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.     

Preparation and rheological characterization of long chain branching polylactide

Long chain branching (LCB) of polylactide (PLA) was successfully prepared by the successive reactions of PLA with pyromellitic dianhydride (PMDA) and 1,4-phenylene-bis-oxazoline (PBOZ) together. The topological structures of the LCB generated from functional group reactions were investigated thoroughly by gel permeation chromatography (GPC) and rheology. Qualitative information about the branching structures could be readily obtained from linear viscoelasticity, nonlinear oscillatory shear experiments and strain hardening in elongational experiments. For quantitative information on chain structure, linear viscoelasticity combined with branch-on-branch (BOB) dynamic model was used to predict probable compositions and chain topologies of the products, which were reasonably explained by the suggested mechanism of functional group reactions. It was found out that the star-like LCB structure generated in these reactions contributed remarkably to the enhancement of strain hardening under elongational flow.     

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 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     

Long chain branching polylactide: Structures and properties

Long chain branching (LCB) of polylactide (PLA) was successfully prepared by the successive reactions of the end hydroxyl groups of PLA with pyromellitic dianhydride (PMDA) and triglycidyl isocyanurate (TGIC) together. The topological structures of the LCB generated from functional group reactions as well as free radical reactions were investigated thoroughly by gel permeation chromatography (GPC) and rheology. Qualitative information about the branching structures could be readily obtained from linear viscoelasticity, non-linear oscillatory shear experiments and strain hardening in elongational experiments. For quantitative information on chain structure, linear viscoelasticity combined with branch-on-branch (BOB) dynamic model was used to predict exact compositions and chain topologies of the products, which were reasonably explained by the suggested mechanism of functional group reactions. It was found out that the tree-like LCB structure generated in these reactions contributed remarkably to the enhancement of strain hardening under elongational flow, which improves the foaming ability substantially.     

SEC-MALS method for the determination of long-chain branching and long-chain branching distribution in polyethylene

This paper systematically describes a LCB determination method that can quantify both LCB content and LCB distribution across the molecular weight distribution in polyethylene homopolymers as well as copolymers. Coupling size-exclusion chromatography with multi-angle light scattering (SEC-MALS), this method quantifies molecular weights (MW) and radii of gyration (R_g) simultaneously. The number of LCB per molecule and LCB frequency as a function of MW can be calculated by comparing R_g of a branched polymer with that of a linear control at the same MW using the Zimm-Stockmayer approach. Because the presence of short-chain branching in copolymers results in changes in R_g of the copolymers, their LCB contents cannot be obtained before the short-chain branching (SCB) effect is corrected. Using well-characterized linear PE copolymers as standards, an empirical method is successfully established in this paper to correct the SCB effect. Consequently, this method can be applied to determine LCB in PE copolymers as well. Some practical aspects, such as the selection of formalism for data processing, the LCB detection sensitivity and precision, and long-term reproducibility of this method are also discussed. Finally, examples are given to demonstrate how this method is applied to determine LCB and LCB distribution in practical PE homopolymers and copolymers.     

Combined effects between activating group Z and leaving group R in dithiocarbamates for controlling degradation and branching reactions of polypropylene

Four dithiocarbamates with different chemical structures (S-Propyl N,N-dipropyldithiocarbamate, S-allyl N,N-dipropyldithiocarbamate, S-Propyl N-pyrrolocarbodithioate and S-allyl N-pyrrolocarbodithioate) were used to adjust the melt radical reaction of polypropylene (PP). The combined effects between activating group Z (N,N-dipropyl and N-pyrrolo) and leaving group R(allyl and propyl) in the dithiocarbamates on melt reaction of PP were studied in the presence of peroxide and trimethylolpropane triacrylate monomer. The results from ¹H NMR, FTIR, GPC, rheological measurements and model experiments showed that chemical structures of activating group Z and leaving group R played a key role in the molecular structures and melt properties of modified PP samples. The presence of S-allyl N-pyrrolocarbodithioate with stronger activating group N-pyrrolo and easier leaving group allyl led to the formation of long chain branching structure with more branched points (comb-like topology). The possible reactions in the above systems were also discussed.     

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.     

Chemical modification of PP architecture: Strategies for introducing long-chain branching

Two strategies for introducing long chain branching (LCB) to a polypropylene homopolymer (PP) are evaluated in terms of the product's molecular weight and branching distributions, and in terms of melt-state shear and extensional rheological properties. Single step processes involving radical-mediated addition of PP to triallyl phosphate are shown to generate bimodal products with highly differentiated chain populations, while a two step sequence involving PP addition to vinyltriethoxysilane followed by moisture-curing is shown to generate more uniform architectures. As a result, the sequential approach can improve low-frequency shear viscosity and extensional strain hardening characteristics while staying below the polyolefin's gel point. The composition and molecular weight distribution transformations that underlie sequential LCB techniques are discussed.     

PP链结构对反应挤出制备长链支化PP的影响

以过氧化二异丙苯(DCP)为引发剂、1,4-丁二醇二丙烯酸酯(BDDA)为接枝单体,通过反应挤出制备长支链聚丙烯(PP),研究了PP链长及主链中乙烯嵌段含量对PP长链支化程度的影响。随着PP树脂分子链长度降低以及乙烯嵌段含量增加,PP大分子自由基发生接枝和双基偶合扩链反应的几率增大,导致BDDA在PP主链上的接枝率提高,反应挤出产物的熔体弹性效应增强以及在Cole-Cole曲线出现上翘所对应的动态黏度降低。黏度降低表明分子链松弛时间增加,PP长链支化程度增大。。     

Preparation and characterization of polypropylene/layered silicate nanocomposites using an antioxidant

Polypropylene (PP)/layered silicate nanocomposites were prepared via simple melt mixing of three components, PP, layered silicates modified with octadecylamine (C18-MMT) and antioxidant, to investigate the role of antioxidant. TEM and X-ray scattering results confirmed the intercalated state of silicates in PP/layered silicate nanocomposites with antioxidant. In rheological and mechanical study, the nanocomposites with antioxidant showed higher properties than those of the unfilled PP. The nanocomposite with 5 wt% C18-MMT and 0.5 phr antioxidant exhibited about 1.4 times higher tensile modulus and 1.3 times higher storage modulus than the unfilled PP. However, PP/C18-MMT without antioxidant showed lower rheological values owing to the thermal decomposition of PP and the poor compatibility between PP and C18-MMT. It could be concluded that antioxidants played an important role in enhancing the compatibility between PP and C18-MMT. According to the real time X-ray diffraction, the nanocomposite showed the weak ordering of PP crystals than the unfilled PP in the load-extension plateau region of elongation.     

A rheology theory and method on polydispersity and polymer long-chain branching

Model calculations were performed to investigate the sensitivity of zero-shear melt viscosity (η₀ or Eta0) on the molecular weight (MW) polydispersity of linear polymers. Simulated MW distributions (MWD) were generated with the generalized exponential (GEX) distribution function for various levels of polydispersity M_w/M_n and M_z/M_w. For linear entangled polymeric chains in the melt, the linear viscoelastic properties were predicted by using the double reptation blending rule and the so-called BSW relaxation time spectrum, named after the authors: Baumgaertel, Schausberger and Winter [Baumgaertel M, Schausberger A, Winter HH. Rheol Acta 1990;29:400-8]. Published rheological parameters appropriate for polyethylene were used in the calculations. It was found that Eta0 depended mostly on M_w, but it also significantly depended on the extent of high-MW polydispersity M_z/M_w. A revision to the fundamental MW dependency of Eta0 was proposed to compensate for this polydispersity effect. To offset the polymer polydispersity differences, we propose a new MW average (M_HV or M_x with x = 1.5) to replace M_w in the historical rheological power-law equation of Eta0 ∝ M_w^a, where the literature value of exponent “a” ranges from 3.2 to 3.6. The use of M_HV instead of M_w in the power-law equation made the calculated Eta0 independent of the sample high-MW polydispersity. With the removal of the complication from polydispersity effect, the new Eta0 power law can now provide a more robust base for studying polymer long-chain branching (LCB). A new LCB index is thus proposed based on this new melt-viscosity power law. The values of M_HV in the new power law can be calculated for polymer samples from the conventional gel permeation chromatographic (GPC) slice data.     

Structure-rheology relationships of long-chain branched polypropylene: Comparative analysis of acrylic and allylic coagent chemistry

The relationship between product structure and melt-state rheological properties is established for series of branched PP derivatives prepared by the radical-mediated grafting of tri-functional coagents. Peroxide-initiated, solvent-free additions of linear PP to triallyl trimesate (TAM), trimethylolpropane triacrylate (TMPTA) and triallyl phosphate (TAP) at high temperature are shown to produce bimodal molecular weight and branching distributions. Low-frequency dynamic shear viscosities as well as extensional viscosities are shown to be highly responsive to a hyper-branched chain population, whose abundance and molecular weight correlate with the kinetic chain length of the grafting process, and the propensity of a coagent to oligomerize.     

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     

Shear and elongational rheology of polyethylenes with different molecular characteristics. II. Elongational rheology

The elongational viscosities of polyethylenes with different molecular characteristics were measured at different Hencky strains and temperatures with a capillary rheometer by the replacement of the capillary cylindrical die with a hyperbolic converging die. The hyperbolic shape of the die established a purely elongational flow field at a constant elongational strain rate throughout the die. The effects of molecular characteristics such as the molecular weight, molecular weight distribution, and long‐chain branching and processing conditions such as the temperature and Hencky strain on the elongational rheology of the polyethylene samples were studied. Good master curves were generated for temperature and Hencky strain shifting and simultaneous shifting with respect to both the temperature and Hencky strain. Both the molecular weight distribution and long‐chain branching seemed to promote strain rate thinning and reduce the elongational viscosity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1184–1194, 2007     

Crystallization behavior and mechanical properties of polypropylene/halloysite composites

In this work, halloysite nanotubes (HNTs), a new type of inexpensive filler, were used for the modification of polypropylene (PP). HNTs were first surface treated by methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium, then melt mixed with PP. Scanning electron microscope (SEM) was used to examine the dispersion of HNTs in PP matrix. Differential scanning calorimetry (DSC), polarized light microscope (PLM), dynamic melt rheometry and wide angle X-ray diffraction (WAXD) were employed to investigate the crystallization behavior of the prepared PP/HNT composites. The mechanical properties were evaluated by Instron and impact tests. SEM results revealed that HNTs could be well-dispersed in PP matrix and had a good interfacial interaction with PP, even up to a high content of 10 wt%. DSC data indicated that HNTs could serve as a nucleation agent, resulting in an enhancement of the overall crystallization rate and the non-isothermal crystallization temperature of PP. PLM showed a constant spherulite growth rate and a decreased spherulite size at given isothermal crystallization temperature, suggesting that nucleation and growth of a spherulite are two independent processes. The result obtained by dynamic melt rheometry indicated that HNTs mainly promoted nucleation and had not much influence on the growth of PP crystallization. Nevertheless, by fast cooling the samples, almost constant spherulite size can be obtained for both pure PP and PP/HNT composites due to the limited nucleation effect of HNTs on PP crystallization. WAXD showed that HNTs mainly facilitated α-crystal form of PP. Though a good dispersion of HNTs in PP matrix was observed, out of our expectation, not much enhancement on mechanical properties of PP/HNT composites had been achieved, and this could be mainly ascribed to the constant crystallinity and spherulite size of PP as well as the small length/diameter ratio of HNTs.     

Preparation and Characterization of Long Chain Branched Polypropylene through UV Irradiation and Coagent Use

Trimethylolpropane triacrylate as coagent was utilized along with benzophenone to modify polypropylene by generating long chain branches in the polypropylene molecular structure. The effects of trimethylolpropane triacrylate concentration, benzophenone concentration, and irradiation duration on viscoelastic properties and gel content were studied. The processing conditions that result in the greatest amount of long chain branching with minimum amount of gel content were identified. Gel permeation chromatography was used to confirm formation of branches and determine the branching content, whereas Fourier transform infrared spectroscopy confirmed the contribution of trimethylolpropane triacrylate in the formation of long chain branches.     

Crystallization behavior and crystallization kinetic studies of isotactic polypropylene modified by long‐chain branching polypropylene

In this article, we discuss the crystallization behavior and crystallization kinetics of isotactic polypropylene (iPP) modified by long‐chain‐branching (LCB) high‐melt‐strength iPP over a wide composition range, that is, LCB‐iPP from 10 to 50 wt %. Over the entire range we investigated, the presence of LCB‐iPP accelerated crystallization in both the isothermal crystallization process and nonisothermal crystallization process, even when the LCB‐iPP content was as low as 10%, and both crystallization processes were enhanced more significantly as the LCB‐iPP content increased. Hoffman–Lauritzen theory analysis revealed that the fold‐free energy decreased effectively with the occurrence of the LCB structure, although the growth rate of spherulites was depressed, as shown by polarized optical microscopy. Meanwhile, the regime III–regime II transition temperature was about 15° higher for all of the LCB‐iPP compositions than that of iPP because the LCB structure reduced the mobility of the polypropylene chains. Furthermore, the γ‐form crystal structure was favored by LCB compared to the β form, which was supported by wide‐angle X‐ray diffraction. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

蒙脱土对聚丙烯熔融接枝马来酸酐的影响

在聚丙烯熔融接枝马来酸酐(MAH)中引入有机蒙脱土(OMMT),讨论了OMMT/DCP(1∶1)、MAH的加入量对PP接枝率以及分子量的影响。结果表明PP接枝MAH的接枝率大大提高,减小了PP链的裂解。