本文選題：環(huán)狀碳酸酯 + 碳酸甘油酯　； 參考：《沈陽工業(yè)大學(xué)》2017年碩士論文

【摘要】：環(huán)狀碳酸酯由于具有高溶解性、高沸點、低毒、可降解等優(yōu)異的物化性能,被廣泛應(yīng)用于混合物的萃取分離、紡織、電化學(xué)、有機合成以及高聚物的制備等領(lǐng)域。因此,環(huán)狀碳酸酯是一類非常重要的化合物。碳酸甘油酯(GC)是一種非常重要的環(huán)狀碳酸酯,被廣泛應(yīng)用于溶劑、化妝品、電解質(zhì)、涂料以及聚酯、聚碳酸酯等領(lǐng)域。將生物柴油的副產(chǎn)物甘油轉(zhuǎn)化為GC,不僅提高了甘油的附加值,而且還會促進生物柴油的發(fā)展。其中,以GC為原料生產(chǎn)的非異氰酸酯型聚氨酯(NIPU)不僅避免了聚氨酯生產(chǎn)制備過程中異氰酸酯對人體和環(huán)境的傷害,而且比傳統(tǒng)的聚氨酯具有更好的耐水解穩(wěn)定性和加工性能,因此GC型NIPU受到人們的廣泛關(guān)注。針對催化制備GC過程中催化劑易失活、難回收的問題,本課題的主要目的是尋找一種可用于催化制備GC的高效、易分離且可循環(huán)使用的固體堿催化劑。首先采用酯交換法,以甘油和碳酸二甲酯(DMC)為原料,考察了400℃煅燒的各種無水硅酸鹽催化劑對反應(yīng)的影響。發(fā)現(xiàn)無水硅酸鈉的催化活性最高,甘油的轉(zhuǎn)化率、GC的選擇性和收率分別高達97.7%、94.0%和91.8%。然后將Na2SiO3·9H2O經(jīng)焙燒、研磨、過篩等工藝制得了系列無水Na2SiO3固體堿催化劑,并將其用于催化甘油與DMC的酯交換反應(yīng),探討了無水硅酸鈉催化劑的制備條件對反應(yīng)的影響。采用TG-DTG、XRD、FT-IR、BET、FESEM和Hammett指示劑法對系列無水硅酸鈉催化劑進行了表征。實驗結(jié)果表明,煅燒溫度對催化劑的堿量和強堿含量有較大影響,但是強堿的增加會促進副產(chǎn)物縮水甘油的產(chǎn)生,進而降低GC的選擇性和收率。催化劑的最佳制備工藝為Na2SiO3·9H2O經(jīng)200℃煅燒2h后,經(jīng)研磨、過篩,選取粒度為120目的組分。甘油與DMC的最佳反應(yīng)條件為:催化劑的加入量為反應(yīng)物質(zhì)量的5%、甘油與DMC的摩爾比為1:4時,75℃常壓反應(yīng)2.5h。甘油的轉(zhuǎn)化率和GC的選擇性分別為97.8%和97.6%。催化劑連續(xù)使用5次后,催化活性并沒有明顯的降低。此外,以GC與癸二酸為原料,4-二甲氨基吡啶和N,N'-二環(huán)己基碳二亞胺為催化劑,室溫反應(yīng)16h后得到了雙(1,10-環(huán)碳酸甘油酯)癸二酸酯。然后將得到的雙五元環(huán)狀碳酸酯與多元胺在有機堿的催化下,150℃下反應(yīng)4h后得到了NIPU。通過對比雙五元環(huán)狀碳酸酯與不同的胺反應(yīng)得到的NIPU的性能,發(fā)現(xiàn)三聚氰胺型NIPU的性能較好。
[Abstract]:Because of their high solubility, high boiling point, low toxicity and biodegradability, cyclic carbonates are widely used in the fields of mixture extraction, separation, textile, electrochemistry, organic synthesis and polymer preparation. Therefore, cyclic carbonate is a very important class of compounds. Glycerol carbonate (GC) is a very important cyclic carbonate, which is widely used in solvents, cosmetics, electrolytes, coatings, polyester, polycarbonate and other fields. The conversion of glycerol, the by-product of biodiesel, to GCnot only increases the added value of glycerol, but also promotes the development of biodiesel. Among them, the non-isocyanate polyurethane (NIPU), which is produced by GC as raw material, not only avoids the harm of isocyanate to human body and environment, but also has better hydrolytic stability and processability than traditional polyurethane. Therefore, GC type NIPU has attracted wide attention. In order to solve the problem that the catalyst is easy to deactivate and difficult to recover in the process of catalytic preparation of GC, the main purpose of this paper is to find a solid base catalyst which can be used in the preparation of GC with high efficiency, separation and recycling. The effects of various anhydrous silicate catalysts calcined at 400 鈩，

本文編號：2098573