Micron-granula polyolefin with self-immobilized nickel and iron diimine catalysts bearing one or two allyl groups

Self-immobilized nickel and iron diimine catalysts bearing one or two allyl groups of [ArN=C](2)(C10H6)NiBr2 [Ar = 4-allyl-2,6-(i-Pr)(2)C6H2] (1), [ArN=C(Me)[Ar'N=C(Me)]C5H3NFeCl2 [Ar = Ar' = 4-allyl-2,6-(i-Pr)(2)C6H3, Ar = 2,6-(i-Pr)(2)C6H3, and Ar' = 4-allyl-2,6-(i-Pr)(2)C6H3] were synthesized and characterized. All three catalysts were investigated for olefin polymerization. As a result, these catalysts not only showed high activities as the catalyst free from the allyl group, such as [ArN=C](2)C10H6,NiBr2 (Ar = 2,6-(i-Pr)(2)C6H2)], but also greatly improved the morphology of polymer particles to afford micron-granula polyolefin. The self-immobilization of catalysts, the formation mechanism of microspherical. polymer, and the influence on the size of the particles are discussed. The molecular structure of self-immobilized nickel catalyst 1 was also characterized by crystallographic analysis.

Self-immobilized metallocene catalysts bearing an allyl group for ethylene polymerization, X-ray crystal structure of [(CH2=CHCH2)CH3Si(C13H8)(2)]ZrCl2

A series of ansa-metallocene complexes with an allyl substituted silane bridge [(CH =CHCH2)CH3Si(C5H4)(2)]TiCl2 (1), [(CH2=CHCH2)CH3Si(C9H6)(2)]MCl2 [M = Ti (2), Zr (3), Hf (4)] and [(CH2=CHCH2)CH3Si(C13H8)(2)]ZrCl2 (6) have been synthesized and characterized. The molecular structure of 6 has been determined by X-ray crystallographic analysis. Complexes 1-4, 6 bearing allyl groups have been investigated as self-immobilized catalysts for ethylene polymerization in the presence of MMAO. The results showed that the self-immobilized catalysts 1-4, 6 kept high ethylene polymerization activities of ca. 10(6) g PE mol(-1) M h(-1) and high molecular weight (M-w approximate to 10(5)) of polyethylene.

Investigation of sol-gel transition in Pluronic F127/D2O solutions using a combination of small-angle neutron scattering and Monte Carlo simulation

Physical gelation in the concentrated Pluronic F127/D2O solution has been studied by a combination of small-angle neutron scattering (SANS) and Monte Carlo simulation. A 15% F127/D2O solution exhibits a sol-gel transition at low temperature and a gel-sol transition at the higher temperature, as evidenced by SANS and Monte Carlo simulation studies. Our SANS and simulation results also suggest that the sol-gel transition is dominated by the formation of a percolated polymer network, while the gel-sol transition is determined by the loss of bound solvent. Furthermore, different diffusion behaviors of different bound solvents and free solvent are observed. We expect that this approach can be further extended to study phase behaviors of other systems with similar sol-gel phase diagrams.

A polymer composite film with reversible responsive behaviors

A responsive polymer composite film was generated by the use of reversibly switchable Surface morphology of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) films in response to different block selective solvents on the rough isotactic poly(propylene) (i-PP) substrate. The Maximum difference of the water contact angle of the composite films increased from 22.6 degrees of PS-b-PMMA films on the smooth substrate to 42.6 degrees when they were treated by PS and PMMA selective solvents, respectively. The mechanisms of the responsive extent enhanced and the superhydrophobicity of the composite films were discussed in detail.

Morphology of high impact polypropylene particles

Morphological features of isotactic polypropylene (iPP) and high impact polypropylene (hiPP) particles produced in a multistage polymerization process were investigated by field-emission electron microscopy (FESEM) and transmission electron microscopy (TEM) techniques. Study was mainly focused on architecture of iPP particle and distribution of elastomer phase (EPR) within the preformed iPP matrix. The iPP particle is an agglomerate of many subglobules (ca. several to hundred microns in diameter), while the subglobule in turn is formed by a great deal of primary globules (ca. 100 nm in diameter). Large macropores between the subglobules and finely distributed micropores within the subglobule constitute a network of pore inside the iPP particle. Ethylene/propylene comonomers can diffuse into the macro- and micropores and copolymerize on catalyst active sites located on periphery of the pores, forming elastomer phase inside.

Crystallization and phase behavior of crystalline syndiotactic 1,2-polybutadiene/isotactic polypropylene blends in solution-cast thin films

Crystallization and phase behavior in solution-cast thin films of crystalline syndiotactic 1,2-polybutadiene (s-1,2-PB) and isotactic polypropylene (i-PP) blends have been investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM) and field-emission scanning electron microscopy (FESEM) techniques. Thin films of pure s-1,2-PB consist of parallel lamellae with the c-axis perpendicular to the film plane and the lateral scale in micrometer size, while those of i-PP are composed of cross-hatched and single-crystal-like lamellae. For the blends, TEM and AFM observations show that with addition of i-PP, the s-1,2-PB long lamellae become bended and i-PP itself tends to form dispersed convex regions oil a continuous s-1,2-PB phase even when i-PP is the predominant component, which indicates a strong phase separation between the two polymers during film formation. FESEM micrographs of both lower and upper surfaces of the films reveal that the s-1,2-PB lamellae pass through i-PPconvex regions from the bottom, i.e. the dispersed i-PP regions lie on the continuous s-1,2-PB phase. The structural development is attributed to an interplay of crystallization and phase separation of the blends in the film forming process.

Highly active, hexabutylguanidinium salt/zinc bromide binary catalyst for the coupling reaction of carbon dioxide and epoxides

An experimentally simple and inexpensive catalyst system based on hexabutylguanidinium/ZnBr, has been developed for the coupling of carbon dioxide and epoxides to form cyclic carbonates with significant catalytic activity under mild reaction conditions without using additional organic solvents (e.g. the turnover frequencies (TOF, h(-1)) values as high as 6.6 x 10(3) h(-1) for styrene oxide and 1.01 x 10(4) h(-1) for epichlorohydrin). This catalyst system also offers the advantages of recyclability and reusability. Therefore, it is a very effective, environmentally benign, and simple catalytic process. The special steric and electrophilic characteristics of hexabutylguanidinium bromide ionic liquid result in the prominent performance of this novel catalyst system.

Preparation of TiO2 nanocrystallites by hydrolyzing with gaseous water and their photocatalytic activity

TiO2 nanocrystallites were prepared front precursors tetra-n-butyl titanate (Ti(OC4H9)(4)) and titanium tetrachloride (TiCl4). The precursors were hydrolyzed by gaseous water in autoclave, and then calcined at predetermined testing temperatures. The samples were characterized by X-ray diffraction (XRD), thermogravimetry-differential thermal analysis (TG-DTA), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectra (FT-IR), and UV-vis diffuse reflectance spectra (DRS). The photocatalytic activities of the samples were evaluated by the photobleaching of methylene blue (MB) in aqueous solution and the photocatalytic oxidation of propylene in gas phase at ambient temperature. The results showed that the anatase phase nanocrystalline TiO2 could be obtained at relatively low temperatures (for precursor Ti(OC4H9)4 at I I VC and for TiCl4 at 140 degrees C, respectively), and that the as prepared samples exhibited high photocatalytic activities to photobleach MB in aqueous solution. As the calcination temperatures increasing. the decolor ratio of MB increased and reached the maximum value of nearly 100% at 600 degrees C, and then decreased. The photobleaching of MB by all samples followed the pseudo-first-order kinetics with respect to MB concentration.

Compatibilization of PP/EPDM blends by grafting acrylic acid to polypropylene and epoxidizing the diene in EPDM

In this article, ethylene-propylene-diene-rubber (EPDM) was epoxidized with an in situ formed performic acid to prepare epoxided EPDM (eEPDM). The eEPDM together with the introduction of PP-g-AA was used to compatibilize PP/EPDM blends in a Haake mixer. FTIR results showed that the EPDM had been epoxidized. The reaction between epoxy groups in the eEPDM and carboxylic acid groups in PP-g-AA had taken place, and PP-g-EPDM copolymers were formed in situ. Torque test results showed that the actual temperature and torque values for the compatibilized blends were higher than that of the uncompatibilized blends. Scanning electron microscopy (SEM) observation showed that the dispersed phase domain size of compatibilized blends and the uncompatibilized blends were 0.5 and 1.5 mu m, respectively. The eEPDM together with the introduction of PP-g-AA could compatibilize PP/EPDM blends effectively. Notched Izod impact tests showed that the formation of PP-g-EPDM copolymer improved the impact strength and yielded a tougher PP blend.

Crystallization and melting behaviors of PPC-BS/PVA blends

The isothermal crystallization and melting behaviors of poly(propylene carbonate) end-capped with benzenesulfonyl/poly (vinyl alcohol) (PPC-BS/PVA) blends over rich PVA composition range were first investigated by differential scanning calorimetry (DSC). PPS-BS/PVA interaction parameter, chi(12), calculated from equilibrium melting temperature depression was -0.44, revealing miscibility of PPC-BS with PVA in the melt and favorable interactions. The temperature dependence of crystallization rate constant at initial crystallization stage was analyzed using the modified Lauritzen-Hoffman expression. The chain width, a(0), the thickness of a monomolecular layer, b(0), the fold and lateral surface-free energies, sigma(e) and sigma, and the work of chain folding, q, for neat PVA were first reckoned to be 4.50 Angstrom, 4.78 Angstrom, 76.0 erg.cm(-2), and 4.70 kcal.mol(-1), respectively. The values of sigma(e) and q for PVA in PPC-BS/PVA blends exhibited a maximum in the neighborhood of 10/90 PPC-BS/PV, respectively.

Brittle-ductile transition in PP/EPDM blends: effect of notch radius

The toughness of polypropylene (PP)/ethylene-propylene-diene monomer (EPDM) blends was studied over wide ranges of EPDM content and temperature. In order to study the effect of notch radius (R), the toughness of the samples with different notch radii was determined from Izod impact test. The results showed that both toughness and brittle-ductile transition (BDT) of the blends were a function of R, respectively. At test temperatures, the toughness tended to decrease with increasing 1/R for various PP/EPDM blends. Moreover, the brittle-ductile transition temperature (T-BT) increased with increasing 1/R, whereas the critical interparticle distance (IDc) reduced with increasing 1/R. Finally, it was found that the different curves of IDc versus test temperature (T) for different notches reduced down to a master curve if plotting IDc versus T-BT(m)-T, where T-BT(m) was the T-BT of PP itself for a given notch, indicating that T-BT(m)-T was a more universal parameter that determined the BDT of polymers. This conclusion was well in agreement with the theoretical prediction.

Ethylene polymerization with porous polystyrene spheres supported Cp2ZrCl2 catalyst

A catalyst with porous polystyrene beads supported Cp2ZrCl2 was prepared and tested for ethylene polymerization with methylaluminoxane as a cocatalyst. By comparison, the porous supported catalyst maintained higher activity and produced polyethylene with better morphology than its corresponding solid supported catalyst. The differences between activities of the catalysts and morphologies of the products were reasonably explained by the fragmentation processes of support as frequently observed with the inorganic supported Ziegler-Natta catalysts. Investigation into the distribution of polystyrene in the polyethylene revealed the fact that the porous polystyrene supported catalyst had undergone fragmentation during polymerization.

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.

Strontium-based initiator system for ring-opening polymerization of cyclic esters

An amino isopropoxyl strontium (Sr-PO) initiator, which was prepared by the reaction of propylene oxide with liquid strontium ammoniate solution, was used to carry out the ring-opening polymerization (ROP) of cyclic esters to obtain aliphatic polyesters, such as poly(epsilon-caprolactone) (PCL) and poly(L-lactide) (PLLA). The Sr-PO initiator demonstrated an effective initiating activity for the ROP of epsilon-caprolactone (epsilon-CL) and L-lactide (LLA) under mild conditions and adjusted the molecular weight by the ratio of monomer to Sr-PO initiator. Block copolymer PCL-b-PLLA was prepared by sequential polymerization of epsilon-CL and LLA, which was demonstrated by H-1 NMR, C-13 NMR, and gel permeation chromatography. The chemical structure of Sr-PO initiator was confirmed by elemental analysis of Sr and N, H-1 NMR analysis of the end groups in epsilon-CL oligomer, and Fourier transform infrared (FTIR) spectroscopy. The end groups of PCL were hydroxyl and isopropoxycarbonyl, and FTIR spectroscopy showed the coordination between Sr-PO initiator and model monomer gamma-butyrolactone. These experimental facts indicated that the ROP of cyclic esters followed a coordination-insertion mechanism, and cyclic esters exclusively inserted into the Sr-O bond.

丙烯在Zr/HZSM-5催化剂上齐聚反应性能的研究

中国科学院山西煤炭化学研究所