Effect of cocatalysts on ethylene polymerization with fluorinated bisphenoxyimine titanium as a catalyst

In this study, we examined various alkylaluminums, including triethylaluminum (TEA), triisobutylaluminum (TIBA), and diethylaluminum chloride (DEAC), as cocatalysts for the activation of ethylene polymerizations in the presence of a fluorinated Fujita group invented titanium (FI‐Ti) catalyst, bis[N‐(3‐tert‐butylsalicylidene)‐2,3,4,5,6‐pentafluoroanilinato] titanium(IV) dichloride (complex 1 ). DEAC, because of the strong Lewis acidity, was an efficient cocatalyst for activating complex 1 for the ethylene polymerizations, whereas TEA and TIBA as cocatalysts could hardly polymerize ethylene. The effects of the polymerization temperature and Al/Ti molar ratio on the formation of active species, properties, and molecular weight of the resulting polyethylene were investigated. In the complex 1 /DEAC catalyst system, the oxidation states of Ti active species were determined by electron paramagnetic resonance. The results demonstrated that Ti(IV) active species were inclined to polymerize ethylene and yielded high‐molecular‐weight polyethylene. Comparatively, Ti(III) active species resulted from the reduction of Ti(IV) by DEAC and afforded oligomers. Moreover, the bigger steric bulk for the cocatalysts was necessary to achieve ethylene living polymerization with the fluorinated FI‐Ti catalyst. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of aluminum alkyls on ethylene/1‐hexene polymerization with supported metallocene/MAO catalysts in the gas phase

The effects of aluminum alkyls on the gas‐phase ethylene homopolymerization and ethylene/1‐hexene copolymerization over polymer‐supported metallocene/methylaluminoxane [(n‐BuCp)₂ZrCl₂/MAO] catalysts were investigated. Results with triisobutyl aluminum (TIBA), triethyl aluminum (TEA), and tri‐n‐octyl aluminum (TNOA) showed that both the type and the amount of aluminum alkyl influenced the polymerization activity profiles and to a lesser extent the polymer molar masses. The response to aluminum alkyls depended on the morphology and the Al : Zr ratio of the catalyst. Addition of TIBA and TEA to supported catalysts with Al : Zr >200 reduced the initial activity but at times resulted in higher average activities due to broadening of the kinetic profiles, i.e., alkyls can be used to control the shape of the activity profiles. A catalyst with Al : Zr = 110 exhibited relatively low activity when the amount of TIBA added was <0.4 mmol, but the activity increased fivefold by increasing the TIBA amount to 0.6 mmol. The effectiveness of the aluminum alkyls in inhibiting the initial polymerization activity is in the following order: TEA > TIBA >> TNOA. A 2‐L semibatch reactor, typically run at 80°C and 1.4 MPa ethylene pressure for 1 to 5 h was used for the gas‐phase polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3549–3560, 2004     

Ethylene and Propylene Polymerization Using In Situ Supported Me2Si(Ind)2ZrCl2 Catalyst: Experimental and Theoretical Study

Summary: Me₂Si(Ind)₂ZrCl₂ was in situ immobilized onto SMAO and used for ethylene and propylene polymerization in the presence of TEA or TIBA as cocatalyst. The catalytic system Me₂Si(Ind)₂ZrCl₂/SMAO exhibited different behavior depending on the amount and nature of the alkylaluminum employed and on the monomer type. The catalyst activity was nearly 0.4 kg polymer · g cat^?1 · h^?1 with both cocatalysts for propylene polymerization. Similar activities were observed for ethylene polymerization in the presence of TIBA. When ethylene was polymerized using TEA at an Al/Zr molar ratio of 250, the activity was 10 times higher. Polyethylenes made by in situ supported or homogeneous catalyst systems had practically the same melting point (T_m). On the other hand, poly(propylenes) made using in situ supported catalyst systems had a slightly lower T_m than poly(propylenes) made using homogeneous catalyst systems. The nature and amount of the alkylaluminum also influenced the molar mass. The poly(propylene) molar mass was higher when TIBA was the cocatalyst. The opposite behavior was observed for the polyethylenes. Concerning the alkylaluminum concentration, the molar mass of the polymers decreased as the amount of TEA increased. In the presence of TIBA, the polyethylene's molar mass was almost the same, independent of the alkylaluminum concentration, and the poly(propylene) molar mass increased with increasing amounts of cocatalyst. The deconvolution of the GPC curves showed 2 peaks for the homogeneous system and 3 peaks for the heterogeneous in situ supported system. The only exception was observed when TEA was used at an Al/Zr molar ratio of 500, where the best fit was obtained with 2 peaks. Based on the GPC deconvolution results and on the theoretical modeling, a proposal for the active site structure was made.

Molar mass distribution deconvolution of polyethylene prepared with the system Me₂Si(Ind)₂ZrCl₂/SMAO/TIBA with 500 mol/mol of alkylaluminum as cocatalyst.     

Highly active Ziegler–Natta catalyst for propylene polymerization

Polymerization of propylene was carried out by using a MgCl₂–EtOH–TiCl₄–ID–TEA–ED catalyst system in n‐heptane, where ID (internal donor) was an organic diester, ED (external donor) was a silane compound, and TEA (triethyl aluminum) was the activator. The influences of temperature, pressure, time, hydrogen, and the molar ratios of Al/Ti and ED/Ti on polymer isotacticity and catalyst activity were studied by solubility in boiling n‐heptane and measuring the polymer produced, respectively. The morphology of the polymers was evaluated through scanning electron microscopy and particle size distribution. The rheological properties of the poly(propylene) were determined by the melt flow index. It was found that the catalyst showed good morphology and high activity and also the produced polymers were characterized by high isotacticity and globulelike shapes. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1744–1749, 2005     

Comparative study of propylene polymerization using monosupported and bisupported titanium‐based Ziegler–Natta catalysts

Heterogeneous Ziegler–Natta systems—MgCl₂ (ethoxide type)/TiCl₄/di‐n‐butyl phthalate (DNBP)/triethylaluminum (TEA)/dimethoxymethylcyclohexylsilane (DMMCHS) and SiO₂/MgCl₂ (ethoxide type)/TiCl₄/DNBP/TEA/DMMCHS—were studied for the polymerization of propylene. The slurry polymerization of propylene was carried out with the catalyst systems in n‐heptane. Both systems performed with optimum activity at a particular [Al]/[DMMCHS]/[Ti] molar ratio. The ratio to reach the highest activity was much lower for the bisupported catalyst system. The productivity of the bisupported catalyst was higher than that of the monosupported one. Polypropylene of a high isotacticity index (II; >96%) was obtained with both systems and did not significantly change with an increasing [Al]/[DMMCHS]/[Ti] molar ratio. The addition of hydrogen as a chain‐transfer agent reduced II of the polymers obtained with both systems. The effect of the polymerization temperature (40–75°C) on the viscosity‐average molecular weight (M_v) and II showed a decrease in both cases. The bisupported catalyst system produced a polymer with higher M_v. The effect of temperature on II was similar for both the monosupported and bisupported systems. A monomer pressure of 2.02 × 10⁵ to 0.8 × 10⁶ Pa increased M_v of the obtained polymer. II of the polymer slightly decreased with increasing monomer pressure. The titanium content of the catalyst was 1.70 and 3.55% for the monosupported and bisupported systems, respectively. The surface area of the bisupported catalyst was higher than that of the monosupported catalyst. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2220–2226, 2006     

Heterogeneous polymerization of ethene with metallocene catalysts. A comparison of poly(organosiloxane) microgels and silica as support materials for MAO‐type cocatalysts

Zirconocene dichloride and bis(n‐butylcyclopentadienyl)zirconium dichloride are used as catalyst precursors for the heterogeneous polymerization of ethene. A methyl‐substituted microgel as support material for heterogeneous cocatalysts on the basis of MAO is compared with different commercially available silica‐supported cocatalysts. The catalyst performances and the properties of the obtained polyethenes show considerable differences. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 613–617, 2001     

Donor Atom‐Stabilized Aluminum Alkyls as Cocatalysts for the Ziegler–Natta Polymerization of Propene

A number of organoaluminum compounds, stabilized with intramolecular nitrogen‐ or oxygen‐donor functions, have been used as cocatalysts for the MgCl₂/TiCl₄‐catalyzed homopolymerization of propene as well as for the copolymerization of ethene with propene. The polymerization behavior of these aluminum alkyls was examined at different Al/Ti ratios within the range of 2 to 50 and compared with the reference of triethylaluminum (TEA). Especially the alkyls [2‐(N,N‐dimethylaminomethyl)phenyl]dimethylaluminum ( 1 ) and [2‐(N,N‐dimethylaminomethyl)phenyl]diethylaluminum ( 2 ) show the highest activities at very low Al/Ti ratios in the homopolymerization of propene, whereas TEA is almost inactive. The species [8‐(N,N‐dimethylamino)naphthyl]dimethylaluminum ( 4 ) reaches the highest activity of all examined alkyls and is very close to the highest value obtained with TEA. Bulky iso‐butyl groups at the aluminum center are responsible for the very poor performance of the nitrogen stabilized cocatalysts [8‐(N,N‐dimethylamino)naphthyl]diisobutylaluminum ( 5 ) and [2‐(N,N‐dimethylaminomethyl)phenyl]diisobutylaluminum ( 3 ). The properties of the polypropenes synthesized with the stabilized organoaluminum species are similar to those produced with TEA but with a distinctly higher molar mass. In the case of 1 , it was possible to increase the molar mass by a factor of three. For the copolymerizations, the compounds [2‐(N,N‐diethylaminomethyl)phenyl]diethylaluminum ( 7 ) and (2‐methoxybenzyl)diisobutylaluminum ( 8 ) were found to be most suitable, producing polymers with significantly higher activities than TEA. For all copolymers two fractions were obtained, one crystalline fraction with a low and an amorphous part with a high amount of comonomer. In both fractions, 7 and 8 provide a higher comonomer incorporation than TEA.     

Microwave‐assisted and classical heating polycondensation reaction of bis(p‐amido benzoic acid)‐N‐trimellitylimido‐L‐leucine with diisocyanates as a new method for preparation of optically active poly(amide imide)s

A new class of optically active poly(amide imide)s were synthesized via direct polycondensation reaction of diisocyanates with a chiral diacid monomer. The step‐growth polymerization reactions of monomer bis(p‐amido benzoic acid)‐N‐trimellitylimido‐L‐leucine (BPABTL) (5) as a diacid monomer with 4,4′‐methylene bis(4‐phenylisocyanate) (MDI) (6) was performed under microwave irradiation, solution polymerization under gradual heating and reflux condition in the presence of pyridine (Py), dibuthyltin dilurate (DBTDL), and triethylamine (TEA) as a catalyst and without a catalyst, respectively. The optimized polymerization conditions according to solvent and catalyst for each method were performed with tolylene‐2,4‐diisocyanate (TDI) (7), hexamethylene diisocyanate (HDI) (8), and isophorone diisocyanate (IPDI) (9) to produce optically active poly(amide imide)s by the diisocyanate route. The resulting polymers have inherent viscosities in the range of 0.09–1.10 dL/g. These polymers are optically active, thermally stable, and soluble in amide type solvents. All of the above polymers were fully characterized by IR spectroscopy, ¹H NMR spectroscopy, elemental analyses, specific rotation, and thermal analyses methods. Some structural characterization and physical properties of this new optically active poly(amide imide)s are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1647–1659, 2004     

Influence of cocatalyst on the stereoselectivity and productivity of styrene polymerization reactions

Influence of different cocatalysts on the polymerization reaction of styrene using heterogeneous nanoparticle NA-MgO and NA-TiO2 (anatase) supported bis (cyclopentadienyl) zirconium dichloride catalysts is studied. Methyaluminoxane, trityl tetrakis(pentafluorophenyl)borate(1), dimethylanilinium tetrakis (pentafluoro-phenyl)borate (2) and tris(pentafluorophenyl)borane (3) are used as cocatalysts for this study. The productivity and stereoselectivity of the catalysts systems are found to be highest with MAO and lowest with the borane 3 (MAO > 1> 2 > 3). Catalysts derived from the borane 3 yield amorphous atactic polystyrenes but those from cocatalysts MAO, 1, or 2 yield crystalline, syndiotactic polystyrenes under the same reaction conditions. Effects of addition of various scavengers and solvents with different polarities on styrene polymerizations are also reported here. Characterization of the obtained polymers is done by Gel Permeation Chromatography, ¹³C-NMR spectroscopy and Differential Scanning Calorimetry.     

Influence of cocatalyst on the structure and properties of polypropylene/poly (ethylene‐co‐propylene) in‐reactor alloys prepared by MgCl2/TiCl4/diester type Ziegler‐Natta catalyst

In this work, a series of polypropylene/poly(ethylene‐co‐propylene) (iPP/EPR) in‐reactor alloys were prepared by MgCl₂/TiCl₄/diester type Ziegler‐Natta catalyst with triethylaluminium/triisobutylaluminium (TEA/TIBA) mixture as cocatalyst. The influence of cocatalyst and external electron donor, e.g., diphenyldimethoxysilane (DDS) or dicyclopentyldimethoxysilane (D ‐donor), on the structure and mechanical properties of iPP/EPR in‐reactor alloys were studied and discussed. According to the characterization results, PP/EPR was mainly composed of random poly(ethylene‐co‐propylene), segmented poly(ethylene‐co‐propylene), and high isotactic PP. Using TEA/TIBA mixture as cocatalyst and DDS as external electron donor, as TEA/TIBA ratio increased, the impact strength of iPP/EPR in‐reactor alloys had an increasing trend. Using TEA/TIBA mixture as cocatalyst and D ‐donor as external electron donor, the impact strength of iPP/EPR in‐reactor alloy were dramatically improved. In this case, the iPP/EPR in‐reactor alloy prepared at TEA: TIBA = 4 : 1 was the toughest. The influence of cocatalyst and external electron donor on the flexural modulus and flexural strength could be ignored. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Ethylene polymerization with iron‐based diimine catalyst supported on MCM‐41

A mesoporous molecular sieve MCM‐41 supported iron‐based diimine catalyst ( MC ) was prepared for the first time. The kinetic behavior of ethylene polymerization with MC was studied. The effects of Al/Fe molar ratio and various cocatalysts on the catalytic activity and properties of the polyethylene obtained were investigated. The results showed that good catalytic activities can be reached with cocatalyst methylaluminoxane (MAO) and triethylaluminium (TEA). Ethylene polymerization with MC gave polymers with higher molecular weight, melting temperature and onset temperatures of decomposition (T_onset) and better morphology than those obtained with the corresponding homogeneous catalyst. Copyright © 2004 Society of Chemical Industry     

Small‐angle X‐ray scattering study of modified porous suspension–poly(vinyl chloride) particles

Small‐angle X‐ray scattering (SAXS) was applied to investigate the microstructure of unmodified and modified porous commercial suspension‐type poly(vinyl chloride) (PVC) particles. The modified PVC particles were prepared by an in situ stabilizer‐free polymerization/crosslinking of particles absorbed with a monomer/crosslinker/peroxide solution. The modifying polymers include styrene with or without divinyl benzene (DVB) as a crosslinker and methyl methacrylate (MMA) with or without ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The SAXS method was used to highlight the effect of polystyrene (PS) on the microstructure of PVC particles and to evaluate the characteristic lengths, both in the PVC/PS and the PVC/XPS (PS crosslinked with 0 and 5% DVB, respectively) systems. A model is suggested, where during the synthesis modification process, swelling of PVC by styrene and styrene polymerization occur simultaneously. PVC swelling by styrene causes destruction of the PVC subprimary particles, whereas styrene polymerization leads to phase separation resulting from incompatibility of the polymers. It was further suggested that because of PVC swelling by styrene, structure of the subprimary particles is lost. Therefore the characteristic lengths of PVC/PS and PVC/XPS, as calculated from the SAXS measurements, were attributed to the size of the phase‐separated PS and XPS inclusions, respectively. The SAXS method also shows that PMMA and XPMMA do not influence the PVC microstructure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1024–1031, 2005     

Preparation of porous spherical MgCl2/SiO2 complex support as precursor for catalytic propylene polymerization

The MgCl₂/SiO₂ complex support was prepared by spray drying using alcoholic suspension, which contained MgCl₂ and SiO₂. The complex support reacted with TiCl₄ and di‐n‐butyl phthalate, giving a catalyst for propylene polymerization. The catalyst was spherical and porous with high specific surface area. TEA was used as a cocatalyst, and four kinds of alkoxysilane were used as external donors. The bulk polymerization of propylene was studied with the catalyst system. The effect of the reaction conditions and external donor on the polymerization were investigated. The results showed that the catalyst had high activity, high stereospecificity, and sensitive hydrogen responsibility. Polypropylene has good grain morphology because of duplicating the morphology of the catalyst. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1296–1299, 2005     

Studies on the preparation of branched polymers from styrene and divinylbenzene

The self‐condensing vinyl polymerization of styrene and an inimer formed in situ by atom transfer radical addition from divinylbenzene and 2‐bromoisobutyl‐tert‐butyrate using atom transfer radical polymerization technique was studied. To study the polymerization mechanism and achieve high molecular weight polymer in a high polymer yield, the polymerization was carried out in bulk at 80°C. Proton nuclear magnetic resonance (¹H‐NMR) spectroscopy and gel permeation chromatography (GPC) coupled with multiangle laser light scattering (MALLS) were used to monitor the polymerization process and characterize the solid polymers. It is proved that the polymerization shows a “living” polymerization behavior and the crosslinking reaction has been restrained effectively due to the introduction of styrene. Polymers with high molecular weight (M_w.MALLS > 10⁵) can be prepared in high yield (near 80%). Comparison of the apparent molecular weights measured by GPC with the absolute values measured by MALLS indicates the existence of branched structures in the prepared polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of high polymerization temperature on the microstructure of isotactic polypropylene prepared using heterogeneous ticl4/mgcl2 catalysts

The effects of alkylaluminum and polymerization temperature on propylene polymerization without an external donor in the use of a TiCl₄–MgCl₂–diether(BMMF) catalyst were investigated. The results indicated that with increasing polymerization temperature the concentrations of [mmmm] of heptane‐insoluble poly(propylene) (PP) fraction increased. Crystallization analysis fractionation (CRYSTAF) results showed the fractions of different crystallization temperatures were changed according to various polymerization temperatures. The activity with Et₃Al as cocatalyst at 100°C was much lower than that at 70°C. However, the activity with i‐Bu₃Al at 100°C was as high as that at 70°C. The fraction of high‐crystallization temperature of PPs obtained with i‐Bu₃Al increased with increasing polymerization temperature, which was opposite to that with Et₃Al, thus implying that the copolymerization of propylene with the monomer arising from Et₃Al led to the lower crystallization ability of PPs obtained with Et₃Al. The terminal groups of PP suggested that the chain‐transfer reaction by β‐H abstraction was the main chain‐transfer reaction at 120°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3980–3986, 2003     

Preparation of bimodal polypropylene in two‐step polymerization

Polymerization of propylene was carried out by using MgCl₂.EtOH.TiCl₄.DIBP.TEA.cHMDMS catalyst system in n‐heptane, where MgCl₂, EtOH, TiCl₄, DIBP (diisobutyl phthalate), TEA (triethyl aluminum), and cHMDMS (cyclohexyl methyl dimethoxy silane) were support, ethanol for alcoholation, catalyst, external donor, cocatalyst (activator), and internal donor, respectively. The catalyst activity and polymer isotacticity were studied by measuring the produced polymer and its solubility in boiling n‐heptane, respectively. The molecular weight and molecular weight distribution of the polymers were evaluated by gel permeation chromatography. Hydrogen was used for controlling the molecular weight. For producing the bimodal polypropylene, the polymerization was carried out in two steps (i.e., in the presence and absence of hydrogen). It was found that the catalyst showed high activity and stereoselectivity, on the other hand, bimodal polymer could simply be produced in two‐step polymerization by using MgCl₂.EtOH.TiCl₄.DIBP.TEA.cHMDMS catalyst system. Meanwhile, the effect of the step of the hydrogen adding on propylene polymerization was investigated. It was shown that the addition of hydrogen in the second step was more suitable. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1456–1462, 2006     

Effect of cocatalyst on the chemical composition distribution and microstructure of ethylene-hexene copolymer produced by a metallocene/Ziegler-Natta hybrid catalyst

A silica-magnesium bisupport (SMB) was prepared by a sol-gel method for use as a support for metallocene/Ziegler-Natta hybrid catalyst. The SMB was treated with methylaluminoxane (MAO) prior to the immobilization of TiCl₄ and rac-Et(Ind)₂ZrCl₂. The prepared rac-Et(Ind)₂ZrCl₂/TiCl₄/MAO/SMB catalyst was applied to the ethylenehexene copolymerization with a variation of cocatalyst species (polymerization run 1: triisobutylaluminum (TIBAL) and methylaluminoxane (MAO), polymerization run 2: triethylaluminum (TEA) and methylaluminoxane (MAO)). The effect of cocatalysts on the chemical composition distributions (CCDs) and microstructures of ethylene-hexene copolymers was examined. It was found that the catalytic activity in polymerization run 1 was a little higher than that in polymerization run 2, because of the enhanced catalytic activity at the initial stage in polymerization run 1. The chemical composition distributions (CCDs) in the two copolymers showed six peaks and exhibited a similar trend. However, the lamellas in the ethylene-hexene copolymer produced in polymerization run 1 were distributed over smaller sizes than those in the copolymer produced in polymerization run 2. It was also revealed that the rac-Et(Ind)₂ZrCl₂/TiCl₄/MAO/SMB catalyst preferably produced the ethylene-hexene copolymer with non-blocky sequence when TEA and MAO were used as cocatalysts.     

Synthesis and antitumour and antiangiogenesis activity of polymers containing methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid

A new monomer, methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid (MTCA), was synthesized from citric acid and methacrylic anhydride. Poly(methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid) and poly(methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid)‐co‐(maleic anhydride) were prepared by radical polymerizations. Terpoly(methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid–maleic anhydride–furan) was obtained by in situ terpolymerization of MTCA and exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalic anhydride. The synthesized samples were identified by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The number‐average molecular weights of the fractionated polymers determined by GPC were in the range 14 900–16 600 and polydispersity indices were less than 1.14. The in vitro IC₅₀ values of the monomer and polymers against cancer and normal cell lines were much higher than those of 5‐fluorouracil (5‐FU). The in vivo antitumour activities of the synthesized samples at a dosage of 0.8 mg kg⁻¹ against mice bearing the sarcoma 180 tumour cell line decreased in the order terpoly(MTCA‐MAH‐FUR) > poly(MTCA‐co‐MAH) > poly(MTCA) > MTCA > 5‐FU. The synthesized samples inhibited DNA replication and angiogenetic activity more than did 5‐FU. © 2001 Society of Chemical Industry     

Development of nanocomposites of bentonite with polyaniline and poly(methacrylic acid)

Nanocomposites of bentonite with polyaniline (PANI), poly(methacrylic acid) (PMAA), and poly(aniline‐co‐methacrylic acid) (PANI‐co‐PMAA) were prepared by in situ intercalative polymerization technique. The nanocomposites were characterized by FTIR and UV–visible spectroscopies, XRD, SEM, TEM, as well as TG‐DTA studies. The in situ intercalative polymerization of PANI, PMAA, and PANI‐co‐PMAA within bentonite layers was confirmed by FTIR, XRD, SEM, as well as TEM studies. XRD confirmed the intercalation of polymers and copolymer in bentonite. The average particle size of the nanocomposites was found to be in the range of 250–500 nm. The thermal stability was found be the highest for PANI‐co‐PMAA‐bentonite. The swelling behavior studies suggest that these nanocomposites hold potential for their utilization in absorption of toxic materials from waste water. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3299–3306, 2007     

Polymerization of propylene using the high‐activity Ziegler–Natta catalyst system SiO2/MgCl2 (ethoxide type)/TiCl4/Di‐n‐butyl phthalate/triethylaluminum/dimethoxy methyl cyclohexyl silane

The bisupported Ziegler–Natta catalyst system SiO₂/MgCl₂ (ethoxide type)/TiCl₄/di‐n‐butyl phthalate/triethylaluminum (TEA)/dimethoxy methyl cyclohexyl silane (DMMCHS) was prepared. TEA and di‐n‐butyl phthalate were used as a cocatalyst and an internal donor, respectively. DMMCHS was used as an external donor. The slurry polymerization of propylene was studied with the catalyst system in n‐heptane from 45 to 70°C. The effects of the TEA and H₂ concentrations, temperature, and monomer pressure on the polymerization were investigated. The optimum productivity was obtained at [Al]/[DMMCHS]/[Ti] = 61.7:6.2:1 (mol/mol/mol). The highest activity of the catalyst was obtained at 60°C. Increasing the H₂ concentration to 100 mL/L increased the productivity of the catalyst, but a further increase in H₂ reduced the activity of the catalyst. Increasing the propylene pressure from 1 to 7 bar significantly increased the polymer yield. The isotacticity index (II) decreased with increasing TEA, but the H₂ concentration, temperature, and monomer pressure did not have a significant effect on the II value. The viscosity‐average molecular weight decreased with increasing temperature and with the addition of H₂. Three catalysts with different Mg/Si molar ratios were studied under the optimum conditions. The catalyst with a Mg/Si molar ratio of approximately 0.93 showed the highest activity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1177–1181, 2003