【作者】 任凤霞；

【导师】 黎钢；

【作者基本信息】 河北工业大学 ， 应用化学， 2007， 硕士

【摘要】 本文研究了壬基萘酚聚氧乙烯醚中间体壬基萘酚的合成方法,并对壬基萘酚聚氧乙烯醚的溶液性质进行了测定。在壬基萘酚的合成中,重点考察了四种质子酸催化剂活性白土、离子交换树脂、沸石分子筛和离子液体对2-萘酚与三聚丙烯烷基化反应的催化效果。得出如下结论:①活性白土催化2-萘酚和三聚丙烯烷基化的较佳条件为:2-萘酚/三聚丙烯(摩尔比)为1: 2,催化剂用量为30%,反应时间10h,反应温度100~110℃。在此条件下,壬基萘酚的产率可达到42.9%。②离子交换树脂NKC-9催化2-萘酚和三聚丙烯烷基化的较佳条件为:2-萘酚/三聚丙烯(摩尔比)为1.5:1,催化剂用量为10%,反应时间6h,反应温度100℃。在此条件下,壬基萘酚的产率可达到60%。③当反应温度为溶剂的回流温度,2-萘酚:三聚丙烯:环己烷=1:2:50 (摩尔比)的条件下,对于沸石分子筛HY、Hbeta和HZSM5,Hbeta的催化效果最好,其转化率和选择性分别为52.1%和86.3%,壬基萘酚产率为45.0%,结合沸石分子筛孔结构和酸性特征,进一步探讨了2-萘酚和三聚丙烯在沸石分子筛上的反应机理。④离子液体[BMIM]BF4催化2-萘酚和三聚丙烯烷基化反应的较佳条件:2-萘酚/三聚丙烯摩尔比为2:1,催化剂用量41.7%(5ml),反应时间2h,反应温度100℃,在此条件下壬基萘酚产率达到86%,选择性为100%,该离子液体循环六次,其活性仍可以保持。通过对上述四种催化剂的对比可知,活性白土作为催化剂时壬基萘酚产率较低,且反应时间长;离子交换树脂NKC-9作为催化剂时虽然壬基萘酚的产率较高,但是所用溶剂氯苯对环境不友好;沸石分子筛虽然环境友好,但是2-萘酚的转化率并不高;离子液体[BMIM]BF4作为催化剂时壬基萘酚的产率和选择性最高,反应时间短,自身是优良的溶剂,可循环使用,环境友好,是较佳的催化剂。由红外、氢核磁谱图和碳核磁谱图表征说明,2-萘酚和三聚丙烯烷基化反应的主要产物为6-壬基-2-萘酚。通过测定壬基萘酚聚氧乙烯醚溶液的部分性质可知,该物质亲水亲油平衡(HLB)值为16.0;临界胶束浓度(CMC)为4.01×10-3mol/L;1%(wt)的壬基萘酚聚氧乙烯醚溶液的浊点为86℃;颜料P.R.146和P.Y.65,在壬基萘酚聚氧乙烯醚溶液中的分散性,对应大于178μm的颜料粒径分布分别占18.6%和4.7%,均好于壬基苯酚聚氧乙烯醚NP21和NP30溶液的分散效果。更多还原

【Abstract】 The synthesis method of nonylnaphthol, an intermediate of nonylnaphthol ethoxylate ether, has been studied, and the properties of nonylnaphthol ethoxylate solution are also researched.In this paper, the reaction conditions for alkylation of 2-naphthol and tripropylene on four different acid catalysts such as active clay、exchange resin NKC-9、zeolites and ionic liquid, are optimized. The optimal alkylation conditions with catalyst active clay are:1:2 for 2-naphthol to tripropylene, dosage of catalyst active clay 30%, reaction time 10 hours, reaction temperature 100~110℃, and then 42.9% yield of nonylnaphthol can be obtained. The optimal alkylation conditions with catalyst exchange resin NKC-9 are as follows:1.5:1 for 2-naphthol to tripropylene, dosage of catalyst NKC-9 10%, reaction time 6 hours and reaction temperature 100℃, the yield of nonylnaphthol can be reached 60%.Comparative studies on the catalytic properties of H-beta, H-Y and H-ZSM5 zeolites are carried out under identical conditions for alkylation of 2-naphthol and tripropylene. The results show that H-beta zeolite exhibits outstanding catalytic performance under the optimal reaction conditions as 1:2:50 = 2-naphthol: tripropylene: cyclohexane within the boiling range temperature of cyclohexane, and the conversion and selectivity of 2-naphthol are 52.1% and 86.3% respectively. It is found that the pore structure and the acidic strength of zeolite catalysts are the major influencing factors for the conversion and selectivity of 2-naphthol.The optimal alkylation conditions with ionic liquid [BMIM] BF4 are as follows:2:1 for 2-naphthol to tripropylene, dosage of catalyst [BMIM] BF4 41.7 %( about 5ml), reaction time 2 hours and reaction temperature 100℃. Consequently, 86% yield and 100% selectivity of nonylnaphthol can be obtained. It has been testified that the separated ionic liquid catalyst still keep its catalysis after six times circular reusing.Having compared the effects of four catalysts, it is sure that there are low yield of nonylnaphthol and long reaction time when using the active clay. Although there are high yield of nonynaphthol when using exchange resin NKC-9, the solvent chlorobenzene is unfriendly for environment. It is environmental friendliness when using zeolite Hbeta, but the conversion of 2-napthol is lower. Ionic liquid [BMIM] BF4 is the best catalyst for alkylation of 2-naphthol with tripropylene. High yield and selectivity of nonylnaphthol、short reaction time、excellent solubility、reusable and environment-friendly are the advantage of ionic liquid catalyst.According to IR spectra and NMR spectra of the separated product, it is certain that 6-nonyl-2- naphthol is the main product of alkylation of 2-naphthol and tripropylene.The hydrophile-lipophilic-balance(HLB) value of nonylnaphthol ethoxylate is 16.0; The critical micelle concentration (CMC) of nonylnaphthol ethoxylate solution is 4.01×10-3mol/L; The cloud point of 1% (wt) nonylnaphthol ethoxylate solution is 86℃; Solution nonylnaphthol ethoxylate has shown better dispersibility to pigments P.R.146 and P.Y.65, and the most distribution of pigments grain are concentrated within 178μm.更多还原