【作者】 陈健；

【导师】 王双飞；

【作者基本信息】 广西大学 ， 化学工艺， 2014， 博士

【摘要】 首先,以三乙烯四胺、四乙烯五胺及多乙烯多胺三种与其他原料合成聚酰胺多胺环氧氯丙烷(PAE)。然后,通过微波辐射的的方法在PAE上成功接枝含氟丙烯酸酯单体(FA),制备出聚酰胺多胺氟代丙烯酸环氧氯丙烷(PAE-PFA),并对PAE制备工艺与微波接枝工艺进行探索,得到如下结论。(1)以三乙烯四胺、四乙烯五胺及多乙烯多胺三种原料与己二酸合成聚酰胺多胺,结果表明：三种多乙烯多胺原料与己二酸的摩尔配比为1：1,维持反应体系在130～135℃温度下30min,之后,以采用冷凝回流法收集馏出液,缓慢加热升温至规定温度保温2h,此条件下缩聚反应程度可达到95%以上。在上述反应条件下的聚酰胺多胺中间体在固含率为50%左右时,粘度为600-800cP能很好地满足下步反应制备聚酰胺多胺环氧氯丙烷树脂。(2)PAE合成单因素试验结果表明：PPC与EPI摩尔比低于1.2时,产品的稳定性差；而比值大于1.8后,产品的增湿强效果不佳,出现减弱趋势。在试验中当EPI与PPC的比值不断增大时,PAE的湿强效果呈较大幅度下降趋势,EPI:PPC=1.3时可得到较好的湿强度。PAE合成正交试验结果表明：影响产品粘度和最终湿强度最显著因素为保温温度,其次为保温时间,而反应的原料配比和升温速率的影响均较小。通过分析PAE湿强度对其稳定性的影响,可知,环氧化合适的反应条件为：EPI/PPC=1.3,反应体系升温速率0.5℃/min,保温温度为50℃,保温时间为40min。所得产品的粘度范围在40-46cp之间,其固含量约为20%。(3)使用微波辐射乳液聚合的方法,成功合成聚酰胺多胺氟代丙烯酸环氧氯丙烷的含氟乳液纸张施胶剂,试验结果表明：①选择乳化剂用量3%,能保持较高的产率并降低乳化剂用量；微波辐射功率为50W时,反应过程较易控制,微波时间4.5min产率就能达到90%以上；含氟乳液的产率在含氟单体用量为15%时已出现最高峰值,之后趋于稳定。②乳化剂用量的增加,乳液平均粒径逐渐减小,同时其粒径分布(PDI)逐渐上升；随着含氟单体用量的增多,乳胶粒的粒径逐渐上升；乳胶粒粒径随着功率的增加先增加,在大于200W处出现转折。③乳胶膜接触角的测定。当乳化剂用量为4%时,含氟单体用量超过10%,微波功率为50W时,微波时间达到4.5min,接触角达到最大值。对于微波法合成PAE-PFA的动力学进行研究。通过单因素分析的方法,考察了乳化剂用量、含氟单体用量以及引发剂用量对微波法合成聚酰胺多胺氟代丙烯酸环氧氯丙烷乳液聚合反应速率的影响,并讨论了微波法合成聚酰胺多胺氟代丙烯酸环氧氯丙烷乳液聚合反应的反应机理。运用线性回归的方法拟合直线,推导出乳化剂用量[E]、含氟单体用量[F]以及引发剂用量[I]与聚合反应速率Rp之间的关系,得Rp∝[E]0.5525[I]0.4559[F]0.505,说明微波含氟乳液聚合反应符合Smith-Ewart理论的反应机理。运用ATRP法对于PAE进行接枝,合成PAE-PFA。合成的过程中,首先合成PAE,然后通过PAE和2-氯丙酰氯反应制备大分子引发剂PAE-Cl,然后将大分子引发剂PAE-Cl、甲基丙烯酸六氟丁酯单体、配体PMEDTA和溶剂甲苯进行ATRP法反应,制备出聚酰胺多胺氟代丙烯酸环氧氯丙烷。运用红外、核磁检测手段进行检查,表征聚酰胺多胺氟代丙烯酸环氧氯丙烷的官能团、分子结构,证明聚酰胺多胺氟代丙烯酸环氧氯丙烷合成成功。运用凝胶渗透色谱GPC对聚酰胺多胺氟代丙烯酸环氧氯丙烷进行分子量及其分布的表征,当转化率达到97.1%时,分子量达到48550,PDI分布为1.36。同时,通过In([M]0/[M])对t作图,并进行拟合,拟合得到线性的曲线,证明ATRP反应过程可控性较好。通过DSC对于聚酰胺多胺氟代丙烯酸环氧氯丙烷共聚物进行玻璃化转变温度的测定,结果证明存在一个玻璃化转变温度,产物较纯。由于硅材料也具有良好的拒油、拒水及防污性能,将硅单体、氟单体与PAE反应,可以制备出新型的含硅氟防油增湿强剂。该研究的主要内容如下。1、本实验以OP-10非离子型乳化剂、离子型乳化剂SDS、含氟乳化剂S200作为复配乳化剂,以偶氮二异庚腈作为引发剂,以甲基丙烯酸十二氟庚酯(G04)为含氟单体,以有机硅大分子作为含硅单体合成新型含硅氟防油增湿强剂。较优合成工艺为复配乳化剂的用量为PAE质量的3%,引发剂偶氮二异庚腈用量为PAE质量的1%,PAE质量与含氟单体质量混合比例为1.5,PAE质量与有机硅大分子质量比为2,反应时间6h,反应温度50℃,合成得到的新型含硅氟防油增湿强剂的湿强度为20%,防油等级为8。2、合成得到的湿强度为20%,防油等级为8的新型含硅氟防油增湿强剂用于纸张涂布,在以增强纸张强度的前提下,采用120℃干燥温度进行干燥处理20min。当新型含硅氟防油增湿强剂的涂布量为2.86g/m2～6.29g/m2时,便可达到食品包装中的防油要求。更多还原

【Abstract】 Firstly, triethylenetetramine, tetraethylenepentamine or the polyethylene polyamine was used as the raw material to prepare the polyamide polyamine epichlorohydrin (PAE), and then, the fluorinated acrylate monomer was grafted onto PAE initiated by microwave radiation. By this way, the PAE-PFA was obtained. In this paper, the synthesis process for PAE and PAE-PFA, and the results were shown as followings,(1) The optimum conditions for preparing polyamide polyamine by adipate reacting with triethylenetetramine, tetraethylenepentamine or the polyethylene polyamine to was discussed. The results shows that the mole ratio of polyethylene polyamine and adipate was1:1at130-135℃for30min, and then it was moved to Condensate backflow at design temperature for2h. The extent for condensation polymerization could reach95%. The condensation polymerization was used as intermediate reacted at optimum condition, the viscidity was600-800cP, which is the good for polyamide polyamine epichlorohydrin resin.(2) The results for preparation of PAE was indicaded that the stability of the products was unstable at the mole rate of PPC and EPI below1.2, and the it could achieve the ideal effect at1.8. The experiments showed that the wet strength would decreased with the rate value of EPI and PPC increasing, and the rate value of EPI and PPC was1:3to be the optimum. The orthogonal analysis suggested that the temperature was the most influential condition; the reaction time was less, and rate for reactant and temperature rising were the least ones. Considering the stable and wet strength of PAE, the condition is EPI/PPC=1.3, the rate of temperature rising0.5℃/min, reaction temperature50℃, reaction time40min, and the viscidity of the products was40-46cP with solid content20%.(3) Via method of microwave radiation emulsion polymerization, the sizing agent, PAE-PFA, was obtained. The results shows:(a) it could be obtained the high yield at3%emulsifier; the yield of products could achieve90%at the power50W reacting4.5min; the15%of functional monomer was the optimal dosage.(b) the PDI would increase with the more emulsifier used and the increase of power of microwave radiation, but it decreased at200W.(c) the wrapping angle will be the maximum at4%emulsifier,10%functional monomer and50W for4.5min.The kinetic study on the synthesis of PAE-PFA by microwave was discussed. By univariate analysis, dosages of emulsifier, fluorine monomer and initiator were investigated, and the synthesis mechanism of PAE-PFA was studied. It was shown that the relation beyond reaction rate, emulsifier, fluorine monomer and initiator was follows the equation Rp∝[E]0.5525[I]0.4559[F]0.505, which indicaded the reaction conform to Smith-Ewart theory.FTIR and NMR were used, and it proved the functional group and structure of the product. The molecular weight and molecular weight distribution was analyzed by GPC. The molecular weight was48550and molecular weight distribution reached1.36, when conversion percent was97.1%. The linearity between In([M]0/[M]) and t showed that the ATRP reaction process is better controlled. glass transition temperature suggested the product was pure.The silicon material also has good oil-repellent, water-repellent and antifouling properties, so a novel silicon-containing fluorine anti-oil moisturizing strength agent could be prepared by the silicon and fluorine monomer reacted with PAE. The contant was as followings.(1) In this experiment, the new fluorine anti-oil containing humidifier strength agent was prepared by using the non-ionic emulsifier OP-10, ionic emulsifiers SDS, fluorinated emulsifier S200as the complex emulsifier, and the azobis isoheptyloxy nitrile as an initiator, methacrylic dodecafluoroheptanoyl ester (G04) as the fluorine-containing monomer, silicone macromolecules as silicon-containing monomers. The optimal process was3%PAE,1%azobis isoheptyloxy nitrile, fluorine-containing monomers/PAE1.5, and silicon-containing monomers/PAE2reacting6h at50℃. The wet strength of the product could reach to, and oil rating could be8.(2) The product, which wet strength and oil rating could reach20%and8, was used for coating paper. The coating paper, preparing at120℃for20min, with2.86g/m2～6.29g/m2of the product could meet the requirements of food packaging for anti-oil.更多还原