Copolymerization of styrene and methyl methacrylate with nickel acetylacetonate/methylaluminoxane catalyst system

The present work deals with copolymerization of styrene (STY) and methyl methacrylate (MMA) catalysed by nickel acetylacetonate - Ni(acac) ₂ , employing methylaluminoxane (MAO) as cocatalyst. This catalyst system presented low catalyst activities for STY homopolymerization and very high activities for MMA. It seems that the catalyst system based on Ni(acac) ₂ /MAO is effective for the copolymerization of MMA and STY to give block copolymer but it also produced polystyrene and poly(methyl methacrylate) homopolymers. The polymers were characterized by ¹³ C NMR, GPC and FTIR. The polystyrene homopolymer was identified by IR and NMR analyses of the cyclohexane soluble fraction. The presence of absorption bands correspondent to carbonyl group and aromatic ring was observed in the IR spectrum of the acetic acid soluble part. This result is a clue that STY-MMA copolymer with low molecular weight was produced. The high molecular weight copolymer (acetic acid insoluble fraction) was also characterized by IR analysis which indicated the presence of characteristic absorption bands of carbonyl group and aromatic ring. These results were confirmed by ¹³ C NMR analysis. Received: 6 August 1997/Revised version: 29 December 1997/Accepted: 7 January 1998     

Copolymerization of styrene and butadiene with nickel compounds–methylaluminoxane catalysts

Copolymerization of styrene (St) and butadiene (Bd) with nickel(II) compound (NiX₂) in combination with methylaluminoxane (MAO) was investigated at the monomer feed ratio of 1:1. Copolymerization of St and Bd induced with NiX₂–MAO catalysts (X = acac, OCOC₆H₅, OCOC₁₈H₃₅, Cl, Cp) gave copolymers with high cis‐1,4 contents of Bd units. The St and cis‐1,4 units of the Bd units in the copolymer were not significantly affected by the X group of NiX₂, although the copolymer yields depended on the substituent. The copolymer yields depended on the solvent used for the copolymerization with the Ni(acac)₂–MAO catalyst; an aromatic hydrocarbon was more favourable than a non‐aromatic hydrocarbon. The effects of triphenylphosphine (TPP) and trifluoroacetic acid (TFA) on copolymerization of St and Bd with the Ni(acac)₂–MAO catalyst were seen the microstructure of Bd units in the copolymer. © 2001 Society of Chemical Industry     

Syndiotactic polymerization of styrene with CpTiCl2(OPri)/methylaluminoxane

Summary CpTiCl₂(OPrⁱ) was a very active catalyst for syndiotactic polymerization of styrene when activated with methyl aluminoxane (MAO). The catalyst activity and syndiospecificity of CpTiCl₂(OPrⁱ)/MAO were about 10⁷ g PS / mol Ti·mol S·h and about 95% respectively, both higher than those of CpTiCl₃ / MAO.     

Novel monotitanocene and methylaluminoxane catalyst for syndiospecific polymerization of styrene

Syndiotactic polystyrene (sPS) was synthesized with a novel monotitanocene complex of η⁵‐pentamethylcyclopentadienyltri‐4‐methoxyphenoxy titanium [Cp*Ti(OC₆H₄OCH₃)₃] activated by methylaluminoxane (MAO) in different polymerization media, including heptane, toluene, chlorobenzene, and neat styrene. In all cases bulk polymerization produced sPS with the highest activity and molecular weight. Solution polymerization produced much better activity in heptane than in the other solvents. Using a solvent with a higher dipole moment, such as chlorobenzene resulted in lower activity and syndiotacticity because of the stronger coordination of solvent with the Ti(III) active species, which controlled syndiospecific polymerization of styrene. With bulk polymerization at a higher polymerization temperature the Cp*Ti(OC₆H₄OCH₃)₃–MAO catalyst produced sPS with high catalytic activity and molecular weight. The external addition of triisobutylaluminum (TIBA) to the Cp*Ti(OC₆H₄OCH₃)₃–MAO system catalyzing styrene polymerization led to significant improvement of activity at a lower Al:Ti molar ratio, while the syndiotacticity and molecular weight of the yields were little affected. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1243–1248, 2001     

Effect of reaction parameters on the polymerization of methyl methacrylate with nickel acetylacetonate/methylaluminoane

Polymerizations of methyl methacrylate (MMA) employing nickel acetylacetonate [Ni(acac)₂] as catalyst combined with methylaluminoxane (MAO) as cocatalyst were investigated. The main purpose of this work is concerned with the study of reaction parameters MMA polymerization. Temperature of polymerization, Al/Ni mole ratio, type of solvent, catalyst concentration and time dependence were examined. The influence of Lewis bases on the polymerization was also studied. The binary system Ni(acac)₂/MAO was the only one able to polymerize MMA at the conditions employed in this work. The cocatalytic activity of MAO was compared to those of common alkylaluminium compounds. The polymers were characterized by gel-permeation chromatography (GPC) and ¹³C-NMR techniques. Received: 20 August 1996/Revised: 4 December 1996/Accepted: 9 December 1996     

Polymerization of ethylene by chromium acetylacetonate/methylaluminoxane catalyst system

Summary The present paper deals with polymerization of ethylene by chromium acetylacetonate - Cr(acac)₃ - activated by alkylaluminium, e.g. Al(C₂H₅)₃ or Al(i-C₅H₉)₃, or methylaluminoxane (MAO). The influence of polymerization parameters on catalyst performance, such as Al/Cr mole ratio, temperature, aging time, type of cocatalyst, was investigated. High activities were obtained only when MAO was the cocatalyst. The polymers were characterized by size exclusion chromatography (SEC) and differential scanning calorimetry (DSC) analyses. Received: 11 September 1997/Revised version: 5 January 1998/Accepted: 20 March 1998     

Preliminary investigations on polymerization catalysts composed of lanthanocene and methylaluminoxane

Summary The polymerization of butadiene(Bd), isoprene(Ip) and styrene(St) has been examined using the six catalyst systems composed of lanthanocene, (C₅H₉Cp)₂NdCl(I), (C₅H₉Cp)₂SmCl(II), (MeCp)₂Sm OAr'(III), (Ind)₂NdCl(IV), Me₂Si(Ind)₂NdCl(V) and (Flu)₂NdCl(VI), and methylaluminoxane(MAO) respectively. All of them can be used to form the polyisoprene with molecular weights of 1 to 10 thousand and cis-1,4-unit contents of 41 to 47%. (I), (II) and (III) of them can be also used to form the polybutadiene with molecular weights of 10 to 20 thousand and cis-1,4-unit contents of 62 to 78%. In addition, the catalysts from (II) to (V) are still active for St polymerization and (II) of them gives a syndio -rich random polystyrene. It is noteworthy that (II) and (III) are active for homopolymerization of Bd, Ip and St in the same polymerization condition. Received: 16 December 1997/Revised version: 17 March 1998/Accepted: 24 March 1998     

Isospecific polymerization of vinyl ethers with titanium catalysts containing modified tridentate anionic donor ligands

BACKGROUND: Stereo‐regulated polymerization of vinyl ethers (VEs) assumes significance because of its elegance and the resultant unique polymer properties. Although several Lewis acid catalysts polymerize VEs with good control of molecular weight, achieving stereo‐regularity is quite challenging. There are literature reports of a few catalyst systems capable of producing highly isotactic poly(vinyl ether) (PVE) only at lower temperatures with the polymer becoming atactic with an increase in reaction temperature. Hence innovating new catalyst systems which can produce highly stereo‐regular PVEs with high molecular weight at ambient temperature is quite challenging. RESULTS: We used two different titanium pre‐catalysts (1‐TiCl₂ and 2‐TiCl₂) for the polymerization of VEs. These pre‐catalysts in combination with methylaluminoxane (MAO)/borate polymerized VEs in higher conversions. Highly isotactic poly(n‐butylvinyl ether) (PBVE; 75% dyad isotactic ratio) was obtained with 1‐TiCl₂/MAO at ambient temperature. CONCLUSION: We synthesized unimodal and highly isotactic PBVE with molecular weights of the order of 10⁵ g mol^?1 using the non‐metallocene‐type single‐site catalyst system 1‐TiCl₂/MAO even at ambient temperature. The symmetry around the metal centre in the pre‐catalyst and the polymerization temperature played a major role in controlling the stereo‐regularization of the olefin inserted. Copyright © 2009 Society of Chemical Industry     

Polymerization of styrene using pyrazolylimine nickel (II)/methylaluminoxane catalytic systems

The polymerization of styrene with two pyrazolylimine nickel (II) complexes of (2-(C₃HN₂Me₂-3, 5)(C(Ph) = N(4-R₂C₆H₂(R₁)₂-2, 6)NiBr₂ (Complex 1 , R₁ = ⁱPr, R₂ = H; Complex 2 , R₁ = H, R₂ = NO₂)) activated by methylaluminoxane was studied. The influences of polymerization parameters such as polymerization temperature, Al/Ni molar ratio, and reaction time on catalytic activity and molecular weight of the polystyrene (PS) were investigated in detail. The electron-withdrawing of nitro group in Complex 2 could not enhance the catalytic activity for styrene polymerization; however, the molecular weights of polymers were increased. Both of the two catalytic systems exhibited high activity [up to 8.45 × 10⁵ gPS/(mol Ni h)] for styrene polymerization and provide PS with moderate to low-molecular weights (M_w = 2.21 × 10⁴∼ 5.71 × 10³ g/mol) and narrower molecular weight distributions about 2.0. The obtained PS were characterized by means of IR, ¹H NMR, and ¹³C NMR techniques. The results indicated that the PS was atactic polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of nitrogen-functionalized polyolefins with metallocene/methylaluminoxane catalysts

Summary Thirteen differently substituted long-chain amide- and amine-functional alkenes were synthesised and used as comonomers in zirconocene/methylaluminoxane-catalysed copolymerizations with ethylene and propylene. Characterization of the prepared copolymers showed the formation of functionalized copolymers with isolated comonomer units. The incorporation level of the comonomers ranged from 0.24 to 1.3 mol % with ethylene and from 0.04 to 0.96 mol % with propylene. The molar masses of the copolymers were lower than those of the corresponding homopolymers. End group analysis of the copolymers by NMR suggested that the dominant chain termination mechanism was chain transfer to aluminium. Received: 8 December 2000/Accepted: 12 February 2001     

Recycling of methylaluminoxane (MAO) cocatalyst in ethylene polymerization with supported metallocene catalyst

The economy of the metallocene catalyst system in olefin polymerization depends more on the cost of methylaluminoxane (MAO) cocatalyst rather than on the catalyst cost since high ratio of cocatalyst to catalyst is required to have sufficient activity. The conditions to minimize the consumption of MAO have been studied for the ethylene polymerization with supported metallocene catalyst. By introducing the prepolymerization step, in which the supported metallocene catalyst is activated at high MAO concentration before polymerization, the MAO could be recovered after the prepolymerization and recycled repeatedly for the subsequent activation with marginal decrease in activity. No extra MAO was needed during the main polymerization. The addition of small amount of MAO or less expensive alkylaluminum at each recycle step kept the catalyst activity to the initial level. It compensates the MAO losses occurring both by the incomplete decantation of MAO solution and by the reaction with metallocene complex or impurities. As a result, the actual consumption ratio of Al/Zr in moles in commercial applications could be reduced to about 30 without sacrificing the activity. This value is significantly low considering that conventionally an Al/Zr ratio of 1,000 is required for sufficient activity. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Syndiospecific polymerization of styrene catalyzed by half-titanocene catalysts

Those effective catalyst precursors for syndiotactic styrene polymerization, Cp*Ti(OCH₂-CHCH₂)₃ (I), Cp*Ti(OCH₂-CHCHC₆H₄)₃ (II), Cp*Ti(OCH₂C₆H₅)₃ (III), Cp*Ti(OCH₂C₆H₄OCH₃)₃ (IV) were synthesized, and the influence of catalyst ligands on the catalytic activity and properties of polymer were investigated. The polymer thus obtained coupled with higher molecular weight and higher syndiotacticity determined by GPC and ¹³C NMR as well as solvent extraction manners, respectively. Those catalysts promoted by methyaluminoxane (MAO) as cocatalyst exhibited higher catalytic activity. Of all catalysts mentioned foregoing, Cp*Ti(OCH₂-CHCHC₆H₄)₃ (II), Cp*Ti(OCH₂C₆H₅)₃/MAO (III) and Cp*Ti(OCH₂C₆H₄OCH₃)₃ (IV) catalysts showed higher activity and stability even at fairly low Al/Ti ratio of 600, and possessed excellent control of the stereoregular insertion of monomer, exhibited a significant increase of the ratio of the propagation rates to chain transfer termination. The kinetic and titration results also indicated that those metallocene catalysts (II), (III), and (IV) showed higher catalytic activity and produced polymer with higher molecular weight, because of a great number of active species, and lower ratio of Kβtr/Kp, higher ratio of Kβtr/Ktrs which indicate that β-H elimination was predominant.     

Preparation of supported vanadium and molybdenum oxide catalysts using metal acetylacetonate complexes

Supported vanadium and molybdenum oxide catalysts were prepared by reaction of the corresponding acetylacetonate complex in a non-aqueous solution with the surface hydroxyl groups of the carrier. Continuous or batch adsorption of the metal acetylacetonate from toluene, as well as wet impregnation from ethanol, resulted in a uniform coverage of the support. The applied metal oxide was probably present on the surface as a monomolecular dispersion. When readsorption or reimpregnation from toluene was carried out with TiO₂ as support, metal oxide crystallites were formed, which could readily be detected with laser Raman spectroscopy. Reimpregnation from ethanol led to a complete occupancy of the surface hydroxyl groups of the carrier without the formation of metal oxide multilayers or crystallites.     

Effects of trisobutylaluminium on styrene polymerization with Ni(acac)2 /MAO/SiO2 catalyst system activated by methylaluminoxane

Summary Styrene polymerization with Ni(acac)₂/MAO/SiO₂ catalytic system was carried out in the presence of methylaluminoxane (MAO), triisobutylaluminum (TIBA) or MAO and TIBA mixture as activators. The catalytic system activated only by TIBA produced polymer with 53% of isotacticity. When the catalytic system was activated by a mixture of MAO and TIBA the polymer isotacticity increases as MAO concentration increases. In this case, the maximum of isotacticity was 59%. The polymer has presented lower molecular weight than the polymer obtained by MAO as activators and the polymer microstructure was not explained by Markov first-order model. In addition, ¹³C NMR spectra of the polymers obtained after extraction with MEK, have indicated that there are two active sites in this catalytic system. Received: 28 November 2001 / Revised version: 24 May 2002 / Accepted: 29 May 2002     

Characterization and methanation activity of supported nickel catalysts

The methanation of carbon monoxide was studied over various supported nickel catalysts in a fixed bed reactor in the temperature range of 250 to 400°C. The hydrogen to carbon monoxide ratio was kept higher than stoichiometric in order to avoid carbon formation. The catalyst particles had an average diameter of 80 pm and nickel contents ranging from 5 to 42 wt %. The performance of laboratory prepared catalysts was compared with commercial ones. The catalysts were characterized by BET surface area, pore volume and carbon monoxide chemisorption. Specific activities for the methanation reaction were obtained and were found to vary with nickel concentration and with crystallite size. There exists a crystallite size range in which the maximum activity was observed. Metal support interactions may also contribute to the vdation in specific activity. The activation energy was found to vary from 58.2 MJ/kmol to 119.4 MJ/kmol. It appears that the methanation reaction over Ni/aIumina catalysts is a structure sensitive reaction. A compensation effect was observed for this reaction.     

氢气高温还原制备的负载型镍基催化剂用于苯酚加氢的性能

通过等体积浸渍法分别将Ni(NO₃)₂、NiCl₂、NiSO₄ 3种镍前体浸渍于A1₂O₃或SiO₂载体上,然后通过H₂高温还原法制备了负载型镍基催化剂,考察了镍前体、载体种类、镍负载量、反应条件等对镍基催化剂苯酚加氢性能的影响。结果表明,对比3种镍前体,在H₂高温还原体系中Ni(NO₃)₂最容易被还原,制备的镍基催化剂苯酚加氢活性最高。SiO₂负载的镍基催化剂活性远高于γ-Al₂O₃催化剂。适宜的Ni负载量有助于活性组分的分散和催化活性的提高。镍基催化剂的苯酚加氢产物以环己醇为主,相对缓和的反应条件更容易生成环己酮。在非极性溶剂正庚烷或环己烷存在下,苯酚加氢反应速率远远高于极性溶剂水或乙醇存在下的结果,而且环己酮的选择性更高。     

Copolymerization of norbornene and ethene with homogenous zirconocenes/methylaluminoxane catalysts

The norbornene/ethene copolymerization was investigated by using two C _S-symmetric ([Me₂C(Fluo)(Cp)]ZrCl₂ III, [Ph₂C(Fluo)(Cp)]ZrCl₂ IB) and two C ₂-symmetric ([Me₂Si(Ind)₂]ZrCl₂ I, [Ph₂Si(Ind)₂]ZrCl₂ II) catalysts with methylaluminoxane (MAO) as cocatalyst. This investigation focussed not only on the different polymerization behavior, like catalyst activity, but also considers the material properties of the synthesized copolymers. It was found, that the C _S-symimetric catalysts are very well suitable to yield amorphous copolymers with glass transition temperatures above 180°C and molecular weights >100.000 g/mol. These copolymers could be used as potential starting materials for optical discs and fibers.     

Gas-phase hydrodechlorination of pentachlorophenol over supported nickel catalysts

The gas-phase hydrodechlorination of pentachlorophenol (PCP) over nickel/silica and nickel/Y zeolite catalysts at 573 K has been studied. Each catalyst was 100% selective in cleaving the C–Cl bonds, leaving the hydroxyl substituent and benzene ring intact. The variation of catalytic activity and selectivity (in terms of partial and full dechlorination) with time-on-stream is illustrated and catalyst deactivation is addressed. Dechlorination efficiency is quantified in terms of dechlorination rate constants, phenol selectivity/yield and the ultimate partitioning of chlorine in the parent organic and product inorganic host. Increasing the nickel loading on silica was found to raise the overall level of dechlorination while the use of a zeolite support introduced spatial constraints that severely limited the extent of dechlorination. Product composition was largely determined by steric effects where resonance stabilisation had little effect. The reaction pathways, with associated pseudo-first-order rate constants, are also presented. This revised version was published online in November 2006 with corrections to the Cover Date.     

Liquid-phase hydrogenation of o-chloronitrobenzene over supported nickel catalysts

The effect of supports (SiO₂, ZrO₂, TiO₂ and Al₂O₃) on the performance of nickel catalysts for the hydrogenation of o-chloronitrobenzene was investigated. It was found that the supports strongly influenced the catalytic performance of the catalysts, and Ni/TiO₂ showed the best catalytic performance. Over Ni/TiO₂, 99.9% conversion of o-chloronitrobenzene and 99.5% selectivity of o-chloroaniline were obtained at 1.5 MPa and 363 K. The good performance of Ni/TiO₂ was perhaps attributed to the strong polarization of NO band induced by oxygen vacancies of TiO_x which was produced by a high temperature reduction, and the NO band polarized was attacked easily by hydrogen dissociatively adsorbed on the nickel particles.     

Vinyl polymerization of norbornene over supported nickel catalyst

A series of nickel complexes, bis(salicylideneiminato)nickel(II), were supported on spherical MgCl₂ and SiO₂. Scanning electron microscopy, energy‐dispersed X‐ray spectroscopy, and the BET method for surface areas measurements were utilized to examine the supporting process of the catalysts. The particle morphology of the original support is retained and replicated throughout the supported catalyst preparation and norbornene polymerization. Spherical polymer particle morphology was achieved, without reactor fouling. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2233–2240, 2006