Quinone-amine polymers. XV. Syntheses and characterization of high-temperature resistant poly(arylamino-quinone)s

Several poly(arylamino-quinone)s (PAAQs) were prepared by the conventional solution polymerization of p-benzoquinone with various aromatic diamines in tetrahydrofuran. Polymers prepared by this method were found to be more soluble in many organic solvents compared to the PAAQs prepared by other reported methods. The poly(arylamino-quinone)s were obtained in 82.3–94.5% yield and had inherent viscosities in the range of 0.073–0.251 dL/g. Among the PAAQs, the polymer prepared from p-benzoquinone and 1,3-bis(3-aminophenoxy)benzene (APB) had demonstrated exceptionally good solubility and thermal stability. © 1994 John Wiley & Sons, Inc.     

Sulfur-containing polymers. II. Preparation and properties of polycarbamoylsulfenamides

Polycarbamoylsulfenamides have been prepared by interfacial and solution polycondensation of chlorocarbonylsulfenyl chloride with diamines. In preparing the polycarbamoylsulfenamides, the following types of diamines were used: primary aliphatic diamines, a mixed primary-secondary aliphatic diamine, primary aromatic diamines, and secondary aromatic diamines. The properties of the resulting polymers depended primarily on the kind of diamines used. Transparent, tough films were obtained from the polymer based on N,N′-dimethyl-4,4′-diaminodiphenylmethane. The photochemical decomposition of the polymers has been studied.     

Preparation of phosphorus-containing polymers. XXV. Polyamide-imides that contain phenoxaphosphine rings

New phenoxaphosphine-containing polyamide-imides were prepared by cyclodehydration of the polyamide-amic acids obtained from 8-chloroformyl-10-phenylphenoxaphosphine-2,3-dicarboxylic anhydride 10-oxide and diamines by a low-temperature solution polycondensation. Polymers with reduced viscosities of 0.10–0.59 dl/g in DMA or concentrated H₂SO₄ at 30°C were obtained in 64–97% yields. All the polyamide-imides were soluble in m-cresol, concentrated H₂SO₄, and dichloroacetic acid and some of them were soluble in DMF, DMA, and DMSO; the polyamide-imides had better solubility in organic solvents than phenoxaphosphine-containing polyimides. The phenoxaphosphine-containing polyamide-imides derived from aromatic diamines exhibited excellent thermal properties and little degradation below about 400°C, whereas the polymers from aliphatic diamines began to lose weight at about 250°C. They appeared to have thermal stability between phenoxaphosphine-containing polyimides and polyamides. These polyamide-imides exhibited self-extinguishing behavior.     

Polyimidines: A new class of polymers. III. A comparison of isomers of polypyromellitimidines

The cis (3,3,5,5-), trans (3,3,7,7-), oxo, and thio analogs of tetraphenylpyromellitide were polymerized with 1, 6-hexane diamine, p-phenylene diamine, and p,p'-diaminodiphenyl ether under various conditions. A comparison was then made of reactivity of the isomers and of the properties of the polymers. In general the thio monomers were more soluble and reactive than the oxo. They also gave more thermally stable polymers. The cis isomers of the monomers were more soluble than the trans, but the trans were more reactive. The least stable of the 12 polymers prepared was that from the cis–oxo monomer and 1,6-hexane diamine. It gave a 10% weight loss at 300°C in air and 340°C in nitrogen by TGA. The most stable polymer was from the reaction of the cis–thio pyromellitide with p,p'-diaminodiphenyl ether, which showed 10% weight losses by TGA at 560 and 650°C in air and nitrogen, respectively. The polymers were stable in hot dilute hydrochloric acid and sodium hydroxide. They were all soluble in chloroform, dimethylformamide, and sulfuric acid. Polymers that contained sulfur were also soluble in carbon tetrachloride, benzene, xylene, and toluene. Brittle films could be cast from solution or melt-pressed.     

New high temperature polymers. I. Wholly aromatic ordered copolyamides

Wholly aromatic ordered copolyamides of unusually high thermal stability were prepared by the condensation of aromatic diacid chlorides with symmetrical diamines containing preformed aromatic amide units in an ordered arrangement. The preservation of order in the condensation step was assured by using interfacial or solution polymerization techniques at temperatures below 50°C. Each polymer contains units derived from aminobenzoic acids, arylene diamines, and arylene diacids. By use of para- and meta- phenylene units, eight different polymers are possible; all were prepared. Differential thermal analyses and thermogravimetric analyses showed these polymers to have melting points or decomposition temperatures in a range from 410°C. for the all-meta polymer to 555°C. for the all-para one. Substitution of the internal N-hydrogens of the diamines with methyl groups or phenyl groups leads to additional ordered copolymers. Several were prepared, but their melting points were much lower than those of the parent polymers limiting their usefulness in high temperature applications. Tough pliable films were prepared from all eight unsubstituted polymers, and crystalline fibers with tenacities of ca. 6 g./den. were prepared from three of the polymers. The properties of the fibers were retained to a high degree even when determined at temperatures up to 400°C. Fibers aged at 300°C. for extended periods of time showed remarkable retention of fiber properties.     

Heat-resistant polymers containing thianthrene analogs units. I. Polyimides

Polyimides that contained thianthrene and dibenzo-p-dioxins units were synthesized. The tricyclic fused rings were successfully incorporated by polymerizing the diamines of the units with aromatic tetracarboxylic dianhydrides. The resulting polyamic acids were converted to polyimides by thermal cyclodehydration. The influence of the tricyclic units on the properties of the polyimides has been investigated. Polyimides that contained dibenzo-p-dioxins (ODP) exhibited sufficient thermal stability but were insoluble even in concentrated sulfuric acid. The introduction of a methyl group did not produce an appreciable increase in solubility. Thianthrene polyimides were considerably less stable than the equivalent polymers derived from open-chain diamine, 4,4′-diaminodiphenyl sulfide but were partly soluble in acid solvents. The results are discussed in terms of packing the polymer molecules.     

Semiconducting polymers based on charge-transfer complexes. III. Complexing and chemical stability of charge-transfer complexes in solution

10-Methylphenothiazine and p-(methylthio)anisole were compared to polymers which contained these donor molecules on the side chains of N-acyl-substituted polyethylenimines. Charge-transfer absorption spectra were compared for these donors with the acceptors: dichlorodicyanobenzoquinone, tetracyanoquinodimethane, tetracyanoethylene, and 2,4,5,7-tetranitrofluorenone. Benesi-Hildebrand plots show that the formation of the polymer complexes have 3 to 50 times higher equilibrium constants than those of the corresponding model complexes. This can be explained by complexing parallel to the polymer backbone. The polymer has the proper geometry for complexing (6.4 Å, repeat distance in the polymer backbone), and an acceptor molecule can therefore be inserted between two adjacent donor molecules for increased stability. Shifts of the absorption maxima to longer wavelength for some of the polymer complexes can be rationalized by the probability that in the polymer, an acceptor is sandwiched between two donors and thus forms 2:1 complexes; the extra resonance energy may shift the absorption maximum to longer wavelength. A second possible explanation is based on solvation of the complex which reduces the energy of the excited state. Polymers absorb mainly in the complex form. Model compounds absorb mainly by contact charge transfer, which is nonsolvated and thus occurs at higher energy or shorter wavelength. Extinction coefficients are higher for the model complexes than for the polymer complexes. Contact charge transfer, which can contribute in greater proportion to the model than to the polymer complexes, explains this. The amount of contact charge transfer can be calculated simply from the probability of a donor being in the solvent shell of an acceptor. Complex decomposition rates were determined based on measuring changes in the intensities of the charge-transfer absorption spectra. Dichlorodicyanoquinone complexes were unstable, while the other complexes were stable.     

Structure–property relationships of ionene polymers

The synthesis of new ionenes was accomplished by the reaction of novel diamines and dihalides. A new class of crosslinkable ionenes was made possible by the synthesis of tertiary diamines with acrylate functionality, generated ultimately from diepoxides and secondary amines. Other tertiary diamines were produced by endcapping of diols with tolylene diisocyanate, followed by reaction with N,N-dimethylethanolamine and also termination of living poly(tetrahydrofuran) polymer with dimethylamine. New dihalides were produced by the opening of diepoxides with ω-bromoacids. These diamines and dihalides underwent Menschutkin reactions providing novel ionenes for structure–property relationship studies. Correlations were drawn concerning amine nucleophilicity, dihalide nucleofugascity, and molecular weight. Stress–strain and thermal data reflected the effects of ionic domains and large flexible segments in the polymers. Also considered were the electrical conductivity, moisture–vapor transmission, and oxygen permeability of these materials.     

Polyimidazopyrrolones and related polymers. I. Dianhydrides and o-acetamidodiamines

Solutions of polyimidazopyrrolone precursors prepared by reaction of tetraamines and dianhydrides in polar solvents tend to crosslink and gel very easily. Substitution of o-acetamidodiamines for the tetraamines gives stable solutions. A study of cure mechanisms by TGA, infrared, and pyrolysis experiments with polymers and model compounds indicates that the acetylated materials are converted cleanly to imides at 150°C. At temperatures above 350°C, structural changes and further polymerization occur, with little imidazopyrrolone formation. Polymers derived from tetraamines cure by multiple mechanisms but finally yield the imidazopyrrolone structure. The acetylated polymers and copolymers give acceptable laminates but poor films.     

Synthesis of formamidine-containing polymers from aromatic diamines

Aromatic polymers containing formamidine groups in the polymer backbone were obtained from aromatic diamines in high yields with α,α-dichloromethyl ether and triethylorthoformate. The latter was the reagent of choice. Soluble, high-molecular-weight products were obtained with m-phenylene diamine and 4,4′ bis(aminophenyl)methane. These polymers were characterized by viscosity, microanalysis, and nuclear magnetic resonance and infrared spectroscopy. Generally, insoluble products were obtained from p-phenylene diamine and 2,6-diaminotoluene, although small amounts of dimethylsulfoxide (DMSO)-soluble fractions could be extracted and examined by NMR spectroscopy. IR analysis of the insoluble fractions confirmed formation of polymers with the formamidine-containing structures. The synthetic procedures developed here make readily available this new class of aromatic polymers.     

Polyimidines. VI. The comparison of polyimidines from bis(3,3-diphenyl-6-phthalidyl) ketone

New thermally stable polyimidines have been synthesized from bis(3,3-diphenyl-6-phthalidyl) ketone and five diamines: o-phenylenediamine, m-phenylenediamine, 1,5-diaminonapthalene, 1,8-diaminonapthalene, and benzidine. Polymers of low molecular weight (inherent viscosity up to 0.24 dl/g) were obtained by solution and sealed-tube polymerizations. The structural differences of the amines provided information concerning the effects on the thermal stability properties of the resulting polyimidines. The yellow to black polymers exhibited a 10% loss ranging from 420–510°C in air and 460–555°C in nitrogen and were soluble in chloroform and dimethylformamide.     

Poly(enamine-ketones) from hydrogen-terminated aromatic dipropynones and aromatic diamines

Poly(enamine-ketones) were prepared by the nucleophilic (Michael-type) addition of various aromatic diamines to 1,1′-(1,3- or 1,4-phenylene)bis(2-propyn-1-one)(1,3 or 1,4-PPO) in m-cresol at 5–23°C. The low molecular weight polymers (inherent viscosity of 0.25 dL/g) exhibited limited solubility in organic solvents. Glass transition temperatures were generally undetectable by differential scanning calorimetry while polymer decomposition temperatures (10% weight loss), as measured by thermogravimetric analysis, were observed from 355 to 419°C. Polymers prepared from 1,4-PPO were semi-crystalline as shown by wide-angle X-ray diffraction. The poly(enamine-ketone) structure was confirmed by matching infrared spectral characteristics of the polymers with those of well-characterized model enamine ketones.     

Functional polymers. XLVIII. Polymerization of ω-alkenoate derivatives

Esters of ω-alkenoic acids have been homopolymerized with transition metal initiating systems. The key to the successful polymerization was the complexation of the monomer prior to its addition to the initiating system. Titanium trichloride, aluminum activated, was found to be best as the transition metal part of the initiator systems, with diethyl-, or better, diisobutylaluminum chloride as the reducing agents and n-hexane or toluene as the solvents. Best results for polymerizations were obtained with 2,6-dimethylphenyl esters of the functional α-olefin monomers; however, other phenyl esters also polymerized well. Attempts to polymerize methyl 10-undecenoate gave the corresponding polymer in only low yields. Polymers of the 2,6-dimethylphenyl esters, obtained in high molecular weight, were characterized. Polymers were also obtained from 2,6-dimethylphenyl 7-octenoate, but not from ω-alkenoates with less than three methylene units between the ester group and the terminal olefin group. Poly(2,6-dimethylphenyl 10-undecenoate) was hydrolyzed in an aqueous sodium hydroxide/1,4-dioxane solution to poly(sodium 10-undecenoate) that in turn was neutralized with acetic acid to poly(10-undecenoic acid).     

Condensation polymers from 1,2,5-thiadiazole-3,4-dicarboxylic acid

A series of polyamides was prepared by interfacial polymerization of diamines with 1,2,5-thiadiazole-3,4-dicarbonyl chloride. Polyamides from secondary cycloaliphatic diamines and aromatic diamines have high softening points, high glass transition temperatures, and good thermal stability. Secondary amines, in particular cycloaliphatic secondary amines, form very high molecular weight polyamides. The polyamide from trans-2,5-dimethylpiperazine and 1,2,5-thiadiazole-3,4-dicarbonyl chloride is soluble in chloroform and 1,1,2-trichloroethane and has been cast into films and spun into fibers from those solvents. Fibers of this polymer are strong and have very high work recovery from small strains. In addition, these fibers show good retention of strength and work recovery over a range of temperatures and humidities.     

Heat-resistant polymers with thianthrene analog units. II . Aromatic polyamides

A series of polyamides which contained thianthrene, phenoxatiin, and dibenzo-p-dioxin units was synthesized from tricyclic fused-ring diamines and aromatic diacid chlorides by solution polycondensations at a low temperature. The amorphous polyisophthalamides were highly soluble in polar organic solvents, whereas some of the polyterephthalamides with a fair degree of crystallinity were insoluble. The solubility of the series of polyamides increased in the order of the dibenzo-p-dioxin-containing polymers < phenoxatiin-containing polymers < thianthrene-containing polymers. The thermal stability increased in the reverse order and the dibenzo-p-dioxinpolyamides were more thermostable than the corresponding open-chain polymers with diphenyl ether linkages. The polyamides derived from 2,8-oriented tricyclic diamines showed somewhat lower glass transition temperatures than those from 2,7-oriented diamines.     

Cyclopolycondensation. XIII. New synthetic route to fully aromatic poly(heterocyclic imides) with alternating repeating units

Fully aromatic poly(heterocyclic imides) of high molecular weight were prepared by the cyclopolycondensation reactions of aromatic diamines with new monomer adducts prepared by condensing orthodisubstituted aromatic diamines with chloroformyl phthalic anhydrides. The low-temperature solution polymerization techniques yielded tractable poly(amic acid), which was converted to poly(heterocyclic imides) by heat treatment to effect cyclodehydration at 250–400°C under reduced pressure. In this way, the polyaromatic imideheterocycles such as poly(benzoxazinone imides), poly(benzoxazole imides), poly(benzimidazole imides) and poly(benzothiazole imides) were prepared, which have excellent processability and thermal stability both in nitrogen and in air. The poly(amic acids) are soluble in such organic polar solvents as N,N-dimethyl-acetamide, N-methylpyrrolidone, and dimethyl sulfoxide, and the films can be cast from the polymer solution of poly(amic acids) (η_inh = 0.8–1.8). The film is made tough by being heated in nitrogen or under reduced pressure to effect cyclodehydration at 300–400°C. The polymerization was carried out by first isolating the monomer adducts, followed by polymerization with aromatic diamines. On subsequently being heated, the open-chain precursor, poly(amic acid), undergoes cyclodehydration along the polymer chain, giving the thermally stable ordered copolymers of the corresponding heterocyclic imide structure.     

Fullerene grafted amine-containing polymers

We have covalently attached fullerenes to amine containing flexible hydrocarbon polymers such as amino-ethylene propylene terpolymer (EPDM-amine) to obtain novel fullerene functionalized polymers. These materials are soluble in solvents such as heptane or tetrahydrofuran (THF), in which the fullerene is essentially insoluble. The reaction of the fullerene and polymer was followed by infra-red spectroscopy and viscosity measurements. Thermogravimetric analysis (TGA) scans of EPDM-amine and Fullerene reacted EPDM-amine show that the fullerene grafted polymer is thermoxidatively more stable than the original polymer. Furthermore, the fullerene grafted polymer could be reacted further with primary-tertiary diamines to obtain novel polymers in which the fullerene acts as a bridging group for attaching polar functional groups to nonpolar hydrocarbon polymers.     

Semiconducting polymers based on charge-transfer complexes. I. Synthesis of electron-donor-containing poly-N-acylethylnimines

Polymers were made which contained 10-methyl, 3-phenothiazinyl, and 4-(methylthio)phenoxy electron-donating groups on side chains. N-Acyl-substituted poly-ethylenimines were chosen because the repeat distance along the polymer chain is the same as the repeat distance in most aromatic charge-transfer complexes (about 6.4 Å) and the side chains do not interfere with each other. This paper describes synthetic routes for preparation of these electron-donor-containing polymers. Synthesis of a polyacrylate donor is also described.     

Syntheses and reactions of ferrocene-containing polymers. III. Cyclopolymerization of 1,1′-divinylferrocene

1,1′-Divinylferrocene was polymerized with BF₃OEt₂ and AIBN initiators. Polymers were separated into benzene-soluble and benzene-insoluble fractions, the latter probably being crosslinked. The polymers obtained with BF₃OEt₂ were shown by infrared and NMR spectroscopy to contain both cyclized (70–80%) and uncyclized units, whereas the radical polymer consisted of more than 96% cyclized units. The benzene-soluble fraction of the cationically obtained polymer softened at temperatures below 150°C, but the insoluble fraction decomposed at 240°C. The radical polymers were stable up to 250–280°C (dec).     

Quinone-amine polymers. XII. Synthesis and characterization of novel polymers from 2-phenylbenzoquinone and aliphatic diamines

In order to study the effect of the presence of phenyl groups in poly (amino-quinone) (PAQ) polymers, several novel poly(amino-2-phenylbenzoquinone) (PhPAQ) polymers have been prepared from 2-phenylbenzoquinone and aliphatic diamines, such as 1,6-diaminohexane, 1,8-diaminooctane, 1,12-diaminodod+++++, and 1,4-diaminocyclohexane. Prior to the polymerization, 2-phenylbenzoquinone was generated in situ from 2-phenylhydroquinone in the presence of calcium hypochlorite as the oxidizing agent in dichloromethane. All of the polymers synthesized have been characterized with respect to their corresponding model compounds. It was also found that unlike their analogous PAQ polymers, PhPAQ polymers were highly soluble in many common organic solvents because of the presence of phenyl groups in their polymer backbone. © 1994 John Wiley & Sons, Inc.