Lipase‐catalyzed synthesis of aliphatic poly(β‐thioether ester) with various methylene group contents: thermal properties,crystallization and degradation

A series of novel aliphatic poly(β‐thioether ester)s with various methylene group contents were prepared by direct lipase‐catalyzed polycondensation of the monomer with an acid‐labile β‐thiopropionate group. The polycondensation reaction using immobilized lipase B from Candida antarctica was carried out in diphenyl ether at 90 °C. Poly(β‐thioether ester)s with high molecular weights of 20 500–57 000 Da and narrow polydispersities in the range 1.40–1.48 were obtained. Thermogravimetric analysis, differential scanning calorimetry and wide‐angle X‐ray diffraction were used to investigate the thermal properties and crystal structures of these polyesters. All the poly(β‐thioether ester)s were semicrystalline polymers and thermally stable up to at least 200 °C. In vitro degradation studies showed that they can rapidly degrade under acidic conditions by the hydrolysis of the β‐thiopropionate groups, suggesting their potential as acid‐degradable polymeric materials. © 2019 Society of Chemical Industry     

Photopolymerization synthesis of polyacrylic acid dispersant with methoxysilicon end groups and its application in a nano‐SiO2 aqueous system

In order to improve the dispersity and stability of the nano‐SiO₂ aqueous system with high solid content, a kind of polyacrylic acid dispersant with methoxysilicon end groups (KH590‐PAA) was synthesized by photopolymerization of acrylic acid (AA) initiated with (3‐mercaptopropyl)trimethoxysilane (KH590). After adding KH590‐PAA into the nano‐SiO₂ aqueous dispersion system (20 wt% solid content), the viscosity and the curing time of the system were measured with a rotational viscometer and the inverted bottle method. Moreover, the dispersion mechanism of KH590‐PAA for the nano‐SiO₂ aqueous system was researched by measuring the adsorption capacity, the particle size and the zeta potential of the nanoparticles with a conductivity meter, dynamic light scattering, SEM and TEM, respectively. The results showed that the methoxysilicon groups in KH590‐PAA could react with hydroxyl groups on the surface of nano‐SiO₂ in the process of stirring, which enhanced the adsorption capacity of the dispersant and then increased the surface charge of the particles. Therefore, electrostatic repulsion and steric hindrance effects between the SiO₂ nanoparticles could be further enhanced by adding the KH590‐PAA dispersant, and then the nano‐SiO₂ aqueous system exhibited better dispersity and stability. Besides, the dispersion properties of SiO₂ nanoparticles in water were closely related to the addition amount and the molecular weight of the KH590‐PAA dispersant. © 2018 Society of Chemical Industry     

Effect of hyperbranched poly(citric polyethylene glycol) with various polyethylene glycol chain lengths on starch plasticization and retrogradation

A series of hyperbranched poly(citric polyethylene glycol) (PCPEG) materials with varied polyethylene glycol (PEG) chain lengths as plasticizers were mixed with maize starch (MS) via cooking and film‐forming. The structure, pasting property, plasticization, aging property, moisture absorption and compatibility of plasticized starches were studied by means of Fourier transform infrared spectroscopy, X‐ray diffraction, rapid viscosity analysis, tension testing, moisture absorption measurements and scanning electron microscopy. Compared with PEG and citric acid, PCPEG was more effective in promoting starch chain movement and inhibiting the retrogradation of starch film. Also, PCPEG/MS had smaller moisture content. The longer the plasticizer chain, the better were the aging resistance and moisture resistance of starch. But with an increase of PEG chain length, mechanical properties of PCPEG/MS deteriorated and the compatibility between PCPEG and MS decreased. The hyperbranched derivative of PEG with longer chain exhibited improved plasticization and compatibility with starch. © 2019 Society of Chemical Industry     

餐饮废油生物柴油低温流动性的改进研究

使用气-质联用仪测定餐饮废油生物柴油(WCME)和-10号柴油(-10PD)的组成,使用冷滤点试验器和运动黏度试验器测定WCME的低温流动性,同时使用调合、添加低温流动性改进剂的方法改进WCME的低温流动性。实验结果表明,WCME主要由饱和脂肪酸甲酯和不饱和脂肪酸甲酯组成,质量分数分别为27.63%和71.81%;WCME冷滤点为0℃,运动黏度(40℃)为4.41mm2/s;WCME与-10PD调合后,冷滤点降低,其中B20的冷滤点最低,为-13℃,运动黏度随着WCME的体积分数的减少,逐渐接近-10PD的运动黏度。通过添加低温流动性改进剂,WCME,B10,B20的冷滤点分别从0,-8,-13℃降至-4,-26,-25℃。     

离子液体中α,β-不饱和化合物的绿色合成

芳香醛和活泼亚甲基化合物为原料,在离子液体中进行Knoevenagel缩合反应。本工艺避开了传统方法中在加入催化剂的有机溶剂中进行Knoevenagel缩合反应的步骤,采用离子液体为反应提供环境和催化,具有操作简单、成本低、对设备无特殊要求和环境友好的优点。     

GOS+MU:一种查询对象选择新方法

在分析单一MU(Most Uncertainty)采样缺陷的基础上,提出一种"全局最优搜寻"方法 GOS(Global Optimal Search),并结合MU共同完成查询选择。GOS+MU方法中,GOS着眼全局寻找目标,在应用环境能提供的训练样本数量有限、分类器受训不充分时,该方法选择的对象学习价值高,能快速推进分类器学习进程;MU则能够在GOS采样失效情形下,利用分类器当前训练成果,选择查询不确定性最强的样本补充训练集。通过对网络商品的用户评论进行分类仿真,并比较其他采样学习方法的效果,证明了GOS+MU方法在压缩学习成本、提高训练效率方面的有效性。