Terpolymerization of ethylene,propylene, and butene-1 with highly active supported titanium catalyst

An investigation of ethylene-propylene-butene-1 terpolymerization in the presence of TiCl₄, Ti(OBu)₄/MgCl₂/ethylbenzoate (EB)/π₂SiCl₂/AlEt₃ catalyst is described. The catalytic efficiency is very high, i.e., 86000g/g Ti under ambient conditions. The decay rate of terpolymerization with time fulfills the equation: R_t = R_s + (R₀ - R_s)e^?βt. Characterizations with DSC, WAXD, ¹³C-NMR, and solvent extraction of the resulting terpolymers were studied. Terpolymers of certain composition are elastomers without detectable crystallinity, which demonstrates a rather random sequence distribution and makes them promising for quality rubber. The assignment of the chemical shifts in ¹³C-NMR spectra is made. The gas permeabilities of the terpolymer membrane is of PO₂ = 2.35 × 10^-9 cm³ (STP) cm/cm² s cm Hg and PO₂/PN₂ = 3.8 under optimum conditions.     

Stereospecific polymerization of styrene using a homogeneous lanthanide catalyst

Stereospecific polymerization of styrene was catalyzed by homogeneous neodymium phosphonate [Nd(P₅₀₇)₃]-H₂O-Al(i-Bu)₃ catalytic system. The polymer was separated into isotactic polystyrene and atactic polystyrene by extracting the latter with boiling 2-butanone. The conversion of styrene and the yield of isotactic polystyrene (IY) were influenced by the [H₂O]/[Al(i-Bu)₃] mole ratio and the solvent polarity. The reaction is first order with respect to monomer at 70°C.     

Copolymerization of ethylene and butadiene with supported titanium catalyst

The copolymerization of ethylene and butadiene with a supported titanium catalyst (TiCl₄/MgCl₂/EB/Φ₂SiCl₂/AlEt₃) is described. The resulting products were characterized by IR, ¹³C-NMR, x-ray diffraction, differential thermal analysis, electron microscopy, and solvent extraction. It was found that the butadiene units are substantially in trans-1,4 configuration and blocked sequences. Both ethylene and butadiene blocks form crystalline phases. The presence of unsaturated bonds made it possible to graft MMA and maleic anhydride. The influences of monomer composition, temperature, Al/Ti ratio, catalyst concentration, and solvents on the copolymerization were investigated.     

Effect of external donor in polymerization of propylene by a MgCl2 supported titanium catalyst

Polypropylene (PP) prepared with a MgCl₂/TiCl₄-Et₃Al/Ph₂Si(OMe)₂ catalyst system was fractionated by temperature rising elution fractionation method in order to investigate the effect of Ph₂Si(OMe)₂ as an external donor (ED). This PP had a broad and continuous distribution of tacticity. In comparison to the system without donor, however, ED brought a decrease of lower isotactic portions and an increase of higher isotactic ones simultaneously to the resulting polymer. The latter portions were eluted at higher temperature than the corresponding component obtained without donor, showing that the higher isotactic PP was newly produced by ED.     

负载钛催化合成高反式丁二烯-异戊二烯共聚物的序列分布

采用TiCl4-MgCl2-Al(i-Bu)3体系催化丁二烯(Bd,M1)-异戊二烯(Ip,M2)共聚合成了高反式-1,4-结构的共聚物,用13^CNMR方法研究了共聚物的结构和组成分布,定量计算了共聚物二元组的浓度和数均序列长度,证明共聚物的序列分布服一级Markov模型,继而根据一张Markov模型预测了一次投料不同转化率下所得共聚物的链段分布。     

Binary metallocene supported catalyst for propylene polymerization

The binary silica supported catalyst system comprising the Cp₂ZrCl₂ and SiMe₂(Ind)₂ZrCl₂ metallocene compounds was prepared with different immobilization methods and evaluated at different propylene polymerization conditions. The performance results of the homogeneous isolated catalysts and also the homogeneous catalyst mixture were also included for comparison. High activities were obtained with the supported systems and the molecular weight of the produced polypropylene was invariably higher than that obtained using the homogeneous precursor.     

Olefin polymerization with titanium tetrachloride catalysts supported on surface-modified silica

After modification of silica with benzoyl chloride (BC) to obtain BC-modified SiO₂ (BC-SiO₂), BC-SiO₂/TiCl₄ and BC-SiO₂/BEM/TiCl₄ catalysts were prepared by treating the BC-SiO₂ with TiCl₄ directly or with butylethylmagnesium (BEM) followed by TiCl₄, respectively. During the modification, BC reacts with hydroxyl groups of silica. In this way the corresponding ester is anchored on the silica surface and the CO group is coordinated with Ti and/or Mg. In addition, BEM is converted to MgCl₂ in the reaction with TiCl₄. These catalysts have reasonable activities for ethylene or propene polymerization.     

Catalytic activity of a supported catalyst for ethylene polymerization,obtained by modification of vulcasil with titanium tetrachloride vapour

Titanium-containing surface compounds have been obtained by the interaction of the silanol groups of Vulcasil with TiCl₄ vapour. These substances have been used, in combination with organ-oaluminium and organo-magnesium compounds, for the polymerization of ethylene. The effects upon the catalyst activity of the reaction conditions (temperature, pressure, duration of polymerization), of the titanium amount on the Vulcasil surface and the Al:Ti and Mg:Ti ratios have been studied.The activity of the catalyst system has been shown to increase with increasing pressure up to 11 kg/cm² and to attain its optimum value at 60°. Polymerization has been found to end 15–20 min after the introduction of the monomer. The highest yields of polymer are obtained at Mg:Ti and Al:Ti ratios of about 30.The amount of titanium on the Vulcasil surface depends on the conditions of preliminary heat-treatment of the Vulcasil and decreases from 0.63 to 0.30 mg at/g with increasing dehydroxylation temperature. Simultaneously, the yield of polymer varies within a narrow range (89–107 g/l), and the productivity increases from 21 to 35.5 kg polyethylene (PE) per 1 g of Ti. This is especially clearly expressed with the samples obtained by preliminary heat-treatment at 400–700°.     

Stereospecific polymerization of acetaldehyde by R2AlOR′ catalyst

Stereospecific polymerization of acetaldehyde was examined by using four possible purified diethylaluminum butoxides, (Et₂AlOBu)₂ [Bu = n-, i-, sec-, or tert-Bu], as catalyst. These catalysts gave isotactic polyacetaldehyde quantitatively irrespective of the degree of branching of the butyl group, only when an optimum amount of water (about 0.03 mole/mole of catalyst) was added to the purified acetaldehyde monomer. Quite similar results were obtained for organozinc catalysts. These results indicate that water is an indispensable cocatalyst in the polymerization reaction with organoaluminum and zinc catalysts. An novel coordinate cationic mechanism was proposed for the stereospecific polymerization of acetaldehyde with organoaluminums, based on the above phenomena and on the inactivation of the catalyst by forming a complex with a strong Lewis base.     

Polymerization of butene-2 with isomerization to butene-1

An attempt has been made to prepare a high molecular weight isotactic polybutene-1 from cis- or trans-butene-2. Polymerization of butene-2 did not occur due to the steric effect of the substituents. In the presence of TiCl₃–Al(C₂H₅)₃ catalyst, however, both butene-2 monomers were found to polymerize at a slower rate than butene-1 and to give polymers consisting of the repeating unit of butene-1. From the gas chromatographic determination of the isomer distribution of the butenes recovered after the polymerization, it was found that the butenes isomerized, in the presence of the catalyst system containing TiCl₃, to approach the thermodynamic equilibrium mixture of butene-1, cis-butene-2, and trans-butene-2. It was also found that the rates of polymerization of butene-2 for the catalyst systems used were proportional to the isomerization rates. These results show that butene-2 isomerizes first to butene-1 which has less steric hindrance and then polymerizes as butene-1, through ordinary vinyl polymerization by a coordinated anionic mechanism. This type of polymerization was observed in some other linear β-olefins such as n-pentene-2 and n-hexene-2.     

Isomerization and hydrogenation of butene-1 on a zirconia aerogel catalyst

Zirconia is well known as a promising support for active metallic centers but it is also by itself an interesting catalyst for reactions involving hydrogen in particular. This paper describes the catalytic properties of ZrO₂-obtained in the form of an aerogel-, towards butene-1-isomerization and/or its hydrogenation at low temperature. Activation at 430°C in vacuum led to the best results in cis-trans isomerization in the temperature range of 80–200°C. It is shown that at temperatures 150°C a carbanion mechanism is operating while at higher temperatures the thermodynamic selectivity is attained. Selective poisoning experiments by NH₃ or CO₂ were carried out in order to identify the catalytic sites for the isomerization of n-butene.

---

, , . ZrO₂, , / -1 . 430°C - 80–200°C. , 150°C , . NH₃ CO₂ -.

     

Polymer‐supported zirconocene catalyst for ethylene polymerization

The use of crosslinked poly(styrene‐co‐4‐vinylpyridine) having functional groups as the support for zirconocene catalysts in ethylene polymerization was studied. Several factors affecting the activity of the catalysts were examined. Conditions like time, temperature, Al/N (molar ratio), Al/Zr (molar ratio), and the mode of feeding were found having no significant influence on the activity of the catalysts, while the state of the supports had a great effect on the catalytic behavior. The activity of the catalysts sharply increased with either the degree of crosslinking or the content of 4‐vinylpyridine in the support. Via aluminum compounds, AlR₃ or methylaluminoxane (MAO), zirconocene was attached on the surface of the support. IR spectra showed an intensified and shifted absorption bands of C N in the pyridine ring, and a new absorption band appeared at about 730 cm⁻¹ indicating a stable bond Al N formed in the polymer‐supported catalysts. The formation of cationic active centers was hypothesized and the performance of the polymer‐supported zirconocene was discussed as well. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 37–46, 1999     

Ethylene polymerization with porous polystyrene spheres supported Cp2ZrCl2 catalyst

A catalyst with porous polystyrene beads supported Cp₂ZrCl₂ was prepared and tested for ethylene polymerization with methylaluminoxane as a cocatalyst. By comparison, the porous supported catalyst maintained higher activity and produced polyethylene with better morphology than its corresponding solid supported catalyst. The differences between activities of the catalysts and morphologies of the products were reasonably explained by the fragmentation processes of support as frequently observed with the inorganic supported Ziegler–Natta catalysts. Investigation into the distribution of polystyrene in the polyethylene revealed the fact that the porous polystyrene supported catalyst had undergone fragmentation during polymerization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3313–3319, 2003     

State of titanium in supported titanium-magnesium catalysts for propylene polymerization

The oxidation state of titanium and the coordination state of Ti³⁺ ions in TiCl₄/D₁/MgCl₂ (D₁ is a phthalate) supported titanium-magnesium catalysts (TMCs) after the interaction with an AlEt₃/D₂ cocatalyst (D₂ is propyltrimethoxysilane or dicyclopentyldimethoxysilane) were studied by chemical analysis and EPR spectroscopy. Different oxidation state distributions of titanium ions were observed in the activated catalyst and mother liquor: Ti³⁺ and Ti²⁺ ions were predominant in the activated catalyst and mother liquor, respectively. The effects of interaction conditions (reaction temperature and time and Al/Ti and D₂/Ti molar ratios) of TMCs with the cocatalyst on the state of titanium in activated samples were studied. The interaction of TMCs with the cocatalyst decreased the titanium content and caused the appearance of aluminum in the activated sample, which was most clearly pronounced at a temperature of 25°C and occurred within the first 10 min of treatment. An increase in the temperature to 70°C and an increase in the interaction time to 60 min only slightly affected the concentrations of titanium and aluminum. The presence of D₂ as a cocatalyst constituent facilitated the removal of titanium compounds and restricted the adsorption of aluminum compounds on the catalyst surface. The main fraction of titanium consisted of Ti³⁺ ions (62–89%), and the rest was Ti⁴⁺ ions (22–35%) under mild interaction conditions (25°C; Si/Ti = 25) or Ti⁴⁺ (0–21%) and Ti²⁺ (9–21%) ions under more severe conditions (50 or 70°C; Si/Ti from 0 to 5). According to EPR-spectroscopic data, at D₂/Ti from 1 to 5, Ti³⁺ ions mainly occurred as associates, whereas they occurred as isolated ions at D₂/Ti = 25. The initial and activated catalysts were similar in activity in the reaction of propylene polymerization, and titanium compounds, which were removed from the catalyst upon interaction with AlEt₃/D₂, were inactive in this process.     

Soluble magnesium and titanium catalyst components for ethylene polymerization

The catalyst system comprised of a heptane solution of magnesiumoctoate-H₂O-Tetrabutoxytitanium/diethylaluminumchloride was highly active for ethylene polymerization at a high temperature. High productivity for the catalyst system at a low temperature was achieved by the aging of the catalyst components. The effect of different orders of addition of the catalyst components on productivity was investigated to assume the role of each components in the formation of active species.     

Reducing consumption of titanium catalyst in stereospecific polymerization of butadiene

The possibility of reducing the consumption of titanium catalyst in butadiene polymerization by using a tubular turbulent prereactor of the diffuser-confuser design in the step of mixing the reaction mixture components was examined.