Showing papers on "Ionic polymerization published in 1984"
01 Jan 1984
TL;DR: Muggins et al. as discussed by the authors presented the Division of polymer chemistry award to Maurice L Muggins for the Structures of Collagen and discussed the effects of exposure of blood coagulation factors and platelets to synthetic polymers.
Abstract: 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--l5H20)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
411 citations
TL;DR: In this paper, the influence of physicochemical factors such as temperature, pH of solution, monomer concentration, type and concentration of electrolyte, stirring rate and acidifying agent on the resultant particle size, and size distribution of poly(butyl-2-cyanoacrylate) nanoparticles was investigated.
149 citations
01 Jan 1984
TL;DR: In this paper, the authors focus on recent advances in selective dimerization and living polymerization of vinyl compounds by cationic mechanisms and discuss the characteristics of the non-associated propagating species formed by non-metal halide (non-MXn) initiators.
Abstract: This review focuses on recent advances in selective dimerization and living polymerization of vinyl compounds by cationic mechanisms. The two reactions, which initially may appear to be completely different, are discussed on the basis of the current understanding of the nature of the propagating species in cationic polymerization. Following a classification of the cationic initiators into metal halide (MXn) and nonmetal halide (non-MXn) types and a clear definition of the differences between the growing intermediates derived from these two classes of initiators, this article emphasizes the characteristics of the nondissociated propagating species formed by non-MXn initiators, including a number of examples of selective dimerization and living polymerization.
90 citations
TL;DR: In this article, the anionic polymerization of β-propiolactone (βPL) in DMF initiated with CH3COO−K+ or CH3O−k+ has been found to proceed via the carboxylate ion as growing species.
Abstract: The anionic polymerization of β-propiolactone (βPL) in DMF initiated with CH3COO−K+ or CH3O−K+ has been found to proceed via the carboxylate ion as growing species. This is valid for all polymerization steps in the former system, starting from the first monomer addition, whereas in the latter CH3O−K+ was found to produce in the initiation reaction both alcoholate and carboxylate anions in almost equal properties. The alcoholate reproduces approximately half of itself in each subsequent step; thus, after a few addition steps all of the active species have become carboxylate ones. The anionic polymerization of e-caprolactone (eCL), on the other hand, can only be induced by alcoholates and the growing species are alcoholate anions. Carboxylate anions, even with crowed cations, are inactive as initiators of eCL. These conclusions are based on NMR studies of the end-groups originating from the initiator and on UV-VIs studies of the reaction products of the active species with 2,4,6-trinitroanisole. The difference between the polymerizations of βPL and eCL are explained in terms of ring strain and conformation.
64 citations
59 citations
TL;DR: In this paper, the mechanism and kinetics of inverse emulsion polymerization of acrylamide in o-xylene containing Tetronic 1102 emulslfier and benzoyl peroxide initiator are described, particularly the formation of 10-200nm multiple emulsion droplets resulting from the particulate emulsifier.
Abstract: Inverse emulsion polymerization confers the benefits of emulsion polymerization kinetics — rapid polymerization rates combined with high polymer molecular weights — on water-soluble polymers, particularly polyacrylamide and its copolymers and derivatives, and allows easy dissolution of the polymer in water by inversion of the latex. The mechanism and kinetics of the inverse emulsion polymerization of acrylamide in o-xylene containing Tetronic 1102 emulslfier and benzoyl peroxide initiator are described, particularly the formation of 10-200nm multiple emulsion droplets resulting from the particulate emulsifier, and their effect on the polymerization process
57 citations
TL;DR: In this paper, the authors studied the structure of poly(β-propiolactone and e-caprolactone) by 1H, 31P{1H} NMR, and IR spectroscopy and revealed that the mode of ring scission in the monomer in the first propagation step depends on the initiator used.
Abstract: The study of the structure of the end-groups of poly(β-propiolactone) and poly(e-caprolactone) by 1H, 31P{1H} NMR, and IR spectroscopy revealed that the mode of ring scission in the monomer in the first propagation step depends on the initiator used. In the initiation of the β-propiolactone and e-caprolactone polymerization with halonium salts ((CH3)2Br⊕SbF6⊖ or (CH3)2I⊕SbF6F6⊖) the exocyclic oxygen atoms in the monomer molecules are attacked and oxonium ions are formed. The propagation steps proceed with alkyl-oxygen bond scission in the active center and with attack at the exocyclic oxygen atom in the subsequent monomer molecule. Thus, the tertiary oxonium ions are the exclusive active species from the very beginning of the polymerization. Acylium cations (CH3CO⊕ SbF6⊖ or CH3CH2CO⊕SbF6⊖) as initiators attack both exo-and endocyclic oxygen atoms in the monomers and the initiation proceeds with almost equal proportions of alkyl-oxygen and acyl-oxygen bond scission. Thus, in the polymerization of β-propiolactone the concentration of the acylium growing species decreases with increasing number of propagation steps and finally the tertiary oxonium ions are becoming the exclusive growing species. In the polymerization of e-caprolactone the active acylium centers apart from propagation participate also in side reactions leading to the cleavage of a proton.
55 citations
TL;DR: In general, the teneur en -1,4 augmente avec la taille de l'ion antagoniste (lithium, sodium ou potassium) as mentioned in this paper.
Abstract: En general la teneur en -1,4 augmente avec la taille de l'ion antagoniste (lithium, sodium ou potassium)
48 citations
TL;DR: In this paper, a "tendency" model of free radical polymerization is used to re-investigate batch polymerization of styrene in solution in cyclohexane with slow and fast decomposing initiators.
30 citations
29 citations
TL;DR: In this paper, the cyclic amide of PIII was described for the first time and the N,N-diethylamine-1,3,2-dioxaphosphorinan was shown to give living reversible polymerization with anionic initiators.
Abstract: Polymerization of the cyclic amide of PIII is described for the first time. The N,N-diethylamine-1,3,2-dioxaphosphorinan was shown to give living reversible polymerization with anionic initiators. Lithium and sodium derivatives were found to be inactive. 1H-, 13C-, and 31P-NMR indicated that the polymer strictly reflects the monomer structure and is formed without any isomerization, the polymer chain being . Initiation involves attack of the anion on the P atom. From the dependence of the equilibrium monomer concentration on temeprature ΔH1s = 1.5 ± 0.2 kcal·mol−1 and ΔS1s = 4.6 ± 0.6 cal·mol−1·°K−1.
Patent•
29 Feb 1984TL;DR: In this paper, a process for the polymerization, in an aqueous suspending medium, of vinylidene fluoride with the aid of an oil-soluble free radical polymerization initiator in the presence of a suspending agent and a chain regulator chosen from the bis(alkyl) carbonates, the alkyl groupings of which contain not more that five carbon atoms, was described.
Abstract: Process for the polymerization, in an aqueous suspending medium, of vinylidene fluoride with the aid of an oil-soluble free radical polymerization initiator in the presence of a suspending agent and a chain regulator chosen from the bis(alkyl) carbonates, the alkyl groupings of which contain not more that five carbon atoms wherein the molecular weight of vinylidene fluoride polymers are effectively regulated without having a detrimental effect on the polymerization yield, thus the vinylidene fluoride polymers have a good stability to heat.
TL;DR: In this article, the polymerization of 6-amino-2,4-trans,trans-hexadienoic acid and various of its salts was studied in the solid state.
Abstract: The polymerization of 6-amino-2,4-trans,trans-hexadienoic acid and various of its salts was studied in the solid state. Crystals of the hydrochloride and organic inorganic double halides with cadmium chloride, manganese (II) chloride, and iron(II) chloride were found to polymerize rapidly upon UV or γ irradiation. An erythro-diisotactic polymer is obtained in the form of extended chain crystals. The polymer behaves as an amphoteric polyelectrolyte. The kinetics and the mechanism of the polymerization as well as morphological changes during the solid state reaction are discussed.
Patent•
25 Jul 1984
TL;DR: In this paper, a quinone-amine compound was used to prevent polymer scale deposition in a polymerization system containing an acrylate or a methacrylate monomer.
Abstract: In a process of emulsion-polymerization in a polymerization system containing an acrylate or a methacrylate monomer at least 60%; the improvement which comprises carrying out the emulsion polymerization in a polymerization vessel having a film of a quinone-amine compound of not less than 3000 in average molecular weight on the inner vessel wall, said quinone-amine compound being prepared by addition-reacting an aromatic quinone and an aromatic diamine in a solvent medium having a solubility parameter of 9.0 to 12.2. According to the process, the polymer scale deposition can be prevented in the acrylate or methacrylate polymerization system.
TL;DR: In this paper, the diphenylzinc-water system was used as catalyst for ethylene oxide polymerization in benzene solution at 60° and the reaction was first order with respect to monomer with kP = 5.7 × 10−5 sec−1 mol−1 l.
Patent•
01 Oct 1984TL;DR: In this article, the rate at which polymerization initiator is added to the polymerizing mixture in a continuous stirred tank reactor is controlled by monitoring an indicator of molecular weight of the polymer in the polymerization mixture.
Abstract: Control of an anionic polymerization is obtained by monitoring an indicator of molecular weight of the polymer in the polymerizing mixture, measuring the molecular weight of the polymer produced therein and using this information to control the rate at which polymerization initiator is added to the polymerizing mixture in a continuous stirred tank reactor.
TL;DR: In this article, a mechanism for the reaction involving initiation of polymerization by hydroxyl radicals is proposed, and the reaction initiated by reaction between hydrogen peroxide and ascorbic acid is also studied.
TL;DR: A new monomer of 5-methyl-2-oxazoline(5-MeOZO) was prepared in this paper, which was found to undergo the cationic ring-opening isomerization polymerization to produce poly(N-formylpropylenimine) 1 of waxy or powdery materials.
Abstract: A new monomer of 5-methyl-2-oxazoline(5-MeOZO) was prepared. It was found that 5-MeOZO underwent the cationic ring-opening isomerization polymerization to produce poly(N-formylpropylenimine) 1 of waxy or powdery materials. Alkaline hydrolysis of 1 gave linear poly(propylenimine) 2. Polymers 1 and 2 are the same as the respective polymers derived from 4-methyl-2-oxazoline.
TL;DR: In this article, the cationic polymerization of N-vinyl carbazole by trityl salts in nitrobenzene at 20°C was studied.
Abstract: The cationic polymerization of N-vinylcarbazole by trityl salts in nitrobenzene at 20°C has been studied. The kp values are independent of initiator concentration and an average value of 8.9.104M−1s−1 has been obtained which, according to the reaction conditions, has been interpreted in terms of propagation by free ions.
TL;DR: In this article, the electro-initiated cationic polymerization of α-methylstyrene in a tetrabutylammonium fluoroborate-dichloromethane system has been investigated at various temperatures by constant potential electrolysis.
TL;DR: The use of organic and inorganic compounds belonging to the class of peroxides in the initiation of addition polymerization is well known as mentioned in this paper, and it has been found that the addition of small amounts of additives brings about the polymerization of vinyl monomers with ease.
Abstract: The use of organic and inorganic compounds belonging to the class of peroxides in the initiation of addition polymerization is well known. It has been found that the addition of small amounts of additives brings about the initiation of the polymerization of vinyl monomers with ease. Such polymerizations have been termed reduction-oxidation or redox. An example of such a reaction is the formation of hydroxy free radicals in the well-known reaction
TL;DR: In this article, the selectivity of ring-opening polysaccharides was investigated under various polymerization conditions with a number of Lewis acids, anionic and coordinated catalysts, and it was shown that the monomer attacks only the C-5 methylene carbon of the active end of the growing chain.
Abstract: The ring-opening polymerization of 3,5-anhydro-1,2-O-isopropylidene-α-D-xylofuranose was studied to investigate the selectivity of ring-opening mode under various polymerization conditions with a number of Lewis acids, anionic and coordinated catalysts. In all the conditions attempted here, the monomer attacks only the C-5 methylene carbon of the active end of the growing chain to form a stereoregular [35]-α-D-xylofuranan structure. With removal of the isopropylidene groups of the polymer, a new class of non-hydrolyzable polysaccharides, [35]-D-xylan, is obtained.
TL;DR: The photo-initiated polymerization of 1-vinylimidazole (VI) does not follow the classical kinetic scheme for free radical polymerization as discussed by the authors, and the experimental results suggest a degradative addition reaction between the macroradical and the monomer to produce a relatively stable, unreactive radical.
Abstract: The photoinitiated polymerization of 1-vinylimidazole (VI) does not follow the classical kinetic scheme for free radical polymerization. Kinetic results for VI suggest a degradative addition reaction between the macroradical and the monomer to produce a relatively stable, unreactive radical, which does not reinitiate polymerization, is low, 1.5 kcal/mol. Among the 3 photoinitiators used, the highest quantum efficiency was demonstrated by 2,2'-diethoxyacetophenone followed by bezoin methyl ether and benzoin isopropyl ether. Under the experimental conditions used, the polymerization of VI does not proceed to complete conversion, and the phenomenon of dead-end polymerization is observed.
01 Jan 1984
TL;DR: The use of phase transfer catalysis (PTC) for the purpose of carrying out ionic reactions has become commonplace in recent years as discussed by the authors, although the techniques of PTC have been concerned for the most part with the transfer of anionic reagents between two immiscible phases for subsequent nucleophilic reactions, the concept is believed to be much more general.
Abstract: The use of phase transfer catalysis (PTC) for the purpose of carrying out ionic reactions has become commonplace in recent years.2 Although the techniques of PTC have been concerned for the most part with the transfer of anionic reagents between two immiscible phases for subsequent nucleophilic reactions, the concept is believed to be much more general.3 Recently, for instance, a few examples describing extension of the process to cationic (electrophilic) reagents have been reported.4,5
TL;DR: In this paper, a comparison between the product distributions in radiation and chemically induced polymerization of cyclosiloxanes has been made, showing that the free propagating cations strongly favored the propagation reaction.