Isospecific Polymerization Research Articles

C 1-Symmetric {cyclopentadienyl/indenyl}-metallocene catalysts: synthesis, structure, isospecific polymerization of propylene and stereocontrol mechanism.

A series of new Me2Si-bridged cyclopentadiene/indene proligands {Me2Si(R2',5'2-R3',4'2-Cp)(R2,R4,R5,R6-Ind)H2} (1a-j) with various substitutions both on the indene and cyclopentadiene moieties was prepared. The corresponding C1-symmetric group 4 ansa-metallocene complexes (M = Zr, Hf), namely, {Me2Si(Me4Cp)(Ind)}ZrCl2 (2a-Zr), {Me2Si(Me4Cp)(2-Me,4-Ph-Ind)}MCl2 (2b-M), {Me2Si(Me4Cp)(2-Me,4-Ph,6-tBu-Ind)}ZrCl2 (2c-Zr), {Me2Si(Me4Cp)(2-Me,4-Ph,5-OMe,6-tBu-Ind)}MCl2 (2d-M), {Me2Si(Me4Cp)(2-R',4-(3',5'-tBu2,4'-OMe-C6H2),5-OMe,6-tBu-Ind)}ZrCl2, R' = Me (2e-Zr), R' = Et (2f-Zr), {Me2Si(2,5-Ph2-3,4-Me2-Cp)(2-Me,4-(3',5'-tBu2,4'-OMe-C6H2),5-OMe,6-tBu-Ind)}ZrCl2 (2g-Zr), {Me2Si(Me4Cp)(2-Me,4-(3',6'-tBu2-carbazol-4'-yl)-Ind)}ZrCl2 (2h-Zr), {Me2Si(2,5-Me2,3,4-iPr2-Cp)(2-Me,4-Ph-Ind)}ZrCl2 (2i-Zr), {Me2Si(2,5-Me2,3,4-iPr2-Cp)(2-Me,4-Ph,6-tBu-Ind)}ZrCl2 (2j-Zr) and {Me2Si(Me4Cp)(2-Me-4,5-[a]anthracene-Ind)}MCl2 (2k-Zr) were synthesized and characterized by NMR spectroscopy and mass spectrometry. The solid-state molecular structures of 2b-Zr, 2d-Zr, 2e-Zr, 2f-Zr, 2j-Zr and 2k-Zr were determined by X-ray crystallography. The zirconocene complexes, once activated with MAO in toluene solution, exhibited propylene polymerization activities at 60 °C up to 161 000 kg(PP) mol(Zr)-1 h-1, affording highly isotactic polypropylenes (iPP) with [m]4 up to 96.5% and Tm up to 157 °C. Also, metallocene complexes 2b-e-Zr were supported on SiO2-MAO and evaluated in slurry bulk propylene polymerization at 70 °C, producing iPPs with [m]4 = 91.7-96.6 mol% and low regiodefects (0.2-0.3 mol%) content, with productivities up to 636 000 kg(PP) mol(Zr)-1 h-1. DFT calculations allowed rationalizing a polymerization reaction mechanism occurring through "chain-stationary" enchainment with preference for 1,2-insertions.

Isospecific Polymerization of Halide- and Amino-Substituted Styrenes Using a Bis(phenolate) Titanium Catalyst

Isospecific polymerization of polar styrenes is a challenge of polymer science. Particularly challenging are monomers bearing electron-withdrawing substituents or bulky substituents. Here, we report the coordination polymerization of halide- and amino-functionalized styrenes including para-fluorostyrene (pFS), para-chlorostyrene (pClS), para-bromostyrene (pBrS), and para-(N,N-diethylamino)styrene (DMAS) using 2,2′-sulfur-bridged bis(phenolate) titanium precursor (1). The combination of 1 and [Ph3C][B(C6F5)4] and AliBu3 provides crystalline poly(pFS)s with perfect isotacticity (mmmm > 95%) and high molecular weights (≤16.0 × 104 g mol−1). Upon activation with a large excess of DMAO, 1 reaches polymerization activity of 5.58 × 105 g molTi−1 h−1 producing isotactic poly(pFS)s featuring higher molecular weights (≤39.6 × 104 g mol−1). The distinguished performance of the 1/DMAO system has been extended to the polymerization of pClS and pBrS, both usually involve halogen abstraction during the polymerization, to produce isotactic and high molecular weight (Mn = 32.2 × 104 vs. 13.7 × 104 g mol−1) polymers in good activities (2.18 × 105 vs. 1.31 × 105 g molTi−1 h−1). Surprisingly, 1/DMAO is nearly inactive for DMAS polymerization, on contrary, the system 1/[Ph3C][B(C6F5)4]/AliBu3 displays isoselectivity (mmmm > 95%) albeit in a moderate activity.

Isospecific (Co)polymerization of Unmasked Polar Styrenes by Neutral Rare-Earth Metal Catalysts.

Syndioselective polymerization of unprotected polar styrenes has achieved great success via specially designed catalysts and the establishment of "self-assisted" theory. In contrast, isospecific polymerization of polar styrenes has remained less explored. Herein, we present new racemic ansa-bis(benz[e]indenyl) rare-earth metal complexes and their high activity and perfect isoselectivity (mmmm>99 %) for the polymerization of unmasked polar styrenes without any activators. Moreover, the copolymerizations of para- and meta-methoxystyrenes with styrene give gradient and random copolymers, respectively. The insertion rate of polar monomers could be readily tuned in the range of 0-100 mol % by changing their loading ratios. The resultant isotactic polar polystyrenes are quantitatively transformed into hydroxyl or methylsulfonyl polystyrenes with high Tg s. DFT calculations reveal the isospecific mechanism.

Isospecific (Co)polymerization of Unmasked Polar Styrenes by Neutral Rare‐Earth Metal Catalysts

AbstractSyndioselective polymerization of unprotected polar styrenes has achieved great success via specially designed catalysts and the establishment of “self‐assisted” theory. In contrast, isospecific polymerization of polar styrenes has remained less explored. Herein, we present new racemic ansa‐bis(benz[e]indenyl) rare‐earth metal complexes and their high activity and perfect isoselectivity (mmmm>99 %) for the polymerization of unmasked polar styrenes without any activators. Moreover, the copolymerizations of para‐ and meta‐methoxystyrenes with styrene give gradient and random copolymers, respectively. The insertion rate of polar monomers could be readily tuned in the range of 0–100 mol % by changing their loading ratios. The resultant isotactic polar polystyrenes are quantitatively transformed into hydroxyl or methylsulfonyl polystyrenes with high Tgs. DFT calculations reveal the isospecific mechanism.

Isospecific Polymerization of Methyl Methacrylate by Intramolecular Rare‐Earth Metal Based Lewis Pairs†

A series of cationic rare‐earth aryloxide complexes, i.e., [LREOAr']+[B(C6F5)4]– (L = CH3C(NAr)CHC(CH3)(NCH(R)CH2PPh2); RE = Y, Lu; Ar' =2,6‐tBu2‐C6H3, 2,6‐(PhCMe2)2‐4‐Me‐C6H2; Ar = 2,6‐iPr2‐C6H3, 2,6‐(Ph2CH)2‐4‐iPr‐C6H2; R = H, CH3, iPr, Ph), were prepared and applied to the Lewis pair polymerization of methyl methacrylate (MMA). The stereoregularity of the resulting PMMA was significantly affected by the R substituent on the pendant arm of the tridentate NNP ligand, and was found to increase with increase in the steric hindrance of R. When using a Ph group as R, the Y complex produced a highly isotactic polymer with an mm value of 95% and a Tg of 54.6 oC. In contrast, the steric hindrance of the Ar and Ar' groups had no effect on the tacticity of the resulting polymer, presumably because these two substituents were situated such that they pointed outward from the cyclic intermediates. Kinetics studies demonstrated that the polymerization was a first‐order process with regard to the monomer concentration prior to catalyst deactivation. End group analysis indicated that the polymerization was accompanied by two possibly competing chain‐termination side reactions that proceeded via intramolecular backbiting cyclization.

Stereoselective cationic polymerization of vinyl ethers by easily and finely tunable titanium complexes prepared from tartrate-derived diols: isospecific polymerization and recognition of chiral side chains

Isotactic poly(vinyl ether)s were generated by titanium TADDOLates, which can be prepared from naturally abundant tartaric acid in a facile and economical manner with well-defined structures.

Synthesis and thermal properties of poly(oligomethylene-cycloalkylene)s with regulated regio- and stereochemistry

This article focuses on the synthesis and thermal properties of poly(oligomethylene-cyclopentylene)s and poly(oligomethylene-cyclohexylene)s with regulated regio- and stereochemistry. Pd complexes with diimine ligands promote controlled isomerization polymerization of 4-alkylcyclopentenes to afford polymers with 1,3-trans-cyclopentylene groups and oligomethylene spacers alternating along the polymer chain. Pd complexes with a C2 symmetric structure enable isospecific polymerization of 4-alkylcyclopentenes, and the resultant isotactic polymers show liquid-crystalline properties. Cyclopolymerization of 1,6-heptadiene by bis(imino)pyridine Fe and Co catalysts produces poly(ethylene-1,2-cyclopentylene) with cis and trans-stereochemistry, respectively. Synthesis of poly(oligomethylene-1,4-cyclohexylene)s with trans or cis structure can be achieved by Pd-catalyzed isomerization polymerization of alkenylcyclohexanes or methylenecyclohexanes. The polymers with 1,4-trans-cyclohexylene show a high melting point that depends on the length of the oligomethylene spacer in the polymer. The thermal properties of the poly(oligomethylene-cyclopentylene)s and poly(oligomethylene-cyclohexylene)s are compared to those of previously reported polymers with different regio- or stereochemistry. Synthesis and thermal properties of poly(oligomethylene-cyclopentylene)s and poly(oligomethylene-cyclohexylene)s with regulated regio- and stereochemistry are described. Pd complexes with diimine ligands promote controlled isomerization polymerization of 4-alkylcyclopentenes and alkenylcyclohexanes to afford poly(oligomethylene-1,3-cyclopentylene)s with trans structure and poly(oligomethylene-1,4-cyclohexylene)s with trans or cis structure, respectively. Poly(ethylene-1,2-cyclopentylene) with cis and trans-stereochemistry can be obtained by Fe- and Co-catalyzed cyclopolymerization of 1,6-heptadiene, respectively. The thermal properties of the poly(oligomethylene-cyclopentylene)s and poly(oligomethylene-cyclohexylene)s are compared to those of previously reported polymers with different regio- or stereochemistry.

Dichlorovanadium(IV) diamine-bis(phenolate) complexes for ethylene (co)polymerization and 1-olefin isospecific polymerization

Two vanadium complexes bearing amine-bis(phenolate) ligands with the amino side-arm donor, [V{Me2NCH2CH2N(CH2-2-O-3,5-tBu2-C6H2)2}Cl2] (1) and [V{Me2NCH2CH2N(CH2-2-O-3,5-tBu2-C6H2)(CH2-2-O-C6H4)}Cl2] (2), were synthesised and characterized by FTIR and 1HNMR spectroscopy. Upon activation with Al(iBu)3/Ph3CB(C6F5)4, these complexes became active catalysts for 1-octene polymerization giving highly stereoregular polymers (mmmm ∼ 90%) having regioirregularly arranged units. The catalytic activity of the catalysts in ethylene homo- and copolymerization, and their ability to incorporate a comonomer were highly dependent on both the activator type and the complex structure. 1/EtAlCl2 exhibited very high activity (up to 3.3 · 107 g/(molV h)) in ethylene polymerization and produced copolymers with the highest comonomer content (up to 9.1 mol%), moderate molecular weight and narrow chemical composition distribution (CCD). Both vanadium complexes, when combined with trityl borate activator, led to ethylene copolymers with lower 1-octene content and broad CCD. In addition, the copolymers were characterized by very high molecular weight (∼1 · 106 g/mol) and narrow dispersity (Mw/Mn = 1.4–2.0).

Confinement effect of mesoporous silica reactors on electron transfer atom transfer radical polymerization of styrene

Controlled/living free radical polymerization in confined space is expected to produce new materials with predetermined structures and special properties. In this work, various morphologies of mesoporous silicas were synthesized and used as a nanoreactor for bulk activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) of styrene. The resulting mesoporous silica/polystyrene (MS/PS) nanocomposites and PS within the pore channels were characterized by scanning electron microscope, transmission electron microscope, nitrogen adsorption–desorption measurements, fourier transform infrared spectrometer, thermogravimetry analysis, gel permeation chromatography, differential scanning calorimetry, and proton nuclear magnetic resonance (1H-NMR) spectra. In comparison to conventional bulk ARGET ATRP of styrene (without MS), the pore channels of the MS show an evident confinement effect on bulk ARGET ATRP of styrene. The morphology, molecular weight and polydispersity, glass transition temperature (Tg), and spatial configuration of PS are strongly related to the morphology and internal pore channels of the MS. The bulk ARGET ATRP of styrene in 3D cubic bicontinuous structure MCM-48 shows a high potential for isospecific polymerization. The PS obtained in rod-like SBA-15 (2D), spherical SBA-15, and MCM-41 (1D) exhibit a higher molecular weight, polydispersity index and Tg. The PS obtained in 3D MCM-48 exhibits enhanced molecular weight along with decreased the polydispersity. Moreover, the morphologies of the polymers obtained in mesoporous silica are consistent with that of the corresponding mesoporous silicas.

Controlled iso-specific polymerization of 2-vinylpyridine catalyzed by arylamide-ligated rare-earth metal aminobenzyl complexes.

Treatment of rare-earth tris(o-dimethylaminobenzyl) complexes Ln(CH2C6H4NMe2-o)3 with one equivalent of the pyrrolyl-functionalized arylamide ligands 2,5-Me2C4H2NCH2CH2NHC6H5 and 2,5-Me2C4H2NSiMe2NHC6H5 in toluene generated arylamide rare-earth metal bis(aminobenzyl) complexes (2,5-Me2C4H2NCH2CH2NC6H5)Ln(CH2C6H4NMe2-o)2 (Ln = Sc (1), La (2), Lu (3)) and (2,5-Me2C4H2NSiMe2NC6H5)Ln(CH2C6H4NMe2-o)2 (Ln = Lu (5), Y (6)) in good isolated yields. Reaction of Y(CH2C6H4NMe2-o)3 with 2,5-Me2C4H2NCH2CH2NHC6H5 in 1 : 1 or 1 : 2 molar ratio specifically yielded bis(arylamide) yttrium mono(aminobenzyl) complex (2,5-Me2C4H2NCH2CH2NC6H5)2Y(CH2C6H4NMe2-o) (4). Complexes 1-6 were characterized by elemental analysis and NMR spectroscopy. Complexes 2, 4 and 5 were structurally validated by single crystal X-ray diffraction. These complexes were highly active for polymerization with 2-vinylpyridine to afford iso-tactic polymers with high molecular weight and narrow molecular weight distribution. Complex 4 promoted the polymerization in a controlled fashion, and the iso-selectivity of the polymerization reached up to a Pm value of 0.98. Analyses of the oligomer by NMR and MALDI-TOF showed that the polymerization proceeded via a group transfer polymerization mechanism.

Strategy for rational control of stereosequence in free radical polymerization of acrylates

ABSTRACTRadical polymerization of cyclic analogs of acrylates, (S)‐ and (R)‐2‐isopropyl‐5‐methylene‐1,3‐dioxolan‐4‐ones (1S and 1R), successfully afforded a functional polymer having the tacticity continuously controlled from 29% to ∼100% of meso triad (mm) over a wide range of temperature only by changing the molar ratio of 1S/1R in feed. Plot of the number fractions of the triad versus diad of poly(1) was in good agreement with the Bernoulli statistics. In the polymerization in chiral solvents having analogs structure of the monomers, the tacticity and specific rotation of the resulting polymer were specifically varied depending on the structure and concentration of the solvents. Model propagation reaction at dimeric radical calculated with density functional theory reproduced a methodical induction of the chirality to the main chain from the branched chiral monomeric unit, which supports the experimental expectations. It is remarkable that the ceiling temperature of 1 is tremendously high, for example, 193 °C in [1 (ee = 72.6%)] = 0.05 mol/L, and the isospecific polymerization is maintained even at such a high temperature, which enabled the control of polymer tacticity over a wide range of temperature. The mechanism of the stereosequence in radical polymerization was discussed experimentally and theoretically. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 184–193

Macrocyclic Trinuclear Nickel Phenoxyimine Catalysts for High-Temperature Polymerization of Ethylene and Isospecific Polymerization of Propylene

A series of macrocyclic multinucleating phenoxyimine ligands and the corresponding neutral binuclear (2-Ni2) and trinuclear (3-Ni3) nickel catalysts have been efficiently synthesized. The trinuclear nickel complex 3-Ni3 showed high activity, high thermal stability, and slow chain transfer in ethylene polymerization, thus producing polyethylene with high molecular weight and low branch density. Highly regiospecific and isospecific polymerization of propylene was also achieved with 3-Ni3, generating regioregular and highly isotactic propylene with high Tm and crystallinity. This is the first example of regio- and stereocontrolled propylene polymerization promoted by nickel phenoxyimine catalysts. Statistical analysis suggested selective 1,2-insertion and enantiomorphic site control mechanism in the chain propagation step, likely caused by the unique steric effect of macrocyclic ligands and the potential cooperative effect.

Effect of Aminosilane Compounds as External Donors on Isospecific Polymerizations of 1-Butene with MgCl2/TiCl4/DIBP Catalyst

Four aminosilane compounds were synthesized and employed as external electron donors for 1-butene polymerization with MgCl2 supported Ziegler-Natta catalyst. The four aminosilane compounds are di(piperidinyl)dimethoxysilane (DPPDMS), di(piperidinyl)- diethoxysilane (DPPDES), di(pyrrolidinyl)dimethoxysilane (DPRDMS) and di(pyrrolidinyl)- diethoxysilane (DPRDES). A detailed study has been performed on the effects of the chemical structure of different external electron donors on the catalytic efficiency, isotacticity, melting temperature and molecular weight distribution of obtained poly(1-butene). Poly(1-butene) products have been characterized with gel permeation chromatography (GPC) and differential scanning calorimetry (DSC) analysis. The results indicated that: first, aminosilane compounds with dimethoxy groups showed higher catalytic efficiency and polymers isospecificity than those of with diethoxy groups. Conversely, the aminosilane compounds with diethoxy groups were conductive to obtaining polymers with broader molecular weight distribution than those of with dimethoxy groups. Second, compared with single DPPDMS or TEOS (tetraethyl orthosilicate), DPPDMS/TEOS complex in a proper molar ratio would not only increase the catalytic efficiency and isotacticity of obtained polymers, but also broaden the molecular weight distribution of polymers. Third, the effects of other factors on catalytic efficiency and isotacticity of polymers product were also studied, including different amount of hydrogen, concentration of external donor and cocatalyst. Di(piperidinyl)dimethoxysilane (DPPDMS) was synthesized and employed as external electron donors for 1-butene polymerization with MgCl2 supported Ziegler-Natta catalyst. Compared with single DPPDMS or TEOS (tetraethyl orthosilicate), DPPDMS/TEOS complex in a proper molar ratio would not only increase the catalytic efficiency and isotacticity of obtained polymers, but also broaden the molecular weight distribution of polymers. The selection of molar ratio should depend on the requirements to the polymer.

Macromol. Rapid Commun. 12/2016

Back Cover: Highly isospecific polymerization of silyl-protected ω-alkenols, using a combination of [OSSO]-type bis(phenolato) dichloro zirconium(IV) complex and dMAO as the precatalyst and the activator, respectively, is established. This method represents the first example for a stereoselective polymerization of polar functional α-olefins ([mmmm] > 95%). Subsequently, the obtained terminal siloxy-substituted isotactic polymer could be readily transformed by a macromolecular desilylation/acetylation reaction sequence to afford the corresponding terminal acetyl-enriched polymer. Further details can be found in the article by Y. Saito, N. Nakata,* and A. Ishii* on page 969.

Completely Isospecific Polymerization of 1-Hexene Catalyzed by Hafnium(IV) Dichloro Complex Incorporating with an [OSSO]-type Bis(phenolate) Ligand

In the presence of dried methylaluminoxane as an activator, the hafnium(IV) dichloro pre-catalyst 4 incorporating with an [OSSO]-type ligand was found to promote precisely isospecific 1-hexene polymerizations of [mmmm] up to 95 % with fairly high activities (1,050–3,180 g mmol(4)−1 h−1) and relatively narrow polydispersities (M w/M n = 1.5–1.8).

Controlled Isospecific Polymerization of α-Olefins by Hafnium Complex Incorporating with a trans-Cyclooctanediyl-Bridged [OSSO]-Type Bis(phenolate) Ligand

Treatment of trans-cyclooctanediyl-bridged [OSSO]-type ligand 1 with Hf(CH2Ph)4 in toluene afforded the corresponding hafnium(IV) dibenzyl complex 5 as pale yellow crystals. X-ray crystallographic analysis of 5 revealed that the six-coordinated hafnium center incorporated in the [OSSO]-type ligand 1 adopted cis-α configuration, and two benzyl ligands were coordinated to hafnium center by η1-fashion. In the polymerization of 1-hexene, the combination of hafnium complex 5 and B(C6F5)3, (Ph3C)[B(C6F5)4], or dMAO (dried methylaluminoxane) as an activator provided poly(1-hexene)s with perfect isotacticity ([mmmm] > 95%) and high molecular weights (Mw = 74 800–421 000 g mol–1). The combination of 5/dMAO catalyst system, in particular, exhibited fairly high activity of 2100 g mmol (5)−1 h–1, which is quite higher than those of previously reported [OSSO]-type hafnium complexes. In addition, the polymerization of 4-methyl-1-pentene (4-MP) catalyzed by the 5/(Ph3C)[B(C6F5)4] system at room temperature produced completely isotactic poly(4-MP)s with good activity (54–101 g mmol (5)−1 h–1) and relatively narrow PDI (Mw/Mn = 1.3). Furthermore, the propylene polymerization catalyzed by the 5/dMAO system at different temperatures (0–70 °C) for 1 h afforded highly isotactic polypropylenes, where the catalyst activity and isotacticity depend on the polymerization temperature. Thus, the activity greatly increased from 500 to 17 000 g mmol (5)−1 h–1 when the polymerization temperature was increased. In contrast, isotacticity and melting transition temperature (Tm) were elevated by decreasing polymerization temperature (at 0 °C: [mmmm] = 93.7%, Tm = 156.2 °C; at 70 °C: [mmmm] = 86.8%, Tm = 140.9 °C).

Octahedral Group IV Bis(phenolate) Catalysts for 1-Hexene Homopolymerization and Ethylene/1-Hexene Copolymerization

Octahedral group IV bis(phenolate) catalysts are highly active catalysts for the isospecific polymerization of 1-hexene and the copolymerization of ethylene with 1-hexene. These catalysts are active for the production of high molecular weight copolymers even at 130 °C. The copolymerization parameters for these complexes were determined; all of the bis(phenolate) complexes tested incorporate 1-hexene with high efficiency to give random copolymers. The complexes prepared from the more sterically demanding ligands showed higher molecular weights but similar comonomer incorporations to those prepared from the less sterically demanding ligands.

Synthesis and self-assembly of isotactic polystyrene-block-poly(ethylene glycol)

Isotactic polystyrene-block-poly(ethylene glycol) (iPS-b-PEG) was synthesized via a thiol–ene click coupling reaction of vinyl-terminated isotactic polystyrene (iPS–) with thiol-terminated poly(ethylene glycol) (PEG-SH). iPS– was prepared by the extremely highly isospecific polymerization of styrene with 1,4-dithiabutandiyl-2,2′-bis(6-tertbutyl-4-methylphenoxy) titanium dichloride and methylaluminoxane (MAO) in the presence of 1,7-octadiene as a chain transfer agent. PEG-SH was synthesized by the direct esterification of hydroxyl-terminated PEG (PEG-OH) with 3-mercaptopropionic acid using HfCl4·2THF as a catalyst. The behavior and micelle morphology of the crystallization-driven self-assembly of iPS-b-PEG in N,N-dimethylformamide (DMF) were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), dynamic light scattering (DLS), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The results revealed that the crystallinity of the iPS blocks in the micelle cores was increased with increasing the storage time of the micelle solution at room temperature, and the increase of crystallinity led to the transition from spherical to petal-like micelles. With time these petal-like micelles could self-associate into flower-like aggregates. Moreover, when the newly prepared micelle DMF solution of iPS-b-PEG was dialyzed against deionized water, bowl-like micelles were formed due to the diffusion of DMF from the iPS cores into the aqueous phase.

Isospecific polymerization of 1-hexene by C1-symmetric half-metallocene dimethyl complexes of group 4 metals with bidentate N-substituted iminomethylpyrrolyl ligands

Non-bridged half-metallocene dimethyl complexes of group 4 metals 2a-4a with an N-4-methoxyphenyl(iminomethyl)pyrrolyl ligand 1a were synthesized and characterized by NMR spectroscopy and X-ray analysis. Upon activation with [Ph3C][B(C6F5)4], these complexes became active catalysts for the polymerization of 1-hexene. A series of hafnium complexes with various N-substituents on the imine group of ligands 1b-1g were also prepared and applied as catalysts for 1-hexene polymerization. The activation parameters for the exchange process between the two methyl groups bound to the metal for Cp*MMe2(R-pyr) complexes were estimated by NMR shape analysis at various temperatures. The findings indicated that the transition state of the ligand flipping process might be associated with the isoselectivity of the polymerization reaction.

Isospecific polymerization of propene by new indolyl-pyridylamido Zr(IV) catalysts

New zirconium complexes bearing indolyl-pyridylamido ligands [−NNN−] have been synthesized and used as catalysts in ethylene and propene polymerization in the presence of AliBu2H/MAO as cocatalytic system. Complexes 1 and 2, bearing ligands with a different steric hindrance on the carbon bridging the pyridine and the aniline moieties, exhibited remarkable catalytic activity for ethylene and propene polymerization, affording ultrahigh molecular weight polymers with monomodal molecular weight distributions. Moreover, the presence of the 2-isopropyl phenyl substituent on the bridging carbon (complex 2) resulted in higher stereoselectivity and regioselectivity providing a polypropylene sample with an [mmmm] content up to 96% and 1.3% of regioinversion. On the other hand, the change of the substituents of the aniline moiety (complex 3) gave a zirconium complex which resulted completely inactive both in the ethylene and propene polymerization.