Most of traditional linear poly(ethylene terephthalate)(PET)resins of relatively low molecular mass and narrow molecular mass distribution have low melt strength at foaming temperatures,which are not enough to support and keep cells.An in-situ polymerization-modification process with esterification and polycondensation stages was performed in a 2 L batch stirred reactor using pyromellitic dianhydride(PMDA)or pentaerythritol(PENTA)as modifying monomers to obtain PETs with high melt strength.The influence of amounts of modifying monomers on the properties of modified PET was investigated.It was found that the selected modifying monomers could effectively introduce branched structures into the modified PETs and improve their melt strength.With increasing the amount of the modifying monomer,the melt strength of the modified PET increased.But when the amount of PENTA reached 0.35%or PMDA reached 0.9%,crosslinking phenomenon was observed in the modified PET.Supercritical carbon dioxide(ScCO2)was employed as physical foaming agent to evaluate the foaming ability of modified PETs.The modified PETs had good foaming properties at 14 MPa of CO2pressure with foaming temperature ranging from 265°C to 280°C.SEM micrographs demonstrated that both modified PET foams had homogeneous cellular structures,with cell diameter ranging from 35μm to 49μm for PENTA modified PETs and38μm to 57μm for PMDA modified ones.Correspondingly,the cell density had a range of 3.5×107cells·cm 3to 7×106cells·cm 3for the former and 2.8×107cells·cm 3to 5.8×106cells·cm 3for the latter.
Based on the kinetic and thermodynamic equations, a comprehensive mathematical model for the con- tinuous esterification process of polyester polyols was developed, which was carried out in an innovational bub- bling reactive distillation tower (BRDT) at atmospheric pressure. In this new type of reactor, direct esterification between ethylene glycol and adipic acid was accomplished efficiently and rapidly. A bench BRDT with the height of 2 m was applied for the esteriflcation process of l^oly (ethylene adlpate) (P'EA). In the continuous operation, Hn- ear oligomers were discharged from the bottom of the column, while water passed a few column trays and a pack- ing section as a condensation byproduct. The influence of major operating conditions on reactor performance was also simulated. Simulation results were in good agreement with experimental data, providing a strategy for devel- oping and optimizing this process.
通过高温高压磁悬浮天平(MSB)测定表观溶解度、高温高压视窗釜进行溶胀度校正的方法研究了CO2在PET熔体中的溶解度,考察了温度、压力对改性前后PET在CO2环境中的溶胀度和CO2溶解度的影响。结果表明,PET在CO2环境中的溶胀度和CO2溶解度均随温度的增加而减小,随压力增加而增加,但高压下溶胀度的增加趋势减缓并趋于某定值;与常规线性PET相比,改性PET具有较小的溶胀度和溶解度。在250~280℃,4~6MPa下,CO2在PET熔体中的溶解度具有10-2 g CO2.(g PET melt)-1的量级。1~6MPa下CO2在PET熔体中的溶解行为符合亨利定律,利用最小二乘法拟合得到了CO2在PET熔体中的溶解热。