Copolymerization of eight-membered ring-opening allylic sulfide lactone and disulfide monomers with methyl methacrylate and styrene

Apparent reactivity ratios and detailed NMR analysis of copolymerizations of eight membered ring-opening allylic sulfide monomers; 3-methylene-1,5-oxathiocan-2-one 2 and 2,2,4-trimethyl-7-methylene-1,5-dithiocane 5 with methyl methacrylate and styrene are presented. The activated double bond of 2 and unactivated double bond and additional methyl substituents of 5 were found to have a profound affect on reactivity. The copolymerization rates were analyzed based on the lumped parameter k_p(f/k_t)^0.5, which was estimated as a function of monomer composition in the feed.     

Copolymerization of propylene oxide and carbon disulfide with diethylzinc–electron-donor catalyst

Copolymerization of propylene oxide with carbon disulfide was studied by using a catalyst consisting of diethylzinc (ZnEt₂) and various electron donors. Tertiary amines, tertiary phosphines, and hexamethylphosphoric triamide were the effective donors for the copolymerization, but ZnEt₂–water, alcohol, and primary or secondary amines having high activities for the homopolymerization of propylene oxide were not effective for the copolymerization of propylene oxide and carbon disulfide. The copolymers obtained were of low molecular weight and had a monomer unit ratio (CS₂/PO) of 0.5–0.7. In addition, a considerable amount of 1,3-oxathioran-4-methyl-2-thion was isolated as a by-product.     

Reactions of in-situ generated acyllithium reagents with carbon disulfide and carbonyl sulfide

In-situ generated (at ?110°C to ?135°C) acyllithium reagents, RC(O)Li (R = $\text{t}$-Bu, $\text{n}$-Bu), react with CS₂, to give [RCOS]Li with loss of Cs. On the other hand, COS reacts to give [RC(O)COS]Li.     

Copolymerization of ethylene/carbon monoxide by a cationic hydridoaquopalladium complex

The cationic hydridoaquopalladium (II) complex, trans-[(PCy₃)₂Pd(H)(H₂O)]⁺BF^?₄, is an excellent catalyst for the ethylene/carbon monoxide alternating copolymerization in the presence of a bidentate phosphorus ligand and p-toluenesulphonic acid. © 1995 John Wiley & Sons, Inc.     

Copolymerization kinetics of ethylene and carbon monoxide in the presence of palladium complexes

The copolymerization kinetics of ethylene and carbon monoxide has been studied for the catalysts: Pd(C₅H₇O₂)₂-P(C₆H₅)₃-p-CH₃C₆H₄SO₃H in the medium of acetic acid (system A), and Pd(CH₃COO)₂-CF₃COOH - (C₆H₅)₂P(CH₂)_nP(C₆H₅)₂(system B), where n=1−6, in the medium of methyl alcohol. The cationic palladium(II) -diphosphine complexes: (Dppp)₂Pd(CF₃COO)₂ (I) and [(Dppp) Pd(μ-OH)₂Pd(Dppp)] (CF₃COO)₂ (II) have been synthesized and investigated by IR, electrospray mass spectrometry and elemental analysis methods. A comparative study of the copolymerization kinetics in the presence of these complexes and system B has been carried out.     

A computational study of adducts between atomic chlorine and carbon dioxide, carbonyl sulfide and carbon disulfide

The geometries and vibrational frequencies of the adducts ClCO₂, ClCOS and ClCS₂ were derived at the Hartree-Fock (HF) 3-21G (^*) level. The C_a, structure of ClCO₂ corresponds to one C-O bond and one C=O bond. Similarly, C_a, ClCS₂ has one C-S and one C=S bond, and ClCOS has one C-S and one C-O bond. Single-point spin-projected fourth-order Møller-Plesset (MP4) 3-21G (^*) calculations at these geometries were used in bond-separation reactions to derive ΔH^o₀ for adduct formation, which is calculated to be about 39 kJ mol⁻¹ exothermic for ClCOS and ClCS₂, but about 39 kJ mol⁻¹ endothermic for ClCO₂. The C_2v structures for ClCO₂ and ClCS₂ were also characterized. The geometry of ClCS₂ has not been determined experimentally; comparison with an available measured entropy for ClCS₂ suggests that the C_2v structure is the one formed by addition of Cl to CS₂, although the energy relative to the C_a form is not reliably calculated because of instability in the HF wavefunction.     

Copolymerization of carbon disulfide and N-(β-cyanoethyl)ethylenimine

It was found that carbon disulfide copolymerizes with N-(β-cyanoethyl) ethylenimine by using water as a catalyst. The copolymerization was conducted in detail by using water as a catalyst in the temperature range between 0 and 50°C with various initial concentrations of carbon disulfide and N-(β-cyanoethyl)ethylenimine in the absence of solvent. The copolymer obtained was always composed of the two monomers: 1:1 ratio, independent of the initial concentration of the monomers. The copolymer was white solid material soluble in dimethyl sulfoxide, insoluble in other usual organic solvents and decomposed at 155°C. Spectroscopic analysis of the copolymer combined with the results of elemental analysis indicates that the copolymer had the following structure:      

Copolymerization of carbon monoxide with ethylene in the presence of palladium phosphine complexes

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2181–2182, September, 1990.     

Reaction of alkenyldichlorophosphines with ethylene oxide and ethylene sulfide

Conclusions In contrast to ethylane oxide, ethylene sulfide reacts with the styryl- and isobutenyldichlorophosphines only in the presence of catalysts. The course of the discussed reactions is facilitated by solvents with a high electron-donor capacity. The obtained results are discussed from the standpoint of primary donor-acceptor interactions of the reactants.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 457–461, February, 1976.     

Copolymerization of carbon dioxide and N-phenylethylenimine

Copolymerizations of carbon dioxide and N-phenylethylenimine were carried out with the use of various catalysts and solvents. The infrared spectrum of the polymer produced showed the characteristic absorption peak at 1730–1735 cm^?1 based on the urethane linkage. The content of the urethane linkage decreased in the following order: Mn(acac)₂ ≈ MnCl₂4H₂O > Al(OBu)₃ > Ti(OBu)₄ > ZnCl₂ ? BF₃OEt₂ = VCl₃ = Mn(acac)₃ = FeCl₃ = CrCl₃ · 6H₂O = 0. The manganase (bivalent) catalyst in combination with n-hexane solvent was found to be the best system for the copolymerization, and this system received detailed study. Generally speaking, both the polymer yield and the content of the urethane linkage increased with increasing content of carbon dioxide in the feed as well as with increasing polymerization temperature. From the fractionation of polymer in methanol, it was found that the produced polymer is composed of both homopolymer of N-phenylethylenimine and copolymer of N-phenylethylenimine and carbon dioxide. The content of the urethane linkage of the copolymer thus fractionated was as high as about 80%.     

Copolymerization of carbon dioxide and epoxide

The original article to which this Erratum refers was published in J Polym Sci Part A: Polym Chem (2004) 42(22) 5561‐5573 . No abstract.     

Copolymerization of carbon dioxide and epoxide

An erratum has been published for this article in J Polym Sci Part A: Polym Chem (2005) 43(4) 916 . The alternating copolymerization of carbon dioxide and epoxide to produce polycarbonate has attracted the attention of many chemists because it is one of the most promising methodologies for the utilization of carbon dioxide as a safe, clean, and abundant raw material in synthetic chemistry. Recent development of catalysts for alternating copolymerization is based on the rational design of metal complexes, particularly complexes of transition metals with well‐defined structures. In this article, the history and recent successful examples of the alternating copolymerization of carbon dioxide and epoxide are described. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5561–5573, 2004     

Copolymerization of ethylene and non-conjugated diene using homogenous catalyst

Ethylene and different amounts of 1,7-octadiene were copolymerized using the metallocene catalyst system ethylidene-bis(fluorenyl) zirconium dichloride and methylaluminoxane (MAO) at both 50 and 90 °C. The catalyst activity has slightly increased with the addition of low amounts of the diene in relation to the homopolymerization of ethylene. The obtained polymers were characterized according to their melting temperature (T_m) and crystallinity degree (x_c) by differential scanning calorimetry (DSC). Weight-average molecular weight (M_w) and polydispersity were determined by gel permeation chromatography (GPC). Diene contents in the copolymer were obtained through the FTIR spectroscopy. The results indicated that at polymerization temperature of 90 °C, crosslinking bonds in the obtained copolymers were low, differently from what was observed at 50 °C. The diene content in the copolymer achieved more than 3 mol% and the comonomer conversion was around 15%. Moreover, the obtained copolymers have M_w around 100,000 and large polydispersity.     

Copolymerization of ethylene and butadiene with supported titanium catalyst

The copolymerization of ethylene and butadiene with a supported titanium catalyst (TiCl₄/MgCl₂/EB/Φ₂SiCl₂/AlEt₃) is described. The resulting products were characterized by IR, ¹³C-NMR, x-ray diffraction, differential thermal analysis, electron microscopy, and solvent extraction. It was found that the butadiene units are substantially in trans-1,4 configuration and blocked sequences. Both ethylene and butadiene blocks form crystalline phases. The presence of unsaturated bonds made it possible to graft MMA and maleic anhydride. The influences of monomer composition, temperature, Al/Ti ratio, catalyst concentration, and solvents on the copolymerization were investigated.     

Metal sulfide: An efficient promoter for the synthesis of 2-mercaptobenzothiazoles from 2-haloanilines and carbon disulfide

A convenient method has been developed for the preparation of a variety of 2-mercaptobenzothiazoles from 2-haloanilines and CS₂ mediated by metal sulfide. In this reaction, 2-haloanilines reacted with CS₂ in the presence of Na₂S?·?9H₂O to form 2-mercaptobenzothiazoles. Na₂S?·?9H₂O functioned both as an activator of CS₂ and as a base. Furthermore, NMR analysis was used to identify the different reaction mechanisms of 2-haloanilines and CS₂ mediated by Na₂S or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), which demonstrated that Na₂S interacted only with CS₂, while DBU reacted with both 2-iodoaniline and CS₂.     

Catalytic synthesis of dimethyl sulfide from dimethyl disulfide and methanol

The reaction of dimethyl disulfide with methanol was studied at atmospheric pressure and temperature of 350°C in the presence of catalysts containing acid and basic sites.     

Simultaneous catalytic hydrolysis of carbonyl sulfide and carbon disulfide over AlzO3-K/CAC catalyst at low temperature

In this work, a series of coal-based active carbon(CAC) catalysts loaded by Al2O3were prepared by sol-gel method and used for the simultaneous catalytic hydrolysis of carbonyl sulfide(COS) and carbon disulfide(CS2) at relatively low temperatures of 30-70 ℃. The influences of calcinations temperatures and operation conditions such as: reaction temperature, O2concentration, gas hourly space velocity(GHSV) and relative humidity(RH) were also discussed respectively. The results showed that catalysts with 5.0 wt% Al2O3calcined at 300 ℃ had superior activity for the simultaneous catalytic hydrolysis of COS and CS2. When the reaction temperature was above 50 ℃, catalytic hydrolysis activity of COS could be enhanced but that of CS2was inhibited. Too high RH could make the catalytic hydrolysis activities of COS and CS2decrease. A small amount of O2introduction could enhance the simultaneous catalytic hydrolysis activities of COS and CS2.