Effect of the comonomer content on the solid‐state mechanical and viscoelastic properties of poly(propylene‐co‐1‐butene) films

In this study, we quantified the thermal and solid‐state mechanical and viscoelastic properties of isotactic polypropylene (i‐PP) homopolymer and poly(propylene‐1‐butene) copolymer films having a 1‐butene ratio of 8, 12, and 14 wt %, depending on the comonomer content. The uniaxial tensile creep and stress‐relaxation behaviors of the samples were studied in a dynamic mechanical analyzer at different temperatures. The creep behaviors of the samples were modeled with the four‐element Burger equation, and the long‐term creep strains were predicted with the time–temperature superposition method. The short‐term mechanical properties of the samples were also determined with tensile and impact testing at room temperature. We found that the Young's modulus and ultimate strength values of the samples decreased with increasing amount of 1‐butene in the copolymer structure. On the other hand, the strain at break and impact strength values of the samples improved with increasing amount of 1‐butene. Creep analysis showed that i‐PP exhibited a relatively lower creep strain than the poly(propylene‐co‐1‐butene)s at 30 °C. However, interestingly, we discovered that the temperature increase resulted in different effects on the creep behaviors. We also found that short‐chain branching improved the creep resistance of polypropylene at relatively high temperatures. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46350.     

New synthesis methods for polypropylene‐co‐ethylene‐propylene rubber

In this research, the reinforcement of polypropylene (PP) was studied using a new method that is more practical for synthesizing polypropylene‐block‐poly(ethylene‐propylene) copolymer (PP‐co‐EP), which can be used as a rubber toughening agent. This copolymer (PP‐co‐EP) could be synthesized by varying the feed condition and changing the feed gas in the batch reactor system using Ziegler–Natta catalysts system at a copolymerization temperature of 10°C. The ¹³C‐NMR tested by a 21.61‐ppm resonance peak indicated the incorporation of ethylene to propylene chains that could build up the microstructure of the block copolymer chain. Differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and dynamic mechanical analysis (DMA) results also confirmed these conclusions. Under these conditions, the morphology of copolymer trapped in PP matrix could be observed and the copolymer T_g would decrease when the amount of PP‐co‐EP was increased. DMA study also showed that PP‐co‐EP is good for the polypropylene reinforcement at low temperature. Moreover, the PP‐co‐EP content has an effect on the crystallinity and morphology of polymer blend, i.e., the crystallinity of polymer decreased when the PP‐co‐EP content increased, but tougher mechanical properties at low temperature were observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3609–3616, 2007     

The influence of thermal treatment and processing on the structure and morphology of poly(propylene‐ran‐1‐butene) copolymers

New poly(propylene‐ran‐1‐butene) copolymers were analyzed to study the influence of different processing techniques on their structure and morphology. Wide‐angle X‐ray diffraction allowed determination of the percentage of the γ form and the crystallinity in the samples and also the influence of the percentage of 1‐butene on the cell parameters. Furthermore, it was possible to appraise the contributions of different stacks of lamellae to the small‐angle X‐ray diffraction patterns. © 2001 Society of Chemical Industry     

Basic characterization of polypropene‐block‐poly(methylene‐1,3‐cyclopentane‐co‐propene) synthesized from propene and 1,5‐hexadiene with modified stopped‐flow method

Block copolymerization of propene and 1,5‐hexadiene was carried out by a modified stopped‐flow polymerization method with an MgCl₂‐supported Ziegler catalyst. The resulting polymer, polypropene‐block‐poly(methylene‐1,3‐cyclopentane‐co‐propene) (PP‐b‐(PMCP‐co‐PP)), in which the crystallizable PP part was linked with the non‐crystallizable PMCP‐co‐PP part, was characterized by optical microscopy, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and tensile testing. The block copolymer having a chemical linkage between PP and PMCP‐co‐PP showed properties different from those of homopolymer, random copolymer and blend polymer. © 2001 Society of Chemical Industry     

Study of propylene‐1‐butene‐ethylene terpolymer and reactor blend by TREF and 13C‐NMR

A terpolymer of propylene‐1‐butene‐ethylene (TERPO) and a reactor mixture of TERPO with an ethylene‐1‐butene copolymer (BLEND) were completely characterized by TREF, ¹³C‐NMR, DSC, and GPC, from which special equations for quantitative ¹³C‐NMR were derived. TERPO was shown to be composed mainly of highly isotactic propene and similar amounts of ethylene and 1‐butene. BLEND fractions were composed of variable amounts of TERPO and a random copolymer of ethylene‐1‐butene. The blend of TERPO and copolymer acts as two independent phases, each having its own elution temperatures dependent only on its crystallizability, itself only influenced by the comonomer content. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1880–1890, 2001     

Chain structure and mechanical properties of polyethylene/polypropylene/poly(ethylene‐co‐propylene)in‐reactor alloys synthesized with a spherical Ziegler–Natta catalyst by gas‐phase polymerization

Two polyethylene/polypropylene/poly(ethylene‐co‐propylene) in‐reactor alloy samples with a good polymer particle morphology were synthesized by sequential multistage gas‐phase polymerization with a spherical Ziegler–Natta catalyst. The alloys showed excellent mechanical properties, including both toughness and stiffness. With temperature‐gradient extraction fractionation, both alloys were fractionated into five fractions. The chain structures of the fractions were studied with Fourier transform infrared, ¹³C‐NMR, and thermal analysis. The alloys were mainly composed of polyethylene, polyethylene‐b‐polypropylene block copolymer, and polypropylene. There also were minor amounts of an ethylene–propylene segmented copolymer with very low crystallinity and an ethylene–propylene random copolymer. The block copolymer fraction accounted for more than 44 wt % of the alloys. The coexistence of these components with different structures was apparently the key factor resulting in the excellent toughness–stiffness balance of the materials. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 640–647, 2005     

In situ synthesis of polybutene‐1/polypropylene spherical alloys within a reactor with an MgCl2‐supported Ziegler–Natta catalyst

A series of isotactic polybutene‐1/polypropylene (PB/PP) alloys with spherical morphology were prepared by MgCl₂‐supported Ziegler‐Natta catalyst with sequential two‐stage polymerization technology. The first formed PP particles were used as micro‐reactors to initiate the bulk precipitation polymerization of butene‐1 further. The porous PP particles as a hard framework may prevent the adhesion of PB particles during the bulk precipitation polymerization process. At the same time, the bulk precipitation polymerization process allows for maximization of the butene‐1 polymerization rate and simplifies the butene‐1 polymerization process considerably. Finally, spherical PB alloys with a super‐high molecular weight PB component and adjustable PP component were synthesized in situ within the reactor. The structures and properties of the PB/PP alloys were characterized by gel permeation chromatography, ¹³C nuclear magnetic resonance, Fourier transform IR, scanning electron microscopy, differential scanning calorimetry and X‐ray diffraction. The results showed that the MgCl₂‐supported Ziegler‐Natta catalyst showed relatively high stereospecificity and efficiency for both propylene and butene‐1 polymerization. The incorporation of propylene on the PB matrix affects the properties of the final products markedly. The PB/PP alloys are expected to have a broader range of applications as a new family of high performance materials. Copyright © 2012 Society of Chemical Industry     

Poly(N‐vinylpyrrolidone‐co‐2‐acrylamido‐2‐methylpropanesulfonate sodium): Synthesis,characterization, and its potential application for the removal of metal ions from aqueous solution

In the current study, poly(N‐vinylpyrrolidone‐co‐2‐acrylamido‐2‐methylpropanesulfonate sodium), poly(VP‐co‐AMPS), was prepared and used for the removal of Cu²⁺, Cd²⁺, and Ni²⁺ ions via a polymer‐enhanced ultrafiltration (PEUF) technique. The copolymer was synthesized by radical polymerization in an aqueous medium with a comonomer feed composition of 50:50 mol %. The molecular structure of the copolymer was elucidated by ATR‐FTIR and ¹H NMR spectroscopy, and the average molecular weight was obtained by GPC. The copolymer composition was determined to be 0.42 for VP and 0.58 for AMPS by ¹H NMR spectroscopy. The copolymer and homopolymers exhibited different retention properties for the metal ions. PAMPS exhibited a high retention capacity for all of the metal ions at both pH values studied. PVP exhibited selectivity for nickel ions. Poly(VP‐co‐AMPS) exhibited a lower retention capacity compared to PAMPS. However, for poly(VP‐co‐AMPS), selectivity for nickel ions was observed, and the retention of copper and cadmium ions increased compared to PVP. The homopolymer mixture containing PAMPS and PVP was inefficient for the retention of the studied metal ions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41272.     

Air‐hole properties of calcite‐filled polypropylene copolymer films

This work was designed to study the effects of inorganic calcite powder on structurally different copolymer [poly(propylene‐co‐ethylene)] and terpolymer [poly (propylene‐co‐ethylene‐co‐1‐butene)] matrices and the possibility of making a suitable porous composite film. The yield stress of the composites did not improve, but the modulus increased gradually with the filler loading. The theoretical and experimental modulus and yield stress of the composites provided evidence of filler and polymer adhesion behavior. The impact strength showed little enhancement up to a 20 wt % loading for the poly(propylene‐co‐ethylene‐co‐1‐butene) system. The number‐average, weight‐average, and z‐average air‐hole diameters were compared with respect to the draw ratio as well as the calcite loading. The morphology of a micromechanically deformed composite, studied with an image analyzer, revealed that the aspect ratio and area of the air holes increased linearly as a function of the draw ratio, but the change in the aspect ratio upon filler loading was not remarkable. A suitable loading of a filler up to 30 wt % was good for controlling the porosity in the composite films. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Copolymerization of propylene with 1‐octene catalyzed by MgCl2/TiCl4/diether catalyst

MgCl₂/TiCl₄/diether is a fifth‐generation Ziegler–Natta catalyst for the commercial polymerization of propylene. The outstanding features of this catalyst are the high activity and high isotacticity for propylene polymerization without using an external electron donor. In this study, we explored the copolymerization of propylene and 1‐octene with MgCl₂/TiCl₄/diether catalyst. It was found that MgCl₂/TiCl₄/diether catalyst showed higher polymerization activity and led to greater 1‐octene content incorporation, compared with a fourth‐generation Ziegler–Natta catalyst (MgCl₂/TiCl₄/diester). With an increase in 1‐octene incorporation in polypropylene chains, the melting temperature, glass transition temperature and crystallinity of the copolymers decreased distinctly. The microstructures of the copolymers were characterized using ¹³C NMR spectroscopy, and the copolymer compositions and number‐average sequence lengths were calculated from the dyad concentration and distribution. This result is very important for the in‐reactor polyolefin alloying process, especially for the case of a single catalyst and two‐step (or two‐reactor) process. Copyright © 2011 Society of Chemical Industry     

Polymerization of 1,3‐dienes containing functional groups: 8. Free‐radical polymerization of 2‐triethoxysilyl‐ 1,3‐butadiene

The presence of a bulky substituent at the 2‐position of 1,3‐butadiene derivatives is known to affect the polymerization behavior and microstructure of the resulting polymers. Free‐radical polymerization of 2‐triethoxysilyl‐1,3‐butadiene ( 1 ) was carried out under various conditions, and its polymerization behavior was compared with that of 2‐triethoxymethyl‐ and other silyl‐substituted butadienes. A sticky polymer of high 1,4‐structure ( ) was obtained in moderate yield by 2,2′‐azobisisobutyronitrile (AIBN)‐initiated polymerization. A smaller amount of Diels–Alder dimer was formed compared with the case of other silyl‐substituted butadienes. The rate of polymerization (R_p) was found to be R_p = k[AIBN]^0.5[ 1 ]^1.2, and the overall activation energy for polymerization was determined to be 117 kJ mol^?1. The monomer reactivity ratios in copolymerization with styrene were r ₁ = 2.65 and r_st = 0.26. The glass transition temperature of the polymer of 1 was found to be ?78 °C. Free‐radical polymerization of 1 proceeded smoothly to give the corresponding 1,4‐polydiene. The 1,4‐E content of the polymer was less compared with that of poly(2‐triethoxymethyl‐1,3‐butadiene) and poly(2‐triisopropoxysilyl‐1,3‐butadiene) prepared under similar conditions. Copyright © 2010 Society of Chemical Industry     

Biodegradable studies of poly(trimethylenecarbonate‐ε‐caprolactone)‐block‐poly(p‐dioxanone), poly(dioxanone), and poly(glycolide‐ε‐caprolactone) (Monocryl®) monofilaments

The aim of the study was to investigate the mechanical properties and biodegradability of poly(trimethylenecarbonate‐ε‐caprolactone)‐block‐poly(p‐dioxanone) [P(TMC‐ε‐CL)‐block‐PDO] in comparison with poly(p‐dioxanone) and poly(glycolide‐ε‐caprolactone) (Monocryl®) monofilaments in vivo and in vitro. P(TMC‐ε‐CL)‐block‐PDO copolymer and poly(p‐dioxanone) were prepared by using ring‐opening polymerization reaction. The monofilament fibers were obtained using conventional melt spun methods. The physicochemical and mechanical properties, such as viscosity, molecular weight, crystallinity, and knot security, were studied. Tensile strength, breaking strength retention, and surface morphology of P(TMC‐ε‐CL)‐block‐PDO, poly(p‐dioxanone), and Monocryl monofilament fibers were studied by immersion in phosphate‐buffered distilled water (pH 7.2) at 37°C and in vivo. The implantation studies of absorbable suture strands were performed in gluteal muscle of rats. The polymers, P(TMC‐ε‐CL)‐block‐PDO, poly(p‐dioxanone), and Monocryl, were semicrystalline and showed 27, 32, and 34% crystallinity, respectively. Those mechanical properties of P(TMC‐ε‐CL)‐block‐PDO were comparatively lower than other polymers. The biodegradability of poly(dioxanone) homopolymer is much slower compared with that of two copolymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 737–743, 2006     

Synthesis,properties and thermal stability of water‐soluble poly(potassium 1‐hydroxyacrylate‐co‐styrene) copolymer

The present work investigates the structure properties of copolymers using thermogravimetric analysis, hot stage microscopy, static light scattering, field emission scanning electron microscopy, X‐ray diffraction analysis and a Brookfield viscometer. Poly(potassium 1‐hydroxyacrylate) (PKHA) is a water‐soluble polymer. However, the copolymer of styrene and 2‐isopropyl‐5‐methylene‐1,3‐dioxolan‐4‐one is not water soluble at equal molar ratio because the polystyrene reduces the solubility. The effect of styrene on poly(potassium 1‐hydroxyacrylate‐co‐styrene) copolymer, i.e. poly(KHA‐co‐St), was investigated for the increasing solubility of the copolymer. The solubility was increased at a lower molar ratio of styrene such as 0.4 in the copolymer. It was found that the copolymer was soluble in water when a content ratio of 68/32 mol% of homopolymer was incorporated in poly(KHA₆₈‐co‐St₃₂) copolymer as determined by NMR analysis. Also the poly(KHA₆₈‐co‐St₃₂) copolymer was found to be salt tolerant, possessed water absorption capacity and was thermally stable up to 183 °C. Moreover, it is shown that the polystyrene content plays a key role in the thermal stability of the copolymer. © 2017 Society of Chemical Industry     

Influence of the synthesis conditions on the structural and thermal properties of poly(l‐lactide)‐b‐poly(ethylene glycol)‐b‐poly(l‐lactide)

The poly(l ‐lactide)‐b‐poly(ethylene glycol)‐b‐poly(l ‐lactide) block copolymers (PLLA‐b‐PEG‐b‐PLLA) were synthesized in a toluene solution by the ring‐opening polymerization of 3,6‐dimethyl‐1,4‐dioxan‐2,5‐dione (LLA) with PEG as a macroinitiator or by transterification from the homopolymers [polylactide and PEG]. Two polymerization conditions were adopted: method A, which used an equimolar catalyst/initiator molar ratio (1–5 wt %), and method B, which used a catalyst content commonly reported in the literature (<0.05 wt %). Method A was more efficient in producing copolymers with a higher yield and monomer conversion, whereas method B resulted in a mixture of the copolymer and homopolymers. The copolymers achieved high molar masses and even presenting similar global compositions, the molar mass distribution and thermal properties depends on the polymerization method. For instance, the suppression of the PEG block crystallization was more noticeable for copolymer A. An experimental design was used to qualify the influence of the catalyst and homopolymer amounts on the transreactions. The catalyst concentration was shown to be the most important factor. Therefore, the effectiveness of method A to produce copolymers was partly due to the transreactions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40419.     

Carbon‐13 NMR,GPC, and DSC study on a propylene‐1‐butene copolymer fractionated by temperature rising elution fractionation

A random copolymer of propylene with small amounts of 1‐butene comonomer, synthesized with a Ziegler–Natta catalyst, was fractionated by temperature rising elution fractionation (TREF) to systemically investigate the fraction samples' molecular microstructure, as well as their relationship to the melting and crystallization behavior. First, TREF was employed to fractionate the sample, and then crystallization analysis fractionation (Crystaf) was used to check the effect of the TREF experiment. In the characterization of the molecular microstructure, carbon‐13 NMR spectroscopy (¹³C NMR) and gel permeation chromatography (GPC) experiments gave the following results: the fraction samples have relatively uniform molecular microstructure; with an increase in elution temperature, the 1‐butene content in the fraction samples decreases, but the molecular weight (M_n) and number average sequence length of propylene (n?_P) increase. In the study on melting and crystallization behavior, differential scanning calorimetry (DSC) experimental results show that the melting temperature increasingly decreases with an increase in 1‐butene content; however, dependence of the melting temperature on molecular weight becomes weaker and weaker with an increase in the number average molecular weight in the range of number average molecular weight below 1.82 × 10⁵ g/mol. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 845–851, 2006     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006     

Synthesis,characterization, and comparison of self‐doped,doped, and undoped forms of polyaniline,poly(o‐anisidine), and poly[aniline‐co‐(o‐anisidine)]

Polyaniline (PANI), poly(o‐anisidine), and poly[aniline‐co‐(o‐anisidine)] were synthesized by chemical oxidative polymerization with ammonium persulfate as an oxidizing reagent in an HCl medium. The viscosities, electrical conductivity, and crystallinity of the resulting polymers (self‐doped forms) were compared with those of the doped and undoped forms. The self‐doped, doped, and undoped forms of these polymers were characterized with infrared spectroscopy, ultraviolet–visible spectroscopy, and a four‐point‐probe conductivity method. X‐ray diffraction characterization revealed the crystalline nature of the polymers. The observed decrease in the conductivity of the copolymer and poly(o‐anisidine) with respect to PANI was attributed to the incorporation of the methoxy moieties into the PANI chain. The homopolymers attained conductivity in the range of 3.97 × 10^?3 to 7.8 S/cm after doping with HCl. The conductivity of the undoped forms of the poly[aniline‐co‐(o‐anisidine)] and poly(o‐anisidine) was observed to be lower than 10^?5 J/S cm^?1. The conductivity of the studied polymer forms decreased by the doping process in the following order: self‐doped → doped → undoped. The conductivity of the studied polymers decreased by the monomer species in the following order: PANI → poly[aniline‐co‐(o‐anisidine)] → poly(o‐anisidine). All the polymer samples were largely amorphous, but with the attachment of the pendant groups of anisidine to the polymer system, the crystallinity region increased. The undoped form of poly[aniline‐co‐(o‐anisidine)] had good solubility in common organic solvents, whereas doped poly[aniline‐co‐(o‐anisidine)] was moderately crystalline and exhibited higher conductivity than the anisidine homopolymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Three‐site mechanism and molecular weight: Time dependency in liquid propylene batch polymerization using a MgCl2‐supported Ziegler‐Natta catalyst

This article demonstrates that the molecular weight of propylene homopolymer decreases with time, and that the molecular weight distribution (MWD) narrows when a highly active MgCl₂‐supported catalyst is used in a liquid pool polymerization at constant H₂ concentration and temperature. To track the change in molecular weight and its distribution during polymerization, small portions of homo polymer samples were taken during the reaction. These samples were analyzed by Cross Fractionation Chromatograph (CFC), and the resulting data were treated with a three‐site model. These analyses clearly showed that the high molecular weight fraction of the distribution decreases as a function of time. At the same time, the MWD narrows because the weight‐average molecular weight decreases faster than the number‐average molecular weight. A probable mechanism based on the reaction of an external donor with AlEt₃ is proposed to explain these phenomena. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1035–1047, 2001     

Melt‐state miscibility of poly(ethylene‐co‐1‐octene) and linear polyethylene

On purpose to examine the effect of branch length on the miscibility of polyolefin blends, miscibility behavior of linear polyethylene/poly(ethylene‐co‐1‐octene) blend was studied and compared to that of linear polyethylene/poly(ethylene‐co‐1‐butene) blend. Miscibility of the blend was determined by observing the morphology quenched from the melt, and by using the relation between interaction parameter and copolymer composition. When the weight composition and molecular weight was the same, poly(ethylene‐co‐1‐octene) was slightly more miscible with linear polyethylene than poly(ethylene‐co‐1‐butene) was. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Gas transport and optical properties of ABA‐type triblock copolymers designed using fluorine‐containing polyimide macroinitiators with methyl methacrylate

4,4'‐(Hexafluoroisopropylidene) diphthalic anhydride 2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) polyimide macroinitiator was synthesized and reacted with poly(methyl methacrylate) (PMMA) to form an ABA‐type triblock copolymer by atom transfer radical polymerization. The effect of the ABA‐type triblock copolymer structure on solid, thermal, optical and gas transport properties was systematically investigated and compared with the physical blend polymer. The blend polymer was cloudy, whereas the triblock copolymer was colorless and transparent. The PMMA component decomposition temperature for the triblock copolymer slightly shifted to higher temperature, while its gas barrier property was higher than the blend polymer. The refractive index and the gas permeability decreased while maintaining the heat resistance by a high nanoscale distribution of both polymer components. The 6FDA‐TeMPD/PMMA ABA‐type triblock copolymer can be described as a polymer material with high heat resistance, high gas barrier property and low refractive index amongst existing polymers. © 2013 Society of Chemical Industry