Molecular-weight-controlled polymerization of styrene with Mn(acac)3 in combination with organic halides

Summary The control of molecular weight of polymers in polymerization of styrene (St) with manganese(III) acetylacetonate [Mn(acac)₃] in the presence of organic halides (RX) in toluene at 80°C was investigated. In the polymerizations of St with Mn(acac)₃ in combination with benzyl bromide (BzBr) as RX, the molecular weight of the polymer increased with polymer yields, and the relationships between the molecular weight of polymer and polymer yield gave a straight line passing through the original point. However, the molecular weight distribution was not narrow, but kept almost constant (M_w/M_n was about 2) throughout the polymerization. The mechanism of the polymerization of St with Mn(acac)₃-BzBr was also discussed. Received: 18 December 2000/Revised version: 19 April 2001/Accepted: 25 April 2001     

Controlled/living free-radical copolymerization of allyl glycidyl ether with methyl acrylate under Co γ-ray irradiation

An investigation on the copolymerization of allyl glycidyl ether (AGE), an epoxy-functional monomer, with methyl acrylate (MA) was performed in the presence of benzyl 1H-imidazole-1-carbodithioate (BICDT) under ⁶⁰Co γ-ray irradiation. The polymerizations revealed good characteristics of RAFT process. The content of AGE incorporation into the copolymer increased with higher monomer conversion and higher molar fraction of the AGE in the monomer feed. However, the polymerization could slow down when the fraction of AGE increased in the monomer feed, which might be attributed to the low activity of AGE. Taking advantage of RAFT process, functional block copolymer poly(AGE/MA)-block-poly(styrene) was prepared in the presence of poly(styrene) macroRAFT agent, and the copolymer was characterized by ¹H NMR spectra and GPC.     

Separation of Co(II) and Mn(II) from sulphate media via a HFSLM: Reaction flux model and experimental verification

Separation of Co(II) and Mn(II) from sulphate media through triple HFSLM in series using D2EHPA was explored. Mn(II) was extracted preferentially over Co(II) at the pH value of 5, 100 ppm of Co(II) and Mn(II), 5% (v/v) of D2EHPA, 0.2 M HCl. The highest extraction percentage of Mn(II) was 98.14%, and Co(II) remained at 94.05% in the raffinate stream. The reaction order (n) and the reaction rate constant (k_f) were found to be 1.00 and 0.0180 min⁻¹, respectively. Furthermore, the reaction flux model proved to be in good agreement with the experimental data at an average deviation of 2.24%.     

Polymerization of N-vinylcarbazole over cobalt (II) exchanged 13X molecular sieves

Polymerization of N-vinylcarbazole over Co(II)-13X molecular sieves in toluene solution has been studied. The rate of polymerization has been observed to be second order both in monomer concentration and in the exchange level of Co(II), and linearly dependent on catalyst loading. An apparent activation energy of 8.71 kcal mol^?1 (36.41 kJ mol^?1) has been found for the polymerization. The effect of different parameters on molecular weight has also been studied. The general kinetic features of the reaction are somewhat different from those reported for monomers like isobutyl vinyl ether, styrene etc. on simple and rare earth exchanged 13X molecular sieves.     

The polymerization of acrylamide initiated with CE(IV) and KMNO4 redox systems in the presence of glycine

Glycine-Ce(IV) salts and −KMnO₄ initiator systems were used for the polymerization of acrylamide, resulting in water-soluble polyacrylamide, which contains amino acid end groups. The dependence of polymerization yields and molecular weights of polymers on the mole ratio of acrylamide monomer to glycine, the polymerization time, the temperature, and the concentration of sulfuric acid were investigated. The decrease in the mole ratio of acrylamide to glycine resulted in a decrese in the molecular weight, and an increase in the yield of acrylamide polymer, which contains a glycine end group. With increasing acid concentration of the polymeric solution, the polymerization yield and the molecular weight of polymer decrease. Ce(IV) and Mn(IV) reduced to Ce(III) and Mn(II) in the polymerization reaction. The amounts of Ce(III) and Mn(II) bound to polymer were determined. The composition of the polymerization product was investigated and a bimodal character of the molecular weight distribution was observed. The mechanism of this phenomena is discussed. © 1996 John Wiley & Sons, Inc.     

Polymerization of acrylamide and methacrylamide initiated by a potassium peroxydiphosphate/Mn(II) system

The kinetics of aqueous polymerization of acrylamide (AM) and methacrylamide (MAM) have been studied using a potassium peroxydiphosphate (PDP/Mn(II) system in an inert atmosphere at 40°C and at constant pH (1·30). The polymerization rate R_p has been found to be proportional to the half power of PDP and Mn(II) concentrations. The overall energy of activation (ΔE) was found to be 40·2±0·1kJmol^-1 and 45·0±0.1kJmol^-1 for AM and MAM, respectively. Intrinsic viscosity [η], viscometric average molecular weight (M_v) and number average degree of polymerization (P_n) at different concentrations of PDP, Mn(II) and monomer are reported. © 1998 SCI.     

Studies on Ambient Cured Biobased Mn(II), Co(II) and Cu(II) Containing Metallopolyesteramides

In this paper linseed oil based metallopolyesteramides (Mn(II)-/Co(II)-/Cu(II)-LPEA) containing metals [with half filled (d ⁵) and partially filled (d ⁷ and d ⁹) d orbitals] were synthesized via green route for the application of eco-friendly protective green material. This paper also described the role of occupancy of d orbitals on the performance of such polymers. The synthesis reaction was carried out in situ through condensation polymerization among linseed fatty amide diol (HELA), phthalic anhydride and respective metal acetates [M (OCOCH₃)₂; M = Mn(II), Co(II), Cu(II); different mole ratios] in absence of any harmful organic solvent. The structural determination (FTIR, ¹H-NMR and ¹³C-NMR), curing, thermal, physico-chemical, physico-mechanical, anticorrosive/chemical resistance, antibacterial properties of Mn(II)-/Co(II)-/Cu(II)-LPEA were carried out. The curing mechanism of the resin was confirmed by the comparison of FTIR spectra of uncured and cured resin. The curing mechanism of Mn(II)-/Co(II)-/Cu(II)-LPEA is found to be contrary to that of reported oil based polymer that involves the lipid autoxidation (slow process) in which driers are required to speed up the room temperature curing process. The incorporation of metals in Mn(II)-/Co(II)-/Cu(II)-LPEA improved the thermal stability as compared to virgin linseed oil based polyesteramide (LPEA). Mn(II)-/Co(II)-/Cu(II)-LPEA also show excellent antibacterial performance against Staphylococcus aureus and Escherichia coli. The observed diversity in material properties suggests that Mn-LPEA may be useful as an eco-friendly protective green material with thermal stability up to 320–330 °C.     

Tuning of activity, induction period and polymer properties of double metal cyanide catalyzed ring-opening polymerizations of propylene oxide by using quaternary ammonium salts

Polymerizations of propylene oxide (PO) have been carried out by using double metal cyanide (DMC) catalyst prepared by reacting ZnCl₂ and K₃[Co(CN)₆] in the presence of tert-butyl alcohol (^tBuOH) as a complexing agent. The catalytic activity and the induction period for PO polymerizations catalyzed by DMC are tunable by using various quaternary ammonium salts (QAS) as external additives. The DMC/QAS binary catalyst improves polymer properties as well such as molecular weight, molecular weight distribution, viscosity, and unsaturation level.     

Dithioester (ZC(S)SR) mediated ‘controlled/living’ free-radical polymerization of methyl acrylate under Co γ-ray irradiation. Structure effect of Z-group

The free-radical polymerizations of methyl acrylate (MA) have been systematically studied under ⁶⁰Co γ-ray irradiation using benzyl propane(dithioate) (a), benzyl phenylethane(dithioate) (b), benzyl benzenecarbodithioate (c), benzyl 4-cyanobenzenecarbodithioate (d) and benzyl 4-methoxybenzenecarbodithioate (e) as control agents. The results indicate that Z-group of dithioester plays an important role in the polymerization behavior. When Z-group is alkyl or alkyl derivative, in the case of dithioester a and b, the polymerizations reveal quite good living characteristics except for a similar inhibition period of about 40 min, which may be attributed to the lower propagation rate coefficients during the initialization period. However, for dithioesters c, d and e, aryl as Z-group, the polymerizations show very strong inhibitions in the processes. The strong inhibition may be associated with the formation of probable 3 or 4-arm structure compounds. It is worth noting that it is the first report for dithioester a to be used as control agent in ‘controlled/living’ free radical polymerization under γ-ray irradiation.     

Conductometric studies of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) tetrafluoroborates in N,N—dimethylacetamide solutions

Results are reported for the molar conductivities at 25°C of N,N—dimethylacetamide (DMA) solutions of Bu₄NBF₄ and Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) tetrafluoroborates. The limiting molar conductivities of [M(DMA)₆]²⁺ (M  MN, Co, Ni, Cu, Zn) and BF^?₄, as well as association constants for Co(BF₄)₂ in DMA solutions have been calculated. The slight differences between conductometric curves of different metal ions are discussed.     

Fe(III)-catalyzed AGET ATRP of styrene using triphenyl phosphine as ligand

Activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP) is a new technique for conducting ATRP developed recently. In this work, an iron(III)-mediated AGET ATRP of styrene in bulk was carried out at 110 °C, using benzyl bromide as an initiator, oxidatively stable iron(III) chloride hexahydrate (FeCl₃·6H₂O) as a catalyst, triphenyl phosphine as a ligand, and ascorbic acid as a reducing agent. The polymerizations demonstrated the features of “living”/controlled free-radical polymerization, such as the number–average molecular weights increasing linearly with monomer conversion and narrow molecular weight distributions (M _w/M _n = 1.14–1.31).     

Aerial oxidation of substituted aromatic hydrocarbons catalyzed by Co/Mn/Br− in water-dioxane medium

Aerial oxidation of substituted aryl aromatic hydrocarbons were carried out using Co/Mn/Br⁻ catalyst system in water-dioxane medium in the range 14–56 bar air and temperature 383–423 K. The combination of optimum catalyst concentration of salts Co(OAc)₂, Mn(OAc)₂ and NaBr (1:3:10 molar ratio) in water-dioxane (1:2 mole ratio) is found catalyze aerial oxidation of substituted aryl aromatic to give corresponding oxygenated products. Under the optimized conditions, p-cymene gave p-isopropyl benzaldehyde (33.1%), p-isopropylbenzyl alcohol (54.7%) and p-isopropyl benzoic acid (3.3%), respectively, at p-cymene conversion 40.2%. Similarly, oxidation of p-methoxy toluene gave p-methoxy benzaldehyde (87.4%), benzyl alcohol (5.5%), and p-methoxy benzoic acid (6%), while oxidation of p-tert-butyl toluene yielded p-tert-butyl benzaldehyde (87%), p-tert-butyl benzyl alcohol (5.7%) and p-tert-butyl benzoic acid (6.1%), at conversions 16.4% and 36.1%, respectively. It is found that Co/Mn/Br⁻catalyst system in water-dioxane medium is effective in the aerial oxidation of substituted aromatic hydrocarbons to get corresponding alcohol and aldehydes in greater yields.     

H2O2-induced graft polymerization of acrylic acid on poly(ethylene terephthalate) fibers

Graft polymerization of acrylic acid to poly(ethylene terephthalate) fibers using H₂O₂ as initiator was only possible in benzyl alcohol as reaction medium. The effect of initiator and monomer concentrations, reaction time, and temperature as well as addition of metallic salts to the polymerization medium was studied. Percent grafting was enhanced significantly by increasing H₂O₂ concentrations up to 100 mequiv/L and then decreased upon further increase in initiator concentration. The same held true for acrylic acid concentration of up to 10%, but above this concentration grafting leveled off. Raising the polymerization temperature from 85 to 115°C favored grafting at lower H₂O₂concentration. The reverse was the case at higher H₂O₂ concentration (more than 25 mequiv/L). Addition of copper sulfate to the polymerization medium decreased the rate of grafting, and no leveling off of grafting could be achieved even after 5 h. The ferrous ammonium sulfate functioned similarly but to lesser degree, and leveling off of grafting occurred after 4 h. This contrasted with grafting in the absence of metallic salts where grafting leveled off after 1 h. Action of initial graft formation as diffusion barrier is believed to account for this.     

Modeling of the bulk free radical polymerization up to high conversion—three stage polymerization model. II. Number-average molecular weight and apparent initiator efficiency

The equations for predicting the number-average molecular weight are derived on the basis of the three stage polymerization model (TSPM) in this paper. By applying the equations, a plotting approach is proposed to determine the apparent initiator efficiency defined as f[(α_td+1)/2] and the constant of chain transfer to monomer, where f is the initiator efficiency and α_td denotes the fraction of the termination rate constants by disproportionation. Using the approach to plot the experimental data in the literature, it is found that the chain transfer to monomer can be neglected for both methylmethacrylate (MMA) and styrene (St) polymerizations, but it can exert a significant effect on ethylmethacrylate (EMA) polymerization. In addition, the apparent initiator efficiency is found to be independent of reaction temperature and initiator concentration at each stage. The values of f[(α_td+1)/2] at gel effect stage are slightly reduced as compared with that at low conversion stage for MMA and EMA polymerizations. However, it decreases significantly at gel effect stage for St polymerization. Using the equations derived and the apparent initiator efficiencies obtained from TSPM plots, the number-average molecular weights at different conversions can be predicted. Comparisons show that the agreement between predictions and experimental data is satisfactory.     

Novel piperidinium salts as latent initiators for cationic polymerization of epoxide and vinyl ether

Novel dibenzylpiperidinium salts with nonnucleophilic anions (DBPi‐SbF₆, DBPi‐PF₆) have been prepared as latent cationic initiators. Utility of these salts in the photo and thermal‐induced cationic polymerizations of epoxide and vinyl ether monomer systems has been studied. The new initiator, DBPi‐SbF₆ showed good solubility, high reactivity, and high thermal latency for polymerizations of epoxide and vinyl ether monomers with only 1 wt % of concentration. Cationic polymerization of vinyl ether monomer was significantly faster than epoxide monomer by the synthesized initiators. This article describes the synthesis, characterization, and activity of novel initiators. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Reversible addition–fragmentation chain transfer polymerization of styrene with benzoimidazole dithiocarbamate as a reversible addition–fragmentation chain transfer agent

Two novel dithiocarbamates [2‐Y‐benzoimidazole‐1‐carbodithioic acid benzyl esters: Y = methyl (1b) or phenyl (1c)] were synthesized and successfully used in the reversible addition–fragmentation chain transfer (RAFT) polymerization of styrene in bulk with thermal initiation. The effects of the temperatures and concentration ratios of the styrene and RAFT agents on the polymerization were investigated. The results showed that the polymerization of styrene could be well controlled in the presence of 1b or 1c. The linear relationships between ln([M]₀/[M]) and the polymerization time (where [M]₀ is the initial monomer concentration and [M] is the monomer concentration) indicated that the polymerizations were first‐order reactions with respect to the monomer concentration. The molecular weights increased linearly with the monomer conversion and were close to the theoretical values. The molecular weight distributions [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] were very narrow from 5.3% conversion up to 94% conversion (M_w/M_n < 1.3). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 560–564, 2006     

AGET ATRP of methyl methacrylate catalyzed by FeCl3/iminodiacetic acid in the presence of air

The recently developed living free-radical polymerization system, atom transfer radical polymerization using activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP), was used for methyl methacrylate (MMA) polymerization in the presence of a limited amount of air, using a novel catalyst system based on iron (FeCl₃) complexes with iminodiacetic acid (IDA) and using ascorbic acid (VC) as a reducing agent. The kinetics of AGET ATRPs of MMA with different amounts of VC in the presence of air was investigated. The results of the polymerizations demonstrated the features of “living”/controlled free-radical polymerization such as the number-average molecular weights increasing linearly with monomer conversion and narrow molecular weight distributions (M_w/M_n = 1.31–1.44).     

Solid-state intercalation of 8-Hydroxyquinoline into Li(I)-, Zn(II)- and Mn(II)-montmorillonites

Formation of three fluorescent complexes, Li(I)-, Zn(II)- and Mn(II)-8-hydroxyquinoline complexes (Mq_n), was investigated in the interlayer spaces of montmorillonites by solid–solid reactions between homoionic (Li(I), Zn(II) and Mn(II)) montmorillonites and neat 8-hydroxyquinoline at room temperature. The intercalation of 8-hydroxyquinoline molecules into the interlayer spaces of Li(I)-, Zn(II)- and Mn(II)-montmorillonites was confirmed by powder XRD, FT-IR, TG-DTA and chemical analysis. The in-situ complex formation was proved by FT-IR, UV–vis, and photoluminescence spectroscopies. The absorption and luminescence bands of the complexes shifted slightly compared to the corresponding neat complexes, suggesting the different microstructures including molecular packing of the complexes in the interlayer spaces of montmorillonites as a result of host–guest interactions.     

Synthesis and Characterizations of Triphenylamine End-Functionalized Polymers via Reversible Addition-Fragmentation Chain Transfer Polymerization

A novel reversible addition-fragmentation chain transfer (RAFT) reagent bearing triphenylamine (TPA) group, 4-diphenylamino-dithiobenzoic acid benzyl ester (DDABE), was designed and synthesized. It was used in the RAFT polymerizations of styrene (St) and methyl acrylate (MA) to prepare end-functionalized polymers. The results of the polymerization showed that the RAFT polymerizations could be well controlled using DDABE as the RAFT agent. Number-average molecular weight (M_n,GPC) increased linearly with monomer conversion, and molecular weight distributions were relatively narrow (PDI< 1.50). The results of chain-extension reaction, ¹H NMR spectra and UV/Vis spectra confirmed that most of the polymers chains were end-capped by the functional triphenylamine (TPA) groups. The effect of feed molar ratios of St/DDABE/AIBN on polymerization was investigated.     

Convenient synthesis of poly(2,6-dihydroxy-1,5-naphthylene) by Cu(II)-amine catalyzed oxidative coupling polymerization

A convenient synthesis of regiocontrolled poly(2,6-dihydroxy-1,5-naphthylene) (PDHN) with high molecular weights by oxidative coupling polymerization of 2,6-dihydroxynaphthalene (2,6-DHN) has been developed. Polymerizations were conducted in 2-methoxyethanol in the presence of di-μ-hydroxo-bis[(N,N,N′,N′-tetramethylethylenediamine)copper (II)] chloride (CuCl(OH)TMEDA) as the catalyst under air at 25 °C. To determine the optimum conditions, the effects of the amounts of the catalysts and the solvents were investigated. In the presence of 5 mol% of the catalyst to the monomer in 2-methoxyethanol, polymerization proceeded smoothly, giving PDHN with a number average molecular weight (M_n) of 52,000. PDHN was converted to poly(2,6-dibutoxy-1,5-naphthylene) (PDBN) to improve the solubility. The structure of PDBN was characterized by ¹H and ¹³C NMR spectroscopy and was estimated to consist completely of the 1,5-linkage. The average refractive indices (n_AV) of the PDHN and PDBN films were 1.6003 and 1.5815, respectively, and the dielectric constants (ε) estimated from the refractive indices were 2.82 and 2.75, respectively.