本文關(guān)鍵詞： 超支化聚合物 仿貝殼 高強(qiáng)度 高韌性 交聯(lián)　出處：《合肥工業(yè)大學(xué)》2015年碩士論文　論文類(lèi)型：學(xué)位論文

【摘要】：貝殼具有優(yōu)異的性能,如質(zhì)輕,強(qiáng)度大和韌性高,這些都可歸因于貝殼獨(dú)特的“磚”和“泥漿”的層狀結(jié)構(gòu)。受貝殼多層次結(jié)構(gòu)的啟發(fā),人們已經(jīng)可以用許多方法來(lái)制備高強(qiáng)度仿貝殼復(fù)合材料。然而,目前人們雖然在制備高強(qiáng)度仿貝殼材料方面取得了很大進(jìn)展,但是高韌性的仿貝殼材料卻不多見(jiàn)。因此,如何制備兼具高強(qiáng)度與高韌性的仿貝殼材料仍是一項(xiàng)挑戰(zhàn)。研究分析表明,以往制備仿貝殼材料大多數(shù)選用的是線性聚合物,如聚乙烯醇(PVA),聚甲基丙烯酸甲酯(PMMA),聚二烯丙基二甲基氯化銨(PDDA)殼聚糖等。這些線性聚合物帶有大量極性基團(tuán),可與無(wú)機(jī)片層材料形成強(qiáng)的氫鍵,因而制備的復(fù)合材料強(qiáng)度大。但由于這些線性聚合物分子是由共價(jià)鍵連接而成,共價(jià)鍵不能可逆斷裂、重組,使得能量耗散過(guò)程不可分階段完成,因而韌性較低。面對(duì)這個(gè)問(wèn)題,有望通過(guò)引入動(dòng)態(tài)相互作用(如氫鍵、π.π相互作用、范德華力、離子鍵等)來(lái)解決這一問(wèn)題。脂肪族超支化聚合物的結(jié)構(gòu)特點(diǎn)非常適合制備高韌復(fù)合材料。一方面,脂肪族超支化聚合物分子結(jié)構(gòu)中通常具有大量的極性基團(tuán),如氨基、酰胺基、羥基等、易于形成分子內(nèi)與分子間的氫鍵作用；另一方面,脂肪族超支化聚合物的分子結(jié)構(gòu)高度支化、內(nèi)部空腔大、自由體積大,因而分子運(yùn)動(dòng)能力強(qiáng),即便是被夾在片狀增強(qiáng)材料之間,也會(huì)具有很強(qiáng)的運(yùn)動(dòng)能力。這些都具備了形成動(dòng)態(tài)相互作用的基礎(chǔ)。為了進(jìn)一步獲取高強(qiáng)高韌的超支化聚合物仿貝殼復(fù)合材料,有必要對(duì)復(fù)合材料加以適度交聯(lián)。有許多仿貝殼復(fù)合材料方面的研究報(bào)道表明,交聯(lián)后復(fù)合材料的力學(xué)強(qiáng)度將會(huì)有大幅度提高。因而,可以預(yù)期在將超支化聚合物復(fù)合材料交聯(lián)后,有望獲得高強(qiáng)、高韌的仿貝殼復(fù)合材料。本論文中,首先,以亞甲基雙丙烯酰胺和1-(2-氨乙基)哌嗪為單體,經(jīng)邁克爾加成反應(yīng)合成了超支化聚合物聚酰胺.胺(HPAMAM),并將其分別與納米粘土(clay),氧化石墨烯(GO)進(jìn)行組裝制備仿貝殼材料,得到了具有層狀結(jié)構(gòu)的HPAMAM/clay復(fù)合膜和HPAMAM/GO復(fù)合膜。在此基礎(chǔ)上,用京尼平進(jìn)行了交聯(lián)。這些復(fù)合膜都具有很高的強(qiáng)度和很高的韌性。對(duì)于京尼平交聯(lián)的G-HPAMAM/clay復(fù)合體系,拉伸強(qiáng)度達(dá)到了159MPa,韌性高達(dá)2.5MJ·m3：對(duì)于京尼平交聯(lián)G-HPAMAM/GO復(fù)合體系,拉伸強(qiáng)度為165MPa,斷裂伸長(zhǎng)率大于10%。這種復(fù)合膜由于各組分良好的生物相容性,在生物醫(yī)療研究中有很重要的潛在應(yīng)用,如組織工程,韌帶替代或骨修復(fù)。
[Abstract]:Shell has excellent performance, such as light weight, high strength and high toughness, which can be attributed to the shell's unique "brick" and "mud" layer structure. Many methods have been used to fabricate high strength shell-like composite materials. However, at present, great progress has been made in the preparation of high strength shell-like materials. However, there are few shell imitating materials with high toughness. Therefore, it is still a challenge to prepare shell imitating materials with both high strength and high toughness. In the past, most of the shell-like materials were made from linear polymers, such as polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA). Poly (diallyl dimethyl ammonium chloride) chitosan. These linear polymers have a large number of polar groups and form strong hydrogen bonds with inorganic lamellar materials. However, because these linear polymer molecules are covalently bonded, the covalent bond can not be broken and recombined, which makes the energy dissipation process can not be completed in different stages. In the face of this problem, it is possible to introduce dynamic interactions (such as hydrogen bond, 蟺. 蟺 interaction) and van der Waals force. The structural characteristics of hyperbranched aliphatic polymers are very suitable for the preparation of high toughness composites. On the one hand, there are usually a large number of polar groups in the molecular structure of aliphatic hyperbranched polymers. Such as amino, amide, hydroxyl and so on, easy to form intramolecular and inter-molecular hydrogen bond; On the other hand, the molecular structure of hyperbranched aliphatic polymers is highly branched, the internal cavity is large, and the free volume is large, thus the molecular motion is strong, even if it is sandwiched between the flake reinforcement materials. These have the basis of forming dynamic interaction. In order to further obtain high strength and high toughness hyperbranched polymer shell imitation composite. It is necessary to make appropriate crosslinking of composite materials. There are many research reports on shell imitation composite material, which shows that the mechanical strength of the composite will be greatly improved after crosslinking. It can be expected that the hyperbranched polymer composites can be crosslinked to obtain high strength and high toughness shell imitation composites. The hyperbranched polymer polyamide (HPAMAM) was synthesized by Michael addition reaction using methylene bisacrylamide and 1-methylene 2-aminoethyl) piperazine as monomers. It was assembled with nano-clay clayer and graphene oxide to prepare shell-like materials. HPAMAM/clay and HPAMAM/GO composite membranes with layered structure were obtained. These composite membranes have high strength and toughness. The tensile strength of genipine crosslinked G-HPAMAM / clay composite system is 159MPa. The toughness is up to 2.5MJ 路m3: for genipine crosslinked G-HPAMAM / go composite system, the tensile strength is 165MPa. The composite membrane has important potential applications in biomedical research, such as tissue engineering, ligament replacement or bone repair because of its good biocompatibility.
【學(xué)位授予單位】：合肥工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TB33

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本文編號(hào)：1489847