含防污因子的可降解聚氨酯的合成及性能研究
發(fā)布時(shí)間:2018-05-26 16:37
本文選題:海洋防污 + 生物降解 ; 參考:《華南理工大學(xué)》2015年碩士論文
【摘要】:在本論文中,我們采用巰基-烯點(diǎn)擊反應(yīng)和縮合聚合相結(jié)合的方法制備了兩類可應(yīng)于海洋防污的生物降解聚氨酯材料。主要結(jié)果如下:1.以安息香二甲醚(DMPA)為引發(fā)劑,通過巰基-烯點(diǎn)擊反應(yīng)巰基丙二醇(TG)和甲基丙烯酸二甲氨乙酯(DEM)制備了DEM(OH)2。然后通過與聚己內(nèi)酯二元醇(PCL,Mw=2000 g/mol),異佛爾酮二異氰酸酯(IPDI),1,4-丁二醇(1,4-BD)反應(yīng)制備了一種側(cè)鏈含DEM的主鏈可降解型聚氨酯(PU-Dx)。通過調(diào)控DEM(OH)2的含量制備了一系列不同DEM含量的PU-Dx,以調(diào)解其抗蛋白性能。1H-NMR、FTIR、HRMS和GPC的測試表明DEM(OH)2以及PU-Dx成功合成。石英晶體微天平(QCM-D)和表面等離子體共振(SPR)檢測了纖維蛋白原(fibrinogen)、牛血清蛋白(BSA)和溶菌酶(lysozyme)分別在PU-Dx表面的吸附行為。結(jié)果表明,PU-Dx在人工海水中具有抗蛋白性,這是由海水的高鹽度產(chǎn)生的電荷屏蔽和DEM的親水性導(dǎo)致的。我們使用一種海洋細(xì)菌-藤黃微球菌(M.luteus)評(píng)價(jià)了PU-Dx的抗菌性。測試表明,PU-Dx能夠抑制海洋細(xì)菌在其表面附著。此外,酶促降解實(shí)驗(yàn)結(jié)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)為引發(fā)劑,通過巰基-烯點(diǎn)擊反應(yīng)巰基丙二醇(TG)和防污劑N-2,4,6三氯苯基馬來酰亞胺(TCPM)制備了含有雙羥基官能團(tuán)的防污劑TCPM(OH)2。然后通過縮合聚合,TCPM(OH)2與聚己內(nèi)酯二元醇(PCL,Mw=2000g/mol)、L-賴氨酸乙酯二異氰酸酯(LDI)和1,4-丁二醇(1,4-BD)反應(yīng)制備了一種側(cè)鏈含防污官能團(tuán)的主鏈可降解型聚氨酯(PU-Nx)。通過調(diào)控防污劑TCPM(OH)2的含量制備了一系列不同TCPM含量的PU-Nx,以調(diào)解其防污性能。核磁共振(1H-NMR)、傅里葉紅外光譜(FTIR)和高分辨質(zhì)譜(HRMS)的測試表明,TCPM(OH)2以及PU-Nx成功合成。差示掃描量熱(DSC)分析表明,TCPM的引入可以破壞PU-Nx的結(jié)晶性。靜態(tài)水解實(shí)驗(yàn)和酶促降解實(shí)驗(yàn)結(jié)果表明,TCPM的引入可以減緩PU-Nx的降解?咕鷮(shí)驗(yàn)表明PU-Nx對(duì)大腸桿菌和金黃色葡萄球菌的抗菌能力隨著TCPM含量的增加而增強(qiáng)。海洋掛板的結(jié)果表明PU-Nx具有好的防污效果,這是由于降解產(chǎn)生了自更新表面同時(shí)實(shí)現(xiàn)對(duì)防污劑的可控釋放。
[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.
【學(xué)位授予單位】:華南理工大學(xué)
【學(xué)位級(jí)別】:碩士
【學(xué)位授予年份】:2015
【分類號(hào)】:TQ317;X55
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 劉彥;薛巍;毛潤生;;聚己內(nèi)酯型聚氨酯在不同退火條件下的熱行為研究[J];廣州化學(xué);1989年02期
,本文編號(hào):1938027
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