含防污因子的可降解聚氨酯的合成及性能研究

发布时间：2018-05-26 16:37

本文选题：海洋防污 + 生物降解　；参考：《华南理工大学》2015年硕士论文

【摘要】：在本论文中,我们采用巯基-烯点击反应和缩合聚合相结合的方法制备了两类可应于海洋防污的生物降解聚氨酯材料。主要结果如下:1.以安息香二甲醚(DMPA)为引发剂,通过巯基-烯点击反应巯基丙二醇(TG)和甲基丙烯酸二甲氨乙酯(DEM)制备了DEM(OH)2。然后通过与聚己内酯二元醇(PCL,Mw=2000 g/mol),异佛尔酮二异氰酸酯(IPDI),1,4-丁二醇(1,4-BD)反应制备了一种侧链含DEM的主链可降解型聚氨酯(PU-Dx)。通过调控DEM(OH)2的含量制备了一系列不同DEM含量的PU-Dx,以调解其抗蛋白性能。1H-NMR、FTIR、HRMS和GPC的测试表明DEM(OH)2以及PU-Dx成功合成。石英晶体微天平(QCM-D)和表面等离子体共振(SPR)检测了纤维蛋白原(fibrinogen)、牛血清蛋白(BSA)和溶菌酶(lysozyme)分别在PU-Dx表面的吸附行为。结果表明,PU-Dx在人工海水中具有抗蛋白性,这是由海水的高盐度产生的电荷屏蔽和DEM的亲水性导致的。我们使用一种海洋细菌-藤黄微球菌(M.luteus)评价了PU-Dx的抗菌性。测试表明,PU-Dx能够抑制海洋细菌在其表面附着。此外,酶促降解实验结果表明,DEM的引入可以加快PU-Dx的降解。2.以安息香二甲醚(DMPA)为引发剂,通过巯基-烯点击反应巯基丙二醇(TG)和防污剂N-2,4,6三氯苯基马来酰亚胺(TCPM)制备了含有双羟基官能团的防污剂TCPM(OH)2。然后通过缩合聚合,TCPM(OH)2与聚己内酯二元醇(PCL,Mw=2000g/mol)、L-赖氨酸乙酯二异氰酸酯(LDI)和1,4-丁二醇(1,4-BD)反应制备了一种侧链含防污官能团的主链可降解型聚氨酯(PU-Nx)。通过调控防污剂TCPM(OH)2的含量制备了一系列不同TCPM含量的PU-Nx,以调解其防污性能。核磁共振(1H-NMR)、傅里叶红外光谱(FTIR)和高分辨质谱(HRMS)的测试表明,TCPM(OH)2以及PU-Nx成功合成。差示扫描量热(DSC)分析表明,TCPM的引入可以破坏PU-Nx的结晶性。静态水解实验和酶促降解实验结果表明,TCPM的引入可以减缓PU-Nx的降解。抗菌实验表明PU-Nx对大肠杆菌和金黄色葡萄球菌的抗菌能力随着TCPM含量的增加而增强。海洋挂板的结果表明PU-Nx具有好的防污效果,这是由于降解产生了自更新表面同时实现对防污剂的可控释放。
[Abstract]:In this thesis, two kinds of biodegradable polyurethane materials were prepared by mercapto-ene-click reaction and condensation polymerization. The main results are as follows: 1. Dimethylpropanediol (TG) and dimethylaminoethyl methacrylate (DEM) were prepared by using dimethyl benzoin dimethyl ether (DMPA) as initiator and mercapto propylene glycol (TG) and dimethylaminoethyl methacrylate (DEM) as initiators. Then, a side chain degradable polyurethane (PU-DxN) containing DEM was prepared by reaction with PCL (2 000 g / mol / mol) and IP diisocyanate (IPD) (1 ~ (4) -butanediol) (PU ~ (4) -BDD) with a side chain of poly (caprolactone) diol (PCL) and isophorone diisocyanate (IP). A series of PU-Dxs with different DEM contents were prepared by regulating the content of DEM(OH)2 to mediate the protein resistance. 1H-NMRG FTIRMS and GPC tests showed that DEM(OH)2 and PU-Dx were synthesized successfully. The adsorption behavior of fibrinogen fibrinogenin (BSA) and lysozyme on the surface of PU-Dx was measured by quartz crystal microbalance (QCM-D-) and surface plasmon resonance spectroscopy (SPR), respectively. The results show that PU-Dx has protein resistance in artificial seawater, which is caused by the high salinity of sea water and the hydrophilicity of DEM. A marine bacterium, M.luteus, was used to evaluate the antimicrobial activity of PU-Dx. The results showed that PU-Dx could inhibit the adhesion of marine bacteria on its surface. In addition, the results of enzymatic degradation showed that the introduction of Dem could accelerate the degradation of PU-Dx. Using benzoin dimethyl ether (DMPA) as initiator, the antifouling agent TCPMOH2 containing dihydroxyl groups was prepared by mercapto-ene-click reaction of mercaptopropanediol (TG) and antifouling agent N-2O4P6 trichlorophenyl maleimide (TCPM). Then a kind of main chain degradable polyurethane (PU-NxN) with antifouling functional groups was prepared by condensation polymerization of TCPMN OHHN 2 with PCLN MwN 2000g / mol / L L- Lysine ethyl diisocyanate (LDI) and 1-butanediol 1 4-BD- (). A series of PU-Nx with different TCPM content were prepared by regulating the content of antifouling agent TCPM(OH)2 to mediate its antifouling performance. The results of 1H-NMRN NMR, FTIR and HRMS showed that TCPM / OHH ~ (2 +) and PU-Nx were synthesized successfully. Differential scanning calorimetry (DSC) analysis shows that the introduction of TCPM can destroy the crystallinity of PU-Nx. The results of static hydrolysis and enzymatic degradation showed that the introduction of TCPM could slow down the degradation of PU-Nx. The antibacterial activity of PU-Nx against Escherichia coli and Staphylococcus aureus increased with the increase of TCPM content. The results show that PU-Nx has a good antifouling effect, which is due to the self-renewal of the surface and the controllable release of the antifouling agent.
【学位授予单位】：华南理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ317;X55

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