超临界CO₂中疏水改性聚丙烯酰胺及复合材料的合成研究

【作者】 郑岚；

【导师】 陈开勋；

【作者基本信息】 西北大学 ， 化学工程， 2009， 博士

【摘要】 本文以超临界CO₂与丙酮的混合体系作为反应介质,进行了疏水改性丙烯酰胺的合成。成功地得到了多种疏水改性聚丙烯酰胺产品。研究工作为此类化合物在超临界CO₂中的聚合提供了一种新的思路和方法,对扩展聚丙烯酰胺的品种,进而扩大应用范围作出新的尝试。详细探讨了以过氧化苯甲酰（BPO）为引发剂,丙烯酰胺（AM）与甲基丙烯酸十二氟庚酯（G04）在超临界CO₂与丙酮共溶剂体系中的二元共聚合反应。通过单因素实验和正交实验研究了反应规律和最优化工艺条件,并针对产物的水溶性,增粘性,抗盐性等进行了相关应用实验,检验了共聚产物的疏水改性效果。利用红外光谱（IR）,质谱,核磁共振（¹H-NMR）对共聚产物的结构进行表征,利用热重分析仪（TG）分析了产物的热稳定性。通过动力学分析,提出了AM与GO4在超临界CO₂中的自由基共聚合反应机理,求取了共聚合反应过程中两种单体的竟聚率,并考察了温度、压力,助溶剂等因素对丙烯酰胺竟聚率的影响,通过计算得出了共聚物组成与转化率的关系图。完成了AM、G04与甲基丙烯酸甲酯（MMA）,AM、G04与顺酐在超临界CO₂+丙酮体系中的三元共聚合反应。并对聚合产物进行了分析和表征,应用试验表明共聚产物具有优良的吸水性、阻垢性能等。合成了顺酐与聚乙二醇（PEG400）的单酯化缩聚产物,顺酐与牛磺酸缩聚产物,并进行了AM、G04与顺酐—PEG400缩聚物,AM、G04与顺酐-牛磺酸缩聚物在超临界CO₂+丙酮体系中的三元共聚合反应,并对聚合物产物进行了分析和表征,并做了部分应用试验。完成了超临界CO₂+丙酮体系中的AM、G04、MMA与顺酐-PEG400缩聚物四元共聚合反应,AM、G04、丙烯睛与顺酐-PEG400缩聚物的四元共聚合反应;AM、G04、丙烯酸与聚合好的顺酐-PEG400缩聚物的四元共聚合反应,合成了一系列具有特殊性能的新型聚合物材料。并对共聚产物进行了分析和表征,对聚合产物进行了初步应用研究。更多还原

【Abstract】 More than eight kind of hydrophobically-modified polyacrylamide products were successfully synthesized when supercritical CO₂ and the acetone solvent was presented.It will help to develop the producing method of polyacrylamide,widen the applying field of polyacrylamide.Further more,it makes it possible for insoluble solids polymerizing under the condition of supercritical CO₂,helps the researcher find a new way of polymerizing in supercritical CO₂.The copolymerization of acrylamide（AM） and 12 fluorin substituted heptanol methacrylic acid carter（G04） was studied in detail with benzoyl peroxide（BPO） as initiator when supercritical CO₂ and the acetone solvent were presented.Through single factor experiments and orthogonal experiments,the copolymerization law of acrylamide and G04,the optimum reaction conditions were studied.Water-soluble experiment of the products,viscosity of different product solutions were tested to measure the hydrophobic nature.The structure of the copolymer product was illustrated by infrared（IR） spectroscopy,mass spectrum（MS） and ¹H-NMR analysis. The thermal stability of the product was also analyzed by employing thermal gravimetric analysis（TG）.The kinetics of the copolymerization was studied.The free radial reaction of AM and G04 was presented.The competition rate of AM and G04 was calculated.The influences of temperature,pressure and cosolvent were also discussed,the relationship between the composition of copolymerization and translation rate was got.The copolymerizations of AM,G04 and MMA and the copolymerization of acrylamide,G04 and Maleic acid anhydride with supercritical CO₂+acetone solvent were studied.The structure of the copolymer products was illustrated by infrared（IR） spectroscopy and ¹H-NMR analysis..Through the applying experiment,it showed the products had a character.of excellent bibulous and furring preventing. The single esterification of maleic acid anhydride and polyethylene glycol（PEG400） was studied.Then the copolymerization between AM,G04 and Maleic acid anhydride-PEG400 with supercritical CO₂+acetone solvent was studied.The esterification of maleic acid anhydride and Taurine was also got.Then the copolymerization of AM,G04 and Maleic acid anhydride-Taurine maleic acid with supercritical CO₂+acetone solvent was studied.The structure of the copolymer products was illustrated by infrared（IR） spectroscopy,mass spectrum（MS） and ¹H-NMR analysis.The copolymerizations of AM,G04,MMA and Maleic acid anhydride -PEG400,the copolymerizations of AM,G04 vinyl cyanide and Maleic acid anhydride-PEG400,the copolymerizations of AM,G04 crylic acid and Maleic acid anhydride-PEG400 with supercritical CO₂+acetone solvent were studied.The products have some special characters. The structure of the copolymer products were illustrated by infrared（IR） spectroscopy,mass spectrum（MS） and ¹H-NMR analysis.更多还原