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     

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.     

Rheology and melt strength of long chain branching polypropylene prepared by reactive extrusion with various peroxides

Long Chain Branching Polypropylenes were prepared in an extruder by a melt grafting reaction in the presence of various peroxides and a polyfunctional monomer of 1,6‐hexanediol diarylate. Fourier Transformed Infrared spectra and the rheological characteristics indicated that the grafting reaction added long branched chains to linear polypropylene (PP). In comparison to the initial PP, the branched samples exhibited higher melt strength, lower melt flow index, and enhancement of crystallization temperature. The branching number of the modified samples agreed well with their melt viscoelasticity and the improved degree of their melt strength. The branching level in modified PPs could be controlled by the property and structure of the peroxide used. Peroxides with lower decomposition temperature and more stable radicals after decomposition promoted the branching reaction, leading to the modified PPs with higher branching level and melt strength. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

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     

High-melt-strength polypropylene with electron beam irradiation in the presence of polyfunctional monomers

High-melt-strength polypropylene (PP) was achieved with irradiation by an electron beam generated from an accelerator in the presence of polyfunctional monomers (PFM). Among 16 PFMs, the relatively shorter molecular chain bifunctional monomers such as 1,4-butanediol diacrylate (BDDA) and 1,6-hexanediol diacrylate (HDDA) were the most effective for enhancing the melt strength of PP. The concentration and dose of the HDDA to obtain the high melt strength PP in irradiation under nitrogen gas atmosphere were 1.5 mmol/100 g PP and 1 kGy, respectively. DSC measurement and dynamic mechanical analysis showed that the thermal behavior of the high-melt-strength PP was different from that of the original PP. Crystallinity and crystallization temperature during cooling after heating were lower and higher in high melt strength PP than original PP, respectively. Elongational viscosity at 180°C of the high-melt-strength PP showed a remarkable increase at a certain elongational time with constant strain rate, demonstrating the typical property of high-melt-strength samples. This implies that a few higher molecular chains of PP, formed by intermolecular combination of its chain by HDDA in irradiation, give higher melt strength to induce entanglement of molecular chains. © 1996 John Wiley & Sons, Inc.     

Structure and melt rheology of long‐chain branching polypropylene/clay nanocomposites

Long‐chain branching polypropylene (LCB‐PP)/clay nanocomposites were prepared by melt blending in a twin‐screw extruder. The microstructure and melt rheology of these nanocomposites were investigated using x‐ray diffraction, transmission electron microscopy, oscillatory shear rheology, and melt elongation testing. The results show that, the clay layers are intercalated by polymer molecular chains and exfoliate well in LCB‐PP matrix in the presence of maleic anhydride grafted PP. Rheological characteristics, such as higher storage modulus at low‐frequency and solid‐like plateau in tan‐ω curve, indicate that a compact and stable filler network structure is formed when clay is loaded at 4 phr (parts per hundred parts of) or higher. The response of the nanocomposite under melt extension reveals an initial decrease in the melt strength and elongational viscosity with increasing clay concentration up to 6 phr. Later, the melt strength and elongational viscosity show slight increases with further increasing clay concentration. These results might be caused by a reduction in the molecular weight of the LCB‐PP matrix and by the intercalation of LCB‐PP molecular chains into the clay layers. Increases in the melt strength and elongational viscosity for the nanocomposites with decreasing extrusion temperature are also observed, which is due to flow‐induced crystallization under lower extrusion temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Supercritical carbon dioxide-assisted reactive extrusion for preparation long-chain branching polypropylene and its rheology

An environmental benign process, which uses supercritical carbon dioxide (ScCO₂) as a processing aid, is developed in this work to prepare long chain branching polypropylene (LCB-PP). Results from the oscillatory shear rheology, melt elongational behavior and Fourier transformed infrared spectroscopy (FTIR) show that long chains have been linked as branches to the original linear PP chains using scCO₂-assisted reactive extrusion in the presence of cumene hydroperoxide and 1,6-hexanediol diacrylate. Compared to the initial linear PP, the branched samples show higher storage modulus (G′) at low frequency, distinct strain hardening of elongational viscosity, lower melt flow rate, increased crystallization temperature and improvement of the melt strength. ScCO₂ can improve the branching efficiency of modified PPs. The elastic response, melt strength and strain hardening parameter of the modified PPs increase with increasing scCO₂ concentration, which is ascribed to scCO₂ acting as a plasticizer for reducing PP viscosity and a carrier for active chemical species.     

Preparation of long‐chain branching polypropylene and investigation on its foamability

In this work, zinc N,N‐dimethyldithiocarbamate (ZDMC) was used to mediate the melt modification of polypropylene (PP) with 1,6‐hexanediol diacrylate (HDDA) in an internal mixer in the presence of dicumyl peroxide (DCP). Fourier transformed infrared spectroscopy analysis revealed that HDDA was directly grafted onto PP backbone. The dependence of torque on processing time indicated that the presence of ZDMC restrained the degradation of PP, and the end‐torque value increased with the addition of ZDMC. Dynamic rheological measurement indicated that the modified PP possessed higher G′ and lower tan δ at low frequency, displaying an increase in η* and disappearance of Newtonian plateau in η*–ω plot, as well as larger radius of semicircle in Cole–Cole plot. All the rheological characterizations, together with the decreased gel content with the increase of ZDMC, confirmed the formation of long‐chain branching. Subsequently, the foamability of the modified samples was investigated by one‐step compression–molding process. The cellular structure and morphology of the obtained foams were observed by scanning electron microscopy, and the results showed that the addition of ZDMC decreased the cell size, increased the cell density, and brought about well‐defined closed cell structure. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

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     

Controlling melt reactions during preparing long chain branched polypropylene using copper N,N-dimethyldithiocarbamate

Effect of copper N,N-dimethyldithiocarbamate (CDD) on melt reactions during preparing long chain branched polypropylenes (LCB-PP) via free radical grafting was studied. The structure and rheological properties of the modified PPs were characterized. The results showed that CDD could efficiently control two side reactions, i.e. degradation of PP backbone and homopolymerization of multifunctional monomer (trimethylol propane triacrylate (TMPTA)) in the presence of peroxide. Meanwhile the addition of CDD also increased the efficiency of forming LCB structure. The reaction between CDD and active free radicals (carbon centered and alkoxy species) led to forming in situ dithiocarbamate radicals, which cannot attack PP backbone and are weaker initiator for TMPTA. The resultant dithiocarbamate radicals could react with the PP macroradicals and the acrylic radicals reversibly, which prolong the life time of PP macroradical and increase the reaction probability between macroradicals. The obtained LCB-PP showed high melt strength.     

Upcycling of polypropylene—the influence of polyethylene impurities

Long chain branching (LCB)—a well‐known industrial process—is shown as an innovative tool for the treatment of PP post‐consumer waste. The introduction of LCB by reactive extrusion does not only compensate the degradation during product life (e.g., thermally and UV‐induced chain scission), it also improves the melt properties (e.g., melt strength, strain hardening). Thus, not only a re‐cycling process, even a real “up‐cycling” can be achieved. Compared with virgin material, PP from post‐consumer waste contains impurities like other polyolefines (PE‐HD, PE‐LD, PE‐LLD, copolymers), the total removal is economically not viable. Hence, the focus of this work was the influence of PE‐HD on the LCB formation of PP. Based on model mixtures with virgin PP and 10% PE‐HD, it is shown that PE‐HD influences the mechanical properties and gel content of the chemically modified blend but has no detrimental effect on the improved melt properties. POLYM. ENG. SCI., 57:1374–1381, 2017. © 2017 Society of Plastics Engineers     

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     

Rheological properties of polypropylene modified by high‐intensity ultrasonic waves

A new method using high‐intensity ultrasonic waves, instead of peroxide‐aided reactive extrusion, was applied to modify a linear polypropylene into a branched structure. The ultrasonic waves induced chain scission and created reactive macromolecules of polypropylene successfully in the melt state without any peroxide. To enhance and control the recombination reaction during sonication, a multifunctional agent and an antioxidant were used. The rheological property measurements clearly confirmed that the modified polypropylene had a nonlinear branched structure. It showed shear‐thinning behaviors in its viscosities at low frequencies, high elastic behaviors in Cole–Cole plots, and a high rheological polydispersity index in comparison with a linear polypropylene. The degradation or recombination of polypropylene was adequately controlled by an antioxidant, which stabilized the structure during sonication. Also, the use of an antioxidant was quite effective in improving the extrusion processability by delaying the instability of the extrudate to a higher shear rate. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

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     

长链支化制备高熔体强度PP的研究

通过长链支化来改性PP，从而得到高熔体强度的PP。实验以丙烯酸酯类单体为接枝单体，过氧化物为引发剂，对PP进行了熔融接枝，重点考察了二官能团单体的改性情况。实验结果表明，二三官能团单体的改性效果较为明显；熔体流动速率随单体加入量增加而降低，随过氧化物浓度增加而升高；拉伸粘度谱图显示有明显的应变硬化现象；改性后产物的熔体强度变化明显；纯化后的产物经工外，差示扫描量热分析表明接枝反应的发生；索氏萃取法没有检测到凝胶的生成。     

反应挤出法制备高熔体强度聚丙烯

以1,6己二醇二丙烯酸酯（HDDA）为接枝单体,苯乙烯（St）为共聚单体对聚丙烯（PP）进行熔融接枝,并在反应体系中加入β成核剂,从而改变PP晶型,通过接枝长支链提高聚丙烯的熔体强度。研究了螺杆转速、引发剂用量、单体摩尔比及投料量对熔体流动速率和熔体强度的影响。采用傅里叶变换红外光谱仪、热重分析仪及X射线衍射仪等对改性材料的结构和性能进行分析。结果表明,在优化的反应条件下,接枝改性PP的熔体流动速率和熔体强度分别为0.70 g/10 min,10.00 kPa·s;热稳定性也比纯PP有很大程度提高。     

Molecular and structural analysis of epoxide‐modified recycled poly(ethylene terephthalate) from rheological data

A multifunctional epoxide chain extender (ADR4370S) was used to increase the molecular weight of recycled poly(ethylene terephthalate) (R‐PET). The extension processing was carried out by melt mixing reaction. The effects of ADR4370S content on the molecular structure [molecular weight, molecular weight distributions (MWDs), branching, and gel‐like structures] of modified R‐PET were rheologically investigated. The results showed that the complex and apparent viscosity of the modified R‐PET were larger than those of unmodified one. The solid‐like behavior of R‐PET was enhanced after the reactive modification. The increments of balancing torque, reaction peak, and shear‐thinning behavior became more pronounced by increasing the concentration of ADR4370S. Reactive modification was characterized by the presence of long‐chain branching resulted in a wider MWD. Modified Cole–Cole plots demonstrated a shift toward higher storage modulus values at a given loss modulus value for the modified R‐PET samples. High concentration of ADR4370S (>1.5 wt%) resulted in a polymeric structure near the sol–gel transition point whose linear viscoelastic properties obeyed scaling law. The relaxation time was prolonged with the amount of ADR4370S increase. The decrease in the melt point and crystallization temperature of the modified R‐PET was correlated to the presence of chain branching. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Effect of chain structure on the melt rheology of modified polypropylene

The effect of molecular structure of polypropylene (PP) on the melt rheological properties were investigated for electron irradiated polymer and di-2-ethylhexyl peroxy dicarbonate (EHPC)-treated polymer. The modifications were examined in terms of the rheological behaviors, molecular weight distribution, and the degree of branching. The high melt strength PP was obtained by irradiating with 50 and 80 kGy and adding EHPC. The modified PPs showed the strain hardening in the uniaxial elongational viscosity, though the linear elongational viscosity was lower than that of the unmodified PP. Low angle laser light-scattering measurements of the modified PPs showed the interesting results; high irradiation doses such as 50 and 80 kGy caused higher molecular weight chains branching. Nevertheless, the long branching chains were not detected for the EHPC modified PP, which also showed the strain hardening in uniaxial elongational flow. In this article, the relation between chain structure and rheological properties is discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1493–1500, 1999     

二丙烯酸酯参与的反应挤出制备长链支化PP

研究了二丙烯酸酯参与的反应挤出制备长链支化聚丙烯过程,重点考察了二丙烯酸酯双键间链段长度以及单体用量对长链支化程度的影响。结果表明,1,4-丁二醇二丙烯酸酯(BDDA)在聚丙烯分子链上具有较强接枝能力;在接枝率相当的情况下,悬垂双键参与偶合扩链的能力会随双键间链段长度增加而下降。单体接枝率增加以及悬垂双键反应能力增强均会使长链支化程度增大。随着二丙烯酸酯用量增加,长链支化程度增加;单体过量会使大分子自由基偶合扩链程度加重,导致局部交联形成凝胶。     

The melt grafting preparation and rheological characterization of long chain branching polypropylene

To study the rheological properties of long chain branching (LCB) polypropylene (PP), long chain branches (LCB) were grafted onto the linear PP by melt grafting reaction in the presence of a novel chain extender, poly(hexamethylendiamine-guanidine hydrochloride) (PHGH). The branching reactions between the functionalized PP and PHGH were confirmed by transient torque curves and FTIR. By differential scanning calorimetry (DSC) and polarized microscope measurements, the presence of long chain branching structures was further confirmed. Also, the viscoelastic properties of the LCB PP and linear PP under shear flow were investigated for distinguishing LCB PP from linear PP. It was found that the elastic response of LCB PP at low frequencies was significantly enhanced in comparison with that of the linear PP, implying a presence of a long relaxation time mode that was not revealed in linear PP. Moreover, the branching levels of LCB PP were quantified using a detailed method, which was in correspondence with the molar amount of PHGH grafted on PP.