Determination of the content of sulfonyl fluoride groups in the copolymer of tetrafluoroethylene with perfluoro(3,6-dioxa-4-methyl-7-octene)sulfonyl fluoride

The applicability of Fourier IR spectroscopy to determination of the content of sulfonyl fluoride groups in the copolymer of tetrafluoroethylene with perfluoro(3,6-dioxa-4-methyl-7-octene)sulfonyl fluoride (F-4SF copolymer) was examined. A procedure was suggested for determination of sulfonyl fluoride groups, based on a correlation between the analytical signals in the IR absorption spectrum of F-4SF and the sulfur content in F-4SF samples.     

全氟(2,5-二甲基-3,6-二氧杂-8-氟磺酰基辛酰氟)在溶剂中的裂解

本文研究了标题化合物(2)在溶剂存在下与碳酸钠的裂解反应, 反应分二步进行, 第一步, α在60℃下与Na2CO3的反应生成羧酸钠盐(4)。第二步, ψ在180℃-220℃下脱羧, 分离鉴定了裂解产物, 并讨论其反应相理, 在研究副产物砜的形成的基础上, 合成了一系列含氟砜。     

Standard enthalpies of formation of perfluoro(2-methyl-3-oxa)hexanoic and perfluoro(2,5-dimethyl-3,6-dioxa)nonanoic acids

The energies of combustion of perfluoro(2-methyl-3-oxa)hexanoic and perfluoro(2,5-dimethyl-3,6-dioxa)nonanoic acids are for the first time measured in a calorimeter with a rotating platinized bomb and used to calculate the standard enthalpies of formation of these compounds in the liquid state. Based on the enthalpies of formation, the contribution from the [-CF₂OCF(CF₃)-] group to the enthalpies of formation of perfluoro acids is calculated.     

Synthesis of 3,6-dioxa-Δ-4-trifluoromethyl perfluorooctyl trifluoromethyl sulfonimide: bis[(perfluoroalkyl)sulfonyl] superacid monomer and polymer

A new type of ion exchange polymer, bis[(perfluoroalkyl)sulfonyl]imide ionomers (PFSI), were developed by the copolymerization of sodium 3,6-dioxa-Δ⁷-4-trifluoromethyl perfluorooctyl trifluoromethyl sulfonimide with tetrafluoroethylene (TFE) using an aqueous redox initiation system in an emulsion type polymerization. These polymers have been prepared in various equivalent weights and processed into functional membranes. The new ionomers exhibit excellent chemical and thermal stability. The materials have high potential for electrochemical applications especially as solid polymer electrolytes (SPE) in proton exchange membrane (PEM) fuel cells.     

Formation of long-lived radicals in radiolysis of perfluoro(4-methyl-2-pentene)

Conclusions On the basis of the EPR spectrum of perfluoro(4-methyl-2-pentene) (PMP) that has been exposed to gamma radiation at 77–300 K, three types of long-lived radicals have been observed, with lifetimes greater than two years. With increases in the radiolysis temperature for radiation dose, the concentration of long-lived radicals increases. Their relative concentrations depend on the irradiation conditions and the thawing schedule.Under certain conditions, long-lived radicals of a single type can be obtained from the PMP.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1263–1268, June, 1988.     

带功能基的全氟烷基乙烯基醚的研究——4.四氟乙烯与全氟-3,6-二氧杂-4-甲基-△~7-辛基磺酰氟溶液共聚反应单体竞聚率的测定

在乙烯-四氟乙烯溶液共聚合体系研究中,我们曾编制了一个简易的计算机程序,用于测定二种单体的共聚竞聚率,这一方法计算方便,而且可以避免原先作图法中的误差,结果较为可靠。前文我们报道了四氟乙烯与两个新的全氟烷基乙烯基醚的共聚合反应,并对其中一个新单体——7,7-二氯-3-氧杂-全氟庚烯-1——与四氟乙烯的共聚进行了单体竞聚率的测定。结果表明,这一新的含氟烯醚单体的聚合活性较其它已有报道的同类单体大。为了验证这一     

Radiation-induced copolymerization of tetrafluoroethylene with vinyl ethers

Radiation-induced copolymerization of tetrafluoroethylene with various vinyl ethers has been studied. It was found that tetrafluoroethylene can be copolymerized with vinyl ethers to give alternating copolymers over a wide range of the initial monomer concentration in the monomer mixture. The monomer reactivity ratios were determined for the copolymerization of tetrafluoroethylene with n-butyl vinyl ether as 0.005 (r_TFE) and 0.0015 (r_NBVE). The rate of copolymerization is extremely high and has a maximum at an equimolar concentration of two monomers. The alternating structure of the copolymers was confirmed by the analysis of NMR spectra. Some thermal properties of the copolymers were measured by DSC and DTA.     

Synthesis of o-acylamino-4-methyl-7-hydroxycoumarins (4-methylumbelliferones)

Some acylated o-amino-7-hydroxycoumarins have been obtained which may be used as intermediates in the preparation of fluorogenic substrates for certain enzymes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 906–909, July, 1985.     

Structure of the product of the reaction of 3,6-dioxa-1,8-(di-2,3-dichloromaleimido)octane with 3,6-dioxaoctane-1,8-diamine

The reaction of 3,6-dioxa-1,8-(di-2,3-dichloromaleimido)octane with 3,6-dioxaoctane-1,8-diamine gave 7,11-diaza-1,4-dioxa-9-en-7,11-oxo-9-chlorobicyclo-[1.2.9]tridecan-8-one. The steric structure of the last was determined by x-ray structural investigation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 394–398, March, 1992.     

Cationic polymerization of 4-methyl-1,3-dioxene-4 and copolymerization with tetrahydrofuran

A new monomer, 4-methyl-1,3-dioxene-4 was synthesized from allyl chloride and paraformaldehyde. The monomer was polymerized at room temperature or ?78°C. by boron trifluoride etherate catalyst, and the structure of the obtained polymer was determined by infrared, nuclear magnetic resonance spectra, and chemical analysis. It was ascertained that the polymerization process proceeded through a ring-opening mechanism at the dioxane ring. In the presence of tetrahydrofuran, the polymerization of 4-methyl-1–1,3-dioxene-4 led to copolymer. The mechanism of the copolymerization is described in detail.     

Copper(II)–nickel(II) complexes of novel 1,9-dioxa-3,6-dithiacyclotridecane-10,12-dione and 1,4-dioxa-7,10-dithiacyclododecane-2,3-dione ligands

1,9-Dioxa-3,6-dithiacyclotridecane-10,12-dione (L¹), and 1,4-dioxa-7,10-dithiacyclododecane-2,3-dione, (L²), two novel ligands, and their mono- and di-nuclear copper(II) and/or nickel(II) complexes have been prepared and characterized by elemental analyses, ¹H- and ¹³C-n.m.r., i.r., magnetic moments and mass spectral studies. Elemental analyses, stochiometric and spectroscopic data on the complexes indicate that the metal ions are coordinated to the nitrogen, oxygen and sulphur atoms and the data support the proposed structure for the diones and their mono–dinuclear copper(II) complexes. Moreover, copper(II) complexes of the dione ligands have a 1:1 metal:ligand ratio.     

Reactions of perfluoro(2-methylpent-2-ene) and perfluoro(5-azanon-4-ene) with primary amines containing a 2,6-di-tert-butylphenol fragment

Reactions of perfluoro(2-methylpent-2-ene) and perfluoro(5-azanon-4-ene) with 4-(2-aminoethyl)-2,6-di-tert-butylphenol and 4-(3-aminopropyl)-2,6-di-tert-butylphenol in acetonitrile in the presence of triethylamine gave the corresponding azetidine, 1,2-dihydroazete, and 1,2-dihydro-1,3-diazete derivatives, respectively. The reaction mechanisms, role of triethylamine, and factors affecting the intramolecular nucleophilic cyclization process are discussed.     

Molecular structure of 1-methyl-1-fluoroquasisilatrane (2-methyl-2-fluoro-1,3-dioxa-6-aza-2-silacyclooctane)

The molecular structure of 1-methyl-1-fluoroquasisilatrane (2-methyl-2-fluoro-1,3-dioxa-6-aza-2-silacyclooctane) MeFSi(OCH₂CH₂)₂NH (I) is determined by single crystal X-ray diffraction at 100 K. The coordination polyhedron of the silicon atom in this molecule is a slightly distorted trigonal bipyramid with an NH group and a strongly electron-withdrawing fluorine atom in the axial positions, and two endocyclic oxygen atoms and a CH₃ group in three vertices of the equatorial plane. The axial angle N→SiF is 171°. The length of the transannular donor-acceptor bond N→Si (2.058 Å) is as small as in 1-fluorosilatrane. The axial bond F-Si (1.660 Å) is longer than that in 1-fluorosilatrane and tetrahedral silicon compounds.     

Kinetics of reactions of the tris-(4-methyl-1,10-phenanthroline)iron(II) cation

Summary Kinetic parameters are reported for aquation of the tris-(4-methyl-1,10-phenanthroline) iron(II) [Fe(4-Mephen)₃]²⁺, cation and for its reactions with hydroxide, cyanide, and peroxodisulphate. Activation volumes have been determined for the two last-named reactions; they reflect the importance of solvation changes in transition state formation.     

The thermal decomposition of 4-methyl-3,6-dihydro-2H-pyran

The thermal decomposition of the title compound has been studied in the gas phase in the temperature range of 584–634 K. The decomposition was found to be a first-order homogeneous process yielding 2-methylbuta-1,3-diene and formaldehyde. The rate constants obtained at 11 temperatures within the quoted range fitted the Arrhenius equation The decomposition is probably unimolecular and concerted.