Long-chain Branching Research Articles

Dielectric Property and Breakdown Strength Performance of Long-Chain Branched Polypropylene for Metallized Film Capacitors.

At high temperatures, the insulation performance of polypropylene (PP) decreases, making it challenging to meet the application requirements of metallized film capacitors. In this paper, the dielectric performance of PP is improved by long-chain branching modification and adding different kinds of nucleating agents. The added nucleating agents are organic phosphate nucleating agent (NA-21), sorbitol nucleating agent (DMDBS), rare earth nucleating agent (WBG-Ⅱ) and acylamino nucleating agent (TMB-5). The results show that the long-chain branches promote heterogeneous nucleation and inhibit the motion of molecular chains, thereby enhancing the dielectric properties at high temperatures. Nucleating agents modulate the crystalline morphology of long-chain branched polypropylene (LCBPP), which leads to a decrease in the mean free path of carriers and an increase in trap energy level and trap density. Therefore, the conductivity is reduced and the breakdown strength is improved. Among the added nucleating agents, NA-21 showed a significant improvement in the electrical properties of LCBPP films. At 125 °C, compared with PP, the breakdown strength of the modified film is increased by 26.3%, and the energy density is increased by 66.1%. This method provides a reference for improving the dielectric properties of PP.

The Use of Branching Agents in the Synthesis of PBAT.

Biodegradable polyesters represent an advanced alternative to polyolefin plastics in various applications. Polybutylene adipate terephthalate (PBAT) can compete with polyolefins in terms of their mechanical characteristics and melt processing conditions. The properties of PBAT depend on the molecular weight, dispersity, and architecture of the copolymer. Long-chain branching (LCB) of the PBAT backbone is an efficient method for the improvement of the copolymer characteristics. In the present work, we studied branching agents (BAs) 1–7 of different structures in the two-stage polycondensation of 1,4-butanediol, dimethyl terephthalate, and adipic acid and investigated the composition and melt rheology of the copolymers. According to the results of the research, 1,1,1-tris(hydroxymethyl)ethane 2 and 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid 5 outperformed glycerol 1 as BAs in terms of shear thinning behavior and viscoelasticity.

ALTERNATIVE USE OF THE SENTMANAT EXTENSIONAL RHEOMETER TO INVESTIGATE THE RHEOLOGICAL BEHAVIOR OF INDUSTRIAL RUBBERS AT VERY LARGE DEFORMATIONS

ABSTRACT Extensional deformations represent an effective stimulus to explore the rich rheological response of branched polymers and elastomers, enabling the design of polymers with specific molecular structure. However, probing the polymer behavior at large deformations is often limited by the experimental devices. We here present an alternative use of the Sentmanat Extensional Rheometer (SER) that allows Hencky strain units much larger than the maximum value achievable, ∼3.6. The proposed procedure consists of an oblique positioning of the sample in the measuring area. If a small inclination of the sample is used, the departure from the ideal uniaxial flow is negligible at Hencky strains <1, and nearly zero for larger values. Experimental results in the linear viscoelastic regime are compared with the double reptation model in order to discern polydispersity and branching effects, whereas the extensional rheology data are contrasted with the molecular stress function theory (MSF), revealing important information about the polymer structure, especially on the long-chain branching (LCB). Finally, the analysis of sample failure upon elongation allowed us to correlate the polymer structure to the rheological behavior during mixing processes.

Modelling elongational viscosity overshoot and brittle fracture of low-density polyethylene melts

The Hierarchical Multi-mode Molecular Stress Function (HMMSF) model predicts the elongational and multiaxial extensional viscosities of polydisperse linear polymer melts based exclusively on their linear viscoelastic characterization and a single nonlinear material parameter, the so-called dilution modulus {G}_{D}. For long-chain branched (LCB) polymer melts such as low-density polyethylene (LDPE), the HMMSF model describes quantitatively the elongational stress growth coefficient up to the maximum of the elongational viscosity but fails to predict the existence of the maximum and the following steady-state viscosity. By taking into account branch point withdrawal in elongational flow of LCB melts, we extend the HMMSF model and show that the maximum of the elongational viscosity can be characterized by a single additional parameter, the characteristic stretch {overline{lambda }}_{m}, while the steady-state tensile stress and the elongational viscosity depend only on the dilution modulus {G}_{D} as in the case of linear polydisperse melts. Comparison of predictions of the Extended Hierarchical Multi-mode Molecular Stress Function (EHMMSF) model to experimental data of 5 LDPE melts with widely different molecular weights, polydispersities and densities, and a model polystyrene pom-pom polymer shows good agreement within experimental accuracy in constant elongational-rate flow as well as stress relaxation after steady and reversed elongational flow. For the LCB melts considered, we report differences in the specific Hencky strain at the maximum of the tensile stress as quantified by the characteristic stretch {overline{lambda }}_{m}, and we discuss correlations between polydispersity, dilution modulus {G}_{D}, and strain hardening potential of the LDPE melts. We also extend the fracture criterion for brittle fracture of monodisperse polymer melts to the case of polydisperse polymers and find reasonable agreement with experimental evidence.

Breakdown strength improvement of polypropylene by introducing long-chain branched structures for film capacitors

The breakdown strength of polypropylene (PP) for film capacitors drops sharply in a high-temperature environment, which would lead to capacitor insulation failure frequently. This paper proposes a method to improve the breakdown strength of PP at high temperatures by introducing long-chain branches (LCBs). Different from traditional linear PP, the results show that LCBs can increase the number of spherulites and refine the grains due to heterogeneous nucleation, resulting in a reduction in weak areas in the films and an increase in trap densities and energy levels in long-chain branched polypropylene (LCBPP). In addition, the higher melt strength of LCBPP indicates that LCBs promote entanglement between molecular chains and hinder the sliding of chains, thereby reducing the influence of temperature on the free volume. Therefore, compared with PP, the conductivity of LCBPP is lower at high temperatures, and the breakdown strength increases by 16.2% at 105 °C. This method provides an idea for improving the breakdown strength of PP films at elevated temperatures from the perspective of regulating the microstructure.

Crystallization behavior and structure of metallocene polyethylene with long-chain branch

Crystallization behavior and structure of metallocene polyethylene with long-chain branch

Effects of grafting and long-chain branching structures on rheological behavior, crystallization properties, foaming performance, and mechanical properties of polyamide 6

Abstract Polyamide 6 (PA6) was modified with ethylene maleic anhydride syndiotactic copolymer resin (ZeMac), and triglycidyl isocyanurate (TGIC) as modifiers to prepare a grafting structure and a long-chain branching structure, respectively. The effects of two modifiers on the rheological behavior, crystallization properties, foaming performance, and mechanical properties of PA6 were systematically studied by rotating rheometry, differential scanning calorimetry and scanning electron microscopy. The results showed that there were differences in crystallization properties between the two modification methods, but they significantly improved the rheological, foaming performance, and mechanical properties of PA6. In particular, PA6 with long-chain branching structure through TGIC modification showed better performance in various physicochemical characterizations. The introduction of ZeMac reduced the average diameter of bubbles in pure PA6 from 146.32 to 88.12 µm, and the density of bubbles increased from 1.69 × 105 to 5.35 × 105 cells·cm−3. The introduction of TGIC reduced the average diameter of bubbles in pure PA6 from 146.32 to 64.36 µm, and the density of bubbles increased to 1.31 × 106 cells·cm−3. Moreover, the mechanical properties of both nonfoamed and foamed samples were improved after modification.

Photophysical properties of ammonium, pyrrolidinium, piperidinium, imidazolium, and pyridinium as a guide to prepare ionic-organic hybrid materials

Ionic liquid cations (ILCs) have been utilized in hybrid organic-inorganic perovskites (HOIPs) to enhance their photoluminescence performance. However, the high number of possible cations and anions needed to form ILCs makes the experimental measurement time and cost consuming. Computational methods that could assist the selection of ILCs for this task-specific application are highly desirable. Therefore, in this work, the photophysical properties of various ILCs, including linear aliphatic, five-membered, and six-membered cyclic aliphatic, and aromatic ILCs, were investigated using density functional theory (DFT) and time-dependent density functional theory (TDDFT). Fluorescence and phosphorescence were analyzed using excited state dynamics (ESD) modules on ORCA at the B3LYP/def2TZVP level theory. All the investigated cations show fluorescence spectra either the UV or visible range. The cations with long-chain branches show fluorescence spectra in the visible range. Five membered rings show the phosphorescence spectra in the visible range, while the six-membered rings show the phosphorescence spectra in the near-infrared range.

Addition of 1, 4-α-glucan branching enzyme during the preparation of raw dough reduces the retrogradation and increases the slowly digestible fraction of starch in cooked noodles

Consumers significantly prefer wheat noodles that offer both an acceptable texture and health benefits. To this end, a cold-active 1,4-α-glucan branching enzyme from Bifidobacterium longum (BlBE) was expressed in the generally recognized as safe (GRAS) host cell Bacillus subtilis and then used at 120, 240 or 480 U/g flour in the preparation of raw dough. The storage modulus and loss modulus of the BlBE-modified dough decreased, but the pseudo-plasticity increased. The cooked noodles' hardness, gumminess and chewiness decreased by 12.1%–45.8%, 9.7%–40.4% and 16.0%–42.4%, respectively, but both resilience and cohesiveness increased by 4.0%–14.8% and 1.8%–9.0%, respectively. Pearson analysis revealed a correlation between the noodles' textural parameters and the doughs' power law equation parameters. BlBE-modified noodles exhibited significantly (P < 0.05) lower differential scanning calorimetry retrogradation enthalpies during storage at 4 °C for 7 days and released significantly lower levels of glucose during incubation with mammalian α-glucosidase at 37 °C for 10 min–360 min. BlBE at 480 U/g flour increased the slowly digestible portion by 12.6%. BlBE decreased the molecular weight, x-ray diffraction crystallinity, and fourier transform infrared spectroscopy ratio of band's heights at 1045 cm−1 and 1022 cm−1 of starch but increased the amylopectin content and ratio of short- to long-branch chains. These structural changes in starch partially explained the reduced retrogradation and enhanced slowly digestible starch fraction in the noodles.

Flow visualization by Matlab® based image analysis of high-speed polymer melt extrusion film casting process for determining necking defect and quantifying surface velocity profiles

Abstract The primary objective of this research paper is to detect and quantify the necking defect and surface velocity profiles in high-speed polymer melt extrusion film casting (EFC) process using Matlab® based image processing techniques. Extrusion film casting is an industrially important manufacturing process and is used on an industrial scale to produce thousands of kilograms of polymer films/sheets and coated products. In this research, the necking defect in an EFC process has been studied experimentally and the effects of macromolecular architecture such as long chain branching (LCB) on the extent of necking have been determined using image processing methodology. The methodology is based on the analysis of a sequence of image frames taken with the help of a commercial CCD camera over a specific target area of the EFC process. The image sequence is then analyzed using Matlab® based image processing toolbox wherein a customized algorithm is written and executed to determine the edges of the extruded molten polymeric film to quantify the necking defect. Alongwith the necking defect, particle tracking velocimetry (PTV) technique is also used in conjunction with the Matlab® software to determine the centerline and transverse velocity profiles in the extruded molten film. It is concluded from this study that image processing techniques provide valuable insights into quantifying both the necking defect and the associated velocity profiles in the molten extruded film.

Reactive processing of poly(lactic acid)/poly(ethylene octene) blend film with tailored interfacial intermolecular entanglement and toughening mechanism

In order to obtain a uniform and effectively toughened poly (lactic acid) film by blending with low content of poly (ethylene octene) (POE) with high elasticity, the tailored interfacial intermolecular interaction and entanglement between the two phases of the PLA/POE blend was innovatively constructed via the facile reactive melt blending process through the reaction of the epoxy/anhydride groups grafted on the POE chains with the end groups of PLA chains (PLA/GPOE-MPOE). It was observed that POE domains were embedded tightly in PLA matrix with a fuzzy interface and abundant interface transition area, and the impact fractured surface of the blend showed an obvious plastic deformation with less occurrence of fibrillation of PLA matrix or interfacial de-bonding. Compared with neat PLA and directly blended PLA/POE blends, the PLA/GPOE-MPOE blend exhibited much higher complex viscosity/storage modulus, much lower tanδ values in the terminal region, and obvious strain-hardening behavior. The deviation in viscoelastic behavior of PLA/GPOE-MPOE from linear PLA indicated the enhanced molecular entanglement between the long-branched chains, resulting in an enhancement of the stretching ability during biaxial drawing of the blend. Uniform PLA/GPOE-MPOE films with draw ratio as high as 7 × 7 were obtained through biaxial stretching, which showed much higher tensile strength and the elongation at break than that of neat PLA and PLA/POE film. This work provides a facile method for fabricating toughening PLA films with application potentials.

Resolving long-chain branch formation in tandem catalytic coordinative chain transfer polymerization of ethylene via thermal analysis

Resolving long-chain branch formation in tandem catalytic coordinative chain transfer polymerization of ethylene via thermal analysis

Development of high melt strength polypropylene and its application in thermoplastic elastomeric composition

High melt strength polypropylene (HMS-PP) with a long-chain branched structure is a modified form of polypropylene (PP) which has basic properties of regular PP but with superior melt drawability. This paper reports on the development of gel-free HMS-PP from a linear isotactic PP through the introduction of long-chain branching on its backbone via a reactive extrusion process, using dicetyl-peroxydicarbonate (PODIC) alone or in combination with a coagent. The melt strength and the mechanical properties such as impact and flexural strength of PP showed improvements with the modification with PODIC. 5000 ppm by weight of PODIC was found to provide the best balance of properties. The efficacies of zinc diethyldithiocarbamate (ZDC) and tetramethyl thiuram disulphide (TMTD) as coagents in combination with PODIC to augment properties of HMS-PP further were explored. TMTD offered slightly enhanced performance benefits as compared to ZDC at an optimized concentration of 100 ppm by weight. The application potential of HMS-PP in thermoplastic elastomeric blends of HMS-PP with ethylene-propylene-diene monomer (EPDM) rubber at a fixed ratio of 35/65 by weight was also investigated. Structure-property correlations were established between the extent of long-chain branching in the modified PP and the properties of the resultant thermoplastic elastomeric composition.

A comprehensive study on recycled and virgin PET melt-spun fibers modified by PMDA chain extender

The effect of chain extender Pyromellitic dianhydride (PMDA) on the comprehensive properties of the virgin (vPET) and recycled Polyethylene terephthalate (rPET) fibers was investigated. Five different weight fractions of PMDA were melt mixed with PETs to create long-chain branched (LCB) structures. The modified LCB-PET granules were melt spun into fibers using a capillary rheometer at 270 and 280 °C, and then aerodynamically stretched by an aspirator at seven take-up pressures. The different shear viscosity, thermal properties and spinnability of LCB-vPET and LCB-rPET, and the surface morphology, draw ratios, tenacity, elongation at break of PET fibers, as well as the performance-reliability plots using Weibull distribution were well discussed. A semi-empirical mathematical model further confirmed the exponential relationship between the tenacity and elongation at break of the PET fibers. This research depicts a visible window for academic and industrial researchers to produce PMDA modified PET fibers with desirable comprehensive properties.

In Situ Promotion of Long-Chain Branching in Polyethylene from Ziegler–Natta Catalysts

Polyethylene (PE) synthesized by Ziegler–Natta catalysts (MgCl2/TiCl4 catalysts) lack long-chain branching (LCB) structure, which to a great extent limits their end uses. In this paper, we report an in situ methodology of incorporating LCB structure into PE of Ziegler–Natta catalysts. The chemistry centers on a bifunctional reagent, ω-alkenylmethyldichlorosilane, where the reagent is first copolymerized with ethylene to anchor on some polymer chains pendant alkylmethyldichlorosilane groups, then upon treating the polymer with water adjacent polymer chain-borne alkylmethyldichlorosilane groups undergo one-on-one interchain hydrolytic condensation forming a dimeric alkylmethylsiloxane bridge interconnecting two different polymer chains as H-shape LCB structure. Control of ω-alkenylmethyldichlorosilane concentration during copolymerization is key to realize the chemistry. Gel-free LCB-PEs containing controlled amounts of LCB structure were synthesized by accompanying the copolymerization with hydrogen (H2) as chain transfer agent. The effect of alkenyl chain length of ω-alkenylmethyldichlorosilane on the formation efficiency of LCB structure was studied. The chemistry was generally applicable to different Ziegler–Natta catalysts. LCB-PEs containing increasing amounts of LCB structure exhibited proportionally increased extensional flow properties. Moreover, compared to linear plain PE, LCB-PEs were overall found to increase crystallization rates and thus increase crystallinities.

Structure and Properties of Reactively Extruded Opaque Post-Consumer Recycled PET.

The recyclability of opaque PET, which contains TiO2 nanoparticles, has not been as well-studied as that of transparent PET. The objective of this work is to recycle post-consumer opaque PET through reactive extrusion with Joncryl. The effect of the reactive extrusion process on the molecular structure and on the thermal/mechanical/rheological properties of recycling post-consumer opaque PET (r-PET) has been analyzed. A 1% w/w Joncryl addition caused a moderate increase in the molecular weight. A moderate increase in chain length could not explain a decrease in the overall crystallization rate. This result is probably due to the presence of branches interrupting the crystallizable sequences in reactive extruded r-PET (REX-r-PET). A rheological investigation performed by SAOS/LAOS/elongational studies detected important structural modifications in REX-r-PET with respect to linear r-PET or a reference virgin PET. REX-r-PET is characterized by a slow relaxation process with enlarged elastic behaviors that are characteristic of a long-chain branched material. The mechanical properties of REX-r-PET increased because of the addition of the chain extender without a significant loss of elongation at the break. The reactive extrusion process is a suitable way to recycle opaque PET into a material with enhanced rheological properties (thanks to the production of a chain extension and long-chain branches) with mechanical properties that are comparable to those of a typical virgin PET sample.

Engineering of polybutylene succinate with long-chain branching toward high foamability and degradation

Long-chain branched (LCB) polybutylene succinate (PBS) was successfully prepared by the reaction of linear PBS with epoxy-based multifunctional oligomer and triglycidyl isocyanurate. The melt foamability of PBS with different LCB degree were evaluated by the batch foaming with supercritical CO2. The existence of LCB structures led to the increased complex viscosity and storage modulus, reduced loss factor and enhanced strain hardening behavior, leading to the enhancement of the foamability. It is discovered that the LCB-PBS had a broadened foaming window of 30 °C, and can obtained the maximum expansion ratio of 42.5 while that of linear PBS was only 14.5. Moreover, the cell morphology and expansion ratio of foamed sample can be easily adjusted by changing the LCB degree. Importantly, the PBS sample can still maintain good biodegradability with the appropriate modification. The degradability-foamability relationship of PBS was thoroughly discussed, which also can afford shed light upon the large-scale preparation of the biodegradable and foamable polyester.

Modelling of Elongational Flow of HDPE Melts by Hierarchical Multi-Mode Molecular Stress Function Model.

The transient elongational data set obtained by filament-stretching rheometry of four commercial high-density polyethylene (HDPE) melts with different molecular characteristics was reported by Morelly and Alvarez [Rheologica Acta 59, 797–807 (2020)]. We use the Hierarchical Multi-mode Molecular Stress Function (HMMSF) model of Narimissa and Wagner [Rheol. Acta 54, 779–791 (2015), and J. Rheology 60, 625–636 (2016)] for linear and long-chain branched (LCB) polymer melts to analyze the extensional rheological behavior of the four HDPEs with different polydispersity and long-chain branching content. Model predictions based solely on the linear-viscoelastic spectrum and a single nonlinear parameter, the dilution modulus for extensional flows reveals good agreement with elongational stress growth data. The relationship of dilution modulus to molecular characteristics (e.g., polydispersity index (PDI), long-chain branching index (LCBI), disengagement time ) of the high-density polyethylene melts are presented in this paper. A new measure of the maximum strain hardening factor (MSHF) is proposed, which allows separation of the effects of orientation and chain stretching.

Temperature gradient interaction chromatography of linear polyethylene and isotactic polypropylene

Samples of linear polyethylene and isotactic polypropylene were separated according to their average molar mass using temperature gradient interaction chromatography (TGIC) with mobile phases at near critical composition. It is known that at the critical mobile phase composition, the adsorption of polymers is very sensitive to variations of the temperature. This effect was utilized here. The temperature of the column (Hypercarb™) was changed from 80 °C to 170 °C according to a programmed temperature gradient. Polymers were first adsorbed in the column at 80 °C and desorbed by the temperature increase. In effect, the polymers eluted at different temperatures. The higher the molar mass, the higher both the elution temperature and the elution volume. This suggests that TGIC has the potential to improve separations of polyolefins according to their molar mass and will allow to separate polyolefins according to their long-chain branching content.

In Situ Compatibilization of Isotactic Polypropylene and High-Density Polyethylene by a Melt Cobranching Reaction

Incompatible polypropylene (PP) and polyethylene (PE) are difficult to separate in mixed recycling streams such as waste plastic packaging, which makes polyolefin mixtures unsuitable for high-quality products. In this work, based on the free radical branching reaction, a co-branching reaction of isotactic polypropylene (iPP) and high-density polyethylene (HDPE) blends was carried out in the presence of the peroxide, free radical regulator and multifunctional acrylate monomer, and a star-like long-chain branching (LCB) copolymer was obtained. The effect of in situ compatibilization on the structures and mechanical properties of iPP/HDPE was investigated, and the compatibilization mechanism was discussed. Results showed that the mechanical properties of the modified blends were largely improved, and efficient in-situ compatibilization of iPP and HDPE could be taken place in a wide process window. Moreover, the sizes of the dispersed phase in the modified blends were clearly decreased, and the interfacial thickness increased. Compared with the pure iPP/HDPE blend, the initial crystallization temperature of iPP in the modified iPP/HDPE blend was increased, and long branched chains of the LCB copolymers were physically entangled with the chemical identical homopolymers or even participated in the crystallization of iPP and HDPE. Thanks to the in situ compatibilization strategy, the compatibility of iPP/HDPE was significantly improved.