Aromatic polyethers,polysulfones, and polyketones as laminating resins. VII. Polymers with [2.2]-p-cyclophane units

1,3-Bis(p-phenoxybenzenesulfonyl)benzene (I), 4,4′-diphenoxy-diphenyl sulfone (II), diphenyl ether, and 3,9-bis(p-phenoxybenzoyl) [2.2]-p-cyclophane were polymerized with isophthaloyl chloride in Friedel-Crafts type polymerization. The polymers obtained, containing 6–8 wt.-% of p-cyclophane units were moderately soluble in HMPA and sulfuric acid with inherent viscosities, between 0.5 and 1.0. The polymers cured at 375°C for 3 days showed little penetration up to 400°C in the Vicat softening curves. Strong molding disks and laminates on glass fiber can be made with excellent thermal stability.     

Aromatic polyethers,polysulfones, and polyketones as laminating resins. II

1,3-Bis(p-phenoxybenzenesulfonyl)benzene and 4,4′-bis(p-phenoxybenzenesulfonyl)-diphenyl ether were polymerized with isophthaloyl and terephthaloyl chloride in Friedel-Crafts type polymerizations. These polymers had 5-cyanoisophthaloyl units in the backbone, obtained by using 5-cyanoisophthaloyl chloride as part of the acid chloride monomer. A number of catalysts were screened to effect the trimerization of the pendant nitrile groups in the polymer to the triazines. Model reactions were carried out for each polymer. Physical and thermal properties of the laminates obtained from these polymers are discussed.     

Aromatic polyethers,polysulfones, and polyketones as laminating resins. III

4,4′-Diphenoxydiphenylsulfone was polymerized with isophthaloyl chloride and terephthaloyl chloride in Friedel-Crafts polymerizations. These polymers had 5-cyanoisophthaloyl units in the backbone obtained either by using 1,3-bis(p-phenoxybenzoyl)-5-cyanobenzene or 5-cyanoisophthaloyl chloride as part of the acid chloride monomer. A terpolymer having 22 wt-% 5-cyanoisophthaloyl unit was also prepared from the Friedel-Crafts polymerization of 1,3-bis(p-phenoxybenzenesulfonyl)benzene and 5-cyanoisophthaloyl chloride. These terpolymers were crosslinked through heating to give insoluble products which proved to be thermally less stable than the uncrosslinked polymers.     

Aromatic polyethers,polysulfones, and polyketones as laminating resins

m-Hexaphenyl ether, diphenyl ether, and 1,3-bis(p-phenoxybenzenesulfonyl)benzene were polymerized with isophthaloyl and terephthaloyl chloride in a Friedel-Crafts type polymerization. The polymers were endcapped with p-cyanobenzyl chloride or had units of 5-cyanoisophthaloyl chloride in the backbone. They were crosslinked effectively, possibly by the trimerization of the nitrile groups to triazines. Model reactions were carried out for each type of polymer.     

Aromatic polyethers,polysulfones, and polyketones as laminating resins. VI. Polymers from 2,5-dicyanoterephthalic acid

Aromatic poly(keto ether sulfones) containing various amounts of pendant cyano groups were synthesized from 1,4-bis(p-phenoxybenzoyl)-2,5-dicyanobenzene, 1,3-bis(p-phenoxybenzenesulfonyl)benzene, and isophthaloyl chloride by a Friedel-Crafts type polymerization. These polymers softened at 160–190°C and had inherent viscosities of 0.44–0.61 in hexamethylphosphoric triamide. Crosslinkings were made by heating the polymers alone or in the presence of zinc chloride at 360–370°C to give black resinous materials that were insoluble in hexamethylphosphoric triamide in which the original polymers dissolved quite readily.     

Aromatic polyethers,polysulfones, and polyketones as laminating resins. V. Polymers containing acetylenic side groups

1,3-Bis(p-phenoxybenzenesulfonyl)benzene and 4,4′-diphenoxydiphenyl sulfone were polymerized with isophthaloyl and terephthaloyl chloride in Friedel-Crafts type polymerizations. These polymers had 2,4-diphenoxyacetophenone in the backbone. The acetyl group was then converted into an acetylene group. They were crosslinked effectively by cyclization of the acetylene groups with a catalyst or by cyclo-addition with bisnitrile oxides.     

Coupling and Cyclization of Sydnone Compounds

Cyclization were occurred via the coupling reactions of some mercuric chloride derivatives of sydnone with LiPdCl₃-CuCl₂. A unique six-membered ring, 3,3′-ethylene-4,4′-bissydnone, was obtained by the cyclization reation of 1,2-di[3-(4-chloromercuric)sydnonyl]ethane. However, the seven-membered 3,3′-trimethylene-4,4′-bissydnone and 1,3-di[3-(4-chloro)sydnonyl]-propane were obtained from the corresponding mercuric chlroide of sydnone. Onyl substitution reaction took place when 4,4′-di[3-(4-chloromercuric)sydnonyl]biphenyl, 4,4′-di[3-(4-chloromercuric)sydnonyl]benzene, di(p-[3-(4-chloromercuric)sydnonyl]-phenyl}methane and, di(p-[3-(4-chloromercuric)sydnonyl]phenyl]ether were treated using the same process.     

Polyaromatic ether-sulfone-ketones with fluorosubstituted p-cyclophane units as crosslinking sites

Polyaromatic either-sulfone-ketones containing fluoro-substituted p-cyclophane units were prepared from isophthaloyl chloride, terephthaloyl chloride, diphenyl ether, diphenoxydiphenyl sulfone, and a small amount of 1,1,2,2,9,9,10,10-octafluoro-[2,2]-p-cyclophane (type A) or pseudo-p-1,12,2,9,9,10,10-octafluoro-[2,2]-p-cyclophane bis-acid chloride (type B) by Friedel-Crafts-type polymerization. The p-cyclophane units were incorporated as crosslinking sites. Crosslinking was achieved by curing polymers at 300–350°C for several days. The polymers obtained, containing 1–10 wt % fluoro-substituted p-cyclophane units, were moderately soluble in dichloromethane, DMF, and sulfuric acid with inherent viscosities between 0.4 and 0.6. Laminates on glass fiber were made with excellent thermal stability.     

Polyaromatic pyrazines: Synthesis and thermogravimetric analysis

The syntheses of five polyaromatic pyrazine polymers are described. These polymers were synthesized by the condensation of bis-α-haloaromatic ketones with ammonia in N,N-dimethylacetamide (DMAc) solvent in the presence of air or peroxides. The condensation of bis-p-(α-bromoacetyl)benzene (IIIa), bis-p,p′-(α-chloroacetyl)biphenyl (IIIb) bis-p,p′-(α-chloroacetyl)diphenyl ether (IIIc), bis-p,p′-(α-chloroacetyl)diphenylmethane (IIId), and α,α′-dibenzoyl-α,α′-dibromo-p-xylene (V) under these reaction conditions gave poly[2,5-(1,4-phenylene)pyrazine] (IVa), poly[2,5-(4,4′-biphenylene)-pyrazine] (IVb), poly[2,5-(4,4′-oxydiphenylene)pyrazine] (IVc), poly[2,5-(4,4′-methylenediphenylene)pyrazine] (IVd), and poly[2,5-(1,4-phenylene)-3,6-diphenylpyrazine] (VI), respectively. Thermogravimetric analysis (TGA) of these polymers showed them to be thermally stable up to the temperature range of 450–550°C in air for short periods of time. The inherent viscosities of these polymers ranged from 0.18 to 1.30.     

Synthesis of high molecular weight poly(ether ketone)s by polycondensation of activated bis(aryl chloride)s with bisphenolates

The ability to achieve high molecular weight poly(ether ketone)s from the polycondensation of bis(aryl chloride)s with bis(phenolate)s has been consistently demonstrated. The polymerizations presented here help to delineate for specific bis(aryl chloride)/bisphenolate pairs the reaction conditions required to obtain high molecular weight polymers. Polycondensation of 1,3-bis(4-chlorobenzoyl)-5-tert-butylbenzene ( 6 ) and 2,2′-bis(4-chlorobenzoyl)-biphenyl ( 15 ) with various bisphenolates as well as of 2,2′-bis(4-hydroxyphenoxy)biphenyl ( 33 ) with 4,4′-dichlorobenzophenone ( 41 ) and 1,3-bis(4-chlorobenzoyl)benzene ( 43 ) were used as representative model systems to select reaction conditions that led to high molecular weight polymers. © 1995 John Wiley & Sons, Inc.     

Organometallic polymers. XXIX. Synthesis and characterization of ferrocene-containing siloxane polymers from bis(dimethylamino)silane–disilanol condensation

A new monomer, 1,1′-bis(dimethylaminodimethylsilyl)ferrocene, was synthesized by two routes and polymerized with three aryl disilanols: dihydroxydiphenylsilane, 1,4-bis(hydroxydimethylsilyl)benzene, and 4,4′-bis(hydroxydimethylsilyl)biphenyl, yielding three different polysiloxanes. Melt polymerizations carried out at 1 torr pressure and 100°C resulted in the highest molecular weight polymers. Intramolecular cyclization competed with intermolecular chain extension in polymerization of the bis(aminosilane) with dihydroxydiphenylsilane, resulting in isolation of a bridged derivative, 1,3,5-trisila-2,4-dioxa-1,1,5,5-tetramethyl-3,3-diphenyl[5]ferrocenophane. Cyclization did not compete significantly during the formation of polymers from this bisaminosilane and the two remaining diols, as evidenced by higher yields and greater molecular weights. These polymers could be cast as tough flexible films, and fibers could be drawn from their melts. TGA and DSC data showed the polymer formed from 1,1′-bis(dimethylaminodimethylsilyl)ferrocene and 1,4-bis(hydroxydimethylsilyl)benzene to be at least as thermally stable as an arylene siloxane polymer which differed from the ferrocenylsiloxane structure only in the replacement of the ferrocene moiety with a p-substituted phenylene linkage. The ferrocene-containing polymers were generally hydrolytically stable under conditions of refluxing THF–H₂O(10 : 1) for 1 hr. The polymer-forming reaction was found to follow second-order kinetics, and the specific rate constants for formation of two of the polymers were measured.     

300-MHz 1H-NMR spectra of p-cresol-formaldehyde condensates having regular repeating structures

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.     

Synthesis of aromatic polyethers by Scholl reaction. V. Synthesis and polymerization of 1,3-bis[4-(1-naphthoxy) benzoyl]benzene, 1,4-bis[4-(1-naphthoxy)benzoyl]benzene,bis[4-(1-naphthoxy)phenyl]methane, 1,3-bis[4-(1-naphthoxy) phenylmethyl]benzene,and 1,4-bis-[4-(1-naphthoxy)phenylmethyl]benzene

This article describes the synthesis and the cation-radical polymerization (Scholl reaction) of 1,3-bis[4-(1-naphthoxy) benzoyl] benzene ( 6 ) and 1,4-bis[4-(1-naphthoxy) benzoyl]- benzene ( 7 ) initiated by FeCI₃. This polymerization produced poly(ether ether ketone ketone)s (PEEKK) of number average molecular weight (M?_n) up to 5400 g/mol. The synthesis of bis[4-(1-naphthoxy) phenyl] methane ( 8 ), 1,3-bis[4-(1-napthoxy) phenylmethyl] benzene ( 9 ), and 1,4-bis[4-(1-naphthoxy) phenylmethyl] benzene ( 10 ) are also described. Polyethers of M?_n up to 15400 g/mol at a FeCl₃/monomer molar ratio of 2/1 were obtained. An increased polymerizability of the monomers 9 and 10 containing two CH₂ groups versus that of the corresponding monomers containing two carbonyl groups ( 6 and 7 ) was observed. This enhanced polymerizability was explained based on the increased nucleophilicity of monomers 9 and 10 .     

Synthesis of polyesters by the polyaddition of bis(oxetane)s with active di(ester)s

The polyaddition of bis(oxetane)s 1,4‐bis[(3‐ethyl‐3‐oxetanylmethoxymethyl)]benzene (BEOB), 4,4′‐bis[(3‐ethyl‐3‐oxetanyl)methoxy]benzene (4,4′‐BEOBP), 1,4‐bis[(3‐ethy‐3‐oxetanyl)methoxy] ‐benzene (1,4‐BEOMB), 1,2‐bis[(3‐ethyl‐3‐oxetanyl)methoxy]benzene (1,2‐BEOMB), 4,4‐bis[(3‐ethyl‐3‐oxetanyl)methoxy]biphenyl (4,4′‐BEOMB), 3,3′,5,5′‐tetramethyl‐[4,4′‐bis(3‐ethyl‐3‐oxetanyl)methoxy]biphenyl (TM‐BEOBP) with active diesters di‐s‐phenylthioterephthalate (PTTP), di‐s‐phenylthioisoterephthalate (PTIP), 4,4′‐di(p‐nitrophenyl)terephthalate (NPTP), 4,4′‐di(p‐nitrophenyl)isoterephthalate (NPIP) were carried out in the presence of tetraphenylphosphonium chloride (TPPC) as a catalyst in NMP for 24 h, affording corresponding polyesters with M_n's in the range 2200–18,200 in 41–98% yields. The obtained polymers would soluble in common organic solvents and had high thermal stabilities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1528–1536, 2004     

Kinetic and mechanistic studies of the copolymerization of bis-4-substituted-1,2,4-triazoline-3,5-diones with styrenes

Highly reactive 4-substituted-1,2,4-triazoline-3,5-diones (TDs) have been studied extensively as dienophiles, but little work has been done on their role as enophiles and particularly on their use as propagating species in polymerization studies. The copolymerization between bis-4-substituted-1,2,4-triazoline-3,5-diones (bis-TDs) and styrene has been reported. The purpose of the present work was to synthesize new copolymers derived from a variety of substituted styrenes and bis-TDs and to study the mechanism and kinetics of this novel polymerization. Three bis-TDs were prepared: 3,3′-dimethyl-4,4′-bis[3,5-dioxo-1,2,4-triazoline-4-yl] biphenyl (8), t-1,4-bis[3,5-dioxo-1,2,4-triazoline-4-yl] methyl cyclohexane (9), and 4,4′-bis[3,5-dioxo-1,2,4-triazoline-4-yl] phenyl ether (10). Their structures were fully established by spectroscopic studies, elemental analyses, and indirectly, their quantitative ene reactions with 2,3-dimethyl-2-butene. Copolymerization between bis-TDs and substituted styrenes was carried out in dimethylformamide (DMF), tetrahydrofuran (THF), or dichloroethane (DCE). Polymers formed were characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and viscometry. Molecular weights of polymers range from 5000 to 16,000 in most cases. They were stable up to 250°C and higher. Polymers derived from bis-TDs and p-t-butylstyrene, α-methylstyrene, p-nitrostyrene, and p-acetoxystyrene contained only Diels-Alder-ene (DAe) repeating units, whereas those derived from styrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, and 4-vinylbiphenyl contained both DAe and double Diels-Alder (dDA) repeating units. A kinetic study of the copolymerization of 4,4′-bis-(3,5-dioxo-1,2,4-triazoline-4-yl) phenyl ether with α-methylstyrene, p-t-butylstyrene, styrene, p-chlorostyrene, and p-nitrostyrene in DCE was carried out; the copolymerization rate constants were 60.9, 49.8, 8.4, 5.5, and 0.8 (1 mol^?1s), respectively.     

Polybenzopinacols. I. Photolytic coupling of aromatic diketones

Low molecular weight polybenzopinacols were obtained by the photolytic coupling of m- and p-dibenzoylbenzene and 4,4′-dibenzoyldiphenyl ether in isopropanol, tetrahydrofuran–isopropanol, benzene–isopropanol, and benzene–ethanol solutions. The polypinacols were soluble in common organic solvents such as tetrahydrofuran, ether, and benzene. The inherent viscosities ranged from 0.06 to 0.14. Average molecular weight (M?_n) data indicated that the polymers were mostly dimers and trimers.     

Arylidene Polymers. IX. Synthesis,Characterization, and Morphology of New Polyesters of Diarylidenecycloalkanones Containing Thianthrene Units

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.     

Molecular characteristics and solution behavior of prepolymers of several polyimides: Effect of synthesis conditions

With the use of light scattering and viscometry, as well as the employment of various aprotic solvents for the polymer synthesis, the molecular characteristics of two poly(amic acids), namely, poly[4,4′-bis(4″-N-phenoxy)diphenylsulfone]amic acid of 1,3-bis(3′,4-dicarboxyphenoxy)benzene and poly[4,4′-bis(4″-N-phenoxy)diphenyl]amic acid of 1,3-bis(3′,4-dicarboxyphenoxy)benzene, have been studied at various molar ratios of the starting reagents and concentrations of the polycondensation solution. The molecular masses of poly(amic acids) depend on the thermodynamic quality of a solvent which may be changed by varying the nature of the solvent, the structure of the resulting polymer, or the chemical nature of the mixture.     

Polymers from siloxane-containing epoxides

The synthesis and polymerization of seven epoxy polymer precursors which contained the siloxane linkage in varying structural arrangements was carried out. The polymers prepared from such precursors have utility as embedding compounds for electrical circuits. Polymerization of these epoxy intermediates with siloxane-containing diamines resulted in solid, thermosetting materials for which dielectric data were obtained. Dielectric constants of 3.1 were measured at 1 keps for polymers prepared by polymerization of 1,9-bis[p-(2,3-epoxypropyl)phenyl]decamethylpentasiloxane with 1,3-bis(p-am-inophenoxy)tetramethyldisiloxane, whereas polymers derived from 1,4-bis{[p-(2,3-epoxypropyl)phenyldimethylsiloxy]dimethylsilyl}benzene and the same diamine were characterized by slightly higher dielectric constants and a high degree of toughness, being nonbrittle at ?50°C.     

Metallocene monomers and polymers. Ferrocenyl and ferrocenylene derivatives

The synthesis and study of some polyenes, polýiminoimides and Schiff polybases with ferrocene obtained by either polymerization or polycondensation are reported.The following monomers were used: ethynylferrocene, 1-chloro-1′-ethynyl-ferrocene, α-chloro-β-formyl-p-ferrocenylstyrene, p-ferrocenylphenylacetylene, p-ferrocenylacetophenone, 1,1′-diacetylferrocene and 1,1′-bis[β-(2-furyl)acryloyl]ferrocene which were characterized by spectral and thermodifferential analyses and Hückel MO calculations. The polymerization was performed in the presence of benzoyl and lauroyl peroxides, triisopropylboron and complex catalysts of [P(C₆H₅)₃]₂ NiX₂ type. The ferrocene derivatives were polycondensed with biuret, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl thioether, 4,4′-diamino-2,2′-dinitrodiphenyl disulphide in the presence of metallic salts and p-toluene sulphonic acid as catalysts.Polymers with either linear or tridimensional structure showing good thermal stability and semiconducting properties have been obtained. Some polymers show catalytical activity in the polymerization of chloroformylated vinylic derivatives.