醇溶性聚氨酯研究

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醇溶性聚氨酯研究
10nm can be called a solution, APU can be called a polyurethane solution, that is alcohol-based polyurethane; 3 SEM micrographs of ethanol disclosed the morphology of polyurethane particles. The test was introduced in water molecules, so can not truly reflect the alcohol-soluble polyurethane particle morphology, electron microscopy was also failed to see the alcohol-soluble the stretch of the soft segment of polyurethane; 4 GPC tests showed a low molecular weight of single component alcohol-soluble polyurethanes. It is necessary to increase molecular weight of APU; 5 Rheological tests showed that the alcohol-soluble polyurethane has the characteristics of pseudoplastic fluid, which called shear thinning effect, indicating good dispersion of polyurethane in ethanol, the soft segment has a certain degree of stretch, shear stress in the occurrence of chain segments under the direction of one component polyurethane apparent activation energy of ethanol higher, which was necessary to improve; 6 Alcohol-soluble polyurethane has good heat perpfomance.
第一 醇溶性聚氨酯合成与表征 醇溶性聚氨酯合成使用绿色溶剂乙醇为溶剂，是一种准环境友好型聚氨酯。 本课题经过大量实验，摸索出醇溶性聚氨酯的合成工艺。研究结果表明：1 实验 合成出单组分醇溶性聚氨酯 APU，红外测试表明乙醇与聚氨酯分子间有强烈相 互作用，如氢键等，同时发现溶剂乙醇会强烈影响聚氨酯溶液的红外，实验成功 得向 APU 中得引入了少量聚酯成份，分散状态稳定；2 粒径测试表明 APU 的粒 径远小于水性聚氨酯，特别是动态激光光散射（DLS）测得 APU 粒径达到纳米 级，而且分布很窄，按照水性聚氨酯的分类标准——粒径小于 10nm 的分散体可 以称为溶液，APU 可以称为聚氨酯溶液，即醇溶性聚氨酯；3 电镜测试中观察到 醇溶性聚氨酯的粒子形貌，但是因为测试中有水分子干扰，不能真实反映醇溶性 聚氨酯的粒子形态，也未能看到醇溶性聚氨酯软段的舒展；4 GPC 显示出单组分
First : Synthesis of alcohol-soluble polyurethane s and research of their performance properties
Alcohol-soluble polyurethanes which were a quasi-environment- friendly polyurethanes used ethanol as solvent. On the basis of a large number of experiments, the issue explored a unique synthetic route for alcohol polyurethanes. The results showed that:1 Single-component polyurethane called APU was synthesized, two kinds of infrared test methods showed that ethanol and polyurethane have a strong interaction between molecules, such as hydrogen bonding etc. Compared to the potassium bromide tablet method which was more convenient to operate, the silicon chip method can be used as qualitative research methods for its accuracy. The peak width changes in peak shapeprepare among a range of concentrations could be observed , while the infrared absorption of solvent ethanol itself can interfere with infrared liquid system to affect judging. Small amount of polyester was successfully introduced into APU composition and well dispersed; 2 Two sorts of testing showed that the particle sizes of APU were much smaller than those of water-based polyurethanes. In particular, particle sizes measured by dynamic light scattering(DLS) were approach to nano scale and narrow distribution. In accordance with the classification of waterborne polyurethanes, the dispersion of particle size less than
第二 醇溶性聚氨酯的性能研究 醇溶聚氨酯的性能非常重要，人们对聚氨酯胶粘剂的要求越来越高，本论文 主要针对较难复合的 BOPP 薄膜，对单组分醇溶性聚氨酯进行了三个方面的研究 和讨论：1 发现单分组醇溶性聚氨酯优于水性聚氨酯胶粘剂，同时具有溶剂型聚 氨酯的优点，可以用于 BOPP 薄膜的复合，而且可以通过调整配方来满足薄膜复 合时对拉伸强度和剥离强度的不同要求；2 可以向醇溶性聚氨酯中引入多种类型 的紫外吸收剂，以保证和提高抗紫外型 BOPP 薄膜的功能性；3 流平剂不论是通 过添加还是反应的方式引入单组分醇溶性聚氨酯体系中，都可以提高聚氨酯体系 的流平铺展性，添加型用量相对较少，而 反应型的不容易迁移以致影响薄膜的透 明，特别适用于防发雾型 BOPP 薄膜的复合。 总之，通过大量的实验研究可以初步认定醇溶性聚氨酯是一种粒径纳米级的 溶液体系，分散体系中存在很强的氢键作用，本论文合成的醇溶性聚氨酯具有很 好的综合性能。但是醇溶性聚氨酯的国内研究仍相对落后，基础研究需要进一步 深入。 关键词： 醇溶性；聚氨酯；合成；性能
摘要
摘要
聚氨酯是聚氨基甲酸酯(polyurethane)的简称，在聚氨酯分子主链上含有重复 的氨基甲酸酯结构单元，由多异氰酸酯和含多元活泼氢的化合物逐步聚合反应而 成。聚氨酯结构中分为软段硬，且软硬段比例可调，聚氨酯的优异性能大多是通 过软硬段的微相分离而实现。软段由聚酯多元醇和聚醚多元醇组成，硬段由二异 氰酸酯和小分子扩链剂组成，通过分子结构的设计可以调节聚氨酯软硬段的比例 和相分离程度。聚氨酯分子中存在大量的极性键，在大分子间和大分子内可以形 成成千上万的氢键。由于氢键作用，聚氨酯具有优异的耐磨、耐低温和高粘接强 度等性能，使其在涂料、粘合剂、皮革涂饰剂、纺织助剂、造纸工业助剂、医药 和电子材料等行业得到广泛应用。
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Abstract
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PU is shortened from polyurethane, which are polymers in which the principle chain structure is composed of soft chain segment derived from polyol component(polyether or polyester) and rigid chain segment derived from diisocrynate and extender. The hardness can be tuned by designing the structure of the molecules. Meanwhile, resulting from their specific micro-phase separation, PU offer very good mechanical strength. Owing to the abundant polar groups in their structure, hydrogen bonds are readily to be formed between the molecules of polyurethanes. Hydrogen bonds offer PU with excellent abrasion resistance, low temperature and high adhesive strength and other properties. The exceptional combination of those properties made PU widely used in coatings, adhesives, leather finishing agents, textile auxiliaries, paper additives industry, medicine and electronic materials and other industries.
随着科学技术的快速发展和工业化程度的不断深入，环境问题日益引起人们 的重视，人类不断探索新的发展模式和道路，以求实现人与自然的和谐发展。在 聚氨酯行业，传统的溶剂型产品含有 60％以上的有机溶剂，有机溶剂是重要的 环境污染物之一。环境友好型聚氨酯的分散介质节能环保、对空气没ห้องสมุดไป่ตู้污染，符 合人类社会发展的需要。本课题通过阅读大量国内外文献，同时在实验室对水性 聚氨酯研究基础下，对醇溶性聚氨酯合成以及性能进行了深入的研究。具体工作 分为两个部分：
With the rapid development of science and technology and the deepening of industrialization, the environment is of growing importance. The human beings are continuing to explore new models and roads in order to achieve harmonious development between man and nature. In the polyurethane industry, the traditional solvent-based products containing more than 60% organic solvents, which are notorious environmental pollutants. Energy saving, and no pollutant to air, made the environment- friendly polyurethane meet the needs of the development of human society. By reading a large number of domestic and foreign literature and on the basis of laboratory studies of water-based polyurethane, the alcohol-based polyurethanes were synthesized and researched. Specific work was divided into two parts as followed:
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醇溶性聚氨酯研究
醇溶性聚氨酯的分子量较小，但分布较窄，有必要在以后的合成研究中，使 APU 分子量增大；5 流变学研究表明醇溶性聚氨酯具有假塑性流体的特征，存在剪切 变稀效应，说明聚氨酯在乙醇中分散较好，软段有一定程度的舒展，在剪切应力 的作用下发生分子链段的取向，单组分醇溶性聚氨酯的表观活化能较高，表明粘 度对温度敏感；6 醇溶性聚氨酯具有较好的热学性质，乙二醇作扩链剂的耐热性 能较好，PTMEG 作软段的低温柔韧性较好。