Toughening effects of poly(butylene terephthalate) with blocked isocyanate-functionalized poly(ethylene octene)

BACKGROUND: Blocked isocyanate-functionalized polyolefins have great potential for use in semicrystalline polymer blends to obtain toughened polymers. In this study, poly(butylene terephthalate) (PBT) was blended with allyl N-[2-methyl-4-(2-oxohexahydroazepine-1 -carboxamido)phenyl] carbamate-functionalized poly(ethylene octene) (POE-g-AMPC).RESULTS: New peaks at 2272 and 1720 cm(-1), corresponding to the stretching vibrations of NCO and the carbonyl of NH-CO-N, respectively, in AMPC, appeared in the infrared spectrum of POE-g-AMPC. Both rheological and X-ray photoelectron spectroscopy results indicated a new copolymer was formed in the reactive blends. Compared to uncompatibilized PBT/POE blends, smaller dispersed particle sizes with narrower distribution were found in the compatibilized PBT/POE-g-AMPC blends. There was a marked increase in impact strength by about 10-fold over that of PBT/POE blends with the same rubber content and almost 30-fold higher than that of pure PBT when the POE-g-AMPC content was 25 wt%.

Effects of SEBS-g-BTAI on the morphology, structure and mechanical properties of PA6/SEBS blends

Styrene-b-(ethylene-co-1-butene)-b-styrene (SEBS) triblock copolymer functionalized with epsilon-caprolactam blocked allyl (3-isocyanate-4-tolyl) carbamate (SEBS-g-BTAI) was used to toughen polyamide 6 (PA6) via reactive blending. Compared to the PA6/SEBS blends, mechanical properties such as tensile strength, Young's modulus, especially Izod notched strength of PA6/SEBS-g-BTAI blends were improved distinctly. Both theological and FTIR results indicated a new copolymer formed by the reaction of end groups of PA6 and isocyanate group regenerated in the backbone of SEBS-g-BTAI. Smaller dispersed particle sizes with narrower distribution were found in PA6/SEBS-g-BTAI blends, via field emitted scanning electron microscopy (FESEM). The core-shell structures with PS core and PEB shell were also observed in the PA6/SEBS-g-BTAI blends via transmission electron microscopy (TEM), which might improve the toughening ability of the rubber particles.

Preparation of a blocked isocyanate compound and its grafting onto styrene-b-(ethylene-co-1-butene)-b-styrene triblock copolymer

The epsilon-caprolactam was used to block the isocyanate group to enhance the storage stability of allyl (3-isocyanate-4-tolyl) carbamate. The spectra of FTIR and NMR showed that blocked allyl (3-isocyanate-4-tolyl) carbamate (BTAI) possesses two chemical functions, an 1-olefin double bond and a blocked isocyanate group. The FTIR spectrum showed BTAI could regenerate isocyanate group at elevated temperature. DSC and TG/DTA indicated the minimal dissociation temperature was about 135 degrees C and the maximal dissociation rate appeared at 226 degrees C. Then the styrene-b-(ethylene-co-1-butene)-b-styrene triblock copolymer (SEBS) was functionalized by BTAI via melt free radical grafting. The effect of temperature, monomer and initiator concentrations on the grafting degree and grafting efficiency was evaluated. The highest grafting degree was obtained at 200 degrees C. The grafting degree and grafting efficiency increased with the enhanced concentration of BTAI or initiator.

Rhythmic growth of ring-banded spherulites in blends of liquid crystalline methoxy-poly(aryl ether ketone) and poly(aryl ether ether ketone)

Rhythmic growth of ring-banded spherulites in blends of liquid crystalline methoxy-poly(aryl ether ketone) (M-PAEK) and poly(aryl ether ether ketone) (PEEK) has been investigated by means of differential scanning calorimetry (DSC), polarized light microscopy (PLM), and scanning electron microscopy (SEM) techniques. The measurements reveal that the formation of the rhythmically grown ring-banded spherulites in the M-PAEK/PEEK blends is strongly dependent on the blend composition. In the M.-PAEK-rich blends, upon cooling, an unusual ring-banded spherulite is formed, which is ascribed to structural discontinuity caused by a rhythmic radial growth. For the 50:50 M-PAEK/PEEK blend, ring-banded spherulites and individual PEEK spherulites coexist in the system. In the blends with PEEK as the predominant component, M-PAEK is rejected into the boundary of PEEK spherulites. The cooling rate and crystallization temperature have great effect on the phase behavior, especially the ring-banded spherulite formation in the blends. In addition, the effects of M-PAEK phase transition rate and phase separation rate on banded spherulite formation is discussed.

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.

Dewetting of polymethyl methacrylate on the patterned elastomer substrate by solvent vapor treatment

The dewetting evolution process of polymethyl methacrylate (PMMA) film on the flat and prepatterned polydimethylsiloxane (PDMS) substrates (with square microwells) by the saturated solvent of methyl ethyl ketone (MEK) treatment has been investigated at room temperature by the optical microscope (OM) and atomic force microscope (AFM). The final dewetting on the flat PDMS substrate led to polygonal liquid droplets, similar to that by temperature annealing. However, on the patterned PDMS substrate, depending on the microwells' structure of PDMS substrate and defect positions that initiated the rupture and dewetting of PMMA, two different kinds of dewetting phenomena, one initiated around the edge of the microwells and another initiated outside the microwells, were observed. The forming mechanism of these two different dewetting phenomena has been discussed. The microwells were filled with liquid droplets of PMMA after dewetting due to the formation of fingers caused by the pinning of the three-phase-line at the edge of the microwells and their rupture.

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.

Synthesis and characterization of photo-cross-linked hydrogels based on biodegradable polyphosphoesters and poly(ethylene glycol) copolymers

Novel biodegradable hydrogels by photo-cross-linking macromers based on polyphosphoesters and poly(ethylene glycol) (PEG) are reported. Photo-cross-linkable macromers were synthesized by ring-opening polymerization of the cyclic phosphoester monomer 2-(2-oxo-1,3,2-dioxaphospholoyloxy) ethyl methacrylate (OPEMA) using PEG as the initiator and stannous octoate as the catalyst. The macrorners were characterized by H-1 NMR, Fourier transform infrared spectroscopy, and gel permeation chromatography measurements. The content of polyphosphoester in the macromer was controlled by varying the feed ratio of OPEMA to PEG. Hydrogels were fabricated by exposing aqueous solutions of macromers with 0.05% (w/w) photoinitiator to UV light irradiation, and their swelling kinetics as well as degradation behaviors were evaluated. The results demonstrated that cross-linking density and pH values strongly affected the degradation rates. The macromers was compatible to osteoblast cells, not exhibiting significant cytotoxicity up to 0.5 mg/mL. "Live/dead" cell staining assay also demonstrated that a large majority of the osteoblast cells remained viable after encapsulation into the hydrogel constructs, showing their potential as tissue engineering scaffolds.

Facile syntheses and characterization of hyperbranched poly(ester-amide)s from commercially available aliphatic carboxylic anhydride and multihydroxyl primary amine

A new method for synthesis of novel hyperbranched poly(ester-amide)s from commercially available AA' and CBx type monomers has been developed on the basis of a series of model reactions. The hyperbranched poly(ester-amide)s with multihydroxyl end groups are prepared by thermal polycondensation of carboxyl anhydrides (AA') and multihydroxyl primary amine (CBx) without any catalyst and solvent. The reaction mechanism in the initial stage of polymerization was investigated with in situ H-1 NMR. In the initial stage of the reaction, primary amino groups of 2-amino-2-ethyl-1,3-propanediol (AEPO) or tris(hydroxymethyl)aminomethane (THAM) react rapidly with anhydride, forming an intermediate which can be considered as a new AB(x) type monomer. Further self-polycondensation reactions of the AB. molecules produce hyperbranched polymers. Analysis using H-1 and C-13 NMR spectroscopy revealed the degree of branching of the resulting polymers ranging from 0.36 to 0.55. These hyperbranched poly(ester-amide)s contain configurational isomers observed by C-13 and DEPT C-13 NMR spectroscopy, possess high molecular weights with broad distributions and display glass-transition temperatures (T(g)s) between 7 and 96 degreesC.

The use of CE-electrochemiluminescence with ionic liquid for the determination of bioactive constituents in Chinese traditional medicine

CE/tris(2,2-bipyridyl) ruthenium(ll) (Ru(bpy)(3)(2+)) electrochemiluminescence (ECL), CEECL, with an ionic liquid (IL) detection system was established for the determination of bioactive constituents in Chinese traditional medicine opium poppy which contain large amounts of coexistent substances. A minimal sample pretreatment which involves a one-step extraction approach avoids both sample loss and environmental pollution. As the nearby hydroxyl groups in some alkaloid such as morphine may react with borate to form complexes and IL, as a high-conductivity additive in running buffer, could cause an enhanced field-amplified effect of electrokinetic injection. Running buffer containing 25 mM borax-8 mM 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF(4)) IL (pH 9.18) was used which resulted in significant changes in separation selectivity and obvious enhancement in ECL intensities for those alkaloids with similar structures. Sensitive detection could be achieved when the distance between the Pt working electrode and the outlet of separation capillary was set at 150 mu m and the stainless steel cannula was fixed approximately 1 cm away from the outlet of the capillary. Quantitative analysis of four alkaloids was achieved at a detection voltage of 1.2 V and a separation voltage of 15 kV in less than 7 min.

Syntheses and crystal structures of four new organotin complexes with Schiff bases containing triazole

Four new organotin complexes, namely [(Bu2Sn)(2)O(EtO)(L1)](2) (1), [(Bu2Sn)(2)O(EtO)(L2)](2) (2), [(Bu2Sn)(2)O(EtO)(L-3)](2) (3) and [Ph3Sn(L4)]center dot 0.5H(2)O (4), were obtained by reactions of Bu2SnO and Ph3SnOH with 4-phenylideneamino-3-methyl-1,2,4-triazole-5-thione (HL1), 4-furfuralideneamino-3-methyl-1,2,4-triazole-5-thione (HL2), 4-(2-thienylideneamino)-3-ethyl-1,2,4-triazole-5-thione (HL3) and 4-(3,5-di-t-butylsalicylideneamino)-3-ethyl-1,2,4-triazole-5-thione (HL4). Compounds 1-4 were characterized by elemental analysis, IR spectra and their structures were determined by single-crystal X-ray diffraction methods. Complexes 1-3 show similar structures containing a Sn4O4 ladder skeleton in which each of the exo tin atoms is bonded to the N atom of a corresponding thione-form deprotonated ligand. Complex 4 shows a mononuclear structure in which the tin atom of triphenyltin group is coordinated by the S atom of a thiol-form L4(-) anion.

Syntheses, crystal structures and magnetic properties of two heterometallic coordination polymers

Two heterometallic chain coordination polymers with the chemical formula {[Cu2Mn2L2(CH3OH)(H2O)] center dot 0.5CH(3)OH center dot 0.5CH(3)CH(2)OH}(n) (1) and {[Cu2Co2L2(H2O)(2)] center dot H2O}(n) (2) have been synthesized and characterized by IR, UV spectroscopy and single-crystal X-ray structural analysis, where H4L = 2-hydroxy-3-[(E)-({2-[(2-hydroxybetizoyl)amino]ethyl}imino)methyl] benzoic acid. Magnetic measurements showed that the two compounds exhibit antiferromagnetic coupling exchange interactions, and satisfactory fittings to the observed magnetic susceptibility data were obtained by assuming a linear four-spin arrangement with two isotropic magnetic exchange interactions.

High-efficiency spin-coated organic light-emitting diodes based on a europium complex

An organic light-emitting diode fabricated by doping a europium, complex tris(dibiphenoylmethane)-mono (phenanthroline)-europium (Eu(DBPM)(3) (Phen)) into polymer poly(2-methoxy-5-(2-ethyl-hexyloxy)-1,4-phenylene) and poly(N-carbazole) was realized by spin coating. Comparison with other europium complexes, due to the existence of a larger spectral overlap between Eu(DBPM)(3)(Phen) and poly(2-methoxy-5-(2-ethyl-hexyloxy)-1,4phenylene), a high efficiency red emission was achieved. The device showed a turn-on voltage of 5.2 V The maximum efficiency reached 0.47 cd/A at luminance of 50 cd/m(2). The maximum luminance can reach 150 cd/m(2) at 95 mA/cm(2). To the best of our knowledge, this is one of the best results based on europium complexes by spin-casting method.

Synthesis, crystal structure and magnetic properties of a chain coordination polymer {[Cu4L2(H2O)] center dot H2O}(n)

A chain coordination polymer with the chemical formula {[Cu4L2(H2O)] (.) H2O)(n), has been synthesized by the assembly reaction of K(2)CuL(.)1.5H(2)O and Cu(OAC)(2)(H2O)-H-. with a 1:1 mole ratio in methanol., where H4L=2-hydroxy-3-[(E)-({2-[(2-hydroxybenzoyl)imino]ethyl I imino)methyl] benzoic acid, OAC(-) = CH3COO-. The crystal structure was determined by single-crystal X-ray diffraction analysis, the compound has chain molecular structure formed by dissymmetrical tetranuclear units. The magnetic measurements showed that Cu-Cu of the complex exhibit antiferromagnetic interactions, and satisfactory fittings to the observed magnetic susceptibility data were obtained by assuming a binuclear system, and further using molecular field approximation to deal with magnetic exchange interactions between binuclear systems.