Synthesis and characterization of the titanium complexes bearing two regioisomeric trifluoromethyl-containing enaminoketonato ligands and their behavior in ethylene polymerization

A series of new titanium complexes bearing two regioisomeric trifluoromethyl-containing enaminoketonato ligands (3a-h and 6a-h), [PhN=CRCHC(CF3)O](2)TiCl2 (3a, R = Me; 3b, R = n-C5H11; 3c, R = i-Pr; 3d, R = Cy; 3e, R = t-Bu; 3f, R = CH=CHPh; 3g, R = Et; 3h, R = n-C11H23) and [PhN=C(CF3)CHC(R)O](2)TiCl2 (6a, R = Ph; 6b, R = n-C5H11; 6c, R = i-Pr; 6d, R = Cy; 6e, R = t-Bu; 6f, R = CH=CHPh; 6g, R = CHPh2; 6h, R = CF3) have been synthesized and characterized. X-ray crystal structures analyses suggest that complexes 3c-e and 6c-d all adopt a distorted octahedral geometry around the titanium center. Complexes 3c, 3d and 6c display a cis-configuration of the two chlorine atoms around the titanium center, while complex 6d shows a trans-configuration of the two chlorine atoms. Especially, the configurational isomers (cis and trans) of complex 3e were identified both in solution and in the solid state by NMR and X-ray analyses. With modified methylaluminoxane as a cocatalyst, all the complexes are active towards ethylene polymerization, and produce high molecular weight polymers.

CNT Templated Regioselective Enzymatic Polymerization of Phenol in Water and Modification of Surface of MWNT Thereby

Carbon nanotubes (CNTs) are used as templates to synthesize regioselective polymers from enzymatic polymerization of phenol in water. About 90% of total polymeric units in the obtained polymers are the highly thermally stable oxyphenylene units. The polymer-yields are dependent on the quantities of CNTs used. On the basis of MWNT-templated enzymatic polymerization of phenol, covalent attachment of polyphenol chains to the surface of MWNT by way of a linking molecule, hydroquinone, is achieved. This approach supplies a novel way for producing high-performance polymers and for functionalization of the surface of CNT.

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

Soluble NdCl3 center dot 3EHOH (2-ethyl hexanol) in hexane combined with AlEt3 is highly active for isoprene polymerization in hexane. The NdCl3 center dot 3EHOH/AlEt3 has higher activity than the typical binary catalyst NdCl3 center dot 3(i)PrOH (isopropanol)/AlEt3 and ternary catalyst NdV3 (neodymium versatate)/AlEt2Cl/Al(i-Bu)(2)H. The molecular weight of polyisoprenes can be controlled by variation of [Nd], [Al]/[Nd] ratio and polymerization temperature and time. The NdCl3 center dot 3EHOH/AlEt3 catalyst polymerized isoprene to afford products featuring high cis-1,4 stereospecificity (ca. 96%), high molecular weight (ca. 10(5)) and relatively narr ow 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.

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).

Analysis of chemical calorific effect during reactive extrusion processes for free radical polymerization

In the reactive extrusion process for polymerization, the chemical calorific effect has a great influence on the temperature. In order to quantitatively analyze the polymerization trend and optimize the processing conditions, the phenomena of the chemical calorific effect during reactive extrusion processes for free radical polymerization were analyzed. Numerical computation expressions of the heat of chemical reaction and the reactive calorific intensity were deduced, and then a numerical simulation of the reactive extrusion process for the polymerization of n-butyl methacrylate was carried out. The evolutions of the heat of chemical reaction and the reactive calorific intensity along the! axial direction of the extruder are presented, on the basis of which reactive processing conditions can be optimized.

Investigation of the gel effect in reactive extrusion processes for free radical polymerization

The gel effect in the reactive extrusion process for free radical polymerization in a closely intermeshing co-rotating twin screw extruder was investigated. First the reaction kinetic model was constructed mainly on the basis of entanglement theory. Next, numerical calculation expressions for the initiator and monomer concentrations, monomer conversion, average molecular weight and apparent viscosity were deduced. Finally, the evolution of the above variables were shown and discussed for the example of butyl methacrylate. The simulated results of the monomer conversion are in good agreement with experimental results.

Synthesis of Arm-6 polystyrene by atom transfer radical polymerization

A new initiator for atom transfer radical polymerization (ATRP), (Cl-2 HCCOO)(3) -C-6 H-3, (TrDCAP),has been designed and successfully synthesized. ATRP of styrene was carried out by using TrDCAP as hexafunctional initiator and the CuCl/bpy catalyst at 130 degrees C in 30% THF via core-first strategy. The Arm-6 PS-AAP was synthesized by etherealization of Arm-6 PS and 4-(4'-methoxyphenylazomethine) phenol (AAP). The initiator and the architectures of the Arm-6 PS were confirmed by H-1-NMR, FT-IR, UV-Vis and GPC.

Control led/living free-radical copolymerization of 4-(azidocarbonyl) phenyl methacrylate with methyl acrylate under Co-60 gamma-ray irradiation

A new vinyl acyl azide monomer, 4-(azidocarbonyl) phenyl methacrylate, has been synthesized and characterized by NMR and FTIR spectroscopy. The thermal stability of the new monomer has been investigated with FTIR and thermal gravimetry/differential thermal analysis (TG/DTA), and the monomer has been demonstrated to be stable below 50 degrees C in the solid state. The copolymerizations of the new monomer with methyl acrylate have been carried out at room temperature under Co-60 gamma-ray irradiation in the presence of benzyl 1-H-imidazole-1-carbodithioate. The results show that the polymerizations bear all the characteristics of controlled/living free-radical polymerizations, such as the molecular weight increasing linearly with the monomer conversion, the molecular weight distribution being narrow (< 1.20), and a linear relationship existing between In([M](0)/[M]) and the polymerization time. The data from H-1 NMR and FTIR confirm that no change in the acyl azide groups has occurred in the polymerization process and that acyl azide copolymers have been obtained. The thermal stability of the polymers has also been investigated with TG/DTA and FTIR.

Crystallization behavior of poly(epsilon-caprolactone) in poly(epsilon-caprolactone) and poly(vinyl methyl ether) mixtures

The morphological development and crystallization behavior of poly(epsilon-caprolactone) (PCL) in miscible mixtures of PCL and poly(vinyl methyl ether) (PVME) were investigated by optical microscopy as a function of the mixture composition and crystallization temperature. The results indicated that the degree of crystallinity of PCL was independent of the mixture composition upon melt crystallization because the glass-transition temperatures of the mixtures were much lower than the crystallization temperature of PCL. The radii of the PCL spherulites increased linearly with time at crystallization temperatures ranging from 42 to 49 degrees C. The isothermal growth rates of PCL spherulites decreased with the amount of the amorphous PVME components in the mixtures. Accounting for the miscibility of PCL/PVME mixtures, the radial growth rates of PCL spherulites were well described by a kinetic equation involving the Flory-Huggins interaction parameter and the free energy for the nuclei formation in such a way that the theoretical calculations were in good agreement with the experimental data. From the analysis of the equilibrium melting point depression, the interaction energy density of the PVME/PCL system was calculated to be -3.95 J/cm(3).

Synthesis of symmetric H-shaped block copolymer by the combination of ATRP and living anionic polymerization

A novel fluorescent dye labeled H-shaped block copolymer, (PMMA-Fluor-PS)(2)-PEO-(PS-Fluor-PMMA)(2), is synthesized by the combination of atom transfer radical polymerization (ATRP) and anionic polymerization (AP). To obtain the designated structure of the copolymer, a macroinitiator, 2,2-dichloro acetyl-PEO-2,2-dichloro acetyl (DCA-PEO-DCA), was prepared from DCAC and poly(ethylene oxide). The copolymer was characterized by H-1 NMR, GPC and fluorescence spectroscopy.

Computer simulation of reactive extrusion processes for free radical polymerization

The reactive extrusion for polymerization is an integrated polymer processing technology. A new semi-implicit iterative algorithm was proposed to deal with the complicated relationships among the chemical reaction, the macromolecular structure and the chemorheological property. Then the numerical computation expressions of the average molecular weight, the monomer conversion, and the initiator concentration were deduced, and the computer simulation of the reactive extrusion process for free radical polymerization was carried out, on basis of which reactive processing conditions can be optimized.

Study on crystallization of poly(epsilon-caprolactone) in poly(epsilon-caprolactone)/poly(vinyl methyl ether) blends

The crystallization behaviors of poly( E-caprolactone) (PCL) in poly(epsilon-caprolactone) (PCL) and poly(vinyl methyl ether) (PVME) blends were investigated by POM, DSC, WAXD, SAXS. POM results indicated that spherical crystal morphology was present during isothermal process, and the spheric growth rates were reduced with increasing the contents of PVME in PCL/PVME blends. It was found that the crystallinity of PCL in the blends remained almost constant regardless of the blend composition, but it was dependent on preparation technique. Solution-crystallization was found to be a technique capable of increasing crystallinity levels for some compositions. The melting behavior of the blends is a rather complex process. Both solution-crystallized samples and isothermal-crystallized samples exhibited a single endotherm. Oppositely, melting-crystallized samples exhibited dual-melting endotherms whose mangnitudes vary with blend compositions. On the basis of WAXD and SAXS experiments, it is found that the crystal structure is unchanged, but the long period increases with increasing the content of PVME because of the thickening of the amorphous layers.

Synthesis of a (sic)-shaped amphiphilic block copolymer by the combination of atom transfer radical polymerization and living anionic polymerization

The functionalization of monomer units in the form of macroinitiators in an orthogonal fashion yields more predictable macromolecular architectures and complex polymers. Therefore, a new there exists E-shaped amphiphilic block copolymer, (PMMA)(2)-PEO-(PS)(2)-PEO-(PMMA)(2) [where PMMA is poly(methyl methacrylate), PEO is poly (ethylene oxide), and PS is polystyrene], has been designed and successfully synthesized by the combination of atom transfer radical polymerization (ATRP) and living anionic polymerization. The synthesis of meso-2,3-dibromosuccinic acid acetate/diethylene glycol was used to initiate the polymerization of styrene via ATRP to yield linear (HO)(2)-PS2 with two active hydroxyl groups by living anionic polymerization via diphenylmethylpotassium to initiate the polymerization of ethylene oxide. Afterwards, the synthesized miktoarm-4 amphiphilic block copolymer, (HO-PEO)(2)-PS2, was esterified with 2,2-dichloroacetyl chloride to form a macroinitiator that initiated the polymerization of methyl methacrylate via ATRP to prepare the there exists E-shaped amphiphilic block copolymer.

Achiral lanthanide alkyl complexes bearing N,O multidentate ligands. Synthesis and catalysis of highly heteroselective ring-opening polymerization of rac-lactide

Alkane elimination reactions of amino-amino-bis(phenols) H2L1-4, Salan H2L5, and methoxy-beta-diimines HL6,7 with lanthanide tris(alkyl) s, Ln(CH2SiMe3)(3)(THF)(2) (Ln = Y, Lu), respectively, afforded a series of lanthanide alkyl complexes 1-8 with the release of tetramethylsilane. Complexes 1-6 are THF-solvated mono( alkyl) s stabilized by O, N, N, O-tetradentate ligands. Complexes 1-3 and 5 adopt twisted octahedral geometry, whereas 4 contains a tetragonal bipyramidal core. Bearing a monoanionic moiety L-6 (L-7), complex 7 ( 8) is a THF-free bis(alkyl). In complex 7, the O, N, N-tridentate ligand combined with two alkyl species forms a tetrahedral coordination core. Complexes 1, 2, and 3 displayed modest activity but high stereoselectivity for the polymerization of rac-lactide to give heterotactic polylactide with the racemic enchainment of monomer units P-r ranging from 0.95 to 0.99, the highest value reached to date. Complex 5 exhibited almost the same level of activity albeit with relatively low selectivity. In contrast, dramatic decreases in activity and stereoselectivity were found for complex 4. The Salan yttrium alkyl complex 6 was active but nonselective. Bis(alkyl) complexes 7 and 8 were more active than 1-3 toward polymerization of rac-LA, however, to afford atactic polylactides due to di-active sites. The ligand framework, especially the "bridge" between the two nitrogen atoms, played a significant role in governing the selectivity of the corresponding complexes via changing the geometry of the metal center.