Highly 3,4-Selective Polymerization of Isoprene with NPN Ligand Stabilized Rare-Earth Metal Bis(alkyl)s. Structures and Performances

Deprotonation of (ArNHPPh2NAr2)-N-1 (H[NPN](n), n = 1 - 10) by Ln(CH2SiMe3)(3)(THF)(2) (Ln = Lu, Y, Sc, Er) generated a series of rare-earth metal bis(alkyl) complexes [NPN](n)Ln(CH2SiMe3)(2)(THF)(2) (1-10), which under activation with [Ph3C][B(C6F5)(4)] and AliBu(3) were tested for isoprene polymerization. The correlation between catalytic performances and molecular structures of the complexes has been investigated. Complexes 1-5 and 8, where Ar-1 is nonsubstituted or ortho-alkyl-substituted phenyl, adopt trigonal-bipyramidal geometry. The Ar-1 and Ar-2 rings are perpendicular in 1-4 and 8 but parallel in 5. When Ar-1 is pyridyl, the resultant lutetium and yttrium complexes 9a and 9b adopt tetragonal geometry with the ligand coordinating to the metal ions in a N,N,N-tridentate mode, whereas in the scandium analogue 9c, the ligand coordinates to the Sc3+ ion in a N,N-bidentate mode. These structural characteristics endow the complexes with versatile catalytic performances, With increase of the steric bulkiness of the ortho-substituents Ar-1 and Ar-2, the 3,4-selectivity increased stepwise from 81.6% for lutetium complex 1 to 96.8% for lutetium complex 6 and to 97.8% for lutetium complex 7a. However, further increase of the steric bulk of the ligand led to a slight drop of 3,4-selectivity for the attached complex 5 (95.1%).

Polymerization of 2,2 '-Dimethyltrimethylene Carbonate by Lutetium Complexes Bearing Amino-Phosphine Ligands

A series of lutetium alkyl, amino, and guanidinato complexes based upon an amino-phosphine ligand framework had been prepared. These complexes were applied to initiate ring-opening polymerization of 2,2'-dimethyltrimethylene carbonate (DTC). The type of the initiator significantly influenced the catalytic activity of these complexes in a trend as follows: alkyl approximate to guanidinate > amide, whereas the complexes with flexible backbone between P and N atoms within the ligand exhibited higher activity than those with rigid backbone. The isolated PDTC had bimodal-mode molecular weight distribution. The molecular weights of each fraction increased linearly with the conversion, indicating that there might be two active species. This had been confirmed by analyses of oligomeric DTC living species and oligomer with NMR technique as the metal-alkoxide and the four-membered metallocyclic lactate. Kinetic investigation displayed that the polymerization rate was the first order with the monomer concentration.

Copolymerization of ethylene with norbornene catalyzed by cationic rare earth metal fluorenyl functionalized N-heterocyclic carbene complexes

Rare earth metal bis(alkyl) complexes attached by fluorenyl modified N-heterocyclic carbene (NHC) (Flu-NHC)Ln(CH2SiMe3)(2) (Flu-NHC = (C13H8CH2CH2(NCHCCHN)C6H2Me3-2,4,6); Ln = Sc (2a); Y (2b); Ho (2c); Lu (2d)), ((tBu)Flu-NHC)Ln(CH2SiMe3)(2) ((tBu)Flu-NHC = 2,7-(Bu2C13H6CH2CH2)-Bu-t(NCHCCHN)C6H2Me3-2,4,6; Ln = Sc (1a); Lu (1d)) and attached by indenyl modified N-heterocyclic carbene (Ind-NHC)Ln(CH2SiMe3)(2) (Ind-NHC = C9H6CH2CH2(NCHCCHN)C6H2Me3-2,4,6; Ln = Sc (3a); Lu (3d)), under the activation of (AlBu3)-Bu-i and [Ph3C][B(C6F5)(4)], showed varied catalytic activities toward homo- and copolymerization of ethylene and norbornene. Among which the scandium complexes, in spite of ligand type, exhibited medium to high catalytic activity for ethylene polymerization (10(5) g mol(Sc)(-1) h(-1) atm(-1)), but all were almost inert to norbornene polymerization. Remarkably, higher activity was found for the copolymerization of ethylene and norbornene when using Sc based catalytic systems, which reached up to 5 x 10(6) g mol(Sc)(-1) h(-1) atm(-1) with 2a. The composition of the isolated copolymer was varying from random to alternating according to the feed ratio of the two monomers (r(E) = 4.1, r(NB) = 0.013).

Synthesis, Structural Characterization, and Olefin Polymerization Behavior of Vanadium(III) Complexes Bearing Tridentate Schiff Base Ligands

Vanadium(III) complexes bearing tridentate salicylaldiminato ligands (2a-f) [OC6H4CH=NL]VCl2(THF) (L = CH2CH2OMe, 2a; CH2CH2NMe2, 2b; CH2C5H4N, 2c; 8-C9H6N (quinoline), 2d; 2-MeSC6H4, 2e; 2-Ph2PC6H4, 2f) and tridentate beta-enaminoketonato ligands [OC6H8CH=N-2-Ph2PC6H4]VCl2(THF) (2g) and [O(Ph)C=CHCH=N-2-Ph2PC6H4]VCl2(THF) (2h) were prepared from VCl3(THF)(3) by treating with 1.0 equiv of the deprotonated ligands in tetrahydrofuran (THF). These complexes were characterized by FTIR and mass spectrometry as well as elemental analysis. Structures of complexes 2e, 2f, and 2h were further confirmed by X-ray crystallographic analysis. These complexes were investigated as catalysts for olefin polymerization in the presence of organoaluminum compounds. On activation with Et2AlCl, complexes 2a-h exhibited high catalytic activities toward ethylene polymerization (up to 20.64 kg PE/mmol(v) center dot h center dot bar) even at high temperature, suggesting these catalysts possess high thermal stability.

Highly Active Neutral Nickel(II) Catalysts for Ethylene Polymerization Bearing Modified,beta-Ketoiminato Ligands

A series of novel neutral nickel complexes 4a-e bearing modified beta-ketoiminato ligands [(2,6-(Pr2C6H3)-Pr-i)N=C(R-1)CHC(2 '-R2C6H4)O]Ni(Ph)(PPh3) (4a, R-1 R-2 = H; 4b, R-1 = H, R-2 = Ph; 4c, R-1 = H, R-2 = Naphth; 4d, R-1 = CH3, R-2 = Ph; 4e, R-1 = CF3, R-2 Ph) have been synthesized and characterized. Molecular structures of 4b and 4e were further confirmed by X-ray crystallographic analysis. Activated with B(C6F5)(3), all the complexes are active for the polymerization of ethylene to branched polyethylenes. Ligand structure, i.e., substituents R-1 and R-2, greatly influences not only catalytic activity but also the molecular weight and branch content of the polyethylene produced. The phenyl-substituted complex 4b exhibits the highest activity of lip to 145 kg PE/mol(Ni)center dot h center dot atm under optimized conditions, which is about 10 times more than unsubstituted complex 4a (14.0 kg PE/mol(Ni center dot)h center dot atm). Highly branched polyethylene with 103 branches per 1000 carbon atoms has been prepared using catalyst 4e.

Ethylene Polymerization by the New Chromium Catalysts Based on Amino-Pyrrolide Ligands

A series of amino-pyrrolide ligands (1-4a) and their derivatives aminothiophene ligand (5a), amino-indole ligand (6a) were prepared. Chromium catalysts, which were generated in situ by mixing the ligands with CrCl3(thf)(3) in toluene, were tested for ethylene polymerization. The preliminary screening results revealed that the tridentate amino-pyrrolide ligands containing soft pendant donor, 3a, 4a/CrCl3(thf)(3) systems displayed high catalytic activities towards ethylene polymerization in the presence of modified methyaluminoxane. The electronic and steric factors attached to the ligand backbone significantly affected both the catalyst activity and the polymer molecular weight. Complex 4b was obtained by the reaction of CrCl3(thf)(3) with one equivalent of the lithium salts of 4a, which was the most efficient ligand among the tested ones. The effect of polymerization parameters such as cocatalyst concentration, ethylene pressure, reaction temperature, and time on polymerization behavior were investigated in detail. The resulting polymer obtained by 4b display wax-like and possess linear structure, low molecular weight, and unimodal distribution.

Ethylene Polymerization and Ethylene/Hexene Copolymerization with Vanadium(III) Catalysts Bearing Heteroatom-Containing Salicylaldiminato Ligands

A series of novel vanadium(III) complexes hearing heteroatoill-containing group-substituted salicylaldiminato ligands [RN=CH(ArO)]VCl2(THF)(2) (Ar = C6H4, R = C3H2NS, 2a; C7H4NS, 2c; C7H5N2, 2d; Ar = C(6)H(2)tBu(2) (2,4), R = C3H2NS, 2b) have been synthesized and characterized. Structure of complex 2c was further confirmed by X-ray crystallographic analysis. The complexes were investigated as the catalysts for ethylene polymerization in the presence of Et2AlCl. Complexes 2a-d exhibited high catalytic activities (up to 22.8 kg polyethylene/mmolv h bar), and affording polymer with unimodal molecular weight distributions at 25-70 degrees C in the first 5-min polymerization, whereas produced bimodal molecular weight distribution polymers at 70 degrees C when polymerization time prolonged to 30 min. The catalyst structure plays an important role in controlling the molecular weight and molecular weight distribution of the resultant polymers produced in 30 min polymerization. In addition, ethylene/hexene copolymerizations with catalysts 2a-d were also explored in the presence of Et2AlCl, which leads to the high molecular weight and unimodal distributions copolymers with high comonomer incorporation.

Polymerization of 1,3-butadiene with VO(P-204)(2) and VO(P-507)(2) activated by alkylaluminum

The oxovanadium phosphonates (VO(P-204)(2) and VO(P-507)(2)) activated by various alkylaluminums (AlR3, R = Et, i-Bu, n-Oct; HAIR(2), R = Et, i-Bu) were examined in butadiene (Bd) polymerization. Both VO(P-204)(2) and VO(P-507)(2) showed higher activity than those of classical vanadium-based catalysts (e.g. VOCl3, V(acac)(3)). Among the examined catalysts, the VO(P-204)(2)/Al(Oct)(3) system (I) revealed the highest catalytic activity, giving the poly(Bd) bearing M-n of 3.76 x 10(4) g/mol, and M-w/M-n ratio of 2.9, when the [Al]/[V] molar ratio was 4.0 at 40 degrees C. The polymerization rate for I is of the first order with respect to the concentration of monomer. High thermal stability of I was found, since a fairly good catalytic activity was achieved even at 70 degrees C (polymer yield > 33%); the M-n value and M-w/M-n, ratio were independent of polymerization temperature in the range of 40-70 degrees C. By IR and DSC, the poly(Bd)s obtained had high 1,2-unit content (> 65%) with atactic configuration. The 1,2-unit content of the polymers obtained by I was nearly unchanged, regardless of variation of reaction conditions, i.e. [Al]/[V], ageing time, and reaction temperature, indicating the high stability of stereospecificity of the active sites.

Influence of montmorillonite on syndiotactic polymerization behavior of styrene

The influence of montmorillonite (MMT) on the syndiotactic polymerization behavior of styrene was studied. To avoid the hydrophilic surface of the MMT coming into contact with the catalyst, which could poison it, SAN was introduced between the MMT and Cp*Ti (OCH3)(3). MMT was introduced into the catalytic system as a supporter for the Ti catalyst (supported catalytic system) or just dispersed in the polymerization solvent directly (in situ polymerization system). The polymerization results showed that surface modification of MMT dramatically affected the catalytic activity as well as the syndiotacticity of the polymers. This is mainly explained by the insulator SAN preventing the formation of the inactive/little active species Si-O-Ti and other atactic active species resulting from the reaction of the -OH on the MMT layer surface with Cp*Ti(OCH3)(3).

Syntheses and ethylene polymerization behavior of supported salicylaldimine-based neutral nickel(II) catalysts

Two novel salicylaldimine-based neutral nickel(II) complexes, [(2,6-iPr(2)C(6)H(3))NCH(2-ArC6H3O)]Ni(PPh3)Ph (6, Ar = 2-(OH)C6H4; 8, Ar = 2-OH-3-(2,6-iPr(2)C(6)H(3)NCH)C6H3), have been synthesized, and their structures have also been confirmed by X-ray crystallography, elemental analysis, and H-1 and C-13 NMR spectra. An important structural feature of the two complexes is the free hydroxyl group, which allows them to react with silica pretreated with trimethylaluminum under immobilization by the formation of a covalent bond between the neutral nickel(II) complex and the pretreated silica. As active single-component catalysts, the two complexes exhibited high catalytic activities up to 1.14 and 1.47 x 10(6) g PE/mol(Ni)center dot h for ethylene polymerization, respectively, and yielded branched polymers. Requiring no cocatalyst, the two supported catalysts also showed relatively high activities up to 4.0 x 10(5) g PE/mol(Ni)center dot h and produced polyethylenes with high weight-average molecular weights of up to 120 kg/mol and a moderate degree of branching (ca. 13-26 branches per 1000 carbon atoms).

Syndiospecific polymerization of styrene with multi-nuclear titanium complexes

Two multi-nuclear titanium complexes [Ti(eta(5)-Cp-*) Cl(mu-O)](3) ( 1) and [(eta(5)-(CpTiCl)-Ti-*)(mu-O)(2)(eta(5)-(CpTi)-Ti-*)(2)(mu-O)(mu-O)(2)](2)Ti (Cp-* = C5Me5) ( 2) have been investigated as the precatalysts for syndiospecific polymerization of styrene. In the presence of modified methylaluminoxane ( MMAO) as a cocatalyst, complexes 1 and 2 display much higher catalytic activities towards styrene polymerization, and produce the higher molecular weight polystyrenes with higher syndiotacticities and melting temperatures ( T-m) than the mother complex (CpTiCl3)-Ti-* does when the polymerization temperature is above 70 degrees C and the Al/Ti molar ratio is in the low range especially.

Enolic Schiff-base aluminum complexes and their application in lactide polymerization

A series of NNOO-tetradentate enolic Schiff-base ligands were prepared where ligand L-1 = bis(benzoylacetone)propane-1,2-diimine, L-2 = bis(acetylacetone)-propane-1,2-diimine, L-3 = bis-(acetylacetone)cyclohexane-1,2-diimine. Their further reaction with aluminum tris(ethyl) formed complexes LAlEt (1a, 2a and 3a). The solid structure of complexes la, 2a and 3a confirmed by X-ray single crystal analysis manifested that these complexes were all monomeric and five-coordinated with an aluminum atom in the center. The configurations of these complexes varied from trigonal bipyramidal geometry (tbp) to square pyramidal geometry (sqp) due to their different auxiliary ligand architectures. H-1 NMR spectra indicated that all these complexes retained their configuration in solution states. Their catalytic properties to polymerize racemic-lacticle (rac-LA) in the presence of 2-propanol were also studied. The diimine bridging parts as well as the diketone segment substituents had very close relationship with their performance upon the polymerization process. All these complexes gave moderately isotactic polylactides with controlled molecular weight and very narrow molecular weight distributions.

Preparation of a phosphopolyoxomolybdate P2Mo18O626- doped polypyrrole modified electrode and its catalytic properties

A phosphopolyoxomolybdate (P2Mo18) doped polypyrrole (PPy) modified electrode was prepared in aqueous solution by a one-step method. During the polymerization of PPy, P2Mo18 acted as both catalyst and dopant. The electrochemical behavior of the PPy/P2Mo18 modified electrode before and after the overoxidation of PPy was investigated. Both of these showed a catalytic effect toward bromate. The PPy/P2Mo18 composite film was characterized by chronoamperometry, cyclic voltammetry, the rotating disk electrode technique, X-ray photoelectron spectroscopy and Raman spectroscopy.

Polymerization of methyl methacrylate by iron(II) pyridinebisimine complexes

Fe(II) pyridinebisimine complexes activated with trialkylaluminium or modified methylaluminoxane (MMAO) as catalysts were employed for the polymerization of methyl methacrylate. Polymer yields, activities and polymer molecular weights as well as molecular weight distributions can be controlled over a wide range by the variation of the structures of the Fe(II) pyridinebisimine complexes and the reaction parameters such as Al/Fe molar ratio, monomer/catalyst molar ratio, monomer concentration, reaction temperature and time applied to the polymerization of methyl methacrylate. Under optimum condition, the catalytic activity of Fe(II) complex is of up to 74.5 kg(polym)/mol(Fe)h.

The synthesis and catalytic activity of poly(bis(imino)pyridyl) iron(II) metallodendrimer

The first and second generation carbosilane dendrimers with silicon hydride terminated were synthesized, and then reacted with bis(imino)pyridyl containing allyl [4-CH2==CHCH2-2,6-(Pr2C6H3N)-Pr-i==CMe(C5H3N)MeC==N(2,6-'Pr2C6H3)], in the presence of H2PtCl6 as a hydrosilylation catalyst, to afford the first and second generation carbosilane supported ligands. Complexation reactions with FeCl(2)(.)4H(2)O give rise to iron-containing carbosilane dendrimers with FeCl2 moieties bound on the periphery. The metallodendrimers were used as catalyst precursors, activated with modified methylaluminoxane, for the polymerization of ethylene. In the case of low Al/Fe molar ratio, the metallodendrimers display much higher catalytic activity towards ethylene polymerization and produce much higher molecule weight polyethylenes than the corresponding single-nuclear complex under the same conditions.