Mechanism of internal and external electron donor effects on propylene polymerization with MgCl2‐supported Ziegler–Natta catalyst: New evidences based on active center counting

Two TiCl₄/Di/MgCl₂ type supported Ziegler–Natta catalysts were prepared by loading dibutylphthalate or dicyclopentyldimethoxysilane (DCPDMS) (internal donor, Di) and TiCl₄ on activated δ‐MgCl₂ in sequence, and a blank catalyst was prepared by loading TiCl₄ on the same δ‐MgCl₂ without adding Di. These catalysts have similar specific surface area and pore size distribution, thus form a suitable base for comparative studies. Propylene polymerization with the catalysts was conducted in n‐heptane slurry using triethylaluminum (TEA) as cocatalyst, and the effects of Di as well as De (external donor, in this work it was DCPDMS) on the number of active centers, the distribution of active centers among three polypropylene (PP) fractions (isotactic, medium isotactic, and atactic PP chains), and chain propagation rate constants of the PP fractions were studied by counting the number of active centers in the PP fractions using a method based on selective quench‐labeling of the propagation chains by 2‐thiophenecarbonyl chloride. When De was not added in the polymerization, introducing a phthalate type Di in the catalyst evidently changed the active center distribution by enhancing the proportion of active centers producing isotactic PP (iPP) ( ), but scarcely changed reactivities of the three groups of active centers forming the three fractions. When the De was added in the polymerization system with TiCl₄/phthalate/MgCl₂ catalyst, further shifting of active center distribution in favor of took place, meanwhile reactivities of the three groups of active centers also remarkably changed in favor of . Mutual effects of these changes led to overwhelming dominance of iPP production in the TiCl₄/Di/MgCl₂–TEA/De system (Di = phthalate, De = alkoxysilane). In contrast, though using alkoxysilane as Di also caused shifting of active center distribution in favor of when De was not added, addition of alkoxysilane De caused reverse shifting of active center distribution in favor of those producing PP of lower stereoregularity. This unfavorable change largely counteracted the reactivity changes in favor of caused by the De, rendering the catalytic system rather poor isospecificity. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46605.     

Reactive compatibilization of poly(styrene‐ran‐acrylonitrile)/poly(ethylene) blends through the acid–epoxy reaction

Two families of acid functional styrene/acrylonitrile copolymers (SAN) for application as dispersed phase barrier materials in poly(ethylene) (PE) were studied. One type is SAN made by nitroxide mediated polymerization (NMP), which was subsequently chain extended with a styrene/tert‐butyl acrylate (S/tBA) mixture to provide a block copolymer (number average molecular weight M_n = 36.6 kg mol^?1 and dispersity ? = 1.34, after which the tert‐butyl protecting groups were converted to acid groups (SAN‐b‐S/AA). The other acid functional SAN is made by conventional radical terpolymerization (SAN‐AA). SAN‐AA and SAN‐b‐S/AA were each melt blended with PE grafted with epoxy functional glycidyl methacrylate (PE‐GMA) at 160 °C in a twin screw extruder (70:30 wt % PE‐GMA:SAN co/terpolymer). The non‐reactive PE‐g‐GMA/SAN blend had a volume to surface area diameter = 3.0 μm while the reactive blends (via epoxy/acid coupling) (PE‐GMA/SAN‐b‐SAA and PE‐GMA/SAN‐AA) had = 1.7 μm and 1.1 μm, respectively. After thermal annealing, the non‐reactive blend coarsened dramatically while the reactive blends showed little signs of coarsening, suggesting that the acid/epoxy coupling was effective for morphological stability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44178.     

Propylene polymerization over supported Ziegler–Natta catalysts: Effect of internal and external donors on distribution of active sites according to stereospecificity

Data on the content of fractions with different microtacticities for polypropylene (PP) samples produced over three catalysts [the “donor‐free” titanium–magnesium catalyst and catalysts with dibutyl phthalate and 1,3‐diether(fluorene) used as internal donors] upon polymerization in the absence/presence of an external donor (ED) have been obtained by preparative temperature rising elution fractionation method. The effect of internal and EDs on the distribution of PP fractions with different microtacticity is discussed. Data on molecular weight and thermophysical characteristics were obtained for individual fractions with different microtacticities. Correlations were found between microtacticity, molecular weight, and the melting points of these fractions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46291.     

Reactive compatibilization of poly(methyl acrylate‐ran‐acrylonitrile)/poly(ethylene) blends through amine–anhydride coupling

Methyl acrylate/acrylonitrile copolymers (MA/AN) were reactively compatibilized as the dispersed phase into poly(ethylene) (PE) for potential hydrocarbon barrier materials. The MA/AN was made reactive by including p‐aminostyrene (PAS), yielding terpolymers (MA/AN/PAS) with pendant primary amine functionality (number average molecular weight = 65–133 kg mol^?1, dispersity (?)=1.83–2.53, molar composition of PAS in copolymer F_PAS = 0.03–0.14, molar composition of AN = F_AN = 0.27–0.52). The non‐functional MA/AN and amino functional MA/AN/PAS were each melt blended into PE that was grafted with maleic anhydride (PE‐g‐MAnn) at 200 °C at 70:30 wt % PE‐g‐MAnn:co/terpolymer. After extrusion, the dispersed phase particle size (volume to surface area diameter, ) was coarse (12.6 μm) for the non‐reactive blend whereas it was much lower for the reactive blend ( = 1.2 μm). Coarsening after annealing at 150 °C was slow, but the domain sizes increased only slightly for both cases. The reactive blend was deemed sufficiently stable and thus was suitable as a candidate barrier material for further testing against olefins. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44177.     

琥珀酸酯为内给电子体的新型MgCl2载体催化剂用于丙烯聚合

A novel MgCl2-supported Ziegler-Natta catalyst containing diethyl diisopropylsuccinate donor was prepared and propylene polymerizations with the combination of such catalyst and four external donors were investigated in detail. The catalyst was compared with a commercial one with phthalate as internal donor in terms of catalytic activity, hydrogen sensitivity and stereospecificity in propylene polymerization. The molecular weight, molecular weight distribution and microstructure of the produced polypropylenes were compared also. It was found that the novel catalyst containing succinate internal donor showed higher activity and higher stereospecificity than those with phthalate as internal donor. Consequently, polypropylenes obtained by the succinate-based catalyst showed high molecular weight, high melting temperature, high isotactic index and broad molecular weight distribution than those obtained with the commercial catalyst.     

Preparation and characterization of poly(ethylene terephthalate) copolyesters modified with sodium‐5‐sulfo‐bis‐(hydroxyethyl)‐isophthalate and poly(ethylene glycol)

Two types of poly(ethylene terephthalate) (PET) copolyesters were successfully prepared with sodium‐5‐sulfo‐bis‐(hydroxyethyl)‐isophthalate (SIPE) and poly(ethylene glycol) (PEG) units with different molecular weights named as cationic dyeable polyester and easy cationic dyeable polyester. Their chemical and crystalline structures were characterized by the nuclear magnetic resonance (NMR), wide angle X‐ray diffraction (WAXD), and small angle X‐ray scattering measurement, and their thermal properties were tested by differential scanning calorimetry and thermogravimetric analysis, respectively. NMR experimental results showed that the actual molar ratio of comonomers was basically consistent with the correlative feed ratio. WAXD results indicated that the crystalline structures of prepared copolyesters were similar to that of PET. Moreover, the glass transition temperature, melting temperature, and thermal degradation temperature were found to decrease with the reduction of the of PEG units as the incorporation of lower of PEG units brought more ether bonds into molecular chains, which increased the irregularity of molecular chain arrangement and led to lower crystallinity. In addition, because the incorporation of PEG units with lower molecular weight led to more ether bonds and hydroxyl end‐groups in molecular chains, the value of contact angle of PET copolyesters dropped, manifesting PET copolyesters had better hydrophilicity with the decreasing molecular weight of PEG units.© 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39823.     

Effect of Ca2+ induced crosslinking on the mechanical and barrier properties of cast alginate films

The use of alginate as a coating material for packaging applications is currently limited due to its difficult processability and high moisture sensitivity. Therefore, this study addresses the crosslinking and scale‐up to a continuous application. Three different crosslinking agents were applied: CaCl₂ with ethylene diamine tetraacetic acid and two low soluble salts (CaHPO₄ and CaCO₃). Those were incorporated by internal setting in an alginate matrix with varying Ca²⁺ concentration ( ) and ratio. With the addition of Ca²⁺, the tensile strength and elongation at break of the cast alginate films increased. This was optimal for a of 0.010–0.015 g (g alginate)^?1 dependent on the crosslinking agent. The decrease in water vapor and oxygen permeability due to crosslinking was independent of the crosslinking agent. However, the optimal aiming to decrease permeability was different for the crosslinking agents: CaHPO₄ showed best results at a of 0.010 g (g alginate)^?1, CaCl₂ at 0.012 g (g alginate)^?1, and CaCO₃ at 0.027 g (g alginate)^?1. Upon all analyzed properties CaHPO₄ was the most promising crosslinking agent for alginate. Moreover, selected alginate formulations were successfully processed in a continuous lacquering plant. The produced two‐layer systems have very low oxygen permeabilities which can be further reduced by crosslinking. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45754.     

Morphologies of electrospun fibers of lignin in poly(ethylene oxide)/N,N‐dimethylformamide

The effects of polyethylene oxide (PEO) molecular weight (Mv), and volume fraction ( ) on the morphology of electrospun sulfur free softwood lignin nanofibers were investigated. Small amounts of PEO were used during preparations of the solutions to aid the electrospinning process. It was found that tripling the PEO volume fraction resulted in a transition from semi‐dilute un‐entangled to semi‐dilute entangled solutions. Conversely, the solution remained in the semi‐dilute un‐entangled regime as the molecular weight was increased by five times. The effects of molecular weight and volume fraction of PEO both on entanglement density and fiber morphology were unified by scaling PEO viscosities as a function of . We investigated and discussed conditions that would produce smooth fibers and conditions that would produce fibers with beads. In the case of beads‐on‐a‐string formation, bead widths remained constant regardless of the molecular weight and concentration of PEO, but the bead length changed. Additionally, we observed a decrease in the diameter of the fibers and the dimension of beads (length and width of beads) with an increase in the electric field used for electrospinning. The aspect ratio of beads increased with increases to both the electric field and the PEO molecular weight or concentration. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44172.     

Heat‐ and light‐induced thiol‐ene oligomerization of soybean oil‐based polymercaptan

Polymercaptanized soybean oil (PMSO), the product of a thiol‐ene reaction between soybean oil and hydrogen sulfide, is a material of interest as a lubricant additive and polymer precursor. We investigated with gel permeation chromatography, nuclear magnetic resonance (one‐dimensional and two‐dimensional), gas chromatography–mass spectrometry, and viscometry the changes that occur with PMSO upon heating or ultraviolet irradiation. The observed changes were due to a further thiol‐ene reaction between the thiol groups and the residual unsaturation. The formation of oligomers was a result of new sulfide bridges. Additionally, tetrahydrothiophene moieties were detected. An almost linear increase of the average molecular weight (MW) and the polydispersity index (PDI) was observed upon heat treatment [number‐average MW ( ) = 1180 Da, PDI = 1.32 for PMSO, = 1720 Da, PDI = 2.17 for PMSO that was heated for 1000 h at 130 °C]. PDI correlated best with the z‐average MW. The was the best predictor of the viscosity. For samples with close , the higher PDI corresponded to a higher viscosity index. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46150.     

Structure and properties of polypropylene alloy in situ blends

A series of polypropylene (PP) alloys containing different ethylene contents have been prepared by the in situ sequential polymerization technique, using Ziegler–Natta catalyst (MgCl₂/TiCl₄/BMF; BMF is 9,9‐bis(methoxymethyl)fluorine, as an internal donor) without any external donor. The structure and properties of PP alloys obtained have been investigated by nuclear magnetic resonance, Fourier transform infrared spectroscopy, dynamic mechanical analysis, differential scanning calorimetry, and scanning electron microscopy (SEM). The results have suggested that PP alloys are the complex mixtures containing PP, the copolymer with long sequence ethylene chain, ethylene‐propylene rubber (EPR), and block copolymer etc. In the alloys, PP, EPR, and the copolymer with long sequence ethylene chain are partially compatible. The investigation of the mechanical properties indicates that notched Izod impact strength of PP alloy greatly increases at 16°C/?20°C in comparison with that of pure PP. The noticeable plastic deformation is observed in SEM photograph. The increase in the toughness, the mechanical strength of PP alloy decreases to a certain extent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4804–4810, 2006     

Nucleation parameter and size distribution of critical nuclei for nonisothermal polymer crystallization: The influence of the cooling rate and filler

The nucleation parameter K_g of filled PP, HDPE, and PA6 is determined through nonisothermal DSC measurements. A novel method is proposed for the determination of the size distribution of critical nuclei, where the most commonly found fraction was obtained as a peak value. The models are tested at different cooling rates and different filler loadings. K_g varies up to a certain cooling rate and afterwards remains constant. The introduction of talc in PP and HDPE facilitates nucleation and thus reduces K_g. An opposite trend occurs upon the addition of bentonite in PA6. The changes of K_g and are reflected on sample morphology, as confirmed with SAXS. The ratio between the final crystal thickness and amounts to approx. 2 and thus agrees well with the one listed in literature. The simple linear correlations of the obtained K_g are established with Young's modulus and yield stress. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41433.     

内给电子体在气相聚乙烯催化剂中作用的研究

采用浸渍法制备工艺,在MgCl2/SiO2复合载体齐格勒-纳塔(Z-N)催化剂制备过程中加入了醇、酯、醚和硅烷四类内给电子体,考察了不同内给电子体对气相聚乙烯催化剂的活性、产物堆密度、细粉含量的影响;结果表明:正硅酸乙酯作为聚乙烯催化剂的内给电子体效果较好,催化剂活性达到3447.5g·PE/g·Cat·h,聚合物堆密度达到0.33g·cm-3,细粉含量仅占0.052%,电子显微镜下催化剂颗粒呈均匀的球形。     

Control of molecular weight distribution for polypropylene obtained by a commercial Ziegler–Natta catalyst: Effect of a cocatalyst and hydrogen

The polymerization of propylene was carried out with an MgCl₂‐supported TiCl₄ catalyst (with diisobutyl phthalate as an internal donor) in the absence and presence of hydrogen (H₂) as a chain‐transfer agent. Different structures of alkylaluminum were used as cocatalysts. The effects of the alkyl group size of the cocatalyst, H₂ feed, and feed time on the propylene polymerization behaviors were investigated. The catalyst activity significantly decreased with increasing alkyl group size in the cocatalyst. The molecular weight and polydispersity index (PDI) increased with increasing alkyl group size. With the introduction of H₂, the catalyst activity increased significantly, whereas the molecular weight and PDI of polypropylene (PP) decreased. Additionally, the effect of the polymerization time in the presence of H₂ on the propylene polymerization was studied. The molecular weight distribution curve was bimodal at short polymerization times in the presence of H₂, and we could control the molecular weight distribution of PP by changing the polymerization time in the presence of H₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Capacitance properties of unipolar pulsed electro‐polymerized PEDOT films

Poly(3,4‐ethylenedioxythiophene) (PEDOT) film has been prepared on conductive carbon paper (CP) substrates by unipolar pulse electrochemical deposition. The effects of different polymerization parameters, including pulse potential and width, deposition frequency, and duty cycle on the capacitance of PEDOT films, were studied by cyclic voltammetry in 0.5 M sulfuric acid solution. The PEDOT‐coated CP electrode was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy to confirm the three‐dimensional porous structure and the presence of dopant ion conjugation during the electro‐polymerization. The results of cyclic voltammetry and galvanostatic charge‐discharge show that the PEDOT electrodes exhibit good specific capacitance of 151.31 F/g, rate performance and stability with a retention rate of 80.25% after 5000 cycles. The thin, lightweight electrode materials show considerable potential for low‐cost, high‐performance energy storage applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46729.     

Copolymers from methyl methacrylate and butyl acrylate with hyperbranched architecture

This is a first report of the synthesis and characterization of acrylic copolymers from methyl methacrylate (MMA) and butyl acrylate (BA) with hyperbranched architecture. The copolymers were synthesized using a free radical polymerization (Strathclyde method) in emulsion technique. Divinyl benzene was used as the brancher which acted as a comonomer and 1‐dodecanethiol was used as a chain terminating agent. A linear copolymer from MMA and BA was also synthesized for comparison. The hyperbranched architecture was established from spectroscopic and rheological measurements. The gel permeation chromatography showed all hyperbranched copolymers were low molecular weight with lower polydispersity index (PDI) ( 23,000, PDI ～ 2.00) compared to the linear grade ( 93,000, PDI ～ 2.20). They were more spherical and achieved lower viscosity (yet higher solubility, >90%) than the linear grade (<50%) which was mostly open ended. Lower viscosity at equivalent solid content made the hyperbranched polymers a potential binder for adhesive and coating application. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45356.     

Processing behavior and mechanical properties of autopolymerizing hypoallergenic denture base polymers

Driven by the phenomenon of increasing irritations and allergic reactions of dental prosthesis carriers preferably due to residual methyl methacrylate monomer in conventional dental materials, autopolymerizing hypoallergenic denture base polymers were prepared as two‐component materials in the shape of paste/paste‐ or powder/liquid systems. The processing behavior of these materials was investigated regarding the processing and solidification times also in dependence on the polymerization catalyst concentration, whereas the whole processing and curing characteristics and the final polymer properties were evaluated by dynamic mechanical analysis in shear mode in the temperature range from ?145°C to 200°C. The mechanical properties of the hypoallergenic denture base polymers were validated regarding stiffness (flexural modulus E') and fracture toughness (maximum factor of loading intensity , total work of fracture ) and the effects of monomer composition, kind of resin powder, impact modification by the liquid component, and water immersion on these properties were investigated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41378.     

Kinetic study on the synergistic effect between molecular weight and phosphorus content of flame retardant copolyesters in solid-state polymerization

2-Carboxyethyl(phenyl phosphinic) acid has been proved to modify flame retardant properties of poly(ethylene terephthalate) (PET) through copolymerization; however, there is no industrial technological breakthroughs in polyester industrial yarns which requires high strength and modulus, because it is related to the coordinated control of molecular weight and flame retardancy. In this work, the influence of solid-state polymerization reaction kinetics and parameters on flame retardancy retention have been investigated, based on the prepared precursors optimized at 6,000 ppm phosphorus content and 0.64 dL/g intrinsic viscosity (I.V). Results showed that the copolyester polydispersity index increase was significant compared to PET with molecular weight increase. The I.V of optimized precursor could be increased to 1.31 dL/g at 220°C in 20 hr, but at higher phosphorus content loses up to 7%. Flame retardant component deteriorates with increasing reaction rate and temperature as a result of severe side reactions. Optimized precursor at the optimum temperature (210°C) reacted for 20 hr, copolyester with the phosphorus content of 5,910 ppm and the I.V of 1.12 dL/g (( was about 3.5 × 10⁴ g/mol) was prepared. The coordination between high molecular weight and flame retardant performance was realized.     

Preparation of ultra high molecular weight polyethylene with MgCl<Subscript>2</Subscript>/TiCl<Subscript>4</Subscript> catalyst: effect of internal and external donor on molecular weight and molecular weight distribution

Ultra high molecular weight polyethylene (UHMWPE) was prepared by using MgCl₂-supported TiCl₄ catalyst in conjunction with triethylaluminium (TEA) cocatalyst. The effects of internal and external donor on polydispersity index (PDI) of UHMWPE were investigated. The catalyst activity with various kinds of internal donor decreased in the following order: none > succinate > phthalate > diether, while the catalyst activity was less influenced by the structure of external donor. The PDI of UHMWPE was examined by using gel permeation chromatography (GPC) analysis and/or rheometry measurements. The PDI obtained by rheometer was matched with the results obtained by GPC within an error of max. 20%. The highest molecular weight and PDI of UHMWPE were obtained by the catalyst of succinate as internal donor. It was also observed that the molecular weight and PDI of UHMWPE were less affected by the introduction of external donor.     

Effect of K0.5Na0.5NbO3 filling particles on the charge carrier trap distribution of polyimide films

Polyimide (PI) films filled with K_0.5Na_0.5NbO₃ (KNN50) particles at different weight 0, 5, 10, and 15 wt % had been prepared by in‐situ dispersion polymerization process. The thermally stimulated current (TSDC) method was used to investigate the charge carrier trap levels and their distribution of the composite films. The TSDC spectra show that pure film has ‐peaks and ‐peak, but the composite films only have ‐peaks and an extraordinary peak at high temperature region. The trap parameters were calculated by an approximate model, and the results indicate that charge released of the shallow traps show a nonlinear behavior. The trap energies decrease from 0.879–0.968 eV to 0.549–0.839 eV with the increase of the KNN50 content. The surface and interface between KNN50 and PI matrix was considered to the variation of the trap levels. The extraordinary peak of the composite films was correlated with the phase transition of the KNN50 particles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39828.     

Ultrasound assisted continuous‐mixing for the preparation of PP/SEBS/OMMT ternary nanocomposites

Polypropylene (PP)/polystyrene‐block‐poly(ethylene‐co‐butylenes)‐block‐polystyrene (SEBS)/organo‐montmorillonite (OMMT) nanocomposites of varying concentrations of maleic anhydride‐grafted polypropylene (PP‐g‐MA) were prepared by continuous mixing assisted by ultrasonic oscillation. The structure and morphology of nanocomposites were investigated by X‐ray diffraction (XRD), transmission electron microscopy, and scanning electron microscopy. It was found that both PP‐g‐MA and ultrasonic oscillation could enhance the intercalation and exfoliation of OMMT in PP matrix. Meanwhile, the formation of PP could be induced by ultrasonic irradiation at a power of more than 540 W. Rheological properties including complex viscosity, storage, and loss modulus of nanocomposites were increased after adding PP‐g‐MA or ultrasonic treatment. The results of mechanical properties showed that PP‐g‐MA could improve the tensile strength and tensile modulus of nanocomposites, but with the sacrifice of impact strength. This problem could be improved by ultrasound due to the reduced particle size of SEBS. However, the mechanical properties would be reduced by ultrasonic treatment with higher intensity due to the polymer degradation. Therefore, the synergistic effect of both compatibilizer and ultrasound should account for the balance between toughness and stiffness of PP/SEBS/OMMT ternary nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41202.