Lactic acid based poly(ester-urethane)s: The effects of different polymerization conditions on the polymer structure and properties

A two-step process for lactic acid polymerization is studied: in the first step the lactic acid is condensation-polymerized to a low-molecular-weight hydroxyl-terminated prepolymer; and then the molecular weight is raised by joining prepolymer chains together using diisocyanate as the chain extender. The resulting polymer is a thermoplastic poly(ester-urethane). In this study, we synthesized three different prepolymers and used three different diisocyanates as chain extenders. All of the prepolymers were hydroxyl-terminated, and their weight average molecular weights were 5,500 g/mol, 11,900 g/mol, and 26,000 g/mol. One of the diisocyanates was aliphatic, and the other two were stiff cycloaliphatic diisocyanates. The results indicate that of the tested diisocyanates, high weight average molecular weight can be achieved only by using aliphatic 1,6-hexamethylene diisocyanate. The cycloaliphatic diisocyanates produced poly(ester-urethane)s with weight average molecular weights which were quite low, but due to the stiffness of the polymer chains the glass transition temperatures can be as high as 60°C. The 1,6-hexamethylene diisocyanate (HDI) results also indicate that the molecular weight and network formation can be controlled independently by the amount of diisocyanate used and the polymerization conditions. Only the poly(ester-urethane)s which were produced with HDI had good mechanical properties, while the stiff diisocyanates produced very brittle polymers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 865–873, 1997     

The forced gas sweeping process for semibatch melt polycondensation of poly(ethylene terephthalate)

The experimental and modeling studies are presented on the melt polycondensation of poly(ethylene terephthalate) by a gas sweeping process. In this process, low molecular weight prepolymer is polymerized to a higher molecular weight polymer in a molten state at ambient pressure as ethylene glycol is removed by nitrogen gas bubbles injected directly to the polymer melt through a metal tube. In the temperature range of 260–280°C, the rate of polymerization by the gas sweeping process is quite comparable to that of conventional high vacuum process. The effects of nitrogen gas flow rate and reaction temperature on polymerization rate and polymer molecular weight were investigated. Polymer molecular weight increases with an increase in gas flow rate up to certain limits. A dynamic mass transfer–reaction model has been developed, and the agreement between experimental data and model simulations was quite satisfactory. The effect of ethylene glycol bubble nucleation on the polymerization has also been investigated. It was observed that the presence of nucleated ethylene glycol bubbles induced by the bulk motion of polymer melt has negligible impact on the polymerization rate and polymer molecular weight. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1388–1400, 2001     

Synthesis of succinic acid-based polyamide through direct solid-state polymerization method: Avoiding cyclization of succinic acid

Succinic acid is an important synthetic monomer but it is difficult to use it as a precursor for synthesizing high molecular weight polyamide, due to its tendency to perform intra-cyclization reaction at high temperature. In order to solve this problem, in this paper, the direct solid-state polymerization (DSSP) method with the initial reactant, nylon salt which was composed of 1, 5-diaminopentane, succinic acid, and terephthalic acid, was applied to synthesize the bio-based copolyamide PA 5T/54. In comparison with the conventional melting polymerization method, the DSSP method can prevent the cyclization reaction of succinic acid effectively due to the lower reacting temperature as well as the restriction effect of the nylon salt. As a result, the product fabricated by DSSP method has higher molecular weight and much lighter color from red to white. Therefore, the DSSP method is advantageous for the synthesis of the polymers or copolymers composed of the succinic acid as the monomer. Furthermore, the polymerization mechanism proposed in this work can serve as a guidance for the design of the molecular structure and control of the polymerization process.     

Kinetic and property parameters of poly(ethylene naphthalate) synthesized by solid-state polycondensation

A low molecular weight prepolymer with reactive end groups was annealed at temperatures between 200 and 245°C to obtain kinetic parameters for solid-state polymerization of poly(ethylene naphthalate) (PEN). An equation was developed to describe the relationships among time, temperature, and final molecular weight for PEN. The intrinsic viscosity and melting point during polymerization were used to monitor the molecular weight and the thermal stability of the resulting resins. The effect of moisture concentration on solid-state polymerization was also investigated. Hydrolytic degradation caused initial reductions of the molecular weight if prepolymers were solid-stated without being dried. With increased exposure to solid-state conditions, however, the hydrolytically degraded resin dried and repolymerized at rates similar to those samples that had undergone hydrolysis. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2055–2061, 2001     

The effect of prepolymer crystallinity on solid-state polymerization of poly(bisphenol A carbonate)

The effect of prepolymer crystallinity on the solid-state polymerization (SSP) of poly(bisphenol A carbonate) was examined using nitrogen as a sweep fluid. A low-molecular-weight prepolymer was synthesized by melt transesterification and prepolymers with different crystallinities (11.7%, 23.3%, 33.7%) were prepared with supercritical carbon dioxide treatment. SSP of the three prepolymers was then carried out at reaction temperatures in the range of 150-190 °C, with a prepolymer particle size of 75 μm and a N₂ flow rate of 1600 ml/min. The glass-transition temperature (T_g), absolute weight-average molecular weight (M_n), and percent crystallinity were measured at various times during each SSP. At each reaction temperature, SSP of the lower crystallinity prepolymer (11.7%) always resulted in higher-molecular-weight polymers, compared with the polymers synthesized using the higher crystallinity prepolymer (23.3% and 33.7%). The crystallinity of the polymers synthesized from the high crystallinity prepolymer was significantly higher than for those synthesized from the low crystallinity prepolymer. Higher crystallinity of the prepolymer and the synthesized polymers may lower the reaction rate by reducing chain-end mobility or/and by inhibiting byproduct diffusion.     

Effects of long-chain branching on distribution of degree of polymerization

The method of generating functions is used to calculate the number fraction of molecules having any specified degree of polymerization and number of long branches for polymers produced under conditions in which the probabilities of chain propagation and of branching on a monomer unit incorporated in the polymer are both constant; termination by combination is assumed absent. Expressions are given for the moments of degree of polymerization and the first two moments of branch number. It is shown that all moments of degree of polymerization are finite, for this model. An asymptotic expression for the number distribution at very high degrees of polymerization is obtained. The way in which the average number of branches per monomer unit varies with degree of polymerization is studied.     

Mechanistic investigation of the simultaneous addition and free-radical polymerization in batch miniemulsion droplets: Monte Carlo simulation versus experimental data in polyurethane/acrylic systems

A detailed kinetic Monte Carlo simulation was used to predict the characteristics of the batch miniemulsion polymerization of an isocyanate and an acrylic monomer mixture that contains a hydroxyl functional monomer (HEMA). The simulation takes into account the simultaneous polyaddition of the polyurethane prepolymer with the hydroxyl group of HEMA and the free radical polymerization of the acrylic monomers and all reactions in aqueous and polymer particle phases. The model has been assessed by batch miniemulsion polymerizations carried out using an aliphatic isocyanate prepolymer, n-butyl acrylate, 2-hydroxyethyl methacrylate monomers and potassium persulfate as an initiator. It was found that partitioning of water had a significant effect on both kinetics and microstructure of the resulting polymer. Evolution of different species of PU prepolymer produced in the reaction and the sol and gel fractions revealed that the terminal pendent double bond of the HEMA in polymer chains has significantly lower reactivity than that of the HEMA free monomer. Detailed information on gel microstructure has been derived in the model by both distribution of molecular weight between crosslinking points in acrylic chains and distribution of chain extension of PU prepolymers. These crosslinking density distributions can be related to mechanical and adhesive properties of the polymer.     

The role of diffusion in the Ziegler polymerization of ethylene

A theoretical and experimental study has been made of the polymerization of ethylene in a slurry reactor using a highly active Ziegler catalyst in the presence of hydrogen. A model of the polymerization system has been set up in which polymerization is assumed to proceed with encapsulation of catalyst subparticles. Allowance is made for an experimentally observed first-order decay in intrinsic catalyst activity. The theoretical prediction of the model for the monomer absorption rate behavior and the molecular weight characteristics of the polymers formed are in agreement with experimental findings. Experimental evidence is presented that in the earliest moments of a polymerization significant amounts of polymer are formed with molecular weights 100 times those in the balance of the polymerization. It is concluded that in this system the polymerization is diffusion controlled throughout the major part of the catalyst lifetime. This diffusion phenomenon, together with the gradual loss of active sites, is of vital importance in determining the molecular weight and molecular weight distribution of the polyethylene product.     

Two-Component initiator systems for the ring-opening polymerization of oligomeric cyclic bisphenol-A carbonates. Studies with in situ generated wittig salts

A two-component initiator system based on the in situ generation of Wittig salts (alkytriarylphosphonium bromides) has been developed for the ring-opening polymerization of cyclic bisphenol-A (BPA) carbonate oligomers for potential use in composite applications so that the prepolymer can suitably wet the composite material before being converted to high molecular weight polymer. The Wittig salt precursors (an alkyl bromide, such as hexadecyl bromide, and a triarylphosphine, such as triphenylphosphine) did not independently initiate significant ring-opening polymerization of the oligomeric cyclic BPA carbonate mixture. However, when the two mixtures of cyclic BPA carbonate oligomers and initiator component were combined, a high molecular weight polymer (M_w = ∼ 65,000) was produced. The polymerization initiating species is thought to be hexadecyltriphenyl-phosphonium bromide. Consistent with this hypothesis is the observation that authentic Wittig salts did initiate ring-opening polymerization to provide high molecular weight polycarbonate. The effects of structure and concentration of the initiator components, reaction temperature, time, etc. on polymerization were studied; in general, the degree of polymerization ranged from 65 to 85%. © 1996 John Wiley & Sons, Inc.     

Lactic acid based poly(ester-urethanes): Use of hydroxyl terminated prepolymer in urethane synthesis

We studied a two step process for lactic acid polymerization: in the first step, the lactic acid is condensation polymerized to a low molecular weight hydroxyl terminated prepolymer and then the molecular weight is raised by joining prepolymer chains together using diisocyanate as the chain extender. The resulting polymer is a thermoplastic poly(ester-urethane). The polymer samples were carefully characterized with ¹³C-NMR, GPC, DSC, and IR. The results indicate that high conversions of lactic acid can be achieved, as well as independent control of the stereostructure, long chain branches, molecular weight average, and molecular weight distribution. Lactic acid is converted into a poly(ester-urethane) with a weight average molecular weight as high as 390,000 g/mol and a glass transition temperature of 53.7°C. The analyzed content of the monomer in the prepolymer is less than 1 mol % and the lactide content 2.4 mol %, while the final poly(ester-urethane) is essentially monomer and lactide free. The mechanical properties of the poly(ester-urethane) are comparable to those of polylactides. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1091–1100, 1997     

A journey across the solid state polymerization to assess the role of critical factors influencing the molecular weight of polylactic acid

Solid state polymerization (SSP) offers an effective route for synthesizing green polymers with variable molecular weights depending on polymerization condition. In this work, critical factors governing the molecular weight of polylactic acid (PLA) in the course of SSP are manipulated systematically and their contributions to the efficiency of SSP process are discussed. The initial molecular weight of the prepolymer formed, the degree of crystallinity of prepolymer, and the SSP time are changed and analyzed for their effects through different analyses including differential scanning calorimetry, gel permeation chromatography, and Fourier‐transform infrared spectroscopy techniques. It was observed that PLA having highest molecular weight would be the result of formation of a prepolymer having low‐molecular weight, as detected by the analysis of functional group concentration. For the optimized sample, the rate of mass loss in SSP was 12,263 g/mol.day and a crystallinity drop over the hydrolysis process was 3.14 per day. The crystallinity of prepolymers was optimized at ca. 26% in regard with the PLA showing the highest molecular weight. J. VINYL ADDIT. TECHNOL., 25:165–171, 2019. © 2018 Society of Plastics Engineers     

双酚A聚碳酸酯合成新方法的研究进展

介绍了双酚A聚碳酸酯不同于工业生产中常用的光气法和熔融酯交换法的3种新的合成方法,即固相缩聚法、开环聚合法、完全非光气法的实施方法、主要特点及其新进展,探讨了各种方法存在的主要问题以及对生成的聚合物结构和性能的影响。固相缩聚是由预聚物结晶后在固相缩聚,可以获得结晶型双酚A聚碳酸酯并提高聚合物质量;开环聚合法首先合成环状碳酸酯低聚物再开环聚合得到聚合物,可以获得很高分子质量聚合物;完全非光气法在合成过程中完全避免了光气的使用,环境友好,聚合物质量高,很有发展前景。     

Effect of the addition of inert or TEMPO‐capped prepolymer on polymerization rate and molecular weight development in the nitroxide‐mediated radical polymerization of styrene

The importance of diffusion‐controlled (DC) effects on controlled radical polymerization (CRP) processes has been rather controversial and usually considered only if there is some mismatch between experimental data and model predictions of polymerization rate and molecular weight averages. Results from an experimental study designed to create conditions in which DC effects may be present from the outset for the bimolecular nitroxide‐mediated radical polymerization (NMRP) of styrene in the presence of 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) and dibenzoyl peroxide (BPO), are presented herein. The experiments consisted of adding size exclusion chromatography (SEC) polystyrene (PS) standards or nitroxyl‐capped PS (of different molecular weights, in several proportions), to a conventional recipe of bimolecular NMRP of styrene, and studying the effect of their presence on polymerization rate and molecular weight development. A previously developed kinetic model for NMRP of styrene was modified to take into account the presence of prepolymer as an inert “solvent,” or as a monomolecular “controller” of high molecular weight. The effects of DC reactions (propagation, termination, activation, and deactivation of polymer radicals) were modeled using conventional free‐volume theory. Reasonably, good agreement between experimental data and model predictions with either modeling approach was obtained. It was concluded that DC effects are weak in the NMRP of styrene, even in the presence of prepolymer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Solid-state polymerization vis-à-vis fiber formation of step-growth polymers. I. Results from a study of nylon 66

This study is directed toward synergistic integration of processing of nylon 66 fibers with solid-state polymerization. The following two goals are sought through the incorporation of solid-state polymerization after the initial shaping operation: eliminating some of the processing problems in the production of high molecular weight, high performance industrial fibers and attainment of improved mechanical properties via high molecular weight. Successful solid-state polymerization has been achieved with as-spun fibers of nylon 66 and molecular weights up to 280,000 g/mol have been obtained from a starting molecular weight of 40,000 g/mol. It is shown that much of the ductility of the starting fiber can be retained, or even enhanced, with solid-state polymerization. Simulated drawing experiments using a thermal deformation analysis technique show an increase in the drawing potential of the solid-state polymerized fiber as compared to the starting material. This has important implications regarding the ultimate properties that can be achieved in fibers of condensation polymers. © 1994 John Wiley & Sons, Inc.     

尼龙6固相聚合建模与计算机仿真

在一定假设基础上建立了尼龙６固相聚合过程模，并用实验数据验证了模型的正确性，结果表明随着固相聚合时间的延长，数均聚合度Ｕｎ增加。     

Computer-Aided Design of Crosslinked Polymer Membrane Using Machine Learning and Molecular Dynamics

The formation of crosslinking network between polymer chains has significant influence on polymer properties. In particular, the crosslinked structure of ionic networks like proton exchange membrane affects the conductivity performance. To further develop in this area, a framework for polymer membrane design based on the developed quantitative prediction model of the properties of crosslinked polymer is proposed. First, polymers with different crosslinking degrees are constructed by a crosslinking algorithm. Next, molecular dynamics is used to calculate the properties of crosslinked polymers. Then, the quantitative relationship between crosslinked polymer structures and macroscopical properties is developed. Subsequently, computer-aided polymer design method is integrated with the developed quantitative predict model. The crosslinked polymer design problem is expressed as an optimization problem to obtain the optimal crosslinking degree. Bayesian optimization strategy is used to solve the established optimization model. Finally, two case studies of perfluoro sulfonic acid and perfluoro imide acid design are given to illustrate the application of the proposed polymer design framework.     

Solid‐state polymerization of bisphenol A polycarbonate with a spray‐crystallizing method

A novel crystallization method for the production of high‐molecular‐weight bisphenol A polycarbonate by solid‐state polymerization is suggested. In this method, a low‐molecular‐weight polycarbonate prepolymer is dissolved in a solvent and then partially crystallized with a novel spray‐crystallizing method to prepare crystallized polycarbonate particles having a very uniform and porous structure with a narrow melting region. As a result, during solid‐state polymerization, the phenol byproduct can be easily removed from the polymerizing porous polycarbonate particles, and the polymerization rate is dramatically increased. In particular, the effects of the crystallization methods on secondary crystallization during solid‐state polymerization and the melting behavior have been investigated with differential scanning calorimetry studies. The final product, a high‐molecular‐weight polycarbonate, displays a very narrow molecular weight distribution and uniform physical properties. A simultaneous process and an adequate reactor design for spray crystallization and solid‐state polymerization are also suggested. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Modeling of molecular weights in industrial autoclave reactors for high pressure polymerization of ethylene and ethylene‐vinyl acetate

We have incorporated mass balances of monomer, radical and polymer species to a previously developed mixing model for high pressure autoclave polymerization reactors. The customary quasi steady state approximation is not used, and the method of moments is used to simplify the mass balance calculations. The resulting moment model is able to calculate conversions, average molecular weights, long chain branching and melt flow indexes at any point in the reactor. It may also calculate concentration and temperature profiles along the reactor. Results for two base cases are presented in detail. Model predictions were compared with experimental data obtained at the industrial reactor; excellent agreement was obtained. The moment balance equations are presented in a modular way so that they may be easily adapted to be used with any other mixing model for this type of reactor.     

Prediction of molecular weight distributions by probability generating functions. Application to industrial autoclave reactors for high pressure polymerization of ethylene and ethylene‐vinyl acetate

We develop a mathematical model able to describe the complete molecular weight distributions of polyethylene and elhylene‐vinyl acetate copolymers obtained in high pressure autoclave reactors. We apply probability generating function definitions to the mass balances of radical and polymer species in the reacting medium. We use three different definitions of probability generating functions, each one directly applicable either to the number, weight or chromatographic distributions. These probability generating functions are numerically inverted to obtain the corresponding calculated molecular weight distribution. The capabilities of two different inversion methods are compared. Predictions are compared with experimental data obtained in an industrial reactor; good agreement is obtained. The approach presented here is applicable to other types of polymerization reactors and post‐polymerization processes.     

Study of chain sequence in the controlled radical telomerization of vinyl acetate with Co(acac)2 catalyst in bulk

A series of porphyrin-containing polymers with triazole rings as linkers have been successfully synthesized by click polymerization. The polycycloadditions of porphyrin-containing dialkyne 1 and 1,4-diazidobenzene 2 were initiated either by simple heating or by Cu(I)-catalyst, affording polymers P1-P8 with relatively high molecular weight. The polymerization process was monitored by gel permeation chromatography analysis. The polymer prepared by thermally initiated click polymerization has unimodal molecular weight distribution and moderate polydispersity index after prolonging reaction time to 170?h. Compared with the metal-free click polymerization, the rate of molecular weight growth in Cu(I)-catalyzed click polymerization declined, leading to relatively low molecular weight of the resulting polymer. The as-synthesized polymers are soluble in common organic solvents and stable at a temperature up to 350?°C. The photophysical properties of the porphyrin monomer and the polymer were investigated by UV?Cvis and fluorescence spectroscopy. This approach offers practical advantages over other synthetic methods used to prepare main-chain porphyrin-containing polymers with regard to the absence of byproducts generated during the polymerization reaction.