CHARACTERIZATION AND PROPERTIES OF URUSHIOL POLYMER CONTAINING BORON-NITROGEN COORDINATE BOND

Urushiol polymer containing B--N bond (PUBN) was synthesized with urushiol-boronpolymer and diethylene triamine. Its structure was characterized by XPS, IR, UV, HPLC,DTA-TG and elemental analysis. The physico-mechanical and anticorrosive propertiesof the polymer were also investigated. The results show that the coating of PUBN canbe hardened in 2h at room temperaure and its film has excellent physico-mechanicalproperties and good anticorrosive properties.     

EFFICIENT POLYMER PHOTOVOLTAIC DEVICES BASED ON POLYMER D-A BLENDS*

Recent work demonstrated that efficient solar-energy conversion could be achieved in polymer photovoltaic cells(PVCs) based on interpenetrating bi-continuous networks. In this paper we present a comprehensive study on improvingenergy conversion efficiencies of PVCs based on composite films of MEHPPV and fullerene derivatives. Carrier collectionefficiency of ca. 30% el/ph and energy conversion efficiency of 3.9% were achieved at 500 nm. At reverse bias of 15 V, thephotosensitivity reached 0.8 A/W, corresponding to a quantum efficiency over 100% el/ph. These results suggest that highefficiency photoelectric conversion can be achieved in polymer devices with M-P-M structure. These devices are promisingfor practical applications such as plastic solar cells and plastic photodetectors.     

STUDY ON THE SYNTHESIS OF COPOLYMER CONTAINING N-SUBSTITUTED ACRYLAMIDE COMPONENT

In this paper the synthesis of linear and crosslinked N-substituted acrylamide copolymer is reported. In order to obtain the terpolymer with appropriate hydrophilicity, the conditions of aminolysis of St-MMA copolymer have been selected.It is shown that the copolymer with predictable hydrophilicity possesses good blood compatibility.     

PHOTOINDUCED ALIGNMENT OF OPTICALLY ACTIVE POLYMER CONTAINING A TEMPO RADICAL END GROUP

A new azobenzene side-chain polymer (TEMPO-PAZ) containing TEMPO (4-hydroxy-2, 2, 6, 6-tetramethyl-piperidinooxy) radical end group was synthesized by free radical copolymerization. Photoinduced alignment was studied onthe polymer films at room temperature with linearly polarized light of 514.5 nm, The experimental results showed that themagnetic response intensity of the TEMPO-PAZ could be easily controlled by choosing the appropriate polarized lightirradiating times, presumably due to the nitroxide radical in the TEMPO-PAZ molecular structure. For the polymerinvestigated here, the photoinduced alignment technique was introduced to increase the magnetic response intensity ofpolymer under irradiation, aiming originally at searching for a new photo-active organic magnetic multifunctional materials.On the other hand, experimental results also showed that the TEMPO-PAZ can be used as a material for optical image storage.     

SYNTHESIS AND CHARACTERIZATION OF TITANOCENE POLYMER DERIVATIVES

Titanocene polymer derivatives with potential antitumor properties were synthesized by interfacial condensation. The preformed polymers used are PAA (polyacrylic acid), CPSMA (1:1 alternating copolymer of styrene and maleic anhydride) and DVEMA (1:2 copolymer of divinyl ether and maleic anhydride). The ratio of practical and theoretical titanium content is 73.6%, 92.2% and 86.2% for PAA, CPSMA and DVEMA polymer derivatives respectively. The IR spectra of the polymer derivatives possess the characteristic absorptions of titanocene. XPS (X-ray photoelectron spectroscopy) of O_(1s) and Ti_(2p3/2) supports the existence of Ti-O bonding.     

MOLECULAR SIMULATION STUDY ON THE CHANGE OF POLYMER STRUCTURE DURING YIELDING*

A better understanding of a recently raised argument on whether there occurs a structure change during yieldinghas been acquired by using molecular simulation. That is, when monitoring the displacements of all atoms before and afterthe yield, a structure transition does occur, which is the "atomic jump" that coordinates the amount of the atoms in thepolymer and makes a large step beyond～0.05 nm for all those atoms. Results indicate that the complex of polymer chainpacking induces the multiple atomic jumps around the yield point. This explains why polymers have a broader yielding peak.     

THE CORRELATION EFFECT ON THE CHAIN MOTION CONTRIBUTION TO IONIC TRANSPORT IN POLYMER ELECTROLYTES

The ionic transport process in polymer electrolytes (such as polyethylene oxide) wassimulated numerically on a two dimensional square lattice where charge carriers areaccommodated by the lattice sites connected randomly with available bonds to represent theamorphous chain configuration. Following the dynamic bond percolation theory(DBPT),the chainmotion contribution to the ionic conduction was incorporated via periodical renewal of the randombond configuration. To check and extend the prediction made by DBPT employing global abruptbond renewal,spatial correlation of the bond reassignment was introduced to the system by: 1)regional bond renewal and 2) organized bond motion. It is found that the difference between thediffusivities simulated involving regional bond renewal and those of DBPT becomes negligiblewhen the bond renewal rate approaches the carrier hopping rate.     

CHARACTERIZATION AND LUMINESCENCE PROPERTIES OF THE DYE-DOPED POLYMER LANGMUIR-BLODGETT FILMS*

1,1,4,4-Tetraphenyl-1,3-butadiene (TPB) was successfully introduced into the polymer multilayerfilms by means of Langmuir-Blodgett (LB) technique. Results of UV-VIS spectra and X-ray diffractionshowed that the uniform films had a layer structure similar to the superlattice of organic multiple quantumwells. The electroluminescence (EL) devices fabricated from the doped polymer LB films emitted blue light.Compared with the casting films, the photoluminescence (PL) and EL spectra showed that the exciton energyshifts to higher and the half-width of the emission peak becomes narrower due to exciton confinement effect.     

SYNTHESIS AND PROPERTIES OF A NEW AZOBENZENE SIDE-CHAIN POLYMER CONTAINING A TEMPO RADICAL

To allow anisotropies of optical properties in a magnetic field, nitroxide radical is introduced into the ortho-position of the phenylene ring in the side chain. A new azobenzene side-chain polymer (TEMPO-PAZ) containing TEMPOradical was synthesized. The polymer has a good solubility in organic solvents. The ESR spectrum of the polymer indicatedthree absorption lines characteristic of TEMPO radical. The optical phase conjugated responses (I_4) of the polymer filmswere investigated by degenerate four-wave mixing (DFWM). The experimental results showed that optical phase conjugatedresponse of the TEMPO-PAZ could be easily controlled by choosing the appropriate direction of magnetic field presumablydue to the nitroxide radical in the TEMPO-PAZ molecular structure. For the polymer investigated here, the nitroxide radicalwas introduced to increase optical phase conjugated response intensity in a magnetic field, aiming originally at searching fora new photo-active organic magnetic multifunctional materials.     

OPTICAL PHASE CONJUGATION RESPONSE OF PHOTOINDUCED POLYMER FILMS CONTAINING AZOBENZENE MOIETIES WITH CHIRAL GROUP

An optically active monomer containing azobenzene moieties with chiral group (s-2-methyl-butyl), 4-[2-(methacryloyloxy)ethyloxy]-4'-(s-2-methyl-1-butyloxycarbonyl) azobenzene(Ml) was synthesized. Polymer (PMl)possessing optical phase conjugated response was obtained by homopolymerzation of the optically active monomer (Ml)using free radical polymerization. The polymer was very soluble in common solvents and good optical quality films could beeasily fabricated by spin coating. The optical phase conjugated responses of the polymer PM1 were measured by degeneratefour-wave mixing (DFWM). In comparison with polymer containing no chiral group, it was found from the preliminarymeasurement of photoisomeric change that optical phase conjugated response of the PM1 in the long-range order hexagonalsymmetry microstructure could be easily controlled by choosing the appropriate polarization direction of the irradiatingbeams (514.5 nm) and the irradiating number, presumably due to the chiral group in the PM1 molecular structure. For thecase of the polymer investigated here, a chiral group side chain was introduced to increase optical phase conjugated responseintensity with different polarization directions of the irradiating beams, which aims originally at searching for a new photo-ative material.     

STUDY ON UV CURABLE POWDER COATINGS BASED ON HYPERBRANCHED POLYMERS*

By introducing semicrystalline moieties into hyperbranched molecular smictures three kinds of prepolymers of potential use as UV powder coatings were prepared and characterized.     

STUDY ON A HYDROPHOBIC-HYDROPHILIC GRADIENT ROD

INTRODUCTIONGradient materials constitute a special case of various materials. The concentration of one of the components ofthe material, being chemically and/or physically different from other components, is allowed to change as afunction of its position in the sample, producing a predetermined gradient profile. The gradient material can be inany shape — i.e., linear, sigmoid, parabolic, flat or rod. Generally, this kind of material should have gradientsalong one direction in their stru…     

EFFECT OF ADSORPTION ON THE VISCOSITY OF DILUTE POLYMER SOLUTION*

Careful measurements of the dilute solution viscosities of polyethylene glycol and polyvinylalcohol in water were carried out. The reduced viscosities of both polymer solutions plot upward curves atextremely dilute concentration levels similar to the phenomena observed for many polymer solutions in theearly 1950's. Upon observation of the changes of the flow times of pure water in and the wall surfacewettability of the viscometer after measuring solution viscosity, a view was formed that the observed viscosityabnormality at extremely dilute concentration regions is solely due to the effect of adsorption of polymerchains onto the wall surface of viscometer. A theory of adsorption effect based on the Langmuir isothermswas proposed and a mathematical analysis for data treatment was performed. The theory could adequatelydescribe the existing viscosity data. It seems necessary to correct the viscosity result of dilute polymersolutions measured by glass capillary viscometer by taking into account the effect of adsorption in all cases.     

STUDY OF THE MOLECULAR MOTION AND COMPATIBILITY IN AB-CROSSLINKED POLYMER BASED ON POLYURETHANE AND POLYSTYRENE-co-ACRYLIC ACID BY SOLID STATE HIGH RESOLUTION NMR

The ~(13)C T_(1s) of --CH_3 side group in PPU/P (St-co-AA), AB-crosslinked polymers (i. e.ABCP) was studied by using high resolution solid state NMR. The rotation motion of --CH_3 sidegroup in PPU was analyzed by means of the average spectral density functions of internal rota-tion. The results showed that the rotation of the --CH_3 side group is related closely to the com-patibility between the two components. The compatibility was studied by analyzing the protonspin-lattice relaxation in rotating frame, spin-spin relaxation and spin-diffusion. The resultsshowed that the hydrogen bonds between the components play a major role in determining thecompatibility. Through spin diffusion studying, the soft phase domain size was calculated. Bystudying proton spin-spin relaxation, the content of each component in each phase and that ofeach phase in the samples can be obtained. The result shows that the content of interphase is related closely to the compatibility.     

SYNTHESIS AND CHARACTERIZATION OF NOVEL BIPOLAR PPV-BASED COPOLYMER CONTAINING TRIAZOLE AND CARBAZOLE UNITS*

Two new blue light-emitting PPV-based conjugated copolymers containing both an electron-withdrawing unit(triazole-TAZ) and electron-rich moieties (carbazole-CAR and bicarbazole-BCAR were prepared by Wittig condensationpolymerization between the triazole diphosphonium salt and the corresponding dialdehyde monomers. Their structures andproperties were characterized by FT-IR, TGA, DSC, UV-Vis, PL spectroscopy and electrochemical measurements. Theresulting copolymers are soluble in common organic solvents and thermally stable with a T_g of 147℃ for TAZ-CAR-PPVand of 157℃ for TAZ-BCAR-PPV. The maximum photoluminescence wavelengths of TAZ-CAR-PPV and TAZ-BCAR-PPV film appear at 460 nm and 480 nm, respectively. Cyclic voltammetry measurement demonstrates that TAZ-BCAR-PPVhas good electrochemical reversibility, while TAZ-CAR-PPV exhibits the irreversible redox process. The triazole unit wasfound to be an effective π-conjugation interrupter and can play the rigid spacer role in determining the emission colour ofthe resulting copolymer.     

DYNAMIC MONTE CARLO STUDY ON THE CORRELATION BETWEEN SHAPE AND SIZE OF LINEAR POLYMER CHAINS

The correlation between shape and size of linear chains on the simple cubic lattice is investigated using a dynamicMonte Carlo technique. A positive correlation between the asphericity parameter A and the square of the end-to-end distanceR~2, as well as that between A and the square of the radius of gyration S~2, is found for both RW and SAW chains, indicatingthat a chain conformation of small size is usually more spherical than one of large size. The result can explain why the shapeof the SAW chain deviate much more from a sphere than that of the RW chain, and can also explain the similar dependenceof size and shape on chain stiffness and on the distance of the first bead of a chain from an infinitely large flat surface.     

STUDY ON FLUORESCENCE BEHAVIOUR OF EU~(3+) CONTAINING POLY(METHYL METHACRYLATE)

Fluorimetry has been used to characterize ionomers synthesized by copolymerization ofmethyl mehacrylate, methacrylic acid and europium methacrylate (EMA). Under excita-tion of UV light at 375 nm no seif-quenching was found in fluorescence of EMA containingionomers at 615nm within the concentration range of 1.6×10~(-2) to 11.49×10~(-2) mol%.This means that the distance between two Eu~(3+) ions is larger than 5nm. In the sameconcentration range seif-quenching took place in europium octanoate (EOA) containingpoly(methyl methacrylate) in which EOA was doped as an additive.     

THE ROTATION BARRIER OF ELECTRON SPIN PROBE IN THE STUDY OF POLYMER SYSTEM

In the study of molecular motion of polymer by means of ESR in combination with spin probe, owing to that the ESR spectrum depicts only the behavior of spin probe, the information obtained is of indirect nature. Hence the relationship between them must first be investigated before any conclusion could be drawn. In this paper, two parameters T_R and C_R are introduced to characterize the changing of tumbling rate of spin probe, and the concept of rotation barrier of spin probe is proposed. It is considered that the magnitude of the rotation barrier is determined by the internal cavity size and distribution in polymer. When the temperature is raised, the size and distribution of the cavities change accordingly, thus the tumbling of spin probe changes gradually from a slower to a higher rate.     

AN EPOXY/(METHYL METHACRYLATE)INTERPENETRATING POLYMER NETWORK FOR NONLINEAR OPTICS*

An interpenetrating polymer networks (IPN) consisting of an epoxy-based polymer network and apolymethyl methacrylate network were synthesized and characterized. The IPN showed only one T_g, andhence a homogeneous-phase morphology was suggested. The second-order nonlinear optical coefficient (d_(33))of the IPN was measured to be 1.72×10~(-7) esu. The study of NLO temporal stability at room temperature andelevated temperature (100℃) indicated that the IPN exhibits a high stability in the dipole orientation due tothe permanent entanglements of two component networks in the IPN system. Long-term stability of secondharmonic coefficients was observed at room temperature for more than 1000 h.     

SHAPE OF POLYMER CHAINS ON A TETRAHEDRAL LATTICE*

The shape of unperturbed polymer chains was studied using the Monte Carlo technique on a tetrahedral lattice.The asphericity A, the ratios/and/ were calculated for different values of polymer chain length n,conformational energy ε (ε≥0) and temperature T. The asphericity A decreases with the increase of chain length and tends toreach its limiting value rapidly with the decrease of γ(γ=ε/k_BT). For large n, A is about 0.525±0.005, the ratios/ and/ are about 2.7 and 12.0, respectively, and are almost independent of γ, but for short chains, theydepend on γ.