The Synthesis and Characterization of High Molecular Weight Poly(phenylene sulfide/ether)

Poly（phenylene sulfide/ether） （PPSE） was synthesized from 4,4＇-dihydroxydiphenyl sulfide and 4,4＇-dichlorodiphenyl sulfide in solution by nucleophilic substitution reaction. The resulting polymer was characterized by viscosity measurement, elemental analysis, FT-IR, ^1H NMR, X-ray diffraction and thermal analysis. The results showed that the viscosities of the resulting polymer were above 0.68 dL/g, and the linear chain structure of product was confirmed. PPSE had the same reflex indices as poly（p-phenylene sulfide）, an orthorhombic crystalline with unit cell a=0.853, b=0.562, c=1.026nm. The melting temperature, glass transition temperature and initial decomposition temperature were found to be 228℃, 85℃ and 325℃, respectively. The product was soluble in common organic solvents such as NMP, N, N＇-dimethylformamide, N, N＇-dimethylacetamide and 1,2-dichloroethane.

Effect of Curing Poly(<i>p</i>-Phenylene Sulfide) on Thermal Properties and Crystalline Morphologies

Commercial poly(p-phenylene sulfide) (PPS) was thermally cured, which resulted in an increase of molecular weight due to cross-linking. Non-isothermal crystallization studies of samples cured for up to 7 days at 250?C showed a monotonous increase of crystallization temperature compared to pure PPS. However, a further increase of curing time decreased the crystallization temperature. The change in the half-crystallization time (t1/2) was similar to the crystallization temperature. Thus, the cross-linking of PPS affected crystallization behaviors significantly. To a certain extent, crosslinks acted as nucleation agents, but excessive cross-linking hindered the crystallization. Morphologies observed by polarized optical microscopy suggested that thermal curing for as little as 1 day contributed to the spherulitic structure having a smaller size, that was not observed with pure PPS.

SYNTHESIS AND MORPHOLOGICAL STRUCTURE OF POLY (PHENYLENE SULFIDE AMIDE)

Poly(phenylene sulfide amide) (PPSA) has been synthesized by using sulfur as S source which reacts with dichlorobenzamide (DCBA) and alkali in polar organic solvent at the atmospheric pressure. The polymer structures were determined by elemental analysis, FT-IR and H-1-NMR. It is shown that the yielded polymer has linear structure and its structure unit is -p-C6H4-CONH -p-C6H4-S-. The polymer morphology was studied by X-ray diffraction and polarized microscopy. The results show that PPSA is a crystalline polymer and its spherulites are the aggregation of nontwisting lamella or micro-thread structure. Under shearing force, these crystals are dispersed to form micro-fibrillar structure. The decomposition kinetics of PPSA was also studied at different heating rates. The decomposition energy of PPSA is higher than that of PPS.

Preparation of Poly (Phenylene Sulfide Amide) by Sulfur Solution Route

A new process for preparing poly(phenylene sulfide amide, PPSA), which is by reaction of sulfur instead of sodium sulfide as S source with dichlorobenzamide (DCBA) and alkali in polar organic solvent at the atmospheric pressure (called sulfur solution route), is reported in the present paper. The influences of polymerization time, molar ratio of precursors, catalyst and solvent upon the polymer were investigated. To seek the best parameters of polymerization, orthogonal design was employed in the experiments. The results indicate that the molar ratio of precursors is the most significant effect on both of viscosity and yield of the polymer. The suitable parameters for preparing the related polymer are presented. The polymer was characterized by IRspectrum, 1HNMRspectrum and Raman spectrum, etc.

INFLUENCE OF TRACES OF WATER ON THE SYNTHESIS AND ELECTROLUMINESCENCE PROPERTIES OF POLY(2-METHOXY, 5- (2' -ETHYLHEXYL OXY)- 1, 4-PHENYLENE VINYLENE)

It was found that traces of water in the reaction medium would result in a great increase of gel and a decrease of Molecular weight of the poly(2-methoxy,5-(2'-ethylhexyloxy)-1,4-phenylene vinylene) during the polymerization, which ultimately led to inferior film qualities and device properties. The device (ITO/PEDOT/MEH-PPV/Ba/Al) with MEH-PPV prepared under dry conditions has an external quantum efficiency of above 2.0%.

THERMAL DEGRADATION OF POLY(ARYLENE SULFIDE SULFONE)/NMETHYLPYRROLIDONE CRYSTAL SOLVATE

The thermal degradation of poly（arylene sulfide sulfone）/N-methylpyrrolidone （PASS/NMP） crystal solvate was studied by thermogravimetric analysis （TGA） and was compared with pure PASS in order to determine the way in which the formation of the crystal solvate affected the thermal properties of the polymer. The activation energy of the solid state process was determined using Kissinger＇s method, which does not require knowledge of the reaction mechanism （RM）, to be 174.18 kJ/mol which was lower than that for pure PASS （E = 214 kJ/mol）. The study of master curves together with interpretation of integral methods, allows confirmation that the thermal degradation mechanism for PASS in the crystal solvate system is a decelerated Rn type, which is a solid-state process based on a phase boundary controlled reaction, in the conversion range considered. Whereas, the pure PASS follows a decelerated Dn thermodegradation mechanism in the same conversion range.

NOVEL HYPERBRANCHED POLY(PHENYLENE OXIDE)S WITH PHENOLIC TERMINAL GROUPS: EFFECTS OF REACTION TIME AND CORE MOLECULES ON THE MOLECULAR WEIGHT AND POLYDISPERSITY

A novel hyperbranched poly（phenylene oxide） （HPPO） with phenolic terminal groups was prepared from 4-bromo-4＇,4＂-dihydroxytriphenylmethane as AB2 monomer in dimethylsulfoxide （DMSO） via a modified Ullmann reaction. The molecular weight and polydispersity （PD） of the resulting polymers increased with increasing reaction time. In the presence of core molecules （bisphenol A and 1,3,5-trihydroxybenzene）, which have the similar molecular backbones to the reactive monomer, the molecular weight could be controlled by varying the core-to-monomer ratio. Incorporation of a very small amount of core molecules could lead to a higher molecular weight as compared with that without the addition of core molecules. However, when the core content reached certain extent, the molecular weight would decrease with the further increase in the core content. A new similar behavior of control over the PD was also obtained. The resulting polymers were characterized by ^1H-NMR, ^13C-NMR, FT-IR, and GPC.

CRYSTAL STRUCTURE AND MORPHOLOGY OF NASCENT SAMPLES OF SYMMETRIC AROMATIC POLYESTERS——Ⅰ.POLY(P-PHENYLENE TEREPHTHALATE)

The morphology and crytal structure of poly(p-phenylene terephthalate) (PPT), prepared by confined thin filmmelt (CTFMP) and solution (CTFSP) and bulk solution polymerization, were characterized by transmission electronmicroscopy, electron dimaction and molecular modeling. The unit cell is monoclinic (P2_1/a space group) with parameters a =7.89, b = 5.49, c = 12.65 A, α=γ= 90°, β=100.33°, density = 1.48 g/cm^3, the a, b and β values differing slightly from thosereported previously in the literature. A degree of variation in relative intensities of hk0 reflections in, apparently, untilted[001] ED patterns was observed from a given sample, suggesting some variation in molecular packing. ED evidence wasfound for a second phase, with [001] appearing the same as for phase Ⅱ of the related poly(p-oxybenzoate) (PpOBA)polymer. CTFMP crystals polymerized above 220℃ (up to 370℃) and CTFSP crystals polymerized at 300℃ consisted oflamellae 100-200 A thick.

Effect of Added Poly (vinyl pyrrolidone) during Condensation on Properties of Poly(p-phenylene terephthalamide)Pulp

Poly(p-phenylene terephthalamide)(PPTA)pulp was prepared by polycondensation of the p-phenylene diamine(PPDA)with terephthaloyl chloride(TPC)in the completely anhydrous solvent system of N-methyl pyrrolidone(NMP)having calcium chloride,in the presence of poly(vinyl pyrrolidone)(PVP)having a viscosity average molecular weight lower than 40 000.It was confirmed that the polycondensation could be accelerated,the inherent viscosity of the polymer could be increased,and the polymers could be fibrillated more easily by the addition of the PVP.FTIR and X-ray spectra proved that PVP had not combined into molecular chains of the resultant PPTA pulps.The morphology of the resultant pulps,the effect of viscosity average molecular weight,amount and adding mode of PVP on inherent viscosity,specific surface area,and mean length of the resultant pulps were discussed in detail.And the friction and wear properties of the compound reinforced by the resultant pulps were simply investigated.

The Insulator-to-Conductor Transition in Sulphonated Poly(Phenylene Oxide)Polymer membranes:Percolation Theory Approach

In this paper the percolation theory is employed to study the insulator-to-conductortransition in sulphonated poly（phenylene oxide）（SPPO） polymer membranes.The membranes withdifferent sulphonation degree were prepared and infrared characterized.The transition thresholdwas calculated by the experimental data of membrane conductivities and the coordination numberwas thus estimated.The functional group-SO3H distribution in the membrane was evaluated inaccordance with the calculations and showed a non-random dispersion on the microscopic scale.

GAS SORPTION AND TRANSPORT IN POLY (PHENYLENE OXIDE)(PPO)AND ARYL-BROMINATED PPO MEMBRANES

The apparent solubility (S), concentration-average diffusivity (D), and permeability (P), for C0_2, CH_4 and N_2 through PPO and aryl-brominated PPO at 35℃ for pressure ranging from 1 to 26 atm are reported. It is found that P, D, and S of the membranes to all the three gases vary with the extent of bromination. S increases with the increase of the percent of bromine in each case, but D to CO_2 increases remarkably only at higher degree of brominafion, and therefore, P to CO_2 is increased by more than 100% over a wide range ofpressure in the case. The solubility data are well described by the dual mode sorption model. It is found that the gas molecules sorbed by the Langmuir mode are relatively more immobilized and the contribution of the nonequilibrinm character of the polymer to gas permeation increases obviously for CO_2 and is hardly changed for CH_4 with increasing bromine content. These observations are interpreted in terms of changes in specific free volume (SFV)and the cohesive energy density (CED) of the polymers.

EFFECT OF SOLVENT COMPOSITION ON THE SULFONATION DEGREE OF POLY(PHENYLENE OXIDE) (PPO)

This paper investigates the possibility of attaining sulphonated poly(phenylene oxide) (SPPO) with a relativelyhigher sulfonation degree. To achieve this aim, the approach we adopt is to improve the solubility of the final product in themixed solvent so that the sulfonation may take place between the bulk solutions and PPO powders even at higher sulfonationdegree. It is shown that the addition of a proper amount of dimethyl formide (DMF) to the conventional PPO-chloroformsystem can actually enhance the sulfonation effect. The solvent composition is then correlated with the sulfonation degreebased on the solubility parameters. It is interesting to find that solubility parameters between the mixed solvent and theprecipitated products keep an approximately unchanged value at about 4.9, which is just equal to that when pure chloroformis used, though the solubility parameters of both solvents increase with the content of DMF in solution. This may be the mainreason why the addition of DMF can reduce the precipitation and improve the ion exchange capacity (IEC) of SPPOpolymer.

Poly(meta-phenylene) Derivative with Rigid Twisted Biphenyl Units in Backbone:Synthesis,Structural Characterization,Photophysical Properties and Electroluminescence

A soluble poly（meta-phenylene） derivative with rigid twisted biphenyl unit was synthesized by the Yamamoto coupling reaction. The polymer is soluble in common organic solvents, and the number-average molecular weight is about 6500. The UV-Vis and quantum chemical calculation indicate that the different conformation segments named ＂conformers＂ exist in the polymer backbones; it was also further confirmed by the single crystal X-ray diffraction study of the dimeric model compound. The π-π^＊ transition of biphenyl segments of twisted and planar conformations made the polymer exhibit a strong absorption around 256 nm and a weak absorption at about 300 nm. Furthermore, the polymer exhibits a strong UV photoluminescence at 372 nm when the excitation wavelengths are longer than 300 run. The ultraviolet-emitting electroluminescence（EL） device with the single layer structure shows EL λmax of the derivative at 370 nm.

Effect of Chemical Doping and Ion Implantation on Cond uctivity of Poly(p-phenylene vinylene) Derivatives

The surface conductivity of poly [2-methoxy-5-(3 '-methyl)butoxy]-p-phenylene vinylene (PMOMBOPV) films doped with FeCl3 and H2 SO4 by chemical method and implanted by N+ ions was studied and the comparison of environmental stability of conductive behavior was also investigated. The energy and dose of N+ions were in the rang 15～35 kev and 3. 8× 1015 ～9. 6× 1016 ions/cm2, respectively. The conductivity of PMOMBOPV film was enhanced remarkably with the increases of the energy and dose of N+ ions. For example, the conductivity of PMOMBOPV film was 3.2 × 10-2 S/cm when ion implantation was performed with an energy of 35 kev at a dose of 9. 6 × 1016 ions/cm2 , which was almost seven orders of magnitude higher than that of film unimplanted. The environmental stability of conductive behavior for ionimplanted film was much better than that of chemical doped films. Moreover, the conductive activation energy of ion-implanted films was measured to be about 0.17 eV.

Thermal Stability Improvement and Structural Change of Oil Gels Formed by Styrene-Butadiene-Styrene Triblock Copolymer Induced by Adding Poly(phenylene ether)

The thermal stability of oil gels formed by styrene-butadiene-styrene triblock copolymer (SBS) was improved by adding a small amount of poly(phenylene ether) (PPE), which has a higher glass transition temperature (Tg). In naphthenic oil which is a good solvent for the butadiene blocks, but a non-solvent for the styrene blocks and PPE, PPE was selectively included into styrene blocks in SBS, and induced the increase of the Tg of these blocks. The melting temperature determined by viscoelastic measurements and softening temperature of the gels were elevated by adding PPE, while no significant change was detected by adding polystyrene. The gel became opaque by adding PPE, and partially separated phases were observed by field emission scanning electron microscopy (FE-SEM). The dependence of the viscoelastic behavior on the PPE concentration can be explained by the structural change observed by FE-SEM.

RAMAN SPECTROSCOPIC STUDY ON THE CHAIN CONFORMATION OF ELECTROSYNTHESIZED POLY(ρ-PHENYLENE)FILMS

Poly（p-phenylene） （PPP） films have been electrochemically deposited on mirrorlike stainless steel （SS） electrode surfaces by direct oxidation of benzene in boron trifluoride diethyl etherate （BFEE） solutions at a constant applied potential of 1.7 V （versus Ag/AgCl）. The chain conformations of as-grown PPP films have been studied by Raman spectroscopy. The results demonstrated that high synthesis temperature favors the formation of planar PPP, and the conformation of planar PPP can be changed into torsional PPP by cooling treatment.

ELECTRICALLY CONDUCTIVE COMPOSITE PREPARED BY ELECTROCHEMICAL POLYMERIZATION OF PYRROLE IN POLY-(p- PHENYLENE TEREPHTHALAMIDE) MATRIX

The preparation of PPy/PPTA conductive composite films by electrochemical method is presented.The first step is to cast a thin layer of poly (p-phenylene-terephthalamide) (PPTA) on a slice of Pt working electrode. The second step is to electrochemically polymerize pyrrole on the PPTA/Pt working electrode. Both of the electrical conductivity and the mechanical properties of the PPy/PPTA composite film are better than those of the pure PPy film, and the film has excellent flexibility at low temperature, even in liquid nitrogen.The SEM picture of the cross-section of PPy,/PPTA composite film showed that the two components were well mixed.Cyclic voltammograms of PPy,/PPTA film in aqueous solution showed that the conductive films could be reduced and reoxidized.

CRYSTAL STRUCTURE AND MORPHOLOGY OF NASCENT SAMPLES OF SYMMETRIC AROMATIC POLYESTERS——Ⅱ. POLY(p-PHENYLENE 2,6-NAPHTHALATE)

Confined thin film melt polymerization (CTFMP) of naphthalene chloride/hydroquinone (NCMQ, 1/1, molar)mixtures at polymerization temperatures (T_p) below ca. 300℃ resulted in relatively thick, elongated crystals. Polymerizationof NC/HQ above 300℃ between glass yielded well-formed lamellar crystals ca. 100 A thick. Phase Ⅰ and Ⅱ [001] EDpatterns were obtained for all T_p, the relative amount of phase Ⅰ increasing with T_p. Polymerization of naphthalenedicarboxylic acid/hydroquinione diacetate 1/1 mixtures at high T_p also yielded lamellar crystals that "curled up" off of thesubstrate. When the high temperature CTFMP polymerization was conducted between mica, aggregates of lamellae on-edgedeveloped but epitaxial growth did not occur. Epitaxial growth of lamellae between mica could be obtained, however, byconfined thin film solution polymerization, with both of the latter samples yielding apparently related ED patterns from adifferent unit cell than phase Ⅰ or Ⅱ. Fiber patterns, obtained from sheared samples, indicated considerably greater crystaldisorder than in the nascent crystals. Refinement of the phase Ⅰ unit cell parameters, based on the [001] and [01 1] EDpatterns, with modeling based on Cerius^2, suggests a monoclinic phase Ⅰ unit cell with a = 7.76, b = 5.71, c = 14.99 A, α = γ= 90°, β= 99.7°, ρ = 1.47 g/cm^3, space group P12_1/al.