Iron‐based electrochemically mediated atom transfer radical polymerization with tunable catalytic activity

An iron‐based electrochemically mediated atom transfer radical polymerization (eATRP) system with tunable catalytic activity was developed by adjusting the supporting electrolyte formula. Kinetic behaviors of the systems using four typical supporting electrolytes (namely, TBABr, TBAPF₆, TBACl, and TBABF₄) were investigated. The type of anions was found to significantly affect the polymerization kinetics. TBAPF₆ system proceeded with a considerable polymerization rate, whereas TBABr system showed better controllability. Importantly, the effect of supporting electrolyte on eATRP kinetics (mainly on ATRP equilibrium) was confirmed through kinetic modeling. Furthermore, the effect of catalyst loading using TBAPF₆ as supporting electrolyte was also studied, and the results showed an uncontrolled polymerization for catalyst loading lower than 500 ppm. When hybrid supporting electrolyte (TBAPF₆/TBABr) was used to tune catalytic activity, the polymerization slows down and the dispersity decreases with the increase in TBABr ratio. Polymers with a narrow molecular weight distribution (dispersity index <1.5) were obtained using 100% TBABr under 100 ppm catalyst. Besides, experimental attempt to improve the controllability by adding halogen donors was made, whereas the halogen donors just prolonged the induction period and no improvement was achieved. As a whole, a deeper understanding of kinetic studies is obtained by these controlled trials. © 2017 American Institute of Chemical Engineers AIChE J, 64: 961–969, 2018     

Fe‐mediated ARGET atom transfer radical polymerization of methyl methacrylate in ionic liquid‐based microemulsion

Poly(methyl methacrylate) (PMMA) was synthesized by activator regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) of MMA in ionic liquid‐based microemulsion with polyoxyethylene sorbitan monooleate (Tween 80) as surfactant. The polymerization was carried out at 25°C with CCl₄ as initiator, FeCl₃·6H₂O/N,N,N′,N′‐tetramethyl‐1,2‐ethanediamine (TMEDA) as catalyst complex in the presence of reducing agent ascorbic acid (VC). The polymerization kinetics showed the feature of controlled/″living″ process as evidenced by a linear first‐order plot. The well‐controlled polymers were obtained with narrow polydispersity indices and the ionic liquid‐based microemulsions were transparent with a particle size less than 30 nm. The obtained polymer was characterized by ¹H NMR and gel permeation chromatography. The chain extension was successfully achieved by the obtained PMMA macroinitiator/FeCl₃·6H₂O/TMEDA/VC initiator system based on ARGET ATRP method. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Reverse atom transfer radical polymerization of acrylonitrile under microwave irradiation

Reverse atom transfer radical polymerization was first used to successfully synthesize polyacrylonitrile under microwave irradiation. FeCl₃, coordinated by isophthalic acid, was used as the catalyst, and 2,2′‐azobisisoheptonitrilewas used as the initiator. N,N‐Dimethylformamide was used as the solvent to improve the solubility of the ligand. Under the same experimental conditions, the apparent rate constant under microwave irradiation was higher than that under conventional heating. The polymerization not only showed the best control of the molecular weight and its distribution but also provided a rather rapid reaction rate with the [acrylonitrile]/[2,2′‐azobisisoheptonitrile]/[FeCl₃]/[isophthalic acid] ratio of 300 : 1 : 1 : 2. The polymers obtained were used as macroinitiators to initiate the chain extension and successfully synthesize acrylonitrile polymers with a molecular weight higher than 50,000 and a narrow polydispersity as low as 1.30. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and photoinduced surface‐relief grating of well‐defined azo‐containing polymethacrylates via atom transfer radical polymerization

A well‐defined photoresponsive polymethacrylate containing azo chromophores, poly[6‐(4‐phenylazophenoxy)hexylmethacrylate] [Poly(PPHM)], was prepared with azo‐based monofunctional and difunctional initiators via atom transfer radical polymerization in the presence of CuCl/1,1,4,7,10,10‐hexamethyltriethylenetetramine. The polymerizations with first‐order kinetics were well controlled with theoretical expected molecular weight and narrow molecular weight distributions in two initiation systems. The UV absorption intensities of the poly (PPHM)s increased with increasing molecular weight of the poly(PPHM)s in all cases. The 80‐nm surface‐relief gratings with 2.7% efficient diffraction formed on the poly (PPHM) film surface were obtained with a linearly polarized krypton laser with 10 min of irradiation at a recording beam intensity of 188 mW/cm² with a wavelength of 413.1 nm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and characterization of PMMA‐b‐PBMA block copolymers by atom transfer radical polymerization

The synthesis of diblock copolymers using atom transfer radical polymerization, ATRP, of n‐butyl methacrylate, BMA, and methyl methacrylate, MMA, is reported. These copolymers were prepared from 2‐bromoisobutyryl‐terminated macroinitiators of poly(MMA) and poly(BMA), using copper chloride, CuCl,/N,N,N′,N″,N″‐pentamethyldiethylenetretramine, PMDETA, as the catalyst system, at 100°C in bulk and in benzonitrile solution. The block copolymers were characterized by means of size‐exclusion chromatography, SEC, and ¹H‐NMR spectroscopy. The SEC analysis of the synthesized diblock copolymers confirmed important differences in the molecular weight control depending on the reaction medium (solvent effect) and the chemical structure of the macroinitiator used. In addition, differential scanning calorimetry, (DSC) measurements were performed, showing for all the copolymers a phase separation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2683–2691, 2002     

Evaluation of the confinement effect of nanoclay on the kinetics of styrene atom transfer radical polymerization

The grafting through method was employed to study the effect of nanoclay confinement on the atom transfer radical polymerization (ATRP) of styrene. An ammonium salt containing a double bond on its structure was used as a clay modifier. Employing ATRP to polymerize styrene in the presence of modified montmorillonite resulted in a finely well‐defined polystyrene nanocomposite. The gas chromatography (GC) results showed the linear increase of ln(M₀/M) versus time, which indicated the controlled behavior of the polymerization. Another confirmation of the living nature of the polymerization was the linear increase of molecular weight against monomer conversion concluded from the gel permeation chromatography (GPC) data. Nanoclay exerted acceleration on the polymerization of free polystyrene chains. The polydispersity indexes of polymer chains increased by the addition of nanoclay. In the case of clay‐attached polystyrene chains, number and weight‐average molecular weights were lower than that of freely dispersed polystyrene chains. The polydispersity index of the clay‐attached chains was higher in respect to the freely dispersed polystyrene chains. The living nature of polymer chains was more elucidated by Fourier transform infrared spectroscopy (FTIR). Exfoliation of the clay layers in the polymer matrix of polystyrene nanocomposite containing the lowest amount of nanoclay has proven by Transmission Electron Microscopy (TEM). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of tailor‐made polystyrene nanocomposite with mixed clay‐anchored and free chains via atom transfer radical polymerization

Tailor‐made polystyrene nanocomposite with mixed free and clay‐attached polystyrene chains was synthesized using atom transfer radical polymerization. Vinylbenzyl trimethylammonium chloride having a double bond, which could be incorporated into polystyrene chains by a grafting through process, was used as a nanoclay modifier. Conversion and molecular weight evaluation was carried out using gas chromatography and gel permeation chromatography, respectively. The thermogravimetric analysis results confirmed the elevated thermal stability of the nanocomposites in comparison with the neat polystyrene sample. Additionally, the T_g increases by clay loading was confirmed by differential scanning calorimetry (DSC). The difference in the degradation temperature of C? Br bond in attached and free polystyrene chains was well revealed in DSC thermograms. Finally, a lower clay loading resulted in an exfoliated structure as proved by X‐ray diffraction and transmission electron microscopy results. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Novel comb‐structured‐polymer‐grafted carbon black by surface‐initiated atom transfer radical polymerization and ring‐opening polymerization

Novel comb‐structured‐polymer‐grafted carbon black (CB) was synthesized with a combination of surface‐initiated atom transfer radical polymerization and ring‐opening polymerization. First, poly(2‐hydroxyethyl methacrylate) (PHEMA) was grafted onto the CB surface by surface‐initiated atom transfer radical polymerization. The prepared CB‐g‐PHEMA contained 35.6–71.8% PHEMA, with the percentage depending on the molar ratio of the reagents and the reaction temperature. Then, with PHEMA in CB‐g‐PHEMA as the macroinitiator, poly(?‐caprolactone) (PCL) was grown from the CB‐g‐PHEMA surface by ring‐opening polymerization in the presence of stannous octoate. CB‐g‐PHEMA and CB‐g‐(PHEMA‐g‐PCL) were characterized with Fourier transform infrared, ¹H‐NMR, thermogravimetric analysis, dynamic light scattering, and transmission electron microscopy. The resultant grafted CB had a shell of PHEMA‐g‐PCL. On the whole, the CB nanoparticles were oriented in dendritic lamellae formed by these shells. This hopefully will result in applications in gas sensor materials and nanoparticle patterns. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Pseudohalogens in atom transfer radical polymerization of methyl methacrylate

In recent advances in controlled radical polymerization, atom transfer radical polymerization (ATRP) has achieved increasing interest. This investigation reports the ATRP of methyl methacrylate (MMA) using pseudohalogens as initiator as well as an anion for copper catalyst. The results were compared with the conventional halide system. Different pseudohalides were used as the initiator for the ATRP of MMA in combination with CuX (X = pseudohalide or halide) as the catalyst. Pseudohalide initiator in combination with Cu(halide) catalyst leads to inefficient ATRP due to slow initiation. Pseudohalide initiator in combination with Cu(pseudohalide) catalyst leads to uncontrolled or no polymerization. The polymers were characterized by using GPC, IR, MALDI‐TOF‐MS, and TGA analysis. IR and MALDI analysis showed that the resultant polymer had pseudohalide as the end group. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3857–3864, 2007     

Surface‐initiated atom transfer radical polymerization of regenerated cellulose membranes with thermo‐responsive properties

Using atom transfer radical polymerization (ATRP), thermo‐responsive regenerated cellulose membranes were synthesized. Regenerated cellulose membranes were firstly modified by reacting the hydroxyl groups on the surface with 2‐bromoisobutyryl bromide, followed by grafting with poly(N‐isopropylacrylamide). The membranes had obvious thermally modulated permeability properties. Analysis was carried out by means of X‐ray photoelectron spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. The results showed that N‐isopropylacrylamide had been grafted successfully on the surface of the regenerated cellulose membranes. The thermally modulated permeability properties of the grafted membranes were studied using water flux measurements. It was found that the thermally modulated permeability properties of a cellulose surface can be tailored by the use of the ATRP method. Copyright © 2010 Society of Chemical Industry     

原子转移自由基聚合负载化催化剂研究进展

综述了几种原子转移自由基聚合(ATRP)用负载化催化体系的组成及应用,主要包括硅胶或石英、交联聚苯乙烯或其它聚合物为载体进行的催化剂负载化,它们都能够部分解决催化剂残留问题,但却有一定的局限性;负载/可溶性混杂催化体系成为解决这一问题的新方法,而且它与传统的均相催化体系相比,可控性没有明显差异,有希望作为未来解决催化剂残留的有效方法.最后展望了ATRP负载化催化荆的发展方向.     

Effect of ferrocene moieties on the copper‐based atom transfer radical polymerization of methyl methacrylate

The atom transfer radical polymerization (ATRP) of methyl methacrylate catalyzed by copper–tripodal complexes with ferrocene moieties (CuX/TRENFcImine, where X is Br or Cl, and TRENFcImine is tris‐[2‐(ferrocenylmethyleneimino)ethyl]amine) was investigated to understand the effect of redox active moieties on the performance of ATRP catalysts. The CuBr/TRENFcImine system was highly active, with 82% conversion in 2 h. However, the polymerization became slower at higher molar ratios of monomer to catalyst. The polydispersity index was broad, and the initiation efficiency was relatively low. On the basis of the conformational analysis, the highly active and less controlled polymerization was probably caused by the electronic effect rather than the steric effect on the ferrocene moieties, which led to the higher and lower values in the activation and deactivation steps, respectively. The polydispersity index was improved by the addition of CuBr₂, but this led to slower rates of polymerization. The effect of halide groups on ATRP caused a faster rate in the CuBr/TRENFcImine polymerization system than in the CuCl/TRENFcImine system. The higher molar ratio of monomer to catalyst had no significant effect on the CuCl/TRENFcImine system. Nonetheless, the trace of water in the CuCl₂·2H₂O system accelerated the rate of propagation, which led to a higher molecular weight. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Reverse atom transfer radical polymerization of MMA via immobilized catalysts in imidazolium ionic liquids

Reverse atom transfer radical polymerization (RATRP) of methyl methacrylate (MMA) employing immobilized catalyst was approached at 50 and 60°C in [C₈mim]PF₆, and compared with the polymerization of MMA DMF as solvent. Other ionic liquids, [C₆mim]BF₄, [C₈mim]BF₄, and [C₁₂mim]BF₄, were used as solvents to perform the RATRP of MMA. By comparison, we found that the [C₈mim]PF₆ was the best solvent in this immobilized catalyst system and the polymerization was best controlled. In addition, the immobilized catalyst spherules can easily separate from the reaction mixture, which avoids the prevalent problem of the catalyst residual in RATRP and also gives us a possibility to recycle the catalyst system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3915–3919, 2007     

Kinetic study of the atom transfer radical polymerization of n‐docosyl acrylate

The atom transfer radical polymerization (ATRP) of n‐docosyl acrylate (DA) was studied at 80°C in N,N‐dimethylformamide using the carbon tetrabromide/FeCl₃/2,2′‐bipyridine (bpy) initiator system in the presence of 2,2′‐azobisisobutyronitrile (AIBN) as the source of reducing agent. The rate of polymerization exhibits first‐order kinetics with respect to the monomer. The linear relationship between the molecular weight of the resulting poly(n‐docosyl acrylate) with conversion and the narrow polydispersity of the polymers indicates the living characteristics of the polymerization reaction. The significant effect of AIBN on the ATRP of DA was studied keeping [FeCl₃]/[bpy] constant. A probable reaction mechanism for the polymerization system is postulated to explain the observed results. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2147–2154, 2005     

Graft copolymers and high‐molecular‐weight star‐like polymers by atom transfer radical polymerization

Grafting of tert‐butyl acrylate (tBuA), methyl methacrylate (MMA), and styrene (St) monomers (M) by Cu(I)‐mediated ATRP from polystyrene (PSt) macroinitiator (M_n = 5620, polydispersity index, PDI = 1.12), containing initiating 2‐bromopropionyloxy groups (I) (bound to 34% of aromatic cores; 11 groups per backbone), was performed using conditions suitable for the respective homopolymerizations. The preparation of PSt‐g‐PtBuA in bulk using an initial molar ratio [M]₀/[I]₀ = 140 had a controlled character up to M_n = (132–148) × 10³ (PDI = 1.08–1.16). With MMA and St and using the same [M]₀/[I]₀, preliminary experiments were made; the higher the monomer conversion, the broader was the distribution of molecular weight of the products. Graft copolymerizations of all these monomers at [M]₀/[I]₀ = 840 or 1680 were successfully conducted up to high conversions. Low‐polydispersity copolymers, with very long side chains, in fact star‐like copolymers, were obtained mainly by tuning the deactivator amount in the reaction mixture. (PSt‐g‐PtBuA, DP_n,sc (DP of side chain) = 665, PDI = 1.24; PSt‐g‐PMMA, DP_n,sc = 670, PDI = 1.43; PSt‐g‐PSt, DP_n,sc = 324, PDI = 1.11). Total suppression of intermolecular coupling was achieved here. However, the low concentrations of initiator required long reaction times, leading sometimes to formation of a small amount (～5%) of low‐molecular‐weight polymer fraction. This concomitant process is discussed, and some measures for its prevention are proposed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3662–3672, 2006     

Synthesis and characterization of Pst‐b‐PDMS‐b‐PSt copolymers by atom transfer radical polymerization

Polystyrene‐b‐poly(dimethylsiloxane)‐b‐polystyrene (Pst‐b‐PDMS‐b‐PSt) triblock copolymers were synthesized by atom transfer radical polymerization (ATRP). Commercially available difunctional PDMS containing vinylsilyl terminal species was reacted with hydrogen bromide, resulting in the PDMS macroinitiators for the ATRP of styrene (St). The latter procedure was carried out at 130°C in a phenyl ether solution with CuCl and 4, 4′‐di (5‐nonyl)‐2,2′‐bipyridine (dNbpy) as the catalyzing system. By using this technique, triblock copolymers consisting of a PDMS center block and polystyrene terminal blocks were synthesized. The polymerization was controllable; ATRP of St from those macroinitiators showed linear increases in M_n with conversion. The block copolymers were characterized with IR and ¹H‐NMR. The effects of molecular weight of macroinitiators, macroinitiator concentration, catalyst concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3764–3770, 2004     

Synthesis and characterization of PBMA‐b‐PDMS‐b‐PBMA copolymers by atom transfer radical polymerization

Poly(butyl methylacrylate)–b–poly(dimethylsiloxane)–b–poly(butyl methylacrylate) (PBMA–b–PDMS–b–PBMA) triblock copolymers were synthesized by atom transfer radical polymerization (ATRP). The reaction of α,ω‐dichloride PDMS with 2′‐hydroxyethyl‐2‐bromo‐2‐methylpropanoate gave suitable macroinitiators for the ATRP of BMA. The latter procedure was carried out at 110°C in a phenyl ether solution with CuCl and 4,4′‐di (5‐nonyl)‐2,2′‐bipyridine (dNbpy) as the catalyzing system. The polymerization was controllable, with the increase of the monomer conversion, there was a nearly linear increase of molecular weight and a decrease of polydispersity in the process of the polymerization, and the rate of the polymerization was first‐order with respect to monomer conversion. The block copolymers were characterized with IR and ¹H‐NMR and differential scanning calorimetry. The effects of macroinitiator concentration, catalyst concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP were reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 532–538, 2004     

Trimethylsilyl‐substituted triazole‐based ligand for copper‐mediated single‐electron transfer living radical polymerization of methyl methacrylate

The tripodal ‘click’ compound tris(4‐trimethylsilylmethyl‐1,2,3‐triazolylmethyl)amine (TTTA) was prepared and investigated as a ligand for copper‐catalysed single‐electron transfer living radical polymerization of methyl methacrylate (MMA). Bulk polymerizations catalysed by Cu⁰/CuBr₂/TTTA with a molar ratio of [MMA]₀/[ethyl‐2‐bromoisobutyrate]₀/[CuBr₂]₀/[TTTA]₀ = 200:2:1:1 and a 1.0 × 1.0 cm² Cu⁰ sheet were fast and well controlled (76% conversion with M_w/M_n = 1.19 after 3.5 h). Greater amounts of added air generally gave slower polymerizations although M_w/M_n remained low (<1.3) even when the polymerization was carried out under aerobic conditions. Decreasing initial concentrations of the Cu⁰/CuBr₂/TTTA catalyst system or polymerization temperatures also resulted in slower polymerizations and yielded polymers with broader dispersity. Kinetic studies in the temperature range 40–90 °C revealed an apparent activation energy of 22.6 kJ mol^?1. © 2014 Society of Chemical Industry     

Synthesis and coordination of oxyquinolyl end‐functionalized polystyrene by atom transfer radical polymerization

The end‐functionalized polystyrene is synthesized by a new initiator, 5‐chloromethyl‐8‐hydroxyquinoline (5‐ClCH₂Q), via atom transfer radical polymerization. The existence of the oxyquinoline group on the chain end was confirmed by ¹H‐NMR. The polymers can be easily changed into films with good fluorescence property and nonlinear third‐order optical property. Coordinating the oxyquinoline group with Eu³⁺ and La³⁺, the fluorescent intensity and third‐order nonlinear optical coefficient will be enhanced much more. The proportion of the oxyquinoline group coordinating and rare‐earth metal is 3:2 determined by titrimetric analysis. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2067–2071, 2005     

Development of multimodal membrane adsorbers for antibody purification using atom transfer radical polymerization

This contribution describes a graft polymerization strategy to prepare multimodal membranes, a new class of high-productivity adsorptive materials for the purification of therapeutic proteins. Surface-initiated atom transfer radical polymerization was used to graft poly(glycidyl methacrylate) ‘tentacles’ from the pore surfaces of macroporous regenerated cellulose membranes. Subsequently, 4-mercaptobenzoic acid was coupled to the membranes by an epoxide ring-opening reaction. ATR-FTIR measurements support successful ligand incorporation. Graft polymerization studies from cellulose-coated silicon substrates were done in parallel to measure the thickness evolution of the polymer coating, which plays an important role on protein binding capacities. Protein binding experiments with bovine immunoglobulin G show that the multimodal membranes have high equilibrium capacities, up to 150 mg IgG/mL. The binding capacities are pH-dependent, with maximum binding at pH near the protein isoelectric point. Characteristic of multimodal adsorbers, the membranes retain about 70% of their equilibrium binding capacity at moderate ionic strength (300 mM) and about 40% at high ionic strength (1.6 M).