Polymerization of vinyl chloride with Cp*Ti(OPh)3/MAO catalyst in toluene

Polymerization of vinyl chloride (VC) with a Cp*Ti(OPh)₃/MAO catalyst in toluene was investigated. The polymerization rate was lower than that in CH₂Cl₂, and the mm triad concentration of the PVC obtained in toluene was somewhat higher than that of the PVC obtained in CH₂Cl₂. As the polymerization in toluene proceeded at a considerable rate, a kinetic study of this polymerization was undertaken. The polymer yield increased with reaction time, and the molecular weight of the polymer increased with increasing polymer yield. The M_w/M_n ratio of the polymer decreased with increasing polymerization temperature. The initiator efficiency of the catalyst was low at the initial stage of the polymerization in toluene, but it reached nearly 100% when the polymerization was carried out for more than 30 h. The control of both themolecular weight of PVC and its main‐chain structure was found to be possible in the polymerization of VC with the Cp*Ti(OPh)₃/MAO catalyst in toluene. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Polymerization of vinyl chloride with butyllithiums and metallocene catalysts

Polymerizations of vinyl chloride (VC) with butyllithium (BuLi) and metallocene catalysts were investigated. In the polymerization of VC with BuLi, the activity for polymerization decreased in the following order; t‐BuLi > n‐BuLi > s‐BuLi. A polymer controlled structurally in the main chain was found to be synthesized from the polymerization of VC with BuLi. The molecular weights of polymers obtained in bulk polymerization were higher than those of polymers obtained in solution. A linear relationship of the M_n of the polymer and the polymer yields was observed. The M_w/M_n of the polymer did not change significantly during polymerization, although the M_w/M_n was around 2. Thermal stability of the polymer obtained with BuLi was higher than that of polymer obtained with radical initiators, as determined by TGA measurements. In the polymerization of VC with Cp*TiX₃/MAO (X: Cl and OCH₃) catalysts, polymers were obtained with both catalysts, although the rate of polymerization was slow. The Cp*Ti(OCH₃)₃//MAO catalyst in CH₂Cl₂ gave higher‐molecular‐weight polymers in a better yield than in toluene. From elemental analysis and the NMR spectra of the polymers, the Cp*Ti(OCH₃)₃/MAO catalyst gave polymers consisting of repeating regular head‐to‐tail units, in contrast to the Cp*TiCl₃/MAO catalyst, which gave polymers having anomalous units.     

Rate and molecular weight distribution modeling of syndiospecific styrene polymerization over silica-supported metallocene catalyst

The kinetics of syndiospecific polymerization of styrene over silica-supported Cp^∗Ti(OCH₃)₃/MAO catalyst has been investigated through experimentation and theoretical modeling. At low monomer concentrations, the polymerization rate increases almost linearly with monomer conversion, but the reaction rate becomes independent of monomer concentration at high bulk phase monomer concentrations. A kinetic model that incorporates the monomer partition effect between the solid and the liquid phases has been proposed. The model simulations show that the observed non-linear kinetics can be adequately modeled by the monomer partition model. The polymer molecular weight has also been found to increase with the monomer concentration and the polymer molecular weight distribution (MWD) is quite broad, suggesting that the catalytic behavior deviates from the single site catalytic polymerization model. The MWD broadening is modeled by a two-site kinetic model and a good agreement between the model and the experimental data has been obtained.     

Control of main chain structure and possibility of molecular weight control of polymer on polymerization of vinyl chloride with tert-butyllithium

The controlled polymerization of vinyl chloride (VC) with tert-butyllithium (tert-BuLi) was investigated. The polymerization of VC with tert-BuLi at −30 °C proceeded to give a high molecular weight polymer in good yield. In the polymerization of VC −30 to 0 °C under nearly bulk, the relationship between the M_n of polymers and polymer yields gave a straight line passed through the origin, but the M_w/M_n of PVC was not narrow. When CH₂Cl₂ was used as polymerization solvent, the M_n of PVC increased with the polymer yield, and the M_w/M_n of 1.25 was obtained. Structure analysis of the resulting polymers indicates that the main chain structure could be regulated in the polymerization of VC with tert-BuLi. Accordingly, a control of molecular weight of polymer and main chain structure is possible in the polymerization of VC with tert-BuLi.     

Nascent morphology of syndiotactic polystyrene synthesized over silica-supported metallocene catalyst

The nascent morphology of semi-crystalline syndiotactic polystyrene (sPS) polymerized over silica-supported pentamethyl cyclopentadienyl titanium trimethoxide (Cp^∗Ti(OCH₃)₃) catalyst in a liquid slurry polymerization has been investigated under various reaction conditions. The scanning electron microscopic analysis of nascent polymers reveals that sPS molecules grow as long nanofibrils of 30-50 nm diameter and X-ray diffraction analysis shows the co-crystalline phases including both sPS and low molecular weight guest molecules of monomer and diluent. The energy dispersive X-ray spectroscopy also shows that the disintegration of silica primary particles occurs during the polymerization as evidenced by the uniform dispersion of silicon and aluminum in a polymer particle. The fibrous growth of the polymer inside a polymer particle leads to the shape replication of the original silica particles.     

The synthesis of high molecular weight polybutene‐1 catalyzed by Cp★ Ti(OBz)3/MAO

A new stereoregular polybutene‐1 was synthesized with a novel catalyst precursor η⁵‐pentamethyl cyclopentadienyl titanium tribenzyloxide (CpTi(OBz)₃) and methylaluminoxane (MAO). The effects of polymerization conditions on the catalytic activity, molecular weight and stereoregularity of the products were investigated in detail. It was found the catalyst exhibited highest activity of 91.2 kgPB mol Ti⁻¹ h⁻¹ at T = 30 °C, Al/Ti = 200. The catalytic activity and molecular weight were sensitive to the Al/Ti (mole/mole), polymerization temperature; they also depended on the Ti concentration. The molecular weight of the products increased with decreasing temperature. The structure and properties of the polybutene‐1 were characterized by ¹³C NMR, GPC, DSC and WAXD. The result showed the microstructure of polybutene‐1 extracted by boiling heptane was stereoregular, whereas the ether‐soluble fraction was atactic. The molecular weight of polybutene‐1 was over one million g mol⁻¹ and its molecular weight distribution ( M _w/ M _n) was from 1.1 to 1.2. © 2001 Society of Chemical Industry     

Copolymerization of Vinyl Chloride and Ethylene with Cp<Superscript>*</Superscript>Ti( OCH<Subscript>3</Subscript>)<Subscript>3</Subscript>/MAO Catalyst

Summary Copolymerization of vinyl chloride (VC) and ethylene with Cp^*Ti( OCH₃)₃/MAO catalyst was investigated. The Cp^*Ti( OCH₃)₃/MAO catalyst initiated the copolymerization of VC with ethylene, although the copolymer yields were low. In the ¹³C NMR spectra of the copolymers, the peaks based on junction part between VC and ethylene was observed, but the signals were small. From DSC measurement of the copolymers, only one glass transition temperature was observed. Thus, it is clear that the copolymerization with Cp^*Ti( OCH₃)₃/MAO catalysts gave the copolymer, and the copolymer consisting of block sequence rather than random copolymer. Received: 13 November 2002/Revised: 6 January 2003/Accepted: 10 January 2003 Correspondence to Kiyoshi Endo     

Late Transition Metal Catalyst Based on Cobalt for Polymerization of Ethylene

The late transition metal catalyst of [2,6-diacethylpyridinebis(2,6-diisopropylphenylimine)]cobalt(II) dichloride was prepared under controlled conditions and used for polymerization of ethylene. Methylaluminoxane (MAO) and triisobuthylaluminum (TIBA) were used as a cocatalyst and a scavenger, respectively. The highest activity of the catalyst was obtained at about 30°C; the activity decreased with increasing temperature. At polymerization temperatures higher than 50°C not only was a sharp decrease in the activity observed but also low molecular weight polyethylene product that was oily in appearance was obtained. The polymerization activity increased with increasing both of the monomer pressure and [MAO]:[Co] ratio. However, fouling of the reactor was strongly increased with increasing both of the monomer pressure and the amount of MAO used for the homogeneous polymerization. Hydrogen was used as the chain transfer. The activity of the catalyst and the viscosity average molecular weight (M_v) of the polymer obtained were not sensitive to hydrogen concentration. However, the viscosity average molecular weight of the polymer decreased with the monomer pressure. The (M_v), the melting point, and the crystallinity of the resulting polymer at the monomer pressure of 1 bar and polymerization temperature of 20°C were 1.2 × 10⁵, 133°C, and 67%, respectively. Heterogeneous polymerization of ethylene using the catalyst and the MAO/SiO₂ improved morphology of the resulting polymer; however, the activity of the catalyst was also decreased. Fouling of the reactor was eliminated using the supported catalyst system.     

Polymerization of styrene using bis(β‐ketoamino)nickel(II)/methylaluminoxane catalytic systems

Styrene (St) was polymerized in toluene solution by using bis(β‐ketoamino)nickel(II) complex as the catalyst precursor and methylaluminoxane (MAO) as the cocatalyst. The polymerization conditions, such as Al : Ni ratio, monomer concentration, reaction temperature, and polymerization time, were studied in detail. Both of the bis(β‐ketoamino)nickel(II)/MAO catalytic systems exhibited higher activity for polymerization of styrene, and polymerization gave moderate molecular weight of polystyrene with relatively narrow molecular weight distribution (M_w/M_n < 1.6). The obtained polymer was confirmed to be atactic polystyrene by analyzing the stereo‐triad distributions mm, mr, and rr of aromatic carbon C¹ in NMR spectrum of the polymer. The mechanism of the polymerization was also discussed and a metal–carbon coordination mechanism was proposed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Syndiospecific Polymerization of Styrene Using Half-Titanocene Catalyst Covalently Supported on MgCl<Subscript>2</Subscript>/AlEt<Subscript>n</Subscript>(OEt)<Subscript>3-n</Subscript>

The novel half-titanocene catalyst bearing reactive functional amino group, η⁵-pentamethylcyclopentadienyltri(p-amino-phenoxyl) titanium [Cp^∗Ti(p-OC₆H₄NH₂)₃], was easily synthesized by the reaction of η⁵-pentamethylcyclopentadienyltrichloride titanium (Cp^∗TiCl₃) with p-amino phenol in the presence of triethyl amine (NEt₃). Cp^∗Ti(p-OC₆H₄NH₂)₃ covalently anchored on MgCl₂/AlEt_n(OEt)_3-n support obtained from the reaction of triethylaluminium (AlEt₃) with the adduct of magnesium chloride (MgCl₂) and ethanol (EtOH), has been investigated and used to catalyze syndiospecific polymerization of styrene. Influences of the support structure, cocatalyst, and the molar ratio of Al in methylaluminoxane (MAO) and Ti (Al_MAO/Ti) on catalytic activity, syndiotacticity and molecular weight of the resultant polystyrene were investigated. Compared with the corresponding Cp^∗Ti(p-OC₆H₄NH₂)₃ homogeneous catalyst, a considerable increase in activity and molecular weight of syndiotactic polystyrene (sPS) was observed for the Cp^∗Ti(p-OC₆H₄NH₂)₃-MgCl₂/AlEt_n(OEt)_3-n supported catalyst even at a relatively low Al_MAO/Ti ratio of 50, and the kinetics of polymerization was stable during the reaction process.     

Polymerization of vinyl ethers using titanium catalysts containing tridentate triamine ligand of the type N[CH2CH(Ph)(Ts)N]2

Titanium complexes having tridentate triamine of the type N[CH₂CH(Ph)(Ts)N]₂²⁻ in combination with methylaluminoxane (MAO) was able to polymerize ethyl vinyl ether in good yields. The polymers obtained in general were having molecular weight in the order of 10⁵ with narrow molecular weight distributions. Polymerization conditions had an impact on the molecular weight and the polydispersity index (PDI). Using chlorobenzene as the solvent the polymer had an M_n of 350?000 and PDI of 1.21, where as under neat conditions the M_n was 255?000 with PDI of 1.21. The type of solvent and the temperature dictated the polymerization rate and the polymer stereo regularity. The molecular weight of the polymer is distinctly governed by the polymerization temperature. Temperature ranging between −50 and ambient (30 °C) resulted in high molecular weight polymers and vice versa at a temperature of 60-70 °C resulted in low molecular weight polymers in moderate yields. The polymers obtained below 30 °C are highly stereo-regular compared to that of the ones produced at and above ambient temperature. The polymerization of iso-butyl vinyl ether (IBVE) was faster than that of linearly substituted n-butyl vinyl ether (BVE) and less bulky ethyl vinyl ether (EVE). The order of isotacticities of the polymers obtained are polyIBVE > polyBVE > polyEVE. The use of borate cocatalyst for activation generated narrow molecular weight polymers with a linear increase in the yield and molecular weight over time suggesting the living nature of the catalyst system.     

Methylaluminoxane‐activated neodymium chloride tributylphosphate catalyst for isoprene polymerization

The polymerization of isoprene was examined by using a novel binary catalyst system composed of neodymium chloride tributylphosphate (NdCl₃·3TBP) and methylaluminoxane (MAO). The NdCl₃·3TBP/MAO catalyst worked effectively in a low MAO level ([Al]/[Nd] = 50) to afford polymers with high molecular weight (M_n ～10⁵), narrow molecular weight distribution (M_w/M_n = 1.4–1.6), and high cis‐1,4 stereoregularity (> 96%). The catalytic activity increased with an increasing [Al]/[Nd] ratio from 30 to 100 and polymerization temperature from 0 to 50°C, while the M_n of polymer decreased. The presence of free TBP resulted in low polymer yield. Polymerization solvent remarkably affected the polymerization behaviors; the polymerizations in aliphatic solvents (cyclohexane and hexane) gave polymer in higher yield than that in toluene. The M_w/M_n ratio of the producing polymer remained around 1.5 and the gel permeation chromatographic curve was always unimodal, indicating the presence of a single active site in the polymerization system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40153.     

Ethylene polymerization using fluorinated FI Zr-based catalyst

A fluorinated FI Zr-based catalyst of bis[N-(3,5-dicumylsalicylidene)-2′,6′-flouroanilinato]zirconium(IV) dichloride was prepared and used for polymerization of ethylene. It was revealed that ortho-F-substituted phenyl ring on the N electronically plays a key role in the suppression of chain transfer reactions especially β-hydride transfer which resulted in an increase in the molecular weight of the obtained polymer and moderation of the catalyst activity as well. Methylaluminoxane (MAO) and triisobuthylaluminum (TIBA) were used as a cocatalyst and a scavenger, respectively. The catalyst showed the maximum activity at about [Al]:[Zr] = 32000:1 M ratio and further addition of MAO did not affect the activity of the catalyst. Ortho-F not only impressed the activity, but also reduced the [Al]:[Zr] molar ratio needed to reach the highest activity in comparison with the similar non-fluorinated FI catalysts. The highest activity of the prepared catalyst was obtained at 35 °C. At the monomer pressure of 3 bars polyethylene was obtained with the viscosity average molecular weight (M _v) of 1.3 × 10⁶ indicating the dramatic effect of ortho-F substitution on the polymerization mechanism. The polymerization was carried out using different amounts of hydrogen. Neither the activity of the catalyst nor the viscosity average molecular weight (M _v) of the obtained polymer was sensitive to the hydrogen concentration. However, higher amount of hydrogen could slightly increase the activity of the catalyst.     

Soluble neodymium chloride 2-ethylhexanol complex as a highly active catalyst for controlled isoprene polymerization

Soluble NdCl₃·3EHOH (2-ethyl hexanol) in hexane combined with AlEt₃ is highly active for isoprene polymerization in hexane. The NdCl₃·3EHOH/AlEt₃ has higher activity than the typical binary catalyst NdCl₃·3ⁱPrOH (isopropanol)/AlEt₃ and ternary catalyst NdV₃ (neodymium versatate)/AlEt₂Cl/Al(i-Bu)₂H. The molecular weight of polyisoprenes can be controlled by variation of [Nd], [Al]/[Nd] ratio and polymerization temperature and time. The NdCl₃·3EHOH/AlEt₃ catalyst polymerized isoprene to afford products featuring high cis-1,4 stereospecificity (ca. 96%), high molecular weight (ca. 10⁵) and relatively narrow molecular weight distributions (M_w/M_n = 2.0-2.8) simultaneously. More importantly, some living polymerization characteristics were demonstrated: (a) absence of chain termination; (b) linear correlation between M_n and polymer yield; (c) increment of molecular weight in the ‘seeding’ polymerization. Though some deviation from the typical living polymerization such as molecular weight distribution is not narrow enough and the line of M_n and polymer yield does not extrapolate to zero, controlled polymerization with the current catalyst can still be concluded.     

Synthesis of high molecular weight copolymer of styrene and butadiene bearing high 1,4‐cis butadiene unit from copolymerization with CpTiCl3/methylaluminoxane catalyst

Copolymerization of styrene (St) and butadiene (Bd) with CpTiCl₃/methylaluminoxane (MAO) catalyst in the presence or absence of chloranil (CA) was investigated. The CpTiCl₃/MAO catalyst showed a high activity for the copolymerization of St with Bd. The 1,4‐cis contents in the Bd units for the copolymerization of St and Bd with the CpTiCl₃/MAO catalyst was observed, and the 1,4‐cis content was optimum at a MAO/Ti mole ratio of around 225. The effect of the polymerization temperature on the copolymerization was noted, as was the effect of the 1,4‐cis microstructure in the Bd units for the copolymerization of St and Bd. The addition of CA to the CpTiCl₃/MAO catalyst was found to influence the molecular weight of the copolymer. The high weight‐average molecular weight copolymer (M_w = ca. 50 × 10⁴) consisting of mainly a 1,4‐cis microstructure of Bd units (1,4‐cis = 80.0%) was obtained from the copolymerization with the CpTiCl₃/MAO catalyst in the presence of CA (CA/Ti mole ratio = 1) at 0°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2942–2946, 2003     

Synthesis of star polymer by means of the living polymerization of [(o-trifluoromethyl)phenyl]acetylene using a MoOCl4-based catalyst and the linking method

A star polymer was synthesized by addition of 1,4-diethynyl-2,5-dimethylbenzene as linking agent (30 °C, 24 h) after living polymerization of [(o-trifluoromethyl)phenyl]acetylene (o-CF₃PA) with MoOCl₄-n-Bu₄Sn-EtOH catalyst (in anisole, 30 °C, 20 min; [Mo]=10 mM, [P^∗]/[Mo]=40%, [o-CF₃PA]₀=200 mM). The M_n values of the living and star polymers were 8.1×10³ and 5.3×10⁴, respectively, according to gel permeation chromatography, while these values determined by multi-angle laser light scattering (MALLS) were 7.8×10³ and 2.5×10⁵. The M_w/M_n and arm number of the star polymer were 1.04 and 29, respectively, according to MALLS. The molecular weight and arm number of star polymer increased with increasing linking agent concentration and polymerization temperature.     

Homogeneous neodymium iso-propoxide/modified methylaluminoxane catalyst for isoprene polymerization

The neodymium iso-propoxide [Nd(Oi-Pr)₃] catalyst activated by modified methylaluminoxane (MMAO) is homogeneous and effective in isoprene polymerization in heptane to provide polymers with high molecular weight (M_n∼10⁵), narrow molecular weight distribution (M_w/M_n=1.1-2.0) and mainly cis-1,4 structure (82-93%). The polymer yield increased with increasing [Al]/[Nd] ratio (50-300 mole ratio) and polymerization temperature (0-60 °C), while the molecular weight and cis-1,4 content decreased. On the other hand, the same catalyst resulted in relatively low polymer yield and low molecular weight in toluene. The cyclized polyisoprene was formed in dichloromethane, which is attributable to the cationic active species derived from MMAO alone. When chlorine sources (Et₂AlCl, t-BuCl, Me₃SiCl) were added, the cis-1,4 stereoregularity of polymer improved up to 95% even at a high temperature of 60 °C, though the polymer yield decreased.     

Preparation of ultra‐high‐molecular‐weight polyethylene and its morphological study with a heterogeneous Ziegler–Natta catalyst

Ultra‐high‐molecular‐weight polyethylene (PE) with viscosity‐average molecular weight (M_v) of 3.1 × 10⁶ to 5.2 × 10⁶ was prepared with a heterogeneous Ziegler–Natta MgCl₂ (ethoxide type)/TiCl₄/triethylaluminum catalyst system under controlled conditions. The optimum activity of the catalyst was obtained at a [Al]/[Ti] molar ratio of 61 : 1 and a polymerization temperature of 60°C, whereas the activity of the catalyst increased with monomer pressure and decreased with hydrogen concentration. The titanium content of the catalyst was 2.4 wt %. The rate/time profile of the catalyst was a decay type with a short acceleration period. M_v of the PE obtained decreased with increasing hydrogen concentration and polymerization temperature. The effect of stirrer speeds from 100 to 400 rpm did not so much affect the catalyst activity; however, dramatic effects were observed on the morphology of the polymer particles obtained. A stirrer speed of 200 rpm produced PE with a uniform globulelike morphological growth on the polymer particles. The particle size distributions of the polymer samples were determined and were between 14 and 67 μm. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Ethylene polymerization over MgO‐supported zirconocene catalysts

Supported zirconcene catalysts on a new support, MgO, were prepared and tested in ethylene polymerization. Three types of impregnation methods were employed to find an optimum supporting method for MgO. The direct impregnation of Cp₂ZrCl₂ on MgO showed low metal loading and polymerization activity, while the catalyst had a higher metal loading and polymerization activity when MgO was treated with methylaluminoxane (MAO) before supporting. Treatment of MgO with MAO during the supporting step invoked two types of catalytic sites, which was evidenced by the bimodal molecular weight distribution of the polymer products. MgO is considered to have potential as a support for metallocenes.