A review of copolymerization of green house gas carbon dioxide and oxiranes to produce polycarbonate

Terpolymers with various l-lactic acid content in the polypropylene carbonate chain were synthesized by copolymerization of carbon dioxide, propylene oxide, and l-lactide. Zinc adipate was used as a catalyst. Terpolymerization products were characterized by 1H and 13C NMR, 2D {1Н—13С} HMBC, IR spectroscopy, and gel-permeation chromatography. The influence of monomer molar ratio, temperature, and reaction duration on the composition and molecular-mass characteristics of terpolymers was studied. A few questions of terpolymerization mechanism were discussed.

Diethylzinc was allowed to react with various metal oxides in n‐heptane at 60°C, and the copolymerization of propylene oxide and carbon dioxide was investigated at 60°C in solution in dioxane with reaction products as catalysts. An alternate copolymer was obtained with every catalyst, but the yield of copolymer and the number‐average molecular weight depended significantly on the supporting materials. In a kinetic study of the copolymerization we found that the catalytic efficiency (number of propagating species per number of zinc supported) was only a few percent with every catalyst. The copolymerization was also examined by using several kinds of silica, whose pore diameters are markedly different, as supports. The results obtained strongly suggested that only the active species existing in large pores act as the propagating species.

Copolymerization of carbon dioxide and propylene oxide with highly effective zinc hexacyanocobaltate(III)-based coordination catalyst

Summary: The reaction of 2‐lithio‐6‐methylpyridine or 2‐lithiopyridine and the appropriate diaryl ketone followed by hydrolysis yields 6‐Me‐pyCAr2OH pyridine alcohols or pyCAr2OH pyridine alcohols. The reactions of zinc acetate with 1 equiv. of the lithiated products of the ligands proceed rapidly to afford LiOAc salt and mono‐ligand complexes (6‐Me‐pyCAr2O)Zn(OAc) and (pyCAr2O)Zn(OAc), respectively, in high yield. The copolymerizations of carbon dioxide with cyclohexene oxide were investigated. The (6‐Me‐pyCAr2O)Zn(OAc) showed moderate yield and CO2 incorporation. The [6‐Me‐pyC(4‐Cl‐C6H4)2O]Zn(OAc) complex gave large polymers with high proportions of carbonate linkage (>60%) and narrow polydispersity, indicating single active sites.The monoligated Zn complexes synthesized and used here as catalysts for the copolymerization of cyclohexene oxide and carbon dioxide.imageThe monoligated Zn complexes synthesized and used here as catalysts for the copolymerization of cyclohexene oxide and carbon dioxide.

Although carbon dioxide has attracted broad interest as a renewable carbon feedstock, its use as a monomer in copolymerization with olefins has long been an elusive endeavour. A major obstacle for this process is that the propagation step involving carbon dioxide is endothermic; typically, attempted reactions between carbon dioxide and an olefin preferentially yield olefin homopolymerization. Here we report a strategy to circumvent the thermodynamic and kinetic barriers for copolymerizations of carbon dioxide and olefins by using a metastable lactone intermediate, 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one, which is formed by the palladium-catalysed condensation of carbon dioxide and 1,3-butadiene. Subsequent free-radical polymerization of the lactone intermediate afforded polymers of high molecular weight with a carbon dioxide content of 33 mol% (29 wt%). Furthermore, the protocol was applied successfully to a one-pot copolymerization of carbon dioxide and 1,3-butadiene, and one-pot terpolymerizations of carbon dioxide, butadiene and another 1,3-diene. This copolymerization technique provides access to a new class of polymeric materials made from carbon dioxide.

Ceremony for the Presentation of the Division of Polymer Chemistry Award to Maurice L. Muggins.- The Structures of Collagen.- Panel Discussion with Dr. Muggins.- Head to Mead Polymers.- Polycondensation Reactions in the Presence of Polymer Matrices.- Telechelic Polyethylene.- Soluble Ladder Type of Poly(silesquioxanes) Maving Functional Groups.- New Phosphorus-Containing Bisimide Resins.- Crosslinking of Gelatin by Reactive Polymers Effect of Polymer Structure on Gelation Time.- Study of Dextran-Methyl Methacrylate Graft Copolymer.- The Kinetics and Mechanisms of the Dehydrohalogenation of the Poly(vinyl halides), PVC, PVDC and PVF.- 1H NMR Studies on Conformation of Poly(vinylidene Fluoride) in Solution and Its Relation with Crystal Modification.- Syntheses of Polymeric Azo Dyes of Pyrazolone Series.- New Oligomeric Flame Retardants Containing s-Triazine Ring.- Functional Effects of Exposure of Blood Coagulation Factors and Platelets to Synthetic Polymers.- Analysis of Dielectric ?-Relaxation in Poly(methyl Acrylate) and Poly(t-butyl Acrylate).- Effects of Poisson's Ratio and Electrostriction Constant on Piezoelectricity in Poly(vinylidene Fluoride).- Influence of Shearing Histories on the Rheological Properties and Processability of Branched Polymers.- Effects of Molecular Weight on the Aggregation of Poly(?-benzyl L-Glutamate in Dilute Solution.- The Conformational Order in Hexadecane Solutions and Polyethylene.- Entanglement Networks of 1,2-Polybutadiene Cross-linked in States of Strain: XV. Simple Extension Special Case Comparison of the CKF Theory to Swelling Equilibrium Data.- Electrophilic Olefins Containing Anionic Leaving Groups as New Cationic Initiators.- Synthesis and Properties of Some Polymers Related to Biological Functions: Metal Transport and Template-directed Oligonucleotide Synthesis.- Copolymerization of Carbon Dioxide and Epoxide and Related Reactions.- Interactions Between Blood and Foreign Surfaces of Synthetic Polymers-Especially in Vascular Prothesis.- Anionic Polymerization of p-Styrenyl Substituted Derivatives of Silicon, Germanium and Tin.- Rare Earth Metal Containing Polymers: Energy Transfer Uranyl to Europium Ions in lonomers.- Extration of Uranium from Sea Water by Synthetic Polymer Adsorbent.- Selective Synthesis of Macrocyclic Oligoesters from a Bicyclic Oxalactone and Cation Transport through their Organic Liquid Membranes.- The Efficiency of Glow Discharge Polymerization in Tubular Reactors.- Interpolymer Association of Exciplex Forming Polymers under Extremely Dilute Conditions.- Surface Modification of Aromatic Polyamides by Microwave Plasma Treatment.- Modification of Polymer Surfaces by Surface Active Graftcopolymers.- The Triplet State of Polymers with Pendent Aromatic Chromophores.- Radiation-Induced Ionic Polymerization.- Hydration of Poly(ethylenimine) Structures of Sesquihydrate (-Ch2Ch2Nh--l.5H20)n and Dihydrate (-Ch2Ch2NH--2H20)n.- Quantum Chemistry of Gauche-Oxygen Effect Observed in Polyethers.- Transients in the Structure and Stress of Entangled Polymers Subjected to Step Changes in Shear Rate.- New Emulsion System - Polymeric "Water in Water" Emulsion.- Peel Behavior of Pressure-Sensitive Adhesives.- Modeling the Viscoelastic Behavior of SBS Block Copolymer Solids.- Physical Aging and Its Long-term Effect on the Durability and Reliability of Advanced Structural Epoxies and Epoxy-based Graphite-fiber Composites.- On the Effect of Thermal Stability of Electron Donor, AIR3 Complex for the Property of High Active Supported Catalyst for PP.- Membrane Separation and Its Industrial Applications.- Structure and Properties of Polypeptide Block Copolymer Membranes.- Structure and Properties of Poly(amino Acid) Solids.- Specific Multi-layer Structure Polymer Composition.- Strong Piezoelectric Activity in Simultaneously Streched and Poled Poly(vinylidene Flouride).- Vinylidene Fluoride-Hexafluoropropylene Copolymer Having Terminal Iodines.- Hydrophilic Polyamide Membrane Prepared from Optically Active Bicyclic Oxalactam.- Interfacial Tension of Demixed Polymer Solutions near Critical Solution Temperature.- Fourier Transform-Infrared Studies of Polymer Blends: IV. Poly(?-caprolactone)-Poly(Bis-phenol A-Carbonate) System.- Crystal-Liquid Crystal Phase Transformation of Synthetic Bimolecular Membranes.- Non-Equilibrium Processes in Stressed Polymeric Glasses.- Energy and Electron Transfer in Mi cellar and Polymeric Systems: Kinetic Mimicry of Chlorophyll.- Microstructure and Piezoelectricity in Poly(vinylidene Fluoride) Films.- Stripping Rate of Residual Styrene Monomer from Latexes of Polystyrene and SBR.- Characterization of Thermal and Optical Properties of Polymers by Thermal Lensing Technique.- Fraction of Polymers by U1trafiltration: A Computer Simulation Study.- Entanglement Networks of 1,2-Polybutadiene Cross- Linked in States of Strain. XV. Simple Extension Case: Application of the CKF Theory to Stress Strain and Stress Relaxation Data.- Poly(aryl Ether)-Poly(arylate) Block Copolymers: I. Polysulfone-Bis-A Terephthalate Systems.- Stress-Related Surface Tension Effects in Hard Elastic Polymers.

Carbon dioxide and N-phenylethylenimine were allowed to copolymerize using a Bronsted acid such as phenol or acetic acid to give a white powder, melting at 160–270°C, with a carbon dioxide content of 2.90–20.5 mol %. The content of carbon dioxide in the copolymer increased with carbon dioxide in the feed, while the melting point decreased. The infrared spectrum of the copolymer showed the characteristic peak of urethane linkage. 3-Phenyl-oxazolidone-2, which might be produced by the reaction of carbon dioxide and N-phenylethylenimine, did not react with carbon dioxide or N-phenylethylenimine and was not contained in the copolymer. Carbon dioxide did not react with poly(N-phenylethylenimine) or phenol. From the facts mentioned above, it was concluded that the formation of urethane linkage was due to the copolymerization of carbon dioxide and N-phenylethylenimine. From ultraviolet spectroscopic analysis of the mixture of carbon dioxide and N-phenylethylenimine, an appreciable interaction between two monomers was observed. From the experimental data on the monomer composition in the feed and copolymer, the apparent monomer reactivity ratios were evaluated. On the basis of these results, the probable mechanism of the copolymerization via a complex of carbon dioxide and N-phenylethylenimine was proposed.

Syntheses of high polymers using carbon dioxide as a direct starting material have been discovered rather recently. The first example is the alternating copolymerization of carbon dioxide and epoxide to give aliphatic polycarbonate with high molecular weight. Effective catalyst system is the reaction mixture of diethylzinc and water or other compounds with two active hydrogens. The mode of ring opening of epoxide in the copolymerization has been studied intensively. Carbon dioxide-epoxide copolymer is thermally decomposed to give cyclic carbonate. The copolymer is rather readily hydrolyzed. N-phenylethyleneimine copolymerizes with carbon dioxide by acidic catalyst to give copolymer with urethane linkage. Ethyleneimine and propyleneimine give similar copolymers without using any catalyst. Vinyl ether copolymerizes with carbon dioxide to give copolymer having keto and ester groups. Butadiene also copolymerizes to give a rubbery, insoluble product. Copolymerization of cyclic phosphonate, acrylonitrile and carbon dioxide gives a sequential ternary copolymer. Condensation polymerization of carbon dioxide and aromatic diamine in the presence of diphenyl phosphite and pyridine gives polyurea with high molecular weight under mild conditions.

Carbon dioxide and epoxide copolymerize in the presence of some organometallic catalyst systems under moderate conditions to give aliphatic polycarbonates of high molecular weight. Some metalloporphyrins of aluminum and zinc were found to act as novel catalysts for the polymerization of epoxide and for the copolymerization of carbon dioxide and epoxide, though not alternating. The polymers are characterized by the narrow molecular weight distribution and the unusual stereoregularity. Starting from the copolymerization of carbon dioxide and trimethylsilyl glycidyl ether with diethylzinc-water catalyst system, a readily degradable polycarbonate having hydroxyl group was obtained.

Three salen complexes N,N'-bis(salicylidene)-1,2-phenylenediamino MⅢ Cl were prepared and employed for the copolymerization of carbon dioxide with propylene oxide. FT-IR and UV-Vis spectra confirmed the characteristic of metal salen complexes obtained. The central metal atoms in the salen complexes have great influence on the copolymerization of carbon dioxide with propylene oxide. The result shows that chromium metal is more effective to synthesize PPC copolymer. The structure of the resulting PPC was characterized by IR 1H NMR and GPC. 86.3% carbonate content of the PPC was achieved with chromium salen complexes.

The reaction kinetics of the copolymerization of carbon dioxide and cyclohexene oxide to produce poly(cyclohexene carbonate), catalyzed by a dizinc acetate complex, is studied by in situ attenuated total reflectance infrared (ATR-IR) and proton nuclear magnetic resonance ((1)H NMR) spectroscopy. A parameter study, including reactant and catalyst concentration and carbon dioxide pressure, reveals zero reaction order in carbon dioxide concentration, for pressures between 1 and 40 bar and temperatures up to 80 °C, and a first-order dependence on catalyst concentration and concentration of cyclohexene oxide. The activation energies for the formation of poly(cyclohexene carbonate) and the cyclic side product cyclohexene carbonate are calculated, by determining the rate coefficients over a temperature range between 65 and 90 °C and using Arrhenius plots, to be 96.8 ± 1.6 kJ mol(-1) (23.1 kcal mol(-1)) and 137.5 ± 6.4 kJ mol(-1) (32.9 kcal mol(-1)), respectively. Gel permeation chromatography (GPC), (1)H NMR spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry are employed to study the poly(cyclohexene carbonate) produced, and reveal bimodal molecular weight distributions, with narrow polydispersity indices (≤1.2). In all cases, two molecular weight distributions are observed, the higher value being approximately double the molecular weight of the lower value; this finding is seemingly independent of copolymerization conversion or reaction parameters. The copolymer characterization data and additional experiments in which chain transfer agents are added to copolymerization experiments indicate that rapid chain transfer reactions occur and allow an explanation for the observed bimodal molecular weight distributions. The spectroscopic and kinetic analyses enable a mechanism to be proposed for both the copolymerization reaction and possible side reactions; a dinuclear copolymerization active site is implicated.

A novel aliphatic polycarbonate, poly[(propylene oxide)‐ co ‐(carbon dioxide)‐ co ‐(γ‐butyrolactone)] [P(POCO 2 GBL)], was synthesized by the copolymerization of carbon dioxide, propylene oxide (PO) and γ‐butyrolactone (GBL). The resulting copolymers were determined by FTIR and NMR spectral analysis with viscosity‐average molecular weights ( M v ) from 50 000 to 120 000 g mol −1 . According to elemental analysis, the calculated data of elemental contents in P(POCO 2 GBL)44 were close to the found data. The result showed that GBL was inserted into the backbone of poly[(propylene oxide)‐ co ‐(carbon dioxide)] successfully. GBL offered an ester structural unit that gave the copolymer better degradability. The correlations between reaction conditions and properties were studied. When GBL content increased, the M v and the glass transition temperature ( T g ) of the copolymers improved relative to an identical copolymer without GBL. Prolonging the reaction time of the copolymerization resulted in increases in M v and T g . P(POCO 2 GBL) exhibited a high T g above 40 °C. The rate of backbone degradation increased with increasing GBL content. Copyright © 2005 Society of Chemical Industry

CO2 conversion and utilization

Fifteen metals (lead, cadmium, arsenic, inorganic mercury, organic mercury, iron, manganese, magnesium, chromium, zinc, copper, nickel, cobalt, tin, and aluminum) were determined in the hepatic bile and urine collected simultaneously from three Japanese individuals (2 males, 1 female). The presence of these metals was classified as follows: hepatic biliary concentrations were higher than urinary concentrations (lead, arsenic, and iron); urinary concentrations were higher than hepatic biliary concentrations (cadmium, inorganic mercury, tin, cobalt, magnesium, chromium, copper, zinc, and nickel); hepatic biliary concentrations were almost equal to urinary concentrations (manganese and organic mercury); and relationship between hepatic biliary and urinary concentrations changed occasionally (aluminum). Eight essential metals (iron, manganese, magnesium, zinc, chromium, copper, nickel, and cobalt) were detected at considerable concentrations in hepatic bile. Accounting for the daily flow volume of hepatic bile and the reabsorption of these metals, the supplementation of these metals should occur during treatment of diseases accompanied by loss of hepatic bile.

To determine the effect of irrigation with wastewater on soil and plant contamination with some heavy metals, according to international pollution standards, a pot experiment was conducted in a field belonging to the Karbala Governorate sewage treatment plant using soil with a silty, mixed texture. A completely randomized design (CRD) was used with two types of irrigation water (sewage and tap water) and six replicates. Maize seeds of Sumer variety were planted at a rate of 5 seeds per pot, thinned to three seeds per pot after 15 days of planting. The experiment continued until appearance of male inflorescences. Soil and plant samples were taken after the end of experiment. The results showed the following: Total heavy metals concentration in soil increased compared to its counterpart in soil irrigated with tap water, reaching 3396.10, 16.13, 16.98, 0.68, 15.59, 20.33, 89.00, 13.15, and 98.23 mg kg-1 for heavy metals Iron, Zinc, Copper, Vanadium, Cadmium, Lead, Nickel, Manganese, Cobalt, and Chromium, respectively. Concentration of heavy metals in tissues of Maize plants increased, reaching 20.30, 20.58, 5.00, 4.63, 2.16, 1.20, 6.55, 10.77, 4.91 and 10.73 mg kg-1 dry matter for above heavy metals, respectively. High values ​​of pollution factor for heavy metals in soil reached 1.106, 1.015, 1.166, 1.110, 1.545, 1.111, 1.110, 5.350, 1.214, and 8.724 for heavy metals Zinc, Iron, Copper, Vanadium, Cadmium, Lead, Nickel, manganese, Ccobalt, and Chromium, respectively, which indicates the presence of medium pollution. As for Environmental Hazard Index (EHI) for heavy metals, values ​​decreased for all elements except Cadmium. Meanwhile, contamination degree (Cdeg) values ​​for soil irrigated with wastewater increased to 23.451, which falls within range of high contamination. Bioconcentration factor (BCF) values ​​for Zinc and Cadmium increased above one, it reached 1.275 and 3.176, respectively, indicating the movement and transfer of these two elements from soil to plant. The remaining elements had coefficient values ​​less than one, making them slow-moving and slow-transferring elements from soil to plant.