【作者】 杨杰；

【导师】 王家喜；

【作者基本信息】 河北工业大学 ， 有机化学， 2020， 硕士

【摘要】 水杨酸、苯胺是有机污染物中一类具有高毒性的环境污染物,水中有机污染物的去除已经引起人们广泛关注。本文对芳烃Friedel-Crafts反应在功能材料合成中的应用及有机污染物的去除方法进行了文献调研,在此基础上提出了利用芳烃Friedel-Crafts反应合成吸附材料,评价其吸附性能,具体研究内容及结果如下:利用氯化苄苄基化合成多苄基预聚体,考察了催化剂对苄基化反应的催化性能,确定氯化铁在超交联树脂（n BCE）的合成反应过程中具有较好的催化性能。FI-IR分析表明,30 min后氯化苄的-CH₂Cl的信号峰几乎消失。APCI质谱分析表明,苄基化反应主要形成聚合度为2-20的不含氯的低聚物。苄基化产物与三甲胺反应产物的ESI质谱分析表明,苄基化产物中含有少量含氯甲基的低聚物。结合FT-IR,Q-TOF高分辨质谱数据,研究了苄基化的反应机理。探讨了所得低聚物经氯化铁催化氧化、高温脱氢法合成石墨烯多孔碳材料（n BCET）的可能性。SEM分析表明,催化氧化产物n BCET-1及高温脱氢产物n BCET-2均具有层状孔结构。n BCET-2对苯胺具有较弱的吸附性能,平衡吸附量仅为6.0 mg/g。初步考察了OP-10与氯化苄的反应,Q-TOF分析表明OP-10与氯化苄反应形成1～3次苄基化产物（BCEOP-x）,吊环法测定BCEOP-30的临界胶束浓度（CMC）为0.10 g/L,达到CMC时的表面张力γCMC为30.50 m N/m。利用1,4-二（氯甲基）萘（BN）和三苯基膦（TPP）的Friedel-Crafts苄基化反应、季膦化反应,合成了磷改性的交联树脂TPPBN-X。利用Q-TOF高分辨质谱、FT-IR、XPS、SEM和N₂吸附-脱附表征了所得树脂的结构和形貌。Q-TOF高分辨质谱分析表明TPP与BN的季膦化反应快于苄基化反应,生成了单季鏻盐和双季鏻盐。XPS分析表明,TPPBN-X中磷以季鏻盐与三苯基氧膦的形式存在。评价了TPPBN-X对水杨酸（SA）的吸附性能,研究了SA浓度、吸附时间、温度、p H对吸附性能的影响。结果表明,TPPBN-3可在10 min内对SA（500.0 mg/L）达到吸附平衡,吸附量为191.92mg/g。溶液的p H值对SA吸附有很大影响,最佳p H约为3-4。在p H为3.67,SA的浓度为1033.2 mg/L时,最大平衡吸附容量为449.7 mg/g。动力学数据可以用准二级动力学模型拟合,等温线数据可以用Langmuir模型和Tempkin模型拟合,说明TPPBN-3对SA的吸附主要为离子交换作用。TPPBN-3第四次吸附-解吸后,吸附效率为94.3%,表现出良好的可重复性。TPPBN-3对BN吸附过程的ΔH为-18.25 KJ/mol,ΔS为-57.92 J/（mol.K）,表明吸附是熵减和放热过程。更多还原

【Abstract】 Salicylic acid and aniline are a class of highly toxic environmental pollutants among organic pollutants.The removal of organic pollutants from water has caused widespread concern.In this paper,the application of aromatic Friedel-Crafts reaction in the synthesis of functional materials and the removal method of organic pollutants have been summarized from the literature.Based on this summary,the adsorption material was synthesized using Friedel-Crafts reaction of aromatic and the adsorption performance was evaluated.The specific research contents and the results are summarized as follow:Polybenzyl prepolymers were synthesized by benzylation of benzyl chloride.The catalytic performance of the catalyst for benzylation was investigated.Ferric chloride has a good catalytic performance during the synthesis of hyper cross linked resin（n BCE）.FI-IR analysis showed that the signal peak of-CH₂Cl of benzyl chloride almost disappeared after30 min.APCI mass spectrometry analysis showed that the benzylation reaction mainly formed chlorine-free oligomers with a degree of polymerization of 2-20.The ESI mass spectrometric analysis of the reaction product of benzylated product and trimethylamine showed that the benzylated product contained a small amount of chloromethyl-containing oligomers.Combining FT-IR and Q-TOF high resolution mass spectrometry data,the reaction mechanism of benzylation was studied.The possibility of synthesizing graphene porous carbon material（n BCET）through catalytic oxidation of ferric chloride and high temperature dehydrogenation was investigated.SEM analysis shows that both the catalytic oxidation product n BCET-1 and the high-temperature dehydrogenation product n BCET-2have a layered pore structure.n BCET-2 has a weak adsorption capacity for aniline,and its equilibrium adsorption capacity is only 6.0 mg/g.The benzylation reaction of OP-10 with benzyl chloride was initially investigated.Q-TOF analysis shows that OP-10 can react with benzyl chloride to form benzylation products 1 to 3 times（BCEOP-x）.The hydrophilicity of benzylated OP-10 decreases.The critical micelle concentration（CMC）of BCEOP-30measured by the hanging ring method is 0.10 g/L,and the surface tensionγCMC when reaching CMC is 30.50 m N/m.Phosphorus modified cross-linked resins TPPBN-X were synthesized by using Friedel-Crafts benzylation and quaternization reaction of 1,4-dichloromethylnaphthalene（BN）and triphenylphosphine（TPP）.The structure and morphology of the obtained resin were characterized by Q-TOF high resolution mass spectrometry,FT-IR,XPS,SEM and N₂adsorption-desorption.Q-TOF high-resolution mass spectrometry analysis showed that the quaternization reaction of TPP with BN was faster than the benzylation reaction,and single-quaternary phosphonium salt and double-quaternary phosphonium salt were formed.XPS analysis showed that phosphorus in TPPBN-X existed as quaternary phosphonium salt and triphenylphosphine oxide.The adsorption performance of TPPBN-X on salicylic acid（SA）was evaluated,and the effects of SA concentration,adsorption time,temperature,and p H on the adsorption performance were studied.The results showed that TPPBN-3 could reach the adsorption equilibrium of SA（500.0 mg/L）within 10 minutes,and the adsorption capacity was 191.9 mg/g.The p H of the solution has a great effect on SA adsorption,and the optimal p H is about 3-4.When the p H is 3.67 and the SA concentration is 1033.2 mg/L,the maximum equilibrium adsorption capacity is 449.7 mg/g.Kinetic data can be fitted with a quasi-second-order kinetic model,and isotherm data can be fitted with Langmuir model and Tempkin model,indicating that the adsorption of TPPBN-3 on SA is mainly ion exchange.After the fourth adsorption-desorption of TPPBN-3,the adsorption efficiency is94.3%,showing good repeatability.TheΔH of TPPBN-3 adsorption process on BN is-18.25 KJ/mol andΔS is-57.92 J/（mol.K）,indicating that the adsorption is an entropy reduction and exothermic process.更多还原