本文關(guān)鍵詞：雙端官能化聚丁二烯液體橡膠的合成及其紫外光固化研究　出處：《北京化工大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 3D打印材料 陰離子聚合 雙端官能化 點擊化學(xué) 自由基光固化 光固化動力學(xué)

【摘要】：3D打印屬于增材制造,是一種跨學(xué)科交叉技術(shù)。近幾年來,國內(nèi)外都非常重視3D打印技術(shù)的研發(fā),大大推進(jìn)了這項技術(shù)的發(fā)展進(jìn)程。原材料是3D打印技術(shù)的物質(zhì)基礎(chǔ),也決定著這項技術(shù)能否得到更廣泛的應(yīng)用,新技術(shù)對打印產(chǎn)品要求的精密度越來越高,同時不斷提升打印速度,這樣對于材料的要求也隨之越高。如何提高材料性能、降低材料成本,更大程度地提高3D打印產(chǎn)品性價比,成為3D打印材料研發(fā)的重點。液體橡膠的相對分子質(zhì)量低于10000,在室溫下具有流動性的粘稠狀液體材料。其應(yīng)用優(yōu)勢主要是加工過程中可以不加入溶劑,既節(jié)能又環(huán)保,精簡了操作,被廣泛地譽(yù)為“未來橡膠”。本文設(shè)計合成雙端為高活性雙鍵的官能化聚丁二烯液體橡膠,聚合物鏈中和鏈段均具有碳-碳雙鍵結(jié)構(gòu),可以進(jìn)一步發(fā)生光固化反應(yīng)。以環(huán)己烷為溶劑,自制的齊聚異戊二烯雙鋰引發(fā)劑,采用活性陰離子聚合法合成低分子量、窄分布的雙端活性聚丁二烯。然后加入過量的環(huán)氧乙烷進(jìn)行封端反應(yīng),先得到端羥基聚丁二烯液體橡膠,再加入丙烯酰氯進(jìn)行端基官能化反應(yīng),得到具有雙端高活性雙鍵的聚丁二烯液體橡膠。通過NMR、IR、GPC等手段對產(chǎn)物進(jìn)行表征。合成的液體橡膠數(shù)均分子量在4000-10000,分布最窄可以到達(dá)1.16,聚丁二烯1,2-結(jié)構(gòu)60%左右。環(huán)氧乙烷封端率可以達(dá)到80%,丙烯酰氯封端率大于90%。合成的雙端官能化聚丁二烯液體橡膠將用作3D打印材料,由于分子鏈兩端和鏈中都具有碳-碳雙鍵,可以通過加入化學(xué)添加劑使其發(fā)生紫外光固化反應(yīng)。通過調(diào)整體系配方,控制光引發(fā)位置,使紫外光照后的液體橡膠體系發(fā)生擴(kuò)鏈或交聯(lián)固化反應(yīng),得到具有彈性體特征的固體產(chǎn)品。一是采用雙硫醇,利用“點擊化學(xué)”原理進(jìn)行紫外光固化,在有光引發(fā)劑的體系中,光照60s內(nèi)端雙鍵轉(zhuǎn)化率可達(dá)到90%左右,繼續(xù)反應(yīng)可接近100%,鏈中1,2-結(jié)構(gòu)雙鍵轉(zhuǎn)化率在5-12%；二是以丙烯酸酯作為活性稀釋劑,加入光引發(fā)劑,利用自由基光聚合原理進(jìn)行紫外光固化,光照60s內(nèi)端雙鍵轉(zhuǎn)化率90%,繼續(xù)反應(yīng)可接近100%,采用不同的光引發(fā)劑可控制鏈中1,2-結(jié)構(gòu)雙鍵是否發(fā)生反應(yīng)。光固化后得到的材料具有彈性體特征,表面光滑柔軟,無需添加固體補(bǔ)強(qiáng)劑,彈性體材料的拉伸強(qiáng)度5.91-12.88MPa,扯斷伸長率223-523%,硬度45-95。以丙烯酸叔丁酯作稀釋劑的固化膜較丙烯酸甲酯體系的玻璃化轉(zhuǎn)變溫度更高,耐溫性強(qiáng),其材料硬度更高。
[Abstract]:3D printing is a kind of cross-disciplinary technology. In recent years, the research and development of 3D printing technology has been attached great importance at home and abroad. Raw materials are the material basis of 3D printing technology, and also determine whether the technology can be used more widely. The new technology requires higher precision of printing products. At the same time, constantly improve the printing speed, so the higher the requirements for materials. How to improve the performance of materials, reduce the cost of materials, and improve the performance and price ratio of 3D printing products to a greater extent. The relative molecular weight of liquid rubber is less than 10000. Viscous liquid material with fluidity at room temperature. The advantage of its application is that the solvent can not be added in the process of processing, saving energy and environmental protection, and simplifying the operation. In this paper, the functionalized polybutadiene liquid rubber with two ends of high active double bond is designed and synthesized. The polymer chain and chain have carbon-carbon double bond structure. Low molecular weight was synthesized by active anionic polymerization using cyclohexane as solvent and self-made oligopolyisoprene dilithium initiator. Narrow distribution of two-terminal active polybutadiene, then added excessive ethylene oxide to seal reaction, the first hydroxy-terminated polybutadiene liquid rubber, and then the addition of acryloyl chloride for the end group functionalization reaction. Polybutadiene liquid rubber with double terminal high activity and double bond was obtained. The product was characterized by NMR-IR GPC. The average molecular weight of the synthesized liquid rubber was 4000-10000. The narrowest distribution can reach 1.16, the polybutadiene 1 / 2- structure is about 60%, and the sealing efficiency of ethylene oxide can reach 80%. The synthetic bifunctional polybutadiene liquid rubber will be used as a 3D printing material because of the carbon-carbon double bond at both ends of the molecular chain and in the chain. The UV curing reaction can be made by adding chemical additive, and the chain extension or crosslinking curing reaction of the liquid rubber system after UV irradiation can take place by adjusting the formula of the system and controlling the position of photoinitiation. A solid product with elastomer characteristics was obtained. One was to use bismercaptan and "click-chemistry" principle for UV curing in the system with photoinitiator. The conversion rate of double bond at the end of 60 s can reach about 90%, and the reaction can be close to 100. The conversion rate of double bond of 1 + 2-structure in the chain is 5-12. The other is to use acrylic ester as active diluent, add photoinitiator, use the principle of free radical photopolymerization to cure UV, the conversion of double bond at the end of 60 s is 90, and the reaction can be close to 100%. Different photoinitiators can be used to control the reaction of 1 / 2- structure double bond in the chain. The prepared material has the characteristics of elastomer, smooth and soft surface and no need to add solid reinforcing agent. The tensile strength of the elastomer is 5.91-12.88MPa and the elongation at break is 223-523%. Hardness 45-95. The curing film with tert-butyl acrylate as diluent has higher glass transition temperature, higher temperature resistance and higher hardness than methyl acrylate system.
【學(xué)位授予單位】：北京化工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TQ333.2

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