【作者】 金志来；

【导师】 杨建军；

【作者基本信息】 安徽大学 ， 高分子化学与物理， 2010， 硕士

【摘要】 在环保要求日趋严格的今天,对化工产品的环保性能提出了新的挑战,绿色化工、低碳化工是未来的发展趋势。在包装行业也不例外,随着包装行业的发展,复膜胶的需求量也与日俱增。目前,在复膜胶领域中主要有溶剂型胶粘剂和水基胶粘剂两种,但更多的仍使用溶剂型胶粘剂,这主要是因为水基胶粘剂存在表面张力大、固含量低、干燥速度慢、粘接强度不够等尚未得到很好解决的一些问题,而溶剂型胶粘剂多数使用对环境及人体有害的溶剂。为平衡这一矛盾,本文以绿色环保的乙醇为溶剂,合成出了一种环保型胶粘剂,它能够较好的平衡水性胶粘剂与溶剂型胶粘剂的缺点。本文第一章介绍了醇溶性聚丙烯酸酯及聚氨酯的研究现状以及目前常用的改性方法,指出了各自的优缺点和以后的发展趋势；然后分别介绍了单、双组分复膜胶的研究现状,复膜胶的粘接机理以及影响粘接强度的因素。本文第二章以丙烯酸乙酯为主要单体,配合以自制的醇溶性单体以及功能性丙烯酸酯单体,合成了醇溶性聚丙烯酸酯胶粘剂,该胶粘剂醇溶性良好,为淡黄色透明的粘稠液体。其后用有机硅进行了改性,并将改性好的胶液涂覆于经电晕处理的薄膜上研究该胶对薄膜的粘接性能,初步探讨了影响粘接性能的因素,实验测定了单体的转化率、胶膜的吸水率,并用DSC、TG、SEM对胶膜的其它性能进行了表征。结果表明,有机硅的加入降低了单体的转化率、增加了胶膜的吸水率、一定程度上降低了聚合物的玻璃化转变温度、提高了聚合物的耐热性,并最终提高了胶粘剂对塑料薄膜的粘接性能。扫描电镜表明,有机硅的过量加入不是成比例的提高胶粘剂的粘接性能,而是降低了粘接性能。本文第三章用聚氨酯对醇溶性聚丙烯酸酯复膜胶进行了改性,实验合成了-种单组分聚丙烯酸酯-聚氨酯复膜胶。本章通过一种较新颖的设计思路,合成了一种梳状结构的聚合物,解决了常规接枝共聚中聚氨酯的加入量极为有限的问题。该胶粘剂既具有刚性的聚丙烯酸酯主链又具有柔性的聚氨酯侧链,能更好的提高胶粘剂的粘接性能。具体方法是用聚醚多元醇和异氰酸酯合成出聚氨酯预聚体,然后用含双键的丙烯酸酯单体进行封端,通过控制加入量得到单双键封端的聚氨酯预聚体,再将其与丙烯酸酯单体在乙醇中共聚,最终得到梳状结构的聚合物。实验用核磁、红外表征了聚氨酯预聚体的结构；红外分峰表明,聚氨酯的加入增强了聚氨酯与聚丙烯酸酯间的氢键相互作用,这对提高二者的相容性起到了一定的作用；热分析表明,聚氨酯的加入降低了聚合物的玻璃化转变温度,提高了聚合物在低温区域的耐热性；T型剥离强度表明,聚氨酯的加入在一定程度上提高了胶粘剂的剥离强度。本文第四章合成了一种双组分聚丙烯酸酯-聚氨酯胶粘剂。首先合成了含环氧功能基团的醇溶性聚丙烯酸酯,将它作为双组分胶粘剂中的主剂；然后合成出氨基封端的聚醚型聚氨酯作为固化剂,通过调节二者的比例来得到满足不同要求的胶粘剂。实验用核磁、红外表征了主剂与固化剂的结构,研究了主剂、固化剂的不同配比对胶粘剂力学性能、耐水、耐热性以及粘接性能的影响。结果表明,该胶粘剂的力学性能、粘接强度、耐热性等性能不仅与固化剂的比例有关还与所加的聚氨酯的结构有关。此外,该胶粘剂成膜性好,固化后不收缩,粘接性能优异,是理想的双组分胶粘剂。更多还原

【Abstract】 With the development of the environmental protection rules, chemical industry also full of challenges. Green and low carbon chemical industry will become the developing trend. Consequently, the packing industry is also included. With the big market demanding of the packing industry, the laminating adhesives also developed rapidly. Though the water-based laminating adhesive was exist at present, the solvent-based adhesive remain widely used because of its excellent properties comparing with the disadvantages which the water-based adhesive have, such as high surface tension, low solid content, low drying speed and so on. So the problem that most of solvents are bad to the health and environment is not solved. To the solution, this paper has got a kind of environmental friendly adhesive which was synthesize in alcohol solvent. It can keep the balance between water-based adhesives and solvent-based adhesives.At the beginning of the paper, current research situation and modification methods of alcohol soluble polyacrylate and polyurethane were reviewed, and the developing trend was also discussed. Then the adhesion mechanism and influence factors of adhesion strength of the laminating adhesive were introduced.In the second chapter, a kind of well alcohol soluble, transparent, yellow and viscidity solution was get from ethyl acrylate as a main alcohol soluble monomer, functional acrylate and self-synthesized monomer by free radical polymerization. This adhesive was cast on the plastic film to testing the adhesion properties after modified by siloxane. The influence factors of adhesion were roughly researched. The overall conversion rate, water absorption rate were tested. Other properties were also conferred by DSC, TG and SEM. The result shows that the incorporation of siloxane lowered the overall conversion rate of monomer, water resistance and the Tg of polymer, but improved heat resistance and adhesion strength. SEM shows that when the siloxane content surpassed a proper amount, the improving of adhesion strength was not ratio with the contents of siloxane but decreasing when the contents of siloxane surpass a proper amount.In the third chapter, one-pot polyacrylate-polyurethane adhesives were also got. For the one-pot adhesive, a new designed method was used to getting a comb liked structure. Here, single double carbon bond blocked polyurethane pre-polymer was got firstly, then, it was used to copolymerize with the acrylate monomers. At last, we get the comb liked copolymers. The contents of the polyurethane were improved greatly comparing with the multi double carbon bond blocked polyurethane. This adhesive has a rigidity polyacrylate main chain and a soft polyurethane side chain which can improve the adhesion strength dramatically. In this experiment, the structure of polyurethane pre-polymer was confirmed by HMR, and the peak decomposition of IR shows that the incorporation of polyurethane can improve the hydrogen bond interaction between polyurethane and polyacrylate. Thermal analysis indicated that the Tg of the polymer was lowered, heat resistance and T peel off strength were improved due to the introducing of polyurethane.In the fourth chapter, two-pot polyacrylate-polyurethane adhesive was got in the following method. The main agent of alcohol soluble polyacrylate with epoxy group was got firstly. Then the polyurethane with ethyl ammine blocked was got as the curing agent. Different kinds of adhesives were got by adjusting the ratio of the two components. NMR and IR were used to confirming the structure of the main agent and curing agent. Influence of different ratio of main agent and curing agent on the mechanical properties, water absorption rate, heat resistance and adhesion strength was researched. The result shows that these properties were not only related with the ratio between main agent and curing agent, but also related with the structure of the polyurethane. Besides these, the adhesive has good film formation properties, and not shrinks during the curing process.更多还原