Amorphous Elastomeric Ultra-High Molar Mass Polypropylene in High Yield by Half-Titanocene Catalysts.

Propylene polymerizations with different ketimide-modified half-titanocene catalysts, Cp'TiCl2(N=CtBu2) [Cp' = C5H5 (1), C5Me5 (2), Me3SiC5H4 (3)], with MAO as a cocatalyst, were investigated. The obtained polymers were studied in detail by determining their microstructure, molar masses, thermal, and mechanical properties. The Cp*-ketimide, (C5Me5)TiCl2(N=CtBu2) (2), exhibited higher catalytic activities than Cp'TiCl2(N=CtBu2) (1,3), yielding higher molar mass polymers, Mw up to 1400 Kg/mol. All the synthesized polypropylenes (PP) are atactic and highly regioregular, with predominant rrrr pentads, especially PP prepared with catalyst 1. Differential scanning calorimetry (DSC) established that the polymers are fully amorphous aPP, and no melting endotherm events are detected. Glass transition temperatures were detected between -2 and 2 °C. These polypropylenes have been established to be high-performance thermoplastic elastomers endowed with remarkably high ductility, and a tensile strain at break higher than 2000%.

Flexible Polyurethane Foams from Epoxidized Vegetable Oils and a Bio-Based Diisocyanate.

Bio-polyols from epoxidized soybean and linseed oils and caprylic acid or 3-phenyl butyric acid were prepared using an environmentally friendly, solvent-free method evaluating the presence of triethylamine as catalyst. Side reactions, leading to a cross-linking structure with high density, were reduced, introducing the catalyst and properly tuning the reaction conditions. A medium functionality value of around 3 along with a hydroxyl number up to around 90 mg KOH/g, narrow polydispersity index, and relatively low molecular mass up to 2400 g/mol were the experimental targets. From selected bio-polyols and an aliphatic partially bio-based isocyanate, a series of water blown polyurethane (PU) foams was produced, estimating the effect of the chemical nature of substituents in the polyol backbone on the PU properties. The apparent density of the foams was in the range of 79-113 kg/m3, with higher values for foams from the aromatic acid. Flexible polyurethane foams with open cell structure from bio-based polyols were obtained, with higher cavity size and lower pore sizes for foams from caprylic acid. The bio-based flexible PU foams showed comparable Young's moduli (14-18 kPa) and compression deflection values (4.6-5.5 kPa) and exhibited an almost complete recovery of their initial size.

Influence of Co-Catalysts and Polymerization Conditions on Properties of Poly(anhydride-alt-epoxide)s from ROCOP Using Salen Complexes with Different Metals.

Cyclohexene oxide (CHO) and phthalic anhydride (PA) have been reacted in the presence of commercial salen-type complexes with different metals Cr (1), Al (2), and Mn (3) in combination with 4-(dimethylamino) pyridine (DMAP), bis-(triphenylphosphorydine) ammonium chloride (PPNCl) and bis-(triphenylphosphoranylidene)ammonium azide (PPNN3) as co-catalysts to obtain alternating poly(PA-alt-CHO)s by ring-opening copolymerization (ROCOP). The effect of different reaction conditions (pre-contact between catalyst and co-catalyst, polymerization time) on the productivity, molecular weight and glass transition temperature has been evaluated. By using a 24 h pre-contact, the aliphatic polyesters obtained were characterized by high molecular weight (Mn > 15 kg/mol) and glass transition temperature (Tg) up to 146 °C; the more sustainable metals Al and Mn in the presence of PPNCl give comparable results to Cr. Moreover, biodegradability data of these polyesters and the study of the microstructure reveal that the biodegradability is influenced more by the type of chain linkages rather than by the molecular weight of the polyesters.

Ethylene-co-norbornene Copolymerization Using a Dual Catalyst System in the Presence of a Chain Transfer Agent.

Ethylene-co-norbornene copolymers were synthesized by a dual catalyst system at three concentrations of norbornene in the feed and variable amounts of ZnEt2, as a possible chain transfer agent. The dual catalyst system consists of two ansa-metallocenes, isopropyliden(η5-cyclopentadienyl)(η5-indenyl)zirconium dichloride (1) and isopropyliden(η5-3-methylcyclopentadienyl)(η5-fluorenyl)zirconium dichloride (2), activated with dimethylanilinium tetrakis(pentafluorophenyl)borate, in presence of TIBA. Values of norbornene content, molecular mass, glass transition temperature, and reactivity ratios r11 and r21 of copolymers prepared in the presence of 1+2 are intermediate between those of reference copolymers. The study of tensile and elastic properties of ethylene-co-norbornene copolymers (poly(E-co-N)s) gave evidence that copolymers were obtained in part through transfer of polymer chains between different transition metal sites. Mechanical properties are clearly different from those expected from a blend of the parent samples and reveal that copolymers obtained in the presence of 1+2 and ZnEt2 consist of a reactor blend of segmented chains produced by exchange from 2 to 1 and 1 to 2 acting as the ideal compatibilizer of chains produced by the chain transfer from 1 to 1, and from 2 to 2.

Microstructure of Copolymers of Norbornene Based on Assignments of 13C NMR Spectra: Evolution of a Methodology.

An overview of the methodologies to elucidate the microstructure of copolymers of ethylene and cyclic olefins through 13C Nuclear magnetic resonance (NMR) analysis is given. 13C NMR spectra of these copolymers are quite complex because of the presence of stereogenic carbons in the monomer unit and of the fact that chemical shifts of these copolymers do not obey straightforward additive rules. We illustrate how it is possible to assign 13C NMR spectra of cyclic olefin-based copolymers by selecting the proper tools, which include synthesis of copolymers with different comonomer content and by catalysts with different symmetries, the use of one- or two-dimensional NMR techniques. The consideration of conformational characteristics of copolymer chain, as well as the exploitation of all the peak areas of the spectra by accounting for the stoichoimetric requirements of the copolymer chain and the best fitting of a set of linear equation was obtained. The examples presented include the assignments of the complex spectra of poly(ethylene-co-norbornene (E-co-N), poly(propylene-co-norbornene (P-co-N) copolymers, poly(ethylene-co-4-Me-cyclohexane)s, poly(ethylene-co-1-Me-cyclopentane)s, and poly(E-ter-N-ter-1,4-hexadiene) and the elucidation of their microstructures.

Propene Polymerization with C1-Symmetric Fluorenyl-Metallocene Catalysts.

Propene homopolymers have been produced by employing three C1-symmetric metallocene molecules (1, 2 and 3), each having t-butyl substituent(s) on the Cp, on the fluorenyl or on both aromatic moieties activated with methylaluminoxane at different polymerization temperatures and monomer concentrations. Polymers' microstructures determined by 13C NMR spectroscopy suggest that the otherwise dominant alternating mechanism governed by the chain migratory insertion is largely replaced by the competing site epimerization mechanism, as a direct result of the imposing steric bulk of the t-butyl substituent on one of the distal positions of the Cp moiety. This phenomenon is more pronounced with 3 when a second t-butyl is present in the same half-space of the molecule making the site epimerization mandatory. The lower activity of catalyst 3 with respect to catalyst 2 is also in line with the necessity for the polymer chain to back-skip (or the site to epimerize) to its original position before the subsequent monomer insertion. Chain end group analyses by ¹H NMR spectroscopy have revealed that the formation of vinylidene end groups, either via ß-H elimination or as a result of direct chain transfer to the monomer after an ordinary 1,2-insertion is the prevailing chain termination route. A correlation between the relative concentrations of vinylidene end groups of polypropene (PP) polymers produced with each catalyst and the corresponding polypropenes' molar masses was found, indicating the lower the relative concentrations of vinylidene end groups, the higher the molar masses.

Terpolymerization of Substituted Cycloolefin with Ethylene and Norbornene by Transition Metal Catalyst.

Ethylene-norbornene terpolymerization experiments using 5-alkyl-substituted norbornenes (5-pentyl-2-norbornene (C5N) and 5-octyl-2-norbornene (C8N)) or dicyclopentadiene (DCPD) were conducted with two ansa-metallocenes, [Zr{(η5-C9H6)2C2H4}Cl2] (1) and [Zr{(η5-2,5-Me2C5H2)2CHEt}Cl2] (2), activated by methylaluminoxane (MAO). The terpolymers obtained were investigated in detail by determining the microstructure and termonomer contents by 13C NMR, molar masses and thermal properties. Results were compared to those of ethylene (E)-norbornene (N) terpolymerizations with 1-octene. 2, with lower steric hindrance and a shorter bridge, gave the best activities, termonomer incorporation and molar masses. The size of the substituent in 5-alkyl substituted norbornene also plays a role. C8N gives the highest activities and molar masses, while DCPD terpolymers have the highest cycloolefin content. Terpolymers are random; their molar masses, much higher than those in 1-octene terpolymers, are in a range useful for industrial applications. Finally, Tg values up to 152 °C were obtained. For similar N content, poly(E-ter-N-ter-C8N)s and poly(E-ter-N-ter-DCPD)s have the lowest and the highest Tg values, respectively. Thus, the presence of an eight-carbon atom pendant chain in C8N increases the flexibility of the polymer chain more than a five-carbon atom pendant chain in C5N. The higher rigidity of C5N may lead to lower activities and to increasing probability of σ-bond metathesis and chain termination, as evidenced by chain-end group analysis.

Facing unexpected reactivity paths with Zr(IV)-pyridylamido polymerization catalysts.

This work provides original insights to the better understanding of the complex structure-activity relationship of Zr(IV)-pyridylamido-based olefin polymerization catalysts and highlights the importance of the metal-precursor choice (Zr(NMe(2))(4) vs. Zr(Bn)(4)) to prepare precatalysts of unambiguous identity. A temperature-controlled and reversible σ-bond metathesis/protonolysis reaction is found to take place on the Zr(IV)-amido complexes in the 298-383 K temperature range, changing the metal coordination sphere dramatically (from a five-coordinated tris-amido species stabilized by bidentate monoanionic {N,N(-)} ligands to a six-coordinated bis-amido-mono-amino complexes featured by tridentate dianionic {N(-),N,C(-)} ligands). Well-defined neutral Zr(IV)-pyridylamido complexes have been prepared from Zr(Bn)(4) as metal source. Their cationic derivatives [Zr(IV) N(-),N,C(-)}Bn](+)[B(C(6)F(5))(4)](-) have been successfully applied to the room-temperature polymerization of 1-hexene with productivities up to one order of magnitude higher than those reported for the related Hf(IV) state-of-the-art systems. Most importantly, a linear increase of the poly(1-hexene) M(n) values (30-250 kg mol(-1)) has been observed upon catalyst aging. According to that, the major active species (responsible for the increased M(n) polymer values) in the aged catalyst solution, has been identified.

Silyl-Terminated Ethylene-co-Norbornene Copolymers by Organotitanium-Based Catalysts.

Ethylene (E) and norbornene (N) were copolymerized in the presence of PhSiH(3) as chain-transfer agent with [Ti(η(5) :η(1) -C(5) Me(4) SiMe(2) NBu(t) )(η(1) -Me)(2) ] precatalyst combined with [Ph(3) C][B(C(6) F(5) )(4) ]. The silane was introduced at chain-ends of E-co-N copolymers with concomitant reinitiation of the growing polymer chain. The concentrations of the silane and polymer molecular weight are inversely correlated. The characteristic signals of SiH(2) Ph chain-ends were observed by (1) H NMR. The Si heteroatom is predominantly adjacent to ethylene units in E-co-N copolymers with high N content.