Polymerization of diethylene glycol bis(allyl carbonate) by means of di-sec-butyl peroxydicarbonate

The initial stages of the free radical polymerization of diethylene glycol bis(allyl carbonate) at temperatures of 35–65°C have been studied. The polymer is unsaturated and cyclization to give a 16-membered ring occurs only to a small extent. The kinetic order with respect to the initiator, di-sec-butyl peroxydicarbonate, has an average value of 0.79; the order increases slightly with peroxydicarbonate concentration over the range 0.018–0.22M. The molecular weight of the polymer isolated after 3% polymerization is close to 19,000. It shows no significant dependence on initiator concentration or on temperature. The dominant feature of the bulk polymerization, as in free radical polymerization of the other allyl and diallyl monomers, is degradative chain transfer in which the growing polymer radical abstracts a hydrogen atom from a monomer unit to give a relatively unreactive allylic radical. The dependence of rate on initiator concentration is rationalized if some of these allylic radicals are able to reinitiate polymerization. The transfer constant to monomer is 0.014 at 50°C, assuming that the main termination step involves mutual termination of allylic radicals. Carbon tetrachloride is an active transfer agent with a transfer constant of 0.20 ± 0.04 at 50°C. Toluene, which is less active, has a transfer constant of 0.0064 at 50°C and also retards the polymerization. Some kinetic studies have been made with other initiators, including di-2-methyl-pentanoyl peroxide which initiates polymerization at temperatures as low as 13°C.     

Poly(N-n-butylitaconimide). Preparation and characterization

Poly(N-n-butylitaconimide) was prepared by radical polymerization in benzene and in bulk at 60°C and was subsequently fractionated at 30°C with benzene and methanol as solvent and nonsolvent, respectively. Relationships between molecular weight and intrinsic viscosity (Mark-Houwink-Sakurada equations) in tetrahydrofuran, benzene, and toluene at 30°C are established. From the Burchard-Stockmayer-Fixman plot, the characteristic ratio of this polymer is determined, and local chain conformation is discussed in relation to the termination process in radical polymerization. © 1993 John Wiley & Sons, Inc.     

Anomalous solubility of polyacrylamide prepared by dispersion (precipitation) polymerization in aqueous tert‐butyl alcohol

Polyacrylamide prepared by dispersion (precipitation) polymerization in an aqueous t‐butyl alcohol (TBA) medium is only partially soluble when the TBA concentrations in the polymerization media are in the range 82 vol % < TBA < 95 vol %. Independent experiments with a soluble (linear) sample of polyacrylamide show that the polymer swells sufficiently in the aforementioned media to lower the glass‐transition temperature of the polymer below the polymerization temperature (50 °C). The anomalous solubility has been attributed to the crosslinking of polymer chains that occurs during the solid‐phase polymerization of acrylamide in the swollen polymer particles. It is postulated that some of the radical centers shift from the chain end to the chain backbone during solid‐phase polymerization by chain transfer to neighboring polymer molecules, and when pairs of such radicals come into close vicinity, crosslinking occurs. However, dispersion (precipitation) polymerization in other media such as aqueous methanol and aqueous acetone yields polymers that are soluble. This result has been attributed to the fact that the polymer radical undergoes a chain‐transfer reaction with these solvents at a much faster rate than with TBA, which overcomes the effect of the polymer‐transfer reaction. Even the addition of as little as 5% methanol to a TBA–water mixture (TBA:water = 85:10) gives rise to a soluble polymer. The chain‐transfer constants for acetone, methanol, and TBA have been determined to be 9.0 × 10^?6, 6.9 × 10^?6, and 1.48 × 10^?6, respectively, at 50 °C. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3434–3442, 2001     

Kinetics of polymerization of acrylonitrile initiated by the Mn3+-thioacetamide redox system

Kinetics of the polymerization of acrylonitrile has been investigated in aqueous sulfuric acid in a temperature range of 25–45°C. The rate of polymerization (R_p) and the rate of managanic ion disappearance, etc., have been measured. The effect of the various additives, such as water-miscible organic solvents, neutral electrolytes, complexing agents, and surfactants, on the rate has been thoroughly studied. A mechanism that involves the initial complex formation between the thiol form of the thioamide and Mn³⁺, whose decomposition yields the initiating free radical with the polymer chain terminated by mutual combination of growing radicals, has been suggested.     

Redox polymerization of acrylonitrile. Kinetics of the reaction initiated by the redox system tartaric acid–V5+

Kinetics of vinyl polymerization of acrylonitrile initiated by the redox system tartaric acid–V⁵⁺ have been investigated in aqueous sulfuric acid in the temperature range 30–40°C. The rates of polymerization and V⁵⁺ disappearance and the chain lengths of polyacrylonitrile were measured. From the results it is concluded that the polymerization reaction is initiated by an organic free radical arising from the V⁵⁺–tartaric acid reaction with termination by V⁵⁺ ions. A suitable kinetic scheme has been proposed, and the various rate and energy parameters were evaluated.     

Polymerization of vinyl monomers by a new oligoperoxide: Oligo(adipoyl-5-peroxy-2,5-dimethyl n-hexyl peroxide)

A new polymeric initiator, oligo(adipoyl-5-peroxy-2,5-dimethyl n-hexyl peroxide), was synthesized by interfacial condensation of adipoyl chloride with 2,5-dimethyl-2,5-dihydroperoxy hexane. This can be used as an initiator to prepare block copolymers by free radical mechanism in a procedure involving several steps, since the colorless, viscous liquid, oligoperoxide, has 8–10 peroxide groups per molecule. The thermal decomposition of this oligoperoxide in benzene solution at 98°C was first order and its half life was 9.75 h. The results of the polymerization kinetics show that this oligoperoxide lies in between of 2,5-dimethyl-2,5-dihydroperoxyhexane and benzoyl peroxide for empirical polymerization rates of styrene and methyl methacrylate at 80°C.     

Controlled free radical ring-opening polymerization and chain extension of the “living” polymer

Free radical ring-opening polymerization of 2-methylene-1,3-dioxepane (MDP) in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy free radical (TEMPO) has been achieved to afford a chain polyester (PMDP) with di-t-butyl peroxide (DTBP) as an initiator at 125°C. The polydispersity of the polymers decreases as the concentration of TEMPO is increased. At high TEMPO concentrations, the polydispersity as low as 1.2 was obtained, which is below the theoretical lower limit for a conventional free radical polymerization. A linear relationship between the number-average molecular weight (M_n) and the monomer conversion was observed with the best-fit line passing very close to the origin of the M_n-conversion plot. The isolated and purified TEMPO-capped PMDP polymers have been employed to prepare chain extended polymers upon addition of more MDP monomer. These results are suggestive of the “living” polymerization process. A possible polymerization mechanism might involve thermal homolysis of the TEMPO-PMDP bonds followed by the addition of the monomers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 761–771, 1998     

Polymerization of methyl methacrylate initiated by Mn(III)–glycerol redox system

The kinetics of thermal polymerization of methyl methacrylate initiated by the redox system Mn(III)–glycerol was studied in aqueous sulfuric acid in the temperature range of 30–40°C, and the rates of polymerization, R_p, and Mn³⁺ disappearance, etc., were measured. The effect of certain water-miscible organic solvents and certain cationic and anionic surfactants on the rates of polymerization has been investigated. A mechanism involving the formation of a complex between Mn³⁺ and glycerol whose decomposition yields the initiating free radical with the polymerization being terminated by the metal ion has been suggested.     

Kinetics of free-radical polymerization of p-vinylbenzyl methyl ether: Crosslinking by initiator free radicals

Kinetics of polymerization of p-vinylbenzyl methyl ether at low conversion either in bulk or in benzene have been found to be quite similar to those of the unsubstituted monomer styrene. Rates of polymerization initiated by peroxides or α,α′-azobisisobutyronitrile over the temperature range 50–70°C. have been found to be proportional to [Monomer][Initiator]^1/2 with an activation energy difference E_propagation – 1/2 E_termination ≈ 6 kcal./mole. Azo initiation leads to essentially unbranched poly(vinyl-benzyl methyl ether) even at very high conversions, whereas initiation of undiluted monomer by diacyl peroxides results in some crosslinking at high conversion. Use of biacetyl as a photoinitiator of polymerization over the temperature range 0–60°C. with either bulk monomer or monomer solutions in benzene has been found in each instance to yield crosslinked, insoluble polymers at low degrees of conversion. Benzene solutions of soluble polymer have been converted to high molecular weight branched polymers by free radicals generated by photolysis of biacetyl, and a substantial preference of methyl free radicals to abstract benzyl hydrogens of poly(p-vinylbenzyl methyl ether) rather than add to solvent benzene has been observed.     

Living free‐radical polymerization of sterically hindered monomers: Improving the understanding of 1,1‐disubstituted monomer systems

The sterically hindered, 1,1‐disubstituted monomers di‐n‐butyl itaconate (DBI), dicyclohexyl itaconate (DCHI), and dimethyl itaconate (DMI) were polymerized with reversible addition–fragmentation chain transfer (RAFT) free‐radical polymerization and atom transfer radical polymerization (ATRP). Cumyl dithiobenzoate, cumyl phenyl dithioacetate, 2‐cyanoprop‐2‐yl dithiobenzoate, 4‐cyanopentanoic acid dithiobenzoate, and S‐methoxycarbonylphenylmethyl dithiobenzoate were employed as RAFT agents to mediate a series of polymerizations at 60 °C yielding polymers ranging in their number‐average molecular weight from 4500 to 60,000 g mol^?1. The RAFT polymerizations of these hindered monomers displayed hybrid living behavior (between conventional and living free‐radical polymerization) of various degrees depending on the molecular structure of the initial RAFT agent. In addition, DCHI was polymerized via ATRP with a CuCl/methyl benzoate/N,N,N′,N″,N″‐pentamethyldiethylenetriamine/cyclohexanone system at 60 °C. Both the ATRP and RAFT polymerization of the hindered monomers displayed living characteristics; however, broader than expected molecular weight distributions were observed for the RAFT systems (polydispersity index = 1.15–3.35). To assess the cause of this broadness, chain‐transfer‐to‐monomer constants for DMI, DBI, and DCHI were determined (1.4 × 10^?3, 1.3 × 10^?3, and 1.0 × 10^?3, respectively) at 60 °C. Simulations carried out with the PREDICI program package suggested that chain transfer to monomer contributed to the broadening process. In addition, the experimental results indicated that viscosity had a pronounced effect on the broadness of the molecular weight distributions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3692–3710, 2006     

Low‐temperature controlled free‐radical polymerization of vinyl monomers in the presence of a novel cyclic dixanthate under γ‐ray irradiation

The free‐radical polymerization of methyl acrylate (MA) has been studied in the presence of a novel cyclic dixanthate under γ‐ray irradiation (80 Gy min^?1) at room temperature (～28 °C), ?30 °C, and ?76 °C respectively. The resultant polymers have controlled molecular weights and relatively narrow molecular weight distributions, especially at low temperatures (i.e., ?30 and ?76 °C). The polymerization control may be associated with the temperature: the lower the temperature is, the more control there is. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis of poly(methyl acrylate) (PMA) samples shows that there are at least three distributions: [3‐(MA)_n‐H]⁺ cyclic polymers, [3‐(MA)_n‐THF‐H]⁺, and [3‐(MA)_n‐(THF)₂‐H]⁺ linear PMAs. The relative content of the cyclic polymers markedly increases at a lower temperature, and this may be related to the reduced diffusion rate and the suppressed chain‐transfer reaction at the low temperature. It is evidenced that the good control of the polymerization at the low temperature may be associated with the suppressed chain‐transfer reaction, unlike reversible addition–fragmentation chain transfer polymerization. In addition, styrene bulk polymerizations have been performed, and gel permeation chromatography traces show that there is only one cyclic dixanthate moiety in the polymer chain. This article is the first to report the influence of a low temperature on controlled free‐radical polymerizations. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2847–2854, 2007     

Free‐radical polymerization of dioxolane and dioxane derivatives: Effect of fluorine substituents on the ring opening polymerization

Partially fluorinated and perfluorinated dioxolane and dioxane derivatives have been prepared to investigate the effect of fluorine substituents on their free‐radical polymerization products. The partially fluorinated monomer 2‐difluoromethylene‐1,3‐dioxolane (I) was readily polymerized with free‐radical initiators azobisisobutyronitrile or tri(n‐butyl)borane–air and yielded a vinyl addition product. However, the hydrocarbon analogue, 2‐methylene‐1,3‐dioxolane (II), produced as much as 50% ring opening product at 60 °C by free‐radical polymerization. 2‐Difluoromethylene‐4‐methyl‐1,3‐dioxolane (III) was synthesized and its free‐radical polymerization yielded ring opening products: 28% at 60 °C, decreasing to 7 and 4% at 0 °C and −78 °C, respectively. All the fluorine‐substituted, perfluoro‐2‐methylene‐4‐methyl‐1,3‐dioxolane (IV) produced only a vinyl addition product with perfluorobenzoylperoxide as an initiator. The six‐membered ring monomer, 2‐methylene‐1,3‐dioxane (V), caused more than 50% ring opening during free‐radical polymerization. However, the partially fluorinated analogue, 2‐difluoromethylene‐1,3‐dioxane (VI), produced only 22% ring opening product with free‐radical polymerization and the perfluorinated compound, perfluoro‐2‐methylene‐1,3‐dioxane (VII), yielded only the vinyl addition polymer. The ring opening reaction and the vinyl addition steps during the free‐radical polymerization of these monomers are competitive reactions. We discuss the reaction mechanism of the ring opening and vinyl addition polymerizations of these partially fluorinated and perfluorinated dioxolane and dioxane derivatives. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5180–5188, 2004     

Relevance of a prereaction for the in situ NMP of styrene using the C‐Phenyl‐N‐tert‐butylnitrone/2,2′‐azobis(isobutyronitrile) pair

In this article, we compare two routes for carrying out in situ nitroxide‐mediated polymerization of styrene using the C‐phenyl‐N‐tert‐butylnitrone (PBN)/2,2′‐azobis(isobutyronitrile) (AIBN) pair to identify the best one for an optimal control. One route consists in adding PBN to the radical polymerization of styrene, while the other approach deals with a prereaction between the nitrone and the free radical initiator prior to the addition of the monomer and the polymerization. The combination of ESR and kinetics studies allowed demonstrating that when the polymerization of styrene is initiated by AIBN in the presence of enough PBN at 110 °C, fast decomposition of AIBN is responsible for the accumulation of dead polymer chains at the early stages of the polymerization, in combination with controlled polystyrene chains. On the other hand, PBN acts as a terminating agent at 70 °C with the formation of a polystyrene end‐capped by an alkoxyamine, which is not labile at this temperature but that can be reactivated and chain‐extended by increasing the temperature. Finally, the radical polymerization of styrene is better controlled when the nitrone/initiator pair is prereacted at 85 °C for 4 h in toluene before styrene is added and polymerized at 110 °C. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1085–1097, 2009     

Radical polymerization of vinyl thiocyanatoacetate: Participation of group‐transfer mechanism

Vinyl thiocyanatoacetate (VTCA) was synthesized, and its radical polymerization behavior was studied in acetone with dimethyl 2,2′‐azobisisobutyrate (MAIB) as an initiator. The initial polymerization rate (R_p) at 60 °C was expressed by R_p = k[MAIB]^0.6±0.1 [VTCA]^1.0±0.1 where k is a rate constant. The overall activation energy of the polymerization was 112 kJ/mol. The number‐average molecular weights of the resulting poly (VTCA)s (1.4–1.6 × 10⁴) were almost independent of the concentrations of the initiator and monomer, indicating chain transfer to the monomer. The chain‐transfer constant to the monomer was estimated to be 9.6 × 10^?3 at 60 °C. According to the ¹H and ¹³C NMR spectra of poly (VTCA), the radical polymerization of VTCA proceeded through normal vinyl addition and intramolecular transfer of the cyano group. The cyano group transfer became progressively more important with decreasing monomer concentration. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 573–582, 2002; DOI 10.1002/pola.10137     

Chain transfer to solvent in the radical polymerization of N‐isopropylacrylamide

Chain transfer to solvent has been investigated in the conventional radical polymerization and nitroxide‐mediated radical polymerization (NMP) of N‐isopropylacrylamide (NIPAM) in N,N‐dimethylformamide (DMF) at 120 °C. The extent of chain transfer to DMF can significantly impact the maximum attainable molecular weight in both systems. Based on a theoretical treatment, it has been shown that the same value of chain transfer to solvent constant, C_tr,S, in DMF at 120 °C (within experimental error) can account for experimental molecular weight data for both conventional radical polymerization and NMP under conditions where chain transfer to solvent is a significant end‐forming event. In NMP (and other controlled/living radical polymerization systems), chain transfer to solvent is manifested as the number‐average molecular weight (M_n) going through a maximum value with increasing monomer conversion. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Effect of glyoxylic oxime ether on radical polymerization of styrene

Methyl benzyloxyiminoacetate (MBOIA), a glyoxylic oxime ether, revealed different behaviors depending on the kinds of monomers used in the radical polymerization. MBOIA served as a retarder for styrene (St) and an inhibitor for vinyl acetate, whereas it showed little effect on the polymerization of methyl methacrylate. The retardation effect of MBOIA on the polymerization of St with dimethyl 2,2′‐azobisisobutyrate (MAIB) was examined in detail in benzene. The rate constant (k_x) of the reaction of MBOIA with polystyrene (PS) radical was 92 L/mol s at 50 °C, 112 L/mol s at 60 °C, and 143 L/mol s at 70 °C, indicating that the reactivity of MBOIA toward PS radical is less than that of St by a factor of about 3. The Arrhenius plot of k_x gave an activation energy of 20.3 kJ/mol. A nitrogen‐centered radical of a stationary state was observed by electron spin resonance (ESR) in the polymerization of St with MAIB at 60 °C in benzene in the presence of MBOIA, which is assignable to the radical (MBOIA ·) formed by addition of PS radical to MBOIA. The stationary MBOIA · concentration increased with increasing MBOIA concentration and then tended to be saturated at high concentrations. The rate constant of termination between MBOIA · radicals was 1.87 × l0⁵ L/mol s at 60 °C with ESR. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2772–2781, 2002     

Initiator‐fragment incorporation radical polymerization of divinylbenzene in the presence of glyoxylic oxime ether: Formation of soluble hyperbranched polymer

The copolymerization of divinylbenzene (DVB) and ethylstyrene (EtSt) was carried out at 70 and 80 °C in benzene with dimethyl 2,2‐azobisisobutyrate (MAIB) at high concentrations as initiator in the presence of methyl benzyloxyiminoacetate (MBOIA), a glyoxylic oxime ether, as a retarder. The copolymerization system of DVB (0.25 mol/L), EtSt (0.25 mol/L), MBOIA (0.5 mol/L), and MAIB (0.5 mol/L) gave benzene‐soluble copolymers despite a considerably high concentration of DVB as an excellent crosslinker. The yield and molecular weight of the resulting copolymers increased with time both at 70 and 80 °C and then leveled off because of initiator consumption. The homogeneous polymerization system involved electron spin resonance (ESR), observable nitrogen‐centered polymer radicals (MBOIA·) under the actual polymerization conditions. The MBOIA· concentration increased with time despite a homogeneous polymerization system, suggesting the formation of rigid hyperbranched polymers. A benzene solution of isolated copolymer also showed an ESR signal. The copolymer was soluble in acetone, toluene, chloroform, ethyl acetate, tetrahydrofuran, and N,N‐dimethylformamide but insoluble in n‐hexane, methanol, and dimethyl sulfoxide. MAIB fragments as high as 30–40 mol % were incorporated into the copolymers through initiation and primary radical termination, on the basis of which this polymerization was named the initiator‐fragment incorporation radical polymerization. MBOIA (13–16 mol%) was also incorporated into the copolymers through an opening of the C?N bond. The intrinsic viscosity of the copolymers was very low (0.08 dL/g), and the reduced viscosity was almost independent of the polymer concentration, supporting a hyperbranched structure of them. Gel permeation chromatography and multi‐angle laser light scattering and transmission electron microscopy revealed that the copolymer was formed as a hyperbranched nanoparticle. The thermal behavior of the copolymer was examined by dynamic thermogravimetry and differential scanning calorimetry. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3038–3047, 2003     

Radical polymerization of allylbiguanide

Monoallyl compounds are not readily homopolymerized by a conventional free‐radical mechanism. However, we successfully performed the radical polymerization of allylbiguanide hydrochloride in a concentrated acid solution (hydrochloric acid or phosphoric acid) in the presence of a radical initiator at 50 °C. The polymer product was precipitated from the reaction solution through the addition of an excess amount of acetone. The precipitated crude polymer [polyallylbiguanide (PAB)] was then purified by dialysis. PAB was confirmed by elemental analysis, infrared spectroscopy, and ¹H NMR. The molecular weight range of PAB was 10,340–113,200, and PAB exhibited a low polydispersity (weight‐average molecular weight/number‐average molecular weight = 1.04–1.68) by multi‐angle laser light scattering. The polymerization of allylbiguanide was quite sensitive to the protonic concentration of the inorganic acid. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1707–1711, 2004     

Controlled radical polymerization of styrene mediated by the C‐phenyl‐N‐tert‐butylnitrone/AIBN pair: Kinetics and electron spin resonance analysis

Kinetics of the free radical polymerization of styrene at 110 °C has been investigated in the presence of C‐phenyl‐N‐tert‐butylnitrone (PBN) and 2,2′‐azobis(isobutyronitrile) (AIBN) after prereaction in toluene at 85 °C. The effect of the prereaction time and the PBN/AIBN molar ratio on the in situ formation of nitroxides and alkoxyamines (at 85 °C), and ultimately on the control of the styrene polymerization at 110 °C, has been investigated. As a rule, the styrene radical polymerization is controlled, and the mechanism is one of the classical nitroxide‐mediated polymerization. Only one type of nitroxide (low‐molecular‐mass nitroxide) is formed whatever the prereaction conditions at 85 °C, and the equilibrium constant (K) between active and dormant species is 8.7 × 10^?10 mol L^?1 at 110 °C. At this temperature, the dissociation rate constant (k_d) is 3.7 × 10^?3 s^?1, the recombination rate constant (k_c) is 4.3 × 10⁶ L mol^?1 s^?1, whereas the activation energy (E_a,diss.), for the dissociation of the alkoxyamine at the chain‐end is ～125 kJ mol^?1. Importantly, the propagation rate at 110 °C, which does not change significantly with the prereaction time and the PBN/AIBN molar ratio at 85 °C, is higher than that for the thermal polymerization at 110 °C. This propagation rate directly depends on the equilibrium constant K and on the alkoxyamine and nitroxide concentrations, as well. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1219–1235, 2007     

New ligands for atom‐transfer radical polymerization

A new type of ligands based on organic acids, such as acetic acid, iminodiacetic acid, succinic acid and isophthalic acid, has been successfully employed in the iron‐mediated atom‐transfer radical polymerization (ATRP) of vinyl monomers, such as styrene (St) and methyl methacrylate (MMA). The systems containing different organic acids can react at 250°C to 1300°C in “living”/controlled radical polymerizations giving polymers with relatively narrow molecular weight distributions (M_w/M_n = 1.2–1.5). ¹H NMR spectroscopy has been used to study the structure of the resulting polymers. Block copolymers were synthesized to confirm the ìlivingî nature of the system. The measured molecular weights are close to the calculated values for the polymerization of MMA and are somewhat lower than the theoretical ones for styrene.