Synthesis And Characterization Of The Odd-numbered Carbon Oil Fermentation Nylon 1111

1. we synthesize nylon 1111 using 1,11-tridecanedioic acid, which can be got from light wax, as raw material in industry set. The reaction of 1,11-tridecanedioic acid with ammonia for the preparation of azelanitrile gave 1,11-dicyanoundecane in 92% yield. Catalytic hydrogenation of the dinitrile in the presence of Rayni—Ni alloy powder as catalyst gave 1,11-diaminotridecane in 88% yield. The 1,11-tridecanedioic acid and 1,11-diaminotridecane were combined in a 1:1 molar ratio to produce the nylon salt in 97% yield. Melt polymerization of nylon 1111 salt gave nylon 1111 in 92.8% yield. The entire products are determined by NMR and IR at the same time. The influences of reaction time, reaction temperature, the ratio of ammonia and space velocity on the conversion of 1,11-dicyanoundecane were researched. The effects of reaction conditions and catalysts upon the component and ratio in the product were also studied. The basal physical and mechanical properties of nylon1111 were also determined.2. The morphology of melting-crystallization nylon1111 was observed by PLM from 140℃to T_m. There are four kinds of spherulite as crystalline temperature changed and different crystalline conditions. The melting behaviors of nylon1111 are studied by DSC. After the samples of nylon1111 are treated by different heat treatment, their melting behaviors have great change. Two melting peaks appear, and the temperature of the low melting peak is close to the annealing temperature, because of irregular crystallization. When the temperature of crystallization becomes high, the only melting peak appears. The band assignments of nylon1111 were determined by FTIR. From infrared spectroscopy, we confirmed that theα-form of nylon1111 could be transformed from the pform with the crystalline temperature increasing.3. The TG results of nylon 1111 indicate that the thermal degradation process of nylon1111 is one-step reaction in the N₂. The activation energy of the solid-state process was determined using Kissinger and Flynn - Wall - Ozawa methods, and results were 239.3kJ/mol and 240.9kJ/mol.4. A systematic study of the isothermal and nonisothermal melt crystallization kinetics of nylon 1111 was carried out with DSC. The Avrami exponent was determined for nylon 1111 under isothermal conditions to be 2.64～3.39, which means that the crystallization of nylon 1111 during isothermal conditions is of two-dimensional growth. The nonisothermal crystallization process of nylon 1111 was analyzed by Avrami equation modified by Jeziorny and a novel equation combining the Avrami and Ozawa equation. The Avrami exponent n is greater than that in the isothermal crystallization process, which indicates that the mode of nucleation and the growth of the nonisothermal crystallization for nylon 1111 are complicated and that the nucleation mode might include homogeneous and heterogeneous nucleation at the same time. The calculated activation energy is -133.2kJ/mol for isothermal crystallization by Arrhenius form and the activation energy determined by Arrhenius forms for nonisothermal crystallization was -121kJ/mol.5. The dynamic mechanical properties of nylon1111 were investigated by dynamic mechanical analysis (DMA). The peak at 77℃, -37℃and -127℃were to be a relaxation,βrelaxation andγrelaxation of nylon1111, respectively.6. A comprehensive rheological study for nylon 1111 melt was carried out by using parallel-plate rheometer and capillary rheometer. The nylon 1111 melt showed shear-thinning behavior for all discussed temperatures. The flow behavior indexes for different temperatures were obtained. The results show that nylon 1111 melt belongs to pseudoplastic liquid with the flow behavior index less than 1. A creep-recovery test was carried out to define the linear viscoelastic range as 20 Pa for the temperature range 190-220℃. A time-dependent response was found for the creep and recovery phases at a lower constant applied shear stress. Dynamic tests were carried out to reveal the viscoelastic behavior of the nylon 1111 melt. The linear viscoelastic range for all tested temperatures according to these tests were 100 Pa. Nylon 1111 melt showed viscous behavior at very lower range of frequency except the lower applied stress(lower than 10Pa).