Dichlorodiphenyl Sulfone Research Articles

Synthesis of a novel macrocyclic arylene ether sulfone

The synthesis in two steps of a macrocyclic arylene ether sulfone, 4, is reported. In the first step dichlorodiphenylsulfone (1) was substituted with two Bisphenol A (2) moieties by a nucleophilic substitution reaction using three solvents and reagent systems: (a) K 2 CO 3 /DMAc, (b) NaH/DMF or (c) KOH/DMSO. The products was cyclized with dichlorodiphenyl sulfone to form 4 using the first and second procedures. 4 was found to be thermally stable up to 572°C under nitrogen with 60% degradation at 616°C

Synthesis and characterization of new aromatic sulfone ether polyamides containing pendant pentadecyl groups

AbstractA series of new polyamides and copolyamides containing aromatic sulfone ether linkages was synthesized from 4,4′‐[sulfonyl‐bis(4,1‐phenyleneoxy‐3‐pentadecyl)]bisphenylamine (SPPBA) and isophthaloyl chloride (IPC), terephthaloyl chloride (TPC), bis(4‐chlorocarbonylphenyl)dimethylsilane (DMSC) and bis(4‐chlorocarbonylphenyl)diphenylsilane (DPSC) by a low‐temperature inter‐facial polymerization technique. SPPBA was prepared from 4,4′‐dichlorodiphenyl sulfone and 4‐amino‐3‐pentadecyl phenol derived from cashew‐nut shell liquid and was characterized by spectral methods and elemental analysis, whereas the polyamides were characterized by solution viscosity, IR spectroscopy, thermogravimetric analysis, X‐ray diffraction and solubility. These polyamides showed enhanced solubility in organic solvents and no weight loss below 405°C in nitrogen. The effect of pendant penladecyl substituents and silicon in the main chain of polyamides on the properties of these polymers was studied by comparing their properties with those of unsubstituted polyamides prepared from 4,4′‐[sulfonylbis(4,1 ‐phenyleneoxy)] bisphenylamine.

New polymer syntheses, 47. Synthesis of aromatic polyethers from silylated diphenols and activated dichloro‐substituted aromatics

AbstractBis(trimethylsilyl)bisphenol‐A was condensed with 4,4′‐dichlorodiphenyl sulfone under various reaction conditions. Satisfactory yields and molecular weights of the resulting poly(ethersulfone)s were only obtained when the condensation was conducted in amide solvents (e. g., N‐methyl‐2‐pyrrolidone) in the presence of equimolar amounts of K2CO3. The purity of the solvent plays an important role for the molecular weights. By light scattering, weight‐average molecular weights (Mw's) up to 130000 were found. Further polycondensations were conducted with 2,6‐dichlorobenzonitrile, 2,6‐dichloropyridine or 3,6‐dichloropyridazine. For polyethers derived from 2,6‐dichlorobenzonitrile Mw's up to 106000 were found and for copoly(pyridine‐ether‐sulfone)s Mw's up to 220 000. The corresponding difluoroaromatics gave similar results. In contrast to the polycondensation of free diphenols with dihaloaromatics under alkaline conditions, no water is formed when silylated diphenols are used.

The Properties of 'RADEL R' Polysulfone

A series of aromatic polyethersulfones based on biphenol and dichlorodi phenylsulfone have been prepared and fractionated. The fractions have been character ized by light scattering and intrinsic viscosity measurements. The characteristic ratio C ∝ = 1.96 which is in agreement with the freely rotating nature of the polyethersulfone chain. The molecular weight dependence of the glass transition temperature is established. The low temperature β-transition is at -113°C when measured at 1 rad/s with a mechanical spectrometer.

Incommensurate Phase Transition in 4,4'-Dichlorodiphenyl Sulfone

The structural phase transition in a 4,4 ′ -dichlorodiphenyl sulfone single crystal was investigated by means of X-ray diffraction. It has been found that the crystal shows the normal-incommensurate phase transition at 150 K with the modulation wavevector q = a * ±(1/5+δ) b * , where a * and b * represent the reciprocal lattice vectors in the normal phase and δ represents the small misfit parameter in the incommensurate phase. No lock-in phase transition was confirmed within the temperature range 20-150 K.

Effect of antiplasticization on gas sorption and transport. I. Polysulfone

AbstractThe addition of tricresyl phosphate, N‐phenyl‐2‐naphthylamine, and 4,4′‐dichlorodiphenyl sulfone to polysulfone causes changes in thermal and mechanical properties of the glassy mixtures associated with antiplasticization, i.e., reduction in glass transition temperature and increase in stiffness. These changes are also found to be accompanied by reductions in sorption of carbon dioxide and the permeability coefficients for helium, carbon dioxide, and methane at low diluent concentrations with reversal of these trends at higher levels as also occurs for the mechanical properties. Detailed analyses of data for carbon dioxide are given in terms of the dual sorption and mobility models often used for glassy polymers. The mobility for gas transport was found to decrease with diluent addition. The major cause for the decreased sorption is the reduction in glass transition temperature accompanying addition of the diluents. The changes in transport behavior approximately parallel the changes in mechanical behavior. These trends are not even qualitatively correlated with estimates of the excess volume changes associated with addition of the diluents to polysulfone.

ChemInform Abstract: Synthesis and Anthelmintic Activity of 2,2′‐Disubstituted 5,5′‐Dibenzimidazolylsulfides and Sulfones.

A number of substituted diphenylsulfides and sulfones (4-11) and 2,2'-disubstituted-5,5'-dibenzimidazolyl sulfides and sulphones (12-19) have been synthesized starting from 5-chloro-2-nitroacetanilide and (3) 4,4'-dichlorodiphenyl sulfone (9), respectively. Among the compounds tested against Ancylostoma ceylanicum in hamsters and Hymenolepis nana in rats and mice, 14, 15, 18 and 19 removed 100% of the worms at an oral dose of 25 mg/kg X 1 to 250 mg/kg X 3. Some of the compounds were tested for their blood schizontocidal activity against Plasmodium berghei in mice but none showed any activity up to an oral dose of 10 mg/kg given for 6 days.

Radiation resistant amorphous–all aromatic polyarylene ether sulfones: Synthesis, characterization, and mechanical properties

AbstractThe synthesis and characterization of amorphous, aromatic, polyaryl ethers has been investigated. Detailed synthesis procedures are provided. The main thrust of these activities was to synthesize polymers which could serve as castable amorphous matrix resins for carbonfiber composites and which would be highly resistant to radiation degradation. It was important that these polymers not contain any aliphatic groups in order to contrast their behavior with the commercially available Bisphenol‐A polysulfones. The approach taken was to synthesize a series of statistical or random copolymers derived from hydroquinone and biphenol together with 4,4′‐dichlorodiphenyl sulfone. In order to produce copolymers of high molecular weight, modified techniques were developed which utilized potassium carbonate as a weak base and N‐methyl‐2‐pyrrolidone as the aprotic dipolar solvent. Detailed procedures are provided in this paper for the synthesis of high molecular weight copolymers of this type. In addition, stress‐strain, dynamic mechanical properties and preliminary electron beam (e‐beam) degradation studies are reported significantly. Improved mechanical property retention after e‐beam exposure was observed with the all aromatic polyether sulfones.

Bisindoles. 7. Synthesis of di(5-indolyl) sulfone

The parent compound of a new heterocyclic system, viz., di(5-indolyl) sulfone, was synthesized by the classical scheme of the Fischer reaction by means of polyphosphoric acid. The starting dihydrazine was obtained from 4,4'-dichlorodiphenyl sulfone.

Characterization of 4,4'-dichlorodiphenyl sulfone impurities by gas chromatography and mass spectrometry

Characterization of 4,4'-dichlorodiphenyl sulfone impurities by gas chromatography and mass spectrometry

High temperature polymers. I.—Sulfone ether diamines as intermediates for tractable high temperature polymers

AbstractA useful synthesis of a series of new aromatic sulfone ether diamines, H2NC6H4O\documentclass{article}\pagestyle{empty}\begin{document}$\hbox{---}\hskip-5pt[\ {\rm C}_{\rm 2} {\rm H}_{\rm 4} {\rm SO}_{\rm 2} {\rm C}_{\rm 6} {\rm H}_{\rm 4} \hbox{--} {\rm ORO}\hbox{---}\hskip-5pt ]_n {\rm OC}_{\rm 6} {\rm H}_{\rm 4} {\rm SO}_{\rm 2} {\rm C}_{\rm 6} {\rm H}_{\rm 4} \hbox{---} {\rm OC}_{\rm 6} {\rm H}_{\rm 4} {\rm NH}_{\rm 2} $\end{document}, where n = 0, 1, 2…, which increases the tractability of polyimides, polyamide‐imides, and polyamides, was developed. These diamines were prepared by condensing various proportions of sodium p‐aminophenate, sodium bisphenates, and dichlorodiphenyl sulfone. The synthetic procedures are now refined to the point where simply coagulating these diamines into water yields high purity polymer‐grade sulfone ether diamines. The latter have good tractability; and in some cases, it is possible to extrude and injection‐mold these high temperature polymers.

Aromatic sulfonation 20: The sulfonation of some chlorobenzenes with sulfur trioxide in nitromethane as solvent

AbstractThe sulfonation of chlorobenzene and p‐dichlorobenzene with sulfur trioxide in nitromethane as solvent has been studied. The main reaction products are arenesulfonic anhydride and probably arenepyrosulfonic acid. With p‐dichlorobenzene as substrate the amount of diaryl sulfone is undetectably small; with chlorobenzene it is < 1‐mole % relative to the converted substrate. The sulfonation is of the first order with respect to the substrate and of the second order with respect to sulfur trioxide. For each mole of converted substrate two moles of sulfur trioxide are consumed. The sulfonation of p‐dichlorobenzene proceeds without a primary kinetic isotope effect of hydrogen.It is suggested that the sulfonation proceeds via 1‐arenonium‐1‐sulfonate and 1‐arenonium‐1‐pyrosulfonate as the subsequent reactive intermediates, with the formation of the latter intermediate as the rate‐limiting step. The kinetics of the formation of 4,4′‐dichlorodiphenyl sulfone are compatible with a mechanism in which the species p‐ClC6H4S3O9H is the effective sulfonylating entity.The literature on aromatic sulfonation with sulfur trioxide in aprotic solvents is critically reviewed.

Poly(Aryl ethers) by nucleophilic aromatic substitution. II. Thermal stability

AbstractThe thermal stability and degradation process for a specific poly(aryl ether) system have been studied. In particular, the polymer which is available from Union Carbide Corporation as Bakelite polysulfone has been examined in detail. Polysulfone can be prepared from 2,2‐bis(4‐hydroxyphenyl)propane and 4,4′‐dichlorodiphenyl sulfone by nucleophilic aromatic substitution. Because of a low‐temperature transition at − 100°C. and a glass transition at 195°C., polysulfone retains useful mechanical properties from −100°C. to 175°C. A number of experimental methods were utilized to study the thermal decomposition process for this polymer system. Polysulfone gradually degraded in vacuum above 400°C. as demonstrated by mass spectrometry. Thermogravimetric analysis in argon, air, or high vacuum indicated that rapid decomposition began above 460°C. From gas chromatography, mass spectrometry and repeated laboratory pyrolyses, a number of products from polymer decompositions were identified. The most important degradation process in vacuum or inert atmosphere was loss of sulfur dioxide. Several model compounds representative of portions of poly(aryl ether) molecules were synthesized and the relative thermal stabilities determined. Possible mechanisms for pure thermal decomposition of polysulfone were derived from the product analyses, model studies, and consideration of bond dissociation energies.

Poly(aryl ethers) by nucleophilic aromatic substitution. I. Synthesis and properties

AbstractA series of new aromatic polyethers have been prepared by solution condensation polymerization. The synthesis involves the condensation of a dialkali metal salt of a dihydric phenol with an “activated” or negatively substituted aromatic dihalide in an anhydrous dipolar aprotic solvent at elevated temperatures. The reaction is rapid, free of side reactions, and yields polymers of excellent color. Bakelite polysulfone can be prepared in this manner by reaction of the disodium salt of bisphenol A with 4,4′‐dichlorodiphenyl sulfone in dimethyl sulfoxide (DMSO). Only dipolar aprotic solvents are useful for conducting the polymerization. Of these, DMSO and Sulfolane (tetrahydrothiophene 1,1‐dioxide) are the most effective. Water or other competing nucleophiles must be absent if high molecular weight is to be obtained. Besides providing the necessary solubility, this highly polar solvent is believed to be essential in providing the rapid polymerization rates observed. The rates are further found to depend on the basicity of the bisphenol salt and upon the electron‐withdrawing power of the activating group in the dihalide. As is usual for this type of reaction, the difluorides are found to be more reactive than the corresponding dichlorides. Most of the polyethers are amorphous, rigid, tough thermoplastics with high second‐order transitions (Tg). Thermal stability and electrical properties are noteworthy. These and other properties are described for polysulfone, and glass transitions are given for a selected list of the other polyethers.

Poly(aryl ethers) by nucleophilic aromatic substitution. III. Hydrolytic side reactions

AbstractThe molecular weight of polysulfone, i.e., the aryl polyether that is prepared by the reaction of the disodium salt of bisphenol A with 4,4′‐dichlorodiphenyl sulfone in dimethyl sulfoxide (DMSO) solvent is shown to depend, among other things, on the moisture content of the polymerizing system. In the presence of water, hydrolysis of the sulfone monomer occurs concomitant with the polymerization. This leads to a deviation from the desired 1:1 ratio of coreactant groupings and therefore in attendant reduction in possible molecular weight. The hydrolysis is shown to lead to the formation of the sodium salt of 4‐chloro‐4′‐hydroxydiphenyl sulfone and to a lesser extent polymer derived from self‐condensation of this salt. At low levels this salt is essentially inert towards the principal polymerization at hand but in somewhat greater amounts functions as an effective chain terminator. Similar hydrolysis of polysulfone chloro endgroups is believed to occur under the aqueous conditions of polymerization but to a lesser extent than for the sulfone monomer. It is shown that polysulfone or similar polyethers are subject to chain cleavage by bases in DMSO solvent. The base attacks the activated position para to the sulfonyl group with the formation of a chain terminating in a bisphenol A type phenolic group and a chain terminating in a phenolic group of the bisphenol S (p‐hydroxyphenyl sulfonyl) type. It is shown that cleavage is probably not important under normal conditions of polymer formation. The effect of these hydrolytic side reactions on the attainment of high molecular weight under conditions of imperfect reaction stoichiometry is shown to be consistent with the above conclusions.