Linear polythioesters. V. Products of interfacial polycondensation of 4,4′-di(mercaptomethyl)-benzophenone with some aliphatic acid dichlorides

New polythioesters by interfacial polycondensation of 4,4′-di(mercaptomethyl) benzophenone with oxalyl, succinyl, adipoyl, suberoyl, and sebacoyl chlorides were obtained. To determine the optimal conditions for interfacial polycondensation the influence of the following factors on yield and value of reduced viscosity were studied: type of organic phase, the quantitative ratio of aqueous and organic phase, concentration of hydrogen chloride acceptor, molar ratio of reagents, temperature of reaction, rate of acid chloride addition, and contribution of catalyst and emulsifier. A thorough examination was carried out only for polycondensation of dithiol with adipoly and sebacoyl chlorides. The structure of all polythioesters obtained under the model conditions was determined by elementary analysis and infrared spectra. Initial decomposition and initial intensive decomposition temperature were defined from the curves of thermogravimetric analysis. Some mechanical and electrical properties of the polythioesters obtained from 4,4′-di(mercaptomethyl)benzophenone and adipoyl and sebacoyl chlorides were determined. The molecular weight was not measured because of the low solubility of the obtained polythioesters.     

Linear polythioesters. VII. Products of interfacial polycondensation of 1,4-di(mercaptomethyl)-2,3,5,6-tetramethylbenzene with some aliphatic acid dichlorides

Several polythioesters by interfacial polycondensation of 1,4-di(mercaptomethyl)-2,3,5,6-tetramethylbenzene with oxalyl, succinyl, adipoyl, suberoyl, and sebacoyl chlorides were obtained. To determine the optimal conditions for interfacial polycondensation, the influence of the following factors on yield and value of reduced viscosity were studied: type of organic phase, concentration of hydrogen chloride acceptor, the quantitative ratio of aqueous to organic phase, molar ratio of reagents; temperature of reaction, rate of acid chloride addition, and contribution of catalyst. Thorough studies were carried out only for polycondensation of the dithiol with adipoyl and sebacoyl chlorides. The structure of all polythioesters obtained under the model conditions was determined by elementary analysis and infrared spectra. Initial decomposition temperature, mass loss in percentage at the same temperature, maximum rate of decomposition, and mass loss percentage at 100–400°C were defined by thermogravimetric analyses. Chemical resistance of the polythioesters was determined by treatment with some organic solvents, mineral acids (concentrated and 10%), and sodium hydroxide (10 and 50%). Some mechanical and electrical properties of the polythioesters obtained from dithiol and adipoyl and sebacoyl chlorides were determined. The molecular weight was not measured because of the low solubility of the polythioesters.     

Linear polythioesters. VI. Products of interfacial polycondensation of bis/4-mercaptophenyl/ether with some aliphatic acid dichlorides

New polythioesters by interfacial polycondensation of bis/4-mercaptophenyl/ether with oxalyl, succinyl, adipoyl, suberoyl, or sebacoyl chlorides were obtained. To define the optimal conditions of the process, the polythioesters of dithiol and adipoyl or sebacoyl chlorides were chosen as a model system. Yield for all reaction products and reduced viscosity were found. The following factors were studied: organic phase, contribution of catalyst, concentration and molar ratio of reagents, rate of addition of acid chloride, temperature of reaction, contribution of emulsifier, and concentration of hydrochloride acceptor. The structure of all polythioesters was determined by elementary analysis, infrared spectra, and x-ray. Initial decomposition and initial intensive decomposition temperature were defined by the curves of thermogravimetric analysis. Some mechanical and electrical properties of polythioesters from dithiol and adipoyl or sebacoyl chlorides were studied. The molecular weights for these polymers were also determined by gel-chromatography.     

Linear polythioesters. VIII. Products of interfacial polycondensation of 1,4-di(mercaptomethyl)-tetramethylbenzene with isomeric phthaloyl chlorides

New polythioesters by interfacial polycondensation of 1,4-di(mercaptomethyl)-tetramethylbenzene with phthaloyl, isophthaloyl, and terephthaloyl chlorides were obtained. To determine the optimal conditions of interfacial polycondensation the influence of the following factors on yield and value of reduced viscosity were studied: type of organic phase, the quantitative ratio of aqueous to organic phase, concentration of hydrogen chloride acceptor, molar ratio of reagents, rate of acid chloride addition, contribution of benzyltriethylammonium chloride as a catalyst, and the temperature of the reaction. The yield of all reaction products and the reduced viscosity of polythioesters which were soluble in the mixture of phenol-tetrachloroethane were found. A thorough examination was carried out only for the polycondensation of dithiol with isophthaloyl chloride. The structure of all polythioesters obtained under the model conditions was determined by elementary analysis and infrared spectra. Initial decomposition temperature and maximum rate of decomposition temperature were defined from the curves of thermogravimetric analysis. Some mechanical and electrical properties of the polythioesters were determined. The molecular weight was not measured because of the low solubility of the obtained polythioesters.     

Linear polythioesters. III. Products of interfacial polycondensation of 1,4-, 1,5-di(mercaptomethyl)-naphthalene,and their mixture with adipoyl and sebacoyl chlorides

New polythioesters of naphthalene derivatives by polycondensation of 1,4-di(mercaptomethyl)-naphthalene, 1,5-di(mercaptomethyl)naphthalene, as well as their mixture with adipoyl and sebacoyl chlorides have been obtained. Low-temperature and high-temperature solution polycondensation as well as interfacial polycondensation have been used. Interfacial polycondensation proved to be the most useful. To define the optimal conditions of interfacial polycondensation, the following factors influencing the process have been studied: ratio of aqueous to organic phase, concentration of hydrochloride acceptor, temperature of reaction and rate of addition of acid chloride, contribution of emulsifier and catalyst. Yield for all reaction products and reduced viscosity have been found. The structure of polythioesters of high-value viscosity and good yield was determined from elementary analysis, infrared spectra, x-ray, and thermogravimetric analysis. Some mechanical and electrical properties of the polythioesters obtained from the mixture of 1,4- and 1,5-di(mercaptomethyl)naphthalene have been studied after pressing in increased temperature. The molecular weight was not determined because of very low solubility.     

Linear polythioesters. II. Products of interfacial polycondensation of 1,4-di(mercaptomethyl)-naphthalene, 1,5-di(mercaptomethyl)naphthalene,and a mixture of 1,4- and 1,5-di(mercaptomethyl)-naphthalene with terephthaloyl and isophthaloyl chlorides

New polythioesters of naphthalene derivatives produced by interfacial polycondensation of 1,4-di(mercaptomethyl)naphthalene and 1,5-di(mercaptomethyl)naphthalene and their mixture with isophthaloyl and terephthaloyl chlorides were obtained. To define the optimal conditions of interfacial polycondensation the following factors that influence the process were studied: the ratio of the aqueous phase to the organic (water–benzene), the concentration of the hydrochloride acceptor, the contribution of emulsifier and catalyst, and the temperature of the reaction. Yield for all reaction products and the reduced viscosity of phenol–tetrachloroethane soluble in the mixture were found. The structure of polythioesters with high-value reduced viscosity and good yield was determined by elementary analysis, infrared (IR) spectra, and x-ray analysis; the glassy temperature, initial decomposition, and maximum velocity of decomposition were obtained by thermogravimetric analysis (TGA); and the thermal, mechanical, and electrical properties of the polythioesters were determined. Their molecular weight was not measured because of their low solubility. The good yields, short process time, and good chemical and thermal properties of the polymers showed that the interfacial polycondensation method could be effective in obtaining polythioesters by using aliphatic–aromatic dimercaptans of naphthalene with terephthaloyl and isophthaloyl chlorides.     

Linear polythioesters. I. Products of interfacial polycondensation of 4,4′-di(mercaptomethyl)benzophenone with terephthaloyl,isophthaloyl, and phthaloyl chlorides

New polythioesters have been obtained in the interfacial polycondensation of 4,4′-di(mercaptomethyl)benzophenone with terephthaloyl, isophthaloyl and phthaloyl chlorides. The reactions were carried out at room temperature with the use of 10% excess of acid chloride per mole of mercaptan with vigorous stirring (2000 rpm). The organic phase was composed of benzene and hexane in equal volumes and the ratio of this mixture to water also was 1:1. The structure of the polythioesters was determined from elementary analysis and the infrared spectra. The molecular weight was not determined because of the very low solubility of polythioesters. Some thermal, mechanical, and electrical properties of the products have been determined. Products of dimercaptan with the terephthaloyl and isophthaloyl chlorides show the best properties.     

Arylidene Polymers. V. Synthesis,Characterization, and Thermal Studies of New Polydibenzylidenecyclopentanonehydrazides Containing Aliphatic,Aromatic, Azo,Azomethine, and Thianthrene Moieties

A new [(2-oxo-l,3-cyclopentanediylidene)bis(methylidyne-p-phenyleneoxy)]diacetic acid dihydrazide III has been prepared via interaction of 2,5-bis(p-hydroxybenzylidene) cyclopentanone I with ethyl chloroacetate in basic medium to give diester II, followed by hydrazinolysis with hydrazine. The synthesized compounds were confirmed by IR, NMR, and elemental analyses. Unreported poly-hydrazides by the low temperature interfacial polycondensation technique of III with adipoyl, sebacoyl, 4,4′-diphenic, isophthaloyl, terephthaloyl, 4,4′-azodibenzoyl, 3,3′-azodibenzoyl, 4,4′[1,4-phenylene-bis(methylidynenitrilo)]dibenzoyl dichlorides, and 2,7-dichloroformylthianthrene-5,5′,10,10′-teraoxide were prepared. In order to characterize the polymers, a model compound was synthesized from III and benzoyl chloride. The resulting polyhydrazides were confirmed by IR, UV, viscometry, DSC measurements, and thermogravimetric analysis. The crystallinities of all polyhydrazides were investigated by x-ray analysis. The effect of the nature of different moieties on the properties of these polyhydrazides was explored by comparing their physical, spectral, thermal, and x-ray analysis data.     

Synthesis of inherently dissymmetric polyamides,

The preparation of polyamides from derivatives of optically active biphenic acid is described. The diacid chlorides chosen were 2,2′-dinitro-6,6′-dimethylbiphenyl-4,4′-dicarbonyl chloride and 2,2′-dichloro-6,6′-dimethylbiphenyl-4,4′-dicarbonyl chloride, the diamines were phenyldiamines (o-, m-, p-) piperazine, trans-2,5-dimethylpiperazine, and 1,2-piperaazolidine. Polymerization was carried out by the method of interfacial polycondensation. The polymers of aromatic diamines were insoluble in common organic solvents but soluble in dimethylformamide containing 5% lithium chloride, triesters of phosphoric acid, and methanesulfonic acid. The polymers of aliphatic diamines were also insoluble in common organic solvents but soluble in trifluoroethanol. All polymers had melting points higher than 280°C.     

Aryudene Polymers. II Synthesis and Characterization of some New Polyesters of Diarylidenecyclopentanone

New polyesters formed by interfacial polycondensation of 2,5-bis(4-hydrox-ybenzylidene)cyclopentanone (I) and 2,5-bis(4-hydroxy-3-methoxybenzyli-dene)cyclopentanone (II) with 4,47prime;-diphenic, isophthaloyl, terephthaloyl, adi-poyl, suberoyl, and sebacoyl dichlorides were obtained. The yield and the values of the reduced viscosity of the produced polyesters were found to be affected by the type of organic phase, the quantitative ratio of organic to aqueous phase, the concentration of the hydrogen chloride acceptor, and the contribution of benzyltriethylammonium chloride as a catalyst. In order to characterize these polymers, the necessary model compounds were prepared from I, II, and benzoyl chloride. The resulting polyesters were confirmed by IR, elemental analysis, viscometry, DTA, DSC measurements, and thermogravi-metric analysis. The crystallinities of all polyesters were examined by x-ray analysis, and the electrical properties of the polyesters were tested.     

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.     

Aromatic-aliphatic copolyesters—II. Various polycondensation processes

Aromatic aliphatic copolyesters, using hydroquinone, resorcinol, 4,4′-dihydroxybiphenyl (DHBP) 2,2 bis(4-hydroxyphenyl)propane and 4,4′-dihydroxydiphenyl sulphone (DHDPS) as bisphenols and ethylene glycol as diol, have been synthesized by interfacial, low temperature and high temperature solution condensation. Relative reactivities of these bisphenols and ethylene glycol have been evaluated by various polycondensation methods at a fixed ratio of bisphenol/glycol. Decrease in the extent of polymerization and viscosity was observed by incorporation of aliphatic diol. Viscosity was also influenced by the chemical structure of the bisphenol.     

A study of novel heat-resistant polymers: Preparation of photosensitive fluorinated polybenzoxazole precursors and physical properties of polybenzoxazoles derived from the precursors

A series of novel photosensitive polybenzoxazole precursors were prepared from polycondensation of 2,2-bis(3,3′-amino-4,4′-hydroxyphenyl)hexafluoropropane with photosensitive dicarboxylic acid chlorides such as p-phenylenediacryloyl chloride and benzophenone-4,4′-dicarboxylic chloride. The precursors are soluble in common organic solvents owing to the presence of perfluoromethyl groups in the chain structure, and insolubilized in the solvents on irradiation with the light. Polybenzoxazole patterns with high resolution as well as high aspect ratio were reproduced by baking the precursor patterns at 300°C. The pattern shrinkage on the conversion to polybenzoxazole was slight. The polybenzoxazole films offered good heat-resistance up to 400°C in addition to good electrical properties.     

Methylene-bridged aromatic polyesters. Synthesis,characterization, and radiation-induced crosslinking

Aromatic polyesters connected by methylene groups were synthesized. Two pairs of aromatic diacid chlorides, 3,3′-methylenedibenzoyl chloride and 4,4′-methylenedibenzoyl chloride were each polymerized via interfacial polycondensation with 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 3,3′-methylenediphenol, and 4,4′-methylenediphenol. For comparison, 3,3′-carbonyldibenzoyl chloride and 4,4′-carbonyldibenzoyl chloride were similarly polymerized with bisphenol A. Substitution of meta,meta' oriented phenylene groups for para,para' oriented phenylene groups had a significant and cumulative effect in reducing the glass transition temperatures of the polymers, thereby enhancing their processability. In air the methylene groups of the polyesters undergo oxidation and crosslinking at elevated temperatures. Electron beam irradiation of thin films of the methylene-linked polyesters at room temperature resulted in some chain extension and crosslinking, as evidenced by increased solution viscosity and gel formation. Irradiation at a temperature near or above the glass transition temperatures of the polymers greatly enhanced the tendency for the polymers to crosslink.     

Preparation and properties of brominated poly(arylcarboxylate)s via interfacial polycondensation

The interfacial polycondensation method has been used for the preparation of brominated poly(arylcarboxylate)s. Brominated poly(arylcarboxylate)s can be prepared easily by mixing a solution of diacid chloride in a water-immiscible organic solvent with an aqueous alkaline solution of bisphenol in the presence of catalyst such as quaternary ammonium salts. First, in a dichloromethane-water system using triethylbenzylammonium chloride (TEBAC) as the catalyst a series of 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane (3,3′,5,5′-tetrabromobisphenol A, TBBPA) with isophthaloyl (I) and terephthaloyl chlorides (T) has been prepared and some properties as inherent viscosity, solubility, crystallinity, and flammability have been measured. Copolymers prepared from TBBPA and mixed T/I with 33/67–67/33 molar ratios show good solubility and amorphous nature, and can be cast into transparent and tough films with limiting oxygen index of 58–59 (ANSI/ASTM D2683-77). Second, the effects of some variables as the nature of organic phase and catalysts, concentration of reactants, and basicity of aqueous phase on the interfacial polycondensation of TBBPA with equal parts of T and I [T/I (50/50)] was investigated in some detail. Among the solvents tested dichloromethane was found to be the best solvent and quaternary ammonium salts such as TEBAC and tetra-n-butylammonium bromide (TBAB) were highly efficient catalysts. Poly(arylcarboxylate)s with the highest molecular weights were obtained at an acid chloride concentration of 0.2 mol/L in dichloromethane and a concentration of TBBPA of 0.1 mol/L in alkali when TEBAC was used as catalyst. A maximum of inherent viscosity was obtained at two equivalent amounts of alkali corresponding to bisphenol. Polycondensation of several combinations of T/I (50/50) with some other tetrabromobisphenols, such as 3,3′,5,5′-tetrabromo-4,4′-biphenol, 3,3′,5,5′-tetrabromobisphenol S, 3,3′,5,5′-tetrabromo-4,4′-thiodiphenol, and 3,3′,5,5′-tetrabromophenolphthalein, were carried out with limited success. Whereas, a more favorable result could be obtained by the mixed copolycondensation of these tetrabromobisphenols and bisphenol A (BPA) with T/I (50/50). Finally, the copoly(arylcarboxylate)s from TBBPA, BPA, T, and I were prepared and characterized. The incorporation of bromine on the polymer backbone caused a decrease of inherent viscosity, glass transition temperature, crystallinity, and thermal stability of copolyarylates, whereas it caused a great enhancement of flame retardancy.     

Novel one-pot syntheses of sulfur-containing polymers from a bifunctional five-membered cyclic dithiocarbonate

Novel one-pot syntheses of sulfur-containing polymers from a bifunctional five-membered cyclic dithiocarbonate ( 1a ) were carried out. Polythiourethanes were obtained by the polyaddition of 4,4′-methylenebis(phenyl isocyanate), tolylene 2,6-diisocyanate, and hexamethylene diisocyanate with a dithiol ( 2a ) obtained by the reaction of 1a and benzylamine under mild conditions. Polythioesters were also obtained by the polycondensation of terephthaloyl and succinyl chlorides with 2a . Further, polythioether was obtained by the polycondensation of α,α′-dibromo-p-xylene with 2a . © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1189–1195, 1998     

Synthesis and Characterization of Polyesterimides Containing Ether Linkages

Abstract

Three novel dicarboxylic acids, bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl sulfone, bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl methane, and bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl ether, were synthesized, and several polyesterimides were prepared from diacid chlorides and bisphenols by solution polycondensation. The polymers were obtained in 65–88% yield and had inherent viscosities in the 0.18 to 0.64 dL/g range. The polymers were characterized by IR, elemental analysis, x-ray, TGA, DSC, and solubility tests. All the polymers were readily soluble in polar aprotic solvents and had a 10% weight loss temperature above 375°C in nitrogen.     

Polymers from 4,4′-thiodiphenol

Polyesters were made with aromatic diacid chlorides and 4,4,-thiodiphenol. Isophthaloyl chloride and/or terephthaloyl chloride were used as acid chlorides alone or together with 5-cyanoisophthaloyl chloride or [2.2]p-cyclophane-3,9-dicarboxylic acid chloride. The latter components were incorporated in order to make the polymers useful for crosslinking. A polyether could be obtained by polycondensation of 2,4-dichloro-benzonitrile and 4,4′-thiodiphenol. The polycondensations were run in nitrobenzene as solvent.     

Liquid crystalline semirigid polyesters based on phenylstilbene analogues of 1,3,4-thiadiazole

Semirigid polyesters composed of phenylstilbene analogues of 1,3,4-thiadiazole, 2-(2-phenylethenyl)-5-phenyl-1,3,4-thiadiazole (PEPT), linking an octamethylene chain at different disubstituted (3,3'-, 3,4'-, 4,3'- and 4,4'-) positions, were prepared from four diphenols of the PEPT and sebacoyl chloride by interfacial polycondensation. The effect of polymer structure on thermotropic liquid crystalline (LC) and optical properties is discussed. Differential scanning calorimetry (DSC) measurements, optical texture observations and powder X-ray diffraction patterns showed that the polymer linking the octamethylene chain at the 4,4'-position (4,4'-PEPT) has a linear structure and forms an enantiotropic nematic LC phase. Polymers linking the octamethylene chains at the 4,3'- (4,3'-PEPT), the 3,4'- (3,4'-PEPT) and the 3,3'-positions (3,3'-PEPT) positions have a less linear structure and display monotropic smectic phase or no LC phase. Solution and solid-state UV-visible and emission spectra indicated that the polyesters exhibit absorption maxima due to the PEPT moieties and fluoresce blue light, but low or no quantum efficiencies were recognized. The polyesters emitted weak polarized fluorescent light at room temperature.     

New processable poly(ether-keto-sulfone)s,poly(arylene sulfone)s,and polyesters curable by intramolecular cyclization. XVII

New processable polyaromatic ether-keto-sulfones were prepared from 2,2′-diiododiphenyl-4,4′-dicarbonyl dichloride (I), bis(p-phenoxybenzene)sulfone (V), isophthaloyl chloride (VI), terephthaloyl chloride (VII), and diphenylether (IX) in Friedel-Crafts-type polymerizations. By varying (VI):(VII) ratio and (V):(IX) ratio and by reducing the polymerization time, soluble, processable polymers were obtained. In these polymers, phenylacetylenyl groups were introduced by replacing the iodine. This process led to soluble and curable polymers. Transparent, tough films and fairly flexible glass fiber laminates can readily be prepared. After curing, the polymers were insoluble and showed excellent chemical and thermal resistance. The curing process increased the polymers' softening temperature by ca. 20°C and produced intersting new useful materials for laminates. Processable poly(arylene sulfone)s were prepared from I, V, and diphenylether-4,4′-disulfonylchloride (X) in a Friedel-Crafts-type polymerization. Different monomer ratios and polymerization times were used. Only low-molecular-weight polymers were obtained. The same result was shown by curable polyester formation from I, VI, VII, and 4,4′-sulfonyldiphenol (XI) in an interfacial polycondensation.