2 for the modulus of elasticity. The highest tensile strength and modulus of elasticity among the considered materials are achieved in rice starch, plasticized with sorbitol. Corn starch in the composition with glycerin and stearic acid has the lowest values. Starch films plasticized with sorbitol have higher tightness than films plasticized with glycerin. Urea, formamide and ethanolamine work better as plasticizers than glycerin, promoting stronger and more homogeneous films. The strength of hydrogen bonds is correlated in the following order: urea> formamide> acetamide> polyols. We believe that one of the most important issues in the technology of producing thermoplastic material based on starch is the correct selection of plasticizers, their concentrations, and mode parameters, which are necessary for the material to acquire the specified physical and mechanical characteristics.
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