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).     

Polymerization of methyl methacrylate with metal acetylacetonates and triethylaluminum catalysts

Polymerization of methyl methacrylate (MMA) with metal acetylacetonates, especially vanadium (III) acetylacetonate [V(acac)₃], in combination with AIEt₃ was studied. V(acac)₃–AIEt₃ catalyst could initiate the polymerization of MMA, although other Mt(acac)_xs are also effective. It was found that the polymerization of MMA with V(acac)₃–AIEt₃ catalyst proceeded through a coordination mechanism, from the results of copolymerization with styrene and polymerization in the presence of radical inhibitors. The resulting polymers were found to form stereocomplexes in acetone. Based on these results, it is concluded that multi-active sites in the polymerization of MMA with V(acac)₃–AIEt₃ catalyst were produced.     

Unexpected effect of the monomer concentration on the rate of a radical polymerization

The radical polymerization of vinyl monomers is usually initiated by physical and chemical means. After an increasing polymerization rate, R_p, at low monomer concentrations, some reactive systems show an unexpected minimum for R_p at high enough monomer concentrations. The radical polymerization of methyl methacrylate (MMA) initiated by the redox system D -glucose–ceric ion at varying MMA concentration is discussed. The peculiar behaviour of R_p is explained by the presence of two circumstances: the initiation rate from D -glucose radicals does not depend on MMA concentration when most of the D -glucose radicals formed react by adding to monomer, and the radical chains initiated by D -glucose radicals undergo mutual termination with a portion of the radical chains initiated by monomer radicals. Some information about the nature of the polymer end-groups is reached from the mechanistic approach.     

Free radical copolymerization of 4-phenylbut-1-en-3-yne with methylmethacrylate

Summary Free radical copolymerization of 4-phenylbut-1-en-3-yne (PB) with methyl methacrylate(MMA) was studied. The polymerization of MMA was inhibited by the presence of small amounts of PB, but the copolymerization yield increased with increase in the PB concentration, and PB-rich copolymers were obtained. The monomer reactivity ratios, r_MMA and r_PB, were found to be 0.096 and 2.83, respectively. The Q and e values of PB were calculated by using the values of MMA and were found to be 2.69 and 0.74, respectively. The slow polymerization and low molecular weights were attributed to the low propagating activity of PB radicals.     

Towards a one‐pot synthesis of a polystyrene–PMMA block copolymer via atom‐transfer radical polymerization

The solution atom‐transfer radical copolymerization of styrene and methyl methacrylate in butyl acetate at 110 °C in the presence of Cu(II) bromide and 2,2′‐bipyride was investigated. Polystyrene was polymerized by atom‐transfer radical polymerization using benzyl bromide as initiator and MMA was then added to the system. Block copolymers were formed when MMA was added at ≤90% styrene conversion. Molecular weight distributions (M_w/M_n) of the block copolymers were ≤1.5. The possibility of end‐capping the polystyrene precursor as a means of improving its initiating efficiency towards MMA was also investigated but did not improve the system. © 2002 Society of Chemical Industry     

Studium der lebenden radikalischen Polymerisation mit der Differential Scanning Calorimetry (DSC)

The living radical polymerization of styrene, some styrene-analogous vinyl monomers as well as methyl methacrylate (MMA) and butyl methacrylate (BuMA) was investigated with a differential scanning calorimeter. The ability to polymerize was estimated by dynamic measurements, showing that p-methylstyrene, p-chlorostyrene, 3,4-dimethoxystyrene and 4-vinylpyridine polymerize in the presence of 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) while MMA and BuMA do not. Isothermal measurements revealed an activation energy of E_A = 81 kJ mol^–1 for thermal bulk polymerization of styrene and values of E_A = 78–94 kJ mol^–1 were measured with different iniferter systems. These polymerizations have induction times which depend on the reaction temperature and the initial concentration of the iniferter systems. An influence of the kind of nitroxyl radical on the induction times was not observed.     

Addition-fragmentation of 5-bromopenta-1,3-diene in free radical polymerization of methyl methacrylate

5-Bromopenta-1,3-diene (BPD) was examined as an addition-fragmentation chain transfer agent (AFCTA) in the free radical polymerization of methyl methacrylate (MMA). Studies of the kinetics of polymerization in the presence of this compound showed it to be a very effective chain transfer agent and that retardation was not significant, implying efficient reinitiation by the expelled Br radical. Analysis of the resulting polymers showed that the intermediate radical formed by the addition of the propagating radical to the C₁ carbon of BPD underwent exclusive fragmentation. However, addition on the C₄ carbon, with a relative probability of 0·6, led to its copolymerization with MMA. Kinetic studies showed BPD to be a better chain-end functionalization agent than its 5-t-butyl thio derivative for deriving pentadiene-functional macromonomer. © 1998 SCI.     

Plastification sélective dans le cas d'alliages de polymères II) Systèmes ternaires — Rôle de l'adhésion interfaciale

Polymerization of methly methacrylate (MMA) was carried out in the presence of nylon-6 with different content of amino end groups and water. The more the content of amino end groups of the nylon molecule, the lower is the conversion of MMA. The rate of polymerization, R_p, is proportional to the amount of nylon. However, as for the amount of MMA, the rate increased at first amount of MMA, but then became independent of the amount of MMA. These kinetical behaviours suggest a model of an enzyme-like reaction. MICHAELIS -MENTEN'S equation was found to be able adequately to be applied. The polymerization was confirmed to proceed through a radical mechanism. By the activation analysis, it was found that the nylon used here contained a slight amount of copper (5 – 8 · 10^?7 g Cu/g fiber). When the nylon was dissolved in formic acid and reprecipitated by adding hot water, the nylon was found to lose the activity for the polymerization. However, when a trace of CuCl₂ was absorbed on the nylon, the nylon was confirmed to regain the activity. As a conclusion, an assumed mechanism similar to an enzymatic reaction in which nylon plays as enzyme and copper as coenzyme was proposed. In the second part of the present paper, a study on the polymerization in the presences of carbon tetrachloride was made. Regardless of the content of the NH_2? end groups, the conversion was always near to quantitative yield. The mechanism was found to be a radical one. An initiation mechanism, in which a complex of nylon, CCl₄, H₂O and MMA is formed, was proposed.     

Photo-induced atom transfer radical polymerization of MMA with chlorophll A as photoinitiator

In this work, photoinduced free radical polymerization of methyl methacrylate (MMA) was performed at ambient temperature in dimethyl sulfoxide with chlorophll A as a photosensitizer. Well controlled polymerization of MMA was achieved. The linear first order plot of ln([M]₀/[M]) vs time was observed. Well-defined polymethyl methacrylates (PMMA) with narrow molecular weight distribution (M_w/M_n) were prepared. It indicated that the polymerization was controllable. The chain-end fidelity was demonstrated by ¹H NMR spectra. Chain extension experiments demonstrated the living feature of polymerization. The initiation and moderation of polymerization were manipulated by the periodic light on-off experiments.     

Controlled radical polymerization of methyl methacrylate in the presence of 2-bromoethanol

Summary The radical polymerization of methyl methacrylate (MMA) and styrene (St) initiated by 2,2’-azobis(isobutyronitrile) (AIBN) at 60 °C in the presence of haloalkyl alcohol are studied. The influence of structure and concentration of haloalkyl alcohol as a transfer agent are investigated. For the radical polymerization of MMA in the presence of large amount of 2-bromoethanol, controlled radical polymerization is proceeded. The 2-bromoethanol is, thus, one of the transfer agents for radical polymerization to control the molecular weight and the structure of poly(MMA).     

Polymerization in magnetic field: XVIII. Influence of surfactant nature on the synthesis and thermal properties of poly(methyl methacrylate) and poly[(methyl methacrylate)‐co‐(epoxypropyl methacrylate)]

BACKGROUND: The possibility to use β‐cyclodextrin as biodegradable tensioactive and an electromagnetic field in order to improve the kinetic parameters of radical emulsion polymerization is of interest. Thus, the influence of different surfactants—sodium lauryl sulfate (SLS) and β‐cyclodextrin (CD)—on the pathway of emulsion polymerization of methyl methacrylate (MMA) and emulsion copolymerization of MMA with 2,3‐epoxypropyl methacrylate (GMA) performed with or without the presence of a continuous electromagnetic field (MF) was studied. RESULTS: The presence of the MF leads to a considerable increase of the conversion during the first part of the reaction if the classic surfactant (SLS) is used. The reactions performed without MF and with CD exhibit a decrease of the conversion and of the polymerization rate as compared with the variants using SLS. The swelling rate and the maximum degree of swelling vary with the surfactant nature and with the reaction conditions and MF presence. Data from thermogravimetry and differential scanning calorimetry evidence the dependences between the polymer characteristics and the preparation conditions. CONCLUSION: This research underlines the coupling possibilities of the influence of a MF—growth of the reaction rate and conversion explained through radical pairs mechanism—with a combination of the ‘cage’ effect and ‘conformational control’ afforded by CD. The presence of MF and CD during the syntheses leads to an increase of T_g and an increase of PMMA and P(MMA‐co‐GMA) thermal stability. Copyright © 2007 Society of Chemical Industry     

Free radical polymerizations of some vinyl monomers in carbon dioxide fluid

The effect of pressure ranging from ambient atmosphere to 28.5 MPa on the free radical polymerizations of methyl methacrylate (MMA) in carbon dioxide (CO₂) was investigated and discussed. The poly(methyl methacrylate) (PMMA) with high molecular weight was synthesized at quite high conversion of MMA in the polymerization at or below 9.2 MPa, as compared to those polymerized under 11.8–28.5 MPa. A phase transition behavior of MMA‐CO₂ binary mixture from homogeneous state to vapor‐liquid equilibrium (VLE) state was observed below 10.51 MPa. In such a VLE system, almost all MMA was found to exist in the liquid phase with higher concentration than that in homogenous system. Thus, the fast polymerization rate of MMA and high molecular weight of PMMA could be related to the VLE state of MMA/CO₂ under low pressure. Similar phenomena were also observed in the polymerization systems of styrene and vinyl acetate in CO₂, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of well‐defined poly(methyl methacrylate) nanoparticles by reverse atom transfer radical polymerization in a microemulsion

Well‐defined poly(methyl methacrylate) (PMMA) with an α‐isobutyronitrile group and an ω‐bromine atom as the end groups was synthesized by the microemulsion polymerization of methyl methacrylate (MMA) at 70°C with a 2,2′‐azobisisobutyronitrile/CuBr₂/2,2′‐bipyridine system. The conversion of the polymerization reached 81.9%. The viscosity‐average molecular weight of PMMA was high (380,000), and the polydispersity index was 1.58. The polymerization of MMA exhibited some controlled radical polymerization characteristics. The mechanism of controlled polymerization was studied. The presence of hydrogen and bromine atoms as end groups of the obtained PMMA was determined by ¹H‐NMR spectroscopy. The shape and size of the final polymer particles were analyzed by scanning probe microscopy, and the diameters of the obtained particles were usually in the range of 60–100 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3670–3676, 2006     

Photopolymerization of methyl methacrylate and 2-(dimethylamino) ethyl methacrylate induced by diacetoxyiodobenzene in the presence of radical inhibitors

Summary Polyvalent iodine compounds such as diacetoxyiodobenzene, (CH₃COO)₂IC₆H₅ (DAI), and bis(trifluoroacetoxy) iodobenzene, (CF₃COO)₂IC₆H₅ (BTI), are efficient initiators of cationic and radical polymerizations. To confirm the radical mechanism of DAI-induced polymerization of methyl methacrylate (MMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA), a study has been performed in the presence of the radical inhibitor 2,3,5,6-tetrachloro-p-benzoquinone (TCQ) and its complex with triethylamine (TEA). The polymerization kinetics and the effect of irradiation intensity have been studied.     

Radical Copolymerization of 2-(3′-Acryloxy)propoxythioxanthone and 1-Methyl-4-(3′-acryloxy)propoxythioxanthone with Methyl Methacrylate

Two new monomers based on thioxanthone, 2-(3′-acryloxy)propoxythioxanthone (M-2) and 1-methyl-4-(3′-acryloxy)propoxythioxanthone (M-4), were prepared and their radical copolymerization at 70°C with methyl methacrylate (MMA) was studied. By varying the conversion reached for a fixed feed composition, f_MMA=0·983, and using Jaacks method, the reactivity ratios were determined. Identical values of reactivity ratios were found for both systems, with values of r_MMA=2·46 and r_M-2=r_M-4=0·4. The homopolymerization of MMA in the presence of a model compound, 1-methyl-4-propoxythioxanthone, was also examined and confirmed that the thioxanthone chromophore does not have any influence on the free radical polymerization of MMA. © of SCI.     

Polymerization of methyl methacrylate by imidazole–carbon tetrachloride charge-transfer system

The kinetics of charge-transfer (CT) polymerization of methyl methacrylate (MMA) in the presence of imidazole (Imy) and CCl₄ was studied in dimethyl sulfoxide (DMSO) at 60°C. The rate of polymerization (R_p) is sensitive to the [CCl₄] up to a concentration of 0.60 mol L⁻¹, but at a higher concentration, it is practically independent of the [CCl₄]. When [CCl₄] > [Imy], R_p is proportional, to [MMA]^1.45±0.15 and [Imy]^0.53±0.04 and the average rate constant for the polymerization of MMA is 3.25±0.41 × 10⁻⁶ L mol⁻¹ s⁻¹. This article also reports the polymerization of MMA initiated by Imy and CCl₄ and accelerated by hexakis (dimethyl sulfoxide) iron (III) perchlorate, [Fe(DMSO)₆] (CIO₄)₃ (A), at 60°C. The presence of Fe(Imy)³⁺₃ in the polymerization system produced well-defined induction periods. The rate constant at 60°C for the interaction of the poly(MMA) radical toward Fe(Imy)³⁺₃ is 7.19 × 10⁴ L mol⁻¹ s⁻¹. A probable reaction mechanism for the polymerization system has been postulated to explain the observed results. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of new soluble multisite phase transfer catalysts and their catalysis in free radical polymerization of methyl methacrylate aided by ultrasound—A kinetic study

Four different soluble phase transfer catalysts (PTCs) containing single, di, tri, and tetra active sites have been prepared and proved by FT-IR, ¹H NMR, ¹³C NMR, mass, elemental analysis, and conductivity measurement. The presence of the number of active sites in each catalyst was also been confirmed by determining their rate of polymerization of methyl methacrylate (MMA) using potassium peroxydisulfate (PDS) as a water soluble initiator in biphase medium. The comparative study reveals that the R_p of MMA determined in the presence of PTC combined with ultrasound has shown twofold enhancement in the activity than PTC alone. The observed order of activity was found to be of single-site < di-site < tri-site < tetra-site. Further, the thorough kinetic study of free radical polymerization of MMA has been investigated using superior tetra site viz., HBTAMPDTC and by varying the experimental parameters such as [MMA], [K₂S₂O₈], [MPTC], and the temperature. Based on the observed kinetic results and activation parameters, a suitable mechanism was proposed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Photo‐Induced atom transfer radical polymerization with nanosized α‐Fe2O3 as photoinitiator

Photo‐induced atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was achieved in poly(ethylene glycol)‐400 with nanosized α‐Fe₂O₃ as photoinitiator. Well‐defined poly(methyl methacrylate) (PMMA) was synthesized in conjunction with ethyl 2‐bromoisobutyrate (EBiB) as ATRP initiator and FeCl₃·6H₂O/Triphenylphosphine (PPh₃) as complex catalyst. The photo‐induced polymerization of MMA proceeded in a controlled/living fashion. The polymerization followed first‐order kinetics. The obtained PMMA had moderately controlled number‐average molecular weights in accordance with the theoretical number‐average molecular weights, as well as narrow molecular weight distributions (M_w/M_n). In addition, the polymerization could be well controlled by periodic light‐on–off processes. The resulting PMMA was characterized by ¹H nuclear magnetic resonance and gel permeation chromatography. The brominated PMMA was used further as macroinitiator in the chain‐extension with MMA to verify the living nature of photo‐induced ATRP of MMA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42389.     

Photomediated atom transfer radical polymerization of MMA under long-wavelength light irradiation

In this study, a novel photocatalyst, pentarylenebis(dicarboximide) dye: (1,6,13,18-tetra(4-(2,3,3-trimethylbut-2-yl)phenoxy)-N,N’-(2,6-diisopropylphenyl)-pentarylene-3,4,15,16-tetracarboxidiimide) (TTPDPT), was first used in metal-free photoinduced atom transfer radical polymerization (ATRP) of methyl methacrylates (MMA). The initiator was methyl α-bromoisobutyrate (MBI) and the light source was mild near-infrared (NIR) light irradiation (λ_max?≈?870 nm). The TTPDPT-mediated ATRP relies on in situ photoreduction of a MBI through an electron transfer process to generate the desired alkyl radical, which could induce polymerization of the monomer. The photoinduced metal-free ATRP of MMA shows typical characteristics of controlled free radical polymerization, showing the linear evolution of number-average molecular weight (M_n,GPC) with monomer conversion, where polymers with predetermined degree of polymerization have well-controlled molecular weights and narrow molecular weight distribution (M_w/M_n). The photoinduced metal-free ATRP of MMA can be carried out with just ppm level of TTPDPT. The polymerization initiation and propagation can be operated by the aid of pulsed light sequences while NIR light source was used to promote carbon–carbon bond formation and to produce poly(methyl methacrylate) (PMMA) with M_w/M_n as low as 1.5. The synthesized PMMA was characterized by ¹H nuclear magnetic resonance (¹H NMR). The resultant PMMA contained a bromide end group that can be employed to reinitiate styrene polymerization to produce block copolymers through chain extension experiments.