【作者】 饶舟；

【导师】 许戈文；

【作者基本信息】 安徽大学 ， 高分子化学与物理， 2013， 硕士

【摘要】 21世纪以来,随着人们对环境保护意识的提高以及各种环保法规的完善,溶剂型聚氨酯中含有的有机溶剂导致的负作用越来越明显。因此,水性聚氨酯(WPU)的发展就具有非常重要的意义,其具有有机挥发物含量低,无毒无污染等优点。WPU是在聚氨酯预聚体生成的过程中,加入具有亲水性能的小分子扩链剂,在反应结束后,加入中和剂中和,成盐后加水乳化就制备出了水性聚氨酯乳液,这种方法就是一般通用的自乳化法。自乳化法的原理是将亲水基团引入到聚氨酯分子侧链或者主链上,乳化的时候不用加入乳化剂,就能使聚氨酯分散于水中,乳液粒径比较小,成膜性能优异,能长期稳定存在。另一种制备水性聚氨酯的方法是在乳化过程中加入乳化剂,采用高速搅拌的方法进行强制分散,制备的乳液粒径较大,稳定性较差,固含量可达到50%以上,外乳化法一般用的较少。水性聚氨酯现在广泛应用于皮革涂饰剂、木器漆、胶黏剂、涂料等行业,已经开始逐步取代溶剂型聚氨酯。在这些应用中,大多用的都是阴离子水性聚氨酯,在这方面的研究报道很多,而阳离子水性聚氨酯方面的研究较少,这主要是因为阳离子水性聚氨酯在制备过程中使预聚体季铵盐化的工艺复杂,加之成本比较高,乳化产品稳定性也比阴离子水性聚氨酯差。与阴离子水性聚氨酯相比较,阳离子水性聚氨酯有其独特的性能,应用价值较大,开发新型阳离子水性聚氨酯具有重要的研究意义。现在石油资源日益枯竭、石化产品价格不断走高,对可再生能源进行研究已经势在必行,用生物质多元醇代替石化原料来生产聚氨酯是可行的趋势,生物质多元醇主要有植物油、植物纤维素、木质素等,据报道,生物质多元醇相比于石油多元醇能耗降低达到23%左右,不可再生能源消耗降低了61%,使用lkg生物质聚氨酯能够少向大气中排放1.2kg二氧化碳。在本论文中采用的生物质多元醇中的植物油改性阳离子水性聚氨酯。本文以聚醚(N-210)、异佛尔酮二异氰酸酯(IPDI)、开环环氧大豆油(KESO)、N-甲基二乙醇胺(MDEA)、一缩二乙二醇(DEG)为主要原料,运用三步法合成一系列开环环氧大豆油量改性的阳离子水性聚氨酯乳液。通过对乳液粒径、胶膜红外光谱、力学性能、邵氏硬度、热重分析、耐水性、耐酸碱等测试研究KESO含量对阳离子水性聚氨酯乳液及胶膜性能的影响。结果表明,当KESO的质量含量在20.4%以下时都能合成稳定的阳离子水性聚氨酯乳液；随着KESO含量的增加,乳液的粒径会变大；由于KESO中含有三个羟基,使聚氨酯分子结构变成三维网状结构,提高了胶膜的力学性能,热稳定性也得到一定程度提高。以异佛尔酮二异氰酸酯(IPDI)、聚己二酸1,4丁二醇酯二醇(PBA)、聚氧化丙烯二醇(N-210)、蓖麻油(C.O)、一缩二己二醇(DEG)、N-甲基二乙醇胺(MDEA)、三羟甲基丙烷(TMP)等为主要原料合成了一系列蓖麻油改性的阳离子水性聚氨酯。运用红外光谱、吸水率、热重分析、摆杆硬度、拉伸实验等测试,研究了蓖麻油的加入量对WPU乳液稳定性、耐水性、热稳定性、硬度、力学性能等性能的影响。测试结果显示,蓖麻油的加入使得聚氨酯乳液的粒径不断增大,乳液的稳定性随着蓖麻油的不断加入,会有稍微降低；蓖麻油的引入能够提高材料的力学性能,且能使胶膜在有较好的拉伸强度的前提下还有很好的断裂伸长率,当蓖麻油含量达到8.3%,胶膜的拉伸强度能达到20.1MPa,热稳定性有提高；聚氨酯胶膜的吸水率下降,聚氨酯的吸水率最多能降低至1%左右。用聚酯型阳离子水性聚氨酯和聚醚型阳离子水性聚氨酯加入一定比例的助剂配制成水性胶黏剂,与阴离子水性聚氨酯胶黏剂进行比较。结果显示,聚酯型胶黏剂的各项性能都优于聚醚型胶黏剂,已经非常接近阴离子水性聚氨酯,其T型剥离强度达到3.21N/mm,软化点在65℃,72小时吸水率9.8%。更多还原

【Abstract】 Since the21st century, along with the improvement of the consciousness of people’s environmental protection and various environmental laws and regulations,the negative effects caused by the organic solvent contained in the solvent-based polyurethane are becoming more and more obvious. Therefore, the development of waterborne polyurethane (WPU) which has many advantages such as non-toxic、pollution-free and low organic volatile content etc, has a very important significance. In the process of polyurethane prepolymer formation, small molecule chain extender with the performance of hydrophilic is added, at the end of the reaction, the neutralizer and salt-forming agent are added, after emulsion with water, the waterborne polyurethane emulsion is prepared. This is the generic self-emulsification method.The general principle of self-emulsification method is that the hydrophilic group is introduced into the side chain or the main chain of the polyurethane molecule, thus without adding an emulsifier, the polyurethane pre-polymer can be dispersed in water, small emulsion particle size、excellent performance of the film and long-term stability can be achieved. Another method of preparing water-borne polyurethane is to add the emulsifier in the process of emulsification, forcibly dispersed using the high-speed stirring method,making the particle size of the emulsion larger and the stability poorer. The solid content can reach more than50%, the external emulsification method is not commonly used.The waterborne polyurethane now widely used in industries such as leather finishing agent、wood lacquer、 adhesive、coating etc, has begun to replace solvent-based polyurethane gradually. In these applications, the anionic waterborne polyurethane has been widely used,many researches in this area have been reported,while the cationic waterborne polyurethane research is less.This is mainly because in the preparation process of cationic aqueous polyurethane, the process of quaternary ammonium salt of the pre-polymer is complex, in addition, the cost is quite high,the stability of the emulsion products are worse than the anionic waterborne polyurethane. Compared with anionic waterborne polyurethane,cationic waterborne polyurethane has its unique properties, and has great application value,the development of novel cationic waterborne polyurethane has important research significance. With increasing depletion of oil resources and higher prices of petrochemical products, research about renewable energy has been imperative. Production of polyurethane with biomass polyols instead of petrochemical raw materials is a viable trend.The biomass polyol mainly includes vegetable oil、plant cellulose、lignin etc,it has been reported that, compared to petroleum polyols, biomass polyol reduced energy consumption to around23%, non-renewable energy consumption was reducesd by61%, the use of lkg of biomass polyurethane let off less1.2kg of carbon dioxide emissions into the atmosphere. This paper mainly discussed the vegetable oil-modified cationic waterbrne polyurethane.A series of waterborne polyurethane emulsions modified by KESO were synthesized using the method of three steps, adopting polyether diols(N-210)、 isophorone diisocyanate(IPDI)、N-methyl diethanolamine (MDEA)-、 diethylene glycol(DEG) as the principal raw materials. The influence of the amount of KESO on the performance of polyurethane emulsion and film were studied by emulsion particle size、infrared spectrum、 mechanical propertie、s hardness、thermal properties、water resistance、acid and alkali resistance etc. tests. The results showed that, stable cationic waterborne polyurethane emulsion can be synthesized when the mass content of KESO belows20.4%; with the increase of the content of KESO, the emulsion particle size became larger; because the KESO contains three hydroxyl groups, the polyurethane molecular structure turned into three-dimensional net-like structure, the mechanical properties of the film were improved, and thermal stability can also be improved to some extent.The cationic waterborne polyurethane modified by caster oil were synthesised by caster oil(C.O.)s isophorone diisocyanate(IPDI)、 N-methyl diethanolamine (MDEA)、diethylene glycol(DEG)、polyether diols(N-210)、 poly-1,4-butylene adipate glycol(PBA) trimethylolpropane(TMP) etc. The influence of the amount of C.O on the performance of polyurethane such as emulsion stability、water resistance、 thermal properties、hardness and mechanical properties were studied by infrared spectrum、water absorption、 thermogravimetric analysis、 rocker hardness、tensile experiment etc. tests.The test results indicated that, with the addition of C.O, the polyurethane emulsion particle size became larger and stability of polyurethane emulsions were reduced; while tensile strength and thermal stability of materials were improved, and can make the films had good elongation at break on the premise of good tensile strength. When the c.o content was up to8.3%, the tensile strength of the film can reach 20.1Mpa, the thermal stability was improved. The water absorption of the polyurethane films can reduce to about1%at most.Using the polyester type cationic waterborne polyurethane and the polyether type cationic waterborne polyurethane,adding a certain percentage of additives,the cationic water-based adhesives can be made, then compared with anionic waterborne polyurethane adhesives.The results showed,each performance of polyester adhesives was better than that of polyether adhesives, and the performance was very close to the anionic waterborne polyurethane. The T-type peeling strength can reach up to3.21N/mm,the softening point can reach65℃, the water absorption of72hours was9.8%.更多还原