Studies on the charge transfer complex and polymerization. XVI. Spontaneous copolymerization of cyclopentene and sulfur dioxide

The alternating copolymerization of cyclopentene and sulfur dioxide was studied. It takes place spontaneously at ?15°C. The rate of copolymerization in toluene was found to be proportional to [CPT]³ and [SO₂]² with the overall activation energy of 16.5 kcal/mole. Terpolymerizations with eight different third monomers were carried out to examine the character and behavior of the copolymerization system of CPT and SO₂. However, the polymerizations with styrene and methyl methacrylate as the third monomers were found to be extraordinary, in that all the three components are not incorporated into the polymer chain.     

Propagation Mechanism of Radical Copolymerization of Sulfur Dioxide and Vinyl Chloride

Radical copolymerization of sulfur dioxide and vinyl chloride (VC) has been studied by the comparison of the composition of copolymers obtaining from different reaction conditions, i.e., reaction temperatures, feed compositions, and total monomer concentrations. The composition of VC in copolymer is independent of comonomer composition except at high concentration of VC in feed; it increases with increasing reaction temperature or decreasing total monomer concentration. At lower temperature, the composition of copolymer becomes independent of total monomer concentration. The overall rate of polymerization is proportional to [VC]^1,7 and [SO₂]^0.5. These results were compared with those obtained in our previous study on the SO₂-styrene copolymerization. A propagation mechanism for radical copolymerization of SO₂ and VC is also proposed.     

Free radical copolymerization of sulfur dioxide with 1-alkynes

Free radical copolymerization of SO₂ with 1-alkynes (AY) was studied by evaluation of the copolymerization rate under controlled conditions of copolymerization temperature and monomer concentration product ([AY][SO₂]). The poly(alkyne sulfone)s always contained equimolar units of SO₂ and alkyne, regardless of the copolymerization conditions. Using 1-hexyne (HY) and 1-octyne (OY) as comonomers of SO₂, the values of ceiling temperature (T_c) were determined: when [HY][SO₂] = [OY][SO₂] = 0.25 mol²/L², the values of T_c were 90.5 and 84.5°C, respectively. T_c increases with increasing monomer concentration product. The activation energies for propagation (E_p) and depropagation (E_d) of the SO₂-alkynes copolymerization system were investigated, using the SO₂? OY copolymerization system, and estimated to be 12.2 and 26.7 kcal/mol, respectively. The value of E_d is high compared with that of the copolymerization of SO₂ and 1-butene (20.3 kcal/mol), demonstrating that the free radical endings (～ OY? SO₂ and ～ SO₂? OY) are difficult to depropagate, compared with those formed from the copolymerizaton of SO₂ and 1-butene. ΔS and ΔH_p, calculated from experiments, were found to be ?37.7 cal/mol K and ?14.3 kcal/mol, respectively     

Emulsion copolymerization of tetrafluoroethylene and propylene with redox system containing tert-butylperbenzoate. I. Polymerization conditions and components

Emulsion polymerization of tetrafluoroethylene and propylene with ammonium perfluorooctanoate, initiated by a redox system containing tert-butylperbenzoate (TBPB) was carried out. The effect of the components of the redox system Is (TBPB, FeSO₄.7H₂O, ethylenediamine tetraacetic acid (EDTA), and CH₂(OH)SO₂Na.2H₂O) on the polymerization rate (R) and molecular weight () was studied. Among redox system components, Fe²⁺ concentration exerts the most significant effect (by power of 0.54) on the polymerization rate. It was found that R ∝ [Is]^0.2–0.54 and M_n ∝ [Is]^0.0–0.1 and polymerization reaction scheme was suggested for the action of the initiating system. The influence of the copolymerization conditions (pressure, temperature, stirring speed, and pH) is also discussed. The apparent activation energy of the reaction was found to be 46.0 kJ/mol. © 1994 John Wiley & Sons, Inc.     

Copolymerization of vinyl chloride with sulphur dioxide—I molecular association between vinyl chloride and sulphur dioxide

The formation of VC-SO₂ and VC-(SO₂)₂ complexes in liquid mixtures of vinyl chloride (VC) and sulphur dioxide has been shown by (a) the freezing point composition diagram and (b) chemical shifts in the PMR spectrum of VC over the complete composition range. It is postulated that SO₂ can associate with the CC bond and the Cl atom. These complexes may be involved in the copolymerization and influence the composition and stereochemistry of the product. PMR spectra of VC-SO₂-ethane(E) mixtures with [SO₂] ? [E] ? [VC] gave K_v = 2·0 ± 0·5, 1·5 ± 0·1 and 1·1 ± 0·3 at 232·6, 272·6 and 301·3 K with ΔH_f⁰H_f = ?6·6 ± 1·4 kJ mol^?1 for the VC -(SO₂)₂ complex. The chemical shift of the trans β-proton was twice that of the other two protons. indicating that SO₂ adopts an asymmetric orientation to the double bond.     

Studies on the copolymerization of norbornene with CO catalyzed by a new catalytic system PdCl<Subscript>2</Subscript>/phen/M(CF<Subscript>3</Subscript>SO<Subscript>3</Subscript>)<Subscript>n</Subscript>

A new three-component catalytic system, PdCl₂/phen/M(CF₃SO₃)_n where M = La, Y, Yb, Zn, and Cu, was studied for the copolymerization of norbornene (NBE) with CO to prepare polyketone (PK). It was found that the CF₃SO₃H catalytic system gave a low catalytic activity for the copolymerization of norbornene with CO, but when M(CF₃SO₃)_n was introduced instead of CF₃SO₃H, the PdCl₂/phen/M(CF₃SO₃)_n catalytic system exhibited much higher activity. The effects of ligands, M(CF₃SO₃)_n, solvents, and temperatures on the copolymerization have been discussed in detail. The results showed that with 1,10-phenanthroline (phen) and Cu(CF₃SO₃)₂ used as cocatalysts, the corresponding reaction rate reached 82 000 g PK (mol Pd)⁻¹h⁻¹ when the reaction was carried out in methanol at 90°C and 3.0 MPa of CO, and the weight average molecular weight (M _w) of the resultant copolymer is 1090 g/mol. The copolymer was characterized with various techniques such as FT-IR, ¹HNMR, ¹³CNMR, TGA, and DSC. The infrared spectrum of the product includes two features at 1697 and 1732 cm⁻¹ for the NBE/CO copolymer in CH₃OH that are attributed to carbonyl groups in ketones (repeating unit) and esters (end group), respectively. Due to the tension of the ring of norbornene, the degree of copolymerization is not high. Published in Russian in Kinetika i Kataliz, 2007, Vol. 48, No. 1, pp. 51–58. This article was submitted by the authors in English.     

Vinyl Polymerization Initiated by Sulfur Dioxide

Abstract

A number of monomers have been polymerized in the presence of catalytic and higher concentrations of SO₂. The addition of t-butyl hydroperoxide greatly accelerates the rate of polymerization. The use of ³⁵SO₂ indicates that at catalytic concentrations of SO₂ (10^?2 mole/liter), only one or two molecules of SO₂ are incorporated in the chain, but, at high SO₂ concentrations, copolymerization of SO₂ with vinyl monomers occurs.     

Grafting onto wool. XXV. Effect of acids on γ-radiation-induced graft copolymerization of methyl methacrylate onto wool fiber

Graft copolymerization of methyl methacrylate (MMA) onto Himachali wool fiber has been investigated in aqueous medium by using γ irradiation from a 2100 Ci⁶⁰CO source as means of initiation. Graft copolymerization was carried out by the mutual method in nitrogen atmosphere as well as in air. Effect of mineral acids and acetic acid on percentage of grafting was studied. Percentage of grafting was determined as functions of total dose, concentration of monomer, and concentration of acids. Maximum percentage of grafting in the presence of acids occurred in nitrogen atmosphere at a total dose of 1.05 MR. All the acids were found to influence grafting and the reactivity of different acids towards graft copolymerization was found to follow the order: H₂SO₄ > HCl > HNO₃ > HC1O₄ > HOAc. An attempt has been made to explain the reactivity order of different acids in the light of the mechanism proposed for γ-irradiation-induced graft copolymerization of vinyl monomer onto wool fiber.     

COPOLYMERIZATION OF 1-OCTENE WITH STYRENE BY RARE EARTH COORDINATION CATALYSTS

The copolymerization of l-octene with styrene catalyzed by rare earth coordination catalysts has been studied for the first time. Some features and kinetic behavior are described. The overall activation energy of the copolymerization was 22.2 KJ/mol and the copolymerization rate could be expressed as R_p=K_p [Nd] [M]~2. (=1.68×10~(-3) L~2/mol~2. S, 50℃, [Oct]/[St]=1). The catalytic activity of various rare earth elements in Ln (naph)_3 for the copolymerization was compared and shows the following sequence: Dy, Y, Yb>Ho>Sm, Gd, Nd>Pr>Ce>La>Tm. Both monomers of l-octene and styrene in the copolymerization by Nd (naph)_3-AlEt_3 have the tendency of constant proportion copolymerization. The structure of the copolymers was studied by ~1H-NMR.     

Copolymerization of Vinyl Chloride and Sulfur Dioxide. II. Copolymerization Rates and Copolymer Compositions

The rate of copolymerization of vinyl chloride (VC) with sulfur dioxide and the composition of the poly (vinyl chloride sulfone) formed have been measured for comonomer liquid mixtures with X_VC = 0.1 to 1.0 and over the temperature range -95 to +46°C.

Polymerization was initiated by γ-irradiation (-95 to +46°C) and with the t-butyl hydroperoxide/SO₂/methanol redox system (-95 to -18°C). The copolymerization rates and copolymer compositions indicated two distinct temperature regions, with a change in mechanism around 0°C. For radiation initiation below 0°C, the rate versus comonomer composition relationship showed a maximum at an x_VC value which increased with increasing temperature. Above 0°C, the rate decreased with increasing temperature and was greatly retarded by SO₂. No high molecular weight copolymer or VC homopolymer was formed on irradiation of comonomer mixtures above ～55°C.     

Vinyl polymerization by cobaltic ions in aqueous solution. Part II. Polymerization of acrylonitrile and methyl acrylate

Polymerization of methyl acrylate in HClO₄ and HNO₃ was studied in the temperature range 10–15°C. The kinetics of the polymerization were found to be very simple, involving initiation and termination by cobaltic ions. Kinetic studies on polymerization of acrylonitrile in HClO₄ and HNO₃ revealed that water oxidation, and monomer oxidation were side reactions as in the case of methyl methacrylate. Experimental evidence favored the simultaneous initiation by Co³⁺ and CoOH²⁺ species. In H₂SO₄, certain unusual features were encountered. At low [Co³⁺], linear termination as well as termination by mutual combination occurred. Another interesting aspect was that CoSO₄⁺ initiated at low [Co³⁺]. This was unlike the case of other monomers in H₂SO₄. The rates of polymerization and rates of cobaltic ion disappearance were measured with respect to changes in [M], [Co³⁺], [H⁺], temperature, etc. The various rate constants were evaluated.     

CsSbF2SO4: An Excellent Ultraviolet Nonlinear Optical Sulfate with a KTiOPO4 (KTP)‐type Structure

A novel noncentrosymmetric (NCS) polar fluoride sulfate, CsSbF₂SO₄, was obtained by ionothermal synthesis. A meticulously designed co‐substitution approach was used to successfully replace the [TiO₆]^8? and [PO₄]^3? functional groups in KTiOPO₄ (KTP) with [SbO₄F₂]^7? and [SO₄]^2? units, respectively. The structure of CsSbF₂SO₄ features a pseudo‐3D framework consisting of interconnected 1D [SbF₂O₂SO₄]^5? chains of corner‐sharing [SbO₄F₂]^7? octahedra and [SO₄]^2? tetrahedra. The title compound exhibits a sharply enlarged band gap compared to its parent compound, KTP, benefitting from the introduction of F^? ions and the displacement of Sb³⁺ cations. Second harmonic generation (SHG) measurements manifested that CsSbF₂SO₄ is phase‐matchable and revealed a strong SHG response of about 3.0 KH₂PO₄ (KDP), which is the highest value reported for any metal sulfate reported to date. The reported fluoride sulfate is a promising near ultraviolet (UV) nonlinear optical (NLO) material.     

Kinetics and mechanism of metallocene‐catalyzed olefin polymerization: Comparison of ethylene,propylene homopolymerizations,and their copolymerization

A series of ethylene, propylene homopolymerizations, and ethylene/propylene copolymerization catalyzed with rac‐Et(Ind)₂ZrCl₂/modified methylaluminoxane (MMAO) were conducted under the same conditions for different duration ranging from 2.5 to 30 min, and quenched with 2‐thiophenecarbonyl chloride to label a 2‐thiophenecarbonyl on each propagation chain end. The change of active center ratio ([C^*]/[Zr]) with polymerization time in each polymerization system was determined. Changes of polymerization rate, molecular weight, isotacticity (for propylene homopolymerization) and copolymer composition with time were also studied. [C^*]/[Zr] strongly depended on type of monomer, with the propylene homopolymerization system presented much lower [C^*]/[Zr] (ca. 25%) than the ethylene homopolymerization and ethylene–propylene copolymerization systems. In the copolymerization system, [C^*]/[Zr] increased continuously in the reaction process until a maximum value of 98.7% was reached, which was much higher than the maximum [C^*]/[Zr] of ethylene homopolymerization (ca. 70%). The chain propagation rate constant (k_p) of propylene polymerization is very close to that of ethylene polymerization, but the propylene insertion rate constant is much smaller than the ethylene insertion rate constant in the copolymerization system, meaning that the active centers in the homopolymerization system are different from those in the copolymerization system. Ethylene insertion rate constant in the copolymerization system was much higher than that in the ethylene homopolymerization in the first 10 min of reaction. A mechanistic model was proposed to explain the observed activation of ethylene polymerization by propylene addition. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 867–875     

A new catalytic system for the copolymerization of dicyclopentadiene with CO: PdCl2/phen/M(CF3SO3)n

A new three-component catalytic system, PdCl₂/phen/M(CF₃SO₃)_n, was studied in the copolymerization of dicyclopentadiene (DCPD) with CO. It was found that the PdCl₂/phen/CF₃SO₃H catalytic system gave a very low catalytic activity, and the PdCl₂/phen/M(CF₃SO₃)_n catalytic system exhibited high activity when M(CF₃SO₃)_n was introduced instead of CF₃SO₃H. The resultant cooligomer was analyzed using various techniques such as FT-IR, ¹H NMR, ¹³C NMR, DSC and TGA. The results indicated that the copolymer was a polyspiroketal (PS) of CO and DCPD. Due to the tension of the ring of DCPD, the degree of copolymerization is low and the degree of crystallinity is also not high. The effects of ligands, M(CF₃SO₃)_n, solvents, 1,4-benzoquinone/PdCl₂ molar ratio, and temperatures on the copolymerization have been discussed in detail. The results showed that this novel catalytic system exhibited highly efficient activity, especially when 1,10-phenanthroline (phen) was used as ligand and Cu(CF₃SO₃)₂ was used as cocatalyst. The corresponding reaction rate was 49 000 g PS/molPd h when the reaction was carried out at 60 °C and 3.0 MPa of CO. The weight average molecular weight (M_w) and the number average molecular weight (M_n) of the resultant cooligomer were 1180 g/mol and 564 g/mol, respectively.     

The SO2-sensitized phosphorescence of biacetyl vapor in photolyses at 2650 and 2875 Å. The intersystem crossing ratio in sulfur dioxide

Quantum yields of the triplet sulfur dioxide (³SO₂)-sensitized phosphoresence (Φ_sens) in biacetyl (Ac₂) have been determined in experiments over a wide range of pressures of SO₂ and Ac₂. Excited singlet sulfur dioxide (¹SO₂) was generated using 2650-Å and 28757hyphen;Å light. The values of Φ_sens were dependent on the [SO₂]/[Ac₂] ratio, as anticpated theoretically. However, in runs at a fixed [SO₂]/[Ac₂] ratio, the measured Φ_sens values were dependent on the total pressure. This theoretically unexpected effect is probably largely the result of biacetyl triplet diffusion with deactivation at the cell wall. Treatment of the quantum yield data in terms of the complete mechanism gave new estimates of the following rate functions: ¹SO₂ + SO₂ → (2SO₂) (1), ¹SO₂ + SO₂ → ³SO₂ + SO₂ (2), k₂/(k₁ + k₂) = 0.082 ± 0.003 (2650 Å), 0.095 ± 0.005 (2875 Å) ³SO₂ + Ac₂ → SO₂ + ³Ac₂ (9a), ³SO₂ + Ac₂ → SO₂ + Ac₂ (9b), k_9a + k_9b = (8.4 ± 2.1) × 10¹⁰ (2650 Å), (8.1 ± 3.0) × 10¹⁰ l./mole-sec (2875 Å) ³SO₂ → SO₂ + hv_p (6), k₆ = (7.3 ± 1.3) × 10¹ sec^?1.     

Schwefelmonoxid-komplexe: III. Ein kationischer eisen-so-komplex

The compounds [cpFe(dppe)(SO)]PF₆, the first mononuclear cationic complex of sulfur monoxide, and [cpFe(dppe)(SO₂)]PF₆ were obtained in high yield from the corresponding carbonyl [cpFe(dppe)(CO)]PF₆. From spectroscopic studies the sulfur monoxide was found to be coordinated to iron in the usual bent η¹-fashion; the sulfur dioxide complex, as expected, contains SO₂ in an η¹-planar fashion.     

Pseudoelementverbindungen. IV. Modifizierung der Ionen Sulfit [SOY2]2−, Sulfat [SO4−nYn]2− und Sulfonat [RSO2Y]− durch Einführung der Pseudochalkogengruppen NCN und C(CN)2

Pseudoelement Compounds. IV. Modification of the Ions Sulfite [SO₂Y]^2?, Sulfate [SO_4?nY_n]^2?, and Sulfonate [RSO₂Y]^? by Introducing Pseudochalcogen Groups NCN and C(CN)₂ . Described is the synthesis of pseudochalcogen modified sulfites M₂[SOY₂], sulfates M₂[SO_4?nY_n] (Y = NCN), and arylsulfonates M[RSO₂Y] (Y = NCN, C(CN)₂). The ¹³C-NMR and IR spectra of the new compounds are discussed.     

Polysulfonylamine. LXIX. Neuartige Pniktogendisulfonylamide: Synthese von Bismutdimesylamiden und Kristallstrukturen des zwölfgliedrigen Cyclodimers [Ph2BiN(SO2Me)2]2 und des ionischen Komplexes [H(OAsPh3)2]⊕(MeSO2)2N⊖

Polysulfonyl Amines. LXIX. Novel Pnictogen Disulfonylamides: Synthesis of Bismuth Dimesylamides and Crystal Structures of the Twelve-Membered Cyclodimer [Ph₂BiN(SO₂Me)₂]₂ and of the Ionic Complex [H(OAsPh₃)₂]^⊕(MeSO₂)₂N^? The novel bismuth(III or V) disulfonylamides Ph₂BiN(SO₂Me)₂ ( 1 ), PhBi[N(SO₂Me)₂]₂ ( 2 ), PhBi[N(SO₂Me)₂]Br ( 3 ), Bi[N(SO₂Me)₂]₂Cl ( 4 ), Bi[N(SO₂Me)₂]Cl₂ · 12-crown-4 ( 5 ) and Ph₃Bi[N(SO₂Me)₂]Cl ( 6 ) were obtained by acidolysis of Ph₃Bi with HN(SO₂Me)₂ (→ 1 ), by metathesis of AgN(SO₂Me)₂ with Ph₂BiCl (→ 1 ) or PhBiBr₂ (→ 2, 3 ), by condensation of BiCl₃ with Me₃SiN(SO₂Me)₂ (→ 4 ; in presence of 12-crown-4: → 5 ), or by oxidative addition of ClN(SO₂Me)₂ to Ph₃Bi (→ 6 ). Independently of the molar ratio employed, triphenylarsane oxide and dimesylamine form the crystalline 2/1 complex [H(OAsPh₃)₂]^⊕(MeSO₂)₂N^? ( 7 ). The crystal packing of 7 (monoclinic, space group C2/c) consists of discrete cations displaying crystallographic C_i symmetry and a strong O …? H …? O hydrogen bond (H atom located on a centre of symmetry, O …? O′ 241.2 pm, As? O …? O′ 120°, As? O 168.3 pm), and chiral anions with crystallographic C₂ symmetry (N? S 157.3 pm, S? N? S 122,9°). In the solid state, the bismuth(III) compound 1 (triclinic, space group P1 ) is a cyclodimer with crystallographic C_i symmetry, in which two Ph₂Bi^⊕ cations are connected through two (α-O, ω-O)-donating dimesylamide ligands to form a roughly twelve-membered [BiOSNSO]₂ ring (Bi? O 239.7 and 246.6, O? S 148.0 and 145.4, S? N 157.7 and 159.2 pm, Bi? O? S 126.6 and 127.5°). The bismuth atom adopts a pseudo-trigonal-bipyramidal geometry (O? Bi? O 165.4, C? Bi? C 93.0, O? Bi? C 83.8 to 86.5°). The essentially similar conformations of the discrete anion in 7 and of the bidentate bridging ligand in 1 are discussed in detail.     

The photochemically induced reaction of sulfur dioxide with alkanes and carbon monoxide

Abstract— The gas phase photochemical reactions of SO₂ induced by 3130 Å radiation have been studied in the presence of added alkanes or added CO. The quantum yields obtained in the reactions with the low molecular weight alkanes employed are lower than those obtained by previous workers. The quantum yields were found to be pressure dependent increasing slowly with increasing pressure. A stoichiometric ratio of one SO₂ removed per molecule of hydrocarbon consumed was observed only under experimental conditions of [SO₂] < [RH]. For reaction mixtures where [SO₂] < [RH] the ratio of [SO₂]/[RH] reacted always exceeded unity. The quantum yields decreased slightly with increasing temperature. In all the alkane reaction systems studied, the deposition of viscous, nonvolatile reaction products was observed. In the experiments with added CO, the quantum yields were computed with respect to the rate of CO₂ formation. At 25°C and equal pressures of SO₂ and CO, φco₂ was observed to be 0.005 and it decreased slightly with increasing temperature. The results obtained are interpreted in terms of the sulfoxidation of the alkanes and the oxidation of CO proceeding by way of a ³SO₂ reaction intermediate.     

Analysis of organic salts by laser ionization mass spectrometry. Sulfonates,sulfates and thiosulfates

Sodium and potassium salts of organic sulfonates (1-decyl, 1-dodecyl and 1-hexadecyl), sulfates (1-hexyl, 1-decyl and 1-octadecyl) and thiosulfates (1-octyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, benzyl and β-phenylethyl) were ionized by laser irradiation and the positive ions were analyzed by time-of-flight mass spectrometry. The organic ions observed were always intense and due to the molecular species plus a cation or a dimer plus a cation. The spectra of the thioslufates and sulfates show an abundance of inorganic ions in contrast to the sulfonates. The thiosulfate spectra are characterized by intense [Na₃SO₃]⁺ or [K₃SO₃]⁺ ions and the sulfates by intense [Na₃SO₄]⁺ or [K₃SO₄]⁺ ions.