Fractionation and characterization of an ethylene–propylene copolymer produced with a MgCl2/SiO2/TiCl4/diester‐type ziegler–natta catalyst

An ethylene–propylene copolymer synthesized with a Ziegler–Natta catalyst was fractionated by a combination of dissolution/precipitation and temperature‐gradient extraction fractionation. The fractions were characterized with ¹³C‐NMR, differential scanning calorimetry, and wide‐angle X‐ray diffraction. The fractionation was carried out mainly with respect to the content of ethylene, but the crystallizable propylene sequences could also exert an influence on the fractionation. The copolymer contained a series of components with wide variations in the compositions. With an increase in the ethylene content, the structure of the fractions became blockier and blockier, and the fraction extracted at 111°C had the blockiest structure. A further increase in the ethylene content led to a decrease in the length and number of the propylene sequences. Differential scanning calorimetry results showed that the composition distribution in single fractions was not homogeneous, and multiple melting peaks were observed. Wide‐angle X‐ray diffraction results revealed both polyethylene and polypropylene crystals in most of the fractions. Short propylene sequences could be included in the polyethylene crystals, and short ethylene sequences could also be incorporated into the polypropylene crystals. The incorporation of propylene sequences into polyethylene crystals strongly depended on the sequence distribution and crystallization conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Copolymerization of ethylene and propylene catalyzed by novel magnesium chloride supported,vanadium‐based catalysts

Two novel magnesium chloride supported, vanadium‐based Ziegler–Natta catalysts with 9,9‐bis(methoxymethyl)fluorene and di‐i‐butyl phthalate as internal donors were prepared and used in the copolymerization of ethylene and propylene. The catalytic behaviors of these catalysts were investigated and compared with those of traditional magnesium chloride supported, vanadium‐based catalysts without internal donors. Differential scanning calorimetry, gel permeation chromatography, and ¹³C‐NMR spectroscopy analysis were performed to characterize the melting temperatures, molecular weights, and molecular weight distributions as well as structures and compositions of the products. The copolymerization kinetic results indicated that the novel catalyst with 9,9‐bis(methoxymethyl)fluorene as an internal donor had the highest catalytic activity and optimal kinetic behavior in ethylene–propylene copolymerization with an ethylene/propylene molar ratio of 44/56. Low‐crystallinity and high‐molecular‐weight copolymers were obtained with these novel magnesium chloride supported, vanadium‐based catalysts. The reactivity ratio data indicated that the catalytic systems had a tendency to produce random ethylene–propylene copolymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The role of two different internal donors (phthalate and 1,3‐diether) on the formation of surface structure in MgCl2‐supported Ziegler–Natta catalysts and their catalytic performance of propylene polymerization

The role of two different internal donors [a phthalate (diisobutylphthalate) and a 1,3‐diether (2,2‐diisobutyl‐1,3‐dimethoxypropane)] on the formation of surface structure in MgCl₂‐supported Ziegler–Natta catalysts and their catalytic performance of propylene polymerization was investigated by comparing and correlating the catalyst structures and the polymerization characteristics. In the catalyst formation, the 1,3‐diether had better affinity for the MgCl₂ surface than the phthalate and the 1,3‐diether generated the (110) surface more than the (104) surface while the phthalate generated both the (110) and (104) surfaces of MgCl₂. With both donors introduced, the (110) and (104) surfaces were generated simultaneously, although the (110) surface was dominant due to the higher affinity via the 1,3‐diether. In addition, it seemed probable that the active sites formed on the (110) plane showed isospecific characteristics in the presence of a donor while those formed on the (104) plane could be isospecific regardless of a donor. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40536.     

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     

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     

Liquid Pool Copolymerization of Propylene/1‐Butene with a MgCl2‐Supported Ziegler‐Natta Catalyst

Summary: Liquid pool propylene/1‐butene copolymerizations were carried out in a batch reactor with a high activity Ziegler‐Natta catalyst system. Experimental runs were performed to evaluate the effect of the 1‐butene content on the crystallinity and melt temperature of the polymer resins. According to the results, 1‐butene can be significantly incorporated into the polymer chain at high polymerization rates over the whole range of copolymer compositions, leading to a decrease in the melting temperature (T_m) of the polymer, when compared to the poly(propylene) homopolymer, allowing for reduction of the sealing initiation temperature. It was observed by GPC and MFI measurements that the average molecular weights and the polydispersity index of the copolymer significantly decreased when compared to the ones obtained from poly(propylene). Despite high polymerization rates, polymer particles with good morphological features were produced in all cases. It was also observed that the absence of an external electron donor led to low crystallinity values for both the poly(propylene) homopolymer and for copolymers with different fractions of 1‐butene, when compared to literature values frequently reported for polymer resins based on 1‐butene and propylene. The obtained results indicate that a family of bulk propylene/1‐butene copolymer grades can be successfully developed for packaging and film applications.

Surface morphology and molecular weight distribution (deconvoluted into Schulz‐Flory distributions) of the propylene/1‐butene copolymer.     

Influence of the Form II/Form I crystal polymorphism of random copolymers of butene‐1 with ethylene or propylene on the peel behavior of peel films

Peel films of blends of low density polyethylene (LDPE) and random isotactic copolymers of butene‐1 with either ethylene (iPB‐Eth) or propylene (iPB‐Prop) were investigated regarding the effect of the copolymer composition on both the Form II mesophase to Form I crystal transformation of the copolymers, and the time‐dependent peel behavior of their blends with LDPE in peel films. In general, there is observed a decrease of the peel force with increasing concentration of both ethylene and propylene co‐units in random iPB‐1 based copolymers and their blends with LDPE, after completion of the Form II to Form I transformation. Thus, to tailor the peel force, either the content of the peel component in the blends, or the concentration of ethylene or propylene co‐units in the peel component may be varied. The effect of ethylene co‐units in the random copolymers on the peel force is distinctly larger than that of propylene co‐units. Parallel to the Form II to Form I transition of butene‐1 based copolymers, the peel force decreases with a rate which depends on the copolymer composition. The Form II to Form I transition in iPB‐Prop copolymers proceeds distinctly faster than in iPB‐Eth copolymers of identical concentration of co‐units. POLYM. ENG. SCI., 55:1749–1757, 2015. © 2014 Society of Plastics Engineers     

A new post‐metallocene catalyst for alkene polymerization: copolymerization of ethylene and 1‐hexene with titanium complexes bearing N,N‐dialkylcarbamato ligands

A new type of post‐metallocene polymerization catalyst based on titanium complexes with N,N‐dialkylcarbamato ligands was used to copolymerize ethylene and 1‐hexene. These easy‐to‐synthesize and stable complexes in combination with different organoaluminium co‐catalysts produce random ethylene/1‐hexene copolymers characterized by a broad molecular weight distribution and high 1‐hexene incorporation, as confirmed by SEC, DSC and ¹³C NMR analysis. The influence of the main reaction parameters on the polymerization reactions was studied including the type of catalyst components, solvent, temperature, the ethylene partial pressure and the [Al]/[Ti] ratio in the catalyst. A higher activity and a higher 1‐hexene incorporation were achieved with AlMe₃‐depleted methylalumoxane as co‐catalyst and chlorobenzene as solvent. © 2013 Society of Chemical Industry     

Poly(propylene‐co‐ethylene) produced with a conventional and a self‐supported ziegler–natta catalyst: Effect of ethylene and hydrogen concentration on activity and polymer structure

A novel self‐supported emulsion‐based catalyst and a conventional MgCl₂‐supported Ziegler–Natta catalyst were used in the copolymerization of propylene and ethylene under industrial conditions using triethyl aluminium as cocatalyst and dicyclopentyl dimethoxy silane as external donor. The effects of the concentration of ethylene and hydrogen on the polymerization behaviors and polymer properties were investigated. The combined effect of both ethylene and hydrogen increased the relative activity of the novel catalyst more than for the conventional catalyst. This trend was consistent with our earlier observed higher degree of dormancy, due to 2,1 insertions, found with the novel catalyst. More importantly, the work has uncovered that the self‐supported catalyst incorporates ethylene in a more random fashion and produces copolymers with relatively narrow molecular weight distribution (MWD). These results in combination with polymer microstructure studies using Fourier transform infrared spectroscopy, ¹³C‐NMR spectroscopy, and differential scanning calorimetry all indicated that the novel catalyst has a narrower distribution of active site types than the conventional reference catalyst. The narrow composition of active site structures, the narrow MWD, and the random incorporation of ethylene into the polymer chain indicated that the emulsion‐based catalyst possesses features that to a certain degree tend to be more indicative for a single‐site‐like catalyst structure and behavior. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of diether as internal donor on MgCl2‐supported Ziegler–Natta catalyst for propylene polymerization

This article demonstrates the influence of the molar ratio between diether as internal donor and Magnesium dichloride in processing of the catalyst preparation on the catalytic performance for propylene polymerization with MgCl₂‐supported Ziegler–Natta catalyst. The effect of electron donor on catalyst is investigated. The experimental data find that diether content on catalyst increases and Ti content on catalyst decreases with the increase of diether/Mg molar ratio. This result indicates that diether as internal donor is not coordinated to Ti species but to Mg species on catalyst. The introduction of diether remarkably improves the catalytic activity. The extents of improvement closely connect with diether/Mg molar ratio. The stereospecificity of catalyst intensively depends on the structure of diether as internal donor. The possible model of multi‐active sites on heterogeneous Ziegler–Natta catalyst is proposed to explain these phenomena. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1399–1404, 2006     

丙烯/1-丁烯无规共聚物与丙烯/乙烯抗冲共聚物的对比研究

对丙烯/1-丁烯无规共聚物(PPB)与丙烯/乙烯抗冲共聚物(PPE)的结晶行为进行对比,在等温结晶时,通过相对结晶度随时间的变化关系、等温结晶曲线等研究,表明丙烯/1-丁烯无规共聚物结晶速率明显低于丙烯/乙烯抗冲共聚物,同时丙烯/乙烯抗冲共聚物的等温结晶速率随乙烯单元含量增加没有明显降低。根据Avrami方程计算了共聚物的结晶活化能,证明丙烯/1-丁烯无规共聚物的结晶能力较丙烯/乙烯抗冲共聚物低。扫描电镜分析丙烯/1-丁烯无规共聚物在丁烯单元摩尔分数2.39%时没有韧性拉伸,而丙烯/乙烯抗冲共聚物在乙烯单元摩尔分数3%时出现韧性拉伸。     

Alkoxysilane modification of a Ti‐based catalyst system for ethylene dimerization: A step forward in enhancing productivity and selectivity

Alkoxysilanes were used as novel enhancing agents in the Ti‐based catalyst for the highly selective ethylene dimerization to butene‐1. The dimerization of ethylene was carried out using the homogeneous Ti(OBu)₄/THF/TEA/alkoxysilane catalyst system, where Ti(OBu)₄, THF (tetrahydrofuran), TEA (triethylaluminum), and alkoxysilane were used as catalyst, additive, activator, and modifier, respectively. The nature and concentration of alkoxysilanes on the dimerization rate, catalyst yield, by‐products production, and selectivity to butene‐1 were investigated in detail. It was found that the performance of alkoxysilanes assisted with the class of the Ti‐based catalyst system, developed in this work, has been furthered by high productivity and selectivity with respect to the bare catalyst system. It proved that alkoxysilanes could play an excellent improving role in the selective ethylene dimerization process. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44615.     

Photodegradation of ethylene/propylene/polar monomers,co‐, and terpolymers. II. Prepared by Ni catalyst systems

The copolymers of ethylene/propylene as well as their terpolymers with polar monomers were prepared by Ni‐catalyst systems and their photodegradation behavior was studied by Fourier transform infrared spectroscopy. The polar monomers used to synthesize co‐ and terpolymers of ethylene/propylene/polar monomer were 5‐hexen‐1‐ol, 10‐undecen‐1‐ol, acrylamide, methylmethacrylate, acrylonitrile, and methylvinyl ketone. The morphological changes of the irradiated samples were determined by scanning electron microscopy. The photodegradation kinetics has also been studied. The surface damage caused by polychromatic irradiation (λ ≥ 290 nm) at 55 °C in atmospheric air is presented in different micrographs. The rate of photo‐oxidative degradation is very fast in terpolymers containing polar monomers as compared with copolymers and homopolymers. The morphological study of the photodegraded samples showed a very good correlation with the photodegraded results. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1783–1791, 2007     

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     

Novel MgCl2-supported catalyst containing diol dibenzoate donor for propylene polymerization

A novel MgCl₂-supported Ziegler-Natta catalyst containing 2-isoamyl-2-isopropyl-1,3-propandiol dibenzoate donor for propylene polymerization was studied, and compared with catalysts with different internal donors, such as benzoate, phthalate and diether, in polymerization dynamic behavior, activity, hydrogen response and stereospecificity. It was found that there are two highly isospecific active sites in the catalyst with dibenzoate internal donor system and the effections of temperature are different on the performances of the two highly isospecific sites.     

Comparative study of copolymerization and terpolymerization of ethylene/propylene/diene monomers using metallocene catalyst

(Ind)₂ZrCl₂ catalyst was synthesized and used for copolymerization of ethylene and propylene (EPR) and terpolymerization of ethylene propylene and 5‐ethyldiene‐2‐norbornene (ENB). Methylaluminoxane (MAO) was used as cocatalyst. The activity of the catalyst was higher in copolymerization of ethylene and propylene (EPR) rather than in terpolymerization of ethylene, propylene and diene monomers. The effects of [Al] : [Zr] molar ratio, polymerization temperature, pressure ratio of ethylene/propylene and the ENB concentration on the terpolymerization behavior were studied. The highest productivity of the catalyst was obtained at 60°C, [Al] : [Zr] molar ratios of 750 : 1 and 500 : 1 for copolymerization and terpolymerization, respectively. Increasing the molar ratio of [Al] : [Zr] up to 500 : 1 increased the ethylene and ENB contents of the terpolymers, while beyond this ratio the productivity of the catalyst dropped, leading to lower ethylene and ENB contents. Terpolymerization was carried out batchwise at temperatures from 40 to 70°C. Rate time profiles of the polymerization were a decay type for both copolymerization and terpolymerization. Glass transition temperatures (T_g) of the obtained terpolymers were between ?64 and ?52°C. Glass transition temperatures of both copolymers and terpolymers were decreased with increased ethylene content of the polymers. Dynamic mechanical and rheological properties of the obtained polymers were studied. A compounded EPDM showed good thermal stability with time. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of copolymerization conditions on the structure and properties of polyethylene/polypropylene/poly(ethylene‐co‐propylene) in‐reactor alloys synthesized in gas‐phase with spherical ziegler‐natta catalyst

A spherical TiCl₄/MgCl₂‐based catalyst was used in the synthesis of polyethylene/polypropylene/poly (ethylene‐co‐propylene) in‐reactor alloys by sequential homopolymerization of ethylene, homopolymerization of propylene, and copolymerization of ethylene and propylene in gas‐phase. Different conditions in the third stage, such as the pressure of ethylene–propylene mixture and the feed ratio of ethylene, were investigated, and their influences on the compositions, structural distribution and properties of the in‐reactor alloys were studied. Increasing the feed ratio of ethylene is favorable for forming random ethylene–propylene copolymer and segmented ethylene–propylene copolymer, however, slightly influences the formation of ethylene‐b‐propylene block copolymer and homopolyethylene. Raising the pressure of ethylene–propylene mixture results in the increment of segmented ethylene–propylene copolymer, ethylene‐b‐propylene block copolymer, and PE fractions, but exerts a slight influence on both the random copolymer and PP fractions. The impact strength of PE/PP/EPR in‐reactor alloys can be markedly improved by increasing the feed ratio of ethylene in the ethylene–propylene mixture or increasing the pressure of ethylene–propylene mixture. However, the flexural modulus decreases as the feed ratio of ethylene in the ethylene–propylene mixture or the pressure of ethylene–propylene mixture increases. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2481–2487, 2006     

Rheological,mechanical and thermal properties of propylene‐ethylene block copolymer/polyalphaolefins blends

The rheological, thermal, and mechanical properties of propylene–ethylene block copolymer (PPB) blends with predominantly atactic molecular structure of low molecular weight polypropylene and propylene copolymers with either ethylene or 1‐butene (APAO) have been studied. It has been found that blend properties depend on comonomer type, content, and molecular weight of APAO as well as blend composition. APAO having ethylene comonomer showed better miscibility with PPB than the other ones, and high comonomer content of APAOs gave dramatic increase in impact strength over 30 wt%. It has been concluded that APAO can be used as an effective modifier of PPB. POLYM. ENG. SCI., 47:1905–1911, 2007. © 2007 Society of Plastics Engineers     

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     

Synthesis and surface‐active properties of a trisiloxane‐modified oligo(propylene oxide‐block‐ethylene oxide) wetting agent

Polydisperse 1,1,1,3,5,5,5‐heptamethyltrisiloxane‐oligo(propylene oxide‐block‐ethylene oxide) wetting agents were synthesized through the hydrosilylation of 1,1,1,3,5,5,5‐heptamethyltrisiloxane (HMTS) with active hydrogen and allyl oligo(propylene oxide‐block‐ethylene oxide) [allyl oligo(PO‐b‐EO)] with hexachloro dihydrogen platinate(IV) as a catalyst. Allyl oligo(PO‐b‐EO) with a hydrophilic–hydrophobic balance was synthesized through the combination of propylene oxide (PO) and ethylene oxide with allyl alcohol. The wetting agents with a hydrophilic–hydrophobic balance were synthesized. The aqueous solutions of the wetting agents (0.1 wt %) were almost visibly turbid. An increase in the number of hydrophobic groups of HMTS and PO for the wetting agents resulted in a lower critical solution temperature. Lower surface tensions of 20–25 dyn/cm were found above the critical micelle concentration (cmc), and they decreased with an increase in the number of hydrophobic groups. The cmc's were below 0.01 wt %, decreasing with as the number of hydrophobic groups increased. The wetting power and emulsion stability for the oil‐in‐water systems increased as the concentration of the wetting agents increased, and they decreased as the number of hydrophobic groups increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3292–3302, 2004