Preparation and properties of polyethylene/montmorillonite nanocomposites by in situ polymerization

Polyethylene (PE)/montmorillonite (MMT) nanocomposites were prepared by in situ coordination polymerization using a MMT/MgCl2/TiCl4 catalyst activated by AI(Et),. The catalyst was prepared by first diffusing MgCl2 into the swollen MMT layers, followed by loading TiCl4 on the inner/outer layer surfaces of MMT where MgCl2 was already deposited. The intercalation of MMT layers by MgCl2 and TiCl, was demonstrated by the enlarged interlayer spacing determined by WAXD. The nanoscale dispersion of MMT layers in the polyethylene matrix was characterized by WAXD and TEM. As a consequence, the crystallinity of the nanocomposite decreased sharply, whereas the tensile strength was significantly improved compared to that of virgin polyethylene of comparable molecular weight. The confinement of the nanodispersed MMT layers to molecular chain and the strong interaction between the nanoscale MMT layers and the resin matrix were thought to account for the decrease of crystallinity and the remarkable enhancement of strength.

Ring-opening polymerization of epsilon-caprolactone and L-lactide using organic amino calcium catalyst

Poly (6-caprolactone) (PCL) and poly (L-lactide) (PLA) were prepared by ring-opening Polymerization catalyzed by organic amino calcium catalysts (Ca/PO and Ca/EO) which were prepared by reacting calcium ammoniate Ca(NH3)(6) with propylene oxide and ethylene oxide, respectively. The catalysts exhibited high activity and the ring-opening polymerization behaved a quasi-living characteristic. Based on the Fr-IR spectra and the calcium contents of the catalysts, and based on the H-1 NMR end-group analysis of the low molecular weight PCL prepared using catalysts Ca/PO and Ca/EO, it was proposed that the catalysts have the structure of NH2-Ca-O-CH(CH3)(2) and NH2-CaO-CH2CH3 for Ca/PO and Ca/EO, respectively. The ring-opening polymerization of CL and LA follows a coordination-insertion mechanism and the active site is the Ca-O bond.

Reverse atom transfer radical polymerization of (-)-menthyl methacrylate

The reverse atom transfer radical polymerization(RATRP) of (-)-menthyl methacrylate ((-)-MnMA) with AIBN(AIBN/CuCl2/bipyridine(bipy) or (-)sparteine((-)Sp) =1/2/4) initiating system in THF has been studied. The dependence of the specific rotation on molecular weight was investigated.

Polymerization of acrylonitrile with (diisopropylamido) bis (indenyl) lanthanides

The polymerization of acrylonitrile was studied using ( diisopropylamido) his ( indenyl) lanthanides, Ind(2)LnN(i-Pr)(2)(Ln = Y, Yb) as a single-component catalyst. The effects of the amount of catalyst, monomer concentration and polymerization temperature on catalytic activity and molecular weight of polyacrylonitrile (PAN) were studied. The results show that the catalytic activity is raised obviously with rising polymerization temperature. The monomer conversion reaches 64% under polymerization temperature, monomer concentration and catalyst concentration are 50 degreesC, 5.1 mol . L (-1) and 0. 3 % (molar ratio) sequentially. The conversion and molecular weight of the polymer increase appreciably with adding additive, PhONa. When the molar ratio of PhONa to the catalyst is three I the conversion and the molecular weight is 76% and 1.32 x 10(4), respectively. The initiation mechanism for the polymerization of acrylonitrile was proposed.

The preparation of phenolic resin/montmorillonite nanocomposites by suspension condensation polymerization and their morphology

Phenolic resin/clay nanocomposites were prepared using a suspension condensation polymerization method that was suitable to both novolac and resole. Natural montmorillonite and two kinds of organic modified montmorillonite were adopted to investigate the effect of modification on the final morphology of the nanocomposites. X-ray diffraction (XRD) measurements and Transmission Electron Microscope (TEM) observations showed that clay platelets were easier to be exfoliated or intercalated in novolac than in resole because novolac usually has a linear structure. The modifier with a phenyl ring was more compatible with novolac (or resole) than the aliphatic type modifier. The influence of curing on the morphology was studied as well. An exfoliation-adsorption and in situ condensation mechanism was proposed on the formation of the nanocomposites.

Polymer immobilized silane bridged metallocene catalysts for ethylene polymerization

Ansa-zirconocene complex with an allyl substituted silane bridge [(CH2=CHCH2)CH3Si(C5H4)(2)]ZrCl2 (1a) has been synthesized and characterized. The molecular structure of la has been determined by X-ray crystallographic analysis. The polymer immobilized metallocene catalyst 1b is prepared by the co-polymerization of la with styrene in the presence of radical initiator. The result of ethylene polymerization showed that the polymer immobilized metallocene catalyst kept high activity for ethylene polymerization and was a potential supported catalyst for olefin polymerization.

Vinylic polymerization of norbornene by neutral nickel(II)-based catalysts

Neutral Ni(II) salicylaldiminato complexes activated with modified methylaluminoxane as catalysts were used for the vinylic polymerization of norbornene. Catalyst activities of up to 7.08 x 10(4) kg(pol)/(mol(Ni) (.) h) and viscosity-average molecular weights of polymer up to 1.5 x 10(6) g/mol were observed at optimum conditions. Polynorbornenes are amorphous, soluble in organic solvents, highly stable, and show glass-transition temperatures around 390 degreesC. Catalyst activity, polymer yield, and polymer molecular weight can be controlled over a wide range by the variation of the reaction parameters such as the Al/Ni ratio, monomer/catalyst ratio, monomer concentration, polymerization reaction temperature, and time.

Synthesis and characterization of (C5H9C9H6)(2)Yb(THF)(2)(II) (1) and [(C5H9C5H4)(2)Yb(THF)](2)O-2 (2), and ring-opening polymerization of lactones with 1

Reaction of YbI2 with two equivalents of cyclopentylindenyl lithium (C5H9C9H6Li) affords ytterbium(II) substituted indenyl complex (C5H9C9H6)(2)Yb(THF)(2) (1) which shows high activity to ring-opening polymerization (ROP) of lactones. The reaction between YbI2 and cyclopentylcyclopentadienyl sodium (C5H9C5H4Na) gives complex [(C5H9C5H4)(2)Yb(THF)](2)O-2 (2) in the presence of a trace amount of O-2, the molecular structure of which comprises two (C5H9C5H4)(2)Yb(THF) bridged by an asymmetric O-2 unit. The O-2 unit and ytterbium atoms define a plane that contains a C-i symmetry center.

Preparation and characterization of poly(ethyl acrylate)/bentonite nanocomposites by in situ emulsion polymerization

Transparent poly(ethyl acrylate) (PEA)/bentonite nanocomposites containing intercalated-exfoliated combinatory structures of clay were synthesized by in situ emulsion polymerizations in aqueous dispersions containing bentonite. The samples for characterization were prepared through direct-forming films of the resulting emulsions without coagulation and separation. An examination with X-ray diffraction and transmission electron microscopy showed that intercalated and exfoliated structures of clay coexisted in the PEA/bentonite nanocomposites. The measurements of mechanical properties showed that PEA properties were greatly improved, with the tensile strength and modulus increasing from 0.65 and 0.24 to 11.16 and 88.41 MPa, respectively. Dynamic mechanical analysis revealed a very marked improvement of the storage modulus above the glass-transition temperature. In addition, because of the uniform dispersion of silicate layers in the PEA matrix, the barrier properties of the materials were dramatically improved. The permeability coefficient of water vapor decreased from 30.8 x 10(-6) to 8.3 x 10(-6) g cm/cm(2)s cmHg. (C) 2002 Wiley Periodicals, Inc.

Preparation of functionalized montmorillonites and their application in supported zirconocene catalysts for ethylene polymerization

Ethylene polymerization was carried out with zirconocene catalysts supported on montmorillonite (or functionalized montmorillonite). The functionalized montmorillonite was from simple ion exchange of [CH3O2CCH2NH3](+) (MeGlyH(+)) ions with interlamellar cations of layered montmorillonites. The functionalized montmorillonlites [high-purity montmorillonite (MMT)-MeGlyH(+)] had larger interlayer spacing (12.69 Angstrom) than montmorillonites without treatment (9.65 Angstrom). The zirconocene catalyst system [Cp2ZrCl2/methylaluminoxane (MAO)/MMT-MeGlyH(+)] had much higher Zr loading and higher activities than those of' other zirconocene catalyst systems (Cp2ZrCl2/MMT, Cp2ZrCl2/MMT-MeGlyH(+), Cp2ZrCl2/MAO/MMT, [CP2ZrCl](+)[BF4]/MMT, [Cp2ZrCl][BF4](-)/MMT-MeGlyH(+), [CP2ZrCl](+)[BF4](-)/MAO/MMT-MeGlyH(+), and [Cp2ZrCl](+)[BF4](-)/MAO/MMT). The polyethylenes with good bulk density were obtained from the catalyst systems, particularly (CP2ZrCl2/MAO/MMT-MeGlyH(1)). MeGlyH(+) and MAO seemed to play important roles for preparation of the supported zirconocenes and polymerization of ethylene. The difference in Zr loading and catalytic activity among the supported zirconocene catalysts is discussed.

Silane bridged polymerized metallocene catalyst for ethylene polymerization

The polymerized metallocene catalyst 4 was prepared by the co-polymerization of ansa-zirconocene complex [CH3Si(2)]ZrCl2 (3) containing vinyl substituted silane bridge with styrene in the presence of radical initiator. Catalyst 4 was found to display high ethylene polymerization activity of 2.28 x 10(6) g PE/(mol . h) with a viscosity average molecular weight (M-eta) value of 61.6 x 10(3) using methylalumoxane (MAO) as a co-catalyst. The ethylene polymerization has been investigated under different conditions.

Self-immobilized catalysts for ethylene polymerization: neutral, single-component salicylaldiminato phenyl nickel(II) complexes bearing allyl substituents

A new family of self-immobilized ethylene polymerization catalysts, derived from neutral, single-component salicylaldiminato phenyl nickel complexes, is described.

Thermally crosslinkable poly(phenylene sulfide)/poly (ether sulfone)/polymerization of monomer reactant-polyimide blends

The effects of thermally crosslinkable polymerization of monomer reactant-polyimide (POI) on the miscibility, morphology, and crystallization of partially miscible poly(ether sulfone) (PES)/poly(phenylene sulfide) (PPS) blends were investigated with differential scanning calorimetry and scanning electron microscopy. The addition of POI led to a significant reduction in the size of PPS particles, and the interfacial tension between PPS and crosslinked POI was smaller than that between PES and crosslinked POI. During melt blending, crosslinking and grafting reactions of POI with PES and PPS homopolymers were detected; however, the reaction activity of POI with PPS was much higher than that with PES. The crosslinking and grafting reactions were developed further when blends were annealed at higher temperatures. Moreover, POI was an effective nucleation agent of the crystallization of PPS, but crosslinking and grafting hindered the crystallization of PPS. The final effect of POI on the crystallinity of the PPS phase was determined by competition between the two contradictory factors. The crosslinking and grafting reactions between the two components was controlled by the dosage of POI in the blends, the premixing sequence of POI with the two components, the annealing time, and the temperature.

Polymerized unsymmetrical iron post-metallocene catalyst for ethylene polymerization

The unsymmetrical allyl containing post-metallocene complex [ArN = C( Me)] [(ArN)-N-' = C(Me)]C5H3NFeCl2 [Ar = 2,6(i- Pr)(2)C6H3, Ar' = 4-allyl-2,6-(i-Pr)(2)C6H3] (3) has been prepared and characterized. Complex (3) can be co-polymerized with styrene in the presence of radical initiator to produce polymerized post-metallocene catalyst which exhibits high activity for ethylene polymerization (2.5 x 10(6) g PE/mol Fe.h).