Metallocene ethylene-1-octene copolymers: Effect of extrusion conditions on thermal oxidation of polymers with different comonomer content

Metallocene ethylene-1-octene copolymers having different densities and comonomer content ranging from 11 to 36 wt% (m-LLDPE), and a Ziegler copolymer (z-LLDPE) containing the same level of short-chain branching (SCB) corresponding to one of the m-LLDPE polymers, were subjected to extrusion. The effects of temperature (210-285 °C) and multi-pass extrusions (up to five passes) on the rheological and structural characteristics of these polymers were investigated using melt index and capillary rheometry, along with spectroscopic characterisation of the evolution of various products by FTIR, ¹³C-NMR and colour measurements. The aim is to develop a better understanding of the effects of processing variables on the structure and thermal degradation of these polymers. Results from rheology show that both extrusion temperature and the amount of comonomer have a significant influence on the polymer melt thermo-oxidative behaviour. At low to intermediate processing temperatures, all m-LLDPE polymers exhibited similar behaviour with crosslinking reactions dominating their thermal oxidation. By contrast, at higher processing temperatures, the behaviour of the metallocene polymers changed depending on the level of comonomer content: higher SCB gave rise to predominantly chain scission reactions whereas polymers with lower level of SCB continued to be dominated by crosslinking. This temperature dependence was attributed to changes in the different evolution of carbonyl and unsaturated compounds including vinyl, vinylidene and trans-vinylene.     

Stabilisation of metallocene ethylene-1-octene copolymers during multiple extrusions

The melt stabilising efficiency of antioxidants with different structures based on hindered phenols, phosphite esters, phosphonite and a lactone was examined during multi-pass extrusions at 265 °C in three metallocene ethylene-1-octene copolymers (m-LLDPE) having different extent of short chain branching (SCB) and one Zeigler copolymer (z-LLDPE) containing the same level of SCB corresponding to one of the m-LLDPE polymers. The effect of the different antioxidants, when used separately and in combination, was investigated by characterising the changes in the polymer's rheological behaviour, colour formation and structural changes based on unsaturated groups and carbonyl content during five multi-pass extrusions. The results showed that all stabilisation systems examined offered higher efficiency in the metallocene polymers compared to the Zeigler. The effect of the extent of SCB in the metallocene polymers on the stabilising efficacy of the antioxidant systems was also examined, and it was shown that it had a significant effect, with both single and combinations of antioxidants giving higher efficiency in the m-LLDPE polymer containing higher extent of SCB. The presence of the lactone HP136 in mixtures containing hindered phenol-phosphite antioxidant systems gave a higher melt stabilisation efficiency than in its absence and this has been attributed to a co-operative antioxidant reaction steps that take place between the antioxidants resulting in the possible regeneration of the lactone antioxidant through a redox reaction. In all the metallocene PE polymers examined, the biologically hindered phenol, Irganox E, was shown to be more effective than the conventionally hindered phenol Irganox 1076, when examined alone or in combination with phosphite esters.     

Ethylene/1-Butene Copolymerization over Heterogeneous Metallocene Catalyst

Summary: Nowadays, bimodal polyethylene obtained in a two step cascade process is a matter of intensive research in polyolefin field. In the second stage of this process, a high molecular weight ethylene-α-olefin copolymer is formed over the homopolymer produced in the first step. In this work, a study of reaction variables on this second step using an heterogeneous metallocene catalyst was carried out. The effect of reaction temperature (70–85 °C) and comonomer concentration (0–0.32 mol/l) was evaluated. Polymerization results showed that activity increases with temperature and 1-butene initial concentration. Moreover, higher comonomer concentrations and lower temperatures involve higher short chain branching (SCB). Copolymers characterization indicated that melt temperature and density values have a lineal decrease with the SCB content in the polymer, regardless of the reaction temperature. As well, for every temperature, higher comonomer concentrations do not seem to affect to molecular weight, whereas a decrease of crystallinity was observed, which may explain the increase of catalyst activity.     

The thermo-oxidative degradation of metallocene polyethylenes: Part 2: Thermal oxidation in the melt state

The thermo-oxidative melt degradation of different metallocene polyethylenes (mPEs) was investigated in a torque rheometer open to air at 225 °C and 10 rpm. The mPEs differed essentially according to their initial melt index, molar mass distribution, density and ash content, but one characteristic was changed at a time in order to assess the influence of each specific property in the thermo-oxidative degradation of the PEs investigated. Crosslinking was found to dominate at the early stages of degradation during mastication for most polymers where reactions of alkyl radicals to vinyl groups were considered to be the dominant reaction. Furthermore, discolouration was attributed to both excessive levels of catalyst residues and extensive formation of conjugated systems. Finally, it was concluded that the polymer melt viscosity, i.e., molar mass and shape of molar mass distribution, appeared to govern the processing stability of the mPE. These results confirm the importance of shear as the major source for initiation of free radicals formed by homolytic fission caused via mechanical cleavage of polymer chains.     

Studies of comonomer distributions and molecular segregations in metallocene-prepared polyethylenes by DSC

This paper is devoted to the study of crystallization and melting of two metallocene polyethylenes (m-PEs). A metallocene linear low density polyethylene (m-LLDPE) and a metallocene very low density polyethylene (m-VLDPE) were used consisting of 3.3 mol% butyl and 6 mol% ethyl branches, respectively. Several melt endotherms after stepwise crystallization revealed that the two m-PEs consisted of molecular fractions with different molecular weight and branch distribution. More segregation was observed for the m-VLDPE comparing with m-LLDPE. Using the relationships proposed by Hosoda, the short chain branching distribution (SCBD) and the average methylene groups in the lamella thickness were also calculated for the two polymers. These values were compared with the values obtained from theory of rubber elasticity. There was a very good correlation between the data.     

Melting behavior of polyethylene/α‐olefin copolymers: Narrow composition distribution copolymers and fractions from Ziegler–Natta and single‐site catalyst products

The melting temperature and heat of fusion were measured for an extensive series of compositionally uniform copolymers of ethylene with butene‐1, hexene‐1, and octene‐1. Fractions and whole polymers that exhibited minimal interchain compositional heterogeneity were from commercial copolymers made with either Ziegler–Natta (ZN) or single‐site metallocene catalysts. The present results do not support recent claims that ZN and corresponding metallocene catalyst copolymers melt at significantly different temperatures, nor the implication that comonomer incorporation is “blocky” in ZN copolymers. In five of the six comonomer/catalyst systems the dependencies of the melting temperature on comonomer type and amount were scarcely distinguishable. This common behavior is the same as that for a model random copolymer, so we conclude that most ethylene/α‐olefin copolymers have random distributions of ethylene sequences. The exception in the present study is a metallocene ethylene/butene‐1 copolymer that melts at lower temperatures and apparently has perceptibly alternating sequence distributions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3416–3427, 2004     

Processability and Application of Metallocene Linear Low Density Polyethylene

1. The structure and feature ofm-LLDPE Due to having a kind of active site in metallocene catalyst, the rate of polymerization and insertion of comonomer are very uniform. Compared with conventional LLDPE, the structure of m-LLDPE has such features: (1) a narrow molecular weight distribution, about 2.0-2.5. The conventional LLDPE, however, has a wide molecular weight distribution, about 4.0-8.0, (2) the distribution of comonomer between different m-LLDPE molecular chain is very uniform, (3) the distribution of comonomer intermolecular-chain is very uniform.     

Synthesis and Characterization of Ethylene/Propylene Copolymers in the Whole Composition Range

Summary: The incorporation of comonomer molecules in the backbone of a homopolymer can influence the final properties of the material, decreasing its crystallinity and the melting and glass transition temperatures, and increasing its impact resistance and transparency. In the present work, ten ethylene/propylene copolymers have been synthesized using a supported metallocene catalytic system covering the whole composition range. Any desired composition was obtained by controlling the feed composition during the reaction. These synthesized copolymers have been characterized by different techniques in order to study the effect of the comonomer incorporation onto their final properties. When the comonomer content is low, the behaviour of the copolymer is similar to that of the corresponding homopolymer. Nevertheless, if the comonomer content increases, the copolymer becomes more amorphous (low crystallization temperature and soft XRD signals) and easily deformable, reaching a behaviour close to that corresponding to an elastomeric material. In order to corroborate these results the samples have been characterized by TREF and GPC-MALS. TREF analysis showed that copolymers containing less than 10% and more than 80% of ethylene are semicrystalline, with elution temperatures typical of this kind of polymers. Molecular weights are higher for homopolymers and they decrease as the comonomer concentration increases, whereas the polydispersity index keeps almost constant at the expected value for this kind of samples.     

不同分子量的高密度聚乙烯与茂金属线型低密度聚乙烯的相容性

采用动态流变学测试和结晶动力学的方法研究了两种分子量的高密度聚乙烯(HDPE)与茂金属线型低密度聚乙烯(m-LLDPE)共混体系的相容性.流变学研究表明,HDPE/m-LLDPE共混物在低ω区域lgG′-lgω关系曲线偏离线性规律,在熔融态为非均相体系.DSC分析发现HDPE/m-LLDPE共混物体系中HDPE的熔点随着m-LLDPE含量的增多而逐渐下降,说明HDPE与m-LLDPE二者具有机械相容性.当HDPE在m-LLDPE的熔体中等温结晶,分子量较高的HDPE结晶速率与纯HDPE相近,m-LLDPE的含量变化对Avrami指数n的影响不大;分子量较低的HDPE指数n和半结晶时间t1/2随m-LLDPE含量的增加逐渐增大,结晶速率随着m-LLDPE含量的增加逐渐下降,表明熔融态的m-LLDPE和HDPE存在着较强的分子间相互作用,二者具有一定的相容性.     

Rheological investigation of the influence of molecular structure on natural and accelerated UV degradation of linear low density polyethylene

Metallocene and Ziegler-Natta (ZN) linear low density polyethylenes (LLDPEs) of different branch types and contents as well as linear high density polyethylene (HDPE) were exposed to natural and accelerated weather conditions. The degree of UV degradation of exposed samples was measured by rheological techniques and results were compared with unexposed polymers. Dynamic shear measurements were performed in an ARES rheometer in the linear viscoelastic range. The degree of enhancement or reduction in viscosity and elasticity was used as a measure of the degree of cross-linking or chain scission, respectively. The degradation results of LLDPE suggest that both cross-linking and chain scission are taking place. Chain scission dominated the degradation at high levels of short chain branching (SCB) and long exposure times. The degradation mechanism of m-LLDPE and ZN-LLDPE is similar; however, m-LLDPE showed a higher degradation rate than ZN-LLDPE of similar M_w and average SCB. ZN-LLDPE was found to be more stable than a similar m-LLDPE. Comonomer type had little influence on degradation. Dynamic shear rheology was very useful in revealing the influence of different molecular parameters and it exposed the degradation mechanism.     

High temperature reactions of an aryl-alkyl phosphine, an exceptionally efficient melt stabiliser for polyethylene

Bis(diphenylphosphino)-2,2-dimethylpropane (PMP) is a highly efficient melt stabiliser of polyethylene. This aryl-alkyl phosphine hinders the degradation of the polymer during processing even in small concentrations and in combination with a phenolic antioxidant its consumption rate is considerably slower than that of phosphites and phosphonites. In this study the reactions of PMP were studied at temperatures corresponding to those used for the processing of polyethylene in order to explore the processing stabilisation mechanism of this additive. Thermal and thermo-oxidative stability were determined by DSC and TGA, respectively by heating PMP in argon and oxygen at 200 and 240 °C. Reactions with peroxy, carbon-centred and oxy radicals, as well as with hydroperoxide were investigated at 200 °C. Reaction products were identified by FT-IR and solution-state NMR spectroscopy. The results revealed that the phosphine studied has sufficient thermal- and thermo-oxidative stability under the processing conditions of polyethylene. It oxidises easily with any oxidising agent including molecular oxygen of air. Consequently, PMP does not only decompose hydroperoxide groups and react with oxy macroradicals during the processing of polyethylene, as claimed by most references on phosphorous antioxidants, but it can also hinder the formation of peroxy macroradicals, i.e., the initiation reaction of thermo-oxidative degradation.     

Polymerization of propylene by mixed Ziegler–Natta and metallocene catalysts

The polymerization of propylene using a mixture of racemic metallocenes and Ziegler–Natta catalysts was investigated. The polypropylene was obtained as a mixture of a fine powder and beads, with the powder being absorbed partially on the beads. The relative amount of the powder can be controlled by the concentration of the metallocene. The compatibility between the components of the mixed catalytic systems and the effect of the components on the rate of polymerization and on the properties of the new polymers were studied. The metallocene system dramatically affects the melt viscosity, isotacticity and molecular weight of the polymers. The two catalytic systems are able to act jointly, producing different polymers, for which separate melting and crystallization temperatures are obtained. © 1998 John Wiley & Sons, Ltd.     

Thermomechanical behavior of metallocene ethylene-α-olefin copolymers

The thermal, dynamic mechanical and stress-strain properties of a set of commercial LLDPEs prepared by metallocene catalysts were studied and compared with two LLDPEs obtained with traditional Ziegler-Natta catalysts. The type and amount of comonomer strongly affects the degree of crystallinity and branching, resulting in different material morphology and macroscopic thermomechanical behavior. Within each set of ethylene-α-olefin copolymers a gradual decrease in the percentage crystallinity and position and intensity of β- and γ-transition is observed, with respect to the comonomer content. In addition, the studied materials are characterized by the absence of an α-transition. This behavior is attributed to the high comonomer content (5-24)%. Tensile behavior changes from the typical necking, cold drawing and strain hardening to the uniform elastomeric deformation, as the comonomer content increases.The experimental methods used, in combination with scanning electron microscopy, lead to converged results, while tensile testing proved to be sensitive to the crystallite size and distribution.     

Comonomer Distribution in Polyethylenes Analysed by DSC After Thermal Fractionation

Ethylene copolymers exhibit a broad range of comonomer distributions. Thermal fractionation was performed on different grades of copolymers in a differential scanning calorimeter (DSC). Subsequent melting scans of fractionated polyethylenes provided a series of endothermic peaks each corresponding to a particular branch density. The DSC melting peak temperature and the area under each fraction were used to determine the branch density for each melting peak in the thermal fractionated polyethylenes. High-density polyethylene (HDPE) showed no branches whereas linear low-density polyethylenes (LLDPE) exhibited a broad range of comonomer distributions. The distributions depended on the catalyst and comonomer type and whether the polymerisation was performed in the liquid or gas phase. The DSC curves contrast the very broad range of branching in Ziegler—Natta polymers, particularly those formed in the liquid phase, with those formed by single-site catalysts. The metallocene or single-site catalysed polymers showed, as expected, a narrower distribution of branching, but broader than sometimes described. The ultra low-density polyethylenes (ULDPE) can be regarded as partially melted at room temperature thus fractionation of ULDPE should continue to sub-ambient temperatures. The thermal fractionation is shown to be useful for determining the crystallisation behaviour of polyethylene blends.This revised version was published online in November 2005 with corrections to the Cover Date.     

茂金属聚乙烯的短链支化结构不均匀性研究进展

茂金属支化聚乙烯技术是聚烯烃工业发展史上最重要的技术进展之一,该类产品具有优异的抗穿刺、抗撕裂、抗冲击性质,在薄膜、重包装等领域具有广泛的用途,其力学性能与共聚单体的种类、含量及其在分子链上的分布有密切关系。本文从催化剂活性中心特点和聚合反应工艺条件两方面对聚合物结构的影响出发,阐述了茂金属聚乙烯短链支化结构不均匀性产生的原因,通过核磁共振、升温淋洗分级和热分级等表征支化不均匀性的研究方法,介绍了茂金属支化聚乙烯分子主链上共聚单体的序列结构组成及分布,以及共聚物的结晶性能等方面的差异。     

Miscibility and enzymatic degradation studies of poly(ε-caprolactone)/poly(propylene succinate) blends

In the present study the miscibility behaviour and the biodegradability of poly(ε-caprolactone)/poly(propylene succinate) (PCL/PPSu) blends were investigated. Both of these aliphatic polyesters were laboratory synthesized. For the polymer characterization DSC, ¹H NMR, WAXD and molecular weight measurements were performed. Blends of the polymers with compositions 90/10, 80/20, 70/30 and 60/40 w/w were prepared by solution-casting. DSC analysis of the prepared blends indicated only a very limited miscibility in the melt phase since the polymer-polymer interaction parameter χ₁₂ was −0.11. In the case of crystallized specimens two distinct phases existed in all studied compositions as it was found by SEM micrographs and the particle size distribution of PPSu dispersed phase increased with increasing PPSu content. Enzymatic hydrolysis for several days of the prepared blends was performed using Rhizopus delemar lipase at pH 7.2 and 30 °C. SEM micrographs of thin film surfaces revealed that hydrolysis affected mainly the PPSu polymer as well as the amorphous phase of PCL. For all polymer blends an increase of the melting temperatures and the heat of fusions was recorded after the hydrolysis. The biodegradation rates as expressed in terms of weight loss were faster for the blends with higher PPSu content. Finally, a simple theoretical kinetic model was developed to describe the enzymatic hydrolysis of the blends and the Michaelis-Menten parameters were estimated.     

Thermal and thermo-oxidative stabilities of some poly(siloxane-azomethine)s

Thermal and thermo-oxidative stability of some poly(siloxane-azomethine)s obtaining starting from bis(formyl-p-phenoxymethyl)tetramethyldisiloxane and different organic diamines have been investigated by TG+DTG+DSC simultaneous analyses performed in argon flow and air static atmosphere, respectively. TG, DTG and DSC curves of each polymer showed three or four successive degradation steps at different temperatures according to the composition of the sample and the gaseous atmosphere in which the thermal analysis was performed. For each process, the following parameters were evaluated: total mass loss, temperature corresponding to the maximum reaction rate, maximum reaction rate, temperature corresponding to certain mass loss. In order to determine the thermal and thermo-oxidative stabilities of investigated polymers, the following values were determined: T _x% — temperature corresponding to x% mass loss, and %Δm _T — mass loss at a given temperature T. The obtained orders of stability were correlated with the structure of investigated polymers.     

Melt drawing of ultra‐high molecular weight polyethylene: Comparison of Ziegler‐ and metallocene‐catalyzed reactor powders

The drawing behavior of the ultra‐high molecular weight polyethylene (UHMW‐PE) melts has been studied by comparing the stress/strain curves for two types of samples as polymerized using conventional Ziegler and newer metallocene catalyst systems. Two UHMW‐PE samples, having the same viscosity average molecular weight of 3.3 × 10⁶, but different molecular weight distribution, have been drawn from melt at special conditions. The sample films for drawing were prepared by compression molding of reactor powders at 180°C in the melt. Differences in the structural changes during drawing and resultant properties, ascribable to their broad or narrow molecular weight distribution, were estimated from tensile tests, SEM observations, X‐ray measurements and thermal analyses. The metallocene‐catalyzed sample having narrower molecular weight distribution, could be effectively drawn from the melt up to a maximum draw ratio (DR) of 20, significantly lower than that obtained for the Ziegler‐catalyzed sample, ∼ 50. The stress/strain curves on drawing were remarkably influenced by draw conditions, including draw temperature and rate. However, the most effective draw for both was achieved at 150°C and a strain rate of 5 min⁻¹, independent of sample molecular weight distribution. The efficiency of drawing, as evaluated by the resultant tensile properties as a function of DR, was higher for the metallocene‐catalyzed sample having narrower molecular weight distribution. Nevertheless, the maximum achieved tensile modulus and strength for the Ziegler sample, 50–55 and 0.90 GPa, respectively, were significantly higher than those for the metallocene sample, 20 and 0.65 GPa, respectively, reflecting the markedly higher drawability for the former than the latter. The stress/strain behavior indicated that the origin of differences during drawing from the melt could be attributed to the ease of chain relaxation for the lower molecular weight chains in the melt. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1921–1930, 1999     

Impact of fullerenes on the thermal stability of melt processed polystyrene and poly(methyl methacrylate) composites

The impact of the two fullerenes C₆₀ and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) on the thermal and thermo-oxidative stability of the corresponding melt processed composites with the two polymers polystyrene (PS) and poly(methyl methacrylate) (PMMA), was studied using both dynamic and isothermal thermogravimetric analysis (TGA). For each polymer, three different composites with C₆₀ loadings of 1.0 wt% and 3.0 wt% and PCBM loadings of 1.0 wt% were considered. The aim of this work was to compare the stabilization effect of both fullerenes on PS and PMMA. The results obtained show unequivocally that, although PCBM has lower thermal and thermo-oxidative stability than C₆₀, the PS-PCBM and PMMA-PCBM composites have higher thermal and thermo-oxidative stability than the corresponding PS-C₆₀ and PMMA-C₆₀ composites. These results corroborate our previous reports, on showing that PCBM is better than C₆₀ at improving the thermal and thermo-oxidative stability of polymers which degrade through radical degradation mechanisms.     

Thermal Behaviour of Blends of HDPE with Long-chain Branched HBPE

The thermal behaviour of new blends on the base of high-density polyethylene (HDPE) and of long-chain branched polyethylenes (HBPE) made by means of new metallocene catalysts has been studied by DSC in relation to the melting and crystallisation characteristics and discussed in the phase behaviour of the mixtures. While HBPE's with 7.5 to 12 per cent by mass of octene as comonomer in the blends with HDPE are relevant for the formation of homogeneous composition regions. Especially, with higher HBPE contents, the phase separation and splitting of the melting and crystallisation peaks is observed. This behaviour has not been observed with 2 per cent by mass of octene in HBPE. The dependence of the melting and crystallisation temperatures of HDPE/HBPE blends on the octene content of the HBPE's for constant composition of mixtures have been shown for both the homogeneous and heterogeneous mixing. Blends of a high-molecular HDPE and a HBPE resulted in a reduction of the composition range not effected by phase separation. This revised version was published online in July 2006 with corrections to the Cover Date.