Effect of radiation on the crosslinking and branching of polypropylene

To make crosslinked polypropylene (PP) and PP with high melting strengths, we studied the effects of radiation on the crosslinking and branching of PP in detail with the Charlesby–Pinner (C–P) equation. We studied the radiation crosslinking and branching behavior of homopolypropylene (HPP), impact copolypropylene (IPP), and random copolypropylene (RPP) and used the C–P equation for some parameter calculations. We found that (1) the C–P equation seemed applicable when PP with a multifunctional crosslinking agent was irradiated within a certain dose range in air and (2) IPP had the highest gel dose value, crosslinking G value/scission G value, and gel fraction after irradiation among HPP, RPP, and IPP; therefore, IPP is the best material for making radiation crosslinking and radiation branching PP among HPP, RPP, and IPP. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1758–1764, 2002     

Grafting modification and properties of polypropylene with pentaerythritol tetra-acrylate

The α-β transition of isotactic polypropylene (PP) under stress hasn’t received much attention although it may cause deterioration of mechanical properties. PP was modified by grafting polyfunctional monomer, pentaerythritol tetra-acrylate (PETeA) carried out in a Haake mixer at 180 °C in the presence of 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane peroxide (DDHP) to enhance the melt strength and suppress formation of β crystal and α-β transition. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-rays diffraction (XRD), polarized optical microscopy (POM) and melt flow index (MFI) were used to characterize the microstructure and properties of the grafted PPs. The FTIR spectra and transient torque results indicated that the acrylic polymers were grafted onto the polypropylene chains. The grafted polypropylenes gave both high crystallization and melting temperatures, and lowered the spherulite dimensions, and increased the melt strength. The grafted branching polyacrylics retarded segmental chain movement during processing and seemed to recover the depression in fatigue experiment to some extent. This work will be benefit to the extensional processing and especially provide the information on the fatigue stability of crystal structure of isotactic polypropylene during the engineering application.     

Effects of linear low density polyethylene on physical properties and irradiation effectiveness of polypropylene

Blends of polypropylene (PP)/linear low density polyethylene (LLDPE) were prepared by melt mixing in twin screw extruder at 190 °C. Polyfunctional monomer TMPTMA (trimethylolpropane-trimetacrylate) was added to the mixture as a crosslinking co-agent to improve the crosslinking or branching efficiency of the olefins during irradiation. The effect of LLDPE on the crosslinking or branching effectiveness and physical properties of PP was investigated in conjunction with the monomer content of LLDPE in the blends. Thermal stability, rheological properties and electron beam irradiation effectiveness of PP in presence of LLDPE were analyzed by DSC, TGA and RDS. Solution gel analysis and the presence of ?C=O in FT-IR test supported some crosslinking or branching that occurred after irradiation. Certain decrease in melting temperature (T _m ) that was noticed after irradiation could have been the result of chain scissioning, which decreases the number of tie molecules in the amorphous region and consequently weakens the lamellar connections. Shear thinning effect and zero shear viscosity were improved by irradiation in the PE incorporated samples.     

Improving melt strength of polypropylene by minimal branching and blending

Branched polypropylenes (PPb) with markedly improved melt strength were produced without significantly affecting the processability of the original PP. A two-step process of functionalization with MA and crosslinking with m-XDA was used, both by batch mixing and by extrusion. Branching degrees of ~0.06 LCB/1000 monomer units or smaller were obtained. All PPbs display clear and significant strain hardening, being the PPb obtained by extrusion the one that shows the largest melt strength. This polymer has a zero-shear-rate viscosity slightly smaller than that of PP while its strain-hardening index is about 10 times higher. Moreover, the nonlinear behavior of PP at elongation begins at a time similar to its terminal relaxation time or larger, while the ratio of these times reduces significantly with branching. PP/PPb blends were prepared to extend the range of obtainable melt strength in PP. They display rheological behavior between those of the mixed polymers with slight positive deviation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48845.     

Reactive extrusion of PP/natural rubber blends

Reactive extrusion of polypropylene (PP)/natural rubber (NR) (90/10) blends was conducted in the presence of a peroxide [1,3-bis(t-butylperoxy)benzene] and coagent (trimethylolpropanetriacrylate, TMPTA). Effects of peroxide and coagent content were studied in terms of melt index (MI), melt viscosity, morphology, thermal, and mechanical properties. At a constant content of the coagent, melt viscosity increased at a low and decreased at a high content of the peroxide. On the other hand, melt viscosity increased monotonically with the coagent concentration at constant peroxide content. The increase and decrease of viscosity were interpreted in terms of crosslinking and chain scission of PP, which governed the rubber domain size and mechanical properties of the reactive blends. © 1995 John Wiley & Sons, Inc.     

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.     

Structure and mechanism of functional isotactic polypropylene via in situ chlorination graft copolymerization

This paper discusses the structure and mechanism of maleic anhydride (MAH) grafted onto isotactic polypropylene (iPP) via in situ chlorination graft copolymerization (ISCGC). The molecular structure of the grafted iPP was characterized using ¹H NMR and ¹³C NMR spectroscopy, viscosity‐average molecular weight and gel content. The structure of un‐grafted MAH present in the reaction system was investigated using Fourier transform infrared spectroscopy in order to explore the grafting of MAH on iPP. The main side‐reactions, including iPP chain scission and crosslinking, during the grafting reaction were explored. From the experimental results obtained, the reason for controlled macromolecular chain degradation and crosslinking of grafted iPP in ISCGC is proposed. Based on the structural characterization of the grafted polymer, the mechanism of grafting onto iPP obtained via ISCGC was deduced. Mechanical properties, both static and dynamic, of grafted iPP were also investigated and the results showed that the properties of the material changed due to grafted MAH. Copyright © 2011 Society of Chemical Industry     

长链支化聚丙烯的流变性能研究

利用反应挤出法制备了长链支化聚丙烯,采用旋转流变仪和毛细管流变仪对纯聚丙烯及其改性聚丙烯进行测试,用流变学理论进行表征。结果表明,聚丙烯加入支化剂后,产生了长支链,分子量增大,分子量分布变宽;在一定范围内,随着支化剂量的增大,其支化程度增加;在低频处,能模量G'比损耗模量G″对长支链的出现及量变更敏感;加入支化剂后熔体强度明显增大,且支化的程度越高熔体强度越大,可拉伸性变小,能有效地改善材料的加工性能。     

X‐ray irradiated LDPE/PP blends with high mechanical and dielectric performance

In this study, the influences of polypropylene (PP) additive (varying from 20% to 80% wt) and low dose X‐ray irradiation (changing from 25 to 100 Gy) on the mechanical and dielectric properties of low‐density polyethylene (LDPE) were investigated. LDPE/PP film blends were prepared by hot press technique. While the highest Young modulus and tensile strength were observed for the 20%LDPE/80%PP blend at 25 Gy X‐ray irradiation, the same blend had the highest energy at break and percentage strain at break values for 50 Gy X‐ray exposure. These results also indicated a chain scission in the material. The differential scanning calorimetry curves also indicated a chain scission and crosslinking effects in the blends due to X‐ray irradiation. Hence, the higher concentration of PP additive and exposure of low dose X‐ray resulted in a polymer composite with high mechanical performance. On the other hand, the dielectric investigations revealed that the 25 Gy X‐ray irradiated 20%LDPE/80%PP blend may also attract attention for capacitor applications due to its increased static dielectric constant and reduced dielectric loss. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46571.     

Experimental verification on UCST phase diagrams and miscibility in binary blends of isotactic, syndiotactic, and atactic polypropylenes

Issues in blends of polymers of the same chemical repeat unit but with different tacticities were addressed by investigating on the phase behavior and interaction strength of binary blends of three polypropylenes of different tacticities, i.e., isotactic polypropylene (iPP), syndiotactic polypropylene (sPP), and atactic polypropylene (aPP) using polarized optical microscopy (POM) and differential scanning calorimetry (DSC). Although blends of polypropylenes have been widely studied in the past, there are still on-going debates on true phase behavior (miscibility vs. upper critical solution temperature (UCST) or immiscibility). Except for several earlier theoretical predictions based on the Flory-Huggins mean field theories, UCST behavior had not been experimentally proven for blends of sPP/iPP or aPP/sPP, owing to interference from PP crystallinity. In addition, interaction strength of the blends of different tactic polypropylenes is yet to be established. Using the method of equilibrium melting points, the Flory-Huggins interaction parameter of the aPP/iPP blend was shown to possess a significantly negative value (χ₁₂ = −0.21), which proves that the blend is indeed miscible in the melted amorphous as well as semicrystalline states as previously reported in the literature. However, the interaction parameters for the sPP/iPP and aPP/sPP blends were found to be nearly zero (χ₁₂ = −0.02 and −0.0071, respectively, at T = 150-180 °C), indicating that the interactions in two blends are weak and that the corresponding phase behavior for them borders on immiscibility at ambient temperature. This study also utilized novel approaches in constructing UCST phase diagrams by separating the amorphous phase domains from the crystalline spherulites, yielding data plausible for experimentally determining the UCST in iPP/sPP blend vs. aPP/sPP blend.     

Crystallization and orientation development in fiber and film processing of polypropylenes of varying stereoregular form and tacticity

We investigated the crystallization and orientation development in melt spinning and tubular blown film extrusion of several different types of polypropylenes, including conventional high tacticity isotactic polypropylenes (iPP) and metallocene catalyst low tacticity iPPs and syndiotactic polypropylenes (sPP). The fiber and film samples were characterized by wide‐angle X‐ray diffraction (WAXD), birefringence and differential scanning calorimetry (DSC). In melt spinning iPP, we found that the mesomorphic structure of iPP is more readily formed in lower tacticity fibers, and significant amounts of hexagonal β‐form crystals are found in low tacticity iPP fibers spun at high draw‐down ratios. Low tacticity iPP fibers exhibited a significant decrease in the crystalline chain‐axis orientation at high draw‐down ratios, resulting from increased epitaxially branched lamellae. Melt‐spun sPP fibers exhibit Form I helical structure at low spinning speeds and Form III zigzag all trans structure at high spinning speeds. We found that the level of spinline stress is the governing factor for this structural change. Melt‐spun sPP fibers exhibit much higher chain‐axis (c‐axis) orientation factors (f_c) and lower birefringence than iPP fibers spun at the same spinline stresses. In tubular blown sPP films, the a‐axis of Form I unit cell tends to orient perpendicular to the film surface, while the b‐axis of monoclinic α unit cell does so in iPP blown films.     

Study on mechanical properties of perlite‐filled gamma‐irradiated polypropylene

This study covers the preparation and characterization of perlite‐filled polypropylene (PP). The compositions of 15, 30, and 50 % by weight perlite–PP composites were prepared by melt‐mixing. The PP used in this study was either applied in the virgin form or γ‐irradiated in air at the doses of 10, 25, 50, and 100 kGy to determine the effect of oxidative degradation in composite properties. Furthermore, the active sites containing oxygen produced by γ‐irradiation in PP may provide a possible enhancement by the interfacial interaction between perlite and PP. An initial sharp drop in torque readings during the melt‐mixing of perlite–PP composite preparation indicated an extensive chain scission and degradation by γ‐irradiation. The thermal properties of the composites were characterized by DSC. The ultimate tensile strength and elongation and also impact strength decreased in all composites with γ‐irradiation. Yet, these changes appeared not to be faster than was the change in unfilled PP upon irradiation. Scanning electron microscopy revealed an interfacial adhesion between perlite and irradiated PP while virgin PP did not show any evidence of adhesion. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2670–2678, 2001     

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     

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     

A 13C-n.m.r. study of radiation-induced racemization in isotactic polypropylene

Unexpectedly large changes in the stereochemistry of isotactic polypropylene have been observed by ¹³C-n.m.r. following γ-irradiation at 25°C up to 250 kGy. The observed G-value of 64 for the loss of isotactic triads is much higher than previously reported G-values for scission, crosslinking or hydrogen formation in irradiated polypropylene. A mechanism of initial chain scission, racemization and subsequent recombination is indicated. The pattern of pentad sequences is inconsistent with the occurrence of isolated random racemization events; this suggests that the energy released on recombination promotes a second racemization within a range of 1–3 monomer units.     

苯乙烯接枝改性聚丙烯制备及其性能

以过氧化苯甲酰为引发剂,采用反应挤出法将苯乙烯(St)接枝到等规聚丙烯(iPP)上,并考察了St浓度对接枝PP结晶性能、流变性能和发泡性能的影响。由FTIR、GPC和MFR表征结果表明St成功接到PP上;DSC结果表明,接枝PP结晶峰值温度与iPP相比最大提高了15.4℃;由剪切流变测试结果,在低频区,接枝PP的G'值增大,出现明显的剪切变稀现象,tan δ-ω曲线中出现平台,说明接枝PP中有长支链结构的存在;由于接枝PP的熔融流动速率降低即熔体强度提高,使得接枝PP的泡孔更规则。     

Degradation of poly(D,L‐lactic acid)‐b‐poly(ethylene glycol)‐b‐poly(D,L‐lactic acid) copolymer by electron beam radiation

This article investigates the effects of electron beam (EB) radiation on poly(D ,L ‐lactic acid)‐b‐poly (ethylene glycol) copolymer (PLA‐b‐PEG‐b‐PLA). The copolymer films were EB irradiated at doses from 0 to 100 kGy. The degradation of these films was studied by measuring the changes in their molecular weight, mechanical and thermal properties. The dominant effect of EB radiation on PLA‐b‐PEG‐b‐PLA is chain‐scission. With increasing irradiation dose, recombination reactions or partial crosslinking may occur in addition to chain scission. The degree of chain scission G_s and crosslinking G_x of sample are calculated to be 0.213 and 0.043, respectively. A linear relationship is also established between the decreases in molecular weight with increasing irradiation dose. Elongation at break of the irradiated sample decreases significantly, whereas its tensile strength decreases slightly. The glass transition temperature (T_g) is basically invariant as a function of irradiation dose. Thermogravimetric analysis shows that its thermal stability decreases with increasing dose. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of gamma radiation on two aromatic polysulfones

Two aromatic polysulfones, poly(oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4-phenyleneisopropylidene-1,4-phenylene) (I) and poly (oxy-1,4-phenylenesulfonyl-1,4-phenylene) (II), undergo crosslinking and chain scission at 30°C during γ-irradiation, the former being predominant in vacuum and the latter in air. Both processes occurred more readily in I, which contains isopropylidene linkages. Gel measurements gave G(crosslink) = 0.051, G(scission) = 0.012 for this polymer at 30°C in vacuum. Increased irradiation temperatures resulted in higher crosslinking and gas yields, especially above the glass transition temperature. The tensile strength, flexural strength, and modulus of I were unaffected by γ-irradiation up to about 50 Mrad in air, but the strength decreased markedly at higher doses. The elongation at break decreased progressively with dose. For both polymers, G(gas) = 0.04 at 30°C with the main products being SO₂, H₂, CO₂, CH₄, and H₂O.     

Effect of matrix graft modification using acrylic acid on the PP/Mg(OH)2 composites and its possible mechanism

The matrix graft modification using an acrylic acid (AAc) was employed on the polypropylene/Mg(OH)₂ flame-retardant composite. The graft modification of PP matrix was carried out via an in-situ reactive extrusion by a twin-screw extruder. The tensile strength of the composites was analyzed using an equation developed by Pukanszky from which both matrix tensile strength σ₀ and interfacial adhesion strength were found to be increased. The enhancement of σ₀ is due to the intermolecular crosslinking of PP by AAc grafting. This crosslinking causes increases of tensile strength, Young’s modulus, impact resistance, and thermal resistance, but decreases the elongation at break of the composites.     

Rheological analysis of the degradation of HDPE during consecutive processing steps and for different processing conditions

Using a twin‐screw extruder, HDPE has been processed six times consecutively under a range of processing conditions (changing barrel temperature, screw speed, and feed rate). After each pass, the product has been analyzed in terms of the melt flow index (MFI) and G_C(ω_C), the crossover point of the viscoelastic moduli as a function of the angular velocity at which it occurs. MFI data show changes in the structure of the HDPE after each processing step, but this information is limited in quality and quantity. G_C data show the mechanism for degradation (side‐chain branching and chain scission) and allow us to track relative changes in mean molecular weight (MMW) and molecular weight distribution (MWD). MMW and MWD both increase as a result of continued reprocessing. The apparent changes in MWD are substantial indicating significant chain scission initially, accompanied and followed during subsequent processing by a combination of side‐chain branching and further chain scission. A relative measure of the polydispersity index (PI) of the melt is calculated and the PI increases as the HDPE is further reprocessed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009