脂族酰基过氧化物分解动力学的研究V.对称脂族酰基过氧化物的羧基转化反应

测定了过氧化月桂酰(1),过氧化辛酰(2),过氧化己酰(3)和过氧化3,5,5-三甲基己酰(4)在热分解过程中生成的羧基转化产物[RC(O)OC(O)OR,R=正十一烷基(5),正庚基(6),正戊基(7),2,4,4-三甲基戊基(8)]的含。在同样条件小,4生成的羧基转化产物比1,2和3的多。羧基转化反应受溶剂极性和粘度的影响,但温度的影响较小。转化产物的分解受体系中相应脂肪酸的催化。直接光照可生成少量转化产物,二苯酮光敏化不产生羧基转化产物,文中对反应机理进行了讨论。     

INFLUENCE OF ALCOHOL-BASED NONSOLVENTS ON THE FORMATION AND MORPHOLOGY OF PVDF MEMBRANES IN PHASE INVERSION PROCESS

Through the preparation of PVDF membranes using various nonsolvent coagulation baths following the phase inversion process, the influence of alcohol-based nonsolvents on the formation and structure of PVDF membranes were investigated. The light scattering and light transmission measurements were used to characterize the equilibrium phase diagram and the gelation speed, respectively. The locations of the crystallization-induced gelation boundaries for various systems and precipitation processes were explained from the corresponding thermodynamic and kinetic parameters. It was found that the better affinity between alcohol-based nonsolvents and DMAc solvent caused the gelation boundaries further away from the PVDF-DMAc axis with the coagulation bath varying from water, methanol, ethanol to iso-propanol. Due to the lower exchange rate of DMAc and alcohols, the delayed demixing took place for the membrane-forming using alcohols as baths, and the delayed time became longer when the coagulation bath was changed from methanol, ethanol to iso-propanol. The characterization results of membranes indicate that the influence of nonsolvents on the phase diagram and the precipitation process are in agreement with those on the membrane morphology. The better thermodynamic stability and a low exchange diffusion rate of PVDF/DMAc/alcohols favor the liquid-solid phase separation in gelation process, and therefore yield the membranes with a porous upper surface, a particular bottom surface and symmetrical structure.