UV‐Visible Spectroscopic Study of rac‐Et(Ind)2ZrCl2/Aluminoxanes

The UV‐visible spectroscopic study of the interaction between rac‐Et(Ind)₂ZrCl₂ and different aluminoxanes, such as isobutylaluminoxane (BAO) and ethyl(isobutyl)aluminoxane (EBAO), was conducted under normal polymerization conditions. UV‐visible absorption spectra of rac‐Et(Ind)₂ZrCl₂/aluminoxanes were correlated with the formation of ionic zirconium species. The influence of different aluminoxanes on the tightness of the metallocenium‐aluminoxane ionic pairs was interpreted in terms of the aluminoxane structure. The loose ionic pairs formed in the EBAO system causes a fast decaying kinetic profile, advantageous for copolymerization.     

Performance of various activators in ethylene polymerization based on an iron(II) catalyst system

Ethylisobutylaluminoxane (EBAO) and its analogues were synthesized by a reaction between an triethylaluminum (Et₃Al)/triisobutylaluminum (i‐Bu₃Al) mixture and 4‐fluorobenzeneboronic acid, phenylboronic acid, or n‐butaneboronic acid and subsequent hydrolysis with water. They were used as cocatalysts in ethylene polymerization catalyzed by an iron complex {[(ArN?C(Me))₂C₅H₃N]FeCl₂, where Ar is 2,6‐diisopropylphenyl}. Polyethylene with a high molecular weight and a narrow molecular weight distribution was prepared with modified EBAOs, and the performance of the iron complex at high polymerization temperatures was greatly improved. The activators for the iron complex also affected the polymerization activity and the molecular weight of the resultant polyethylene. It was suggested that the stereo and electronic effects of the substitute groups of aluminoxane contributed to the improved performance of the new activators. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1093–1099, 2004     

混合铝氧烷的紫外研究及其对乙烯聚合的影响

自从 Kaminsky发现茂金属 /MAO催化体系具有高聚合活性以来 ,人们对茂金属 /MAO体系进行了大量研究 ,以确定活性中心的性质[1～ 7] .一般认为 ,活性中心是阳离子型的 ,并与 [MAOX- ]阴离子形成离子对 [L2 Mt X]+ [MAOX]- ,其中 Mt=Ti,Zr,Hf… ,X=Cl,CH3 … .Marks等 [8,9] 的研究结果表明 ,活性中心离子对的疏松程度对烯烃聚合活性有较大影响 .Giannetti等 [6]认为 ,茂金属 /铝氧烷体系形成的活性中心的紫外吸收波长与金属原子的正电性相关 ,可以通过紫外吸收来反映活性中心离子对的疏松程度 .为了进一步证明离子对的性质对聚合…     

Stereospecific polymerization of 1‐hexene catalyzed by ansa‐metallocene/methylaluminoxane systems under high pressures

Stereospecific polymerization of 1‐hexene under high pressures (up to 1,000 MPa = ca. 10,000 atm) using metallocene/methylaluminoxane (MAO) catalysts was investigated. Several C₂‐symmetric ansa‐metallocenes, their meso‐isomers, and two C_s‐symmetric ansa‐metallocenes were employed as catalyst precursors. In the course of this study, novel C₂‐symmetric germylene‐bridged ansa‐metallocenes, (rac‐[Me₂Ge(η⁵‐C₅H‐2,3,5‐Me₃)₂MCl₂] (M = Zr, rac‐4a; M = Hf, rac‐4b), have been prepared. High pressures induced enhancement of the catalytic activity and the molecular weight of the polymers in most of the catalysts. The maximum of both the catalytic activity and the molecular weight of the polymers was mostly observed at 100–500 MPa in each catalyst, although the enhanced ratio was smaller than that observed for nonbridged metallocenes. Isospecificity of the C₂‐symmetric ansa‐metallocene catalysts was essentially maintained even under high pressure. Highly isotactic polyhexene ([mmmm] = 91.6%) with very high molecular weight (M_w = 2,360,000) was achieved by rac‐4b under 250 MPa. High pressures slightly decreased syndiotacticity when the C_s‐symmetric ansa‐metallocene, isopropylidene(1‐η⁵‐cyclopentadienyl)(9‐η⁵‐fluorenyl)zirconium dichloride 5, was employed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 283–292, 1999     

Molecular modeling on the prediction of silolene‐bridged indenyl metallocene catalysts for isotactic polypropylene

Two new silolene‐bridged metallocenes for isotactic polypropylene, racemic (1,4‐butanediyl) silylene‐bis (1‐η⁵‐2‐methyl‐indenyl) dichlorozironium and racemic diphenyl silylene‐bis (1‐η⁵‐2‐methyl‐indenyl) dichlorozironium, were designed in terms of the mechanism and concept of the activity and selectivity of metallocenes. The predictions on which the designs were based were carried out for four metallocene catalysts through molecular modeling methods such as molecular mechanics and charge equilibrium. In a comparison of the data from three of the catalysts that were successfully synthesized, the predicted orders of the activity and selectivity were consistent. This shows that classical methods such as charge equilibrium are useful in predicting the activity of catalysts. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2232–2238, 2000     

Influence of mixed aluminoxane systems on ethylenenorbornene copolymerization catalyzed by metallocene

The norbornene/ethylene copolymerization was investigated using Me₂SiCp₂MCl₂ (M = Zr, Ti)/EBAO and MAO as catalyst systems (EBAO: mixed ethyl-isobutylaluminoxane, MAO: methylaluminoxane). The copolymers were characterized by DSC and ¹³C NMR. Copolymers with high content of norbornene and high T_g were obtained with the mixed EBAO. It is suggested that the copolymerization is greatly influenced by the state of the ion pair of the metallocene catalyst. The effect of aluminoxane on the composition and the microstructure of copolymer is discussed.     

AlR2Cl/MgR2 combinations as universal cocatalysts for Ziegler–Natta,metallocene, and post‐metallocene catalysts

Combinations of dialkylaluminum chlorides and dialkylmagnesium compounds, when used at molar [AlR₂Cl]:[MgR₂] ratios ≥ 2, act as universal cocatalysts for all three presently known types of alkene polymerization catalysts—Ziegler–Natta, metallocene, and post‐metallocene. When these cocatalysts are used with supported Ti‐based Ziegler–Natta catalysts, they produce catalyst systems which are 1.5–2 times more active than the systems utilizing AlR₃ compounds as cocatalysts. Combinations of AlR₂Cl/MgR₂ cocatalysts and various metallocene complexes produce single‐center catalyst systems similar to those formed in the presence of MAO. The same cocatalysts activate numerous post‐metallocene Ti complexes containing bidentate ligands of a different nature and produce multicenter systems of very high activity. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3271–3285, 2009     

Synthesis and morphology of polyethylene‐block‐poly(methyl methacrylate) through the combination of metallocene catalysis with living radical polymerization

Polyethylene‐block‐poly(methyl methacrylate) (PE‐b‐PMMA) was successfully synthesized through the combination of metallocene catalysis with living radical polymerization. Terminally hydroxylated polyethylene, prepared by ethylene/allyl alcohol copolymerization with a specific zirconium metallocene/methylaluminoxane/triethylaluminum catalyst system, was treated with 2‐bromoisobutyryl bromide to produce terminally esterified polyethylene (PE‐Br). With the resulting PE‐Br as an initiator for transition‐metal‐mediated living radical polymerization, methyl methacrylate polymerization was subsequently performed with CuBr or RuCl₂(PPh₃)₃ as a catalyst. Then, PE‐b‐PMMA block copolymers of different poly(methyl methacrylate) (PMMA) contents were prepared. Transmission electron microscopy of the obtained block copolymers revealed unique morphological features that depended on the content of the PMMA segment. The block copolymer possessing 75 wt % PMMA contained 50–100‐nm spherical polyethylene lamellae uniformly dispersed in the PMMA matrix. Moreover, the PE‐b‐PMMA block copolymers effectively compatibilized homopolyethylene and homo‐PMMA at a nanometer level. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3965–3973, 2003     

Permeation measurements in ethylene‐1‐hexene,ethylene‐1‐octene,and ethylene‐1‐dodecene copolymers synthesized with metallocene catalysts

The permeation behavior of different ethylene‐1‐hexene, ethylene‐1‐octene, and ethylene‐1‐dodecene copolymers synthesized with metallocene catalysts has been analyzed. These copolymers cover a wide range of comonomer contents, so their crystallinities display rather considerable variations. The results for the permeability to oxygen of the different ethylene copolymers show that the main factor influencing the permeability is the noncrystalline fraction, although some influence of the kind of comonomer may also be present, which may be explained by the fact that when the alkyl branch of the α‐olefin is longer, there is an increase in the free volume in the amorphous and interfacial regions, causing slightly higher values of the permeability coefficient. From the results with different gases, it follows that, in general, an increase in the size of the penetrant (as expressed by its kinetic diameter or critical molar volume) leads to an increase in the solubility and a decrease in the diffusion coefficient. A wide range of permeability values is covered by these ethylene copolymers, depending basically on the crystallinity of the sample, but the permselectivity of CO₂ with respect to oxygen (and probably between other pairs of gases) does not differ very much among the different copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2174–2184, 2003     

Polymerization of vinyl ethers with transition‐metal catalysts: An examination of the stereoregularity of the formed polymers

The polymerization of isobutyl vinyl ether (IBVE) and tert‐butyl vinyl ether (TBVE) was carried out with metallocene and nonmetallocene catalysts, and the stereoregularity of the formed polymers was examined with ¹³C NMR spectroscopy. IBVE afforded polymers with 63–68% dyad isotacticity by polymerization with mixtures of metallocene catalysts and methyl aluminoxane as a cocatalyst in toluene as a solvent. However, TBVE yielded polymers with 47–52% dyad isotacticity (21–28% triad isotacticity) under the same conditions, the isotacticity being lower than that of poly(isobutyl vinyl ether) (PIBVE). Nonmetallocene catalysts, including Ti, Zr, and Hf complexes with two phenoxy imine chelate ligands, provided PIBVE and poly(tert‐butyl vinyl ether) with 63–68 and 45–51% dyad isotacticity, respectively. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3938–3943, 2002     

Heterogenized methylaluminoxane and isobutylaluminoxane as activators for metallocene catalysts

Heterogenized alkylaluminoxanes prepared in situ on the montmorillonite (MMT) surface by the partial hydrolysis of AIR₃ with water of the support are effective activators for metallocenes. The thermal destruction of isobutylaluminoxane molecules in the MMT-H₂O/Al(i-Bu)₃ system has been studied by the temperature-programmed desorption method coupled with mass spectrometry (TPD-MS). The process begins at a lower temperature and is more complicated than the destruction of methylaluminoxane (MAO) in MMT-H₂O/AlMe₃. Isobutyl-substituted aluminoxane and the ansa-metallocene Me₂Si(Ind)₂ZrCl₂ form metal-alkyl complexes that are more active in propylene polymerization than methyl-substituted aluminoxane. The TPD-MS study of the initial stages of gas-phase ethylene and propylene polymerization shows that the nature of the metallocene in the heterogenized metallocene catalysts is an essential factor in the distribution of active sites by the activation energy of the thermal destruction of active Zr-C bonds.     

A kinetic study of metallocene‐catalyzed ethylene polymerization using different aluminoxane cocatalysts

The kinetics of ethylene polymerization using homogeneous Cp₂ZrCl₂/aluminoxane catalysts in toluene has been investigated at 70 °C with an ethylene pressure of 30 psi. Four aluminoxanes were used: methylaluminoxane, modified methylaluminoxanes with a fraction of methyl groups substituted with isobutyl (MMAO‐4) or octyl (MMAO‐12) groups, and polymethylaluminoxane (PMAO‐IP). The cocatalyst‐to‐catalyst ratio, [Al]/[Zr], varied from 1000 to 10,000. The experimental results obtained using the four cocatalysts were compared and a model was proposed to fit the rate of polymerization as a function of polymerization time and [Al]/[Zr] ratio. Molecular weight distributions with polydispersities between three and four indicate the presence of more than one active site type. We proposed a model that explained these broad molecular weight distributions using an unstable active complex that is formed in the early stages of the reaction and is transformed over time to a more stable active complex via an intermediate. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1677–1690, 2007     

Tacticity of poly‐α‐olefins from poly‐1‐hexene to poly‐1‐octadecene

A systematic study of the influence of the α‐olefin size, the catalyst stereospecificity and the reaction temperature was done on the catalytic activity and tacticity of poly‐α‐olefins from 1‐hexene to 1‐octadecene. The metallocenes used were rac‐Et[Ind₂]ZrCl₂ ( 1 ) and Me₂C[Cp(9‐Flu)]ZrCl₂ ( 2 ) to obtain isotactic and syndiotactic polyolefins. Some catalysts giving atactic polymers were also used in order to study all the possible ¹³C NMR pentades. Catalytic activities increased and isotacticity and syndiotacticity decreased with temperature, but no real trend was found with the α‐olefin size. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4744–4753, 2005     

Novel polystyrene‐supported zirconocene catalyst for olefin polymerization and its catalytic kinetics

Through the Diels–Alder reaction between cyclopentadiene groups attached to polystyrene in the presence of zirconocene, novel polystyrene‐supported metallocene catalysts were prepared. A novel method for immobilizing metallocene catalysts was investigated, and the resultant polystyrene‐supported metallocene for olefin polymerization was studied. The results of olefin polymerization showed that different crosslinking degrees of support in the catalyst system had significant effects on the catalytic behavior. The influence of the [Al]/[Zr] molar ratio and the temperature on the (co)polymerization activity was studied. When 1‐hexene and 1‐dodecene were used for copolymerization with ethylene, an obvious positive comonomer effect was observed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2650–2656, 2005     

Living/controlled radical copolymerization of N‐substituted maleimides with styrene in 1‐butyl‐3‐methylimidazolium hexafluorophosphate and anisole

The atom transfer radical copolymerization of N‐substituted maleimides such as N‐phenylmaleimide (PhMI), N‐cyclohexylmaleimide (ChMI), and N‐butylmaleimide (NBMI) with styrene initiated with dendritic polyarylether 2‐bromoisobutyrates in an ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim][PF₆]), at room temperature and anisole at 110 °C was investigated. The dendritic‐linear block copolymers obtained in ionic liquid possessed well‐defined molecular weight and low polydispersity (1.05 < M_w/M_n < 1.32) and could be used as a macroinitiator for chain‐extension polymerization, suggesting the living nature of the reaction system. The ionic liquids containing catalyst could be recycled in the atom transfer radical polymerization systems without further treatment. Compared with polymerization conducted in anisole, the polymerization in ionic liquid had a stronger tendency for alternation. The tendency for alternation decreased in the order PhMI > NBMI > ChMI in [bmim][PF₆] and PhMI > ChMI > NBMI in anisole. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2156–2165, 2003     

Batch emulsion copolymerization of 3‐O‐methacryloyl‐1,2:5,6‐di‐O‐isopropylidene‐α‐D‐glucofuranose and butyl acrylate: Synthesis and properties of the sugar latices

To obtain new polymer latices based on sugar derivative, batch emulsion copolymerizations of 3‐O‐methacryloyl‐1,2:5,6‐di‐O‐isopropylidene‐α‐D ‐glucofuranose (3‐MDG) and n‐butyl acrylate (BA) were carried out at 70 °C, with potassium persulfate as the initiator. 3‐MDG polymerizes faster than BA because of its higher reactivity ratio, r_(3‐MDG) = 1.94 versus r_(BA) = 0.54. The effect of the initial monomer composition on the polymerization rate and the thermal properties of the end copolymers was investigated. The overall rate of polymerization increases by enhancing the sugar content in the initial monomer composition. The glass‐transition temperature is linearly related to the sugar content in the copolymer. The influence of the type of surfactant showed that the particle size increases by changing from ionic to nonionic surfactant. Furthermore, the effect of the added acrylic acid (AA) on the rheological properties suggests that the sugar latices exhibit different non‐Newtonian flows depending on the pH of the latex and on the AA concentration on the particle surface. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 788–803, 2003     

Toward block copolymers from nonliving isospecific single‐site catalytic systems

Ethene/1‐olefin blocky copolymers were obtained through nonliving insertion copolymerizations promoted by an isospecific single site catalyst. Propene or 4‐methyl‐1‐pentene were copolymerized with ethene with metallocenes endowed with different stereospecificity in propene polymerization: (i) aspecific “constrained geometry” half‐sandwich complex, {η¹:η⁵‐([tert‐butyl‐amido)dimethylsilyl](2,3,4,5‐tetramethyl‐1‐cyclopentadienyl)}titanium dichloride [Me₂Si(Me₄Cp)(N‐^tBu)TiCl₂] ( CG ), (ii) moderately isospecific rac‐ethylenebis(indenyl)zirconium dichloride [rac‐(EBI)ZrCl₂] ( EBI ), (iii) slightly more isospecific hydrogenated homologue, rac‐ethylenebis(tetrahydroindenyl)zirconium dichloride [rac‐(EBTHI)ZrCl₂] ( EBTHI ), (iv) highly iso‐specific rac‐[methylenebis(3‐tert‐butyl‐1‐indenyl)]zirconium dichloride [rac‐H₂C‐(3‐^tBuInd)₂ZrCl₂] ( TBI ), (v) most isospecific rac‐[isopropylidene‐bis(3‐tert‐butyl‐cyclopentadienyl)]zirconium dichloride [rac‐Me₂C‐(3‐^tBuCp)₂ZrCl₂] ( TBC ). Copolymerizations were described by a 2^nd order Markovian copolymerization model and data are proposed to correlate the formation of 1‐olefin sequences with catalytic site isospecificity, made by the cooperation of organometallic complex and growing chain. Blocky copolymers were prepared over wide ranges of compositions: with any of the isospecific metallocenes when 4‐methyl‐1‐pentene was the 1‐olefin and only with the highly isospecific ones ( TBI , TBC ) when propene was the comonomer. A penultimate unit effect was observed with TBI as the metallocene, whereas a 1^st order Markov model described the ethene/propene copolymerization from TBC . A moderately isospecific metallocene, such as EBI , is shown to be able to prepare blocky ethene copolymers with 4‐methyl‐1‐pentene. These results pave the way for the synthesis of new ethene based materials. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2063–2075, 2010     

Polymerization of methyl methacrylate by metallocene imido complexes and tris(pentafluorophenyl)alane

The polymerization of methyl methacrylate (MMA) was investigated with tris(pentafluorophenyl)alane [Al(C₆F₅)₃] and four metallocene imido complexes that varied in the complex symmetry/chirality, metal, and R group in the ?NR moiety, as well as a zirconocene enolate preformed from the imido zirconocene and MMA. This study examined four aspects of MMA polymerization: the effects of the metallocene imido complex structure on the polymerization activity and polymer tacticity, the degree of polymerization control, the elementary reactions of the imido complex with Al(C₆F₅)₃ and MMA, and the polymerization kinetics and mechanism. There was no effect of the imido complex symmetry/chirality on the polymerization stereochemistry; the polymerization followed Bernoullian statistics, producing syndiotactic poly(methyl methacrylate)s with moderate (～70% [rr]) to high (～91% [rr]) syndiotacticity, depending on the polymerization temperature. Polymerization control was demonstrated by the number‐average molecular weight, which increased linearly with an increase in the monomer conversion to 100%, and the relatively small and insensitive polydispersity indices (from 1.21 to 1.17) to conversion. The reactions of the zirconocene imido complex with Al(C₆F₅)₃ and MMA produced the parent base‐free imido complex and the [2 + 4] cycloaddition product (i.e., zirconocene enolate), respectively; the latter product reacted with Al(C₆F₅)₃ to generate the active zirconocenium enolaluminate. The MMA polymerization with the metallocene imido complex and the alane proceeded via intermolecular Michael addition of the enolaluminate to the alane‐activated MMA involved in the propagation step. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3132–3142, 2003     

Stereoregular P(MMA)‐clay nanocomposites by metallocene catalysts: In situ synthesis and stereocomplex formation

This contribution reports the synthesis and characterization of stereochemically controlled, as well as crystalline stereocomplex, P(MMA)‐clay nanocomposites using metallocene complexes and alane‐intercalated clay activators. The ligand elimination and exchange reactions involving Lewis acids E(C₆F₅)₃ (E = Al, B) and an organically modified montmorillonite clay were employed to synthesize the alane‐intercalated clay activators. When combined with dimethyl metallocenes of various symmetries, these clay activators brought about efficient MMA polymerizations leading to in situ polymerized, stereochemically controlled P(MMA)‐intercalated clay nanocomposites. The most noticeable thermal property enhancement observed for the clay nanocomposite P(MMA), when compared with the pristine P(MMA) having similar molecular weight and stereomicrostructure, has a considerable increase in T_g (≥10 °C). Mixing of dilute THF solutions of two diastereomeric nanocomposites in a 1:2 isotactic to syndiotactic ratio, followed by reprecipitation or crystallization procedures, yielded unique double‐stranded helical stereocomplex P(MMA)‐clay nanocomposites with a predominantly exfoliated clay morphology. Remarkably, the resulting crystalline stereocomplex P(MMA) matrix is resistant to the boiling‐THF extraction and its clay nanocomposites exhibit high T_m of 201 to 210 °C. Furthermore, the stereocomplex P(MMA)‐clay nanocomposite shows a one‐step, narrow decomposition temperature window and a single, high maximum rate decomposition temperature of 377 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2581–2592, 2007