Creep and Dynamic Mechanical Analysis Studies of Peroxide‐Crosslinked Ethylene‐Octene Copolymer

An ethylene‐octene copolymer (EOC) (45 wt% octene) is crosslinked using dicumyl peroxide (DCP). Differential scanning calorimetry (DSC) reveals a very low melting temperature (50 °C). The network density is evaluated by gel content. While 0.2–0.3 wt% of peroxide leads only to a molecular weight increase (samples completely dissolved in xylene), 0.4–0.6 wt% of peroxide caused network formation. High‐temperature creep was measured at 70, 120, and 200 °C at three stress levels. At 200 °C and above 0.6 wt% of peroxide, degradation due to chain scission is observed by rubber process analyzer (RPA) and is again supported by creep measurements. Residual strain at 70 °C is found to improve with increasing peroxide level. Dynamic mechanical analysis (DMA) reveals a strong influence of peroxide content on storage modulus and tan δ, in particular in the range 30–200 °C.

     

High-temperature study of radiation cross-linked ethylene–octene copolymers

Polymer Bulletin - Three ethylene–octene copolymers (EOC) with a wide range of octene content (17, 30, and 38 wt%) and with the same melt flow index of 1 g/10 min...     

Cross‐linking of ethylene‐octene copolymer (EOC) by dicumyl peroxide (DCP)

Ethylene‐octene copolymer (EOC) was crosslinked by dicumyl peroxide (DCP) at various temperatures (150–200°C). Six concentrations of DCP in range 0.2–0.7 wt % were investigated. cross‐linking was studied by rubber process analyzer (RPA) and by differential scanning calorimetry (DSC). From RPA data analysis real part modulus s', tan δ, and reaction rate were investigated as a function of peroxide content and temperature. The highest s'_max and the lowest tan δ were found for 0.7% of DCP at 150°C. Chain scission was analyzed by slope analysis of conversion ratio, X in times after reaching the maximum. Less susceptible to chain scission are temperatures in range 150–170°C and peroxide levels 0.2–0.5%. Heat of reaction was analyzed by DSC at various heating rates (5–40°C min⁻¹). It was found to be exothermic. By projection to zero heating rate, the reaction was found to start at 128°C with the maximum at 168°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Physical and mechanical properties of Al(OH)3/polypropylene composites modified by in situ‐functionalized polypropylene

Al(OH)₃/polypropylene (PP) composites modified by in situ‐functionalized polypropylene (FPP) were prepared by a one‐step melt‐extrusion process. The effect of in situ FPP on the crystallization and melting behavior, melt‐flow index, limiting oxygen index, thermal degradation, mechanical properties, and fracture morphology of Al(OH)₃/PP composites was studied. Formation of in situ FPP resulted in a decreased crystallization temperature and melting point of PP in the composites, an increased melt‐flow index, and improved tensile and flexural strengths of Al(OH)₃/PP composites, whereas the thermal degradation behavior and limiting oxygen index was not been influenced. The impact strength of the Al(OH)₃/PP composites modified by in situ FPP depended upon the content of the initiator, dicumyl peroxide, and the monomer, acrylic acid. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2850–2857, 2002; DOI 10.1002/app.10269     

封闭型异氰酸酯基功能化的POE对PBT的增韧研究

以封闭型异氰酸酯(BTAI)为功能单体、过氧化二异丙苯(DCP)为引发剂,制备了封闭型异氰酸酯基功能化的乙烯辛烯嵌段共聚物(POE-BTAI),并以此为增韧剂对PBT进行增韧.当增韧剂POE-BTAI含量一定时,PBT的抗冲击强度随着BTAI含量的增加而增大;同时,当BTAI含量一定时,PBT的抗冲击强度也随着增韧剂P...     

Crosslinking of poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)] using dicumyl peroxide as initiator

In order to modify poly [(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)] (PHBV), the crosslinking of this copolymer was carried out at 160 °C using dicumyl peroxide (DCP) as the initiator. The torque of the PHBV melt showed an abrupt upturn when DCP was added. Appropriate values for the gel fraction and crosslink density were obtained when the DCP content was up to 1 wt% of the PHBV. According to the NMR spectroscopic data, the location of the free radical reaction was determined to be at the tertiary carbons in the PHBV chains. The melting point, crystallization temperature and crystallinity of PHBV decreased significantly with increasing DCP content. The effect of crosslinking on the melt viscosity of PHBV was confirmed as being positive. Moreover, the mechanical properties of PHBV were improved by curing with DCP. When 1 wt% DCP was used, the ultimate elongation of PHBV increased from 4 to 11 %. A preliminary biodegradation study confirmed the total biodegradability of crosslinked PHBV. Copyright © 2004 Society of Chemical Industry     

Effect of Peroxide Concentration on the Modification of the LLDPE: Statistical Experimental Design and Thermal Properties

Summary The effect of small concentrations of dicumyl peroxide (DCP) on the modification of a linear low density polyethylene (LLDPE) during a reactive extrusion process was investigated. The experiments were arranged in a two level factorial design in order to evaluate the effect of temperature zones (X₁), peroxide concentration (X₂) and screw rpm (X₃) on the modification of LLDPE. The melt flow index (MFI) was used as a response variable. It was verified that the thermal properties, crystalline melting temperature (T_m), the heat of fusion (Hmelt) and the crystallinity degree (X%) decrease with the increasing of the peroxide concentration. The crystallization temperature (T_c) increased up to 0.05% w/w peroxide, whereafter the level stays almost constant. The gel content of the samples however indicated that a three-dimensional network was negligible in the experimental conditions used.     

Solvothermal process for grafting dibutylmaleate onto poly(ethylene‐co‐1‐octene)

Solvothermal process was successfully developed to graft dibutylmaleate (DBM) onto poly(ethylene‐co‐1‐octene) (POE) with dicumyl peroxide (DCP) as free radical‐initiator. FTIR spectra demonstrate that DBM is successfully grafted onto the backbone of POE by this novel method. The influences of DBM content, DCP concentration, POE concentration, reaction temperature and reaction time on the grafting copolymerization have been investigated in detail through grafting degree (GD). It is worthy to indicate that high grafting degree (above 15%) can be achieved through the one‐pot way when the graft reaction is carried out in 40 mL toluene at 150°C for 5 h with 1.6 g DBM, 6–8 g POE and 0.35 g DCP. This developed solvothermal process is becoming an effective way to prepare POE‐g‐DBM graft copolymers, and can be extended to other systems. In addition, TGA results show that the thermal properties of POE are enhanced after the grafting reaction. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structure development in melt spinning of poly(ethylene‐co‐octene) filaments with various comonomer contents

An experimental study of the spinnability and the variation in crystallinity and orientation of melt spinning of poly(ethylene‐co‐octene) with different contents of comonomers was carried out. The spinning behavior of these polymers was investigated under different draw‐down ratios and temperatures and correlated to spinline stress. The melt‐spun filaments were characterized by wide‐angle X‐ray diffraction birefringence, and differential scanning calorimetry. S‐1 is a high‐density polyethylene and S‐2, S‐3, and S‐4 have 16, 22, and 38 wt % octene. An orthorhombic unit cell was found in all four polymers, but a dominant hexagonal structure (perhaps mesophase) was found for the highest octene level (S‐4). The orientation factors for the a‐, b‐, and c‐axis of the orthorhombic crystal structure and a‐axis of the hexagonal phase were then calculated. The crystalline orientation behavior of the lower octene copolymers (S‐1, S‐2, and S‐3) are similar and can be represented as a “row‐nucleated“ structure. However, the orientation behavior of S‐4 was different. The uniaxial mechanical properties were also measured. The Young's modulus and tensile strength generally increased with birefringence for all polymers. With increasing content of octene, the Young's modulus showed a decrease from semicrystalline thermoplastic toward an elastomer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 9–22, 2004     

Property transitions in high‐density polyethylene/maleated poly(ethylene–octene)/calcium carbonate ternary composites

Ternary composites of high‐density polyethylene (HDPE)/maleated poly(ethylene–octene) (POE‐g)/calcium carbonate (CaCO₃) were prepared by the melt extrusion process. Crystallization behavior investigation and mechanical properties study showed that there existed a transition in both crystallization temperature (T_c) and impact strength of ternary composites. These transitions were attributed to the development of morphology, with variation of concentration of POE‐g in ternary composites. The strength of interfacial adhesion also influenced the property transitions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3361–3366, 2006     

Study on toughening effect of maleic anhydride‐grafted‐poly(ethylene‐octene) to EVOH and their compatibility

Blends of poly(ethylene‐co‐vinyl alcohol) (EVOH) with maleic anhydride‐grafted‐poly(ethylene‐octene) (POE‐g‐MAH) were prepared by blending extrusion in order to improve the toughness and flexibility of EVOH. The compatibility behavior of these blends with POE‐g‐MAH content range from 0 to 25 wt% was studied using mechanical, thermal, infrared, and morphology characterization techniques. The mechanical test results showed that POE‐g‐MAH can significantly improve the impact toughness of EVOH with a brittle‐tough transition appeared at the POE‐g‐MAH content of 20 wt%. A huge increase of toughness of the blend was also observed when the POE‐g‐MAH content was increased to 15 wt%. The thermal analysis of the blends demonstrated that the thermal stability of EVOH is improved with the addition of POE‐g‐MAH, adding 20 wt% or more POE‐g‐MAH can effectively decrease the crystallinity of EVOH and greatly improve compatibility between the two components. The existence of esterification between anhydride groups in POE‐g‐MAH and hydroxyl groups in EVOH in melt processing was confirmed using Fourier transform infrared technique. Morphology analysis of the Izod impact fractures has clearly shown the mechanisms for these blends to change from brittle to tough with increasing the POE‐g‐MAH content. POLYM. ENG. SCI., 53:2093–2101, 2013. © 2013 Society of Plastics Engineers     

Modification of polyethylene–octene elastomer by silica through a sol–gel process

In this study, tetraethoxysilane (TEOS) and a metallocene polyethylene–octene elastomer (POE) were chosen as the ceramic precursor and the continuous phase, respectively, for the preparation of new hybrids by an in situ sol–gel process. To obtain a better hybrid, a maleic anhydride‐grafted polyethylene–octene elastomer (POE‐g‐MAH), used as the continuous phase, was also investigated. Characterizations of POE‐g‐MAH/SiO₂ and POE/SiO₂ hybrids were performed by Fourier transform infrared (FTIR) and ²⁹Si solid‐state nuclear magnetic resonance (NMR) spectrometers, a differential scanning calorimeter (DSC), a thermogravimetry analyzer, and an Instron mechanical tester. The results showed that the POE‐g‐MAH/SiO₂ hybrid could improve the properties of the POE/SiO₂ hybrid because the interfacial force between the polymer matrix and the silica network was changed from hydrogen bonds into covalent Si? O? C bonds through dehydration of hydroxy groups in POE‐g‐MAH with residual silanol groups in the silica network. The existence of covalent Si? O? C bonds was proved by FTIR spectra. For the POE/SiO₂ and POE‐g‐MAH/SiO₂ hybrids, maximum values of the tensile strength and the glass transition temperature were found at 9 wt % SiO₂ since a limited content of silica might be linked with the polymer chains through the covalent bond. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 966–972, 2003     

Dynamically vulcanized blends of polypropylene and ethylene‐octene copolymer: Comparison of different peroxides on mechanical,thermal, and morphological characteristics

Thermoplastic vulcanizates (TPVs) are prepared by the dynamic vulcanization process, where crosslinking of an elastomer takes place during its melt mixing with a thermoplastic polymer under high shear. TPVs based on polypropylene (PP) with different grades of ethylene‐octene copolymers (EOC) were prepared with a coagent assisted peroxide crosslinking system. The effect of dynamic vulcanization and influence of various types and concentrations of peroxide were mainly studied on the basis of the mechanical, thermal, and morphological characteristics. Three structurally different peroxides, namely dicumyl peroxide (DCP), tert‐butyl cumyl peroxide (TBCP), and di‐tert‐butyl peroxy isopropyl benzene (DTBPIB) were investigated. The mechanical properties of the TPVs are primarily determined by the extent of crosslinking in the EOC and the degree of degradation in the PP phase. Among all peroxides used DCP gives best overall properties with low‐molecular‐weight EOC, whereas TBCP shows best property level with high‐molecular‐weight EOC‐based TPVs. These can be explained on the basis of the molecular characteristics of EOC and the nature of the peroxide used. Differential scanning calorimetery (DSC) and morphological analysis reveal that PP and EOC are a thermodynamically immiscible system. The melting endotherm was studied to determine the influence of various peroxides on crystallinity of the PP phase. Tensile fracture patterns were also analyzed to study the failure mechanism of the samples. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of ethylene/1‐octene copolymers from ethylene stock with tandem catalytic system

Tandem catalysis offers a novel synthetic route to the production of linear low‐density polyethylene. This article reports the use of homogeneous tandem catalytic systems for the synthesis of ethylene/1‐octene copolymers from ethylene stock as the sole monomer. The reported catalytic systems involving a highly selective, bis(diphenylphosphino)cyclohexylamine/Cr(acac)₃/methylaluminoxane (MAO) catalytic systems for the synthesis of 1‐hexene and 1‐octene, and a copolymerization metallocene catalyst, rac‐Et(Ind)₂ZrCl₂/MAO for the synthesis of ethylene/1‐octene copolymer. Analysis by means of DSC, GPC, and ¹³C‐NMR suggests that copolymers of 1‐hexene and ethylene and copolymers of 1‐octene and ethylene are produced with significant selectivity towards 1‐hexene and 1‐octene as comonomers incorporated into the polymer backbone respectively. We have demonstrated that, by the simple manipulation of the catalyst molar ratio and polymerization conditions, a series of branched polyethylenes with melting temperatures of 101.1–134.1°C and density of 0.922–0.950 g cm^?3 can be efficiently produced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Modification of acrylonitrile‐butadiene‐styrene terpolymer by graft copolymerization with maleic anhydride in the melt. II. Properties and phase behavior

The graft copolymerization of maleic anhydride (MAH) onto acrylonitrile‐butadiene‐styrene terpolymer (ABS) using dicumyl peroxide and benzoyl peroxide as the binary initiator and styrene as the comonomer in the molten state was described. The properties and phase morphologies of the modified products (ABS‐g‐MAH) were studied. The results indicate that the melt flow index (MFI) of ABS‐g‐MAH increases with the increase of MAH content, the initiator concentration, and the screw speed, whereas the MFI decreases with the increase of temperature. The impact strength and the percentage elongation of ABS‐g‐MAH both decreased and the tensile strength of ABS‐g‐MAH increased slightly as the grafting degree increased. The phase inversion behavior of the modified product was observed by transmission electron microscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2834–2839, 2004     

Methyl acrylate/1‐octene copolymers: Lewis acid‐mediated polymerization

Copolymerization of methyl acrylate (MA) with 1‐octene (1‐Oct) was conducted in the presence of free radical initiator, 2,2′‐azobis(2‐methylpropionitrile) (AIBN) using heterogeneous Lewis acid, acidic alumina. The polymers obtained were transparent and highly viscous liquids. The copolymer composition calculated from ¹H NMR showed alkene incorporation in the range of 10–61%. The monomodal nature of chromatographic curves corresponding to the molecular weight distribution in gel permeation chromatography (GPC) further confirmed that the polymers obtained are true copolymers. The number–average molecular weights (M_n) of the copolymers were in the range of 1.1 × 10⁴–1.6 × 10⁴ with polydispersity index of 1.75–2.29. The effects of varying the acidic alumina amount, time of polymerization, and monomer infeed on the incorporation of 1‐Oct in the polymer chain were studied. Increased 1‐Oct infeed led to its higher inclusion in the copolymer chain as elucidated by NMR. DEPT‐135 NMR spectral analysis was used to explicate the nature of arrangement of monomer sequences in the copolymer chain. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Graft reaction of acrylic acid onto metallocene‐based polyethylene‐octene elastomer

In this study, grafting of acrylic acid (AA) onto metallocene‐based polyethylene‐octene elastomer (POE) was investigated by using benzoyl peroxide as an initiator. Grafted product was characterized by using Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, X‐ray diffraction spectroscopy, and differential scanning calorimetry (DSC). Both the grafting percentage and the gel yield, at equilibrium, were higher for POE containing lower degree of comonomer content. In all cases, the crosslinking reaction was accompanied by the predominant graft reaction due to the competition of POE macroradical and excited AA. From the result of DSC and X‐ray characterizations, it was found that the change of crystallinity is slight when the gel is removed from POE‐g‐AA copolymers. It was also proven that the effect of gel formation on the properties of the copolymer could be neglected because of the low gel yield. So, the graft method proposed in this article can produce low gel yield copolymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2905–2912, 2002     

Fracture behaviour of controlled‐rheology ethylene–propylene block copolymers

The evolution of the molecular weight distribution and the thermal, mechanical and fracture behaviour of controlled‐rheology ethylene‐propylene block copolymers (ca 8 wt% ethylene content) has been analysed. Various concentrations of di‐tert‐butylperoxide were utilized. The melt flow index increased with the peroxide content due to the reduction of the molecular weight and the narrowing of the molecular weight distribution. However, the thermal behaviour and degree of crystallinity were not improved and some mechanical properties, such as the tensile strength and elongation at break, presented an anomalous behaviour. This trend can be explained by the presence of the elastomeric phase. The addition of peroxide influenced strongly the J–R curves obtained via the elastic–plastic fracture mechanics approach. The slope of these curves was markedly reduced with addition of peroxide to almost being flat for the highest concentration. This loss of ductility and the sudden decrease of the fracture toughness values with an increasing amount of peroxide were mainly due to the reduction in the molecular weight. Copyright © 2011 Society of Chemical Industry     

Silane grafting and moisture crosslinking of polyethylene: The effect of molecular structure

The silane grafting and moisture crosslinking of different grades of polyethylene have been investigated. Three types of polyethylene (HDPE, LLDPE, and LDPE) with different molecular structures and similar melt flow indices were selected. The initiator was dicumyl peroxide (DCP), and the silane was vinyltrimethoxysilane. The grafting reaction was carried out in an internal mixer. The extent of grafting and the degree of crosslinking were determined, and hot‐set tests were carried out to evaluate the crosslink structure of the different polyethylenes. The LLDPE had the highest degree of grafting, while the LDPE had the least. The rate of crosslinking for LDPE was higher than that of HDPE and LLDPE. The gel content of LDPE was higher than that of HDPE and LLDPE. Hot‐set elongation and the number‐average molecular weight between crosslinks (M_c) were lower for LLDPE and LDPE than for HDPE. Increasing the silane/DCP percentage led to peroxide crosslinking, thereby decreasing the M_c and hot‐set elongation. The number‐average molecular weight (M_n), molecular weight distribution, and number of chain branches were the most important parameters affecting the silane grafting and moisture crosslinking. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Melt free‐radical grafting of hindered phenol antioxidant onto polyethylene

A monomeric antioxidant (3) was prepared by reacting 3,5‐di‐tert‐butyl‐4‐hydroxybenzyl alcohol (1) with N‐[4‐(chlorocarbonyl) phenyl] maleimide (2). This reactive antioxidant was grafted onto polyethylene (PE) by melt processing with free‐radical initiators in a mini‐max molder. The IR spectra of the grafted PE showed that the monomeric antioxidant was introduced onto the PE. IR spectroscopic methods and titration were used for the quantitative determination of the extent of grafting of the monomeric antioxidant. Also, the extent of crosslinking was indicated by the gel content. Grafting occurred in the following order: dicumyl peroxide (DCP) > benzoyl peroxide > 2,2′‐azobisisobutyronitrile. The influences of the DCP concentration and monomeric antioxidant on the extent of grafting were studied. The effects of the reaction time and temperature were also determined. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2968–2973, 2000