Studies on Polymerization of Vinyl Compounds Initiated by Metal Chelate II Kinetics of Polymerization of Methyl Methacrylate Initiated by Nickel Ethyl Acetoacetate in the Presence and the Absence of Aromatic Amines

The kintetic studies of polymerization of methyl methacrylate initiated with nickel ethyl acetoacetate gave the following equations. R_p=K₁[Monomer]^1.4[Chelate]^0.5, in the absence ox aniline R_p=K₂[Monomer]^1.2[Chelate]^0.5 [Aniline]^0,5, in the presence of aniline. Some aromatic amines such as aniline markedly accelerated the polymerization, while pyridine had no such effect. The activation energy of initiation was 24.8 kcal/mol in the absence of aniline, and 8.8 kcal/mol in the presence of aniline. Both the kinetic data and the infrared spectra of the polymer indicated that the polymerization was radical in nature. The reaction order against monomer varied, as the temperature differed. The spectrophotometric investigation indicated formation of a complex between the chelate and the monomer, or amines. It also showed that the formation of a complex was not a factor which controlled the rate of initiation. A scheme of initiation mechanism was presented on the basis of the above experimental evidence.     

Polymerization of coordinated monomers. V. Polymerization of methyl methacrylate–Lewis acid complexes

The polymerization of the complex of methyl methacrylate with stannic chloride, aluminum trichloride, or boron trifluoride was carried out in toluene solution at several temperatures in the range of 60° to ?78°C by initiation of α,α′-azobisisobutyronicrile or by irradiation with ultraviolet rays. The tacticities of the resulting polymers were determined by NMR spectroscopy. Both the 1:1 and the 2:1 methyl methacrylate–SnCl₄ complexes gave polymers with similar tacticities at the polymerization temperatures above ?60°C. With decreasing temperature below ?60°C, the isotacticity was more favored for the 2:1 complex, whereas the tacticities did not change for the 1:1 complex. On the ESR spectroscopy of the polymerization solution under the irradiation of ultraviolet rays at ?120°C, the 1:1 SnCl₄ complex gave a quintet, while the 2:1 SnCl₄ complex gave both a quintet and a sextet. The sextet became weaker with increasing temperature and disappeared at ?60°C. This behavior of the sextet corresponds to the change of the tacticities of polymer for the 2:1 SnCl₄ complex. An intra–intercomplex addition was suggested for the polymerization of the 2:1 complex, which took a cis-configuration on the basis of its infrared spectra. The sextet can be ascribed to the radical formed by the intracomplex addition reaction, while the quintet can correspond to that formed by the intercomplex addition reaction. The proportion of the intracomplex reaction was estimated to be about 0.25 at ?75°C, and the calculated value of the probability of isotactic diad addition of the intracomplex reaction was found to be almost unity.     

Electro-initiated polymerization of acrylonitrile in aqueous acetic acid containing Mn(OAc)2·4H2O and CNCH2COOH

The electro-initiated polymerization of acrylonitrile initiated by the anodic oxidation of an aqueous acid solution (80% HOAc + 20% H₂O) containing Mn(OAc)₂ · 4H₂O/CNCH₂COOH has been investigated in the 30–40°C temperature range. The kinetics and mechanism of the process has been investigated as a function of variables and a suitable mechanism proposed. From the experimental observations the rate of polymerization is seen to be proportional to [An]^1.5I^0.5[Mn⁺²]^0.5 and [CAA]^0.5. The rate of polymerization gradually decreases at a higher applied current. The rate was independent of [CAA]^0.5. The rate of polymerization gradually decreases at a higher applied current. The rate was independent of CAA at high concentration. The average degrees of polymerization (P _n) increases with increasing AN and decreasing [CAA], [Mn⁺²] and applied current, I. The initiation is due to the anodic oxidation of Mn⁺²–CNCH₂COOH complex. Both the initiation of polymerization by the primary radical, viz., CN? C?? COOH as well as the oxidation of the primary radical at the electrode are equally significant reactions and neither can be neglected in comparison with the other. Predominant mutual termination accounts for all the observed data.     

Raft polymerization of MMA in the presence of ferrocene: A new way to realize the rate enhancement

Ferrocene (Fe(Cp)₂) was added to a thermal initiation of reversible addition‐fragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) with 2‐cyanoprop‐2‐yl 1‐dithionaphthalate (CPDN) as the RAFT agent at 115 °C. It was found that the polymerization was greatly promoted after the addition of Fe(Cp)₂ while retaining the characteristics of a typical RAFT polymerization. It was proposed that the formation of a redox initiation system, in which the poly(methyl methacrylate) peroxide (PMMAP) generated in situ as the oxidizer and Fe(Cp)₂ as the reducer, was possibly the reason for the interesting polymerization phenomenon. Such a redox initiation mechanism was further validated with ascorbic acid (VC) as the reducer instead of Fe(Cp)₂. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3607–3615, 2009     

Effects of phosphorus oxychloride and phenylphosphonic dichloride on the radical polymerization of methyl methacrylate and styrene

Effects of pentavalent phosphorus compounds on the radical polymerization of methyl methacrylate (MMA) and styrene (St) were studied. Phosphorus oxychloride (Cl₃P?O) and phenyl-phosphonic dichloride (C₆H₅Cl₂P?O) were used. Polymerization was carried out in benzene at 50°C by the standard solution method, α,α′-azobisisobutyronitrile (AIBN) being used as the initiator. In the polymerization of MMA, both phosphorus compounds increased the rate of polymerization. NMR spectral data suggested that this increasing effect was due to the complex formation between each phosphorus compound and MMA monomer. In the case of polymerization of St, NMR data also indicated the formation of a complex between the phosphorus compound and St monomer. Both phosphorus compounds showed an increasing effect for the rate of polymerization. Though these increasing effects could be explained by the complex formation, the polymerization of St in the presence of Cl₃P?O was especially found to be due to the cationic polymerization initiated simultaneously by Cl₃P?O in addition to the radical polymerization. These phosphorus compounds acted as chain-transfer agents in both polymerization systems. The parameters (Q_tr,_etr) which indicate the reactivity of a chain-transfer agent were calculated from the observed values of chain-transfer constant for both polymerization systems.     

Polymerization mechanism of trimethylene carbonate carried out with zinc(II) acetylacetonate monohydrate

The proposed mechanism of initiation and course of ring‐opening polymerization of cyclic trimethylene carbonate (TMC) involving zinc(II) acetylacetonate is in accordance with the mechanism of monomer activation. At the first stage of the process, coordination of carbonate to Zn(Acac)₂ · H₂O complex occurs with the release of weakly coordinated water molecules. This free water molecule reacts with active TMC–Zn(Acac)₂ complex. The reaction results in the formation of propanediol and CO₂ emission. During further stages of the investigated process, the formed propanediols, or later the oligomeric diols produced with polymerization, are cocatalysts of the chain propagation reaction. The chain propagation occurs because of repeating activation of the TMC monomer through the creation of an active structure resulting in the exchange/transfer reaction between the zinc complex and the monomer, with its following attachment to the hydroxyl groups, carbonate ring opening, and formation of the carbonic unit of polymer chain. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Polymerization initiated by an electron donor–acceptor complex. Part I. Polymerization of methyl methacrylate initiated by liquid sulfur dioxide–pyridine complex in the presence of carbon tetrachloride

The polymerization of methyl methacrylate can be initiated by a charge-transfer complex of liquid sulfur dioxide and pyridine in the presence of carbon tetrachloride. The molar ratio of sulfur dioxide and pyridine which participated in the complex was found from a spectrophotometric study to be 2:1. The polymerization proceeds through free-radical intermediates. The overall rate of polymerization is proportional to the square root of the concentration of the complex, and the values of k_p/k_t^1/2 under the various polymerization conditions were satisfactorily consistent with the literature value. For the activation energy of the overall reaction, 8.2 kcal./mole was obtained, and for initiation, 9.7 kcal./mole was evaluated from the values of k_p/k_t^1/2. It was deduced from a kinetic mechanism for the initiation that a primary radical may be produced from the reduction of carbon tetrachloride by an associated complex consisting of liquid sulfur dioxide–pyridine complex and the monomer.     

Vinyl Polymerization by Metal Complexes. XV. Polymerization of Acrylonitrile Initiated by Imidazole-Copper(II) Complex

The polymerization of acrylonitrile initiated with the imidazole-copper (II) complexes was studied in dimethylsulfoxide solution. The ability of the complexes to initiate polymerization seems to depend on their anion. 2-Substituted imidazole-copper (II) complexes of the type, CuL₄X₂ (L = imidazole as ligand and X = anion), were also found to initiate vinyl polymerization. From the data of electronic spectra in dimethylsulfoxide solution, the initiation mechanism is discussed in terms of the formation of the active species by the interaction of the complex with monomer molecules.     

Controlled/living polymerization of MMA promoted by heterogeneous initiation system (EPN‐X–CuX–bpy)

The polymerization of methyl methacrylate (MMA) promoted by heterogeneous initiation system (ethyl‐2‐halopropionate (EPN‐X)–CuX–2,2′‐bipyridyl (bpy), where X = Br or Cl) is studied in detail. The results show that ethyl‐2‐bromopropionate (EPN‐Br) is an efficient initiator as expected, and that CuCl–bpy, instead of CuBr–bpy, is a better catalyst for the controlled polymerization of MMA. The solvents with a high value of dielectric constant (ε) will lead to fast initiation and narrow molecular weight distribution (MWD). As a result, the controlled, living polymerization of MMA with EPN‐Br–CuCl–bpy can be got in ethyl acetate (EAc) at 100°C and in acetonitrile at 80°C. All results suggest that the initiation reaction is a controlling step in the controlled polymerization of MMA. The relationship between the UV spectra of CuCl–bpy and the performances of the polymerization in EAc or acetonitrile suggest that the formation of bis‐bpy complex, [Cubpy₂]X⁻, will lead to fast initiation and good control of the polymerization. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1255–1263, 1999     

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.     

Polymerization initiated by an electron donor–acceptor complex. VI. Polymerization of methyl methacrylate initiated by a liquid SO2–nicotine complex and carbon tetrachloride

A kinetic study has been made of polymerization of methyl methacrylate initiated by an electron donor–acceptor complex of liquid SO₂ (electron acceptor) and nicotine (donor) in the presence of carbon tetrachloride. It is concluded that the polymerization proceeds through free-radical intermediates similar to the cases of liquid SO₂–pyridine and liquid SO₂–poly(2-vinylpyridine) complexes. The overall rate of polymerization is proportional to the square root of both liquid SO₂ and nicotine concentrations, and the values of k_p/k_t^½ under various polymerization conditions are in satisfactory agreement with the literature values. For the activation energy of initiation, 13.6 kcal/mole is estimated from the k_p/k_t^½ values obtained at temperatures ranging from 0 to 80°C.     

Polymerization of methyl methacrylate by the binary system of the copper–amine complex type resin and carbon tetrachloride

The polymerization of vinyl monomers initiated by binary initiator systems composed of a copper–amine complex type resin and organic halides has been studied. These binary systems initiated the polymerization of various vinyl monomers. A kinetic study of the polymerization of methyl methacrylate initiated by the copper–amine complex resin–CCl₄ system was carried out, and it was found that the polymerization proceeds by way of a radical mechanism. This fact was also supported by the copolymerization of methyl methacrylate with styrene. The overall activation energy of the polymerization of methyl methacrylate was estimated as 8.4 kcal/mole. The activity of the initiator systems was greatly dependent upon the dissociation energy of carbon–halogen bonds in the organic halides. A possible initiation mechanism with the binary systems is proposed and discussed.     

Metal-Containing Initiator Systems. IX. Radical Polymerizations of Vinyl Monomers by Various Metal Acetylacetonates

Abstract

A study of the polymerization of styrene, methyl methacrylate, acrylonitrile, vinyl acetate, and vinyl chloride initiated by various metal acetylacetonates [Me(acac)_x] has been made. It was found that Mn(acac)₃ was the most effective initiator, and Co(acac)₃, Mn(acac)₂, Cu(acac)₂, and Cr(acac)₃ showed moderate activity for the polymerization of methyl methacrylate at 60°C. However, the other, Me(acac)_x, had no effect or served as inhibitors. The addition of some additives such as halogen compounds did not accelerate polymerization of methyl methacrylate by Mn(acac)₃, From the results of polymerization and copolymerization of methyl methacrylate by Mn(acac)₃, it was concluded that the polymerization proceeded via an ordinary radical mechanism and the activation energy for initiation was 25.2 kcal/mole. The initiation mechanism of vinyl polymerization by Me(acac)_x was studied on the basis of the complex formation with the monomer.     

Metallocene catalysis in the complex-radical polymerization of methyl methacrylate

The initiation stage of methyl methacrylate polymerization in the presence of benzoyl peroxide-metallocene (MC) systems is considered, with MC = Cp₂Fe, (C₅Me₅)₂Fe, (AcC₅H₄)(C₅H₅)Fe, Cp₂TiCl₂, Cp₂ZrCl₂, and (C₅Me₅)₂ZrCl₂. The decomposition of benzoyl peroxide in the presence of a metallocene proceeds via the formation of its complex with the metallocene. The catalytic effect of the metallocenes on the initiation of methyl methacrylate polymerization is due to the formation of a metallocene-benzoyl peroxide complex and its decomposition yielding primary radicals. The chain propagation stage is metallocene-dependent, which is explained by the formation of complex sites. Their formation pathway and structures are analyzed using quantum-chemical calculations.     

Effect of the mixture t - BuCl/SnCl4 on the cationic polymerization of isobutylene

The polymerizations of isobutylene initiated with the system tert-butyl chloride (t-BuCl)/SnCl₄ and carried out in CH₂Cl₂ at −20°C and −78°C were investigated. The results obtained demonstrate that the presence of t-BuCl in the polymerizing system gives rise to a PIB product with a distinctly bimodal MWD. The higher-molecular weight (HMW) PIB, M̄_n = 20000, I=M̄_w/M̄_n ∼ 2.5, is the result of existence of the protogenic initiation with residual water in the reaction system. The lower-molecular weight (LMW) PIB, M̄_n < 600, M̄_w/M̄_n ≤ 1.4, is the product of polymerization initiated presumably with a complex t-BuCl-SnCl₄-H₂O. To elucidate the reaction mechanism of the polymerization initiated with the complex, a series of similar isobutylene polymerizations using the initiation system 2,5-dichloro-2,5-dimethylhexane (DDH)/SnCl₄ was run and the oily LMW PIB samples were investigated by ¹H-NMR. A new polymerization mechanism describing the role of DDH and t-BuCl is suggested.     

Ethylene polymerization reactions with Ziegler–Natta catalysts. III. Chain-end structures and polymerization mechanism

Ethylene polymerization reactions with many Ziegler–Natta catalysts exhibit a number of features that differentiate them from polymerization reactions of α olefins: (1) a relatively low ethylene reactivity, (2) markedly higher polymerization rates in the presence of α olefins, (3) a high reaction order with respect to ethylene concentration, and (4) a strong reversible rate depression in the presence of hydrogen. A detailed kinetic analysis of ethylene polymerization reactions¹ provided the basis for a new kinetic scheme that postulates the equilibrium formation of Ti C₂H₅ species with the H atom in the methyl group β-agostically coordinated to the Ti atom in an active center. This mechanism predicts several new features of ethylene polymerization reactions, one being that chain initiation via insertion of any α-olefin molecule into the Ti H bond should proceed with an increased probability compared to that via ethylene insertion into the same bond. As a result, a significant fraction of ethylene/α-olefin copolymer chains should contain α-olefin units as the starting units. This article provides experimental data supporting this prediction on the basis of both a detailed structural analysis of co-oligomers formed in ethylene/1-pentene and ethylene/4-methyl-1-pentene copolymerization reactions and a spectroscopic analysis of chain ends in the copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4281–4294, 1999     

Phosphorus ligands for iron(III)‐mediated ATRP of styrene via generation of activators by monomer addition

Styrene polymerization via generation of activators by monomer addition (GAMA) for atom transfer radical polymerization (ATRP) has been examined extensively with bulk FeX₃ and FeX₂ at 110 °C in conjunction with various phosphorus‐bearing ligands. It was found that GAMA possesses advantages over normal ATRP. Most importantly, narrower polydispersity index (PDI) values were observed from the styrene polymerizations with Fe(III) over those with Fe(II). Every instance of 2‐(diphenylphosphino)‐N,N′‐dimethyl‐[1,1′‐biphenyl]‐2‐amine and 2‐(diphenylphosphino) pyridine with the Fe(III) system were controlled excellently without addition of any radical initiator or reducing agent additives. Initiator type was found to exert a significant factor to influence on the controllability of polymerization. The initiation of 1‐phenylethyl chloride and methyl‐2‐chloropropionate gave rise to formation of polymers with narrow PDI (1.05–1.20), whereas those from 1‐phenylethyl bromide increased to 1.35. The GAMA of bulk styrene exhibited the best performance in terms of both rate and controllability compared with toluene and anisole. Both formation of block copolymer from the macroinitiator and efficient perturbation of polymerization with 2,2,6,6‐tetramethylpiperidine 1‐oxyl provided firm evidence to support the living and radical characteristics for the GAMA of styrene. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 144–151, 2010     

Anionic polymerization of Lewis acid-activated methyl methacrylate by enamines

A novel ionic polymerization of methyl methacrylate (MMA) with a series of enamines (1) in the presence of methylaluminum bis(2,6-di-tert-butylphenoxide) (2) was examined. Both nucleophile (1) and electrophile (2) are indispensable for the present polymerization, in which (1) acts as initiator and (2) as activator. MMA polymerization proceeded smoothly in toluene at or below room temperature (r.t.) in the presence of 1 and 2 (1 ∼ 4 mol %, respectively), went to completion within 1 h, and afforded syndiotactic-rich PMMA with molecular weight distribution (M_w/M_n) in the 1.1 ∼ 1.4 range. The number-average molecular weight (M_n) of the polymer was significantly higher than that calculated from the feed ratio of 1 to the monomer, indicating low initiating efficiency. Kinetic studies coupled with isolation of an intermediate species proved that the real monomeric species involved in both initiation and propagation was a complex of MMA with 2. The effects of the concentrations of 1, 2, and MMA as well as the temperature of polymerization were also examined. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3671–3679, 1999     

Comparative study of the absolute reactivity of vinyl monomers: Kinetics of polymerization of vinyl monomers initiated by Mn3+–thiodiglycolic acid redox system

The kinetics and mechanism of polymerization of methacrylic acid (MAA) and ethyl acrylate (EA) initiated by the redox system, Mn³⁺–thiodiglycolic acid (TDGA) were investigated in the 15–35°C temperature range. The polymerization kinetics of both the monomers followed the same mechanism, viz., initiation by primary radical and termination by Mn³⁺–thiodiglycolic acid complex. The rate coefficients k_i/k₀ and k_p/k_t were related to the monomer reactivity and polymer radical reactivity, respectively. It was observed that both monomer reactivity and polymer radical reactivity followed the same order, viz., EA > MAA. The polymer radical reactivity varied inversely with the Q values of the monomers.     

Electrochemical and chemical polymerization of acrylamide

The electrochemical and chemical polymerization of acrylamide (AA) has been studied. The electrolysis of the monomer in N,N-dimethylformamide (DMF) containing (C₄H₉)₄NClO₄ as the supporting electrolyte leads to polymer formation in both anode and cathode compartments. The cathodic polymer dissolves in the reaction mixture and the anodic polymer precipitates during the course of polymerization. A plausible mechanism for the anodic and cathodic initiation reaction has been given. The chemical polymerization of acrylamide that has been initiated by HClO₄ is analogous to its anodic polymerization. The polymer yield increases with an increase in concentration of the monomer and HClO₄. Raising the reaction temperature also enhances the polymerization rate. The overall apparent activation energy of the polymerization was determined to be ca. 19 kcal/mole. The copolymerization of acrylamide was carried out with methyl methacrylate (MMA) in a solution of HClO₄ in DMF. The reactivity ratios are r₁ (AA) = 0.25 and r₂ = 2.50. The polymerization with HClO₄ appears to be by a free radical mechanism. When the polymerization of acrylamide is carried out with HClO₄ in H₂O, a crosslinked water-insoluble gel formation takes place.