PET固相缩聚反应动力学模型

总结了ＰＥＴ 固相缩聚反应的原理及其反应动力学,综述了国内外研究ＰＥＴ 固相缩聚动力学模型的进展。指出单纯考虑化学反应或小分子扩散的模型都是不全面的,应该用化学反应过程和物理扩散过程共同控制的模型来描述固相缩聚反应。     

粉状聚酯固相缩聚反应动力学与降解行为的研究

与固相缩聚工业生产用常规粒径聚酯相比,粉状聚酯的传质和反应均可得到增强.实验研究了不同粒径粉状聚酯(0.2～0.8 mm)在氮气氛围中的固相增黏规律,并采用模型方法对缩聚反应与降解行为进行了分析.结果表明粉状聚酯的固相缩聚反应是缩聚与降解的竞争过程,反应初期缩聚反应占主导地位,特性黏度随反应不断增加,后期降解反应占主导...     

十四烷辅助下聚酯的固相缩聚

在200～240℃研究了聚对苯二甲酸乙二醇酯(PET)在十四烷辅助下的固相缩聚反应.结果表明,溶剂辅助下的固相缩聚(分散相固相缩聚)的反应速度较传统气相环境中的固相缩聚更快,最佳反应温度为230℃左右.随着反应温度的升高,分散相固相缩聚得到的PET切片的熔点和结晶度也相应提高.分散相固相缩聚前后PET切片的孔隙率并未发生明显变化.用苯酚处理之后的PET孔隙率增加,有利于小分子扩散,使缩聚反应速率加快.聚合物在十四烷中溶胀导致链活动性增强可能是分散相固相缩聚分子量提高的主要原因.     

瓶级PET固相缩聚反应动力学的研究

对含间苯二甲酸 (IPA)共聚酯固相缩聚进行了研究 ,建立了球形颗粒中可逆化学反应和小分子三维扩散共同控制的模型 ,得到了在氮气保护下 ,2 0 0～ 2 2 0℃条件下PET固相缩聚的反应动力学参数     

聚L-乳酸固相缩聚工艺研究

以L-乳酸为原料,采用复合催化剂熔融缩聚的方法,制备预聚物,然后进行固相缩聚研究。研究了抽真空和通氮气2种固相缩聚工艺方法。在通氮气工艺方法中探讨了反应温度、反应时间、物料颗粒的尺寸等对固相缩聚反应的黏均相对分子质量的影响。根据缩聚反应平衡和水分子扩散传质平衡的原理对实验现象进行了合理的解释。     

固相缩聚PET的分子量分布

在研究聚酯（PET）固相缩聚反应动力学的基础上,进一步利用多组分模型,模拟分析了固相缩聚PET的分子量分布,模拟结果与凝胶渗透色谱测试结果相吻合。     

全芳液晶聚酯固相缩聚及其性能的研究

研究了用固相缩聚方法提高全芳液晶聚酯的分子量。以２，６－萘二甲酸，对／间羟基苯甲酸、双酚类单体为原料，经熔融酯交换合成低聚物，再以固相反应制备共聚酯。通过对共聚酯熔融指数的变化，探讨固相缩聚中反应时间和反应温度的效应，共聚酯分子结构和聚集态结构与固相缩聚反应速率的关系；并通过Ｘ－射线衍射分析，考察固相缩聚对聚酯结晶性的影响。得出全芳聚酯固缩聚过程是一个由化学反应为主要控制，继而转化到物理扩散为主要     

固相缩聚生产高粘度聚酯

叙述了高粘度聚酯的发展概况以及制造工艺,并重点阐述了影响固相缩聚生产高粘度聚酯反应的主要因素。指出聚酯固相缩聚应选择合理的原料路线,严格精选切片颗粒大小及预聚体切片结晶度(预聚体极限密度控制为1.38g/cm~3);根据最终产品需要选取不同的催化体系并通过调整 PTA/EG 配比控制预聚体中醚键含量;反应温度及反应时间是固相缩聚反应的主导影响因素,但控制反应中副产物的去除是破坏反应平衡、提高固相缩聚表观反应速率的重要手段。     

PET固相缩聚工艺技术分析

综述了聚酯(PET)固相缩聚过程特点,重点对比分析了Bepex、Buhler、Sinco及Dupont的NG3连续固相缩聚工艺、关键设备构型及主要操作参数。PET固相缩聚过程中结晶增长与缩聚反应共存并互相耦合,因而结晶工序是固相缩聚工艺的重要组成部分,也是各工艺专利商的专利技术之所在。有效的结晶增长、结晶形态与缩聚反应的解耦合是强化固相缩聚技术的科学基础。     

PET／60PHB热致性液晶共聚酯固相缩聚反应动力学

研究了PET/60PHB共聚酯的固相缩聚反应动力学。研究结果表明,颗粒度为40-60目的预聚体,在170～200℃反应时,化学反应是过程控制步骤,符合二级反应动力学模型;在210～230℃反应时,挥发性反应副产物的物理扩散是控制步骤。借助费克定律和物料平衡方程,提出了动力学模型。     

PET的固相聚合

利用固定床反应器研究聚对苯二甲酸乙二酯（ＰＥＴ）预聚体颗粒在Ｎ２流场中的固相聚合，探讨了聚合温度和Ｎ２流速对聚合反应速率的影响，实验中解决了高温聚合时物料的粘结问题；利用ＤＳＣ分析固相聚合过程中聚合物结晶结构的变化；建立了动力学模型描述了小分子不稳定扩散和化学反应速率共同控制下的聚合反应历程；计算结果较好的反映了工艺操作条件对固相聚合反应的影响。     

Solid-state polycondensation of poly(ethylene terephthalate): Kinetics and mechanism

A numerical method to seek a solution for the solid-state polycondensation (SSP) proces has been proposed to analyze the mechanism of SSP. Results expound that, for the industrial SSP process of PET, the overall reaction rate in a single pellet is appropriately simulated by the diffusion and reaction rate jointly controlling the model. From the core to the surface the SSP rate increase monotonically due to a gradual reduction of the concentration of such by-products as ethylene glycol and water. However, the SSP rate at any location within the pellet is constrained between two purely reaction rate controlling cases. © 1995 John Wiley & Sons, Inc.     

PET固相缩聚反应机理的研究

对ＰＥＴ固相聚合的反应机理进行了较深入地研究。并首次对副产物ＥＧ表面扩散控制机理进行了探讨。通过研究发现：固相聚合机理与温度、预聚体尺寸、惰性气体的流量（或真空度）有关。当反应温度较低时（如１６０～１８０℃），ＰＥＴ固相聚合总是化学反应控制的过程。当反应温度较高（如≥２２０℃），且预聚体的尺寸较大时，ＰＥＴ的固相聚合实际上是由副产物ＥＧ从样品内部向表面的扩散控制的。当反应温度较高，且预聚体的尺寸很小（如几十微米）时，又惰性气体流量较小（或真空度较差），ＰＥＴ固相缩聚反应为副产物ＥＧ从样品表面向外的扩散所控制；若惰性气体流量较大（或真空度较好），反应又转化为化学反应控制。     

双官能团酸调节剂下尼龙6固相聚合模型化

建立了有双官能团酸调节剂时尼龙 6固相聚合过程模型 ,并用实验数据验证了模型的正确性 .结果表明 :数均聚合度Xn 随固相聚合温度和时间增加而增大 ,符合缩聚机理     

Continuous production of polyester‐poly(ethylene terephthalate) resins in melt‐phase and solid‐state reactors

A simple reaction model has applied net polycondensation rates to predict the steady‐state performance of three distinct continuous processes for manufacturing polyester‐PET resins. A net melt‐phase polycondensation rate was described by the simple second‐order kinetics. A net solid‐state polycondensation rate was assumed to follow the modified second‐order kinetics with respect to active end group concentration. A moving‐packed bed requires a longer residence time to deal with the diffusion‐limited SSP of standard pellets or challenging pastilles. The calculations and data showed low IV pastilles to have much slower diffusion‐controlled SSP rates than medium IV pellets. The tanks‐in‐series model demonstrated a narrow RTD in a gas fluidization bed with five mixing stages. Higher reaction temperatures may significantly increase the low diffusion resistance SSP rates of smaller beads or micro‐pellets in a gas‐fluidized reactor. The reaction‐controlled SSP of micro‐beads becomes apparent at 230°C. The high IV melt resins may challenge the slow reaction rates of Ti or Al‐catalyzed SSP resins. The efficacy of catalyst promoters on Ti activity enhancement may depend upon various ligands in Ti glycolate, Ti citrate, or titanic acid. The thermo‐oxidative stability of Ti or Al‐catalyzed resins may decrease at higher hot air drying temperatures (188°C or above). POLYM. ENG. SCI., 57:505–519, 2017. © 2016 Society of Plastics Engineers     

Solid state polymerization (SSP) of low molecular weight poly(ethylene terephthalate) (PET) copolyesters compared to conventional SSP of PET

SSP, starting from very low molecular weight (MW) poly(ethylene terephthalate) (PET) precursors, is claimed to offer significant production cost advantages over conventional PET production. However, as the intrinsic viscosity (IV) of the PET precursor is reduced, there is a significant change in the crystallization behavior of PET and morphology that affects reactivity in SSP. Using small particle size PET to significantly reduce the effects of diffusion so that SSP is under chemical reaction control and using a kinetic model that describes an overall SSP rate, the effect of ethylene isophthalate substitution on the SSP rate from low MW PET precursor was determined. As the ethylene isophthalate comonomer content increases, the rate of SSP for low MW PET increases. The activation energy for SSP of low MW PET decreases with an increase in the ethylene isophthalate content. For the low MW PET copolyesters in this study, the SSP activation energy is comparable to conventional process when the comonomer content of the low MW polyester is around 7 mol % and the conventional precursor is around 3 mol %. However, even though the activation energy is reduced through the use of higher comonomer content, the overall rate of SSP for the low MW copolyesters studied is significantly slower than conventional SSP. This reduction in rate is explained by differences in crystallinity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 230–238, 2002     

PET recycling: Evaluation of the solid state polymerization process

Many studies have been carried out to make bottle‐to‐bottle recycling feasible. One of the difficulties found is the decrease in the polymer's molar mass, which damages the injection blow molding process. A method usually employed to increase the molar mass of virgin PET consists of solid‐state polymerization (SSP). In this work, we studied the SSP process applied to post‐consumer recycled PET by analyzing the inherent viscosity and amount of carboxylic end groups, and the results of dynamic flow rheometry. Although the results show that the recycling process decreases polymer molar mass, and this indicates degradative processes, SSP was successful in increasing molar mass in post‐consumer recycled PET. This made feasible bottle‐to‐bottle recycling. In addition, the parallel plate rheometry technique was powerful in assessing the degradative process and, therefore, that the SSP process was successful. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Effects of the carboxyl concentration on the solid‐state polymerization of poly(ethylene terephthalate)

There are two types of polycondensation reactions in the solid‐state polymerization (SSP) of poly(ethylene terephthalate) (PET), namely, transesterification and esterification. Transesterification is the reaction between two hydroxyl ends with ethylene glycol as the byproduct, and esterification is the reaction between a carboxyl end and a hydroxyl end with water as the byproduct. The SSP of powdered PET in a fluid bed is practically a reaction‐controlled process because of negligible or very small diffusion resistance. It can be proved mathematically that an optimal carboxyl concentration for reaction‐controlled SSP exists only if k₂/k₁ > 2, where k₂ and k₁ are the forward reaction rate constants of esterification and transesterification, respectively. Several interesting observations were made in fluid‐bed SSP experiments of powdered PET: (1) the SSP rate increases monotonously with decreasing carboxyl concentration, (2) k₂ < k₁ in the presence of sufficient catalyst, (3) k₁ decreases with increasing carboxyl concentration if the catalyst concentration is insufficient, and (4) the minimum catalyst concentration required to achieve the highest SSP rate decreases with decreasing carboxyl concentration. In the SSP of pelletized PET, both reaction and diffusion are important, and there exists an optimal carboxyl concentration for the fastest SSP rate because esterification, which generates the faster diffusing byproduct, is retarded less than transesterification in the presence of substantial diffusion resistance. The optimal prepolymer carboxyl concentration, which ranges from 25 to 40% of the total end‐group concentration in most commercial SSP processes, increases with increasing pellet size and product molecular weight. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1288–1304, 2002     

Solid‐state polymerization of poly(ethylene 2,6‐naphthalate)

The solid‐state polymerization (SSP) of poly (ethylene 2,6‐naphthalate) (PEN) was studied and compared with that of poly(ethylene terephthalate) (PET). The SSP of PEN, like that of PET, could be satisfactorily described with a modified second‐order kinetic model, which was based on the assumptions that part of the end groups were inactive during SSP and that the overall SSP followed second‐order kinetics with respect to the active end‐group concentration. The proposed rate equation fit the data of the SSP of PEN quite well under various conditions. PEN prepolymers in pellet and cube forms with intrinsic viscosities (IVs) ranging from 0.375 to 0.515 dL/g, various particle sizes, and various carboxyl concentrations were solid‐state polymerized at temperatures ranging from 240 to 260°C to study the effects of various factors. The SSP data obtained in this study could be readily applied to the design of commercial PEN SSP processes. Because PEN and PET share the same SSP mechanism, in general, the SSP behaviors of PEN are similar to those of PET. Thus, the SSP rate of PEN increased with increasing temperature, increasing prepolymer IV, and decreasing prepolymer particle size. However, because of the much higher barrier properties of PEN, the prepolymer particle size and carboxyl concentration had much greater effects on the SSP of PEN than on the SSP of PET. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1075–1084, 2007