本文選題：反應(yīng)誘導(dǎo)相分離 + 多孔材料��； 參考：《北京化工大學(xué)》2010年博士論文

【摘要】： 反應(yīng)誘導(dǎo)相分離法(Chemically induced phase separation)制備多孔聚合物材料,是在固化反應(yīng)開(kāi)始之前,溶劑或熱塑性塑料與熱固性樹(shù)脂混合均勻后,體系處于均相狀態(tài)。隨著固化反應(yīng)的進(jìn)行,熱固性樹(shù)脂的分子量逐漸增加,與溶劑或熱塑性塑料之間的相容性逐漸變差,體系在熱力學(xué)上不再相容,相分離開(kāi)始發(fā)生,相結(jié)構(gòu)逐步演化并粗大化。固化產(chǎn)物經(jīng)洗滌干燥將溶劑去除后或使熱塑性塑料高溫降解即可得到多孔結(jié)構(gòu)的聚合物材料。與其它制備多孔材料方法相比,工藝簡(jiǎn)單易操作,可以控制孔徑大小及分布。本文主要工作如下： 1.利用反應(yīng)誘導(dǎo)相分離法,以環(huán)氧大豆油為溶劑,雙酚A環(huán)氧樹(shù)脂為單體,4,4-二氨基二苯甲烷為固化劑制備多孔環(huán)氧樹(shù)脂。研究了環(huán)氧樹(shù)脂最終相態(tài)取決于環(huán)氧基體與環(huán)氧大豆油的組成,并通過(guò)光學(xué)顯微鏡對(duì)其相分離過(guò)程進(jìn)行跟蹤。在相態(tài)由分散孔向相反轉(zhuǎn)結(jié)構(gòu)轉(zhuǎn)變時(shí),體系均遵循旋節(jié)線降解機(jī)理；當(dāng)環(huán)氧大豆油濃度較低時(shí),得到了環(huán)氧樹(shù)脂的閉孔結(jié)構(gòu)。研究了溶劑濃度、固化劑用量,固化溫度對(duì)多孔結(jié)構(gòu)的影響,環(huán)氧大豆油濃度增加,孔徑增大,分布變寬,密度降低,孔隙率增大。增加固化劑用量,提高固化溫度,加快固化反應(yīng)速率,得到較大孔徑的環(huán)氧結(jié)構(gòu)。 2.采用熱塑性塑料通過(guò)反應(yīng)誘導(dǎo)相分離法制備了多孔環(huán)氧樹(shù)脂。脂肪族聚碳酸酯作為熱塑性塑料,與環(huán)氧樹(shù)脂制得復(fù)合材料,使脂肪族聚碳酸酯高溫降解即得到環(huán)氧樹(shù)脂多孔結(jié)構(gòu)。利用固化時(shí)間-脂肪族聚碳酸酯質(zhì)量濃度的準(zhǔn)相圖描述了環(huán)氧樹(shù)脂／熱塑性塑料體系的相分離機(jī)理,并利用光學(xué)顯微鏡對(duì)相分離演化過(guò)程進(jìn)行了跟蹤。相分離機(jī)理受控于環(huán)氧樹(shù)脂與脂肪族聚碳酸酯的組成,在脂肪族聚碳酸酯濃度較低時(shí),遵循成核生長(zhǎng),反之,旋節(jié)線降解機(jī)理。隨脂肪族聚碳酸酯濃度增加,環(huán)氧樹(shù)脂／脂肪族聚碳酸酯體系經(jīng)歷了分散相-雙連續(xù)相-相反轉(zhuǎn)結(jié)構(gòu)的轉(zhuǎn)變。增加熱塑性塑料濃度、提高固化溫度,環(huán)氧樹(shù)脂孔徑增大。 3.對(duì)熱塑性塑料的端羥基進(jìn)行了環(huán)氧化反應(yīng),合成了環(huán)氧化脂肪族聚碳酸酯,并利用傅立葉紅外光譜進(jìn)行表征,其環(huán)氧值為6.8%。 4.將環(huán)氧化脂肪族聚碳酸酯作為熱塑性塑料,通過(guò)反應(yīng)誘導(dǎo)相分離法制備了多孔聚合物材料,得到孔隙率較大的多孔結(jié)構(gòu)。在環(huán)氧樹(shù)脂／環(huán)氧化脂肪族聚碳酸酯體系中,當(dāng)環(huán)氧化脂肪族聚碳酸酯濃度較低時(shí),制得分散較為均勻的多孔結(jié)構(gòu)；隨其濃度增加,孔徑增大,分布變寬；在環(huán)氧化脂肪族聚碳酸酯濃度較高時(shí),得到環(huán)氧微球,當(dāng)環(huán)氧化脂肪族聚碳酸酯濃度介于兩個(gè)臨界濃度之間時(shí),體系出現(xiàn)分層,上層和底層為分散孔結(jié)構(gòu),中間層為環(huán)氧微球。 5.通過(guò)光學(xué)顯微鏡研究了環(huán)氧樹(shù)脂／環(huán)氧化脂肪族聚碳酸酯在不同固化溫度下的相分離過(guò)程。當(dāng)環(huán)氧化脂肪族聚碳酸酯濃度為35wt%時(shí),環(huán)氧樹(shù)脂／環(huán)氧化脂肪族聚碳酸酯體系在不同固化溫度下均遵循旋節(jié)線降解機(jī)理,且環(huán)氧化脂肪族聚碳酸酯以分散相分布在環(huán)氧基體中。隨固化溫度升高,體系中環(huán)氧化脂肪族聚碳酸酯的粒徑增大。
[Abstract]:A porous polymer material is prepared by reaction - induced phase separation , which is characterized by that the molecular weight of the thermosetting resin is gradually increased after the curing reaction is started , the compatibility between the solvent or the thermoplastic plastic is gradually deteriorated , the compatibility between the thermosetting resin and the solvent or the thermoplastic plastic is gradually deteriorated , and the system is not compatible with the solvent or the thermoplastic plastic gradually , and the polymer material with the porous structure is obtained after the solvent is removed or the thermoplastic plastic is high - temperature degradation .



1 . A porous epoxy resin was prepared by using epoxy soybean oil as solvent and bisphenol A epoxy resin as monomer , 4,4 - diamino diphenyl methane as curing agent . The final phase state of epoxy resin was determined by the composition of epoxy matrix and epoxidized soybean oil .
When the concentration of epoxy soybean oil is low , the closed pore structure of epoxy resin is obtained . The influence of solvent concentration , dosage of curing agent and curing temperature on porous structure is studied , the concentration of epoxy soybean oil is increased , the pore size is increased , the distribution becomes wider , the density is decreased , the porosity is increased , the curing temperature is increased , the curing reaction rate is increased , and the epoxy structure with larger pore size is obtained .



2 . A porous epoxy resin is prepared by reaction - induced phase separation by using thermoplastic plastics . The aliphatic polycarbonate is used as a thermoplastic material to prepare the composite material with epoxy resin . The phase separation mechanism of the epoxy resin / thermoplastic system is described by the quasi - phase diagram of the mass concentration of the aliphatic polycarbonate .



3 . The cyclic oxidation reaction was carried out on the hydroxyl groups of thermoplastic plastics . The epoxidized aliphatic polycarbonate was synthesized and characterized by FT - IR , and its epoxy value was 6.8 % .



4 . The porous polymer material was prepared by the reaction - induced phase separation method , and the porous structure with larger porosity was obtained .
As the concentration increases , the pore diameter increases and the distribution becomes wider ;
when the concentration of the epoxidized aliphatic polycarbonate is higher , the epoxy microspheres are obtained ; when the concentration of the epoxidized aliphatic polycarbonate is between two critical concentrations , the system is layered , the upper layer and the bottom layer are distributed pore structures , and the middle layer is epoxy microspheres .



5 . The phase separation process of epoxy resin / epoxidized aliphatic polycarbonate at different curing temperatures was studied by optical microscope . When the concentration of epoxidized aliphatic polycarbonate was 35 wt % , the epoxy resin / epoxidized aliphatic polycarbonate system followed the mechanism of spin - on - line degradation at different curing temperatures , and the epoxidized aliphatic polycarbonate was distributed in the epoxy matrix with dispersed phase .
【學(xué)位授予單位】：北京化工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2010
【分類號(hào)】：O631.3

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