Influence of polyfunctional monomer on melt strength and rheology of long‐chain branched polypropylene by reactive extrusion

Long chain branching (LCB) were added to linear polypropylene (PP) using reactive extrusion in the presence of selected polyfunctional monomers (PFMs) and a peroxide of dibenzoyl peroxide (BPO). Fourier Transformed Infrared spectra (FTIR) directly confirmed the grafting reaction occurred during the reactive extrusion process. Various rheological plots including viscosity curve, storage modulus, Cole‐Cole plot, and Van‐Gurp plots, confirmed that the LCB structure were introduced into modified PPs skeleton after modification. In comparison with linear PP, the branched samples exhibited higher melt strength, lower melt flow index, and the enhancement of crystallization temperature. The LCB level in modified PPs and their melt strength were affected by the type of PFM used and could be controlled by the PFM properties and structure. PFMs with lower boiling points, such as 1, 4‐butanediol diacrylate (BDDA), could not produce LCB structure in modified PP skeleton. The shorter molecular chain bifunctional monomers, such as 1,6‐hexanediol diacrylate (HDDA), favored the branching reaction if their boiling points were above the highest extrusion temperature. And some polar groups, such as hydroxyl, in the molecule of PFM were harmful to the branching reaction, which might be attributed to the harm of the polarity of groups to the dispersion of PFM in PP matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of long‐chain branches of polypropylene on rheological properties and foam‐extrusion performances

The effect of modifying polypropylene by the addition of long‐chain branches on the rheological properties and performance of foam extrusion was studied. Three polypropylenes, two long‐chain‐branched polypropylenes and a linear polypropylene, were compared in this study. The modification was performed with a reactive‐extrusion process with the addition of a multifunctional monomer and peroxide. The rheological properties were measured with a parallel‐plate and elongational rheometer to characterize the branching degree. The change from a linear structure to a long‐chain‐branched nonlinear structure increased the melt strength and elasticity of polypropylene. Also, there was a significant improvement in the melt tension and sag resistance for branched polypropylenes. Foaming extrusion was performed, and the effect of the process variables on the foam density was analyzed with Taguchi's experimental design method. For this study, an L₁₈(2¹3⁵) orthogonal array was used on six parameters at two or three levels of variation. The considered parameters were the polypropylene type, the blowing agent type, the blowing agent content, the die temperature, the screw speed (rpm), and the capillary die length/diameter ratio. As a result, the most significant factor that influenced the foam density was the degree of long‐chain branching of polypropylene. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1793–1800, 2005     

A reactive extrusion process with the aid of ultrasound for preparing cross‐linked polypropylene

Introducing the crosslinked structure in polypropylene (PP) was highly desired to meet the requirement of high melt strength, which was a key for the application of PP in thermoforming, blow molding and foaming where elongation flows dominated. In this work, the power ultrasound was introduced into the reactive extrusion at the exit die of an extruder for preparing crosslinked PP. The main target was to maintain the highly crosslinked structure during reactive extrusion process in case of low peroxide concentration. The results of the dynamic rheological properties, melt flow index, and extensional viscosity measurement showed that the content of PP gel and the melt strength of PP increased obviously with the employment of a 300 W ultrasound while the contents of functional monomers and peroxide were constant. Fourier transform‐infrared spectroscopy analysis, differential scanning calorimeter characterization, and gel permeation chromatograph measurement proved that the increases of content of PP gel and melt strength of PP were caused by that the ultrasonic waves could induce the chain scission and recombination reaction when the PP melts flowed through the exit die assembled with a ultrasonic probe. POLYM. ENG. SCI., 57:821–829, 2017. © 2016 Society of Plastics Engineers     

长链支化聚丙烯的反应挤出制备及其流变和热力学性能研究

在过氧化引发剂和季戊四醇三丙烯酸酯(PETA)存在下,采用反应挤出法制备了长链支化聚丙烯（LCB-PP）。用旋转流变仪和差示扫描热法系统研究了纯的和改性PP的流变性能和热力学性能,并考察了不同过氧化引发剂对改性PP的性能和支化情况的影响。研究发现,单纯使用过氧化引发剂改性时,PP以降解为主;加入多功能单体PETA后,PP以接枝反应为主。流变行为研究发现,过氧化引发剂/PETA改性的PP,其流变性能呈现如低频处储能模量增大,剪切变稀行为明显,损耗角随频率变化出现平台区,零剪切黏度增大等特点,证明改性PP存在长链支化结构,通过公式计算发现改性PP的支化度较高。差士扫描量热分析表明,过氧化引发剂/PETA改性PP的结晶温度高于纯PP,这也说明改性PP存在长链支化结构。同时发现过氧化引发剂/PETA改性PP时,过氧化引发剂结构对改性PP的流变性能、热力学性能和支化度影响较小。     

Preparation and characterization of high melt strength polypropylene with long chain branched structure by the reactive extrusion process

The reactive extrusion of maleic anhydride grafted polypropylene (PP‐g‐MAH) with ethylenediamine (EDA) as coupling agent is carried out in a corotating twin‐screw extruder to produce long chain branched polypropylene (LCBPP). Part of PP‐g‐MAH is replaced by maleic anhydride grafted high‐density polyethylene (HDPE‐g‐MAH) or linear low‐density polyethylene (LLDPE‐g‐MAH) to obtain hybrid long chain branched (LCB) polyolefins. Compared with the PP‐g‐MAH, PE‐g‐MAH, and their blends, the LCB polyolefins exhibit excellent dynamic shear and transient extensional rheological characteristics such as increased dynamic modulus, higher low‐frequency complex viscosity, broader relaxation spectra, significantly enhanced melt strength and strain‐hardening behaviors. The LCB polyolefins also have higher tensile strength, tensile modulus, impact strength and lower elongation at break than their blends. Furthermore, supercritical carbon dioxide (scCO₂) is constructively introduced in the reactive extrusion process. In the presence of scCO₂, the motor current of the twin extruder is decreased and LCB polyolefins with lower melt flow rate (MFR), higher complex viscosity and increased tensile strength and modulus can be obtained. This indicates that the application of scCO₂ can reduce the viscosity of melt in extruder, enhance the diffusion of reactive species, and then facilitate the long chain branching reaction between anhydride group and primary amine group. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A rheological evaluation of linear and branched controlled-rheology polypropylenes

Commodity linear and branched polypropylene resins have been modified by means of peroxide initiated chemical degradation in a reactive extrusion process. Data collected from molar mass and linear viscoelastic property measurements have been used to evaluate the L“crossover modulus” and “modulus separation” rheological polydispersity measures and a theoretical justification is provided for the modulus separation index. In the past, these empirical methods have been used successfully to relate molar mass characteristics to rheological properties. Results obtained in this study confirm the validity of the modulus separation index for linear polymers and suggest that it should be used carefully in the analysis of data from branched polymers. Linear viscoelastic data are used to estimate the terminal relaxation time spectra of both the linear and branched materials and a new correlation between modulus separation and relaxation time polydispersity is given.     

Rheology and thermal behavior of long branching polypropylene prepared by reactive extrusion

Long‐chain branching polypropylene (LCB‐PP) was achieved by reactive extrusion in the presence of bifunctional monomer [1,6‐hexanediol diarylate (HDDA)] and peroxide of dicumyl peroxide (DCP). Influences of HDDA and DCP concentrations on the branching efficiency were comparatively evaluated. Fourier transformed infrared spectroscopy (FTIR) results indicated that the grafting reaction took place, and HDDA has been grafted on PP skeleton. In comparison with initial PP, some modified samples showed lower melt flow index because of a large number of LCB in their skeleton. Several rheology plots were used to investigate the rheological properties of the initial PP and modified PPs, and the rheological characteristics confirmed the LCB in modified PPs skeleton. DSC results showed that the crystallization temperatures of modified PPs were higher than those of initial PP and degraded PP, suggesting that the modified PPs had long‐chain branched structure. The contrastive investigation in the rheology of modified PPs suggested that proper concentrations of HDDA and DCP were more beneficial to producing LCB during reactive extrusion. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Reactive processing of LLDPES in corotating intermeshing twin-screw extruder. II. Effect of peroxide treatment on processability

Commercial ethylene–octene linear low-density polyethylenes (LLDPEs) were reactively extruded with low levels of a peroxide [2,5-dimethyl-2,5-di(t-butylperoxy)hexane] to modify polymer molecular structure and processing properties. Peroxide levels were kept low to avoid crosslinking. This article reports the effects of this reactive extrusion on viscoelastic properties. Rheological properties are more sensitive than are molecular structure characteristics to the changes produced by reactions of very low peroxide concentrations. Complex viscosity increases are seen, especially at low frequencies. Shear-thining behavior is also accentuated. The crossover between G′ and G″ moves to lower frequencies. A modified Cole–Cole presentation of these data shows that the elastic component is more predominant for extrusion-reacted materials. Peroxide-modified materials all have higher Bagley end correction values than those of barefoot resins. The former exhibit lower power indices (more shear thinning). All these properties indicate more long-chain branching and higher melt elasticity. However, die swell decreased as a function of peroxide concentration. Peroxide treatment results in an enhancement of elongational viscosity, both under isothermal and cooling conditions, along with a decrease in drawdown ability. The rheological changes parallel those reported earlier in molecular characteristics but are more sensitive and suitable to evaluate the effects of reactive processing. The effectiveness of the reactive extrusion process for improving processability of LLDPEs depends critically on the extrusion conditions. © 1995 John Wiley & Sons, Inc.     

Dynamic rheological properties of high‐density polyethylene/polystyrene blends extruded in the presence of ultrasonic oscillations

The linear rheological properties of high‐density polyethylene (HDPE), polystyrene (PS), and HDPE/PS (80/20) blends were used to characterize their structural development during extrusion in the presence of ultrasonic oscillations. The master curves of the storage shear modulus (G′) and loss shear modulus (G″) at 200°C for HDPE, PS, and HDPE/PS (80/20) blends were constructed with time–temperature superposition, and their zero shear viscosity was determined from Cole–Cole plots of the out‐of‐phase viscous component of the dynamic complex viscosity (η″) versus the dynamic shear viscosity. The experimental results showed that ultrasonic oscillations during extrusion reduced G′ and G″ as well as the zero shear viscosity of HDPE and PS because of their mechanochemical degradation in the presence of ultrasonic oscillations; this was confirmed by molecular weight measurements. Ultrasonic oscillations increased the slopes of log G′ versus log G″ for HDPE and PS in the low‐frequency terminal zone because of the increase in their molecular weight distributions. The slopes of log G′ versus log G″ for HDPE/PS (80/20) blends and an emulsion model were used to characterize the ultrasonic enhancement of the compatibility of the blends. The results showed that ultrasonic oscillations could reduce the interfacial tension and enhance the compatibility of the blends, and this was consistent with our previous work. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3153–3158, 2004     

Investigation on multifunctional monomer modified polypropylene and its foamability

1,6‐Hexanediol diacrylate (HDDA), pentaerythrithyl tetramethacrylate (PETMA), and triallyl‐isocyanurate (TAIC) were used as representative monomers to modify polypropylene (PP) in the presence of dicumyl peroxide (DCP) in a mixer. Fourier transformed infrared spectroscopy (FTIR) results confirmed that all the three polyfunctional monomers have been grafted on PP backbone. The shape of torque curves suggested the occurrence of grafting and/or crosslinking structure. The rheological behaviors of HDDA modified PP showed the highest G′ and lowest tan δ at low frequency, shear‐thinning shifted to lower frequency in η*–ω plot, as well as more deviation from semicircle characteristic of linear PP at high viscosity in Cole–Cole plot. And, the improvement of the mechanical properties followed the order as below: TAIC < PETMA < HDDA. Meanwhile, the foamability of the modified PP samples was also investigated. The cellular structure and morphology of the obtained foams were observed by scanning electron microscopy (SEM), and the results indicated that the foamability of the three modified PPs followed the same order, demonstrating HDDA modified PP foam possessed the highest cell density and expansion ratio, and the most well‐defined closed cell structure and uniformly cellular morphology. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1675–1681, 2013     

A study on the onset surface melt fracture of polypropylene materials with foaming additives

The melt fracture behaviors of linear and branched polypropylene resins with foaming additives were investigated. The effects of branching, processing temperature, additives, and blowing agent on the surface melt fracture of polypropylene materials were thoroughly studied. A CCD camera was installed at the die exit to precisely observe the onset of surface melt fracture of extruded foams. The critical wall shear stress was determined for various linear and branched polypropylene resins using a capillary die. It was found that the branching required to foam polypropylene resins also promotes melt fracture: the critical shear stress was decreased by 0.0175 MPa with an increase of 0.1 n/1000c in long‐chain branching. It was also observed that the dissolved blowing agent (butane) significantly suppressed the melt fracture of both linear and branched polypropylene resins. On the other hand, a noticeable increase in the critical shear stress of branched polypropylene materials was observed with the nucleating agent (talc) and the aging modifier (glycerol mono stearate), whereas almost negligible effect of the additives on the critical shear stress was observed for linear polypropylene materials. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The preparation and rheology characterization of long chain branching polypropylene

In order to study the rheological behavior of long chain branching (LCB) polypropylene (PP), linear polypropylene was modified by melt grafting reaction in the presence of 2,5-dimethyl-2,5(tert-butylperoxy) hexane peroxide and pentaerythritol triacrylate (PETA) in mixer. The transient torque curves and Fourier transformed infrared spectroscopy (FTIR) results indicated that macroradical recombination reactions took place and PETA had been grafted onto PP backbone. Various rheological plots including viscosity curve, storage modulus, loss angle, Han plot, Cole-Cole plot were used to distinguish LCB PP from linear PP. On the other hand, to quantify the LCB level in modified PPs, a new method was suggested on the basis of macromolecular dynamics models. The results showed that the level of LCB was in the range of 0.025-0.38/10⁴ C . Moreover, the length of the branched chains and the content of the branched component increase with PETA concentration. Furthermore, the LCB efficiency of monomer can also be calculated, less than 20% of grafting monomers was used to form branch structure.     

长链支化聚丙烯的制备及其熔体流变性能的研究

在过氧化物引发剂和季戊四醇三丙烯酸酯存在下,利用反应挤出法制备了长链支化聚丙烯(LCB-PP)。采用熔体流动速率(MFR)仪、旋转流变仪和熔体强度测试仪对纯聚丙烯(PP)及其改性PP进行测试与表征。讨论了不同的过氧化物引发剂对改性PP流变性能的影响。结果表明,采用过氧化苯甲酰时,改性PP具有较高的熔体强度、较低的MFR,并且在低频处储能模量增大。同时发现,随温度的升高,改性PP的熔体强度逐渐降低,但升高到一定温度后,熔体强度的变化不明显。     

Rheological behavior of polypropylene/novolac blends

The rheological behavior of polypropylene/novolac blends was investigated with special reference to the effects of the blend ratio, compatibilization, and dynamic cure. The polypropylene and all the polypropylene/novolac blends presented evidence of shear‐thinning behavior. The novolac, compatibilizer, and dynamic cure had dramatic effects on the rheological behavior of the polypropylene. Various rheological plots, including plots of the viscosity, storage modulus, loss modulus, and loss angle, Han plots, and Cole–Cole plots, were used to analyze the polypropylene/novolac blends. The results showed that the compatibilization together with the dynamic cure could increase the viscosity and modulus because of the formation of a grafting polymer between the maleic anhydride grafted polypropylene and the curing novolac resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Strategies for achieving ultra low‐density polypropylene foams

The volume expansion behavior of low‐density polypropylene foams in extrusion is investigated in this paper. Since escape of blowing agent from the foam would cause the foam to contract, and to have low expansion, efforts were made to prevent gas loss during foaming. The basic strategies to the promotion of a large volume expansion ratio are: to use a branched material for preventing cell coalescence; to use a long‐chain blowing agent with low diffusivity; to lower the melt temperature for decreasing gas loss during expansion; and to optimize the processing conditions in the die for avoiding too‐rapid crystallization. Use of a branched polypropylene resin was required to achieve large volume expansion because prevention of cell coalescence will retard gas loss from the extruded foam to the environment. The foam morphologies of linear and branched polypropylene materials at various processing temperatures were studied using a single‐screw tandem foam extrusion system and their volume expansion behaviors were compared. Ultra lowdensity, fine‐celled polypropylene foams with very high expansion ratio up to 90 fold were successfully produced from the branched polypropylene resins.     

Long chain branched impact copolymer of polypropylene: Microstructure and rheology

A biphasic impact copolymer of polypropylene (ICP) was modified with peroxide by reactive extrusion process resulting in reduced melt flow index, improved melt strength, and higher die swell. The polymers were for the first time subjected to systematic rheological and microstructural characterization in an effort to understand their structure‐property relations. In shear rheological tests, the modified ICP displayed higher flow activation energy, reduced values of loss tangent and nearly equal frequency dependence of storage and loss modulli. The modified ICP also showed strain hardening behaviour in uniaxial extensional rheology and higher crystallization temperature in differential scanning calorimetry (DSC). All these are definitive indications of the presence of long chain branches (LCB). Fitting the rheological data of modified ICPs with the eXtended Pom Pom (XPP) model indicated the presence of LCB on the higher molecular weight fraction in the polymer, a result which was corroborated with multi‐detector high temperature gel permeation chromatography (HT‐GPC). More importantly, the matrix and rubber phases of the ICP were separately characterized for presence of long chain branching by rheology, DSC and HT‐GPC. The results indicate that while LCB existed in the matrix phase, microgels were present in both phases indicating that the reaction with peroxide occurred in both phases. POLYM. ENG. SCI., 55:1463–1474, 2015. © 2014 Society of Plastics Engineers     

Shear‐induced β‐form polypropylene in long chain branching isotactic polypropylene

Long chain branching polypropylene (LCBPP) with different long chain branching (LCB) contents were prepared by reactive extrusion in the presence of styrene and benzoyl peroxide, and their shear‐induced crystallization behaviors were investigated. The results indicated that the LCB structure extended the relaxation time of LCBPP in the molten state, which led to the formation of β‐form polypropylene under shear and high cooling rate. The content of β‐form (K_β) increased with the increase of LCB content, shearing rate and cooling rate. The K_β value of LCBPP3 whose weight average molecular weight was 920,000 g mol^?1 could be up to 52.0% with a shear rate of 60 s^?1 associated with a cooling rate of 280°C min^?1. This study is expected not only to have a deeper understanding of the shear‐induced crystallization behavior of LCBPP, but also provide a new strategy to obtain high level β‐form polypropylene. POLYM. ENG. SCI., 56:240–247, 2016. © 2015 Society of Plastics Engineers     

Synthesis and characterization of high‐density polypropylene‐grafted polyethylene via a macromolecular reaction and its rheological behavior

High‐density polyethylene grafted isotactic polypropylene (PP‐g‐HDPE) was prepared by the imidization reaction between maleic anhydride grafted polyethylene and amine‐grafted polypropylene in a xylene solution. The branch density was adjusted by changes in the molar ratio between maleic anhydride and primary amine groups. Dynamic rheology tests were conducted to compare the rheological properties of linear polyolefins and long‐chain‐branched polyolefins. The effects of the density of long‐chain branches on the rheological properties were also investigated. It was found that long‐chain‐branched hybrid polyolefins had a higher storage modulus at a low frequency, a higher zero shear viscosity, a reduced phase angle, enhanced shear sensitivities, and a longer relaxation time. As the branch density was increased, the characteristics of the long‐chain‐branched structure became profounder. The flow activation energy of PP‐g‐HDPE was lower than that of neat maleic anhydride grafted polypropylene (PP‐g‐MAH) because of the lower flow activation energy of maleic anhydride grafted high‐density polyethylene (HDPE‐g‐MAH). However, the flow activation energy of PP‐g‐HDPE was higher than that of PP‐g‐MAH/HDPE‐g‐MAH blends because of the presence of long‐chain branches. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Flow behavior of polypropylenes with different molecular structures in a coat‐hanger die

An experimental investigation of the flow behavior of three polypropylene melts with different molecular structures during extrusion through a coat‐hanger die is presented. Two linear and one long‐chain branched material, rheologically characterized in shear and elongation, were investigated. Using laser–Doppler velocimeter measurements of the velocity profiles across the gap height were performed at five various locations along the die. The uniformity of the velocity distribution along the die has been assessed using the maximum velocities v₀ of the corresponding velocity profiles across the gap. The velocity distribution along the die changes with throughput and temperature. Regarding the rheological properties, it was found that the power‐law index of the viscosity as a function of shear rate has a decisive influence on the uniformity of flow but that the pronounced strain hardening in elongation typical of the long‐chain branched polypropylene is not reflected by the velocity distribution along the die. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Enhancement of graft yield and control of degradation during polypropylene maleation in the presence of polyfunctional monomer

Free‐radical initiated grafting of maleic anhydride (MAH)/polyfunctional acrylate (PFA) multimonomer system onto polypropylene (PP) via reactive extrusion was studied. The effects of PFA and initiator concentration on the grafting reaction were investigated. It was shown that PFA as a comonomer could greatly enhance MAH grafting degree, which increased monotonically as the molar ratio of PFA to MAH increased. The rheology test demonstrated that the viscosity of grafted PP was also promoted as more PFA was used. The formation of branched structure during the grafting process was proved by oscillatory shear rheological analysis. The mechanism of grafting in the presence of PFA was discussed, suggesting PFA had higher reactivity with PP macroradicals than MAH and therefore forming stabilized macroradicals, thus resulting in depression of β‐scission and favoring the formation of branched structure. Higher initiator concentration gave higher MAH grafting degree but more severe degradation. The mechanical properties of the grafted PP were comparable with those of unmodified PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011