本文選題：聚碳酸酯 + 有機(jī)氧化錫催化劑�。� 參考：《天津工業(yè)大學(xué)》2016年碩士論文

【摘要】：聚碳酸酯(Polycarbonate,簡(jiǎn)稱(chēng)PC)是一種無(wú)色透明的無(wú)定形熱塑型材料,屬于五大工程塑料之一。具有優(yōu)良的電絕緣、耐熱、抗沖擊及耐化學(xué)腐蝕等特性。隨著人們對(duì)綠色化學(xué)和可持續(xù)發(fā)展的日益關(guān)注,PC的生產(chǎn)工藝逐漸向著綠色、環(huán)保以及高附加值方向發(fā)展。本文通過(guò)碳酸二甲酯(DMC)酯交換法催化合成PC中間體(MmC(1)和DmC(1)),對(duì)合成過(guò)程中使用的催化劑結(jié)構(gòu)與催化效果進(jìn)行研究,探索其催化機(jī)理,得出結(jié)論如下：首先,通過(guò)TG-MS和In situ DRIFTS研究了非均相催化劑管狀和銳鈦Ti02的催化機(jī)理：DMC在催化劑表面的活化形態(tài)是決定酯交換和烷基化反應(yīng)的關(guān)鍵因素。其次,采用格式試劑法合成了一系列均相有機(jī)氧化錫催化劑：苯基氧化錫2(三氟甲苯)氧化錫((PhCF3)2SnO)和二甲苯基氧化錫((PhCH3)2SnO),雜環(huán)氧化錫二吡啶基氧化錫((C5H4N)2SnO),二噻吩基氧化錫((C4H3S)2SnO)和二呋喃基氧化錫((C4H3O)2SnO)。對(duì)催化劑結(jié)構(gòu)進(jìn)行系統(tǒng)表征,結(jié)合GC對(duì)合成的PC中間體選擇性進(jìn)行研究,探究各個(gè)催化劑的催化效果：在苯基氧化錫中,轉(zhuǎn)化率方面,(PhCF3)2SnO＞Ph2SnO (PhCH3)2SnO, BPA轉(zhuǎn)化率最高可達(dá)42.83%；MmC(1)選擇性方面,Ph2SnO (PhCH3)2SnO (PhCF3)2SnO, MmC(1)產(chǎn)率最高可達(dá)93.33%。在雜環(huán)氧化錫中,(C4H3O)2SnO催化性能最好,BPA轉(zhuǎn)化率可達(dá)75.40%,MmC(1)選擇性為49.08%。然后,利用TG-MS, In situ DRIFTs和計(jì)算機(jī)模擬方法研究均相催化劑的反應(yīng)機(jī)理：Sn=O和DMC之間的結(jié)合模式是決定酯交換反應(yīng)和烷基化反應(yīng)的關(guān)鍵因素。DMC的CH3-O部分的兩個(gè)氧原子與Sn=O結(jié)合,引起C=O鍵縮短,BPA中的氧原子主要進(jìn)攻DMC的羰基碳形成酯交換產(chǎn)物；如果DMC的C=O部分的氧原子與Sn=O結(jié)合,會(huì)引起C=O鍵伸長(zhǎng),BPA中的氧原子進(jìn)攻DMC的甲基碳形成烷基化產(chǎn)物。最后,研究了CO2在高溫高壓條件下對(duì)DMC酯交換法的影響：CO2在高壓下不僅可通過(guò)抑制PC中間體分解抑制烷基化反應(yīng),而且可抑制酯交換反應(yīng)進(jìn)行。溫度對(duì)酯交換影響更顯著,高溫可促進(jìn)PC中間體分解而促進(jìn)烷基化反應(yīng)。
[Abstract]:Polycarbonate polycarbonate (PC) is a colorless and transparent amorphous thermoplastic material, which belongs to one of the five major engineering plastics. Excellent electrical insulation, heat resistance, impact resistance and chemical corrosion resistance and so on. With the increasing attention to green chemistry and sustainable development, the production process of PC is gradually developing towards the direction of green, environmental protection and high added value. In this paper, the catalytic synthesis of PC intermediates MmC1) and DmC1 (DMC) by transesterification of dimethyl carbonate (DMC) was carried out. The structure and catalytic effect of the catalysts used in the synthesis were studied, and the catalytic mechanism was explored. The conclusions are as follows: firstly, The catalytic mechanism of heterogeneous catalyst, tubular and anatase Ti02, was studied by TG-MS and in situ DRIFTS. The activation morphology of Ti02 on the catalyst surface was the key factor to determine the transesterification and alkylation reaction. Secondly, A series of homogeneous organotin oxide catalysts were synthesized by format reagent method: phenyl tin oxide 2 (trifluorotoluene) tin oxide (PhCF3 + 2SnO) and xylene tin oxide (PhCH3 + 2SnO), heterocyclic tin oxide dipyridyl tin oxide C5H4N0 2SnO, dithiophene tin oxide C4H3Sf2SnO) and dithiophene tin oxide. C _ 4H _ 3O _ (2) SnO _ (2). The structure of the catalyst was systematically characterized, and the selectivity of the synthesized PC intermediate was studied in combination with GC. The catalytic effects of each catalyst were investigated: in phenyltin oxide, In the aspect of conversion, the highest conversion rate of Ph2SnO is 42.83% (MmC1). In the aspect of selectivity, the highest yield of Ph _ 2SnO _ (2) C _ (3) C _ (3) O (M _ (mc) ~ (1) can reach 93.33%. The catalytic activity of C _ 4H _ 3O _ 2SnO in heterocyclic tin oxide is the best, the conversion of BPA can reach 75.40 and the selectivity of MmCf-1) is 49.08. Then, TG-MS, In situ DRIFTs and computer simulation were used to study the reaction mechanism of homogeneous catalyst: Sno O and DMC. The two oxygen atoms in the CH3-O part of DMC combined with Sn=O, which were the key factors determining the transesterification and alkylation reaction. The oxygen atoms in DMC mainly attack the carbonyl carbon of DMC to form transesterification products, and if the oxygen atoms in DMC C / O part are bound with Sn=O, the oxygen atoms in C / O bond can attack the methyl carbon of DMC to form alkylation products. Finally, the effect of CO2 on the transesterification of DMC under high temperature and high pressure was studied. At high pressure, the alkylation reaction was inhibited by inhibiting the decomposition of PC intermediate, but also the transesterification reaction was inhibited. The effect of temperature on transesterification is more obvious. High temperature can promote the decomposition of PC intermediates and the alkylation reaction.
【學(xué)位授予單位】：天津工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：TQ323.41;O643.36

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