Polymers having stable radicals. I. Synthesis of nitroxyl polymers from 4-methacryloyl derivatives of 2,2,6,6-tetramethylpiperidine

Polymers having stable nitroxyl free radicals, poly-4-methacryloylamino- and poly-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyls, were synthesized from their precursor polymers by oxidizing them in a methanolic solution of hydrogen peroxide. The precursor polymers were prepared by radical polymerization of 4-methacryloyl-amino/oxy-2,2,6,6-tetramethylpiperidines in various solvents. These polymerizations in acetic acid were found to yield polymers of high molecular weight. The copolymers of the precursor monomers with styrene and methyl methacrylate were also prepared as precursor copolymers. These precursor polymers of a piperidine type were converted to the polymers having stable nitroxyl free radicals by the hydrogen peroxide method. In this report, it was assumed that the post-oxidation reaction introduced a nitroxyl group smoothly and quantitatively at room temperature. Elucidations of the stable radical formation and the electron spin behavior of the stable radical polymers were made in terms of elemental analyses, infrared, ultraviolet, and ESR spectroscopy.     

Computer-simulated ESR spectra of irradiated poly(olefin oxides)—effect of glass transition temperature on the ESR spectra

Investigations on the effects of γ irradiation on poly(methylene oxide) (POM) and poly(ethylene oxide) (PEO) have been made employing electron spin resonance (ESR) spectroscopy. The ESR sextet and doublet spectra, recorded for POM and PEO, respectively, on irradition in air at room temperature are broadened as the temperature is lowered and show a reversible change in line shape with temperature. The spectra are analyzed by computer simulation, employing Lorentzian line-shape functions and the least-squares method of total curve fitting. The component spectra are evaluated and are assigned. Superposition of the component quartet, triplet, and doublet spectra, corresponding to the radicals ?H₃, ?H₂O , and O?HO , respectively, together with a singlet due to the radicals ?CH₂ is considered to be the best fit to the observed spectrum for POM. The doublet spectrum recorded for PEO has been assigned to the radicals ?HO . The reversible broadening of the spectra has been associated with the mechanism of molecular motions around the glass transition temperatures of these polymers.     

The Radicals and Radical Dianions of Bridged [11]- and [15]Annulenyls as Compared with Those of Benzotropyl and 2,3-Naphthotropyl

The 1,6-methano[11]annulenyl ( 1 ·), 1,6:8, 14-propane-1,3-diylidene[15]annulenyl ( 2 ·), benzotropyl ( 3 ·) and 2,3-naphthotropyl ( 4 ·) radicals have been characterized by their ESR. spectra. The corresponding radical dianions, , , and , have also been studied both by ESR. and ENDOR. spectroscopy. Assignment of the coupling constants a_Hμ to protons in the individual positions μ of these radicals and radical dianions is to a large extent based on investigations of specifically deuteriated derivatives. The radicals 1· , 2· , 3· and 4· exist in temperature-dependent equilibria with ( 1 )₂, ( 2 )₂, ( 3 )₂ and ( 4 )₂, respectively, where ( 1 )₂ to ( 4 )₂ denote mixtures of dimers of 1 · to 4 ·. The dissociation enthalpies, ΔH°, of ( 1 )₂ (102 kJ/mol) and ( 2 )₂ (88 kJ/mol) are considerably smaller than those of ( 3 )₂ and ( 4 )₂ which do not significantly differ from the ΔH° value of bitropyl (139 ± 6 kJ/mol). This finding indicates that the gain in π-electron delocalization energies, Δ(DE)_π, upon dissociation markedly increases on going from bitropyl, ( 3 )₂ and ( 4 )₂ to ( 1 )₂ and ( 2 )₂, and thus points to an additional ‘resonance stabilization’ of 1 · and 2 ·, as compared with 3 · and 4 ·. A more pronounced π-spin localization on the 7-membered ring is observed in 3 ·, 4 ·, and relative to the corresponding species, 1 ·, 2 ·, and . It can be interpreted in terms of simple π-perimeter models without explicitly invoking substantial homoconjugative interactions between the bridged centres in 1 ·, 2 ·, and . However, the shortcomings of these crude models do not allow one to make a clear-cut statement about the contributions of the homotropyl structures to the π-systems of these paramagnetic species. The radical dianions and exhibit considerable hyperfine splittings from one ²³Na or ³⁹K nucleus of the counter-ion, whereas for and such splittings stem from two equivalent alkali metal nuclei. This finding is readily rationalized by different geometries of the bridged annulenyls and their benzo- and naphthotropyl analogues. Hyperfine data are also given for the radical anions of 7 H-benzocycloheptene, ( 3-H )\documentclass{article}\pagestyle{empty}\begin{document}$2^{\ominus \atop \dot{}}$\end{document}, and 6 H-(2,3-naphtho)cycloheptene, ( 4-H )\documentclass{article}\pagestyle{empty}\begin{document}$2^{\ominus \atop \dot{}}$\end{document}, as well as for the radical dianion of 1,6:8,14-bismethano[15]annulenyl, 5 \documentclass{article}\pagestyle{empty}\begin{document}$2^{\ominus \atop \dot{}}$\end{document}.     

Lösungsthermodynamik von FeCl2 in Mischschmelzen aus Alkalichloriden und LaCl3 bzw. CeCl3

Solution Thermodynamics of FeCl₂ in Molten Mixtures of Alkaline Chlorides and LaCl₃ or CeCl₃ Activity coefficients and the chemical excess potential of FeCl₂ dissolved in molten chloride mixtures were determined by EMF measurements with galvanic cells of the type in the concentration range from 0.01–5 mole-% at 720 and 820°C. An average cationic potential is defined and used to calculate a distance parameter () for the different solvent melt mixtures. may be estimated by equations of the type      

Beiträge zur Komplexchemie der Phosphine und Phosphinoxide,XXVIII. Übergangsmetall-aminoalkylphosphin-Komplexe Teil 2: Palladium- Und Platinkomplexe

On the Coordination Chemistry of Phosphines and Phosphine Oxides. XXVIII. Transition Metal Aminoalkylphosphine Complexes. Part II: Palladium and Platinum Complexes Aminoalkylphosphines – C₆H₅HP? CH₂ · CH₂? , (C₆H₅)₂P? CH₂ · CH₂ · CH₂? NH₂, (C₆H₅)₂P? CH₂ · CH₂ · CH₂? N?CHC₆H₅ – react with palladium and platinum salts to give coordination compounds of the type MX₂, MX₂()₂, and MX₂()₄ (M = Pd, Pt; X = Cl, BPh₄). The chelating activity of the ligands, structure and properties of the metal complexes are discussed.     

The Electronic Structure of Pentaprismane (C10H10), as Revealed by its Photoelectron Spectrum

The photoelectron (PE.) spectrum of the title compound has been assigned by comparison with the PE. spectrum of cubane ( 2 ), aided by ab initio STO-3G calculations using localized molecular orbitals. On the basis of the information available to date, the most satisfactory orbital sequence, Koopmans theorem implied, is, in descending order of energy: band system : (2e″₂, 3e′₂ 2e″₁, 3e′₁); band system : 3a′₁ (2e′₂, 2a″₂); band : 2e′₁.(Sequence of orbitals in parenthesis uncertain).     

Über Oberflächenverbindungen von Übergangsmetallen. VIII. Die Komplexbildung von koordinativ ungesättigtem Oberflächen-Chrom (II) mit Oxiden des Stickstoffs

On Surface Compounds of Transition Metals. VIII. Complex Formation of a Coordinatively Unsaturated Cr^II Surface Compound with Nitrogen Oxides N₂O forms with surface-Cr(II) a relatively unstable light blue compound of the stoichiometry 1:1, while addition of NO results in formation of a very stable dark brown, diamagnetic surface complex . By reaction with O₂ this complex undergoes — depending on reaction temperature — either replacement of NO unter reoxidation of the metal (→Cr(VI)) or/and reaction of the ligand (→NO₂). Direct reaction of NO₂ with results in the same products as stepwise addition of NO and 1/2 O₂. reacts with HCl/ROH under formation of the soluble, paramagnetic kation [Cr(NO)(ROH)_n]²⁺, which is formulated as [Cr(II)(NO)]²⁺ ? [Cr(I)(NO⁺)]²⁺ accordingly to the e.s.r. spectra.     

13C NMR spectra of 2,3-dihydro-1H-pyrrolo[1,2-c]imidazol-1,3-dione and its thione analogues

Analysis of the ¹³C NMR spectra of a series of 2,3-dihydro-1H-pyrrolo[1,2-c]imidazole derivatives has provided chemical shift data for (?184 ppm), (?173.5 ppm), (?158 ppm) and (?148 ppm) groups. A full analysis of the ¹³C chemical shifts of the C atoms of the pyrrole ring and of an N-phenyl substituent is described.     

Zum thermischen Verhalten der Hydrogensulfate des Magnesiums,Calciums, Strontiums und Bariums

On the Thermal Behaviour of the Hydrogen Sulfates of Magnesium, Calcium, Strontium and Barium The thermal behaviour of the solvent-free crystals of alkaline earth hydrogen sulfates has been investigated. The DTA and TG curves of M^II(HSO₄)₂ indicate a decomposition following the equation Thermal treatment of Mg(HSO₄)₂ in static gas atmosphere yields α-MgSO₄ which is transformed to α-MgSO₄ at higher temperature. Contrary to that in dynamic gas atmosphere direct decomposition to α-MgSO₄ can be observed. T = 356°C, T = 204°C, T = 175°C, T = 156°C. The strong difference between the peak temperatures of Mg(HSO₄)₂ and the other alkaline earth hydrogen sulfates may be explained not only through the higher covalency of the bondings in the Mg compound but, especially, through differences of their structures. Whereas the hydrogen sulfates of Ca, Sr, and Ba contain chains of edge-linked M^IIO₈ polyhedra, in Mg(HSO₄)₂ exist isolated MgO₆ octahedra.     

The kinetics of the interaction of peroxy radicals. I. The Tertiary Peroxy Radicals

Existing data on the self-reactions of tertiary peroxy radicals RO₂ has been reanalyzed and corrected to deduce Arrhenius parameters for both termination and nontermination paths. For R = t-Butyl, these are logk_t(M^?1sec^?1) = 7.1 - (7.0/θ) and logk_nt(M^?1sec^?1) = 9.4 - (9.0/θ), respectively, different from those recommended by other authors. The higher magnitudes observed for termination processes of tertiary peroxy radicals like those of cumyl and 1,1-diphenylethyl have been discussed in terms of a much greater cage recombination of cumyloxy radicals as contrasted with t-butoxy radicals. It is shown that for benzyl peroxy radicals, the R—O bond dissociation energy is sufficiently low (18–20 kcal) that reversible dissociation into R^˙ + O₂ opens a competing second-order path to fast recombination R^˙ + RO → ROOR. This path is probably not important for cumyl peroxy radicals under usual experimental conditions but can become important for 1,1-diphenyl ethyl peroxy radicals at (O₂) < 10^?3M. At very low RO concentrations (<10^?5M), in the absence of added O₂, an apparent first-order disappearance of RO can occur reflecting the rate determining breaking of the cumyl—O bond followed by the second step above. The thermochemistry of RO is used to show that the reaction of R₂O₄ → 2RO + O₂ must be concerted and cannot proceed via RO which is too unstable and cannot form even from RO^˙ + O₂.     

The addition of methyl radicals to hexafluoroacetone

The reaction of methyl radicals (Me) with hexafluoroacetone (HFA), generated from ditertiary butyl peroxide (dtBP), was studied over the temperature range of 402–433 K and the pressure range of 38–111 torr. The reaction resulted in the following displacement process taking place: where TFA refers to trifluoroacetone. The trifluoromethyl radicals that were generated abstract a hydrogen atom from the peroxide: such that k_6a is given by: where θ = 2.303RT kcal/mol. The interaction of methyl and trifluoromethyl radicals results in the following steps: Product analysis shows that k₁₇/kk = 2.0 ± 0.2 such that k₁₇ = 10^10.4±0.5M^?1 · s^?1. The rate constant k₅ is given by: It is concluded that the preexponential factor for the addition of methyl radicals to ketones is lower than that for the addition of methyl radicals to olefins.     

Free radicals in γ-irradiated poly-α-methylstyrene

Electron spin resonance (ESR) spectra were observed at ?160°C and at room temperature for γ-irradiated poly-α-methylstyrene. The spectrum observed at room temperature has been attributed to the radical species while that at ?160°C results from the same radical and superposition of the spectrum due to the radical ?H₂-C(CH₃)(C₆H₅)-. The radicals which are stable at room temperature could be used to graft vinyl acetate.     

Über Chalkogenolate. 125. Untersuchungen über N-Cyanformamidinodithiocarbimidsäure 1. Darstellung und Eigenschaften von N-Cyanformamidinodithiocarbimaten,Umsetzung mit Säuren und elementarem Schwefel

On Chalcogenolates. 125. Studies on N-Cyanformamidino Dithiocarbimic Acid. 1. Synthesis and Properties of N-Cyanformamidino Dithiocarbimates, Reaction with Acids and with Elemental Sulfur N-Cyanguanidine reacts with carbon disulfide in the presence of the corresponding alkali metal hydroxide to form N-cyanformamidino dithiocarbimates M₂[S₂C?N? C(NH₂)?N? CN], where M = K and Rb. They react with acids to form and with elemental sulfur to yield . The potassium salt and the methyl compound were isolated. All compounds have been characterized by chemical and spectroscopic methods.     

Electric conductivity of polymer composites with 7,7,8,8-tetracyanoquinodimethan salts

The electric properties of polymer composites with highly conductive 7,7,8,8-tetracyanoquinodimethan (TCNQ) salts such as quinolinium–TCNQ complex salt (), acridinium–TCNQ complex salt (), and N-methylacridinium–TCNQ complex salt () were studied. Polyacrylonitrile (PAN), poly(N-vinylcarbazole) (PVK), and poly(4-vinylpyridine), (P4VP), etc., were chosen as matrix polymers. The resistivity (ρ) of the was 0.37 Ω cm at the content of 20 wt % in the film. When the content of was increased up to 40 wt%, a phase separation of the needle crystals was observed and the ρ value increased. When was dispersed into PAN or PVK, the separation was also observed and the samples showed low conductivity. The uniform films were obtained in the and systems, but the values of ρ were high because of the degradation of the TCNQ salts. Uniform films with the naked eye were obtained in the and systems, and the values of Ω were 0.37, 1.05, and 3.40 Ω cm, respectively. was stable even when dispersed into P4VP. The properties of the composites were influenced by the combination of the TCNQ salts and the polymers. The uniformity and the stability of the composites were necessary to obtain the high conductive composites.     

Beiträge zur Chemie der Oxidhalogenide von Molybdän und Wolfram. V. Molybdänoxidtetrachlorid und Molybdänoxidtrichlorid

The formation enthalpies were ascertained from the solution enthalpies in 2 n NaOH resp. 2 n NaOH + 1% H₂O₂. The results of equilibrium measurements in the systems give the formation enthalpies and standard entropies: . The value of the standard entropy of the gaseous MoOCl₄ was estimated to be 91 (±3) cl. From the enthalpies and entropies of sublimation the values were obtained.     

The kinetics of the interaction of peroxy radicals. II. Primary and secondary alkyl peroxy

A chain mechanism is proposed to account for the very rapid termination reactions observed between alkyl peroxy radicals containing α-C—H bonds which are from 10⁴ to 10⁶ faster than the termination of tertiary alkyl peroxy radicals. The new mechanism is with termination by . \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R}\overline {{\rm CHOO}} $\end{document} is the zwitterion originally postulated by Criegee to account for the chemistry of O₃-olefin addition. Heats of formation are estimated for \documentclass{article}\pagestyle{empty}\begin{document}$ \overline {{\rm CH}_2 {\rm OO,}} {\rm }\overline {{\rm RCHOO}} $\end{document}, and \documentclass{article}\pagestyle{empty}\begin{document}$ ({\rm C}\overline {{\rm H}_3 )_2 {\rm COO}} $\end{document} and it is shown that all steps in the mechanism are exothermic. The second step can account for (¹Δ)O₂ which has been observed. k₁ is estimated to be 10^9–2/θ liter/M sec where θ = 2.303RT in kcal/mole. The second and third steps constitute a chain termination process where chain length is estimated at from 2 to 10. This mechanism for the first time accounts for minor products such as acid and ROOH found in termination reactions. Trioxide (step 3) is shown to be important below 30°C or in very short time observations (<10 s at 30°C). Solvent effects are also shown to be compatible with the new mechanism.     

Fluorierung von Dioxa- und Oxazaphospholanen

Fluorination of Dioxa- and Oxazaphospholanes The fluoridolysis of cyclic esters and esteramides of phosphorous acid ( 1 , 2 , 4 , 5 , 7 , 11 , and 12 ,) using the acid fluorination reagent Et₃N · nHF (n > 1) or an excess of a basic composed agent (n < 1) yields in all cases HPF₅^? ( 3 ,). With stoichiometric amounts of fluoride, however, the fluorophospholanes ( 4 ,) and ( 5 ,) as well as fac.- and mer.-o- ( 6a, 6b ,) and the spirocyclic fluorohydridophosphate ( 8 ,) are obtained. ( 13 ,) reacts to ( 14 ,) and the spirocyclic compound ( 15 ,) gives ( 16 ,). The fluorophosphoranes ( 18 ,), ( 19 ,), and ( 21 ,) are obtained by oxidative fluorination of the spiro- or bicyclic P? H compounds 11, 12 , and 20 , with CCl₄/Et₃N · nHF (n < 1). The oxidative fluorination of the cyclic triesters of phosphorous acid 7 , and 23 , leads to the cyclic fluorophosphates ( 22 ,) and 16 , as well as 6. , The compounds 18, 19 , and 22 , are also formed by oxidative fluorination of elemental phosphorus, P₄, in the presence of the corresponding bifunctional nucleophile.     

Perfluorovinyl Morpholine and Perfluorovinyl Pyrrolidine with Nucleophiles and Electrophiles

In this study, both monofunctional and bifunctional nucleophiles, as well as the electrophile FNO, are reacted with perfluorovinyl amines. The perfluorovinyl amines CF?CF₂ and CF?CF₂ have been reacted with dimethylamine and diethylamine in the presence of small amounts of water to give CHFC(O)N(CH₃)₂ ( 1 ), CHFC(O)N(CH₃)₂ ( 2 ), and CHFC(O)N(C₂H₅)₂ ( 3 ). With perfluorovinyl pyrrolidine and perfluorovinyl morpholine, ethanolamine gives the cyclized products CHF ( 4 ) and CHF ( 5 ), respectively. Reaction of the vinyl amines with (CH₃)₃SiOCH₂CF₃ in the presence of catalytic amounts of CsF results in the formation of cis- ( 6 ) and trans- ( 7 ) CF?CF(OCH₂CF₃) and cis- ( 8 ) and trans- ( 9 ) CF?CF(OCH₂CF₃). The electrophile FNO reacts slowly with perfluorovinyl pyrrolidine and perfluorovinyl morpholine, and more rapidly with (CF₃)₃CCF?CF₂ to give CF(NO)CF₃ ( 10 ), CF(NO)CF₃ ( 11 ) and (CF₃)₃CF(NO)CF₃ ( 12 ), respectively. Single crystal X-ray analysis is used to confirm the identity of the product obtained from the controlled hydrolysis of the sultone of perfluorovinyl pyrrolidine as the sulfonic acid anhydride C(O)CF₂OS(O)₂OCF₂C(O) ( 13 ). The X-ray crystal structure of perfluorosuccinic acid monohydrate ( 14 ), which is obtained when the perfluorovinyl pyrrolidine sultone is hydrolyzed in excess water, is also reported for the first time.     

The first normal stress difference and viscosity in shear of liquid crystalline solutions of hydroxypropylcellulose: new experimental data and theory

The constitutive equations for liquid crystalline polymers recently proposed by one of us [1] are applied here to interpret the behaviour of the shear viscosity η and the first normal stress difference N₁() measured for liquid crystalline (LC) solutions of hydroxypropylcellulose in acetic acid. N₁( ) is observed to change from positive to negative and again to positive, as the shear rate increases, at lower concentrations, in the LC phase. The -values at which N₁ changes sign depend on the molecular mass (degree of polymerization) and on the concentration. η shows a small Newtonian plateau at low shear rates and a strong shear-thinning at higher values of . The rate of decrease of η in this region shows an “hesitation” similar to one previously observed in LC solutions of poly-γ-benzyl-L-glutamate PBLG. All these observations can be rationalized within the frame-work of Martins' theory. The expressions for N₁() and η derived from this theory fit very well (quantitatively) to the experimental data and some fundamental viscoelastic parameters of the system under study are thereby obtained for the first time.     

The method of asymptotic approximations as applied to analyzing the mechanism of inhibited liquid-phase oxidation

A new method for analyzing the problems of chemical kinetics is elaborated involving the technique of mathematical modeling. Namely, the matching method of the asymptotic expansion is applied to analyzing the inhibition mechanism of oxidation. The proposed approach is an extension of the well-known method of quasi-stationary concentrations and may be applied to study a series of problems in the field of chemical kinetics. Three different time scales were established for the mechanism of inhibited oxidation under restrictions k₇[InH]₀/(2k₆W_i)^1/2 ? 1 and k₈ ? 2k₆ ? k₇. At the first time scale (that is very fast and is measured in second fractions) the concentration of radicals In only changes while [RO₂] ? [RO₂]₀, [In H] ? [In H]₀ are constants. At the second time scale (s), [RO₂] changes while [In] ? [In]_st, [In H] ? [In H]₀ are constants. At the third time scale (min), [In H] changes. An asymptotic analysis of the differential equations allows us to find out both the time duration of each step and the variation of the component which changes at this step. After that the rate constants k₈, 2k₆, k₇ are determined from comparison with the experimental measurements of [In], [RO₂], and [In H]. Due to the simplicity and efficiency of the asymptotic method, one may be applied to treating the complex multicenter radical chain processes such as conjugated oxidation, radical copolymerization, sulfoxidation, etc. © 1993 John Wiley & Sons, Inc.