【作者】 何彦刚；

【导师】 黎钢；

【作者基本信息】 河北工业大学 ， 应用化学， 2006， 硕士

【摘要】 本文研究了等离子体引发水溶液聚合制备聚（丙烯酰胺—co—2-（甲基丙烯酰氧乙基）三甲基氯化铵）（Poly（AM-DMC））阳离子型聚电解质。通过红外光谱分析证明所制备的聚合物是AM和DMC的共聚产物;通过测定不同反应室压力下反应液的沸点,选择反应液引发温度为-9℃,以保证整个引发过程反应器内辉光稳定;在反应室压力133Pa,单体配比为1:1（wt）的条件时优化了反应条件:单体总浓度30wt%,聚合时间24h,聚合温度40℃,pH值4.5,放电时间40s,放电功率60W,所得聚合物特性粘数达到966cm³/g;等离子体引发AM-DMC水溶液聚合的机理为:引发活性较高的自由基是AM与水溶液中H⁺结合形成的HAM·自由基,该自由基可进一步与AM或DMC单体进行反应,生成线性结构共聚物。 将不同放电功率（P）下,反应室温度（T）随等离子体放电时间（t）的变化的函数拟合方程为:T=15.935942+0.279195t+0.200020P-0.000595t²+0.004284tP+0.005297P²,R²=0.9851;通过研究等离子体引发DMC均聚,发现聚（2-（甲基丙烯酰氧乙基）三甲基氯化铵）（Poly（DMC））性质的选择可以通过控制反应室温度来实现:反应室温度低于130℃,生成线性Poly（DMC）,最高特性粘数为420.2cm³/g,反应室温度在130～200℃之间,产物发生交联,Poly（DMC）为吸水性树脂,吸水率最高为15g/g;200℃是DMC开始分解的温度,也是生成交联性PolyfDMC)的上限温度;对于生产线性聚合物时,放电时间与放电功率对聚合物特性粘数及单体转化率的优化反应条件为:放电时间60s,放电功率60W,此时反应室温度为80℃,此时最高特性粘数为420.2cm³/g,单体转化率为83.3%;根据低温等离子体中平均电子能量的方程计算证明,上述条件等离子体产生的电子平均能量（Te）约为8.4～12.6eV,大于DMC单体π键电离能9eV,等离子体引发聚合DMC是可行的。 筛选K₂CO₃溶液为分散聚合溶液介质制备Poly（AM-DMC）。单体AM、DMC及聚合物Poly（AM-DMC）在K₂CO₃溶液中溶解度的测定结果表明:一定浓度的K₂CO₃溶液对于两种单体是良溶剂,而对于聚合产物则为不良溶剂;经红外表征证明聚合产物为Poly（AM-DMC）;考察K₂CO₃浓度对聚合物特性粘数,聚合物粒径以及聚合物粒径分布的影响;优选出25wt%K₂CO₃溶液为分散聚合介质。在聚合温度30℃、放电时间35s、放电功率60W时,单体转化率、聚合物特性粘数分别都达到最高值58%,455cm³/g,而聚合物中K₂CO₃残留量也达到较小值5.3wt%;以实验现象为基础对聚合过程机理进行初步探讨。更多还原

【Abstract】 Polymerization of acrylamide （AM） with （2-methacryloyloxyethyl） thrimethyl ammonium chloride （DMC） in aqueous solution by plasma induced polymerization has been studied, and linear copolymer Poly（AM-DMC） was obtained. The boiling points of cooling solution in different reactor pressure were tested. The factors influencing the intrinsic viscosity of the copolymer were optimized as follows: polymerization time 24h, polymerization temperature 40℃, monomer concentration 30wt%, discharge time 40 s, discharge power 60W and pH value of aqueous solution 4.5. The highest intrinsic viscosity of the linear copolymer could be 966cm³/g. The mechanism of this polymerization was also studied based on the experimental date. The results showed that living radical was HAM which was composed of AM and H⁺.Plasma induced polymerization of （2-methacryloyloxyethyl） thrimethyl ammonium chloride was also studied in this paper. The effects of discharge time, discharge power on reactor temperature were measured, and it was found that the changing of reactor temperature could influenc the properties of Poly（DMC） obviously. The results showed that when the reactor temperature was lower than 130℃, Poly（DMC） was linear, and its highest intrinsic viscosity could be 420.2cm³/g. When the reactor temperature was more than 130℃, Poly（DMC） were molecules crosslinked each other, and its rate of absorbing water was 15g/g. The polymerization condition of linear Poly（DMC） were optimized as follows: discharge time 60s, discharge power 60W, reactor temperature 80℃, and in this condition, the highest intrinsic viscosity of Poly（DMC） was 420.2cm³/g and the monomer conversion was 83.3%. Moreover, the calculated result identified that plasma induced polymerization of DMC was feasible in theory.Dispersion polymerization of Poly（AM-DMC） has been successfully performed in potassium carbonate （K₂CO₃） solution by plasma induced polymerization. K₂CO₃ solution was selected because not only the higher solubility of AM and DMC comparing with that of Poly（AM-DMC）, but the higher intrinsic viscosity of Poly（AM-DMC） could be obtained. A setof experiments were performed using different concentration of K2CO3 solution （from 50wt% down to 10wt%）, thus the dispersion architecture was not obtained below 20wt%. When it was performed using K2CO3 solution that of above 20wt%, the dispersion architecture was obtained. The effects of concentration of K2CO3 solution on particles size, particles size distribution and intrinsic viscosity of Poly（AM-DMC） were also summarized in this paper. The factors were optimized as follows: polymerization temperature 30°C, discharge time 35s, discharge power 60W, and in this condition the highest intrinsic viscosity of Poly（AM-DMC） was 455cm3/g, and monomer conversion was 58%, and K2CO3 residue in copolymer particles was 5.3wt%.更多还原