MWD of i-Polypropylene Under Degradation by Selc Using a New Eluting Solvent

Abstract

A new eluting solvent, cyclohexane, for steric exclusion liquid chromatography (SELC) at 70°C of i-polypropylene (PP) has been applied to the study of molecular weight distribution (MWD) of samples of PP under repeated extrusion and under oxidative degradation in the presence of incorporated organic peroxide. Various parameters characterizing the changes in MW and MWD of the samples are listed in TABLE 1. M_z changed pronouncedly with increasing extent of degradation in both degradation processes, while M_n changed very slightly indicating the average number of chain scission per chain had been very small, much less than one. Difference in the mechanism of the mechanical as compared to the oxidative degradation has shown up in the way the low MW end of the MWD curves changed during the progress of the degradation process.     

Dimensions of branched polymers formed in simultaneous long‐chain branching and random scission

In free‐radical olefin polymerizations, the polymer‐transfer reactions could lead to chain scission as well as the formation of long‐chain branches. The Monte Carlo simulation for free‐radical polymerization that involves simultaneous long‐chain branching and random scission is used to investigate detailed branched structure. The relationship between the mean‐square radius of gyration 〈s²〉 and degree of polymerization P as well as that between the branching density and P is the same for both with and without random scission reactions—at least for smaller frequencies of scission reactions. The 〈s²〉 values were larger than those calculated from the Zimm–Stockmayer (Z‐S) equation in which random distribution of branch points is assumed, and therefore, the Z‐S equation may not be applied for low‐density polyethylenes. The elution curves of size exclusion chromatography were also simulated. The molecular weight distribution (MWD) calibrated relative to standard linear polymers is much narrower than the true MWD, and high molecular weight tails are clearly underestimated. A simplified method to estimate the true MWD from the calibrated MWD data is proposed. The MWD obtained with a light scattering photometer in which the absolute weight‐average molecular weight of polymers at each retention volume is determined directly is considered a reasonable estimate of the true MWD. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2960–2968, 2001     

High-energy radiation forming chain scission and branching in polypropylene

The degradation of high molecular weight isotactic polypropylene (iPP) subjected to gamma rays irradiation up to 100 kGy in inert atmosphere was analyzed. The investigation relied upon complex viscosity, elastic modulus, gel fraction, morphology of the insoluble fraction and deconvoluted molecular weight distribution (MWD) curves. At low irradiation doses, already at 5 kGy, the MWD curve is strongly shifted to the low molecular weight side showing chain scission, which is confirmed using the calculated chain scission distribution function (CSDF). At high dose levels, the appearance of a shoulder in the high molecular weight side of the MWD curve indicates the formation of chain branching. The presence of a considerable insoluble fraction at these high dose levels indicates also the formation of cross-linking, which has different morphology then the insoluble fraction present in the original iPP. The rheological results show changes in the molecular structure of irradiated samples in agreement with the gel content data. The chromatographic and rheological data has shown that gamma irradiation of iPP produces chain scission, branching and cross-linking.     

Degradation of Polystyrene in Solution by Ultrasonation - A Molecular Weight Distribution Study

Ultrasonically induced degradation of polystyrene in tetrahydrofuran solutions has been studied. Four narrow molecular weight distribution (MWD) samples, a material with a wide MWD, and a bimodal MWD sample were degraded at various concentrations, temperatures, and ultrasonic intensities. The MWDs after a number of ultrasonation time periods were obtained from gel permeation chromatograms corrected for instrumental spreading. Degradation index DI, defined as the number of bonds broken per original number of molecules, has been used to describe the extent of degradation. The results of the experiments were used to determine the values of two parameters occurring in the degradation model developed previously. It was found that the course of the changes in MWDs predicted by the model are in good agreement with those observed experimentally when the following values of the model parameters are used. The probability of scission of a molecule with molecular weight M is proportional to the product of its number fraction and the 1.25 power of M. The probability density function of the location of scission along the chain is described by a Caussian curve centered at the midpoint of the chain with a standard deviation of 35% of the chain lengths and truncated 3I the chain ends.

The agreement between observed and calculated MWDs was good for degrees of degradation as high as DI = 15. The course of the changes in MWDs was independent of the initial MWD and of the experimental conditions of concentration, temperature, and sonation intensity and, therefore, independent of the rate of degradation which varied greatly.     

The reciprocal influence between ion transport and degradation of PA66 in acid solution

Transport behavior of acid solution through polyamide was studied by measuring element distribution in cross section, pH, and ion concentration. Degree of degradation that related to the decreasing of molecular weight and flexural strength was observed in order to study the influence of acid solution on the polyamide 66 (PA66) degradation. The permeation mechanism of acid solution can be explained: at first water penetrates into polyamide and it is followed by acid. In this process, water does not affect the molecular weight at 50 °C but only reduces the polyamide strength by plasticization. Moreover, proton (H⁺) has contributed to the anion transport and degradation of polyamide by the hydrolytic reaction. Proton attacks the polyamide chain, and scission of chain occurs, and reacts with anion to form other material substance. This process affects the decrease of molecular weight and the significant loss of polyamide strength. Analysis results from ion concentration measurement shows that the amount of proton and anion transport into deionized waterside was imbalance, which probably due to the different mobility between proton and anion or formation of other material substance by reaction of anion and PA66 bond. Such information is not only necessary for the investigation of hydrolytic degradation of polymer and prediction of lifetimes for a protective polymer lining/coating to chemical attack, but may also be helpful towards gaining a deeper insight into the processes of degradation of other polymer.     

Evaluation of Philips and Ziegler-Natta high-density polyethylene degradation during processing in an internal mixer using the chain scission and branching distribution function analysis

The oxidative and thermo-mechanical degradation of HDPE was studied during processing in an internal mixer under two conditions: totally and partially filled chambers, which provides lower and higher concentrations of oxygen, respectively. Two types of HDPEs, Phillips and Ziegler-Natta, having different levels of terminal vinyl unsaturations were analyzed. Materials were processed at 160, 200, and 240 °C. Standard rheograms using a partially filled chamber showed that the torque is much more unstable in comparison to a totally filled chamber which provides an environment depleted of oxygen. Carbonyl and transvinylene group concentrations increased, whereas vinyl group concentration decreased with temperature and oxygen availability. Average number of chain scission and branching (n_s) was calculated from MWD curves and its plotting versus functional groups' concentration showed that chain scission or branching takes place depending upon oxygen content and vinyl groups' consumption. Chain scission and branching distribution function (CSBDF) values showed that longer chains undergo chain scission easier than shorter ones due to their higher probability of entanglements. This yields macroradicals that react with the vinyl terminal unsaturations of other chains producing chain branching. Shorter chains are more mobile, not suffering scission but instead are used for grafting the macroradicals, increasing the molecular weight. Increase in the oxygen concentration, temperature, and vinyl end groups' content facilitates the thermo-mechanical degradation reducing the amount of both, longer chains via chain scission and shorter chains via chain branching, narrowing the polydispersity. Phillips HDPE produces a higher level of chain branching than the Ziegler-Natta's type at the same processing condition.     

Kinetics of thermal degradation of poly(-caprolactone)

The thermal degradation/modification dynamics of poly(-caprolactone) (PCL) was investigated in a thermogravimetric analyzer under non-isothermal and isothermal conditions. The time evolution of the molecular weight distribution during degradation was studied using gel permeation chromatography. Experimental molecular weight evolution and weight loss profile were modeled using continuous distribution kinetics. The degradation exhibited distinctly different behavior under non-isothermal and isothermal heating. Under non-isothermal heating, the mass of the polymer remained constant at initial stages with rapid degradation at longer times. The Friedman and Chang methods of analysis showed a 3-fold change (from 18 to 55–62 kcal mol⁻¹) in the activation energy from low temperatures to high temperatures during degradation. This suggested the governing mechanism changes during degradation and was explained using two parallel mechanisms (random chain scission and specific chain end scission) without invoking the sequential reaction mechanisms. Under isothermal heating, the polymer degraded by pure unzipping of specific products from the chain end.     

Mathematical Modelling and Computer Simulation of Linear Polymer Degradation: Simple Scissions

Summary: Degradation of a polymer in a reactor by the degrading agent(s) follows a distinct pattern, primarily influenced by structural integrity and reactor environment. This distinct pattern is recorded in the changes in the evolved molecular weight distribution (MWD) or polymer chain length distribution (PCLD) curve characteristics from the initial intact state. Modern size exclusion chromatography (SEC) is the best laboratory‐based method that can clearly provide these plots in the form of chromatogram; however, detailed molecular information is not available. The nature of molecular destruction can be well‐characterised if the distinct MWD shift patterns can be simulated to fingerprint the different chain scission dynamics. This is investigated by our current research using the power of computer simulation techniques to gain insight into the polymer ageing processes. One such technique for studying simple decay processes is presented here, and the results are compared with experimental findings. The concept of a binary tree scission model is introduced to show chain rupture as a sequence of probabilistic events and as a non‐linear function of time. Two new mathematical algorithms, an iterative Monte Carlo structured probability scheme and a semi‐iterative algebraic exact statistical formulation method, are investigated to implement this model and simulate the evolution of resultant temporal MW distribution. The latter, an innovative approach to mathematical modelling, has the potential to generate a statistically perfect instant MWD decay curve. A statistical comparison of the product yield is presented from the data obtained using a wide variety of simulated scission regimes to determine the sources of variability.

Simulated MWD lateral shift for percent cut scission model showing deviation from the initial MWD (red) over degradation time zones T_j(0 ≥ j ≤ 9) with bimodal and curve broadening effect due to accumulation of varied percent cut range 5–30%.     

Molecular coils and their deformation

The study of stress-effects on chain conformation has always been a fruitful - and sometimes highly controversial - issue in macromolecular science. In this paper chain scission in transient elongational flow is investigated. Particular attention is given to the possible nature of stress transfer from the deforming highly dilute polymer solution to the embedded molecular (PS) chain. The dependencies of the measured degradation efficiency on molecular weight, solvent viscosity, nozzle geometry and flow rate exclude the classical mechanism of chain loading through strain-rate dependent viscous friction. On the basis of their findings the authors propose a model where the loading of hairpin-like segments in almost static friction works against the internal relaxation of these structures.     

Dispersion copolymerization of polyoxyethylene macronomer and styrene 4. Solution properties of polystyrene-graft-polyoxyethylene copolymers

The graft copolymers (polystyrene-graft-polyoxyethylene) (PSt-graft-PEO) were prepared by the radical dispersion copolymerization of methacryloyl (MA)-terminated PEO macromonomer and styrene. By means of size-exclusion chromatography, liquid chromatography at the critical adsorption point, and light scattering, the molecular weight parameters and the solution properties of PSt-graft-PEO were investigated. The apparent average molecular weight and the molecular weight distribution (MWD) of graft copolymers were found to decrease with increasing molecular weight of PEO-MA macromonomer. This decreased molecular weight was attributed to the chain transfer to PEO unit and increased contribution of the solution polymerization. The broad MWD varied with the ratio of the polymerization in the continuous phase and the polymer particles. The number of PEO grafts per PSt backbone decreased with increasing molecular weight of the PSt-graft-PEO copolymer, which was attributed to the intramolecular association of PEO segments. The intrinsic viscosity or the coil size of graft copolymer molecules varied with temperature as a result of the dehydration of PEO segments. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3087–3097, 1999     

Enzymatic chain scission kinetics of poly(epsilon-caprolactone) monolayers

The hydrolytic and enzymatic degradation behavior of poly(epsilon-caprolactone) (PCL) is investigated using the Langmuir monolayer technique, and an improved data acquisition and data reduction procedure is presented. Hydrolytic and enzymatic monolayer degradation experiments of PCL with various molecular weights by Pseudomonas cepacia lipase have been carried out to analyze the influence of subphase pH, subphase temperature, enzyme concentration, and the packing density of polymer chains on the degradation kinetics. The enzymatic monolayer degradation results in an exponential increase in the number of dissolved degradation fragments with increasing degradation time, which confirms random chain scission to be the dominant scission mechanism. The increase in the enzymatic scission rate constant with decreasing initial average molecular weight of the polymers is assigned to the influence of the area density of polar terminal groups on the substrate-enzyme complex formation.     

Local segmental relaxation in bidisperse polystyrenes

Dynamic mechanical results are reported for segmental relaxation of monodisperse polystyrenes (PSs) with molecular weights of 0.7, 3, 18, and 104 kg/mol and bidisperse PSs created from blending pairs of these materials. The data for the monodisperse polymers confirm previous findings; namely, there is an increase in the glass‐transition temperature normalized temperature dependence of the segmental relaxation times (fragility) with increasing molecular weight, along with a breakdown of the correlation between the fragility and the breadth of the relaxation function. For both the monodisperse and bidisperse PSs, the glass‐transition temperature is a single function of the average number of chain ends, independent of the nature of the molecular weight distribution. It is also found that these materials exhibit fragilities that uniquely depend on the number‐average molecular weight, that is, on the concentration of chain ends. In blends with linear PS, cyclic PS with a low molecular weight behaves as a high polymer, similar to its neat behavior, reflecting the overriding importance of chain ends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2604–2611, 2004     

Thermal degradation of keto polymers: Part 1—Poly(vinylacetophenone)

The thermal degradation of poly(vinylacetophenone) (PVAP) was studied at 380°C under high vacuum. The degradation products were separated into gaseous and liquid fractions and identified (gc, nmr, ms). The principal reactions are removal and decomposition of acetyl groups, depolymerization and random chain scission, as evidenced by the pattern of number average molecular weight changes. While the basic mechanism of degradation resembles that of poly(styrene) (PS), i.e. initial random chain scission, the number of transfer reactions is considerably greater due to the presence of methyl radicals which abstract from C-atoms in the polymer chain. The resulting chain radicals undergo β-scission (the principal mode of chain scission) to yield a terminally unsaturated molecule and a macro radical. These two species further decompose to give oligomeric products and monomer. The relative abundance of oligomers to monomer is considerably greater than that observed for PS. This has been attributed to shorter zip lengths for depolymerization and to the occurrence of more transfer reactions in PVAP. Plausible mechanisms for the formation of the various reaction products are given.     

Evolution of the termination rate coefficient in styrene polymerization

Styrene bulk polymerization was conducted at 70 °C with a high initiator concentration, and this ensured that the dominant chain‐stopping mechanism was the combination of free radicals. The evolution of the molecular weight distribution (MWD) of the polymer was measured via the periodic removal of samples during the course of the reaction and their analysis with gel permeation chromatography. The overall termination rate coefficient was independent of the conversion in the dilute regime, as observed from cumulative MWDs. In the middle of the conversion range, the observed trend was compatible with a translational‐diffusion‐controlled mechanism for the termination step. A bimodal distribution of the molecular weights was also found at high conversions and could be explained in terms of an increase in the free‐radical concentration and a very low termination rate coefficient. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 178–187, 2005     

Properties of fracture surfaces of glassy polymers: Chain scission versus chain pullout

Fresh fracture surfaces formed by tensile failure of craze in molded polystyrene (PS) bars have been compared with the molded surfaces of the same bars, using an atomic force microscope with a thermal probe and operated in local thermal analysis. The results indicate that molecular weight is much higher in the interior of the sample than at the surface. No evidence was found for degradation of the PS chains via chain scission during crazing. Alternative explanations for the low‐molecular weights at the molded surface are discussed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Influence of n‐dodecyl mercaptan as chain transfer agent in dispersion polymerization of styrene

Dispersion polymerization of styrene with n‐dodecyl mercaptans (DDM) as the chain transfer agent was investigated. PS particles with various molecular weight, molecular weight distribution (MWD), and particle diameter were prepared by varying the concentration of DDM and also the addition time of DDM before and after the particle nucleation. The average particle diameter was increased, whereas polymerization rate, molecular weight, and MWD were decreased with increasing DDM concentrations from 0 to 10 wt %. The effect of addition of DDM before and after particle nucleation was studied at 0.4, 0.8, and 1.0 wt % DDM. The addition of DDM before particle nucleation produced PS particles of relatively large particle diameter and low molecular weight when compared with the addition of DDM after particle nucleation. This study shows that particle nucleation occurs in about 5–6 min, which corresponds to the 15–16% conversion, 372–378 nm in D_n , and provides a facile way to control the particle size and interesting information about the particle formation using the delayed addition of DDM. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6612–6620, 2008     

H_2O/TiCl_4/Py体系引发苯乙烯正离子聚合

研究了在少量吡啶(Py)存在下由水(H2O)四氯化钛(TiCl4)体系引发苯乙烯于二氯甲烷正己烷中进行碳正离子聚合,分别考察[Py]、[H2O]和[TiCl4]对聚合速率、产物分子量与分子量分布的影响.实验结果表明,少量亲核试剂吡啶(Py)对聚合反应起着重要作用,可有效地降低聚合速率和使分子量分布变窄;随着[H2O]和[Py]降低或[TiCl4]增加,聚合产物的分子量增加,而分子量分布指数(Mw Mn)基本维持在1.8左右;随着[Py]增加,聚合速率降低;随着[H2O]和[TiCl4]增加,聚合速率提高.聚合速率对单体浓度呈一级动力学关系,对Py、H2O和TiCl4的反应级数分别为-0.72、0.72和1.86.聚合速率对TiCl4浓度呈接近二级动力学关系,这可能与体系中TiCl4主要以二聚体形式存在有关.聚合转化率和产物分子量均随着反应时间延长而逐渐增大,PS的数均分子量与转化率呈线性增加关系.     

Chemical modification of poly(methylphenylsiloxane)

Poly(methylphenylsiloxane) (PMPS) with a narrow molecular weight distribution (MWD) was prepared by anionic polymerization, and ring‐functionalized using procedures optimized to minimize chain degradation. The products were characterized by NMR and IR spectroscopy, and the MWD of the polymers was analyzed by size exclusion chromatography, to monitor polymer degradation and crosslinking during the functionalization reactions. Electrophilic substitution was used to introduce nitro and bromo groups on the phenyl ring of the polymer. Nitration with fuming nitric acid yielded up to 8 mole % substitution with some chain degradation. Bromination was achieved with bromine in the presence of either pyridine or triethylamine. A substitution level of up to 14 mole % and a small increase in the polydispersity index (M_w/M_n) were obtained with triethylamine. Hydroxyethyl functionalities were obtained by lithiation of the brominated PMPS via metal‐halogen exchange, and reaction with ethylene oxide. A polymer with 3 mole % hydroxyethyl functionalities was obtained with moderate chain degradation. A substitution level of 6 mole % could be achieved under different conditions, but with more extensive chain degradation. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 653–664, 1999     

Polypropylene/polystyrene blends: In situ compatibilization by Friedel‐Crafts alkylation reaction

The application of Friedel‐Crafts alkylation reaction to the compatibilization of polypropylene (PP)/polystyrene (PS) blends was assessed. A PP macrocarbocation is chemically bonded to the PS benzene ring by aromatic electrophilic substitution. The graft copolymer formed at the interphase (PP‐g‐PS) showed relatively high emulsification strength, suggesting an effective behavior as in situ compatibilizer. The critical micelle concentration (CMC) was related to Friedel‐Crafts catalyst concentration. The amount of PS grafting and possible appearance of crosslinking and chain scission side reactions were also analyzed. The reaction products were characterized by a combination of size exclusion chromatography and Fourier transform infrared techniques applied after a careful solvent extraction separation. It was found, from the emulsification curve, that CMC was achieved when 0.7 wt % AlCl₃ was added. This value was confirmed by scanning electron microscopy observation of phase adhesion on fractured sample surfaces. Mass balances of extracted PS showed that at least 15 wt % of the initial PS resulted grafted at the CMC condition. Chain scission reactions, in parallel with grafting, were verified to occur for PP as well as for PS. Instead, crosslinking reactions were not detected. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 452–462, 2004     

Inclusion of the effects of polydispersity and volatility on the random chain scission statistical analysis for polymer degradation

The statistical product distribution for a linear polydisperse polymer of finite molecular weight was included into the statistical analysis for a system undergoing random chain scission showing the effect of volatilization of species other than monomer. Two sets of equations were derived. One set is for the nonvolatile fraction; the other is for the volatile fraction. Within each set there are three equations, one for the number of polymer molecules, the second for the molar (or number) fraction, and the third for the weight fraction of polymer molecules containing a specific number of repeat units. As degradation proceeds the polydispersity index should converge to a value of 1 rather than 2, which has been reported previously. The expected effects of polydispersity, number‐average degree of polymerization, and volatility were treated individually, and we determined that the molecular weight of a polymer has no theoretical influence on the product distribution. As for the effect of volatility, we determined that only the volatile product distribution would change. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3690–3696, 2000