Short-chain branching in γ-radiation-induced polymerization of ethylene

In an attempt to elucidate the mechanism of chain-branch formation in the polymerization of ethylene, the effect of reaction conditions on short-chain branching in γ-radiationinduced polymerization of ethylene was investigated by using infrared spectroscopy. The concentration of methyl groups, i.e., the frequency of short-chain branching, increases with temperature and pressure and is independent of ethylene conversion to polymer and radiation intensity. The number of methyl groups per polymer molecule increases almost proportionally with the degree of polymerization. These facts indicate that short-chain branching occurs mainly by the mechanism of intramolecular hydrogen transfer. The effect of pressure on the rate of chain branching can be postulated by considering the transition state to be six-membered rings in hydrogen transfer reactions. The activation energy of chain branching is found to exceed that of propagation by 6 kcal./mole.     

Initiation and propagation in γ-radiation-induced polymerization of ethylene

The initiation and propagation reaction in γ-ray-induced polymerization of ethylene was studied by the two-stage irradiation method, i.e., a first stage in which initiation and propagation occur at a high dose rate, and a second stage where only the growth of polymer radical occurs. The rate of initiation is calculated from the amount of polymerized monomer and the degree of polymerization as the rate of increase in the number of polymer chains. The initiation rate is shown to be proportional to the ethylene density in the reactor and dose rate. G_R of radical formation is found to be about 1.6 at 30°C. at a dose rate of 2.5 × 10⁴ rad/hr. and is almost independent of ethylene density but decreases slightly with increasing irradiation dose rate. The lifetime of the growing polymer chain radical is shown to be long at normal temperature. The absolute propagation rate is proportional to the square of ethylene fugacity and depends on dose rate to some extent. For chain growth, irradiation of low dose rate is necessary. The apparent activation energy for the propagation reaction is ?9 kcal./mole.     

Simulation of Potentially Possible Reactions at the Initial Stages of Free-Radical Polymerization of Styrene and Methyl Methacrylate in the Presence of Fullerene C<Superscript>60</Superscript>

The quantum-chemical simulation of possible reactions occurring at the initial stage of the free-radical polymerizations of styrene and methyl methacrylate in the presence of fullerene C⁶⁰ is performed. The reactions of interaction between initiating and model short-chain growing radicals containing from one to three monomer units with fullerene are considered. It is shown that, at the initial stage of styrene polymerization, the addition of short-chain growing radicals to fullerene predominates (with respect to the reaction of chain propagation). In the case of methyl methacrylate polymerization in the presence of fullerene C⁶⁰, the induction period is absent because of a higher probability of the initiation and chain propagation reactions (compared with the chain-termination reaction of short growing poly(methyl methacrylate) chains on fullerene C⁶⁰). The formation of bis- and trisadducts of fullerene C⁶⁰ with short-chain styrene and methyl methacrylate growing radicals is analyzed. The quantum-chemical simulation results are confirmed by electron spectroscopy and ESR studies.     

Anionic ring‐opening polymerization of N‐glycidylphthalimide: Combination of phosphazene base and activated monomer mechanism

Anionic ring‐opening polymerization of glycidyl phthalimide, initiated with alcohol–phosphazene base systems and based on monomer activation with a Lewis acid (iBu₃Al), has been studied. No propagation occurred for initiator: iBu₃Al ratios less or equal to 1:3. For larger Lewis acid amounts, the first anionic ring‐opening polymerizations of glycidyl phthalimide were observed. Polymers were carefully characterized by NMR, MALDI‐TOF mass spectrometry, and size exclusion chromatography and particular attention was given to the detection of eventual transfer or side‐reactions. However, polymer precipitation and transfer reaction to aluminum derivative were detrimental to monomer conversion, polymerization control, and limited polymer chain molar masses. The influence of reaction temperature and solvent on polymer precipitation and transfer reactions was studied and reaction conditions have been optimized leading to afford end‐capped poly(glycidyl phthalimide) with narrow molar mass distributions. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1091–1099     

Polymerisation anionique de l'acroleine—I. Polymerisations amorcees par des organo-sodiques dans le tetrahydrofuranne

In tetrahydrofuran, with Na⁺ as counter-ion, the anionic polymerization of acrolein involves numerous transfer reactions to monomer and to polymer; on the other hand, termination of growing chains does not occur. The use of initiators, like carbanions or oxanions, does not affect the polymerization rate. The kinetic order of the reaction is unity for monomer and unity for initiator; these results indicate that the living ends are not associated at the studied concentrations of initiator. Without stating precisely the mechanism of the transfer reactions, we have proposed a kinetic scheme.In tetrahydrofuran, with Na⁺ as counter-ion, the anionic polymerization of acrolein involves numerous transfer reactions to monomer and to polymer; on the other hand, termination of growing chains does not occur. The use of initiators, like carbanions or oxanions, does not affect the polymerization rate. The kinetic order of the reaction is unity for monomer and unity for initiator; these results indicate that the living ends are not associated at the studied concentrations of initiator. Without stating precisely the mechanism of the transfer reactions, we have proposed a kinetic scheme.     

Two-stage irradiation study on propagation and termination in the γ-radiation-induced polymerization of ethylene in liquid carbon dioxide

The propagation and termination reaction in the γ-radiation-induced ethylene polymerization in liquid carbon dioxide were investigated by a two-stage irradiation. After irradiation at high dose rate, the polymerization occured at a considerable rate under the extremely low dose rate without initiation. The absolute propagation rate was determined in the second stage to be proportional to the square of ethylene fugacity and depended slightly on dose rate. The apparent activation energy for the propagation reaction is ?9 kcal./mole. From these observations which are the same as those in bulk polymerization, it is concluded that carbon dioxide acts as a diluent of ethylene monomer in the propagation reaction. Also, carbon dioxide was shown to be inactive to the growing radicals without irradiation, but oxygen which is produced by the radiolysis of carbon dioxide at high dose terminates the growing radicals with formation of carbonyl in the polymer.     

Atom transfer radical polymerization of styrene from different poly(ethylene terephthalate) surfaces: Films, fibers and fabrics

Poly(ethylene terephthalate) (PET) is a semi-crystalline thermoplastic polyester used in many fields. For a variety of applications, however, it is necessary to impart desired properties by introducing specific functional groups on the surface. A simple method for growing polymer brushes by atom transfer radical polymerization (ATRP) on PET films, fibers and fabrics was devised. The different PET surfaces were first reacted with 1,2-diaminoethane by aminolysis reaction to incorporate primary amino and alcohol functions on the surface. Then, in a second step, ATRP initiator was grafted by reaction with bromoisobutyryl bromide. The efficiency of these reactions was confirmed by using colorimetric titration and X-ray photoelectron spectroscopy (XPS). Surface-initiated ATRP was performed in bulk using styrene monomer with CuBr/PMDETA catalytic system in the presence of a sacrificial initiator (ethyl 2-bromoisobutyrate). Good control of the polymerization was obtained as attested by comparison of polystyrene molar masses obtained in solution from sacrificial initiator with those obtained from the surface after cleavage. Wetting properties were found to vary systematically depending to the type of functionalization and grafting. Evolution of surface morphology according to reaction steps was investigated using atomic force microscopy (AFM).     

Synthesis and characterization of poly(ϵ-caprolactone)-poly(ethylene glycol) block copolymer

Poly(ϵ-caprolactone)–poly(ethylene glycol)–poly(ϵ-caprolactone) triblock copolymers (PECL) covering a wide range of poly(ethylene glycol) (PEG) lengths were synthesized with alkali metal alkoxide derivatives of poly(ethylene glycol). The effects of various factors, such as amount of the initiator, reaction time and temperature, polarity of solvent, length of PEG segment, and counterion on the polymerization were investigated. The copolymers were characterized by ¹H-NMR, IR, GPC, and DSC. It was found that THF system is superior to toluene system. The conversion of the monomer increased with increase of the initiator concentration. High molecular weight of the copolymer and high conversion of the monomer was obtained at below 30°C within 5 min. The polymerization process was studied by GPC and the coexistence of propagation and transesterification reaction was found, which leaded to relatively broad molecular weight distribution of the copolymers. © 1997 John Wiley & Sons, Inc.     

Chain termination in polymerization of substituted oxetanes in the presence of boron trifluoride etherate

It has been shown that the polymerization of oxetanes with azidomethyl substituents initiated by boron trifluoride etherate in the absence and the presence of ethylene glycol proceeds via chain termination with fluorine atom transfer. This reaction results in the formation of a polymer that is monofunctional with respect to hydroxyl groups and contains a fluorine atom at one of the chain ends. With the use of ¹⁹F NMR spectroscopy, the number-average functionality of polymer with respect to fluorine atoms was studied. The methods of suppressing the aforementioned reaction, whose intensity decreases during a decrease in the polymerization temperature and an increase in the ethylene glycol concentration, were considered. In the absence of ethylene glycol, the chain termination with fluorine atom transfer is the main reaction of chain-propagation restriction.     

Gel formation in free radical polymerization via chain transfer and terminal branching

Gel formation in free-radical polymerization via chain transfer to polymer, recombination termination, and terminal branching due to either chain transfer to monomer or disproportionation termination is investigated using the method of moments. It is found that no gel can possibly form in the systems consisting of initiation, propagation, and one of the above reactions. However, systems with the following combination of reactions are found to be capable of gelling. They are: chain transfer to polymer + recombination termination; chain transfer to polymer + terminal branching due to disproportionation termination; and terminal branching due to transfer to monomer + recombination termination. Systems with the following combination of reactions are incapable of gelling; transfer to polymer + terminal branching due to transfer to monomer; and terminal branching due to disproportionation termination + recombination termination. An examination of the gelation mechanisms reveals that the formation of multivinyl macromonomers during the course of polymerization is the reason that systems involving terminal branching gel. Sol/gel diagrams are generated to give critical kinetic parameters required for gelation. It is found that terminal branching does not always promote gelation due to the adverse effect on chain length through chain transfer to monomer and termination by disproportionation, reactions which generate terminal double bonds. © 1994 John Wiley & Sons, Inc.     

Simulation of the effects of chain architecture on the sorption of ethylene in polyethylene

An osmotic ensemble hyperparallel tempering technique has been developed to study the solubility of ethylene in amorphous linear low-density polyethylene of different chain architectures. The NERD united-atom force field (Nath, Escobedo, and de Pablo revised united-atom force field) is used in all simulations. We have investigated the effect of polyethylene chain length and branching on ethylene solubility. In this study, we have considered short-chain branching of amorphous linear low-density ethylene-1-hexene copolymers under typical polymerization reactor conditions. It is observed that, in the polymer, ethylene prefers to reside in the vicinity of polymer chain ends. This clustering causes a decrease in ethylene solubility with polymer chain length. When short-chain branches are introduced to a linear polymer chain, however, the chain-end clustering effect is counteracted by a higher density, thereby leading to an ethylene solubility almost identical to that in the linear polymer.     

Hyperbranched polymers generated from oxyanionic vinyl polymerization of commercially available methacrylate inimers

Hyperbranched polymethacrylates were prepared by means of oxyanionic vinyl polymerization of commercially available monomers, including hydroxyethyl methacrylate (HEMA) and poly(ethylene glycol) methacrylate (PEG‐MA). Hyperbranched polymethacrylates with high molecular weight were obtained with the complex of potassium hydride and 18‐crown‐6 as the initiator. The effect of 18‐crown‐6 is very important, and only oligomer can be obtained in the polymerization without 18‐crown‐6. The molecular structure of the hyperbranched polymers was confirmed with ¹H NMR and ¹³C NMR spectra. The ratio of initiator to monomer significantly affects the architecture of the resultant polymers. When the ratio of initiator to monomer equals 1 in the oxyanionic vinyl polymerization of HEMA, the degree of branching of the resulting polymer was calculated to be around 0.49. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3502–3509, 2005     

A novel scheme of heterogeneous polymerization of ethylene

The heterogeneous polymerization of ethylene initiated by radiation in tert-butyl alcohol was studied. The polymerization was carried out in a 100-ml reactor at 25–100°C and pressures of 200–300 kg/cm² in the presence of 50 ml of tert-butyl alcohol containing 7 wt-% water. The amounts of polymerized monomer, the average molecular weight of polymer formed, and the molecular weight distribution of polymer were measured at various stages of reaction and at various temperatures. The molecular weight distribution was found to be very much dependent on the reaction time and temperature. For the polymer formed at 50–60°C in the very early stages of reaction, the molecular weight distribution is unimodal, and in the intermediate stage a shoulder appears at a molecular weight higher than the first peak which increases as the polymerization proceeds; eventually a bimodal curve is formed. The bimodal distribution curves were analyzed to determine the fractions and average molecular weights of the each peak. On the basis of these data for the molecular weight distribution and kinetic behavior, a new scheme for the heterogeneous polymerization is proposed which indicates that the polymerization proceeds via propagating radicals in two different physical states, namely, loose and rigid states.     

Kinetics of the gamma-radiation-induced polymerization of ethylene in tert-butyl alcohol

The gamma-radiation-induced polymerization of ethylene in the presence of 13–30 ml of tert-butyl alcohol was carried out under a pressure of 120–400 kg/cm² at a dose rate of 1 × 10³ to 2.5 × 10⁴ rad/hr at 30°C with a 100 ml reactor. The polymerization rate and the molecular weight of the polymer increased with reaction time and pressure and decreased with amount of tert-butyl alcohol. The polymer yield increased almost proportionally with the dose rate, while the molecular weight was almost independent of it. These results were graphically evaluated, and the rate constants of initiation, propagation, and termination for various conditions were determined. No transfer was observed. On the basis of these results the role of tert-butyl alcohol in the polymerization is discussed.     

Radiation-induced homogeneous polymerization of ethylene in cyclohexane

The radiation-induced polymerization of ethylene in cyclohexane was carried out in a reactor of 100 ml capacity under a range of temperature of 25–150°C, dose rate of 4.1 × 10⁴–2.9 × 10⁵ rad/hr, pressure of 200 kg/cm², and amount of cyclohexane of 20–90 ml. The polymerization was found to proceed at a steady state from the beginning. The polymerization rate is maximum at ca. 50 ml of cyclohexane. The dose rate exponent of the polymerization rate was 0.6 at every temperature from 25 to 150°C. The polymer molecular weight is in the range of 10³–10⁴, independent of dose rate, and decreases with increasing amount of cyclohexane. The molecular weight distribution is unimodal and narrow. Kinetic analysis of these results indicates that the polymerization proceeds via a simple scheme of homogeneous polymerization and the polymer molecular weight was determined by the chain transfer reaction which takes place mostly with cyclohexane. The unimodal and narrow molecular weight distribution is also consistent with the homogeneous polymerization scheme.     

Synthesis of well-defined ABC triblock copolymers with polypeptide segments by ATRP and click reactions

Well-defined ABC block copolymers consisting of poly(ethylene oxide) monomethylene ether (MPEO) as A block, poly(styrene) (PS) as B block and poly(γ-benzyl-l-glutamate) (PBLG) as C block were synthesized by the combination of atom transfer radical polymerization (ATRP) and click reactions. The bromine-terminated diblock copolymer poly(ethylene oxide) monomethylene ether-block-poly(styrene) (MPEO-PS-Br) was prepared by ATRP of styrene initiated with macro-initiator MPEO-Br, which was prepared from the esterification of MPEO and 2-bromoisobutyryl bromide, and converted into the azido-terminated diblock copolymer MPEO-PS-N₃ by simple nucleophilic substitutions in DMF in the presence of sodium azide. Propargyl-terminated PBLGs were synthesized by ring-opening polymerization of γ-benzyl-l-glutamate-N-carboxyanhydride in DMF at room temperature using propargyl amine as an initiator. ABC triblock copolymers MPEO-PS-PBLG with a wide range of number-average molecular weights from 1.55 to 3.75 × 10⁴ and a narrow polydispersity from 1.07 to 1.10 were synthesized via the click reaction of MPEO-PS-N₃ and the propargyl-terminated PBLG in the presence of CuBr and 1,1,4,7,7-pentamethyldiethylenetriamine (PMDETA) catalyst system. The structures of these ABC block copolymers and corresponding precursors were characterized by NMR, IR and GPC. The results showed that click reaction was efficient. Therefore, a facile approach was offered to synthesize ABC triblock copolymers composed of crystallizable polymer MPEO, conventional vinylic polymer PS and rod-like α-helix polypeptide PBLG.     

Radiation-induced emulsion polymerization of ethylene. II. Effect of potassium myristate concentration and dose rate on the rate of polymerization in connection with polymer properties,kinetics, and mechanism

Radiation-induced emulsion polymerization of ethylene with potassium myristate as an emulsifier was studied in connection with the kinetics and the mechanism. The molecular weight of polymer was relatively low, of the order of 10³, when a sufficient amount of emulsifier was used. However, polyethylene gel was produced in the absence of a sufficient amount of emulsifier. The rate of polymerization was proportional to the 0.5 power of dose rate and increased slightly with increasing emulsifier concentration. The rate of seeded polymerization followed a similar trend to that for conventional polymerization. Kinetic analysis of these results suggests that the escape of radicals produced by chain transfer of propagating radical with the emulsifier and the monomer from polymer particles into the aqueous phase plays an important part in the rate of polymerization. The melting temperature and the crystallinity of the polymer significantly decreased with increasing polymerization temperature in the range 40–60°C.     

Mechanistic Investigation of Catalyst‐Transfer Suzuki–Miyaura Condensation Polymerization of Thiophene–Pyridine Biaryl Monomers with the Aid of Model Reactions

We have investigated the requirements for efficient Pd‐catalyzed Suzuki–Miyaura catalyst‐transfer condensation polymerization (Pd‐CTCP) reactions of 2‐alkoxypropyl‐6‐(5‐bromothiophen‐2‐yl)‐3‐(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)pyridine ( 12 ) as a donor–acceptor (D –A) biaryl monomer. As model reactions, we first carried out the Suzuki–Miyaura coupling reaction of X–Py–Th–X′ (Th=thiophene, Py=pyridine, X, X′=Br or I) 1 with phenylboronic acid ester 2 by using tBu₃PPd⁰ as the catalyst. Monosubstitution with a phenyl group at Th‐I mainly took place in the reaction of Br–Py–Th–I ( 1 b ) with 2 , whereas disubstitution selectively occurred in the reaction of I–Py–Th–Br ( 1 c ) with 2 , indicating that the Pd catalyst is intramolecularly transferred from acceptor Py to donor Th. Therefore, we synthesized monomer 12 by introduction of a boronate moiety and bromine into Py and Th, respectively. However, examination of the relationship between monomer conversion and the M_n of the obtained polymer, as well as the matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectra, indicated that Suzuki–Miyaura coupling polymerization of 12 with (o‐tolyl)tBu₃PPdBr initiator 13 proceeded in a step‐growth polymerization manner through intermolecular transfer of the Pd catalyst. To understand the discrepancy between the model reactions and polymerization reaction, Suzuki–Miyaura coupling reactions of 1 c with thiopheneboronic acid ester instead of 2 were carried out. This resulted in a decrease of the disubstitution product. Therefore, step‐growth polymerization appears to be due to intermolecular transfer of the Pd catalyst from Th after reductive elimination of the Th‐Pd‐Py complex formed by transmetalation of polymer Th–Br with (Pin)B–Py–Th–Br monomer 12 (Pin=pinacol). Catalysts with similar stabilization energies of metal–arene η²‐coordination for D and A monomers may be needed for CTCP reactions of biaryl D–A monomers.     

ICAR ATRP of acrylonitrile utilizing a moderate temperature radical initiator

Initiators for continuous activator regeneration atom transfer radical polymerization （ICAR ATRP） of acrylonitrile was first conducted at various ambient temperatures （30-45 ℃）. The key to success is ascribed to the usage of an appropriate low temperature radical initiator （2,2＇-azobis（2,4-dimethylvaleronitrile）） and a high reactivity catalytic system （CuBr2/Me6TREN）. The molar ratio of Cu catalyst tO AN as low as 1：20000 wa.s used to prepare well-defined polyacrylonitrile with controlled molecular weight and a narrow polydispersity index range of 1.08-1.30, while the monomer conversion was up to ca. 98%. The apparent activation energy of the polymerization was calculated to be 128.45 kJ/mol, suggesting that the polymerization strongly depended on reaction temperature. The very high chain-end functionality of the resultant polymer was confirmed by ^1H-NMR and GPC analyses as well as chain extension reaction.     

Kinetic study of ethylene polymerization with chromium oxide catalysts by a radiotracer technique

The quenching of polymerization with a chromium oxide catalyst by radioactive methanol ¹⁴CH₃OH enables one to determine the concentration of propagation centers and then to calculate the rate constant of the propagation. The dependence of the concentration of propagation centers and the polymerization rate on reaction time, ethylene concentration, and temperature was investigated. The change of the concentration of propagation centers with the duration of polymerization was found to be responsible for the time dependence of the overall polymerization rate. The propagation reaction is of first order on ethylene concentration in the pressure range 2–25 kg/cm². For catalysts of different composition, the temperature dependence of the overall polymerization rate and the propagation rate constant were determined, and the overall activation energy E_ov and activation energy of the propagation state E_p were calculated. The difference between E_ov and E_p is due to the change of the number of propagation centers with temperature. The variation of catalyst composition and preliminary reduction of the catalyst influence the shape of the temperature dependence of the propagation center concentration and change E_ov.