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1.
Three series of polymers containing p-phenylene diacrylic group were prepared by direct polycondensation in the presence of diphenylchlorophosphate and pyridine. Series I was prepared from p-phenylene bis(acrylic acid) with various hydroquinones. Series II was prepared from p-phenylene bis (β-cyano acrylic acid) with methylhydroquinone. Series III was prepared from 3-methyl-4-aminophenol with p-phenylene bis(acrylic acid) or p-phenylene bis(β-cyano acrylic acid), respectively. The phase behavior of these polymers was studied by differential scanning calorimetry (DSC), optical polarizing microscopy equipped with a heating stage, and wide-angle x-ray diffraction (WAXD). It was found that these polymers, except IIIb , exhibit thermotropic liquid-crystalline properties and show threaded or Schlieren texture under the optical polarizing microscopic observation. Furthermore, the melting temperatures of these polymers were decreased in the range of 254–354°C by incorporating with p-phenylene diacrylic group into the main chain. © 1993 John Wiley & Sons, Inc.  相似文献   

2.
New polyesters containing thianthrene tetraoxide were synthesized by the interaction of 2,7-dichloroformylthianthrene-5,5′,10, 10′-tetraoxide with 2,5-bis(p-hydroxybenzylidene)cyclopentanone, 2,5-divanillylidenecyclopentanone, 2,6-bis(p-hydroxybenzyiidene)-cyclohexanone, 2,6-divanillylidenecyclohexanone, and 2,7-bis(p-hydroxybenzylidene)cycloheptanone by using the interfacial polycondensation technique. The resulting polyesters were characterized by elemental and spectral analyses. All the synthesized polymers readily dissolved at room temperature in dimethylsulfoxide. The thermal properties of the polymers were evaluated and correlated to their structural units by TGA and DSC measurements. X-ray analysis of polymers showed that all the polyesters are amorphous. Moreover, the morphology of a new high performance polyester, poly[oxycarbonyl-2,7-thianthrene-5,5′,10,10′-tetraox-idecarbonzeoxyl(2-methoxy-p-phenylene)methylidyne(2-oxo-1,3-cyclohexanediylidenemethylidyne)methylidene(3-methoxy-p-phenylene)], has been investigated by scanning electron microscopy.  相似文献   

3.
Polybenzimidazoles (PBI) with p-phenylene and/or cis-vinylene groups in the backbone were prepared from terephthalic acid (T), maleic acid (M), and 3,3′ diamino-benzidine tetrahydrochloride dihydrate (DAB) in poly(phosphoric acid) (PPA). Five polymer samples were prepared by varying the M:T molar ratios in the following order: 1:0, 1:1, 2:1, 1:2, and 1:4. The polymers were characterized by intrinsic viscosity, density, electronic fluorescence, and IR spectra. The effect of composition on the solubility of the polymers in various organic solvents was also investigated. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in air and polybenzimidazoles (PBI) with cis-vinylene groups were found to be less stable.  相似文献   

4.
Aromatic benzimidazole polymers have been prepared by reaction of the corresponding tetraamine and diester in refluxing sulfolane or phenyl sulfone. The convenience of using these sulfone solvents together with the good yields, high viscosities and absence of crosslinking make this procedure an attractive new route to this class of polymers. The preparation by this procedure of poly[2,2′-(m-phenylene)-5,5′-bibenzimidazole], poly-[2,2′-(p-phenylene)-5,5′-bibenzimidazole], poly[2,2′-(m-phenylene)-5,5′-di(benzimidazole) ether], and poly[2,2′-(m-phenylene)-5,5′-di(benzimidazole) ketone] is described.  相似文献   

5.
We describe a new method for the polymerization of perchloroaromatic compounds using Fe(CO)5 as a dechlorinating agent which allows the syntheses of perchloropoly-1,4-phenylene vinylene ( 8 ), perchloropoly-4,4'-biphenylene vinylene ( 9 ), and perchloropoly-1,3-phenylene vinylene ( 10 ) from perchloro-p-xylene ( 5 ), perchlorobi-p-tolyl ( 6 ), and perchloro-m-xylene ( 7 ), respectively. Polymer 10 , a new macromolecular chlorocarbon, was characterized by elemental analysis and infrared and ultraviolet spectra. The molecular weights (MW's) of the polymers were estimated by osmometry. The XPS spectra of these polymers are discussed. Their thermal properties were studied by thermogravimetry. Electron spin resonance (ESR) studies and some preliminary conductivity measurements, made after doping the polymers with SbF5, are reported. © 1992 John Wiley & Sons, Inc.  相似文献   

6.
Described is the synthesis of a ladder polymer with a poly(p-phenylene) (PPP) backbone. The main PPP backbone was synthesized via palladium-catalyzed coupling of an arylbis(boronic ester) with an aryl dibromide. Imine bridges, formed by exposure of the polymer to trifluoroacetic acid, are used to force the consecutive units into planarity. The bridging units are sp2 hybridized thus allowing for greater π-electron flow between the consecutive phenyl units by lowering the band gap between the hydroquinoidal and the quinoidal forms of the phenylene backbone. When the bridges are n-dodecyl substituted, the fully planar structures (with Mn < 5 000) are soluble in hot chlorobenzene from which flexible free standing films can be cast. The n-butyl substituted polymers and the higher molecular weight n-dodecyl substituted polymers are soluble in CH2Cl2/trifluoroacetic acid mixtures. The optical spectra of the planar systems are compared to that of the parent nonplanarized polymers, some analogous planar oligomers, and oligo(p-phenylenes).  相似文献   

7.
We studied the midgap levels appearing in the photoexcited conductive polymers such as trans- and cis-polyacetylenes, poly(p-phenylene), polypyrrole, and polyacene based on the molecular orbital analysis. The midgap levels are constructed from the transformation of the highest occupied molecular orbital and the lowest unoccupied molecular orbital of the ground state. As the result of the localization of the wave functions associated with these midgap levels, large polarization is induced between adjacent carbon atoms. Based on the examination of the energy gap between the two midgap levels, the polymers with a nondegenerate ground state such as cis-polyacetylene, poly(p-phenylene), and polypyrrole would show no sizable photoconductivities.  相似文献   

8.
A group of rodlike polymers soluble only in strong protic acids was studied using light scattering and viscosity techniques. These include poly(1,4-phenylene benzobisoxazole), poly(1,4-phenylene benzobisthiazole) and poly(1,4-phenylene terephthalamide). The solution properties were dependent on the ionic strength of the acid used as solvent. In a low ionic strength acid such as chlorosulfonic acid, the polymer solutions exhibited decreased unpolarized scattering, an extremely small translational diffusion coefficient, and high viscosity. All of these effects could be eliminated by the addition of a salt such as lithium chlorosulfonate, which increased the ionic strength of the solvent. The effects were attributed to a pseudo ordering of the polymer solvent system caused by electrostatic repulsions between protonated polymer chains effective over large distances (ca. 100 Å) in the low ionic strength solvent. This type of ordering is distinct from actual anisotropic phase formation, which occurs at higher concentrations in these systems. Analysis of data at infinite dilution gave a persistence length of at least 45 nm for poly(1,4-phenylene terephthalamide), larger than previous experimental results, but in accord with recent rotational isomeric state calculations and similar to experimental data for poly(p-benzamide).  相似文献   

9.
Two reaction routes for the preparation of aromatic poly-1,3,4-oxadiazoles and poly-1,2,4-triazoles are studied and their influence on the physical properties, i.e., inherent viscosity, glass transition, degradation temperature, and film integrity of the final products are discussed. Aromatic poly-1,3,4-oxadiazoles are prepared by means of a polycondensation reaction of terephthaloyl chloride and isophthalic dihydrazide yielding a precursor polymer, poly(p, m-phenylene) hydrazide, which is converted into the corresponding poly-1,3,4-oxadiazole by means of a cyclodehydration reaction. Poly-1,3,4-oxadiazoles are also prepared by means of a polycondensation reaction between terephthalic and isophthalic acid and hydrazine yielding poly-1,3,4-oxadiazoles with higher inherent viscosities. Flexible poly-1,3,4-oxadiazole films are obtained only if the inherent viscosities of the polymers used are higher than 2.7 dL/g. The thermal stability is found to increase with increasing content of p-phenylene groups in the polymer backbone. Aromatic poly-1,2,4-triazoles are prepared using polyhydrazides with alternating para- and meta-phenylene groups and poly-1,3,4-oxadiazoles with a random incorporation of para- and meta-phenylene groups in the main chain as precursor polymers. The glass transition temperatures are found to increase with increasing content of p-phenylene groups in the main chain of these polymers. Cold crystallization is observed only for the alternating polymer. © 1994 John Wiley & Sons, Inc.  相似文献   

10.
Model p-cresol-formaldehyde condensates having regular sequences of methylene ether and methylene linkages were prepared by the self-condensation of dimethylol derivatives of p-cresol-formaldehyde condensates (2-hydroxy-5-methyl-1,3-benzenedimethanol, 3,3′-methylene-bis[2-hydroxy-5-methylbenzenemethanol] and 3,3′-[(2-hydroxy-5-methyl-m-phenylene)dimethylene]-bis[2-hydroxy-5-methylbenzenemethanol]). 300-MHz 1H-NMR spectra of these polymers and of their acylated derivatives were recorded and used to develop resonance assignments for the various types of protons present in these polymers. The spectra were found to be sensitive to end-group and sequence distribution effects.  相似文献   

11.
Polyimides with different proportions of m-phenylene and p-phenylene (or p,p′-biphenylene) were prepared by polymerizing different molar ratios of m-phenylene diamine and p-phenylene diamine (or p,p′-diaminobiphenyl) with pyromellitic dianhydride in dimethylformamide at 0°C. Chemical cyclodehydration of polyamic acids resulted in the corresponding polyimides. Polymers were characterized by infrared (IR), viscosity, and density measurements. Viscosity and density of polymers decreased with an increase on m-phenylene groups in the backbone. The thermal and thermooxidative stabilities were investigated by dynamic thermogravimetry. Stability decreased when m-phenylene groups were introduced in the backbone.  相似文献   

12.
Poly[N,N′-(sulfo-phenylene)phthalamid]es and poly[N,N′-(sulfo-p-phenylene)pyromellitimide] were prepared in water-soluble form and were found to have unique solution properties, similar in some respects to xanthan. The polymer most investigated, poly[N,N′-(sulfo-p-phenylene)terephthalamide] (PPT-S), is produced as the dimethylacetamide (DMAC) salt by the solution polymerization of 2,5-diaminobenzenesulfonic acid with terephthaloyl chloride in DMAC containing LiCl. The isolated polymer requires heating in water to dissolve; the resulting cooled solutions are viscous or gels at concentrations as low as 0.4%. They are highly birefringent, exhibit circular dichroism properties, and are viscosity-sensitive to salt. Solutions of this polymer mixed with those of guar or hydroxyethyl cellulose give significantly enhanced viscosity. The polymer is relatively low molecular weight, ca. 5000 estimated from viscosity data. Some meta and para isomeric analogs of PPT-S were prepared; these polymers have similar properties except they are more soluble in water, and higher concentrations are required to obtain significant viscosity. Poly[N,N′-(sulfo-p-phenylene) pyromellitimide] (PIM-S) was prepared similarly from 2,5-diaminobenzenesulfonic acid and pyromellitic dianhydride. Its aqueous solution properties are similar to those of PPT-S. It appears that these relatively low-molecular-weight rigid-chain polymers associate in water to form a network that results in viscous solutions at low concentrations.  相似文献   

13.
Polyanhydrides composed of the following diacids–sebacic acid, bis(p-carboxyphenoxy)propane, bis(p-carboxyphenoxy)hexane, isophthalic acid, 1,4-phenylene dipropionic acid, and dodecanedioic acid–were synthesized by a melt polycondensation process. Polymers of molecular weight up to 137,010 (weight average) and intrinsic viscosity of 0.92 dL/g were achieved. These high molecular weight polymers were reached by using pure isolated mixed anhydrides of diacids and acetic acid, under optimized reaction conditions (temperature of 180°C for 90 min under vacuum of 10-4 mm Hg). Polymers of higher molecular weights were synthesized in shorter times by using heterogenic coordination catalysts: cadmium acetate, ZnEt2-H2O (1:1), barium oxide, calcium oxide, and calcium carbonate. By using these catalysts molecular weights of up to 245,000 were reached in 30 min of reaction. Films made of high molecular weight bis(p-carboxyphenoxy)propane–sebacic acid copolymers showed tensile strengths of 40–160 kg/cm2; the strength increased as a function of the bis(p-carboxyphenoxy)propane content and molecular weight.  相似文献   

14.
A series of phenylated polydihydrophthalimides has been synthesized by the Diels-Alder reactions of 3,3′-(oxydi-p-phenylene)bis(2,4,5-triphenylcyclopentadienone) and 3,3′-(p-phenylene)bis(2,4,5-triphenylcyclopentadienone) with N,N′-o-, -m-, and -p-phenylenedimaleimide. The polydihydrophthalimides were soluble in dimethylformamide (DMF) and had intrinsic viscosities that ranged from 0.33 to 1.01, the polymers were dehydrogenated thermally and chemically to afford the corresponding phenylated polyphthalimides. The totally aromatic polyimides were also soluble in DMF but had intrinsic viscosities only as high as 0.41. The thermogravimetric analyses of the polyphthalimides showed breaks near 530°C in air and in nitrogen atmospheres.  相似文献   

15.
A series of poly(aryleneethynylene)s bearing dialkylsilyl (-SiR2H) side substituents has been synthesized by Sonogashira cross-coupling reactions of 1,4-diethynyl-2,5-bis(dialkylsilyl)benzene and diiodoarylene compounds. Their photophysical properties in solution have been studied. All of the polymers showed intense fluorescence with high quantum yield. Compared with their analogues containing para-phenylene units, the polymers with meta-phenylene units in the main chain showed absorption and emission maxima at shorter wavelengths, whereas the polymers having thiophenylene units in their backbones showed bathochromically shifted spectra. For polymers having the same conjugated parent backbone, silyl substituents have been found to exert negligible effect on their photophysical properties.  相似文献   

16.
Aromatic polyelectrolytes based on sulfonated poly(benzobisthiazoles) (PBTs) have been synthesized by a polycondensation reaction of sulfo-containing aromatic dicarboxylic acids with 2,5-diamino-1,4-benzenedithiol dihydrochloride (DABDT) in freshly prepared polyphosphoric acid (PPA). Several sulfonated PBTs, poly[(benzo[1,2-d:4,5-d′]bisthiazole-2,6-diyl)-2-sulfo-1,4-phenylene] sodium salt (p-sulfo PBT), poly[(benzo[1,2-d:4,5-d′]bisthiazole-2,6-diyl)-5-sulfo-1,3-phenylene] sodium salt (m-sulfo PBT), their copolymers, and poly[(benzo[1,2-d:4,5-d′]bisthiazole-2,6-diyl)-4,6-disulfo-1,3-phenylene] potassium salt (m-disulfo PBT), have been targeted and the polymers obtained characterized by 13C-NMR, FT-IR, elemental analysis, thermal analysis, and solution viscosity measurements. Structural analyses confirm the structures of p-sulfo PBT and m-disulfo PBT, but suggest that the sulfonate is cleaved from the chain during synthesis of m-sulfo PBT. m-Disulfo PBT dissolves in water as well as strong acids, while p-sulfo PBT dissolves well in strong acids, certain solvent mixtures containing strong acids, and hot DMSO. TGA indicates that these sulfonated PBTs are thermally stable to over 500°C. Free-standing films of p-sulfo PBT, cast from dilute neutral DMSO solutions, are transparent, tough, and orange in color. Films cast from basic DMSO are also free standing, while being opaque and yellow-green. p-Sulfo PBT was incorporated as the dopant ion in polypyrrole, producing conductive films with conductivities as high as 3 S/cm and electrical anisotropies as high as 10. © 1996 John Wiley & Sons, Inc.  相似文献   

17.
A series of stable, highly fluorescent and highly phenylated isoindoles have been synthesized by treating the respective o-dibenzoylbenzenes with anilines at 200°C in the presence of a catalytic amount of p-toluenesulfonic acid. The correlation between the emission frequences and the structures of the isoindoles is described. The same reaction has also been used to transform a series of poly(o-dibenzoylbenzene)s into poly(isoindole)s. The resulting polymers have been studied by 1H-NMR, DSC, TGA, and fluorescence spectra. They are highly fluorescent materials with high molecular weights, high glass transition temperatures, and high thermal stabilities. The tetraphenyl substituted isoindole-containing polymers have a maximum emission around 468 nm, whereas the diphenyl substituted isoindole-containing polymers have their maximum emission around 486 nm. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3293–3299, 1999  相似文献   

18.
A series of 12 different exactly alternating silarylene-siloxane polymers was prepared by low temperature condensation polymerization of arylenedisilanol with bisureidosilane monomers. The structural characterization of the polymers was carried out by 1H NMR spectroscopy, 13C NMR spectroscopy, infrared (IR) spectrometry, gel permeation chromatography (GPC). dilute solution viscometry, and differential scanning calorimetry (DSC). Homopolymers and copolymers that contained either or both p-phenylene and p,p′-diphenyl ether units in the silarylene group and dimethyl or methylvinyl units in the siloxane group were prepared in high molecular weights.  相似文献   

19.
The effects of incorporating a p-phenylene- (or m-phenylene)-1,3,4-oxadiazole fragment into the backbone of poly[1,4-phenylene(diphenylsilyl)-1,4-phenylene-2,5-(1,3,4-oxadiazole)], which was developed by the authors, was investigated. Bis[(p-carbohydrazidophenyl)]diphenylsilane was copolymerized with dipentachlorophenyl terephthalate or isophthalate to produce the prepolymers poly[N-(p-diphenylsilylbenzoyl)-NN″-(terephthaloyl)-N″′-(p-benzoyl)dihydrazide] and poly[N-(p-diphenylsilylbenzoyl)-N′,-N″-(isophthaloyl)-N″′-p-(benzoyl) dihydrazide], respectively. The polyhydrazides were converted by thermal dehydration into poly[1,4-phenylene(diphenylsilyl)-1,4-phenylene-(1,3,4-oxadiazole-2,5-diyl)-1,4-phenylene-2,5-(1,3,4-oxadiazole)] and poly[1,4-phenyl-ene(diphenylsilyl)-1,4-phenylene-(1,3,4-oxadiazole-2,5-diyl)-1,3,4-(oxadiazole)]. The new polymers were soluble in organic solvents. Films cast from these solutions exhibited good adhesion to glass and metal surfaces. Thermal analysis showed that the heat stability of all these polymers was about the same and that they were resistant to decomposition when heated in air to about 400°C. The results also indicated that these polymers were somewhat less heat-resistant than samples of poly-[1,4-phenylene(diphenylsilyl)-1,4-phenylene-2,5-]1,3,4-(oxadiazole) synthesized from bis(p-carbohydrazidophenyl)diphenylsilane and bis-(p-carbopentachlorophenoxy-phenyl)diphenylsilane.  相似文献   

20.
Miscible blends of the aromatic polybenzimidazole, poly(2,2(m-phenylene)-5,5′-benzimidazole) (PBI), and the aromatic polyimide formed from 3,3′,4,4′-benzophenone tetracarboxylic dianhydride and 3,3′-diaminobenzophenone (LaRC TPI) have been prepared. Blends with PBI were prepared in N,N-dimethylacetamide solution starting with either the polyamic acid or a 95% imidized form of LaRC TPI; the blend was then precipitated into water or cast as films. The mixture was then imidized thermally to obtain PBI/LaRC TPI blends. Evidence for miscibility was obtained in the form of single composition dependent Tg's intermediate between those of the component polymers and single tan δ dynamic mechanical relaxation peaks. The IR spectra displayed shifts in the N? H stretching band, thereby providing evidence for specific interactions related to the miscibility of these two polymers.  相似文献   

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