【作者】 聂超；

【导师】 孟卫东；

【作者基本信息】 东华大学 ， 有机化学， 2011， 硕士

【摘要】 水性聚氨酯因其以水为分散介质,具有挥发性有机物(VOC)含量低、环境友好的特点,在纺织品、涂料等应用领域具有重要的意义和作用。当今人们对功能性整理剂的要求越来越高,作为纺织整理剂的重要一支,合成具有多功能性的水性聚氨酯逐渐成为研究热点。本论文从3,3-双(溴甲基)氧杂环丁烷(BBMO)出发,分别合成了两种具有"Clickable"活性的单体BAMO和BPMO,以及三种分别具有三氟乙基和七氟丁基的氧杂环丁烷单体(FOx、AFOx-C1)。通过对这些单体进行阳离子开环聚合,我们共制备了四种具有不同结构的共聚型含氟聚醚二醇和四种均聚型聚醚二醇。结合红外光谱(FT-IR)、核磁共振(NMR)、凝胶色谱(GPC)等技术分析表征了这八种聚醚二醇的结构。采用以"Click Chemistry"为手段的Step-growth Polymerization方法,我们将磷酸酯结构以侧链的形式引入到“Clickable”聚醚二醇,得到了PEG1-DEP-C1、PEG1-DEP/DFP-C3、PEG2-DEP/DFP-C1这些具有磷酸酯结构的含氟聚醚二醇。同时,将所合成的含氟笼状倍半硅氧烷(POSS-A)经过"Click Chemistry"反应嫁接至“Clickable"聚醚二醇侧链上得到含硅聚醚二醇PEGl-POSS-C1。由FT-IR、NMR、GPC表征经修饰的聚醚二醇结构。分别以上述一种含氟均聚聚醚二醇和六种经修饰的含氟聚醚二醇作为软段部分,与二异氰酸酯(IPDI)顶聚,并依次经扩链聚合、成盐、乳化,制备了不同结构的水性聚氨酯(乳液)：CFPU-C1-E1、CPU-C1-E2、APU-C1-E3、AFPU-C1-E4、APU-C3-E6、APU-C1-E11和APU-C1-E14。同时我们在硬段部分采用BHPP作为扩链剂,分别合成了APU-C3-E8、APU-C3-E9、APU-C3-E10和APU-C3-E12等四种硬段含磷改性的水性聚氨酯(乳液)；为了提高聚氨酯乳液的稳定性,设计并制备了APU-C3-E5、APU-C1-E7-1、APU-C1-E7-2和APU-C3-E10等,软段同时具有含氟聚醚二醇和PPG-2000的水性聚氨酯(乳液)。这些水性聚氨酯均为线性结构,其乳液的固含量平均分布在15-25%。对比线性结构的水性聚氨酯,我们利用三乙醇胺为核,经DMPA扩链两次,制备了具有第二代结构的超支化聚酯作为超支化聚氨酯的核结构。分别以聚醚二醇PEG1-POSS-C1和PEG3-A-C1在核结构上“生长”而制备出具有超支化结构的水性聚氨酯APU-C1-E15和APU-C1-E13。并进一步在APU-C1-E13支链上嫁接十三氟己基碳链,制备出本论文中含氟量最高的超支化水性聚氨酯APU-F。将这些水性聚氨酯乳液用于棉织物的后整理,并测试了整理后棉织物的拒水、拒油和阻燃性能。软段不含有PPG-2000的水性聚氨酯,其整理过的棉织物对水的接触角可以达到130°以上,其中含有POSS结构的水性聚氨酯能够达到140°以上。但只有APU-F的拒油性能能够达到5级,其余均无明显的拒油性能。软段与硬段均含有磷酸酯结构的水性聚氨酯具有一定的阻燃性能,其LOI值超过20%,其中经APU-C3-E9整理过的棉织物其LOI值达到22.7%,其余水性聚氨酯均无明显的阻燃性能。更多还原

【Abstract】 Waterborne polyurethane is dispersible in water medium, which is environmental friendly and possesses the advantages of low volatile organic compounds (VOC) emission. So it has attracted increasing attention and is widely used in producing environment friendly agents of coating, textile finishing and so on. With the improvement of people’s living standard, environmental friendly and multi-functional waterborne polyurethanes will become the main trend.Starting from BBMO, we designed and synthesized the Clickable monomers BAMO, BPMO and three fluorinated monomers FOx-C1/C3, AFOx-C1. Four kinds of co-polyether diols and four kinds of homo-polyether diols were obtained via ring-opening polymerization of these monomers and characterized by FT-IR, NMR and GPC.In this paper we modified the clickable polyether diols by introduction of phosphate-containing groups to give PEG1-DEP-C1, PEG1-DEP/DFP-C3 and PEG2-DEP/DFP-C1. Meanwhile, we obtained PEG1-POSS-C1 by grafting the POSS-A to clickable polyether diols. These modified polyether diols were characterized by FT-IR, NMR and GPC.These modified polyether diols were then condensed with IPDI to form waterborne polyurethanes CFPU-C1-E1, CPU-C1-E2, APU-C1-E3, AFPU-C1-E4, APU-C3-E6, APU-C1-E11 and APU-C1-E14 respectively. APU-C3-E8, APU-C3-E9, APU-C3-E10 and APU-C3-E12 were modified functionally at the hard segment by using BHPP as the chain extender. In order to improve the stability of the emulsions, we designed and prepared APU-C3-E5, APU-C1-E7-1, APU-C1-E7-2 and APU-C3-E10 which contained fluorinated polyether diols and PPG-2000 within the soft segment. These obtained waterborne polyurethanes have linear structures with solid content between 15～20%.In comparison with these linear polyurethanes, we started from trihydroxolethylamine to form the core structure and reacted with PEG1-POSS-Cl or PEG3-A-C1 to form hyper branched polyurethane APU-C1-E15 or APU-C1-E13. APU-C1-E13 was grafted further with perfluorohexyl group to give hyper branched polyurethane APU-F which had the highest content of fluorine.These emulsions were applied on cotton fabrics by pad-dry-cure process. The water-, oil-repellent and flame retardant properties of the treated cotton fabrics were then studied. Cotton fabrics treated with waterborne polyurethanes emulsions showed good water repellent properties with the contact angles of over 130°, and the one treated with polyurethanes containing POSS reached over 140°. However, only fabric treated with APU-F had good oil repellent property as rated in Grade 5, and others were showed no obvious oil repellent property. The polyurethanes containing phosphonate groups in both hard and soft segments possessed slight flame retardant properties with LOI over 20%. Fabrics treated APU-C3-E9 had LOI of 22.7%. Other polyurethanes showed no obvious flame retardant properties.更多还原