用拓扑指数预测LAS的界面张力行为特征值

用拓扑方法研究了LAS的EACN值与分子结构的关系.根据分子结构的特点,用距离矩阵表征分子中原子的连接性.据此提出一个结构基础明确的定量关系式,其复相关系数大于0.99.对LAS各种异构体的预测结果与实验规律一致.应用这一定量关系式,不仅能够合理表征LAS的结构性能关系,而且有助于揭示物质结构与性能之间的关系.     

阴离子表面活性剂HLB值与结构关系的拓扑化学研究

用拓扑方法研究阴离子表面活性剂HLB值与分子结构的关系。根据分子结构的特点,用距离矩阵表征分子中原子的链接性。通过回归分析得到一个结构基础明确的定量关系式,其复相关系数为0.999972。用拓扑方法研究阴离子表面活性剂HLB值与分子结构的定量关系是一种新的尝试,补充和完善了QSPR,引入的的拓扑参数Wn、S和Sn与HLB值相关性高,而且计算简便,物理意义明确,提高了预测结果的合理性和准确性,为众多的同名系列化合物HLB值的预测和评价提供了一种新的方式和手段。应用这一定量关系式,不仅能够合理表征阴离子表面活性剂的结构性能关系,而且有助于提示物质结构与性能之间的关系。为阴离子表面活性剂的研究、产品开发、实际生产和综合应用提供重要的参考数据。     

拓扑指数法研究直链烷基芳基磺酸盐的构效关系

利用拓扑指数法研究了直链烷基芳基磺酸盐的分子结构与等效烷烃碳数和生物降解性的关系.根据分子结构的特点,用距离矩阵表征分子中原子的连接性,据此建立相应的定量结构性能关系式.计算了25个直链烷基芳基磺酸盐的等效烷烃碳数和19个直链烷基芳基磺酸盐的生物降解性,计算结果表明,计算值与文献值的相关系数分别为0.997 2和0.985 0,其相对误差范围分别为-14.38～0.46及-0.06～0.08.     

LAS生物降解性与分子结构的定量相关研究

用量子化学方法计算得到了LAS的分子结构参数，应用这些分子结构参数对LAS生物降解的实验结果进行回归分析，建立了以分子总电子能(Ee)、分子偶极距(μ)、前线轨道电子云密度指数(Fr^N)为结构描述符的降解率D％的数学模型。表明：①烷基碳原子数相等而苯环位置离中心碳原子越近，Ee值越负、Fr^N越大、偶极矩μ越小其生物降解性越低；②苯环离末端碳原子位置不变即碳原子数减少的LAS分子，Ee值越正、Fr^N越大、偶极矩户越小其生物降解性越低。可见μ与Fr^N在各种结构系列中均适用，是与生物降解活性相关的主要结构描述符。     

炸药破甲威力与爆轰参数之间定量关系的探讨

探讨了炸药的破甲威力与爆轰参数之间的关系,发现在一定计算精度范围内,炸药的破甲威力与爆速Ｄ的关系比较复杂,而与爆压Ｐ的关系相对比较简单且具有较高的计算准确度,据此提出,爆压Ｐ与破甲深度ｈ、与破孔体积Ｖ之间的定量关系式。对单质炸药和混合炸药的计算结果表明,计算值与实验值的一致性令人满意。根据这一定量关系,可以确定提高炸药破甲威力的两条件途径,一是提高炸药的爆压,即提高炸药的能量,二是通过设计新型装药结构,提高炸药能量的利用率,应用本文定量关系,不仅能够预测炸药的破甲威力,而且对于寻求具有优良破甲威力的炸药及设计新型装药结构具有一定的参考价值。     

高分子的溶度参数和介电常数的关系

本工作从分子结构出发,根据电磁理论,研究了溶度参数δ和介电常数ε之间的关系,建立了δ和ε的关系式: δ=[c(ε- 1)/(ε+2)-RT/V_v]~(0.5)式中c是和物质结构有关的参数。将聚乙烯等14种聚合物的ε值代入上式,计算了它们的δ,其值和实验值相当吻合。该式适用范围较宽,对δ<7.5的聚合物也可应用,从而解决了Paruta经验关系式中存在的问题。     

高聚物结构对表面张力与相对分子质量关系的影响

以若干组分子结构不同的高聚物为研究体系,采用熔体悬滴测量装置系统地测量了不同相对分子质量的高聚物的表面张力。讨论了高聚物分子结构对其表面张力与相对分子质量关系的影响。通过对实验数据的分析推导出高聚物表面张力与相对分子质量的关系式,并对传统的关系式进行了改进,由于改进后的关系式考虑了高聚物分子结构的影响,因此具有更广泛的适用性,可以较好地解释一些传统关系式不能解释的实验现象。     

聚合物结构对界面张力与相对分子质量关系的影响

以3组分子结构不同的聚合物为研究体系,采用熔融体悬滴测量装置系统地测量了不同相对分子质量的聚合物之间的界面张力,讨论了聚合物分子结构对其界面张力与相对分子质量关系的影响,通过对实验数据的分析推导出聚合物之间的界面张力与相对分子质量的关系式,并对传统的关系式作了改进。改进后的关系式考虑了聚合物分子结构的影响,具有更广泛的适用性。     

用振动力学有限元分析方法估算多类烃的液体热导率

将烃分子结构模拟成弹性体,用振动力学有限元分析方法对分子3D结构进行有限元分析,建立分子结构体系的刚度矩阵和多自由度振动方程,用MATLAB软件包求解得到分子结构固有频率和刚度矩阵特征值,将分子结构固有频率和刚度矩阵特征值作为参数,用多元回归方法建立液态烃类热导率QSPR模型。该模型对训练集581个多类烃的液态热导率的计算值与实验值的相关系数为0.9874,平均绝对误差小于0.00259W·m-1·K-1,平均相对误差小于2.39%;对测试集22个烃类化合物热导率的预测值与实验值的相关系数为0.9550,平均绝对误差小于0.00263 W·m-1·K-1,平均相对误差小于2.42%。该计算模型的计算值和实验吻合,可用于链烃、烯烃、炔烃及单环烷烃、多环烷烃、萘烷、芴烷、菲烷、茚烷、蒎烷等复杂结构烷烃的液体热导率的计算。     

链烷烃的偏心因子和临界压缩因子定量构效关系

在拓扑化学理论的基础上,根据电负性均衡原理,通过逐级加合均分法计算分子中原子的平衡电负性,从而实现对有机化合物中原子的细微差异进行有效合理的表征;同时结合原子支化度对邻接矩阵进行扩展,构建平衡电负性指数AI,该指数对分子结构实现唯一性表征,具有优良的结构选择性;结合路径数P2和P3对链烷烃的偏心因子ω和临界压缩因子Zc进行研究。利用文中所构建的模型对二者进行预测,其计算值与实验值吻合良好,ω和Zc的相关系数分别是0.997 9和0.950 0,标准误差分别是0.002 6和0.023 0。为烷烃的偏心因子ω和临界压缩因子Zc的计算提供了一种新方法。     

季铵盐类阳离子表面活性剂微乳液的增溶性能

以季铵盐类阳离子表面活性剂十八烷基三甲基氯化铵(OTAC)及十六烷基三甲基溴化铵(CTAB)微乳液体系为研究对象,考察了其对单一有机物和有机混合物(正辛烷、正十二烷-正己烷、正十二烷-正庚烷、正十二烷-正辛烷)的增溶性能,探究了WinsorⅢ型微乳液最佳醇用量(A*)及最佳增溶参数(SP*)的变化规律。结果发现:两种阳离子表面活性剂微乳体系表现出相似的规律,即随着Na Cl质量分数的增加,SP*单调递增,A*单调递减;随着表面活性剂质量分数的增加,A*持续增大,SP*先增大后减小。油相为二组分有机混合物的微乳体系时,A*和SP*仅与有机混合物等效烷基碳数(EACN)有关,与混合物的种类无关。将拟合所得二组分有机混合物的微乳体系A*和SP*与EACN关系式用于预测四组分混合有机物的A*和SP*,与实验值对比发现两者吻合较好,表明可以用所得函数关系式预测相近EACN范围内的A*和SP*。     

微乳液最佳中相醇用量和增溶能力与油相等效烷基碳数的定量关系

主要考察了十八烷基三甲基氯化铵(OTAC)和十二烷基硫酸钠(SDS)对油相的增溶规律。通过不同烃类混合,包括两种烃类的混合和4种烃类混合,调整混合油相的等效烷基碳数(EACN),探索最佳中相醇用量(A*)、最佳增溶量(SP*)与EACN的关系。A*、SP*与EACN在两类表面活性剂条件下都呈现二次函数的关系,且在同一表面活性剂体系中,控制其他组分含量恒定的情况下,函数关系与所用的烃无关。     

Effects of Triglyceride Molecular Structure on Optimum Formulation of Surfactant-Oil-Water Systems

The effects of triglyceride molecular structure on the formulation of surfactant-oil-water systems were evaluated by comparing the optimum salinity and the dynamic interfacial tensions. The systems contained an anionic extended surfactant and triglyceride oils with different chain lengths and degrees of unsaturation. The results show that with an increasing degree of oil unsaturation (more double bonds), surfactant interactions with the triglycerides become weaker, thus requiring higher optimum salinity and resulting in higher interfacial tension values. Effects of ester groups and chain length of triglycerides are also discussed and the EACN of the triglycerides and vegetable oils studied are reported.     

Correlation between Detergency of Different Oily and Solid Non-Particulate Soils and Hydrophilic–Lipophilic Deviation

This research examined the correlation between the detergency of soils with varying equivalent alkane carbon numbers (EACN) and hydrophilic–lipophilic deviation (HLD) values. The detergency of oily soils with EACN ranging from 5.2 to 16.6 was evaluated using C₁₀-4PO-SO₄Na as a primary surfactant system and a 1:1 binary mixture of C₁₀-4PO-SO₄Na and AOT as a confirmatory surfactant system (with 65/35 polyester/cotton at 25°C). These surfactant systems were characterized using HLD concepts which showed that C₁₀-4PO-SO₄Na was more hydrophilic (had a higher negative Cc value) than that of the mixed surfactant system. Detergency of the selected soils was evaluated at different salinities corresponding to HLD ranging from negative to positive values. The results showed that detergency of all soils increased with increasing salinity (starting with an HLD = −3.0 (Winsor Type I microemulsion)), reached the maximum at widely different optimum salinity (S*) but at an identical HLD value of zero (optimum Type III), and then decreased with further increasing salt levels corresponding to positive HLD values (Type II). The preferred HLD range from −3.0 to 0.0 showed detergency levels exceeding 80% removal with interfacial tension values (IFT) below 1 mN m⁻¹ for all oily soils studied. Detergency of octadecane (EACN = 18, solid at 25°C) was further conducted and demonstrated that performing detergency at HLD = −3.0 to 0.0 likewise revealed superior soil removal (over 80%) versus systems with HLD values outside this range. Thus, this work highlighted the utility of using the HLD approach in designing surfactant formulations for detergency of soils with widely varying EACN.     

饱和烷烃的化学与分子的拓扑

本文以图论法为基础,从分子的拓扑结构入手探索和揭示结构与性能之间的本质联系,建立一个既能描述饱和烷烃化学火用的变化规律,又能准确预测其值的定量关系式。     

Rheological properties of phase transitions in polydisperse and monodisperse colloidal rod systems

Rheological modifiers are added to formulations to tune rheology, enable function and drive phase changes requiring an understanding of material structure and properties. We characterize two colloidal rod systems during phase transitions using multiple particle tracking microrheology, which measures the Brownian motion of probes embedded in a sample. These systems include a colloid (monodisperse polyamide or polydisperse hydrogenated castor oil), surfactant (linear alkylbenzene sulfonate [LAS]), and nonabsorbing polymer (polyethylene oxide [PEO]) which drives gelation by depletion interactions. Phase transitions are characterized at all concentrations using time-cure superposition. We determine that rheological evolution depends on LAS:colloid. The critical PEO concentration required to form a gel, c_c/c*, is independent of LAS:colloid, critical relaxation exponent, n, is dependent on LAS:colloid, and both are independent of colloid polydispersity. n indicates the material structure at the phase transition. At LAS:colloid > 16, the scaffold is a tightly associated network and at LAS:colloid = 16 a loosely associated network.     

Numerical study of pore structure effect on SO2-CaO reactions☆

The effect of varying pore structures on the kinetics of SO2–CaO reactions is not fully understood in the previous studies. Combining fractal pore model, gas molecular movement model and two-stage reaction model, a new desulfurization model is established in this paper. Fractal pore model is used to simulate CaO particle and gas molecular movement model is used to simulate gas diffusion in pores. Fractal dimension is used to characterize complexity of pore structure instead of tortuosity factor. It is found that the reaction is significantly affected by pore structures. A modulus?is introduced to characterize the relationship between varying pore structures and apparent reaction parameters. And this relationship is verified by thermo-gravimetric analysis (TGA) data. Comparing to the previous models, the effect of varying pore structure on the kinetics of the reaction is described more accurately by the desulfurization model.