Synthesis of water‐soluble and conducting polyaniline by growing of poly (N‐isopropylacrylamide) brushes via atom transfer radical polymerization method

Polyaniline‐graft‐Poly(N‐isopropylacrylamide) copolymers were synthesized by atom‐transfer radical polymerization (ATRP) of N‐isopropylacrylamide using polyaniline macro‐initiators. Polyaniline‐chloroacetylchloride and polyaniline‐chloropropionylchloride macroinitiators were obtained by the reaction of amine nitrogens of polyaniline with chloroacetyl chloride and 2‐choloropropionyl choloride, respectively. Both macroinitiators and graft copolymers were characterized by FT‐IR and ¹H‐NMR spectroscopy. The cyclic voltammetry (CV) and UV‐Vis spectroscopy studies showed that these copolymers are electroactive. The solubility test revealed that the polyaniline‐graft‐poly (N‐isopropylacrylamide) copolymers are water soluble or water/methanol soluble. The Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) images showed the growing of poly (N‐isopropylacrylamide) chains on polyaniline backbone. Investigation of thermal behavior of graft copolymers by thermal gravimetry analysis (TGA) confirmed the results obtained from AFM and SEM images. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structure and properties of tailor‐made poly(ethyl acrylate)/clay nanocomposites prepared by in situ atom transfer radical polymerization

An in‐depth study was carried out on the structure and properties of a series of poly(ethyl acrylate)/clay nanocomposites prepared by in situ atom transfer radical polymerization (PNCIs) with well‐defined molecular weights and narrow molecular weight distributions. Wide‐angle X‐ray diffraction and transmission electron microscopy studies revealed an exfoliated clay morphology, whereas conventional solution blending generated an intercalated structure. The storage moduli of the PNCIs showed a moderate increase over that of the neat polymer [poly(ethyl acrylate)]. The sample containing 4 wt % clay (PNCI4, where the number following PNCI indicates the weight percentage of clay) exhibited the highest improvement (31.9% at 25°C). In PNCIs, the β‐transition temperature showed a remarkable decrease (by 175% in PNCI4) along with a shift toward higher temperatures. This indicated the probability of the anchoring of the ? OH group of the clay layers to the >C?O group of the pendant acrylate moiety, which was also confirmed by Fourier transform infrared analysis. Rheological measurements indicated a significant increase in the shear viscosity [by 9% in PNCI2, 15% in PNCI4, and 6% in the poly(ethyl acrylate)/clay nanocomposite with 2 wt % clay prepared by solution blending]. The PNCIs registered enhanced thermal stability, as indicated by the shift in the peak maximum temperature (388 and 392°C for the neat polymer and PNCI4, respectively) and a decrease in the rate of degradation (by 3.5% in PNCI2, 10.2% in PNCI4, and 49.3% in PNCI6). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of poly(octadecyl acrylate‐b‐styrene‐b‐octadecyl acrylate) triblock copolymer by atom transfer radical polymerization

The synthesis of triblock copolymer poly(octadecyl acrylate‐b‐styrene‐b‐octadecyl acrylate), using atom transfer radical polymerization (ATRP), is reported. The copolymers were prepared in two steps. First, polystyrene was synthesized by ATRP using α,α′‐dichloro‐p‐xylene/CuBr/bpy as the initiating system; Second, polystyrene was further used as macroinitiator for the ATRP of octadecyl acrylate to prepare ABA triblock copolymers in the presence of FeCl₂·4H₂O/PPh₃ in toluene. Polymers with controlled molecular weight (M_n = 17,000–23,400) and low polydispersity index value (1.33–1.44) were obtained. The relationship between molecular weight versus conversion showed a straight line. The effect of reaction temperature on polymerization was also investigated, showing a faster polymerization rate under higher temperature. The copolymers were characterized by FTIR, ¹H‐NMR, DSC, and GPC and the crystallization behavior of the copolymers was also studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1539–1545, 2004     

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     

High‐molecular‐weight polyacrylonitrile by atom transfer radical polymerization

A single‐pot atom transfer radical polymerization was used for the first time to successfully synthesize polyacrylonitrile with a molecular weight higher than 80,000 and a narrow polydispersity as low as 1.18. This was achieved with CuBr/isophthalic acid as the catalyst, 2‐bromopropionitrile as the initiator, and N,N‐dimethylformamide as the solvent. The effects of the solvent on the polymerization of acrylonitrile were also investigated. The induction period was shorter in N,N‐dimethylformamide than in propylene carbonate and toluene, and the rate of the polymerization in N,N‐dimethylformamide was fastest. The molecular weight of polyacrylonitrile agreed reasonably well with the theoretical molecular weight in N,N‐dimethylformamide. When chlorine was used in either the initiator or the catalyst, the rate of polymerization showed a trend of decreasing, and the molecular weight deviated from the theoretical predication significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3372–3376, 2006     

Synthesis and characterization of poly(n‐butyl methacrylate)‐b‐polystyrene diblock copolymers by atom transfer radical emulsion polymerization

Poly(n‐butyl methacrylate) (PBMA)‐b‐polystyrene (PSt) diblock copolymers were synthesized by emulsion atom transfer radical polymerization (ATRP). PBMA macroinitiators that contained alkyl bromide end groups were obtained by the emulsion ATRP of n‐butyl methacrylate with BrCH₃CHCOOC₂H₅ as the initiator; these were used to initiate the ATRP of styrene (St). The latter procedure was carried out at 85°C with CuCl/4,4′‐di(5‐nonyl)‐2,2′‐bipyridine as the catalyst and polyoxyethylene(23) lauryl ether as the surfactant. With this technique, PBMA‐b‐PSt diblock copolymers were synthesized. The polymerization was nearly controlled; the ATRP of St from the macroinitiators showed linear increases in number‐average molecular weight with conversion. The block copolymers were characterized with IR spectroscopy, ¹H‐NMR, and differential scanning calorimetry. The effects of the molecular weight of the macroinitiators, macroinitiator concentration, catalyst concentration, surfactant concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP are also reported. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2123–2129, 2005     

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     

Preparation of nanoclay‐dispersed polystyrene nanofibers via atom transfer radical polymerization and electrospinning

In this study, clay‐dispersed polystyrene (PS) nanocomposites were prepared with the in situ atom transfer radical polymerization method and were subsequently electrospun to form nanofibers 450–650 nm in diameter. The polymer chains extracted from the clay‐dispersed nanofibers exhibited a narrow range of molecular weight distribution. Thermogravimetric analysis (TGA) confirmed a higher thermal stability of the resulting nanocomposites compared to PS. The effect of the weight ratio of montmorillonite on the thermal properties of the nanocomposites was also studied by TGA. Differential scanning calorimetry revealed that the addition of the nanoclay increased the glass‐transition temperature. Moreover, degradation of the bromide chain‐end functionality took place at low temperatures. Scanning electron microscopy showed that the average diameter of the fibers was around 500 nm. The dispersion of clay layers was also evaluated by Al atoms in the PS matrix with the energy‐dispersive X‐ray detection technique. Transmission electron microscopy confirmed the exfoliation of the nanoclay within the matrix. However, the clay layers were oriented along the nanofiber axis. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

原子转移自由基聚合法合成PS-g-PMMA

以氯乙酰化聚苯乙烯微球（PS-acyl-Cl）为大分子引发剂,甲基丙烯酸甲酯（MMA）为单体,CuCl/CuCl₂及N,N,N′,N′-四甲基乙二胺（TMEDA）为催化体系的原子转移自由基聚合反应,成功在PS-acyl-Cl表面接枝上PMMA分子链而获得聚苯乙烯 接枝 聚甲基丙烯酸甲酯（PS-g-PMMA）。考察了催化剂、反应温度、溶剂用量等条件对接枝反应的影响,优化的反应条件下,使用氯乙酰基担载量3.44 mmol.g^-1的PS-acyl-Cl,15 h可获得增重率687% 的PS-g-PMMA,且反应表现出一级动力学特征（k=513×10^-5 s^-1）。通过改变反应条件,可得到不同PMMA接枝链长的PS-g-PMMA。反应得到的PS-g-PMMA经水解后有望作为高担载量弱酸型离子交换树脂或进一步功能化后作为酶的柔性固定化载体。     

Effects of the solvent polarity on the atom transfer radical polymerization of methyl methacrylate initiated by 4‐(chloromethyl)phenyltrimethoxysilane

The controllability of the atom transfer radical polymerization of methyl methacrylate in the polar solvent N,N‐dimethylformamide and the nonpolar solvent xylene with 4‐(chloromethyl)phenyltrimethoxysilane as an initiator and with CuCl/2,2′‐bipyridine and CuCl/4,4′‐di(5‐nonyl)‐2,2′‐bipyridine as catalyst systems was studied. Gel permeation chromatography analysis established that in the nonpolar solvent xylene, much better control of the molecular weight and polydispersity of poly(methyl methacrylate) was achieved with the CuCl/4,4′‐di(5‐nonyl)‐2,2′‐bipyridine catalyst system than with the CuCl/2,2′‐bipyridine as catalyst system. In the polar solvent N,N‐dimethylformamide, unlike in xylene, the polymerization was more controllable with the CuCl/2,2′‐bipyridine catalyst system than with the CuCl/4,4′‐di(5‐nonyl)‐2,2′‐bipyridine catalyst system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2751–2754, 2007     

Synthesis and characterization of poly(vinyl chloride‐co‐vinyl acetate)‐graft‐poly[(meth)acrylates] by atom transfer radical polymerization

The graft polymerization of methyl methacrylate and butyl acrylate onto poly(vinyl chloride‐co‐vinyl acetate) with atom transfer radical polymerization (ATRP) was successfully carried out with copper(I) thiocyanate/N,N,N′,N′,N″‐pentamethyldiethylenetriamine and copper(I) chloride/2,2′‐bipyridine as catalysts in the solvent N,N‐dimethylformamide. For methyl methacrylate, a kinetic plot of ln([M]₀/[M]) (where [M]₀ is the initial monomer concentration and [M] is the monomer concentration) versus time for the graft polymerization was almost linear, and the molecular weight of the graft copolymer increased with increasing conversion, this being typical for ATRP. The formation of the graft polymer was confirmed with gel permeation chromatography, ¹H‐NMR, and Fourier transform infrared spectroscopy. The glass‐transition temperature of the copolymer increased with the concentration of methyl methacrylate. The graft copolymer was hydrolyzed, and its swelling capacity was measured. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 183–189, 2005     

表面引发原子转移自由基聚合制备甲基丙烯酸甲酯接枝废胶粉及其表征

采用原子转移自由基聚合法研究了废胶粉(GTR)的表面化学接枝改性,包括2-溴异丁酰溴(BIBB)与GTR表面羟基的反应,以及形成的大分子引发剂引发甲基丙烯酸甲酯(MMA)的接枝聚合反应;用红外光谱和X射线光电子能谱仪、热重分析和扫描电子显微镜对接枝改性反应前后的GTR表面进行了表征.结果表明,GTR表面含有一定量羟基,...     

原子转移自由基乳液聚合研究进展

原子转移自由基聚合(ATRP)作为一种可控/活性聚合方法,可对聚合物结构进行精确控制;乳液聚合以水作为分散介质,具有经济、环保等特点。因此,乳液ATRP结合了两者的优点,具有工业化生产的潜力。首先分析了影响乳液ATRP的各种因素,然后综述了正向ATRP、RATRP(反向ATRP)、SR&NI ATRP(正向/反向同时进行的ATRP)和AGET ATRP(电子转移活化剂ATRP)等机制及研究进展,最后对乳液ATRP的发展方向进行了展望。     

Graft copolymerization of methyl methacrylate from brominated poly(isobutylene‐co‐isoprene) via atom transfer radical polymerization

Commercial brominated poly(isobutylene‐co‐isoprene) (BIIR) rubber has been directly used for the initiation of atom transfer radical polymerization (ATRP) by utilizing the allylic bromine atoms on the macromolecular chains of BIIR. The graft copolymerization of methyl methacrylate (MMA) from the backbone of BIIR which was used as a macroinitiator was carried out in xylene at 85 °C with CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as a catalytic complex. The polymerization conditions were optimized by adjusting the catalyst and monomer concentration to reach a higher monomer conversion and meanwhile suppress macroscopic gelation during the polymerization process. This copolymerization followed a first‐order kinetic behavior with respect to the monomer concentration, and the number‐average molecular weight of the grafted poly(methyl methacrylate) (PMMA) increased with reaction time. The resultant BIIR‐graft‐PMMA copolymers showed phase separation morphology as characterized by atomic force microscopy, and the presence of PMMA phase increased the polarity of the BIIR copolymers. This study demonstrated the feasibility of using commercial BIIR polymer directly as a macromolecular initiator for ATRP reactions, which opens more possibilities for BIIR modifications for wider applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43408.     

Graft copolymerization of methyl methacrylate with an N‐substituted maleimide–liquid‐crystalline copolymer by atom transfer radical polymerization

The synthesis of novel copolymers consisting of a side‐group liquid‐crystalline backbone and poly (methyl methacrylate) grafts were realized by the use of atom transfer radical polymerization (ATRP). In the first stage, the bromine‐functional copolymers 6‐(4‐cyanobiphenyl‐4′‐oxy)hexyl acrylate and (2,5‐dioxo‐2,5‐dihydro‐1H‐pyrrole‐1‐yl)methyl 2‐bromopropanoate were synthesized by free‐radical polymerization. These copolymers were used as initiators in the ATRP of methyl methacrylate to yield graft copolymers. Both the macroinitiator and graft copolymers were characterized by ¹H‐NMR, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis. The ATRP graft copolymerization was supported by an increase in the molecular weight of the graft copolymers compared to that of the macroinitiator and also by their monomodal molecular weight distribution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Modification of polysulfone membranes via surface‐initiated atom transfer radical polymerization and their antifouling properties

Surface‐initiated atom transfer radical polymerization (ATRP) was used to tailor the functionality of polysulfone (PSF) membranes. A simple one‐step method for the chloromethylation of PSF under mild conditions was used to introduce surface benzyl chloride groups as active ATRP initiators. Covalently tethered hydrophilic polymer brushes of poly(ethylene glycol)monomethacrylate and 2‐hydroxyethyl methacrylate and their block copolymer brushes were prepared via surface‐initiated ATRP from the chloromethylated PSF surfaces. A kinetic study revealed that the chain growth from the membranes was consistent with a controlled process. X‐ray photoelectron spectroscopy was used to characterize the surface‐modified membrane after each modification stage. Protein adsorption experiments revealed substantial antifouling properties of the grafted PSF membranes in comparison with the those of the pristine PSF surface. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of poly(cyclohexene oxide)‐block‐polystyrene by combination of radical‐promoted cationic polymerization,atom transfer radical polymerization and click chemistry

The combination of radical‐promoted cationic polymerization, atom transfer radical polymerization (ATRP) and click chemistry was employed for the efficient preparation of poly(cyclohexene oxide)‐block‐polystyrene (PCHO‐b‐PSt). Alkyne end‐functionalized poly(cyclohexene oxide) (PCHO‐alkyne) was prepared by radical‐promoted cationic polymerization of cyclohexene oxide monomer in the presence of 1,2‐diphenyl‐2‐(2‐propynyloxy)‐1‐ethanone (B‐alkyne) and an onium salt, namely 1‐ethoxy‐2‐methylpyridinium hexafluorophosphate, as the initiating system. The B‐alkyne compound was synthesized using benzoin photoinitiator and propargyl bromide. Well‐defined bromine‐terminated polystyrene (PSt‐Br) was prepared by ATRP using 2‐oxo‐1,2‐diphenylethyl‐2‐bromopropanoate as initiator. Subsequently, the bromine chain end of PSt‐Br was converted to an azide group to obtain PSt‐N₃ by a simple nucleophilic substitution reaction. Then the coupling reaction between the azide end group in PSt‐N₃ and PCHO‐alkyne was performed with Cu(I) catalysis in order to obtain the PCHO‐b‐PSt block copolymer. The structures of all polymers were determined. Copyright © 2010 Society of Chemical Industry     

Atom transfer radical polymerization of methyl methacrylate initiated with a macroinitiator of poly(vinyl acetate)

Well‐defined poly(vinyl acetate‐b‐methyl methacrylate) block copolymers were successfully synthesized by the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in p‐xylene with CuBr as a catalyst, 2,2′‐bipyridine as a ligand, and trichloromethyl‐end‐grouped poly(vinyl acetate) (PVAc–CCl₃) as a macroinitiator that was prepared via the telomerization of vinyl acetate with chloroform as a telogen. The block copolymers were characterized with gel permeation chromatography, Fourier transform infrared, and ¹H‐NMR. The effects of the solvent and temperature on ATRP of MMA were studied. The control over a large range of molecular weights was investigated with a high [MMA]/[PVAc–CCl₃] ratio for potential industry applications. In addition, the mechanism of the polymerization was discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1089–1094, 2006     

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     

Synthesis and characterization of amphiphilic block copolymers of methyl methacrylate with poly(ethylene oxide) macroinitiators formed by atom transfer radical polymerization

Amphiphilic ABA triblock copolymers of poly(ethylene oxide) (PEO) with methyl methacrylate (MMA) were prepared by atom transfer radical polymerization in bulk and in various solvents with a difunctional PEO macroinitiator and a Cu(I)X/N,N,N′,N″,N″‐pentamethyldiethylenetriamine catalyst system at 85°C where X=Cl or Br. The polymerization proceeded via controlled/living process, and the molecular weights of the obtained block copolymers increased linearly with monomer conversion. In the process, the polydispersity decreased and finally reached a value of less than 1.3. The polymerization followed first‐order kinetics with respect to monomer concentration, and increases in the ethylene oxide repeating units or chain length in the macroinitiator decreased the rate of polymerization. The rate of polymerization of MMA with the PEO chloro macroinitiator and CuCl proceeded at approximately half the rate of bromo analogs. A faster rate of polymerization and controlled molecular weights with lower polydispersities were observed in bulk polymerization compared with polar and nonpolar solvent systems. In the bulk polymerization, the number‐average molecular weight by gel permeation chromatography (M_n,GPC) values were very close to the theoretical line, whereas lower than the theoretical line were observed in solution polymerizations. The macroinitiator and their block copolymers were characterized by Fourier transform infrared spectroscopy, ¹H‐NMR, matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry, thermogravimetry (TG)/differential thermal analysis (DTA), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). TG/DTA studies of the homo and block copolymers showed two‐step and multistep decomposition patterns. The DSC thermograms exhibited two glass‐transition temperatures at ?17.7 and 92°C for the PEO and poly(methyl methacrylate) (PMMA) blocks, respectively, which indicated that microphase separation between the PEO and PMMA domains. SEM studies indicated a fine dispersion of PEO in the PMMA matrix. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 989–1000, 2005