New processable polyaromatic ether-keto-sulfones as colorless,clear film-forming materials

New processable polyaromatic ether-keto-sulfones were prepared from 4,4′-diphenoxydiphenyl sulfone, terephthaloyl chloride, isophthaloyl chloride, and bis-p-carboxyphenylacetylene dichloride (IV) in a Friedel-Crafts-type polymerization. The white polymers obtained form colorless, transparent, strong films and can be cast into a glass-fiber laminate. One polymer was prepared which incorporated biphenylene-2,6-dicarboxylic acid dichloride as crosslinking sites; this heat-cured polymer was completely insoluble in sulfuric acid.     

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.     

Extended-chain polyamides: Polyoxamides and polyfumaramides

The synthesis of polyamides from short-chain aliphatic diacids, such as oxalic and fumaric acids, is difficult because of the thermal instability and volatility of the intermediates and side reactions with the polymerization media. A variety of synthetic routes to these polymers has been explored. Several aromatic polyoxamides with high molecular weight were obtained in high yield by an acid chloride vapor-solvent-water interfacial process. Polyoxamides of intermediate molecular weight also were obtained by preparation of oligomers from diamines and oxalic diesters and condensing these oligomers further in a thermal polymerization step. Aromatic polyfumaramides and terephthalamidefumaramides were prepared by modified solution procedures in amide solvents. Another route to polyfumaramides was the synthesis of N,N′-bis(4-aminophenyl) fumaramide and its use as a diamine with diacid chloride. The 1,4-phenylene and benzidine polyfumaramides and oxamides have extended-chain structures in solution in sulfuric, chlorosulfonic, and fluorosulfonic acids. Some of the polymers were soluble enough to yield liquid crystalline solutions. High-tenacity high-modulus fibers from poly(1,4-phenylene fumaramide/terephthalamide)s are described.     

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.     

Suspension polymerization of vinyl chloride initiated by in situ generated diisobutyryl peroxide

It was found that diacyl peroxides can be formed in situ in a polymerization medium by the reaction of an acid anhydride with hydrogen peroxide. For the specific application to aqueous vinyl chloride polymerization, an initiator system based on the base-catalyzed reaction of isobutyric anhydride with hydrogen peroxide to produce diisobutyryl peroxide gave very good results. In contrast, the acid chloride was completely ineffective as a peroxide precursor in this reaction. Studies pointing to diisobutyryl peroxide as the initiating species; investigations of reactant stoichiometry; and comparison of the in situ system with preformed diisobutyryl peroxide were conducted. It was shown that this system makes possible the polymerization of vinyl chloride at 30°C at rates comparable to those obtained with dialkyl peroxydicarbonates at 50°C, thus demonstrating the ability of this system to initiate vinyl chloride polymerization at low temperature. The rates of vinyl chloride polymerization with the use of different concentrations of in situ diisobutyryl peroxide at 30, 40, and 50°C were determined. Similarly, polymerization rates with the use of combinations of in situ diisobutyryl peroxide and n-propyl peroxydicarbonate were determined. The data obtained demonstrate rapid initiation of the polymerization reaction and a reduction in polymerization time made possible by this dual initiator system. These results were verified in pilot-plant and commercial-scale PVC polymerizations.     

Electrochemical polymerization of thianaphthene

Thianaphthene has been electrochemically polymerized in pure boron trifluoride diethyl etherate (BFEE) solution or in a mixed electrolyte of BFEE and concentrated sulfuric acid (SA). The addition of a certain amount of sulfuric acid into BFEE accelerated the polymerization and also increased the current efficiency of the electrosynthesis. Poly(thianaphthene) (PTN) in the dedoped state is soluble in usual strong polar organic solvents such as dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF) and N-methyl pyrrolidinone (NMP). Its structure has been examined by infrared, H¹-NMR and UV spectra. Fluorescent spectral studies indicate that the polymer is a strong blue light emitter.     

Solid-state polymerization of butadienes. Polymerization of salts of 6-amino-2,4-trans,trans-hexadienoic acid

The polymerization of 6-amino-2,4-trans,trans-hexadienoic acid and various of its salts was studied in the solid state. Crystals of the hydrochloride and organic inorganic double halides with cadmium chloride, manganese (II) chloride, and iron(II) chloride were found to polymerize rapidly upon UV or γ irradiation. An erythro-diisotactic polymer is obtained in the form of extended chain crystals. The polymer behaves as an amphoteric polyelectrolyte. The kinetics and the mechanism of the polymerization as well as morphological changes during the solid state reaction are discussed.     

Polymerization of methyl methacrylate initiated by Mn(III)–glycerol redox system

The kinetics of thermal polymerization of methyl methacrylate initiated by the redox system Mn(III)–glycerol was studied in aqueous sulfuric acid in the temperature range of 30–40°C, and the rates of polymerization, R_p, and Mn³⁺ disappearance, etc., were measured. The effect of certain water-miscible organic solvents and certain cationic and anionic surfactants on the rates of polymerization has been investigated. A mechanism involving the formation of a complex between Mn³⁺ and glycerol whose decomposition yields the initiating free radical with the polymerization being terminated by the metal ion has been suggested.     

Regular Copolyamides. IX. Some Aliphatic Aromatic Copolyoxamides

Abstract

Aromatic/aliphatic regular copolyoxamides were prepared from aromatic diamine-oxamides and aliphatic diacid chlorides of various lengths of methylene groups by solution polymerization. The aromatic diamine oxamides, N,N′-bis(4-aminophenyl)oxamide and N,N′-bis(3-aminophenyl)oxamide were prepared and both were reacted with adipoyl chloride, suberoyl chloride, and sebacoyl chloride to form six new regular copolyoxamides. The polymers formed were soluble in sulfuric acid and also in some polar amide solvents. All copolyoxamides were high melting, with the meta-phenylene copolyoxamides melting from 346 to 373°C with decreasing length of the aliphatic diacid chloride, and the para-phenylene copolyoxamides decomposing prior to melting at near 400°C. The new polymers were characterized by UV spectrophotometry, differential scanning calorimetry, and thermal gravitational analysis.     

Polyaromatic ether-ketone-sulfones containing 1,3-butadiene units

The acid chloride of 1,4-bis-p-carboxyphenyl-1,3-butadiene (XI) and isophthaloyl chloride (XIV) were polymerized with 4,4′-diphenoxy-diphenyl sulfone (XII) and diphenyl ether (XIII) in a Friedel-Crafts type of polymerization. The polymers obtained, which contained 5–20 mole % of butadiene units, were insoluble in all solvents. The polyamides prepared from the acid chloride of 1,4-bis-p-carboxyphenyl-1,3-butadiene (XI) and aromatic diamines were also insoluble in all solvents.     

Kinetics of polymerization of acrylic acid initiated by Mn3+–isobutyric acid redox system. II

The kinetics of redox -initiated polymerization of acrylic acid (AA) by the systerm Mn³⁺-isobutyric acid (IBA) in sulfuric acid was studied in the temperature range of 35–50°C. The overall rates of polymerization (R_p), disappearance of manganic ion (?R_m), and degree of polymerization (X _n), were measured with variation in [monomer], [Mn³⁺], [IBA], H⁺, μ, [Mn²⁺], and temperature. The polymerization is initiated by the organic free radical that develops from the Mn³⁺-isobutyric acid oxidation reaction. Two types of termination reactions, one by the metal ion (Mn³⁺) and the other by the MN³⁺-isobutyric acid complex are proposed to explain the kinetic results. The various rate parameters were evaluated an discussed.     

Effect of Glycerol in the Polymerization of Methyl Methacrylate by Mn(III) Acetate

The kinetics of the mechanism of the polymerization of methyl methacrylate initiated by the glycerol/Mn(III) acetate redox system has been investigated in aqueous sulfuric acid medium in the temperature range of 40 to 50 °C. The effects of glycerol, methyl methacrylate, metal ion, acetic acid, and sulfuric acid on the rates of polymerization have been studied. One striking observation is that the increase in monomer concentration steadily decreases the rate of polymerization, contrary to what was observed in the case of acrylonitrile. On the basis of these observations, an appropriate kinetic scheme and rate expression have been developed.     

Polymerization of acrylonitrile. Kinetics of the reaction initiated by the Ce(IV)/thioacetamide redox system

Vinyl polymerization of acrylonitrile initiated by the Ce(IV)/thioacetamide redox system has been investigated in aqueous sulfuric acid in the temperature range of 10–20°C. The rate of polymerization (R_p) and the rate of Ce(IV) disappearance (?R_Ce) were measured. The effect of certain water-soluble organic solvents, added electrolytes, and aromatic and heterocyclic organic nitrogen compounds on the rate of polymerization has been investigated. Depending on the experimental results, we have suggested a suitable reaction scheme for the system which involves the production of initiating radicals from the oxidation of thioacetamide (TAm) by ceric ion and the termination of the polymer chain by metal ions.     

Oxidative polymerization of acrylamide in the presence of thioglycolic acid

Chemical polymerization of acrylamide at room temperature was examined by using thioglycolic acid-cerium (IV) sulfate and thioglycolic acid-KMnO₄ redox systems in acid aqueous medium. Water soluble polyacrylamides containing thioglycolic acid end groups were synthesized. The effects of the molar ratio of acrylamide to Ce(IV) n _AAm /n _Ce(IV) , the polymerization time, the temperature, the monomer concentration, the molar ratio of cerium (IV) sulfate to thioglycolic acid and the concentration of sulfuric acid on the yield and molecular weight of polymer were investigated. Lower molar ratios of acrylamide/Ce(IV) at constant monomer concentration resulted in an increase in the yield but a decrease in molecular weight of polymer. The increase of reaction temperature from 20 to 70°C resulted in a decrease in the yield but generally resulted in a constant value for the molecular weight of polymer. With increasing polymerization time, the yield and molecular weight of polymer did not change substantially. Ce(IV) and Mn(VII) ions are reduced to Ce(III) and Mn(II) ions respectively in the polymerization reaction. The existence of Ce(III) ion bound to polymer was investigated by UV-visible spectrophotometry and fluoresce measurements. The amount of Mn(II) incorporated into the polymer was determined using graphite furnace atomic absorption spectrometry. The mechanism of this phenomenon is 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.     

Synthesis of Some Selectively N-Protected (1S,2S)-p-Nitrophenylserinol–Based Diamino-1,3-dioxanes and Tripodands

The unconventional methodology for the non-epimerizable cycloacetalization of optically active (1S,2S)-2-amino-1-(4-nitrophenyl)propane-1,3-diol (p-nitrophenylserinol) (condensed H₂SO₄ 96% as solvent and catalyst, i.e., sulfuric transacetalization) producing (2R,4S,5S) diamino-1,3-dioxanes was enlarged by the use of N-protected forms of 2,2-dimethoxyethylamine (DMEA, aminoacetaldehyde dimethylacetal). Conversely, N-protected derivatives of p-nitrophenylserinol were successfully cyclocondensed with DMEA in the same sulfuric conditions. N-Functionalization of DMEA upon treatment with trimesic acid trichloride and cyanuric chloride yielded the corresponding triple amide and melamine, respectively. Their adapted sulfuric transacetalization in triplicate in reaction with arylserinols (aryl: phenyl, p-nitrophenyl) afforded a new series of optically active tripodands.     

Application of the Sulfuric Acid-Halide Salt Reaction to the Analysis of Sulfuric Acid Containing Aerosols

Abstract

A new X-ray fluorescence method for the determination of sulfuric acid in sulfuric acid containing aerosols is presented. The technique makes use of the reaction between sulfuric acid and potassium chloride yielding volatile hydrogen chloride and thus changing the C1/K ratio. Nuclepore^R membrane filters are first loaded with potassium chloride and then used for the collection of the aerosol under study. The chlorine and potassium X-ray signals are measured before and after the sampling of the acid aerosol, and the decrease in the Cl/K intensity ratio is taken as a measure for the amount of sulfuric acid collected.     

Polymerization of 1,3,5-Tri(1,3,5,7-tetra)-methyl-1,3,5-tri(1,3,5,7-tetra)-10-carbomethoxydecylctri(tetra)siloxane

The cationic and anionic polymerization of 1,3,5-tri(1,3,5,7-tetra)methyl-1,3,5-tri (1,3,5,7-tetra)-10-carbomethoxydecylcyclotri (tetra) siloxane, catalyzed by sulfuric acid and alkali metal naphthalenes, respectively, was studied. With sulfuric acid the polymer yield increased with increasing catalyst concentration, while the molecular weights decreased. With potassium naphthalene the polymerization reaction was first order to monomer, and the molecular weights increased linearly with increasing the percent conversion in accordance with a “living” polymerization. In both cases the polymerization was an equilibrium reaction and the conversion was about 85%. Only low molecular weight polymers were obtained due to steric effects of the bulky long-chain substituents.     

锰(Ⅲ)离子与羧酸或α-羟基羧酸体系引发丙烯酰胺聚合

锰(Ⅲ)离子可以引发烯类单体自由基聚合。羧酸,α-羟基羧酸对丙烯酰胺聚合有促进作用,其活性顺序为羟基多元羧酸(柠檬酸)>羟基羧酸(乳酸)>羧酸(正丁酸)。测定了在较高酸性([H~+]=3.0M)的硫酸水溶液中,单独Mn~(3+),Nn~(3+)-乙醇酸,Mn~(3+)-乳酸引发丙烯酰胺聚合的活化能与动力学方程。     

Cobalt Porphyrazines with Heterocyclic Substituents

Reactions of 4,5-diaminophthalodinitrile with thionyl chloride, sodium nitrite in concentrated sulfuric acid, and phenanthrenequinone gave, respectively, 5,6-dicyano-2,1,3-benzothiadiazole, 5,6-dicyano- 1H-benzotriazole, and 6,7-dicyano-2,3-(9,10-phenanthro)quinoxaline, from which the corresponding cobalt porphyrazines were prepared. The effect of the heterocyclic moiety on the physicochemical and spectral properties of porphyrazines was elucidated.