Preparation of Waterborne Polyurethane Bonded with Quaternary Ammonium Salts and Antibacterial Properties via Contact-Killing
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摘要: 以叔胺化合物3-二甲胺基-1,2-丙二醇为扩链剂、甲基丙烯酸羟乙酯（HEMA）为封端剂，将叔胺基团、不饱和基团键合到聚氨酯（PU）分子链上，并采用不同烷基链长卤代烷与叔胺基团发生季铵化反应引入亲水性基团，经紫外光固化，制备了水性聚氨酯（WPU）抗菌薄膜。利用红外光谱仪、纳米粒度分析仪、光学接触测试仪等对WPU分散液及其薄膜的结构与性能进行表征，通过震荡摇瓶、抑菌圈进行抗菌性能测试，并探究了叔胺化合物对材料性能的影响。结果表明：当叔胺化合物质量分数为9%、烷基链长为12时，WPU通过接触分别对大肠杆菌、金黄色葡萄球菌的抗菌率达99.5%以上，并表现出优异的抗菌持久性能。此外，所制备的水性聚氨酯材料还具有良好的力学性能。Abstract: Waterborne polyurethane (WPU) antibacterial film was prepared by UV curing after introducing hydrophilic quaternary ammonium salts to polyurethane (PU) molecular chains via quaternization reaction between different alkyl chain haloalkanes and tertiary amine groups. PUs were bonded with tertiary amine group and unsaturated group, using 3-dimethylamino-1,2-propanediol as the chain extender and hydroxyethyl methacrylate as the capping agent. The structure and properties of WPU dispersion and light cured films were characterized by FT-IR, particle size analyzer, optical contact angle instrument, etc. The antibacterial properties of the materials were tested by shaking-flask method and zone of inhibition. And the effects of tertiary amine compounds on the properties of WPU were investigated. When the mass fraction of tertiary amine compound was 9% and the alkyl long chain was 12, the antibacterial rates of WPU against Gram-negative E. coli and Gram-positive S. aureus were more than 99.5%. Meanwhile, the longer the alkyl chain was, the better the effect was. Through UV-curable crosslinking, it could still maintain excellent antibacterial performance and reflect positive durability after 96 h water washing. The zone of inhibition test showed that the prepared quaternary ammonium salts WPU antibacterial film belonged to contact-killing material which avoided the pollution and adverse effects on the environment, human beings and other materials. With the increase of tertiary amine content, the quaternization degree of WPU system first increased and then decreased, and the variation of quaternization degree affected the antibacterial properties. Moreover, polyurethane material also exhibited good mechanical properties. The increase of hard segment content of the system enhanced the tensile strength of polyurethane. And when the alkyl long chain was 12, the waterborne polyurethane material had better toughness.
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Key words:
- waterborne polyurethane /
- UV-curable /
- antibacterial /
- quaternary ammonium salt /
- contact-killing
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图 4 光固化WPU薄膜的（a）TGA与（b）DTG曲线
Figure 4. (a) TGA and (b) DTG curves of UV-curable WPU films
图 6 样品对大肠杆菌与金黄色葡萄球菌的抗菌实验结果照片
Figure 6. Sample photos of antibacterial test results against E. coli and S. aureus
图 7 （a）PU-8与（b）WPU-10-12薄膜对大肠杆菌的抑菌圈数码照片
Figure 7. Bacteriostatic circles digital photos of (a) PU-8 and (b) WPU-10-12 films against E. coli
表 1 季铵盐类水性聚氨酯分散液的组分配比
Table 1. Component ratio of quaternary ammonium salt waterborne polyurethane dispersion
Sample m(PCDL)/g m(PEG)/g m(IPDI)/g m(Chain extender)/g m(HEMA)/g m(1-Bromodecane)/g m(1-Bromododecane)/g V(H2O)/mL PU-8 7.29 4.86 6.25 1.8 0.66 / / / WPU-8-10 7.29 4.86 6.25 1.6 0.66 3.8 / 60 WPU-8-12 7.29 4.86 6.25 1.6 0.66 / 4.3 60 WPU-9-10 7.00 4.66 6.54 1.8 0.70 4.2 / 60 WPU-9-12 7.00 4.66 6.54 1.8 0.70 / 4.7 60 WPU-10-10 6.70 4.47 6.83 2.0 0.73 4.6 / 60 WPU-10-12 6.70 4.47 6.83 2.0 0.73 / 5.1 60 
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表 2 WPU分散液的粒径、分散系数和表面电位
Table 2. Mean size, PDI and surface potential of WPU dispersion
Sample Mean size/nm PDI Surface potential/mV WPU-8-10 46.4 0.271 35.12 WPU-8-12 64.7 0.386 30.51 WPU-9-10 38.3 0.272 51.61 WPU-9-12 40.7 0.293 44.71 WPU-10-10 38.8 0.287 43.42 WPU-10-12 51.1 0.303 33.92
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