EFFECTS OF CHAIN STRUCTURE OF POLYPYRROLONES ON THE ELECTRICAL PROPERTIES OF PYROLYZED POLYPYRROLONES

Three kinds of polypyrrolones (PMDA-DAB, PMDA-TADPE and DEDA-DAB) werepyrolyzed at high temperature in order to study the effect of the chain structure of polypyrro-lones on the electrical properties of the pyrolyzed polymers. Results show that the num-ber of fusing rings in the main chain of polymers has a little effect on the pyrolysis pro-cess, whereas, the ether bond in the main chain plays an important role during pyrolysis.Structure characterizations by elemental analyis, XPS spectra, X-ray diffraction and SEMimages indicate that because the ether bond is easy to break, it is difficult to form largearea planar network. This hampers the formation of the graphite-like structure in thepolypyrrolones containing ether bond even after being pyrolyzed at 1200℃.     

INFLUENCES OF WATER-SOLUBLE CATIONIC MONOMERS ON THE POLYMERIZATION RATE IN THE INVERSE EMULSION

This investigation deals with the free radical polymerization both of (2-methacryloyloxy-ethyl) trimethyl ammonium chloride (QACEMA) and of diallyldimethyl ammoniumcbloride (DADMAC) in inverse emulsion. The influences of some factors, such as theconcentration of monomers, initiator and emulsifier are discussed. The polymerization rateequations of above two monomers can be written as follows:R_p= k[M]~(1.21) [I]~(0.82) [E]~(0.57) (for QACEMA)R_p= k'[M]~(1.34) [I]~(0.90)[E]~(0.62)(for DADMAC)     

THE STRUCTURE AND OPTICAL PROPERTIES OF COPOLYMER OF CHOLESTERIC ESTER

The structure and switching properties of liquid crystalline side chain copolymers of cholesteric ester of 1,2-hydroxypropyl 2,4-di-isocyanatoluene methylmethacrylate (PHCPM) have been studied in detail. The cholesteric mesophase of PHCPM is shown by polarizing microscopy, X-ray diffraction and selective light reflection. Solution of PHCPM in CHCl_3 is optically anisotropic; its optical properties were determined by specific rotation [α], circular dichroism (CD) and wide-angle hght scattering (WALS) methods.     

DMS AND ~(13)C NMR STUDIES ON THE COMPATIBILITY AND DYNAMICS OF LATEX BIDIRECTIONAL IPNS AND LATEX IPN OF PVAc/PBA

The compatibility and dynamics of latex bidirectional/nterpenetrating polymer networks (LBIPNs) and latex IPN(LIPN) of poly(vinyl acetate)(PVAc) and poly (butyl acrylate )(PBA) are investigated by means of dynamic mechanical spectroscopy (DMS) and nuclear magnetic resonance (NMR) techniques. The results of DMS show that the compatibility of the LBIPNs is much better than that of the corresponding LIPN and depends to, a large extent on the distribution of PVAc both in the core and in the shell. The results of NMR measurements indicate that the rotational correlation times of the side- groups of PBA in the LBIPN are longer than those in the LIPN. The relation between the ~(13)C linewidths of PBA and temperature is also discussed.     

A MOLECULAR APPROACH TO THE SYNTHESIS OF NOVEL POLYIMIDES*

In the past ten years there has been a flurry of activity in the synthesis of new specialty polymers,largely as a result of the increased need for high technology materials. Interest is mainly shown in two distinctcategories of polymers: a) polymers which are used in very small quantities to fulfill critical needs as a part ofdevice systems, and b) high-performance engineering polymers which significantly extend their mechanicaland thermal properties for structural applications. Polyimides and their unparalleled versatility have capturedthe attention and imagination of scientists and engineers. This article describes some of the recent work doneby the author's group on the rational design at the molecular level and the synthesis of polyimides that haveunusual structures and novel properties.     

EFFECTS OF PHENOL RESIN ADDITIVE ON DYNAMIC MECHANICAL PROPERTIES OF ACRYLATE RUBBER AND ITS BLENDS*

The dynamic mechanical properties of a new blend system consisting of phenol resin and polar polymer (acrylaterubber and/or chlorinated polypropylene) were investigated. It was found that the addition of phenol resin to acrylate rubberand its incompatible blend can cause a remarkable improvement in the temperature dependence of the loss tangent. As a result, the present blends are very good damping materials.     

INFLUENCE OF BACKBONE RIGIDITY ON THE LIQUID CRYSTALLINITY OF MESOGEN-CONTAINING POLYACETYLENES

Two acetylene polymers containing cyanobiphenyl-based mesogens,poly { 10-[ ((4'- cyano-4-biphenylyl ) oxy ) carbonyl] - 1 -decyne } (PA8CN ), which has a relativelyfiexible polyalkyne backbone, and poly {[4-(((12-((4'-cyano-4-biphenylyl)oxy)dodecyl)oxy)carbonyl) phenyl]-acetylene} (PB12CN), which has a fairly rigid poly (phenylacetylene )backbone, were synthesized using respectively WCl_6 and [Rh(nbd)Cl]_2 as the catalysts.PA8CN exhibits enantiotropic interdigitated smectic A phase (S_(Ad)) over a temperaturerange as wide as ca. 100℃, whereas PB12CN is non-mesomorphic, demonstrating thatthe backbone rigidity plays an important role in determining the liquid crystallinity of thepolyacetylenes.     

STUDIES ON THE MECHANICAL PROPERTIES AND CRYSTALLIZATION BEHAVIOR OF POLYETHYLENE COMPOSITES

The effects of inter facial modifier on the mechanical, dynamic mechanical properties andcrystallization behavior of the polyethylene composites were investigated in the present paper.It was found that the interfacial modifer significantly improved the mechanical properties,influenced the dynamic mechanical spectra and slightly changed the crystallization behavior.The results showed that the interfacial modifier changed the dispersion state of dispersedphase of the composites, resulting in different phase structure, which was the major reasonIeading to different mechanical and crystallization properties.     

NOVEL COMPOSITES OF POLY(L-LACTIDE) AND SURFACE MODIFIED BIOACTIVE SiO2-CaO-P2O5 GEL NANOPARTICLES: MECHANICAL AND BIOLOGICAL PROPERTIES

Bioactive SiO_2-CaO-P_2O_5 gel(BAG)nanoparticles with 40 nm in diameter were synthesized by the sol-gel route and further modified via the ring-opening polymerization of lactide on the surface of particles.Surface modified BAG (mBAG)was introduced in poly(L-lactide)(PLLA)matrix as bioactive filler.The dispersibility of mBAG in PLLA matrix was much higher than that of rough BAG particles.Tensile strength of the mBAG/PLLA composite could be increased to 61.2 MPa at 2 wt%filler content from 53.4 MPa for pur...     

ELECTRONIC EFFECTS OF POLYFLUORINATED SUBSTITUENTS ON THE POLYMERIZATION AND THE PROPERTIES OF POLYTHIOPHENES

Three series of polythiophenes containing fluoroalkoxy and fluoroether substituentswere prepared by electrochemical polymerization. The effect of substituents with fluoro-alkoxy or ether functional groups on the electrochemical polymerization of thiophene mono-mers and properties of the obtained polymers were analyzed. The introduction of a flu-oroether functional group at the 3-position of the thiophene ring leads to an increase ofthe oxidation potential of the monomer and to a decrease of the conductivity of the re-sulting polymers, even with the use of a CH_2 group as spacer. Conversely, the presenceof an oxygen atom directly at the 3-position of the thiophene ring, which offsets the nega-tive withdrawing effect of fluoroalkyl groups, facilitates the synthesis of highly conductingpolythiophenes.     

CHEMICAL STRUCTURE DEPENDENCE OF THE INTERNAL ENERGY CONTRIBUTION IN RUBBER ELASTICITY

Conformational elasticity theory recently developed has been used to explore the internal energy contribution tothe elastic force f_e/f as a function of strain for poly(cis-1,4-isoprene) and poly(trans-1, 4-isoprene). Calculated f_e/f values arein good agreement with those obtained experimentally. Results show that behavior of f_e/f is mainly contributed by chemicalstructure, or intramolecular interaction, supporting the experimental observations, and that the internal energy contribution isstrain dependent.     

STUDY ON LIQUID CRYSTALLINITY OF POLY(N-VINYLCARBAZOLE)

The liquid crystallinity of poly(N-vinylcarbazole) was studied by using powder X-ray diffraction, polarized opticalmicroscopy, and differential scanning calorimetry. The results show that the lower molecular weight fractions of this polymerdo not form a liquid crystalline phase, while the samples of sufficiently high molecular weight do form a mesophase attemperatures above the glass transition. The lowest value of the degree of polymerization for PVK to form a stable liquidcrystalline phase was found to be in the range of 150 to 200, significantly higher than the value of 50 for most conventionalside chain liquid crystaline polymers.     

SYNTHESIS OF POLY(VINYL ACETATE)-INTERCALATED GRAPHITE OXIDE BY AN IN SITU INTERCALATIVE POLYMERIZATION*

Graphite oxide, a pseudo-two-dimensional solid in bulk form, was synthesized from natural graphite powder byoxidization with KMnO_4 in concentrated H_2SO_4. The poly(vinyl acetate)-intercalated graphite oxide nano-composite wasprepared by an in situ intercalative polymerization reaction, in which n-octanol-graphite oxide intercalation compounds werefirst obtained, vinyl acetate monomer was then dispersed into the interlayer of modified graphite oxide, followed by thermalpolymerization of the monomer. It was experimentally shown that the c-axis space of poly(vinyl acetate)-intercalated graphiteoxide was increased to 0.115 nm, which suggested there existed a monolayer of poly(vinyl acetate) chain between the layersof graphite oxide. The nanocomposite was also characterized with thermal analysis and FT-IR spectrometry.     

THEORETICAL ANALYSIS OF KINETICS OF NONISOTHERMAL CRYSTALLIZATION OF POLYMERS

The classical crystallization theories proposed by Avrami, Evans, and Mandelkern wereextended to the nonisothermal situation. The expressions derived from the classical equations canbe expressed in either the differential form or the integral form. A method was provided so as toobtain the parameters characterizing the crystallization rate and mechanism from DSC curves withseveral constant heating or cooling rates. The rate constants of crystallization obtained from bothisothermal and nonisothermal curves of poly(ethylene terephthalate)were compared.     

SYNTHESIS,CHARACTERIZATION AND OPTICAL PROPERTIES OF THE COPOLYMERS OF C_(60) AND 1-PHENYL-1-PROPYNE*

While WCl_6-Ph_4Sn fails to polymerize 1-phenyl-1-propyne (PP) at room temperature, highmolecular weight (M_w up to 410×10~3) polymers are obtained in high yields (up to 80%) when thepolymerizations of PP are carried out in the presence of C_(60) using the W catalyst under the same conditions.The polymers are soluble in common organic solvents such as THF, chloroform, and toluene. Molecularstructures of the polymers are characterized by FT-IR, UV, NMR, GPC and XRD, and it is found that C_(60) iscopolymerized with PP. Thus C_(60) plays the dual roles of comonomer and cocatalyst in the polymerizationreaction. C_(60) contents of the copolymers can be easily changed by varying the C_(60) amounts in the feedmixtures. The copolymers effectively limit strong 532 nm laser pulses, whose limiting performance issuperior to that of parent C_(60).     

STUDY ON THE MICROSTRUCTURE AND PROPERTY OF PET FIBER BY LASER RAMAN MICROSCOPE

In this paper, the microstructure change of one step-draw PET fiber has been studied byvarious methods, such as, Laser Raman Microscope, Wide-angle X-ray, Density-gradient andPolarizing Microscope. The computer has been used to resolve overlapped bands in the Ramanspectra. Then the band changes have been correlated with trans, gauche and stressed trans-conformations indicated by a conformational index. Based on these indices, the relationshipbetween the conformation change of glycol units in the fiber structure and the macromechanicalproperties of fiber is expounded.     

THE EFFECTS OF IRRADIATION ON THE THERMAL PROPERTIES OF SEMI-CRYSTALLINE POLYAMIDES

Irradiation crosslinking of semi-crystalline polyamides was performed by high energy electronswith various dosages. It is known that the melting behavior of the polymers after irradiation is acomplex phenomenon. In company with the wide angle X-ray diffraction and DSC data of irradiatedand unirradiated polyamides it is possible to develop the local order and perfection of the crystallinitiesslightly which resulted from introduction of intermolecular crosslinking in amorphous region, incl-uding in amorphous-crystalline interface and crystalline defect regions due to irradiation. It canbe explained that slight increase of melting temperature (T_m) and heat of fusion (△H_f) with increasingdosage for both of higher crystallinity nylon 4 and nylon 6. For irradiated lower crystallinity nylons,in contrast, the T_m and △H_f decrease obviously with increasing dosage. In this case, radiation cross-linking "freeze in" the pre-existing morphology, and then the prevention for reorganization duringheating is a dominant effect. The T_m from the second melting for all of the samples were depressed,corresponding with Flory theory. Therefore the crosslinks imposed on the molecules restrainedthe molecular mobility, and that not only depresses the crystallinity but also increases the imperfec-tion of crystallites when the radiated polymer melted and then recrystallized. These are also reflectedin the depression of heat and entropy of fusion as well as the appearance of double melting peakson the DSC thermograms.     

A NEW STRATEGY FOR THE DESIGN OF LIQUID CRYSTALLINE POLYMERS WITH FLEXIBLE AND APOLAR BUILDING BLOCKS

The synthesis and characterization of a new series of liquid crystalline polymers, poly(dicycloalkylvinylterephthalate)s, are reported. The basic building blocks of these polymers are not mesogenic by themselves. However,very stable mesophases can be generated by self-assembly of the polymer molecules. This approach suggests a novel designstrategy of liquid crystalline polymers with flexible and apolar building blocks.     

THE EFFECT OF MATRIX TOUGHNESS ON THE BRITTLE-DUCTILE TRANSITION OF HDPE/CaCO_3 BLENDS

The effects of HDPE matrix toughness on the brittle-ductile transition of HDPE/CaCO_3blends are investigated. Not all HDPE can be toughened by CaCO_3 particles. The ability of thematrix to yield plays a fundamental role in determing whether HDPE can be toughened or not.There exists a critical matrix toughness (I_(sc)≈45J/m) below which HDPE can not be toughenedobservably by CaCO_3 particle at given average size, and above which the critical matrix ligamentthickness (τ_?) is proportional to matrix impact strength.     

聚氯乙烯结构缺陷和热不稳定性之间关系的研究 2.各种结构缺陷含量和热脱氯化氢速率之间的关系

本工作采用溴加成法、酚解法、FTIR法及臭氧裂解法分别测定了五种不饱和蒸气压下聚合的PVC样品(u-PVC)和五种商品PVC样品(s-PVC)的总双键、总不稳定氯、孤立双键和内部双键的含量.通过研究结构缺陷和PVC的平均分子量及脱HCl速率的相互关系,揭示了不饱和总双键值,总不稳定氯和孤立双键含量彼此的相关性是建立在它们分别与1/M_n的相关性基础之上,从而得出了这三种定量值测得的主要都是端基烯丙基氯结构.根据三者对脱HCl速率的良好线性相关性,首次提出了端基烯丙基氯结构在HCl催化作用下异构化成内部烯丙基氯从而成为脱HCl速率主要原因的机理.