Thermoplastic elastomers based on high‐density polyethylene,ethylene–propylene–diene terpolymer,and ground tire rubber dynamically vulcanized with dicumyl peroxide

Thermoplastic vulcanizates (TPVs) based on high‐density polyethylene (HDPE), ethylene–propylene–diene terpolymer (EPDM), and ground tire rubber (GTR) were dynamically vulcanized with dicumyl peroxide (DCP). The polymer blend was composed of 40% HDPE, 30% EPDM, and 30% GTR, and the concentration of DCP was varied from 0.3 to 3.6 parts per hundred rubber (phr). The properties of the TPVs were determined by evaluation of the gel fraction content and the mechanical properties. In addition, IR spectroscopy and differential scanning calorimetry analysis were performed as a function of the DCP content. Decreases in the Young's modulus of the blends and the crystallinity of HDPE were observed when the content of DCP was greater than 1.8 phr. The results regarding the gel content indicate that the presence of DCP promoted the crosslinking of the thermoplastic matrix, and optimal properties were obtained with 1.5% DCP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39901.     

Covulcanization of LLDPE/EMA blends using dicumyl peroxide

The effect of dicumyl peroxide (DCP) content on the gel fraction, mechanical, dynamic mechanical, and thermal properties of linear low‐density polyethylene (LLDPE)/ethylene‐co‐methyl acrylate (EMA) blends were studied. Gel content of the blends increases with increasing DCP content, and EMA is more prone to crosslinking than LLDPE. Wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC) were used to study the effect of DCP crosslinking on percent crystallinity and crystalline structure of the blends and individual components. At lower level of DCP loading, crosslinking process does not have significant effect on the crystalline structure of the LLDPE, which was confirmed from the percent crystallinity and lattice distance value. However, at higher DCP content, percent crystallinity decreases significantly. At lower EMA concentration (<50%), percent crystallinity and lattice distance remain unchanged up to 2 wt % of DCP. For EMA contents of more than 50 wt %, increasing DCP content reduces the crystallinity of the blends and increases the lattice distance. The highest level of mechanical and dynamic mechanical properties was observed for 60/40 LLDPE/EMA blends at 2 wt % DCP. Addition of LLDPE‐g‐MA (3 wt %) as a compatibilizer enhances the properties of the vulcanizates. Blends crosslinked with DCP up to 0.3 wt % can easily be reprocessed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal and mechanical properties of silane‐grafted water crosslinked polyethylene

The effects of linear low density polyethylene (LLDPE) grafting with vinyltrimethoxysilane by different types and contents of peroxide were studied. When grafting silane onto LLDPE, with 0.10 phr of Dicumyl peroxide (DCP) or 0.05 phr content of 2,5‐Dimethyl‐2,5‐di (tert‐butyl‐peroxy)‐hexane (DHBP), it was found that the grafting effect was improved; however, as Di(2‐tert‐butylperoxypropyl ‐(2))‐benzene (DIPP) or excess DHBP was used, LLDPE was supposed to cause self‐crosslinking, which reduced the grafting effect of silane and was invalid in the processing of extrusion. In this study, vinyl trimethoxysilane (VTMS) was grafted onto various polyethylenes (HDPE, LLDPE, and LDPE) using DCP as an initiator in a twin screw extruder. The grafted polyethylenes were able to crosslink utilizing water as the crosslinking agent. The effects of varied crosslinking time on the mechanical properties of the crosslinked polyethylenes were studied. It was found that the HDPE and LLDPE were apt to crosslink during the grafting process and thus decreased the grafting ratio. Multiple melting behavior was observed for crosslinked LDPE and LLDPE. Mechanical and thermal properties of the crosslinked PE are much better than that of uncrosslinked PE. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2383–2391, 2005     

DCP用量对动态硫化POE/PP热塑性弹性体性能的影响

研究了过氧化二异丙苯(DCP)用量对动态硫化乙烯一辛烯共聚物聚丙烯(POE/PP)体系的物理性能以及PP结晶形态和POE相态结构的影响。结果表明:随DCP用量的增加,POE/PP体系的交联密度增大,而断裂伸长率、永久变形和拉伸强度下降。过量DCP的加人会导致PP降解,使体系的熔体流动速率随DCP用量的增加呈上升趋势。DSC分析表明,随着DCP用量的增加,POE/PP体系结晶度下降。微观分析得出,DCP对POE/PP体系相态结构影响显著,当DCP用量为1份时交联POE以较小的颗粒均匀分布于PP连续相中。     

An investigation of chemical crosslinking effect on properties of high-density polyethylene

High-density polyethylene (HDPE) was chemically crosslinked with various amounts of di-tert butyl cumyl peroxide (BCUP). Crosslink density determined by rubber elasticity theory using hot set test showed an increase with increasing BCUP. Glass transition temperature (T_g), thermal stability, crystallization, melting behavior and tensile properties were studied. The results showed a new finding about decrease in T_g as a consequence of the ‘chemical crosslinking’ of HDPE. This was explained by observed reduction in crystallinity and expected increase in free volume as a result of restriction in chain packing. However, chemical crosslinking had no significant effect on the thermal stability. The stress at break, Young's modulus yield strength and elongation at break generally decreased with increase in BCUP. By increasing the temperature for slightly crosslinked HDPE, the elongation at break was increased but by increasing the crosslinking level an opposite effect was observed. Crosslinked HDPE showed an decrease in creep strain and an increase in creep modulus with increasing BCUP.     

Enhanced strain hardening in elongational viscosity for HDPE/crosslinked HDPE blend. I. Characteristics of crosslinked HDPE

Blending a crosslinked high‐density polyethylene (xHDPE) enhances melt strength and strain hardening behavior in elongational viscosity of high‐density polyethylene (HDPE) to a great degree. Gel fraction of xHDPE has a stronger effect on the strain hardening than sol fraction, although sol fraction also enhances the strain hardening to some degree. Further, the xHDPE crosslinked by peroxide in a compression mold exhibits more pronounced effect than xHDPE by radiation, which is attributed to the difference in the amount of the gel fraction. The xHDPE, which enhances the strain hardening, has sparse crosslink points in the network. Moreover, it was found from linear viscoelastic measurements, such as oscillatory modulus and relaxation modulus, that the xHDPE is characterized as a critical gel, which was also supported by the result of tensile testing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 73–78, 2002     

Thermal characteristics and temperature profile changes of structurally different polyethylenes with peroxide modifications

Crosslinking and processing characteristics of polyethylenes (PEs) with different molecular architectures, namely high‐density polyethylene (HDPE), linear low‐density polyethylene (LLDPE), and low‐density polyethylene (LDPE), were studied with regard to the effects of peroxide modifications and coolant flow rates. Dicumyl peroxide (DCP) and di‐tert‐butyl peroxide (DTBP) were used as free‐radical inducers for crosslinking the PEs. The characteristics of interest included normalized gel content, real‐time temperature profiles and their cooling rates, exothermic period, crystallinity level, crystallization temperature, and heat distortion temperature. The experiments showed that LDPE exhibited the highest normalized gel content. The real‐time cooling rates, taken from the temperature profiles for all PEs before the crystallization region, were greater than those after the crystallization region. The cooling rate of the PEs increased with the presence of DCP, whereas the crystallization temperature of the PEs was lowered. The HDPE appeared to show the longest exothermic period as compared with those of the LLDPE and LDPE. The exothermic period showed an increase with increasing coolant flow rate, but it was decreased by the use of DCP. As for the effect of peroxide type, the gel content and cooling rate of the PE crosslinked by DCP were higher than those for the PE crosslinked by DTBP. The DTBP was the more effective peroxide for introducing crosslinks and simultaneously maintaining the crystallization behavior of the PE. J. VINYL ADDIT. TECHNOL., 20:80‐90, 2014. © 2014 Society of Plastics Engineers     

Influence of dynamic crosslinking on the morphology,crystallization, and dynamic mechanical properties of PA6,12/EVA blends

This study investigated the effect of dynamic crosslinking of polyamide 6,12 and random copolymers of ethylene and vinyl acetate blends (PA6,12/EVA) on the morphology, crystallinity, and dynamic mechanical properties. The crosslinking agent was dicumyl peroxide (DCP), and the blends were processed in a torque rheometer. The morphology depended on the DCP content, and all blends exhibited the same crystallinity index. However, with increasing crosslinking degree, the interfacial tackiness (E) values increased from 1.8 to 2.7 nm. The lamellar structures of all blends started forming at approximately 160 °C, close to the temperature of pure polyamide. The crosslinked phase enhanced the pseudo‐elastic behavior of the blends and increased their molecular mobility activation energy. Samples with higher crosslinking degree exhibited smaller permanent deformation (0.01%) than those with low crosslinking. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44206.     

Peroxide modification of poly(butylene adipate‐co‐succinate)

We attempted to introduce crosslinking into poly(butylene adipate‐co‐succinate) (PBAS) to improve the properties, such as the mechanical strength and elasticity, by a simple addition of dicumyl peroxide (DCP). Prior to curing, the thermal stability of PBAS was investigated. Above 170°C PBAS was severely degraded, and the degradation could not be successfully stabilized by an antioxidant. The PBAS was effectively crosslinked by DCP, and the gel fraction increased as the DCP content increased. A major structure of the crosslinked PBAS was an ester and aliphatic group. The tensile strength and elongation of PBAS were improved with an increasing content of DCP, but there was little affect on the tear strength. The biodegradability of crosslinked PBAS was not seriously deteriorated. A higher degree of crosslinking gave a lower heat of crystallization and heat of fusion. However, the melt crystallization temperatures of the crosslinked PBAS were higher than that of PBAS. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 637–645, 2001     

化学交联PE-LD/SBS共混物的形状记忆效应研究

分别用3种不同苯乙烯含量的苯乙烯-丁二烯共聚物(SBS)与低密度聚乙烯(PE-LD)混合制成共混物,采用过氧化苯甲酰(BPO)为引发剂,使共混物发生化学交联形成网状结构,对交联共混物的交联度进行了分析,测试了交联共混物的拉伸强度与断裂伸长率,探讨了交联共混物的形状记忆效应。结果表明,在PE-LD/SBS共混物中,随着BPO含量的增加,共混物的交联度增大;BPO含量固定时,随着SBS中丁二烯含量的增大共混物的交联度增大;随着交联度的增加,共混物的拉伸强度与断裂伸长率均下降;当BPO含量为0.5 %～1.5 %时,交联共混物具有良好的形状记忆效应。     

Thermal and wide angle X‐ray analysis of chemically and radiation‐crosslinked low and high density polyethylenes

Low and high density polyethylenes (PE) were crosslinked by two methods, namely, chemically by use of different amounts of tert‐butyl cumyl peroxide (BCUP) and by irradiation with different doses of electron beam. A comparison between the effects of these two types of crosslinking on crystalline structure, crystallinity, crystallization, and melting behaviors of PE was made by wide angle X‐ray diffraction and DSC techniques. Analysis of the DSC first heating cycle revealed that the chemically induced crosslinking, which took place at melt state, hindered the crystallization process and decreased the degree of crystallinity, as well as the size of crystals. Although the radiation‐induced crosslinking, which took place at solid state, had no significant influence on crystalline region, rather, it only increased the melting temperature to some extent. However, during DSC cooling cycle, the crystallization temperature showed a prominent decrease with increasing irradiation dose. The wide angle X‐ray scattering analysis supported these findings. The crystallinity and crystallite size of chemically crosslinked PE decreased with increasing peroxide content, whereas the irradiation‐crosslinked PE did not show any change in these parameters. As compared with HDPE, LDPE was more prone to crosslinking (more gel content) owing to the presence of tertiary carbon atoms and branching as well as owing to its being more amorphous in nature. HDPE, with its higher crystalline content, showed relatively less tendency toward crosslinking especially by way of irradiation at solid state. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3264–3271, 2006     

汽车用PVC/热塑性聚氨酯交联电缆料的研制

以汽车用电缆料为试验目标,研究了增塑剂、引发剂、助交联剂、热塑性聚氨酯(TPU)的用量对PVC/TPU体系硬度、力学性能、热延伸率的影响,并考察了其耐磨性能和耐老化性能。结果表明:①在助交联剂TAIC存在下,引发剂DCP可引发PVC/TPU体系的交联反应,并且随着DCP、TPU用量的增加,交联度增大。②PVC/TPU交联电缆料的优化配方为:PVC 100份,钙锌稳定剂8份,TO TM 50份,TAIC 3份,DCP 0.2份,TPU 30份,抗氧剂0.8份,其他助剂适量;采用该配方能生产出合格的汽车用电缆料。     

Enhanced strain hardening in elongational viscosity for HDPE/crosslinked HDPE blend. II. Processability of thermoforming

Rheological properties and processability of thermoforming were studied for high‐density polyethylene (HDPE) and a blend of HDPE with crosslinked HDPE (xHDPE). Blending the xHDPE, which enhances melt strength and strain hardening in elongational viscosity of HDPE, helps the sheet avoid sagging in thermoforming. Moreover, the product of the blend obtained by vacuum forming has uniform wall thickness. Melt strength and strain hardening of the blend were, however, depressed by a processing history in a single‐screw extruder, whereas reprocessing by a two‐roll mill enhanced the melt strength again. It is considered that the processing history by a single‐screw extruder, in which shear‐dominant flow takes place, depresses the trapped entanglements between network chain of xHDPE and linear HDPE molecules, and results in low level of melt strength. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 79–83, 2002     

Exploring a novel cyclic monofunctional peroxide for curing of silicone rubber at elevated temperature

The curing characteristics of silicone rubber (polydimethylsiloxane [PDMS]) in the presence of structurally different peroxides, namely dicumyl peroxide (DCP) and 3,3,5,7,7‐pentamethyl‐1,2,4‐trioxepane (PMTO), have been studied in details. At moderate temperature, DCP is more prominent for curing the silicone rubber but at high temperatures it suffers from low scorch safety. An inhibitor 2,2,6,6‐tetramethylpiperidinyloxyl (TEMPO) was added with DCP to stabilize the radicals in order to increase the scorch safety time. On the other hand, PMTO showed a prolonged scorch safety and better crosslinking efficiency rather than (DCP + TEMPO) mix at higher temperatures. PMTO‐crosslinked PDMS shows better crosslinking efficiency as indicated by a higher gel content and low swelling index value. Also the mechanical properties, thermal stability, and dynamic mechanical behavior of PMTO‐crosslinked PDMS are much superior than (DCP + TEMPO)‐crosslinked PDMS. Apart from thermoplastic vulcanizates (TPVs) made from PMTO‐crosslinked PDMS show better physicomechanical behavior compared to the TPVs made from (DCP + TEMPO)‐crosslinked PDMS. Moreover, DCP undergoes decomposition reactions at a higher temperature and forms acetophenone, which leads to an unpleasant smell in the final products whereas no such phenomenon is observed for PMTO. Therefore, PMTO turns out to be the suitable peroxide for crosslinking of PDMS at higher temperature. POLYM. ENG. SCI., 57:1073–1082, 2017. © 2016 Society of Plastics Engineers     

SBS/PE-LD的强化交联与形状记忆效应研究

用苯乙烯丁二烯共聚物（SBS）与低密度聚乙烯（PE-LD）共混,采用过氧化二异丙苯（DCP）作为引发剂,3种不同的多官能团单体作为强化交联剂,使共混物发生强化交联形成网状结构,对多官能团单体的强化交联作用进行了分析,测试了交联共混物的拉伸强度与断裂伸长率,探讨了交联共混物的形状记忆效应。结果表明,多官能团单体的加入能够显著提高SBS/PE-LD交联共混物的交联程度,交联SBS/PE-LD共混物具有优异的形状记忆性能,形状固定率和形状回复率均可达100 %。     

Thermal and mechanical properties of uncrosslinked and chemically crosslinked polyethylene/ethylene vinyl acetate copolymer blends

Uncrosslinked and chemically crosslinked binary blends of low‐ and high‐density polyethylene (PE), with ethylene vinyl acetate copolymer (EVA), were prepared by a melt‐mixing process using 0–3 wt % tert‐butyl cumyl peroxide (BCUP). The uncrosslinked blends revealed two distinct unchanged melting peaks corresponding to the individual components of the blends, but with a reduced overall degree of crystallinity. The crosslinking further reduced crystallinity, but enhanced compatibility between EVA and polyethylene, with LDPE being more compatible than HDPE. Blended with 20 wt % EVA, the EVA melting peak was almost disappeared after the addition of BCUP, and only the corresponding PE melting point was observed at a lowered temperature. But blended with 40% EVA, two peaks still existed with a slight shift toward lower temperatures. Changes of mechanical properties with blending ratio, crosslinking, and temperature had been dominated by the extent of crystallinity, crosslinking degree, and morphology of the blend. A good correlation was observed between elongation‐at‐break and morphological properties. The blends with higher level of compatibility showed less deviation from the additive rule of mixtures. The deviation became more pronounced for HDPE/EVA blends in the phase inversion region, while an opposite trend was observed for LDPE/EVA blends with co‐continuous morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3261–3270, 2007     

Silane‐crosslinked ethylene–octene copolymer blends: Thermal aging and crystallization study

Thermally stable materials can be achieved by crosslinking. This article presents the thermal aging and thermal energy storage properties of ethylene–octene copolymer (EOR) and low‐density polyethylene (LDPE) blends as affected by silane crosslinking. Fourier transform infrared spectroscopy revealed a similar degree of silane grafting among the various blend compositions. However, the highest crosslink content was observed in EOR, whereas the lowest was found for LDPE. From melting temperature and heat of fusion data, a linear relationship between the amount of the crystalline component and the crosslink content was found. The decrease in crystallinity due to crosslinking was very limited, which implied a high thermal energy storage capacity of the silane‐crosslinked products and their good mechanical properties at room temperature. Furthermore, a strong ability to retain the properties after thermal aging indicated good thermal stability of the materials. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of EVA copolymer on properties of different polyethylenes in silane crosslinking process

Abstract

The effect of molecular structure of polyethylene (PE) [low density PE (LDPE), linear LDPE and high density PE] and silane/peroxide concentration on the grafting level and gel content in silane crosslinking process has been studied. The effect of incorporation of ethylene vinyl acetate (EVA) copolymer on the rate of crosslinking and thermal properties of PEs has been reported. The order of gel content was LDPE>linear LDPE>high density PE. With the incorporation of EVA, the rate of crosslinking increased. The degree of crystallinity did not change with crosslinking significantly. However, the shape of melting and crystallisation peaks changed, and two regions due to gel and sol parts were formed. In EVA/PE blends, two melting points were observed for both crosslinked and uncrosslinked samples. The SEM images showed the droplet matrix morphology with the EVA as the dispersed phase, especially for EVA/LDPE blend. The EVA/PE blends failed in hot set test, while the origin of PEs passed the hot set test successfully.     

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     

Crystallinity as a selection criterion for engineering properties of high density polyethylene

The Differential Scanning Calorimeter (DSC) was used to discriminate among 25 commercial high density polyethylenes (HDPE) on the basis of their degree of crystallinity and melting temperature. The area under the melting endotherm correlated directly with density and inversely with creep and thermal expansion measurements. Since high crystallinity was related to the design required properties of density, creep, and thermal expansion, DSC studies readily identified eight of the more promising polymers from the group of 25. The overall crystallization kinetics of polyethylenes with 75 percent crystallinity were analyzed by the Avrami and Fischer-Turnbull equations. Results indicate small disk-like spherulites (Avrami n = 2) following nucleation-controlled growth kinetics. These conclusions are in reasonable agreement with polarizing microscope observations. An equilibrium melting temperature between 141 and 142°C was estimated from Hoffman-Weeks plots. Processing thick parts from highly crystalline polyethylene is difficult because of the 14 percent volume change on crystallization. Higher degrees of crystallinity are associated with moderate molecular weight, so the viscosity range of these polyethylenes is not especially suited for processing by extrusion. These caveates necessitate tradeoffs between optimal design properties and processing requirements for HDPE parts.