【作者】 王坚；

【导师】 夏咏梅； 钱飞；

【作者基本信息】 江南大学 ， 材料与化工（专业学位）， 2023， 硕士

【摘要】 壬基酚聚氧乙烯醚（NPEO_n）曾为世界第二大使用量的非离子表面活性剂,广泛用于日化、农业以及纺织等领域。但由于NPEO_n的生态毒性问题,目前已经被多方禁、限用,需要寻找NPEO_n的全面替代品。本课题组前期合成了壬基环己醇聚氧乙烯醚（NCEO_n）,并证明NCEO_n具有与NPEO_n相近的表界面物理化学性能,但所用催化剂对壬基环己醇的催化活性尚低、副产物含量高;而且由于NCEO_n中的疏水基与NPEO_n的不同,不能沿用NPEO_n的构效关系,故而应用技术开发短缺。因此,本实验首先优选NCEO_n合成用催化剂,以及其进料方式并优化乙氧基化反应中的反应条件;然后探究新工艺下所得NCEO_n的溶液表界面物理化学性能与其加成数n的构效关系;最后以几种典型聚氧乙烯醚非离子表面活性剂为参照,分别对照性研究NCEO_n在日化、农业以及洗涤领域的应用,并初步探讨NCEO_n与典型阴离子表面活性剂溶液的表界面物理化学性能及其对洗涤剂用蛋白酶的活性影响。主要研究内容及结果如下:1.探究工艺条件对壬基环己醇乙氧基化反应速率的影响。通过改变催化剂加入方式和优化工艺条件,可以使得氢化钠的催化活性显著提升,其催化活性仅次于三氟化硼的。进一步探究NCEO_n（n=5-11）水溶液的表界面物理化学性能与NCEO_n加成数间构效关系。研究表明,随着NCEO_n的加成数n的增加,NCEO_n水溶液的临界胶束浓度（cmc）、临界胶束浓度下的表面张力(γ_cmc)、浊点、发泡力以及去污力均增大,而润湿力、乳化力以及泡沫稳定性总体呈下降趋势,这与脂肪醇聚氧乙烯醚的一般规律相似。当n=9,11时,NCEO_n水溶液具有与NPEO₁₀相近的临界胶束浓度以及低发泡、快速消泡的能力以及更好的去污力。2.探究了5种亲水基相似的聚氧乙烯醚类非离子表面活性剂,即NCEO₉、NPEO₁₀、异构十三醇聚氧乙烯醚（9）（E1309）、仲醇聚氧乙烯醚（9）（S-90）和十二烷基聚氧乙烯醚（9）（AEO₉）对5种日用化学品油的乳化力。结果表明对于白油、茶籽油和辛癸酸甘油酯,总体上乳化力依次为:S-90～AEO₉<NCEO₉<NPEO₁₀～E1309;对于霍霍巴油的乳化力大小依次为AEO₉>NCEO₉>NPEO₁₀>E1309>S-90;对于二甲基硅油的乳化力大小依次为NCEO₉>NPEO₁₀>E1309>S-90>AEO₉。5种表面活性剂对混合油脂的乳化力大小依次为NPEO₁₀～E1309>NCEO₉>S-90>AEO₉。3.探究了NCEO_n（n=5-11）乳化的农药氟氯氰菊酯O/W型乳液的物理性能。结果表明,考察范围内NCEO_n乳化的氟氯氰菊酯O/W型乳液在标准硬水中具有与NPEO₁₀和三苯乙基苯酚聚氧乙烯醚（E-602）所乳化乳液同样的分散状态和稳定性,但在标准硬水中稀释后乳化状态不如NPEO₁₀的。油相为溶剂油150时,NCEO₁₁以及E-602所制备的乳液具有相对较小的粒径和粒径分布,形成的乳液具有弹性行为。油相为二甲苯时,NPEO₉以及NPEO₁₀制备的乳液粒径更小,具有粘弹性。润湿性研究表明,乳液在上海青叶片上的接触角依照所用乳化剂依次为:NCEO₇<NCEO₉～NPEO₁₀<NCEO₅<NCEO₁₁<E-602;这与氟氯菊酯乳液的表面张力测量结果一致,其依照所用乳化剂依次为:NCEO₅<NCEO₇<NCEO₉<NPEO₁₀<NCEO₁₁<E-602。表面活性剂降低水的表面张力效率下降,表现出更高的表面张力,也导致其乳液的润湿性能下降。在NCEO_n（n=5-11）中,NCEO₇的表面张力较低,接触角较小,在叶片上的滞留率最高。4.探究了NCEO_n（n=7-11）与十二烷基苯磺酸钠（LAS）二元体系水溶液的表界面物理化学性能。NCEO₁₁-LAS混合体系在胶束形成方面有相对较强的协同作用。NCEO_n-LAS混合体系的胶束形成过程主要由熵驱动,均为自发的放热过程。通过研究NCEO_n-LAS（n=7-11）二元混合体系的应用性能,发现NCEO_n摩尔分数（x₂）=0.2的NCEO_n-LAS混合体系在润湿力上为最佳协同作用点,x₂=0.1时为去污最佳协同作用点。总体而言,和LAS复配时,含NCEO_n体系的润湿力和泡沫稳定性大小依次为NCEO₁₁<NCEO₉<NCEO₇;乳化力大小依次为NCEO₇<NCEO₁₁<NCEO₉;发泡力大小依次为NCEO₇<NCEO₉<NCEO₁₁;随着x₂的增加,混合体系对大豆油的乳化力增强,但发泡力和泡沫稳定性下降。实验范围所试混合体系水溶液在750 ppm的硬水下24 h均可保持澄清。与十二烷基聚氧乙烯醚（AEO₉）相比,对于炭黑和脂肪污布去污力大小依次为NCEO₇<NCEO₉～AEO₉<NCEO₁₁;对于蛋白污布的去污力大小依次为NCEO₇<AEO₉<NCEO₁₁<NCEO₉。5.探究了NCEO_n（n=7-11）对蛋白酶Savinase Ultra 16XL和Progress uno 100L稳定性的影响。结果表明,40℃下非离子表面活性剂NCEO_n和AEO_n（n=7,9）在10 h内对2种蛋白酶活性均保持在90%以上,而阴离子表面活性剂LAS在接触蛋白酶Savinase Ultra 16XL的2.5 h内使得酶活性接近于0。进一步地探究上述非离子表面活性剂与LAS混合体系对蛋白酶Progress uno 100L的影响,结果表明随着混合体系中非离子表面活性剂摩尔分数的增加,实验范围所试混合体系对放置7天后的蛋白酶的酶活稳定性均增加,NCEO_n-LAS（n=7-11）体系比AEO₉-LAS体系对蛋白酶Progress uno 100L均展现出更好的酶活稳定性。更多还原

【Abstract】 Nonylphenol polyoxyethylene ethers（NPEO_n）used to be the second most used nonionic surfactant worldwide,widely used in daily chemical,agricultural and textile fields.However,due to the ecological toxicity of NPEO_n,many countries and regions have prohibited its use.Therefore,alternatives of NPEO_n need to be found for their every uasage.In the previous studies,nonylcyclohexanol was applied to replace nonylphenol to synthesize nonylcyclohexanol polyoxyethylene ethers（NCEO_n）from the perspective of structural substitution.It has been proved that NCEO_n possess similar interfacial physicochemical properties as that of NPEO_n,but the catalyst for synthesis of NCEO_n still present low,resultsing high content of byproduct.Furthermore,due to the hydrophobic group in NCEO_nis different from that of NPEO_n,the structure-activity relationship of NPEO_n cannot be directly adapted to NCEO_n,remaining a shortage on application development.Therefore,the catalyst used for NCEO_n synthesis and its feeding style were investigated and selected first,and the reaction conditions of ethoxylation were optimized.Then,the structure-activity relationship between the physico-chemical properties of solution surface interface and its additive number n was investigated.Finally,several typical nonionic polyoxyethylene ether surfactants were used as references to study the application of NCEO_nin daily chemical,agricultural and washing fields,and the physical and chemical properties of the surface interface of NCEO_n and typical anionic surfactants as well as their effects on the activity of protease used in detergent were preliminatively discussed.The main research contents and results are as follows:1.The influence of reaction parameters on the ethoxylation of nonylcyclohexanol was investigated.By changing the adding method of catalyst and optimizing the process conditions,the catalytic activity of sodium hydride can be significantly improved,weaker than that of boron trifluoride among the assayed catalysts.The structure-activity relationship between the interfacial physicochemical properties of NCEO_n（n=5-11）aqueous solution and the adduction number of NCEO_n was investigated.The results indicated that the critical micellar concentration（cmc）,surface tension at cmc(γ_cmc),turbidity point,foaming ability and detergency of NCEO_n aqueous solution increased with the increase of EO adduction number;while the wetting ability,emulsification ability and foam stability present a reverse trend,similar to the general rule of fatty alcohol polyoxyethylene ether.NCEO_n（n=9,11）aqueous solution exhibited a critical micellar concentration similar to that of NPEO₁₀,along with lower foaming,faster defoaming ability,and better detergency.2.The emulsification ability of NCEO₉was studied with other four nonionic polyoxyethylene ether surfactants with similar hydrophilicity,including NPEO₁₀,isomeric alcohol ethers（9）（E1309）,secondary alcohol polyoxyethylene ether（9）（S-90）,and dodecyl polyoxyethylene ether（9）（AEO₉）,on various types of daily chemical oils.The results showed that the emulsifying ability on white oil,tea seed oil and octycapyl glycerol was S-90～AEO₉<NCEO₉<NPEO₁₀～E1309.The emulsifying ability on jojoba oil was AEO₉>NCEO₉>NPEO₁₀>E1309>S-90.The emulsifying ability on dimethyl silicone oil was NCEO₉>NPEO₁₀>E1309>S-90>AEO₉.Further study on the emulsifying ability of the five surfactants on formulated oils showed that the emulsifying ability was in the order of NPEO₁₀～E1309>NCEO₉>S-90>AEO₉.3.The physical properties of cyfluthrin O/W emulsions stablized by NCEO_n（n=5-11）were also investigated.The results indicated that emulsions generated by NCEO_n presented similar dispersion and stability in standard hard water as that of NPEO₁₀ and styryl phenol polyoxyethylene ether（E-602）,but weaker than that of NPEO₁₀.The emulsions of solvent oil150 stablized by NCEO₁₁ and E-602 present smaller particle size and narrow particle size distribution,and the formed emulsion presented viscoelasticity.With xylene,the emulsion prepared by NCEO₉ and NPEO₁₀ had smaller particle size and presnted viscoelasticity.The wettability study showed that the contact Angle of emulsion on vegetable leaves was NCEO₇<NCEO₉～NPEO₁₀<NCEO₅<NCEO₁₁<E-602 according to the emulsifier used.This was consistent with the surface tension measurements of fluthrin emulsions,which was NCEO₅<NCEO₇<NCEO₉<NPEO₁₀<NCEO₁₁<E-602 in accordance with the emulsifiers used.Surfactant reduced the surface tension efficiency of water and showed higher surface tension,which also leads to the wettability of their emulsion decreased.Among the NCEO_n（n=5-11）,NCEO₇ had lower surface tension and smaller contact angle,with highest retention on leaves.4.The interfacial physicochemical properties were studied with the binary aqueous system of NCEO_n（n=7-11）and sodium dodecyl benzene sulfonate（LAS）.The NCEO₁₁-LAS system exhibited a synergistic effect on the mixing micellar behavior.The micellar formation of NCEO_n-LAS was mainly driven by entropy,spontaneous and exothermic.By studying the application performance of NCEO_n-LAS binary system,it was found that the NCEO_n-LAS system with NCEO_n molar fraction（x₂）=0.2 was the best formulation in terms of wettability,while x₂=0.1 was the best for detergency.In general,when combined with LAS,the wettability and foam stability of the system containing NCEO_n were in line with NCEO₁₁<NCEO₉<NCEO₇;emulsifying ability followed NCEO₇<NCEO₁₁<NCEO₉;foaming ability was NCEO₇<NCEO₉<NCEO₁₁.With the increase of x₂,the emulsifying ability on soybean oil increased,but the foaming ability and foam stability decrease.The NCEO_n-LAS binary system can maintain a clear state in 750 ppm hard water for 24 h.As for the detergency,with dodecyl polyoxyethylene ether（AEO₉）as reference,the decontaminate effect on carbon black and fat stain cloth followed the order of NCEO₇<NCEO₉～AEO₉<NCEO₁₁,while the decontamination effect on protein stain cloth was NCEO₇<AEO₉<NCEO₁₁<NCEO₉.5.The influence of NCEO_n（n=7-11）on the stability of protease Savinase Ultra 16XL and Progress uno 100L was investigated.The results indicated that NCEO_n and AEO_n（n=7,9）maintained over 90%of activity of the two proteases in 10 h at 40℃,while the anionic surfactant LAS made the enzyme activity near to 0 in 2.5 h after exposure to the protease Savinase Ultra 16XL.With higher molar fraction of non-ionic surfactant in the binary system,the protease activity remained higher in 7 days.Compared with AEO₉-LAS system,NCEO_n-LAS system presented better stability for protease Progress uno 100L.更多还原