超声场辅助MAA/AN共聚物的制备与表征及热分解动力学研究
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摘要
超声化学已成为目前化学研究领域的前沿学科之一。这是由于超声波可以在液体体系中产生空化、剧烈搅拌等效果，使其在高分子合成及高分子反应机理的研究中有着诸多独特的应用。声化学理论计算和对应实验表明，超声空化作用可使空化泡相界面周围出现5000K高温、66.24kPa高压的极端环境，这样的条件下溶剂、单体或高聚物链会发生分解或破裂产生自由基，更多的自由基有利于反应的引发。此外，超声波有效的混合作用有利于反应的进行。
本论文在超声波辅助作用下，以甲基丙烯酸（MAA）和丙烯腈（AN）为主要原料进行自由基聚合，得到MAA/AN共聚物。研究了单体配比、引发剂用量、超声波频率以及聚合温度等因素对聚合反应的影响，同时计算了MAA和AN的竞聚率。结果表明，单体配比为1:1，引发剂用量为0.2%，超声频率为20kHz以及聚合温度为55～60℃时，聚合反应速率适当，反应过程易于控制，所得共聚物的相对分子质量较高。MAA和AN的竞聚率分别为0.04和0.50。
采用DTG热分析技术研究MAA/AN共聚物的热分解反应动力学，得出聚合温度为50℃、120℃、140℃、160℃的MAA/AN共聚物的热分解反应活化能分别为61.24kJ/mol，101.59kJ/mol，147.46kJ/mol，185.14kJ/mol；指前因子lgA0分别为4.40，7.70，10.35，14.69。通过红外光谱分析（FTIR）、热失重分析（TG）、动态热机械分析（DMA）等方法对共聚物的结构与性能进行了分析，得到相应共聚物的弯曲强度分别为93.8MPa、192.5MPa、55MPa、168.4MPa，弯曲模量分别为4.06GPa、4.79GPa、0.75GPa、6.74GPa，冲击强度分别为7.5kJ/m2、13.2kJ/m2、23.4kJ/m2、18.4kJ/m2。TG曲线表明，不同聚合温度下MAA/AN共聚物800℃时残炭率约为40%，说明MAA/AN共聚物具有良好的热稳定性；通过DMA分析，聚合温度为50℃、120℃、140℃、160℃的MAA/AN共聚物的玻璃化转变温度分别为92.92℃、154.64℃、187.66℃、203.93℃。
Ultrasonic chemistry has become one of the frontiers discipline of chemical researchfield. The effect of cavitation, violent stir can be producted by ultrasonic in liquid system, andwidely used in polymer synthesis and the mechanism of polymer reaction. On the cavitationbubble phase interface, high temperature of 5000K, high pressure of 66.24kPa can be got, andhave been verified by sonochemical theoretical calculation and experiments. Under theextreme environment of high temperature and high pressure, free radicals can be producedfrom the decomposition of solvent, monomer or polymer chain, and the more free radical, theeasier initiated reaction was. In addition, effective mixing action of ultrasonic helps reaction.
In this work, copolymer of MAA/AN was synthetised through ultrasonically inducedfree radical polymerization of methacrylic acid(MAA) and acrylonitrile (AN). The influenceon polymerization, which was caused by monomer ratio, initiator amount, ultrasonicfrequency, reaction temperature, etc, was studied and the reactivity ratio between MAA andAN was calculated. The result shows that, higher molecular weight can be got andpolymerization rate was easied to control, when monomer concentration was 1:1, initiatorconcentration 0.2%, ultrasonic frequency 20kHz, and ultrasonic field temperature was 55～60℃. The reactivity ratio between MAA and AN was 0.04 and 0.50.
The themal degradation kinetics was studied through DTG. Themal degradation reactionactivation energy of MAA/AN copolymer synthesized at 50℃, 120℃, 140℃, 160℃wascalculated, the corresponding value was 61.24kJ/mol, 101.59kJ/mol, 147.46kJ/mol, 185.14kJ/mol and the pre exponential factors lgA0 4.40, 7.70, 10.35, 14.69, respectively. Thestructures and properties of copolymers was analysised through infrared spectroscopicanalysis(FTIR), thermogravimetic analysis(TG), dynamic thermomec- hanical analysis(DMA). Through mechanics performance testing, the flexural strength of the copolymer synthesized at50℃, 120℃, 140℃, 160℃was 93.8MPa, 192.5MPa, 55MPa, 168.4MPa, flexural modulus4.06GPa, 4.79GPa, 0.75GPa, 6.74Gpa, and impact strength 7.5kJ/m2, 13.2kJ/m2, 23.4 kJ/m2,18.4kJ/m2. The carbon residue rate of the copolymer at 800℃was 40%, showed wonderfulthermalstability. The glass transition temperature (Tg) of copolymer synthesized at 50℃, 120℃, 140℃, 160℃, achieved from DMA, was 92.92℃, 154.64℃, 187.66℃, 203.93℃,respectively.
本论文在超声波辅助作用下，以甲基丙烯酸（MAA）和丙烯腈（AN）为主要原料进行自由基聚合，得到MAA/AN共聚物。研究了单体配比、引发剂用量、超声波频率以及聚合温度等因素对聚合反应的影响，同时计算了MAA和AN的竞聚率。结果表明，单体配比为1:1，引发剂用量为0.2%，超声频率为20kHz以及聚合温度为55～60℃时，聚合反应速率适当，反应过程易于控制，所得共聚物的相对分子质量较高。MAA和AN的竞聚率分别为0.04和0.50。
采用DTG热分析技术研究MAA/AN共聚物的热分解反应动力学，得出聚合温度为50℃、120℃、140℃、160℃的MAA/AN共聚物的热分解反应活化能分别为61.24kJ/mol，101.59kJ/mol，147.46kJ/mol，185.14kJ/mol；指前因子lgA0分别为4.40，7.70，10.35，14.69。通过红外光谱分析（FTIR）、热失重分析（TG）、动态热机械分析（DMA）等方法对共聚物的结构与性能进行了分析，得到相应共聚物的弯曲强度分别为93.8MPa、192.5MPa、55MPa、168.4MPa，弯曲模量分别为4.06GPa、4.79GPa、0.75GPa、6.74GPa，冲击强度分别为7.5kJ/m2、13.2kJ/m2、23.4kJ/m2、18.4kJ/m2。TG曲线表明，不同聚合温度下MAA/AN共聚物800℃时残炭率约为40%，说明MAA/AN共聚物具有良好的热稳定性；通过DMA分析，聚合温度为50℃、120℃、140℃、160℃的MAA/AN共聚物的玻璃化转变温度分别为92.92℃、154.64℃、187.66℃、203.93℃。
Ultrasonic chemistry has become one of the frontiers discipline of chemical researchfield. The effect of cavitation, violent stir can be producted by ultrasonic in liquid system, andwidely used in polymer synthesis and the mechanism of polymer reaction. On the cavitationbubble phase interface, high temperature of 5000K, high pressure of 66.24kPa can be got, andhave been verified by sonochemical theoretical calculation and experiments. Under theextreme environment of high temperature and high pressure, free radicals can be producedfrom the decomposition of solvent, monomer or polymer chain, and the more free radical, theeasier initiated reaction was. In addition, effective mixing action of ultrasonic helps reaction.
In this work, copolymer of MAA/AN was synthetised through ultrasonically inducedfree radical polymerization of methacrylic acid(MAA) and acrylonitrile (AN). The influenceon polymerization, which was caused by monomer ratio, initiator amount, ultrasonicfrequency, reaction temperature, etc, was studied and the reactivity ratio between MAA andAN was calculated. The result shows that, higher molecular weight can be got andpolymerization rate was easied to control, when monomer concentration was 1:1, initiatorconcentration 0.2%, ultrasonic frequency 20kHz, and ultrasonic field temperature was 55～60℃. The reactivity ratio between MAA and AN was 0.04 and 0.50.
The themal degradation kinetics was studied through DTG. Themal degradation reactionactivation energy of MAA/AN copolymer synthesized at 50℃, 120℃, 140℃, 160℃wascalculated, the corresponding value was 61.24kJ/mol, 101.59kJ/mol, 147.46kJ/mol, 185.14kJ/mol and the pre exponential factors lgA0 4.40, 7.70, 10.35, 14.69, respectively. Thestructures and properties of copolymers was analysised through infrared spectroscopicanalysis(FTIR), thermogravimetic analysis(TG), dynamic thermomec- hanical analysis(DMA). Through mechanics performance testing, the flexural strength of the copolymer synthesized at50℃, 120℃, 140℃, 160℃was 93.8MPa, 192.5MPa, 55MPa, 168.4MPa, flexural modulus4.06GPa, 4.79GPa, 0.75GPa, 6.74Gpa, and impact strength 7.5kJ/m2, 13.2kJ/m2, 23.4 kJ/m2,18.4kJ/m2. The carbon residue rate of the copolymer at 800℃was 40%, showed wonderfulthermalstability. The glass transition temperature (Tg) of copolymer synthesized at 50℃, 120℃, 140℃, 160℃, achieved from DMA, was 92.92℃, 154.64℃, 187.66℃, 203.93℃,respectively.
引文
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