Photopolymerization of methyl methacrylate in the presence of C-phenyl-N-tert-butylnitrone

The effect of C-phenyl-N-tert-butylnitrone as a source of nitroxyl radicals on the kinetic parameters of radical photopolymerization of methyl methacrylate and the molecular mass characteristics of the resulting polymer was studied. It was shown that the polymerization at 30°C in the presence of this additive proceeds without the gel effect, thus allowing poly(methyl methacrylate) synthesis with a narrower molecular-mass distribution than the additive-free process.     

Polymerization of Styrene in the Presence of Nitroxyl Radicals Generated Directly in the Course of the Polymer Synthesis (in situ)

The features of radical polymerization of styrene in the presence of nitroxyl radicals generated directly in the course of the polymer synthesis (in situ) by irreversible reaction of stable organic compounds 2-methyl-2-nitrosopropane, C-phenyl-N-tert-butylnitrone, and nitrosodurene with propagating polymer radicals were studied.     

Synthesis of block copolymers from polyvinyl chloride prepared in the presence of nitroxyl radicals of the imidazoline series

Specific features of radical polymerization of vinyl chloride in the presence of nitroxyl radicals of the imidazoline series (2-methyl-2,3-diphenyl-1,4-diazaspiro[4,5]dec-3-ene-1-oxyl, 2,2,5,5-tetramethyl-4-phenyl-2,5-dihydroimidazole-1-oxyl, 2,2,5-trimethyl-4,5-diphenyl-2,5-dihydroimidazole-1-oxyl) were studied. The possibility of preparing vinyl chloride-styrene block copolymers in the presence of these nitroxyl radicals was demonstrated, suggesting the occurrence of the polymerization by the reversible inhibition mechanism. The molecular-mass characteristics and the glass transition points of the synthesized samples were determined.     

Addition‐Fragmentation Chain Transfer to Polymer in the Free Radical Ring‐Opening Polymerization of an Eight‐membered Cyclic Allylic Sulfide Monomer

Summary: A detailed investigation of chain transfer to polymer during free radical ring‐opening polymerization of the eight‐membered disulfide monomer 2‐methyl‐7‐methylene‐1,5‐dithiacyclooctane (MDTO) is presented. It has been shown that extensive chain transfer to polymer occurs involving both poly(MDTO) radicals and cyanoisopropyl radicals. Significant decreases in molecular weight were observed when cyanoisopropyl radicals were generated in the presence of poly(MDTO) in the absence of monomer. The molecular weight distribution (MWD) obtained from polymerization of MDTO in the presence of pre‐added poly(MDTO) was markedly different from that obtained without pre‐added polymer. A kinetic model was constructed in an attempt to quantitatively describe the chain transfer to polymer process based on the addition fragmentation chain transfer mechanism. It was found however that the simulated MWDs were considerably broader than the experimental MWDs, which were similar to the Schulz‐Flory distribution.

Mechanism for chain transfer to polymer.     

Kinetics of the decay of nitroxyl radicals during polymerization of a complex of acrylamide with bismuth nitrate

Kinetics of the decay of nitroxyl radicals during spontaneous polymerization of complexes of acrylamide (AAm) with Bi^III nitrate has been studied by ESR. From a comparison of the experimental and calculated kinetic curves, the initiation rate constant of polymerization has been determined. The approach proposed is suitable for determining the main kinetic characteristics of other polymerizable nonparamagnetic AAm complexes with metal nitrates.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1572–1575, September, 1994.This work was carried out with the financial support of the Russian Foundation for Basic Research (Project No93-03-4162).     

Particle nucleation and monomer partitioning in styrene O/W microemulsion polymerization

Particle nucleation in the polymerization of styrene microemulsions was found to take place throughout the polymerization as indicated by measurements of the particle number as a function of conversion. A mechanism based on the nucleation in the microemulsion droplets was proposed to explain the experimental findings although homogeneous nucleation and coagulation during polymerization were not completely ruled out. A thermodynamic model was developed to simulate the partitioning of monomer in the different phases during polymerization. The model predicts that the oil cores of the microemulsion droplets were depleted early in the polymerization (4% conversion). Due to the high monomer/polymer swelling ratio of the polymer particles, most of the monomer resides in the polymer particles during polymerization. The termination of chain growth inside the polymer particles was attributed to the chain transfer reaction to monomer. The low n? (less than 0.5) of the microemulsion system was attributed to the fast exit of monomeric radicals.     

Effects of poly(2-vinylpyridine) as a template for the radical polymerization of methacrylic acid—II: Influence of initiator concentration

The polymerization of methacrylic acid along an atactic poly(2-vinylpyridine) template was studied by varying the initiator concentration, [I]₀. The concentrations of monomer and template were 0.4 M, the temperature 30°. Reaction rates were determined calorimetrically. The experimental results could be well described by a template polymerization model based on a modified mechanism omitting the requirement of a critical chain length of the oligomer radical prior to its association with the template. This view is in line with the existence of preferential adsorption of monomer by the template. In addition, the different ways of termination were also considered. By applying this kinetic model, the various radical concentrations and rate coefficients could be estimated. The termination rate coefficients for template associated polymer radicals appeared to be about 1000 times smaller than termination rate coefficient for non-associated radicals. Moreover, it was found that the initial polymerization rate has 0.26 order with respect to initiator, signifying a predominance of termination between template associated radicals over that between template associated and non-associated radicals (cross termination).     

Specifics of synthesis of styrene homo-and copolymers in the presence of piperidine-base amines and peroxide initiator

The specific features of synthesis of polystyrene, as well as random and block styrene-acrylonitrile and styrene-methyl methacrylate copolymers, in the presence of some alicyclic amines were studied. It was found that chain length regulators are not only amines themselves, but also nitroxyl radicals formed in situ as a result of oxidation of amines by benzoyl peroxide, which acts simultaneously as the initiator of radical polymerization and an oxidant. It was shown that secondary amine-peroxide binary compositions are able to control most effectively the kinetic parameters of polymerization and the molecular-mass characteristics of formed macromolecules.     

Photoinduced controlled/living free‐radical polymerization of 4‐methacryloyl‐1,2,2,6,6‐pentamethyl‐piperidenyl

The photoinduced solution polymerization of 4‐methacryloyl‐1,2,2,6,6‐pentamethyl‐piperidinyl (MPMP), used as a reactive hindered amine piperidinol derivative, was performed. The obtained MPMP homopolymer had a very narrow molecular weight distribution (1.06–1.39) according to gel permeation chromatography. The number‐average and weight‐average molecular weights increased linearly with the monomer conversion, this being characteristic of controlled/living free‐radical polymerizations. Electron spin resonance signals were detected in the MPMP homopolymer and in a polymer mixture solution, and they were assigned to nitroxide radicals, which were bound to the polymer chains and persisted at a level of 10^?9 mol/L during the polymerization. Instead of the addition of mediated nitroxide radicals such as 2,2,6,6‐tetramethyl‐piperidinyl‐1‐oxy (TEMPO), those radicals (>N? O ·) were formed in situ during the photopolymerization of MPMP, and so the reaction mechanism was understood as being similar to that of TEMPO‐mediated controlled/living free‐radical polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2659–2665, 2004     

Nitroxyl radicals and nitroxylethers beyond stabilization: radical generators for efficient polymer modification

Beyond traditional polymer stabilization, sterically hindered piperidine derivatives move into new application areas where radical functions are key elements. Recent achievements in using nitroxyl derivatives in degradation, polymerization and grafting processes are discussed together with the involved chemical reactions and the resulting material properties. The examples shown cover selected nitroxylethers (NORs) performing as flame retardants and flame retardant synergists or replacing peroxides in manufacturing controlled rheology polypropylene (PP). Furthermore, NORs and nitroxyl radicals mediate radical polymerization processes resulting in tailor-made intermediates for polymer modification via radical and condensation steps and offer access to complex polymer architecture. To cite this article: R. Pfaendner, C.R. Chimie 9 (2006).     

Bulk polymerization of α-chloroacrylonitrile

Poly-α-chloroacrylonitrile, which may be regarded as a hybrid of poly(vinyl chloride) and polyacrylonitrile, is, like these polymers, insoluble in its own monomer. Its bulk polymerization is thus heterogeneous, showing abnormal kinetic features by comparison with homogeneous polymerizations. The polymerization exhibits autocatalytic properties. The initiator exponents at 0 and 5% polymerization are 0.45 and 0.44, respectively, and the overall energy of activation is 23.0 ± 2 Kcal./mole. There is no significant change in molecular weight with catalyst concentration in the range 0.057–0.90% nor with conversion up to 12%, but the reaction is accelerated by addition of polymer. Bulk polymerization results in colored products, the color deepening with conversion. These results have been compared with those of Bamford and Jenkins for acrylonitrile and Bengough and Norrish for vinyl chloride and are found to be in closer accord with the latter. They can be accounted for satisfactorily by Bengough and Norrish's suggestion that transfer occurs between growing polymer radicals and dead polymer molecules, the radicals thus formed on the surface of the polymer being removed by transfer to monomer.     

Polymerization of methyl methacrylate with dimethylbenzylanilinium chloride

In order to clarify the mechanism of initiation by dimethylbenzylanilinium chloride (DMBAC), the polymerization of methyl methacrylate with DMBAC has been investigated at 60–80°C. From the results of kinetic and tracer studies, it was found that this polymerization proceeded via a radical mechanism and benzyl radical was not an initiating species. However, it was also noted that DMBAC easily dissociated into dimethylaniline and benzyl chloride under the present conditions, and the overall activation energy for the methyl methacrylate polymerization was 14.6 kcal/mole. These observations indicate that initiating radicals other than benzyl radical, i.e., phenyl or methyl radicals, may be produced through a redox interaction between DMBAC and dimethylaniline dissociated from DMBAC.     

Simulation model for the molecular weight distribution in emulsion polymerization

A Monte Carlo simulation model for the kinetics of emulsion polymerization is proposed. In the present model, the formation of each polymer molecule is simulated by the use of only a couple of probability functions; therefore, the calculation can be handled well even on personal computers. It is straightforward to account for virtually any kinetic event, such as the desorption of oligomeric radicals and chain length dependence of kinetic parameters, and as a consequence very detailed information such as the full distributions of the dead polymer molecular weights and the macroradicals among various polymer particles can be obtained. When bimolecular terminations are the dominant chain stoppage mechanism, the instantaneous molecular weight distribution (produced in a very small time interval) becomes broader than that for homogeneous polymerizations due to a higher possibility that short and long polymer radicals react with each other if bimolecular reactions are fast enough. The increase in the polydispersity of the MWD is fairly large, especially when bimolecular termination by disproportionation is significant; however, the gel permeation chromatography (GPC) may not be a suitable analytical technique to detect such broadening since oligomeric peaks may not be observed in the elution curve. The present simulation method provides greater insight into the complicated phenomena of emulsion polymerizations. © 1995 John Wiley & Sons, Inc.     

Formation of polymer-bonded nitroxyl radicals in the UV stabilization of polypropylene by a bifunctional hindered amine light stabilizer

The formation of polymer-bonded stabilizer derivatives during photooxidation of isotactic polypropylene, which contains the hindered amine light stabilizer bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and the corresponding bisnitroxyl radical, was investigated. The photooxidized polypropylene films that contain these additives were studied by ESR, IR, and nitrogen analysis before and after exhaustive solvent extraction of the photooxidized films. ESR showed that under the conditions in use a maximum of 20% of the nitroxyl radicals formed from the hindered amine was bonded to the polymer chain. Regeneration of nitroxyl radicals from the polymer-bonded stabilizer derivatives under photooxidative conditions indicated that the stabilizer was bonded to the polymer chain by O-alkyl-substituted hydroxylamine linkages >N? O? PP.     

Kinetic studies of photopolymerization using real time FT-IR spectroscopy

The real time FT-IR (RT/FT-IR) technique has been recognized as a very vital tool to quantitatively study the curing parameters such as the effects of initiator (or catalyst) type and concentration, accelerator, stabilizer, irradiation wavelength, temperature, and curing environments. Herein, our results in studies of photoinduced polymerizations for adhesive and coating applications are reported. The photoinduced polymerizations studied included anionic and hydrosilation (a polyaddition polymerization) reactions. In photoinduced anionic polymerization our studies for ethyl cyanoacrylate polymerization are described. The effect of the concentration of photoinitiator and inhibitor on the ethyl cyanoacrylate polymerization kinetic rate will be discussed. In photoinduced catalytic hydrosilation reaction studies, the effects of the catalyst concentration and staging irradiation are disclosed. The hydrosilation reaction was monitored using a Si? H silicone hydride stretching band located at 2169 cm^?1. The cyanoacrylate polymerization was monitored using the C?C stretching band occurring at 1617 cm^?1. The hydrosilation conversion was completed with an appropriate formulation. For monofunctional cyanoacrylate monomer, the photoinduced conversion to straight chain polymer was approximately 85% for a 60 s period. The intrinsic rates of the reactions were calculated for kinetic comparisons. For very fast cyanoacrylate polymerization studies, new FT-IR kinetic software was used to collect 204 spectra/min. Some detailed experimental techniques and polymerization reaction mechanisms are also discussed. © 1993 John Wiley & Sons, Inc.     

Reactions of stabilizer compounds. IV. ESR studies of the formation of stable nitroxyl radicals in the photooxidation of polypropylene containing hindered amine light stabilizers

ESR studies of the formation of stable nitroxyl radicals in the photooxidation of polypropylene containing 2,2,6,6-tetramethyl-4-hydroxypiperidine (II) and the commercial light stabilizer bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate (III) are described. Spectra of the stable nitroxyl radicals in solid polymer and in solution after extraction from the polymer were obtained. The extract from photooxidized polypropylene containing the bifunctional stabilizer (III) showed only the mononitroxyl radical. The possible formation of polymer-bonded nitroxyl radicals from (III) is discussed.     

Nucleation-elongation: a mechanism for cooperative supramolecular polymerization

The kinetic and thermodynamic characteristics of polymerizations following a cooperative, nucleation-elongation mechanism are discussed in comparison to those of non-cooperative, isodesmic polymerizations. Nucleation-elongation polymerization is a relatively unexplored avenue of synthetic polymer chemistry and offers some unique and interesting thermodynamic and kinetic attributes not found in the more classical mechanisms of polymer chemistry.     

A constant shear stress strategy for establishing in situ viscosity models of photoinduced polymerization of acrylamide

In situ viscosity kinetics models for blue light induced radical polymerization of acrylamide (AM) were proposed and established with camphorquinone/4-(dimethylamino)-2-ethylbenzoate/diphenyl iodonium hexafluorophosphateas the photoinitiators. In order to minimize the impact of shear effect on polymer network, a constant shear stress technique of photo-rheometry was proposed to characterize in-situ viscosity behavior of acrylamide solution during the photopolymerization. The effect of various factors, for example, the dosages of initiator, monomer, and light intensities, on viscosity, polymerization and gelation behavior of AM solution was systematically analyzed. The viscosity advancement behavior was shaped by the joint action of the movement, growth and entanglement of molecular chains, and shear orientation. Different power-law kinetic models were found in three curves, time-related viscosity, shear rate-related viscosity and time-related shear rate. Such school of thought on constructing the viscosity advancement model provides a new theory and method of systematical studying on the photorheological theories. Furthermore, a trinitarian theoretical model that represented the access from the microscopic kinetics of free radical polymerization to the movement behavior of polymer chains was successfully established by mapping the photoinduced viscosity kinetics model onto the polymerization and crosslinking kinetics model.     

Polymerization of cyclopentadiene initiated by methylaluminoxane

The polymerization of cyclopentadiene (CPD) was effectively initiated by methylaluminoxane (MAO) to generate poly(cyclopentadiene) (polyCPD). The effects on the polymerization of some reaction parameters such as the monomer concentration, the initiator concentration, and solvents were investigated. The conversion of CPD was monitored with gas chromatography to investigate the reaction kinetics. The polymerization rate was proportional to the concentrations of MAO in the first order and of the CPD monomer in the second order, and a reasonable cationic polymerization mechanism was suggested on the basis of the kinetic study. PolyCPD obtained at a low temperature could be dissolved in toluene or chloroform, and this indicated lower cross‐coupling during the polymerization reaction. ¹H NMR and IR analysis of the polymer indicated that there were almost equal amounts of 1,2‐enchainment and 1,4‐enchainment in the polymer chain. The measurement of polyCPD showed its unique properties as a potential candidate for stable wrappings or electronic packaging materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 264–272, 2006