【摘要】：本論文以改善石墨烯在聚氨酯中的分散性和界面相容性為目的,通過氧化石墨烯的功能化、聚氨酯的分子設(shè)計(jì)及創(chuàng)新共混復(fù)合方法等手段,制備了幾種石墨塑與聚氨酯以不同作用方式形成的水性聚氨酯-石墨烯復(fù)合體系,并分別對其結(jié)構(gòu)、形態(tài)和性能進(jìn)行了分析和研究,主要內(nèi)容如下:1)利用兩親共聚物poly(SS-co-AMPS)對石墨烯進(jìn)行非共價鍵修飾,制備了一種在水或有機(jī)溶劑中均可穩(wěn)定分散的功能化石墨烯FGNs。通過溶液混合的方式實(shí)現(xiàn)了FGNs在磺酸型水性聚氨酯(SWPU)中的均勻分散,制備了SWPU/FGNs復(fù)合體系。對復(fù)合體系的微觀結(jié)構(gòu)分析發(fā)現(xiàn),FGNs呈高度剝離的狀態(tài)均勻分散在聚氨酯中;對SWPU/FGNs的粘結(jié)強(qiáng)度與結(jié)晶性能的研究分析,由于FGNs可提高CWPU的結(jié)晶速率和結(jié)晶度,從而可顯著改善其粘結(jié)強(qiáng)度;另外,FGNs將SWPU的導(dǎo)電率提升了5.5×1010倍,可達(dá)到0.39S.m-1結(jié)果表明,該方法所制備的聚氨酯/石墨烯復(fù)合體系在環(huán)保型聚氨酯導(dǎo)電粘合劑方面具有潛在的應(yīng)用價值。2)將氧化石墨烯(GO)與過量的甲苯二異氰酸酯(TDI)反應(yīng)后用水合肼處理,得到一種表面含伯氨基(-NH2)的功能化石墨烯NH2-graphene,然后以NH2-graphene為擴(kuò)鏈劑通過原位聚合法制備了石墨烯共價鍵改性的水性聚氨酯分散液。由于石墨烯與聚氨酯之間存在共價鍵連接,NH2-graphene在復(fù)合體系中不僅可均勻分散,而且與聚氨酯之間具有較強(qiáng)的界面作用力,另外NH2-graphene可導(dǎo)致聚氨酯微相分離度的增加。性能研究發(fā)現(xiàn),NH2-graphene可顯著改善水性聚氨酯的力學(xué)、耐熱和導(dǎo)熱性能。3)將陽離子水性聚氨酯(CWPU)與GO水分散液混合,利用帶正電荷的CWPU膠粒可通過靜電作用吸附到帶負(fù)電的GO表面發(fā)生共沉淀的原理制備了聚氨酯/石墨烯復(fù)合材料。研究發(fā)現(xiàn),化學(xué)還原氧化石墨烯(RGO)與CWPU之間通過靜電相互作用,均勻的分散在聚氨酯基體中;結(jié)果表明,CWPU/RGO的導(dǎo)電率和導(dǎo)熱率比純的CWPU分別提高了6.1倍和4.9×109倍;另外,涂覆了CWPU/RGO的PET膜的氧氣透過率(OTR)可達(dá)0.6cm3.m-2 day-1,表現(xiàn)出優(yōu)異的氣體阻隔性能。4)將CWPU與GO的水分散液混合制備了CWPU/GO復(fù)合體系,研究了聚氨酯膠粒粒徑、GO的pH值以及Zeta電位對體系穩(wěn)定性的影響。研究發(fā)現(xiàn),CWPU膠粒和片狀GO通過靜電吸附組成的CWPU/GO復(fù)合體受到重力、浮力、分散力和靜電排斥等作叫力,其受力情況是決定復(fù)合體系穩(wěn)定分散或沉淀的主要因素,當(dāng)CWPU膠粒粒徑小于100nm、GO的pH值為9.0左右時可得到穩(wěn)定分散的復(fù)合體系。TEM和SEM的分析發(fā)現(xiàn),GO可均勻地分散在復(fù)合體系中;結(jié)果表明,CWPU/GO的耐熱、力學(xué)和氧氣阻隔性能比純的CWPU均有顯著提高。
文內(nèi)圖片：
圖片說明：圖１－１石墨烯的結(jié)構(gòu)模型（ａ）和微觀形貌圖（ｂ，ｃ，，ｄ）逡逑Ｆｉｇ邋１．１邋Ｈｏｎｅｙ－ｃｏｍｂ邋ｌａｔｔｉｃｅ邋ｓｔｒｕｃｔｕｒｅ邋（ａ）邋ａｎｄ邋ｍｉｃｒｏｍｏｒ－ｐｈｏｌｏｇｉｅｓ邋ｏｆ邋ｇｒａｐｈｅｎｅ邋ｎａｎｏｐｌａｔｅｌｅｔｓ邋（ｂ，邋ｃ，邋ｄ）逡逑且非常穩(wěn)定，使得石墨烯成為目前世界上所發(fā)現(xiàn)的材料中機(jī)械強(qiáng)度最優(yōu)異的材料，Ｌｅｅ等人［２２］逡逑２
[Abstract]:In order to improve the dispersion and interfacial compatibility of graphene in polyurethane, several waterborne polyurethane-graphene composite systems formed by graphite plastic and polyurethane were prepared by means of functionalization of graphene oxide, molecular design of polyurethane and innovative blending method, and their structure, morphology and properties were analyzed and studied respectively. The main contents are as follows: 1) graphene was modified by non-covalent bond modification with Amphiphilic Copolymer poly (SS-co-AMPS). A functional fossil graphene FGNs., which can be stably dispersed in water or organic solvent, was prepared. The uniform dispersion of FGNs in sulfonic acid waterborne polyurethane (SWPU) was realized by solution mixing, and the SWPU/FGNs composite system was prepared. The microstructure analysis of the composite system shows that FGNs is uniformly dispersed in polyurethane in the state of high peeling, and the bond strength and crystallization properties of SWPU/FGNs can be significantly improved because FGNs can increase the crystallization rate and degree of crystallization of CWPU. In addition, the conductivity of SWPU was increased by 5.5 脳 1010 times by FGNs, and the results of 0.39S.m-1 showed that the polyurethane / graphene composite system prepared by this method had potential application value in environmentally friendly polyurethane conductive adhesive. 2) graphene oxide (GO) was reacted with excess toluene diisocyanate (TDI) and treated with hydrazide hydrate. A functional fossil graphene NH2-graphene, containing basic amino group (- NH2) on the surface was obtained and then graphene covalent bond modified waterborne polyurethane dispersion was prepared by in situ polymerization with NH2-graphene as chain extender. Because of the covalent bond connection between graphene and polyurethane, NH2-graphene can not only disperse uniformly in the composite system, but also have a strong interfacial force with polyurethane. In addition, NH2-graphene can lead to the increase of microphase separation of polyurethane. It was found that NH2-graphene could significantly improve the mechanical, heat and thermal conductivity of waterborne polyurethane. 3) Polyurethanes / graphene composites were prepared by mixing cationic waterborne polyurethane (CWPU) with GO water dispersion, and using the principle that positively charged CWPU particles could be adsorbed on the surface of GO with negative electricity by electrostatic interaction. It is found that the chemical reduction graphene oxide (RGO) and CWPU are uniformly dispersed in polyurethane matrix by electrostatic interaction, the results show that the conductivity and thermal conductivity of CWPU/RGO are 6.1 times and 4.9 脳 109 times higher than those of pure CWPU, respectively. In addition, the oxygen transmittance (OTR) of PET film coated with CWPU/RGO showed excellent gas barrier performance. 4) the CWPU/GO composite system was prepared by mixing the water dispersion of CWPU and GO. The effects of particle size of polyurethane particles, pH value of GO and Zeta potential on the stability of the system were studied. It is found that the CWPU/GO complex composed of CWPU colloidal particles and flake GO by electrostatic adsorption is called by gravity, buoyancy, dispersion force and electrostatic exclusion, and its stress is the main factor determining the stable dispersion or precipitation of the composite system. When the particle size of CWPU colloidal particles is less than 100 nm and the pH value of go is about 9.0, the stable dispersion composite system can be obtained. Tem and SEM analysis show that GO can be uniformly dispersed in the composite system. The results show that the heat resistance, mechanics and oxygen barrier properties of CWPU/GO are significantly higher than those of pure CWPU.
【學(xué)位授予單位】：合肥工業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：TQ127.11;TB332

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本文編號：2511587