Regular Copolyamides. III. Preparation and Characterization of Regular Aliphatic/Aromatic Copolyoxamides

Regular aliphatic/aromatic copolyoxamides were prepared from diamine-oxamides and aromatic diacid chlorides by interfacial and solution polymerization. Solution polymerization in chloroform or dimethylacetamide is preferred for the preparation of large quantities of polymers but interfacial polymerization is most conveniently carried out for the preparation of polymers with high molecular weight. Aromatic diacid chlorides used included the diacid chlorides of terephthalic acid, isophthalic acid, 2,6-pyridinedicarboxylic acid, two isomeric naphthalene dicarboxylic acids, two cyclo-hexanedicarboxylic acid isomers, as well as 1,1-cyclobutane-dicarboxylic acid. Copolymers of diamine-oxamides with mixtures of acid chlorides of isophthalic and pyridine dicarboxylic acid and isophthalic acid/tetrachloroterephthalic acid have also been prepared. Most polymers are film-forming and are soluble in concentrated sulfuric acid, trifluoroacetic acid, and dimethylacetamide (containing several per cent LiCl). A number of these polymers gave dense or asymmetric membranes, particularly the polymers from ethylene diamine as the aliphatic diamine, particularly poly(iminoethyleneimino-oxalyliminoethyleneiminoisophthaloyl) (p-222I). Diamine oxamides with more than two amide groups in the molecules have been prepared, and in one case polymers with aromatic diacid chlorides have been prepared by interfacial polymerization. All regular aliphatic/aromatic copolyoxamides are high-melting and generally decompose above 350°C without melting. They can, however, be fabricated from solution into brittle fibers or into desalination membranes.     

Syntheses and Properties of Some New Polyamides. Part II

Interfacial condensation of decamethylenediamine and acid chlorides I, II, and III yielded polyamides the thermal stability of which decreased in the order III, I, II, a finding reasserted by calculating activation energy decomposition temperatures. Irradiation of these polyamides does not appreciably affect their properties, and thus they can be considered satisfactorily γ-irradiation resistant.

It appears that there are only few papers dealing with syntheses and properties of polyamidoarylates. Cleaver and Pratt [1] prepared polyamidoesters by the polymerization of bisoxazolones with glycols. Korshak and others [2], however, obtained a polyamidoester by the aminolysis of polyethylene-sebacate with hexamethylenediamine.

In a previous investigation [3] a few polyamidoarylates were obtained by the condensation of aminophenols with aromatic acid chlorides.

In this work we obtained some new polyamidoarylates by the inter-facial condensation of equimolar ratios of decamethylenediamine with     

Cyclopolycondensations. VI. Fully aromatic polybenzoxazinones from aromatic poly(amic acids)

New high temperature aromatic polybenzoxazinones of high molecular weight have been prepared by the cyclopolycondensation of 4,4′-diaminobiphenyl-3,3′-dicarboxylic acid (I) with aromatic dicarboxylic acid halides (II). The low temperature solution polymerization techniques afforded poly(amic acid) (III) of high molecular weight in the first step. An open-chain precursor subsequently underwent thermal cyclodehydration along the polymer chain at 200–350°C. in the second step, to give in quantitative yield a fully aromatic polybenzoxazinone (IV) of outstanding heat stability both in nitrogen and in air. The poly(amic acid) is soluble in N-methyl-2-pyrrolidone, and tough, transparent films can be cast from solution. Insoluble aromatic polybenzoxazinone films which possess excellent oxidative and thermal stability were obtained by the heat treatment of the polyamic acid. A detailed account of polymerization conditions in the low temperature solution polymerization of polybenzoxazinones is given, and the reaction mechanisms of cyclopolycondensation of poly(amic acids) and the formation of polybenzoxazinones are discussed.     

Synthesis and characterization of new aromatic polyesters and a polyether derived from 2,2-bis(4-hydroxyphenyl)-1,2-diphenylethanone

New polyarylates having benzopinacolone units were synthesized from 2,2-bis(4-hydroxyphenyl)-1,2-diphenylethanone and aromatic dicarboxylic acid chlorides. The polymers having an inherent viscosity of 0.71–0.94 dL/g were obtained by the two-phase method using toluene as an organic solvent. The polymers were easily soluble in various organic solvents and had high glass transition temperatures in the range of 200–240°C. An aromatic polyether having benzopinacolone unit was also prepared. However, its inherent viscosity was low because of the occurrence of a side reaction. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2229–2235, 1998     

New processable polyaromatic esters curable by intramolecular cyclization. XVIII

New processable polyaromatic esters were prepared from 2,2′-diiododiphenyl-4,4′-dicarbonyl dichloride (I), isophthaloyl chloride (II), and/or terephthaloyl chloride (III) with 4,4′-isopropylidene diphenol (IV), 4,4′-sulfonyldiphenol (V), or resorcinol by interfacial condensation. In these polymers phenylacetylenyl groups were introduced by replacing the iodine. This process led to soluble and curable polymers. Polymer films can be prepared. After curing the polymers were insoluble and showed excellent thermal and chemical resistance. The curing process increased the polymers' softening temperature about 20°C.     

New poly(amide-imide) syntheses. XII. Preparation and properties of poly(amide-imide)s based on the diimide-diacid condensed from 9,9-bis[4-(4-aminophenoxy)phenyl] fluorene and trimellitic anhydride

A dicarboxylic acid ( I ) was prepared from the condensation of 9,9-bis[4-(4-aminophenoxy) phenyl] fluorene and trimellitic anhydride. A new family of poly(amide-imide)s having inherent viscosities of 0.75-1.04 dL/g was prepared by the triphenyl phosphite activated polycondensation from the diimide-diacid I with various aromatic diamines in a medium consisting of N-methyl-2-pyrrolidone (NMP), pyridine, and calcium chloride. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 262–325°C and the 10% weight loss temperatures were above 525°C in air. © 1994 John Wiley & Sons, Inc.     

Preparation and properties of aromatic poly(amide–benzothiadiazine dioxides)

New thermostable poly(amide–benzothiadiazine dioxides) of high molecular weights have been prepared by the two-step cyclopolycondensation of diaminobenzenesulfonamides and aromatic bisacyl chlorides. In the first step, the low-temperature solution polymerization technique afforded open-chain polyamides (I) having high molecular weights. In the second step, the polymeric precursors (I) underwent chemical cyclodehydration in the presence of organic basic catalysts at 160°C to give poly(amide–benzothiadiazine dioxides) (II), whereas thermal cyclodehydration gave unsatisfactory results. Not only the open-chain polymers (I) but also the cyclized polymers (II) were soluble in polar solvents, such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone; tough films were cast from these solutions. Thermogravimetric analyses indicated that the cyclized polymers (II) began to decompose at 450–470°C under nitrogen or in air. It is interesting to note that both polymers I and II exhibited self-extinguishing properties against free flame. The cyclodehydration of model compounds was also investigated.     

Synthesis and properties of soluble and light‐colored poly(amide‐imide‐imide)s on the basis of tetraimide‐dicarboxylic acid condensed from 4,4′‐oxydiphthalic anhydride, 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane,and m‐aminobenzoic acid,and various aromatic diamines

A new type of tetraimide‐dicarboxylic acid ( I ) was synthesized starting from the ring‐opening addition of m‐aminobenzoic acid, 4,4′‐oxydiphthalic anhydride, and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane at a 2:2:1 molar ratio in N‐methyl‐2‐pyrrolidone (NMP), followed by cyclodehydration to the diacid I . A series of soluble and light‐colored poly(amide‐imide‐imide)s ( III _a–j) was prepared by triphenyl phosphite‐activated polycondensation from I with various aromatic diamines ( II _a–j). All films cast from N,N‐dimethylacetamide (DMAc) had cutoff wavelengths shorter than 390 nm (374–390 nm) and b* values between 25.26 and 43.61; these polymers were much lighter in color than the alternating trimellitimide series. All of the polymers were readily soluble in a variety of organic solvents such as NMP, DMAc, N,N‐dimethylformamide, dimethyl sulfoxide, and even in less polar m‐cresol and pyridine. Polymers III _a–j afforded tough, transparent, and flexible films that had tensile strengths ranging from 96 to 118 MPa, elongations at break from 9 to 11%, and initial moduli from 2.0 to 2.5 GPa. The glass‐transition temperatures of the polymers were recorded at 240–268 °C. They had 10% weight loss at a temperature above 540 °C and left more than 55% residue even at 800 °C in nitrogen. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 707–718, 2002; DOI 10.1002/pola.10153     

Synthesis and properties of aromatic polyamides containing the cyclohexane structure

1,1-Bis[4-(4-carboxyphenoxy)phenyl]cyclohexane (III) and 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane (V) were prepared in two main steps starting from the aromatic nucleophilic substitution of p-fluorobenzonitrile and p-chloronitrobenzene, respectively, with 1,1-bis(4-hydroxyphenyl)cyclohexane in the presence of potassium carbonate in N,N-dimethylformamide (DMF). Using triphenyl phosphite and pyridine as condensing agents, two series of polyamides with cyclohexylidene cardo groups were directly polycondensated from dicarboxylic acid III with various aromatic diamines or from diamine V with various aromatic dicarboxylic acids in an N-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride. The polyamides exhibited inherent viscosities in the range of 0.45 to 1.78 dL/g. Almost all of the polymers were readily soluble in polar aprotic solvents such as NMP and N,N-dimethylacetamide (DMAc) and could afford transparent, flexible, and tough films by solution casting. The glass transition temperatures (T_g) of these aromatic polyamides were in the range of 180–243°C by DSC, and the 10% weight loss temperatures in nitrogen and air were all above 450°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3575–3583, 1999     

Synthesis and characterization of aromatic polyesteres and polyamide–esters from bisphenols and aromatic aminophenols,and 2,5-bis(4-chloroformyl)-3,4-diphenylthiophene

Polycondensation of 2,5-bis(4-chloroformyl)-3,4-diphenylthiophene ( I ) with various bisphenols afforded tetraphenylthiophene-containing aromatic polyesters by the interfacial or solution polycondensation method. Polyamide–esters were obtained from I and aminophenols by means of the interfacial technique. These polymers had inherent viscosities of 0.4–0.8 dL/g. All the polymers were readily soluble in various organic solvents, and could be cast into transparent and flexible films. Their glass transition temperatures were in the range of 235–335°C. These polymers did not lose weight below 400°C in either air or nitrogen.     

Preparation and structure/property relationships of polyesters containing conjugated diacetylene groups

A series of novel polyesters containing conjugated diacetylenes (DA‐polyesters) were prepared from various diacetylene diols with/without methyl side groups and isomers of aromatic acid chlorides via an interfacial condensation. A fully aliphatic DA‐polyester was also prepared for comparison. All synthesised DA‐polyesters are soluble in m‐cresol, and the intrinsic viscosities were measured. In addition, compact and coherent films and sheets can be obtained from some of the polymers via solution or melt casting. The structure, morphology, and properties were characterized using spectroscopic methods, including FTIR, Raman, and WAXD and thermal analysis including TGA, DSC techniques. DMA was carried out on the solution‐cast thin films and melt‐processed samples. Close correlation was found between the structure and properties in these DA‐polyesters. In particular, through analysis using isothermal DSC and Raman spectroscopy, the solid‐state reactivity of the diacetylene groups in these polyesters was found related to the interchain spacings, which are, in turn, controlled by the molecular structure of the polymers. Results have shown that the aliphatic DA‐polyester behaves very differently compared to the aromatic ones. Distinct differences were also observed among meta‐ and para‐disubstituted isomers of the DA‐polyesters. Furthermore, the introduction of methyl side groups has dramatically affected the thermal and thermal mechanical behavior by altering the interchain spacing of the polymers. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 965–974, 1999     

New poly(amide-lmide)s syntheses. XV. Preparation and properties of poly(amide-imide)s derived from 9, 9-bis[4-(4-aminophenoxy) phenyl]fluorene and various bis(trimellitimide)s

Fifteen bis(phenoxy) fluorene-containing poly(amide-imide)s III were synthesized by the direct polycondensation of 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene (BAPPF) with var-ious aromatic bis(trimellitimide)s II in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly(amide-imide)s III having inherent vis-cosities up to 1.45 dL/g were obtained in quantitative yields. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 263–315°C and the 10% weight loss temperatures were above 510°C in nitrogen. Some properties of poly(amide-imide)s III were compared with those of the corresponding isomeric poly(amide-imide)s III ′ prepared from 9,9-[4-(4-trimellitimidophenoxy)phenyl]fluorene and various aromatic diamines. © 1995 John Wiley & Sons, Inc.     

Syntheses and properties of aromatic polyamides and polyimides derived from 9,9-bis[4-(p-aminophenoxy)phenyl]fluorene

9,9-Bis[4-(p-aminophenoxy)phenyl]fluorene ( II ) was used as a monomer with various aromatic dicarboxylic acids and tetracarboxylic dianhydrides to synthesize polyamides and polyimides, respectively. The diamine II was derived by a nucleophilic substitution of 9,9-bis(4-hydroxyphenyl)fluorene with p-chloronitrobenzene in the presence of K₂CO₃ and then hydro-reduced. Polyamides IV _a-g having inherent viscosities of 0.73–1.39 dL/g were prepared by the direct polycondensation of the diamine II with various aromatic diacids using triphenyl phosphite and pyridine as condensing agents. All the aromatic polyamides were amorphous and readily soluble in various polar solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, and N-methyl-2-pyrrolidone. Transparent and flexible films of these polymers could be cast from the DMAc solutions. These aromatic polyamides had glass transition temperatures in the range of 283–309°C and 10% weight loss occurred up to 460°C. The polyimides were synthesized from diamine II and various aromatic dianhydrides via the two-stage procedure that included ring-opening poly-addition in DMAc to give poly(amic acid)s, followed by thermal or chemical conversion to polyimides. The poly(amic acid)s had inherent viscosities of 0.62–1.78 dL/g, depending on the dianhydrides. Most of the aromatic polyimides obtained by chemical cyclization were found to be soluble in NMP. These polyimides showed almost no weight loss up to 500°C in air or nitrogen atmosphere. © 1993 John Wiley & Sons, Inc.     

Note Synthesis of New Poly(Amide-Hydrazide)s

Poly(amide-hydrazide)s were originally developed to give fibers of high modulus and high strength [1]. They were generally prepared 1) from dicarboxylic acid chlorides and aminohydrazides by low-temperature polycondensation [2,3]; 2) by the phosphorylation method [4, 5]; and 3) from dihydrazides with preformed amide linkages by low-temperature polycondensation [6]. These polymers were found to be thermally stable, but they showed poor solubility in polar aprotic solvents. In this paper we report the synthesis and characterization of some new poly(amide-hydrazide)s with azo groups in the backbone, which were introduced to improve solubility.     

Use of phosphite amides in the synthesis of polyamides

The preparation of polyamides by the phosphite amide procedure was investigated. The yield of amidation was determined in the reaction of diethyl- or o-phenylenephosphite derivatives of piperidine, piperazine, or trans-2,5-dimethylpiperazine with either mono- or dicarboxylic acids. Higher yields were obtained by using diethyl phosphite derivatives; however, for both types of derivatives the yields were never greater than 90%. Only low molecular weight polymers could be obtained under optimum reaction conditions. In the polycondensation of (+)-trans-1,3-cyclohexanedicarboxylic acid or (+)-trans-1,2-cyclohexanedicarboxylic acid with phosphite derivatives of either piperazine or trans-2,5-dimethylpiperazine, the optical rotation of the polymers was lower than the rotation of the corresponding polyamides prepared by the interfacial condensation procedure with dicarboxylic acid chlorides. It was shown that an intermediate mixed anhydride was formed during the amidation reaction. This may account for the observed racemization.     

New poly(amide-imide) syntheses. V. Preparation and properties of poly(amide-imide)s based on the diimide—diacid condensed from 2,2-bis[4-(4-aminophenoxy)phenyl]propane and trimellitic anhydride

A dicarboxylic acid ( 1 ) bearing two pre-formed imide rings, was prepared from the condensation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and trimellitic anhydride. A new family of poly(amide-imide)s having inherent viscosities of 0.53–1.68 dL/g was prepared by the triphenyl phosphite activated polycondensation from the diimide—diacid I with various aromatic diamines in a medium consisting of N-methyl-2-pyrolidone (NMP), pyridine, and calcium chloride. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these poly(amide-imide)s were in the range of 237–293°C and the 10% weight loss temperatures were above 508°C in nitrogen. © 1993 John Wiley & Sons, Inc.     

Synthesis and characterization of soluble aromatic polyurea-amides from new N,N′--dimethyl-N,N′-bis(aminophenyl)ureas and aromatic dicarboxylic acid chlorides

Aromatic polyurea-amides having inherent viscosities of 0.36–0.67 dL/g were synthesized by the low temperature solution polycondensation of new N,N′-dimethyl-N,N′-bis(aminophenyl)ureas with various aromatic dicarboxylic acid chlorides. All the polymers were amorphous, and most of them were soluble in a variety of organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide (DMAc), m-cresol, and pyridine. Some of the polymers could be cast from the DMAc solutions into transparent and flexible films having good tensile properties. The glass transition temperatures of the polyurea-amides obtained from the bis(4-aminophenyl)-substituted ureas were 244–272°C. The temperatures of 10% weight loss under nitrogen of the polymers were in the range of 430 and 480°C. © 1995 John Wiley & Sons, Inc.     

Synthesis and properties of poly(amide-imide)s based on the diimide-diacid condensed from 2,2′- bis(4-aminophenoxy)biphenyl and trimellitic anhydride

A new dicarboxylic acid having a kinked structure was synthesized from the condensation of 2,2′-bis(4-aminophenoxy)biphenyl and trimellitic anhydride. A series of biphenyl-2,2′-diyl-containing aromatic poly(amide-imide)s having inherent viscosities of 0.23–0.94 dL/g was prepared by the triphenyl phosphite activated polycondensation from the diimide-diacid II with various aromatic diamines in a medium consisting of N-methyl-2-pyrrolidone (NMP), pyridine, and calcium chloride. Most of the resulting polymers showed an amorphous nature and were readily soluble in a variety of organic solvents including NMP and N,N-dimethylacetamide (DMAc). Transparent, flexible, and tough films of these polymers could be cast from DMAc or NMP solutions. The glass transition temperatures of these polymers were in the range of 227–261°C and the 10% weight loss temperatures were above 520°C in nitrogen. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1169–1177, 1998     

Aromatic polysulfonamides

Aromatic polysulfonamides have been prepared by solution polycondensation of aromatic disulfonyl chlorides and aromatic diamines with a suitable acid acceptor in such solvents as N,N-dimethylacetamide and tetramethylenesulfone. The highest molecular weight polymers were obtained by using 2,6-dimethylpyridine as the acid acceptor in tetramethylenesulfone as the solvent. Clear, translucent, brittle films of the polysulfonamides may be formed from solution or from melt.     

A preliminary study on polyhydrazides incorporating furan moieties

Solution and interfacial polycondensation of difuranic dihydrazides with aromatic or aliphatic dicarboxylic acid dichlorides led to the corresponding polyhydrazides which were characterized in terms of structure and average chain length. Their conversion to the corresponding polyoxadiazoles was also examined. Model compounds were prepared to facilitate the synthesis and the characterization of the polymers.