Abstract  Phtalic anhydride was esterified with BuOH and iso-BuOH on H(2)SO(4) catalyst at 383 K to 413 K for 550 min to det. the reaction kinetics. Calculation of phtalic anhydride conversion was based on det. the acid no. of the reaction mixt. The reaction was 1st order reaction in respect to the monophthalates. The activation energy was 78.5 kJ/mol for BuOH and 79.2 kJ/mol for iso-BuOH. The reaction rate did not depend on the alc. concns.

Abstract  High performance MgCl2 supported titanium catalyst having diisobutyl phthalate (DIBP) as internal donor has been synthesized. The organic components present in the catalyst have been studied through FTIR, 1D and 2D NMR spectroscopy. The results indicate presence of diethyl phthalate also in addition to DIBP. WAXD analysis has been done to study the features of MgCl2 crystallites. Impact of donor components on the catalyst preparation leading to reaction pathways and performance for propylene polymerization has been evaluated.

Abstract  The spherical MgCl2 supported TiCl4 catalyst(TiCl4/MgCl2/DIBP) was applied to bulk copolymerization of propylene and 1-butene. The influence of comonomer feed ratio on catalyst activity and stereoregularity of the copolymers were studied. The composition and properties of copolymers were investigated by 13C nuclear magnetic resonance(13C NMR), differential scanning calorimetry(DSC), infrared(IR) and gel permeation chromatography(GPC). The results showed that the polymerization activity increased firstly and then decreased with the increasing 1-butene/propylene feed ratio(B/P). The highest polymerization activity was achieved at B/P=0.26. As the 1-butene content in the copolymers increased, the melting point of the copolymers decreased and the molecular weight distribution became narrow. Meanwhile, the mechanical properties of the copolymers were improved significantly, and the transparency was gradually increased.

Abstract  Polypropylene (PP) was synthesized in the presence of Ziegler-Natta catalysts composed of MgCl2-TiCl4-internal donor/AlR3-external donor. Diisobutyl phthalate is a well-known internal donor in current PP production. Nevertheless, phthalates are often blamed as endocrine disruptors. The objective is to find an ecofriendly internal donor producing PP with maintaining its physical properties. When using dibenzoyl sulfide, synthesized PP shows the superiority to diisobutyl phthalate in the activity of catalyst (40 vs. 22 kg PP/g catalyst), the isotacticity of polymer (99.5 vs. 98.0 wt % of heptane insolubles), and the molecular weight distribution of PP product (M-w/M-n = 4.8 vs. 4). (C) 2014 Wiley Periodicals, Inc.

Abstract  This article presents a detailed structural study of a new spherical MgCl2-supported TiCl4 Ziegler-Natta catalyst for isotactic propylene polymerization, and researches on the relationship between catalyst structure and polymer properties. The spherical support with the chemical composition of CH3CH2OMgOCH(CH2Cl)(2) has been synthesized from a new dispersion system and is used as the supporting material to prepare Ziegler-Natta catalyst. The XRD analysis indicates that the catalyst is fully activated with delta-MgCl2 in the active catalyst. The far-IR spectrometric results confirm again the presence of delta-MgCl2 in the active catalyst. Textural property of the active catalyst exhibits high surface area coupled with high porosity. The high activity in propylene polymerization is mainly ascribed to the full activation and the porous structure of the catalyst. Scanning electron microscopy/energy dispersive spectrometer mapping results indicate a uniform titanium distribution throughout the catalyst particles. Particle size analysis shows that the catalyst has a narrow particle size distribution. The perfect spherical shape, uniform titanium distribution and narrow particle size distribution of the catalyst confirm the advantage of polymer particles production with less fines. The solid state C-13 NMR and mid-IR spectroscopic analyses indicate that there exists strong complexation between diisobutyl phthalate and MgCl2, which leads to the high isotacticity of polypropylene.

Abstract  In this study, the structure of methoxymagnesium chloride (MgCl(OMe)) and its interaction with ester electron donors (diisobutyl phthalate and ethyl benzoate) and TiCl4 were studied using experimental (PXRD, DRIFT, CP/MAS 13C NMR) and computational (DFT; M06-2X functional) methods. Alkoxymagnesium chlorides (MgCl(OR)) have been claimed in several patents to be potential support materials for Ziegler–Natta catalysts. We have found that MgCl(OMe) possesses a layered structure similar to that of MgCl2. An energy comparison among MgCl2, Mg(OMe)2, and MgCl(OMe) structures indicates that mixing of Cl and OMe, and thus the formation of methoxymagnesium chloride, is thermodynamically feasible. Computational results suggest an energetic preference for MgCl(OMe) being structurally composed of MgCl2 and Mg(OMe)2 units, which are arranged in a form of alternating stripes. Based on both spectroscopic and computational data, the coordination of ester electron donors on MgCl(OMe) is much weaker than on MgCl2. On the other hand, the coordination of TiCl4 is stronger in the case of MgCl(OMe). TiCl4 prefers to coordinate on the (110)-like surface of MgCl(OMe), whereas ester electron donors exhibit no particular preference for either the (110)-like or (104)-like surfaces. MgCl(OMe)/TiCl4 product was found to be an active catalyst in ethylene polymerization.

Abstract  Five salicylates with different sizes of hydrocarbon substituents were firstly synthesized and employed as ecofriendly internal donors of the Ziegler–Natta catalyst for propylene polymerization. The influences of these salicylates and traditional, industrial, internal donor diisobutyl phthalates on the microstructure of polypropylene and active center in a Ziegler–Natta catalyst were studied. It was found that the catalyst activities of the catalysts containing salicylate internal donors with a proper volume were higher than the catalysts containing diisobutyl phthalate internal donors. GPC results showed that the molecular weights of polypropylene prepared by salicylate internal donors were lower than those prepared by diisobutyl phthalate, which indicated that the polypropylene chains produced by salicylate internal donors were easier to transfer than those prepared by diisobutyl phthalate internal donors. Deconvolution of the GPC curves exhibited that as the volume of the salicylate internal donor increased some of the active centers for low molecular weight transferred into the active centers for high molecular weight. The results of 13C-NMR and SSA both suggested that a salicylate internal donor with an appropriate catalyst size volume was beneficial for increasing the isotactic sequence length, isotacticity index and regular triads “mm” of polypropylene. However, further increasing the volume of the salicylate internal donor in a catalyst would lead to the polypropylene chain containing more stereo-defects. Moreover, the active centers with different stereospecificity parameters, piso, in the catalyst could explain the trend of stereo-defects in polypropylene chains when different internal donors were used. In addition, it was found that the isotactic sequence length and isotacticity index of polypropylene prepared by isobutyl 2-benzyloxy-3,5-isopropyl benzoate were close to that produced by a diisobutyl phthalate internal donor. Moreover, the lamella thickness distribution of the polypropylene produced by a salicylate internal donor was broad, which might have potential application for expanded polypropylene materials.

Abstract  Samples of PVC plasticised by diisobutyl phthalate and di-2-ethylhexyl phthalate, with plasticiser contents varying from 0 to 180 pph, were studied by solid-state proton and carbon-13 NMR spectroscopies. Proton spin-lattice relaxation times in both the laboratory and the rotating frames were measured, with analysis into multi-exponential components where necessary. Cross-polarisation magic angle spinning carbon-13 spectra were also obtained, including variation with contact time. The data were considered in terms of the domain structure of the samples at the microscopic level and of the role of the plasticiser. 20 refs.

Abstract  Thermal and mechanical properties of ethylene/alpha-olefin copolymers (LLDPE) produced over bis(2-methyl indenyl)zirconium dichloride((2-MeInd)2 ZrCl2) are compared with those of LLDPEs synthesised with a conventional heterogeneous Ziegler-Natta (Z-N) catalyst, titanium tetrachloride supported on magnesium diethoxide with diisobutyl phthalate as an internal donor (Mg(OEt)2/DIBP /TiCl4). DSC thermogram of LLDPE by the Z-N catalyst shows that the melting peak moves to a lower temperature region and the peak becomes broader as the density of LLDPE decreases. On the other hand, in case of LLDPE produced over (2-MeInd)2ZrCl2, the melting peak shifts to a lower temperature zone with the decreasing copolymer density without a significant loss in the peak sharpness. The density of LLDPE is a decreasing function of mole fraction of alpha-olefin and the decrease is more pronounced as the molecular weight of the incorporated alpha-olefin increases. However, when the density is plotted against weight fraction of alpha-olefin a similar declining curve is observed irrespective of the type of alpha-olefins except the LLDPE made by the Z-N catalyst in which more alpha-olefin units are required to reach the same density as that of LLDPEs by (2-MeInd)2ZrCl2. LLDPE made by the Z-N catalyst has lower tensile strength but similar elongation and elastic modulus compared to those of polyethylene-co-1-dodecene and polyethylene-co-1-octadecene synthesised by (2-MeInd)2ZrCl2. Polyethylene-co-1-hexene by (2-MeInd)2ZrCl2, however, exhibits lower elastic modulus and higher elongation compared with the other LLDPEs. Measurement of dynamic mechanical properties of LLDPEs reveals that beta-transition peak appears at a lower temperature and becomes more intense, as the density decreases, until the crystallinity of LLDPEs disappears completely when the beta-transition peak becomes fixed around -45 deg.C. Gamma-transition is monitored at around -125 deg.C and is thought to be induced by the limited motion of the main backbone chain. 43 refs.

Abstract  The use of high yield magnesium chloride based and metallocene catalysts in the polymerisation of olefins is examined, and the structure of these catalysts and their influence on polymer structure, molecular weight and properties are discussed. The development by Montell of supported metallocene catalyst systems using branched aluminium alkyls as cocatalysts in place of methyl alumoxane is reported. 22 refs.

Abstract  PPs prepared using magnesium chloride-supported catalysts containing electron donors were characterised using temp. rising elution fractionation(TREF), GPC and carbon-13 NMR analysis. The regio- and stereochemical composition of oligomeric fractions present in selected polymers was also determined. The results indicated that catalysts in which the internal donor was a diether had a relatively narrow distribution of active species, for which the effects of regioselectivity on chain transfer with hydrogen were particularly prominent. The regio- and stereoselectivity of active species in catalysts in which the internal donor was diisobutyl phthalate was dependent on the nature of the alkoxysilane external donor used in polymerisation. The effects of different alkoxysilanes on polymer tacticity and MWD were interpreted in terms of lability of donor coordination in the vicinity of the active species. 35 refs.

Abstract  11 refs.

Abstract  The effects of ethyl benzoate and diisobutyl phthalate as internal donors on the structure of the magnesium chloride matrix in high-performance magnesium chloride-supported titanium catalysts for propylene polymerisation were investigated by means of FTIR spectroscopy and wide angle X-ray diffraction. The internal donors were found to influence the formation of magnesium chloride-crystallite lateral cuts with higher preference for (110) over (104) lateral cuts. The magnesium chloride matrix was formed during catalyst preparation from magnesium ethoxide and was characterised by the presence of alpha-magnesium chloride, beta-magnesium chloride and disordered delta-magnesium chloride phases. The bidentate dialkyl phthalate donor held the adjacent magnesium chloride layers by interlayer binding and (110) zip coordination and even stabilised the same layer via bridging. This was regarded as one of the reasons for the high productivity of dialkyl-phthalate-based catalysts compared with ethyl benzoate-based catalyst systems. 40 refs.

Abstract  An ethanol solution of magnesium chloride and di-t-butyl phthalate (DIBP) was added to a reactor containing a mixture of methyl siloxane and paraffin. The resulting mixture was then added to n-hexane at -20 C, to obtain spherical magnesium chloride-adduct supported Ziegler-Natta catalysts. The strength and particle size of the support could be controlled by varying for DIBP concentration. The catalyst successfully polymerised propylene. 19 refs.

Abstract  Plasticisers based on DIBP.

Abstract  Magnesium dichloride supported titanium catalyst incorporated with varying concentration of ethylbenzoate and diisobutyl phthalate together as internal donor are synthesized. The synthesized catalysts are characterized and compared with respect to composition, phase characteristics, crystallite size, and particle morphology. Performance of catalysts containing mixed donors is compared with the conventional single donor-based catalysts. The polymerization studies of the catalysts for propylene polymerization show dependence of polymerization kinetics on relative concentration of diisobutyl phthalate and ethylbenzoate. Molecular weight characteristics of polypropylene obtained from these catalysts are studied and correlated with the nature and concentration of donors present in the catalyst. Morphology replication from catalyst precursor to polymer is observed irrespective of the nature of donor being incorporated in the synthesized catalyst. (c) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Abstract  Four of 9,10-dihydroanthracene-9,10-alpha,beta-alkyl succinates have been synthesized and used as internal electron donors in MgCl(2)-supported Ziegler-Natta catalysts. The performances of the catalysts on the propylene polymerization have been investigated. The obtained polymers possess high-isotacticity and the polymerization activity is comparable with the catalysts using 9,9-bis(methoxymethyl)fluorene and diisobutyl phthalate as internal donor. With dimethoxydiphenylsilane as external donor, the catalysts for the polymerization of propylene exhibit satisfactory activities and are sensitive toward hydrogen. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 118: 1853-1858,2010

Abstract  The kinetic behaviour of magnesium chloride-supported catalysts with a controlled morphology containing a 1,3-diether [9,9-bis(methoxymethyl)fluorine] (catalysts A and D) or a simple diester such as diisobutyl phthalate (catalysts B, C and E) in the polymerisation of propylene was examined in a glass reactor capable of operating at pressure of 1-7 atm of propylene. The 1,3-diether-based systems were found to be excellent catalyst systems for the polymerisation of propylene, showing high polymerisation activities and stable rate-time profiles and producing spherical polymer particles. Catalyst pretreatment was found to be important in controlling the morphology of the final polymer. The concentrations of active centres were 7.5 and 5.1 mol%, respectively, for catalysts A and D, and 3.5, 2.9, and 2.2 mol%, respectively, for catalysts B, C and E. Catalysts A and D showed very high polymerisation activities and also higher C"0*values. 7 refs.

Abstract  Propylene polymerization on TiCl4/donor/MgCl2 (donor = ethyl benzoate, dibutyl phthalate, diisobutyl phthalate, diethyl 2,3-diisopropylsuccinate) supported catalysts is considered. The states of the donors in the catalysts have been investigated by diffuse reflectance IR spectroscopy. Data characterizing the distribution of the donors and the active component (TiCl4) on the support surface have been obtained. Molecular weight distribution data for polypropylene are presented. The molecular weight distribution of polypropylene depends on the location of the donor and TiCl4 molecules.

Abstract  GPC studies showed that increasing the polymerisation time increased the number-average molecular weight, the weight-average molecular weight, molecular weight distribution (MWD) and relative MWD (the ratio of two MWDs in two consecutive periods of the polymerisation time) of PP in propylene polymerisation carried out using a magnesium diethoxide/diisobutyl phthalate (DIBP)/titanium tetrachloride/phenyl triethoxy silane (PTES)/triethylaluminium (TEA) catalyst system in the slurry phase. Magnesium diethoxide was the support, DIBP the internal donor, titanium tetrachloride the catalyst, PTES the external donor and TEA the cocatalyst. 20 refs.

Abstract  ESR was used to study the interaction between the stable nitroxyl radical TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl) and the Ti/Mg catalysts titanium tetrachloride/magnesium chloride and titanium tetrachloride/magnesium chloride.nD (where D was either diisobutyl phthalate or 2,2-diisobutyl-1,3-dimethoxypropane), as well as titanium tetrachloride/magnesium chloride.nD treated with triethylaluminium. In all cases, only part of the surface Ti complexes (18-53 mol %) exhibited Lewis acid properties and could interact with TEMPO. The portion of Ti complexes with acidic properties depended on the composition and preparation of the catalysts and it decreased upon treatment with triethylaluminium. 13 refs.

Abstract  Emultex 510 is a medium viscosity PVA stabilised, vinyl acetate homopolymer emulsion, externally plasticised with di-isobutyl phthalate. It is designed for use in the building industry as a general purpose adhesive, an additive to concrete and plasters, and as a universal bonding aid. Its properties and uses, technical data, and health and safety guidelines are included.

Abstract  Technical and commercial information is presented for Bisoflex DBP (di-n-butyl phthalate), a plasticiser for use with polyvinyl acetate, PVC, vinyl copolymers, some synthetic rubbers, cellulose nitrate, ethyl cellulose and other resins, and also Bisoflex DIBP (di-isobutyl phthalate) which can be used as an alternative, sometimes with economic advantages.

Abstract  The development of Emultex 510 universal PVA adhesive for use in the building industry, is described. It consists of a medium viscosity, polyvinyl alcohol stabilised, vinyl acetate homopolymer emulsion, externally plasticised with di-isobutyl phthalate. It provides good adhesion to concrete and cement and may be used as a floor sealant. Results of its fulfilment of the requirements to BS 5270 and its performance as a bonding aid in concrete and cement and as a wood adhesive, as compared to a conventional 53% solids bonding aid, are tabulated.