Poly(L-lactide)/starch blends compatibilized with poly(L-lactide)-g-starch copolymer

The poly(L-lactide) (PLLA)/starch blends were prepared by the PLLA grafting starch (PLLA-g-St) copolymers as a compatibilizer, and their thermal, mechanical and morphological characterizations were performed to show the better performance of these blends compared to the virgin PLLA/starch blend without the compatibilizer, including PLLA crystallinity, interfacial adhesion between the PLLA matrix and starch dispersive phases, mechanical test, medium resistance, and contact angle. The 50/50 composite of PLLA/starch compatibilized by 10% PLLA-g-St gave a tensile strength of 24.7 MPa and an elongation at break of 8.7%, respectively, vs. 11.3 MPa and 1.5%, respectively, for the simple 50/50 blend of PLLA/starch.

Hydrazide-functionalized hollow porous poly(2-hydroxyethyl methacrylate-co-ethylene dimethacrylate) spheres for immobilization of enzyme

Hollow porous poly(2-hydroxyethyl methacrylate-co-ethylene dimethacrylate)(HEMA-co-EDMA) spheres were prepared by emulsifier-free emulsion polymerization, swelling, seed emulsion polymerization and extraction. Then the spheres activated with 2,4,6-trichloro-1,3,5-triazine were functioned with adipohydrazide (AH). After periodate oxidation of its carbohydrate moieties, horseradish peroxidase was immobilized on the hydrazide-functionalized hollow porous poly(HEMA-co-EDMA) spheres. The amount of immobilized enzyme was up to 43.4 mu g of enzyme/g of support. Moreover, the immobilized horseradish peroxidase exhibited high activity and good stability.

Synthesis, structure and ethylene polymerization of group 4 complexes with phosphinoamide ligands

Group 4 complexes containing diphosphinoamide ligands [Ph2PNR](2)MCl2 (3: R = Bu-t, M = Ti; 4: R = Bu-t, M = Zr; 5: R = Ph, M = Ti; 6: R = Ph, M = Zr) were prepared by the reaction Of MCl4 (M = Ti; Zr) with the corresponding lithium phosphinoamides in ether or THF. The structure of [(Ph2PNBu)-Bu-t](2)TiCl2 (3) was determined by X-ray crystallography. The phosphinoamides functioned as eta(2)-coordination ligands in the solid state and the Ti-N bond length suggests it is a simple single bond. In the presence of modified methylaluminoxane or i-Bu3Al/Ph3BC(C6F5)(4), catalytic activity of up to 59.5 kg PE/mol cat h bar was observed.

Isothermal crystallization behavior of the poly(L-lactide) block in poly(L-lactide)-poly(ethylene glycol) diblock copolymers: Influence of the PEG block as a diluted solvent

Isothermal crystallization kinetics and morphology of the poly(L-lactide) block in poly(L-lactide)poly(ethylene glycol) diblock copolymers were studied by differential scanning calorimetry (DSC) and polarized optical microscopy (POM), respectively. The results were compared with that of the PLLA homopolymer. The introduction of the PEG block accelerated the crystallization rate of the PLLA block and promoted to form ring-banded spherulites. The analysis of isothermal crystallization kinetics has shown that the PLLA homopolymer accorded with the Avrami equation. But the PLLA block of the diblock copolymers deviated from the Avrami equation, which resulted from increasing of the crystallization rate and occurring of the second crystallization process. The equilibrium melting temperature (T,,) of the PLLA block fell with its molecular weight decreasing. The conditions to obtain more regular ring-banded spherulites were below: the sample was the PLLA block of LA(5) EG(5); the crystallization temperature was about from 95 degrees C to 100 degrees C, which almost corresponded to regime II.

Fabrication of arrays of silver nanoparticle aggregates by microcontact printing and block copolymer nanoreactors

A combination of microcontact printing and block copolymer nanoreactors succeeded in fabricating arrays of silver nanoparticle aggregates. A complex solution of polystyrene-block-poly(4-vinylpyridine) micelles and silver salt was used as an ink to form thin films or droplets on polydimethylsiloxane stamp protrusions. After these complex aggregates were printed onto silicon substrates under controlled conditions, highly ordered arrays of disklike, dishlike, and dotlike complex aggregates were obtained. A Subsequent oxygen reactive ion etching treatment yielded arrays of silver nanoparticle aggregates.

Synthesis and characterization of novel polythiophenes containing poly(ethylene oxide) side chains

Thiophene copolymers and their derivatives with poly(ethylene oxide) side chains were synthesized. The starting monomers were 3-hexylthiophene and 2-(3-thienyl) ethanol with poly(ethylene oxide) grafted to the side chains. New functionalized polythiophenes were prepared by both chemical oxidation with FeCl3 and electropolymerization. The conjugating polymers were characterized. The structures of the polythiophene derivatives agreed with the design.

Compositional differences of propylene-ethylene block copolymers manufactured by degradation and hydrogenation techniques

The purpose of the present work is to investigate the compositional difference of polypropylene-polyethylene block copolymers (PP-b-PE) manufactured industrially by the process of degradation and hydrogenation, respectively. Each of the PP-b-PE copolymers was fractionated into three fractions with heptane and chloroform. The compositions of the three fractions were characterized by C-13 nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy, as well as differential scanning calorimetry (DSC) and thermal fractionation. The results showed that the Chloroform-soluble fraction was amorphous ethylene-propylene rubber, and the content of the rubber in PP-b-PE manufactured by hydrogenation was less than that by degradation. The degree of crystallinity of the chloroform-insoluble fraction of the PP-b-PE manufactured by hydrogenation is higher than that of by degradation.

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.

Electron effect of p-substituent on iron(II) and cobalt(II) pyridinebisimine catalyst for ethylene polymerization

A series of 2,6-bis(imino)pyridyl iron and cobalt complexes bearing p-substituent [2,6-(ArN=CMe)(2)C5H3N]-MCl2 (Ar=2,6-Me2C6H3, 2,4,6-Me3C6H2, 2,6-Me-2-4-BrC6H2, 2,6-Me-2-4-ClC6H2, 2,4-Me-2-6-BrC6H2, 2,4-Me-(2)-6-ClC6H2, while M=Fe, Co) have been synthesized and investigated as catalysts for ethylene polymerization in the presence of modified methylaluminoxane as a cocatalyst. The electron effect and positions of the substitueni of pyridinebisimine ligands were observed to affect considerably catalyst activity and polymer property.

Study on the origin of inverted phase in drying solution-cast block copolymer films

In a previous study, we reported observation of the novel inverted phase (the minority blocks comprising the continuum phase) in kinetically controlled phase separating solution-cast poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer films [Zhang et al. Macromolecules 2000, 33, 9561-7]. In this study, we adopt the same approach to investigate the formation of inverted phase in a series of solution-cast poly(styrene-b-butadiene) (SB) asymmetric diblock copolymers having nearly equal polystyrene (PS) weight fraction (about 30 wt %) but different molecular weights. The microstructure of the solution-cast block copolymer films resulting from different solvent evaporation rates, R, was inspected, from which the kinetically frozen-in phase structures at qualitatively different block copolymer concentrations and correspondingly different effective interaction parameter, chieff, can be deduced. Our result shows that there is a threshold molecular weight or range of molecular weight below which the unusual inverted phase is accessible by controlling the solvent evaporation rate. In comparing the present result with that of our previous study on the SBS triblock copolymer, we find that the formation of the inverted phase has little bearing on the chain architecture. We performed numerical calculations for the free energy of block copolymer cylinders and found that the normal phase is always preferred irrespective of the interaction parameter and molecular weight, which suggests the formation of the inverted phase to have a kinetic origin.

Sol-gel-derived titanium oxide/copolymer composite based glucose biosensor

A new type of sol-gel-derived titanium oxide/copolymer composite material was developed and used for the construction of glucose biosensor. The composite material merged the best properties of the inorganic species, titanium oxide and the organic copolymer, poly(vinyl alcohol) grafting 4-vinylpyridine (PVA-g-PVP). The glucose oxidase entrapped in the composite matrix retained its bioactivity. Morphologies of the composite-modified electrode and the enzyme electrode were characterized with a scanning electron microscope. The dependence of the current responses on enzyme-loading and pH was studied. The response time of the biosensor was < 20 s and the linear range was up to 9 mM with a sensitivity of 405 nA/mM. The biosensor was stable for at least I month. In addition, the tetrathiafulvalene-mediated enzyme electrode was constructed for the decrease of detection potential and the effect of three common physiological sources that might interfere was also investigated.

Electrochemical study of PW12O403- in poly(ethylene glycol) electrolyte

The electrochemical properties Of PW12O403- (abbreviated as PW12) anion in poly(ethylene glycol) (PEG) have been studied by cyclic voltammetry, complex impedance and FT-IR spectroscopy. The PW12 anion in PEG-LiClO4 electrolyte shows reasonable facile electrochemistry, and the diffusion coefficients Of PW12 were measured with microelectrode. It is shown that ionic conductivity of polymer electrolytes based on low molecular weight PEG can be improved by the addition of PW12. The increase of conductivity is coupled with decrease of transient cross-links density of polymer chains which is evidenced by the downshift of C-O-C stretching mode. The phenomena are explained in view of ion-ion and ion-polymer interactions.

Thermodynamical study on pressure-induced compatibility in UCST polymer-containing mixtures

The present calculations were performed on the basis of the Sanchez-Lacombe lattice fluid theory and the new combinatorial rules for block copolymer according to the experimental results on the pressure-induced compatibility in poly(ethylene oxide) (PEO) and poly(ethylene oxide-b-dimethylsiloxane) (P(EO-b-DMS)) mixtures with UCST behavior. The study on enthalpy, combinatorial entropy, vacancy entropy and Gibbs energy upon mixture shows that Sanchez-Lacombe fluid theory and the new combinatorial rules could describe the pressure-induced compatibility (PIC) of polymer mixtures with UCST behavior well.

Abnormal pressure dependence of the phase boundaries in TL/PEO/P(EO-b-DMS) ternary mixtures

The cloud-point temperatures (T-cl's) of both binary poly(ethylene oxide) (PEO)-poly(ethylene oxide-b-dimethylsiloxane) [P(EO-b-DMS)] and ternary[toluene/PEO/P(EO-b-DMS)] systems were determined by light scattering measurements at atmospheric pressure. The phase separation behavior upon cooling in the ternary system has been investigated at atmospheric pressure and under high pressure and compared to the phase behavior in the binary system. The phase transition temperatures have been obtained for all of the samples. As a result, the pressure induces compatibility in the binary mixtures, but for the ternary system, pressure not only can induce mixing but also can induce phase separation.

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.