Two‐stage grafting onto polyethylene fiber by radiation‐induced graft polymerization and atom transfer radical polymerization

Two‐stage graft polymerization onto polyethylene (PE) fiber was demonstrated. The graft side chain was formed by radiation‐induced graft polymerization. A PE fiber was irradiated with an electron beam and immersed in a vinyl monomer solution. The terminal of the formed graft chain was halogenated using N‐bromosuccinimide. The halogenated graft chain was then extended by atom transfer radical polymerization to obtain block‐copolymer grafted PE fibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Atom transfer radical polymerization of styrene initiated by bromoacetylated syndiotactic polystyrene macroinitiator

Atom transfer radical polymerization of styrene was conducted with bromoacetylated syndiotactic polystyrene as macroinitiator and copper bromide combined with N,N,N′,N′,N′‐pentamethyldiethylenetriamine as catalyst. A two‐stage process has been developed to synthesize the macroinitiator. First, syndiotactic polystyrene (sPS) was functionalized in the side phenyl rings with acetyl groups using the Friedel–Crafts reaction; second, the acetyl groups were converted to bromoacetyl groups by an acid‐catalyzed halogenation reaction. The initiator was found to be active in the polymerization of styrene, leading to the production of graft chains with well‐defined structure. The molecular weight and molecular weight distribution of the graft chains were determined using gel permeation chromatography after cleaving from the sPS backbone using peroxide acid oxidation followed by hydrazine‐catalyzed hydrolysis. The results indicated that the polymerization process was characteristic of a ‘living’ nature. Copyright © 2007 Society of Chemical Industry     

Grafting studies onto cellulose by atom‐transfer radical polymerization

Styrene (Sty), methyl methacrylate (MMA), methacrylamide (MAm) and acrylomorpholine (AcM) were grafted onto powder cellulose by atom‐transfer radical polymerization. Cellulose chloroacetate (Cell‐ClAc), as a macro‐initiator, was first prepared by the reaction of chloroacetyl chloride with primary alcoholic OH groups on powder cellulose. CuBr and 1,2‐dipiperidinoethane were used as a transition‐metal compound and as a ligand, respectively. These reactions were monitored by FT‐IR and weight increase in Cell‐ClAc. In case of styrene, although some weight increase occurred, no evidence of grafting could be observed in the FT‐IR spectrum, while there were strong evidence of grafting with MMA, MAm and AcM. Cell‐graft‐MAm, Cell‐graft‐AcM and Cell‐graft‐MMA showed new carbonyl bands at 1665, 1640 and 1735 cm^?1, respectively. Dye‐uptake and dye‐absorption properties of cellulose, for alizarin yellow (basic dye) and bromocresol green (acidic dye), and its moisture‐ and water‐uptake capacities improved with the grafting, but some decrease was observed in thermal stability. Copyright © 2004 Society of Chemical Industry     

Atom transfer radical polymerization of acrylonitrile

Iron(II) chloride coordinated by succinic acid was first used as the catalyst in 2‐chloropropionitrile‐initiated atom transfer radical polymerization (ATRP) of acrylonitrile. N,N‐dimethylformamide was used as a solvent to improve the solubility of the ligand. An iron(II) chloride to succinic acid ratio of 0.5 not only gives the best control of molecular weight and its distribution but also provides rather rapid reaction rate. Effects of solvent on polymerization of acrylonitrile were also investigated. The induction period is shorter in N,N‐dimethylformamide than in propylene carbonate and toluene and the rate of the polymerization in N,N‐dimethylformamide is fastest. The molecular weight of polyacrylonitrile agrees reasonably well with the theoretical molecular weight of N,N‐dimethylformamide. The rate of polymerization increases and the induction period becomes shorter with increasing polymerization temperature, and the apparent activation energy was calculated to be 56.5 kJ mol^?1. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1050–1054, 2006     

Atom transfer radical bulk polymerization of methyl methacrylate under microwave irradiation

Microwave irradiation (MI) was applied to the atom transfer radical bulk polymerization of methyl methacrylate. The influence of the amount of the refluxing solvent used for controlling the polymerization temperature, irradiation power, irradiation time, and initiator concentration on the conversion, molecular weight, and molecular weight distribution of the polymers was studied with a benzyl chloride/cuprous chloride/2,2′‐bipyridyl initiation system and compared with the corresponding conventional heating (CH) process. In comparison with CH, the results can be summarized as follows. The polymerization rate for reaching 70% conversion increased 2.6–5.1 times under an irradiation power of 270–630 W. The apparent increasing rate constant was much larger than that with CH and increased with the irradiation power. MI produced a higher polymerization rate and conversion even if the concentration of the initiation system was very low (initial monomer concentration/initial initiator concentration = 200:0.33 mol/mol) and the polydispersity index (DI) was narrower; however, CH yielded almost no polymers. MI promoted the activities of the catalyst and monomer, and its initiation efficiency was higher than that with CH and increased with the irradiation power. MI obviously played an important role in promoting the polymerization rate of atom transfer radical polymerization (ATRP). MI reduced the concentration of the initiation system and perhaps made ATRP controlled (cf. uncontrolled ATRP with CH); at the same time, it made the DI values of the polymers narrower. In comparison with the initiation efficiencies found with benzyl bromide and 2,2′‐azobisisobutyronitrile used as initiators, the initiation efficiency with p‐toluene sulfonyl chloride used as an initiator was higher; moreover, DI was much narrower (1.17), and the polymerization rate was greater. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1787–1793, 2003     

原子转移自由基法合成乙丙橡胶接枝物中的热聚合研究

采用原子转移自由基聚合法(ATRP)合成了三元乙丙橡胶与苯乙烯的接枝共聚物(EPDM-g-St),动力学研究表明聚合过程为“活性”聚合。在接枝聚合过程中发现了明显的苯乙烯热聚合现象。对接枝聚合中得到的均聚苯乙烯进行表征的结果表明,苯乙烯在ATRP接枝体系中的热聚合过程在一定程度上受到ATRP机理的控制;升高温度和延长反应时间使得热聚合更为显著。     

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     

Primary amine functionalized polystyrenes by atom transfer radical polymerization

Primary amine functionalized polystyrenes were prepared in quantitative yields by atom transfer radical polymerization using the adduct of 1‐(bromoethyl)benzene with 1‐(4‐aminophenyl)‐1‐phenylethylene as initiator for styrene polymerization in the presence of a copper(I) bromide/N,N,N′,N′,N″‐pentamethyldiethylenetriamine catalyst system. The polymerizations proceeded via a controlled free radical polymerization process to afford quantitative yields of the corresponding primary amine functionalized polystyrenes with predictable molecular weights (M_n = 2 × 10³ to 10 × 10³ g mol^?1), relatively narrow molecular weight distributions (M_w/M_n = 1.03–1.49), well defined chain‐end functionalities and initiator efficiencies as high as 0.92. The polymerization process was monitored by gas chromatographic analysis. The primary amine functionalized polymers were characterized by thin layer chromatography, size exclusion chromatography, potentiometry and spectroscopy. Experimental results are consistent with quantitative functionalization via the 1,1‐diphenylethylene derivative. Polymerization kinetic measurements show that the polymerization reaction follows first order rate kinetics with respect to monomer consumption and the number average molecular weight increases linearly with monomer conversion. © 2003 Society of Chemical Industry     

Synthesis of graft copolymers from a linear polyolefin through a combination of coordination polymerization and atom transfer radical polymerization

This article reports on a facile route for the preparation of methyl acrylate and methyl methacrylate graft copolymers via a combination of catalytic olefin copolymerization and atom transfer radical polymerization (ATRP). The chemistry first involved a transforming process from ethylene/allylbenzene copolymers to a polyolefin multifunctional macroinitiator with pendant sulfonyl chloride groups. The key to the success of the graft copolymerization was ascribed to a fast exchange rate between the dormant species and active radical species by optimization of the various experimental parameters. Polyolefin‐g‐poly(methyl methacrylate) and polyolefin‐g‐poly(methyl acrylate) graft copolymers with controlled architecture and various graft lengths were, thus, successfully prepared under dilute ATRP conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of hyperbranched polymers by atom transfer radical polymerization

A cheap acrylic AB* monomer, 2‐(2‐chloroacetyloxy)‐isopropyl acrylate (CAIPA), was prepared from 2‐hydroxyisopropyl acrylate with chloroacetyl chloride in the presence of triethylamine. The self‐condensing vinyl polymerization by atom transfer radical polymerization (ATRP), a “living”/controlled radical polymerization, has yielded hyperbranched polymers. All the polymerization products were characterized by proton nuclear magnetic resonance spectroscopy (¹H NMR). CAIPA exhibited distinctive polymerization behavior that is similar to a classical step‐growth polymerization in the relationship of molecular weight to polymerization time, especially during the initial stage of the polymerization. However, a significant amount of monomer remained present throughout the polymerization, which is consistent with typical chain polymerization. Also, if a much longer polymerization time was used, the polymer became gel. As a result of the unequal reactivity of group A* and B*, the polymerization is different from an ideal self‐condensing vinyl polymerization: the branch structures of polymers prepared depend dramatically on the ratio of 2,2'‐bipyridyl to CAIPA. Hyperbranched polymers exhibit improved solubility in organic solvent, however, they have lower thermal stability than their linear analogs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2114–2123, 2002     

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     

Synthesis of aromatic carboxyl functionalized polymers by atom transfer radical polymerization

The synthesis of aromatic carboxyl functionalized polymers by atom transfer radical polymerization is described. The α‐bromo‐p‐toluic acid ( 1 ) initiated polymerization of styrene in the presence of copper(I) bromide and 2,2′‐bipyridyl affords quantitative yields of the corresponding aromatic carboxyl functionalized polystyrene ( 2 ). Polymerization proceeded via a controlled free radical process to afford quantitative yields of the corresponding aromatic carboxyl functionalized polymers with predictable molecular weights (M_n = 1600–25 900 g mol⁻¹), narrow molecular weight distribution (M_w /M_n = 1.1–1.40) and an initiator efficiency above 0.87. The polymerization process was monitored by gas chromatographic analysis. The functionalized polymers were characterized by thin layer chromatography, size exclusion chromatography, spectroscopy, potentiometry and elemental analysis. © 2000 Society of Chemical Industry     

Atom transfer radical polymerization of styrene using a copper catalyst with a pseudohalogen anion

Atom transfer radical polymerization has been a very useful method in the recent advances in controlled radical polymerization. It needs an activated alkyl halide as an initiator and a copper halide as a catalyst. This investigation reports the successful application of copper thiocyanate, a catalyst with a pseudohalide anion, in the presence of different ligands such as N,N,N=,N″,N?,N?‐hexamethyltriethylenetetramine (HMTETA), pentyl‐2‐pyridylmethaneimine, and substituted bipyridine in the atom transfer radical polymerization of styrene. Among the three ligands used, HMTETA was found to be very efficient. The polymers were characterized with ¹³C‐NMR, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, and gel permeation chromatography analysis. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1418–1426, 2005     

Atom transfer radical polymerization and copolymerization of vinyl acetate catalyzed by copper halide/terpyridine

Copper‐mediated atom transfer radical polymerization (ATRP) is versatile for living polymerizations of a wide range of monomers, but ATRP of vinyl acetate (VAc) remains challenging due to the low homolytic cleavage activity of the carbon‐halide bond of the dormant poly(vinyl acetate) (PVAc) chains and the high reactivity of growing PVAc radicals. Therefore, all the reported highly active copper‐based catalysts are inactive in ATRP of VAc. Herein, we report the first copper‐catalyst mediated ATRP of VAc using CuBr/2,2′:6′,2″‐terpyridine (tPy) or CuCl/tPy as catalysts. The polymerization was a first order reaction with respect to the monomer concentration. The molecular weights of the resulting PVAc linearly increased with the VAc conversion. The living character was further proven by self‐chain extension of PVAc. Using polystyrene (PS) as a macroinitiator, a well‐defined diblock copolymer PS‐b‐PVAc was prepared. Hydrolysis of the PS‐b‐PVAc produced a PS‐b‐poly(vinyl alcohol) amphiphilic diblock copolymer. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Cationic graft polymerization of polymers from carbon fiber initiated by acylium perchlorate groups introduced onto the surface

The cationic graft polymerization of several monomers initiated by acylium perchlorate groups introduced onto the carbon fiber surface was investigated to modify the surface. The introduction of acylium perchlorate groups was successfully achieved by the reaction of silver perchlorate with acyl chloride groups, which were introduced by the reaction of surface carboxyl groups with thionyl chloride. It was found that the cationic polymerization of styrene is initiated by acylium perchlorate groups on the carbon fiber. In the polymerization, polystyrene was grafted onto the carbon fiber surface through the propagation of polystyrene from the surface. Ungrafted polymer was also formed by the chain transfer reaction of growing polymer cation to the monomer. The acylium perchlorate groups have the ability to initiate cationic ring-opening polymerization of tetrahydrofuran (THF) and ε-caprolactone (CL), polyTHF and polyCL being grafted onto the carbon fiber surface, respectively. Polyacetals, such as poly(1,3-dioxolane) and polyoxymethylene, were able to graft onto the carbon fiber by cationic ring-opening polymerization of the corresponding monomers.     

Atom transfer radical polymerization of lauryl methacrylate

The atom transfer radical polymerization (ATRP) of lauryl methacrylate (LMA) with an ethyl 2‐bromobutyrate/CuCl/N,N,N′,N″,N″‐pentamethyldiethylenetriamine initiation system was successfully carried out in toluene, and poly(lauryl methacrylate) with a low polydispersity (1.2 < weight‐average molecular weight/number‐average molecular weight < 1.5) was obtained. Plots of ln ([M])₀/([M]) versus time and plots of the molecular weight versus conversion showed a linear dependence, indicating a constant number of propagating species throughout the polymerization. The rate of polymerization was 0.56‐order with respect to the concentration of the initiator and 1.30‐order with respect to the concentration of the Cu(I) catalyst. In addition, the effect of the solvent on the polymerization was investigated, and the thermodynamic data and activation parameters for the solution ATRP of LMA were reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1117–1125, 2003     

Uniform star‐polystyrene nanoparticles prepared by emulsion atom transfer radical polymerization

Pentaerythritol (PT) was converted into four‐arm initiator pentaerythritol tetrakis(2‐chloropropionyl) (PT‐Cl) via reaction with 2‐chloropropionyl chloride. Uniform (monodisperse) star‐polystyrene nanoparticles were prepared by emulsion atom transfer radical polymerization of styrene, using PT‐Cl/CuCl/bpy (bpy is 2,2′‐dipyridyl) as the initiating system. The structures of PT‐Cl and polymer were characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance. The morphology, size and size distribution of the star‐polystyrene nanoparticles were characterized by transmission electron microscopy, atomic force microscopy and photon correlation spectroscopy. It was found that the average diameters of star‐polystyrene nanoparticles were smaller than 100 nm (30–90 nm) and monodisperse; moreover, the particle size could be controlled by the monomer/initiator ratio and the surfactant concentration. The average hydrodynamic diameter (D_h) of the nanoparticles increased gradually on increasing the ratio of styrene to PT‐Cl and decreased on enhancing the surfactant concentration or increasing the catalyst concentration. Copyright © 2011 Society of Chemical Industry     

甲基丙烯酸2,2,2-三氟乙酯的原子转移自由基聚合

以α-溴代丙酸乙酯(EPN-B)/CuCl/ 联二吡啶(bpy)作为引发/催化体系、环己酮为溶剂,对甲基丙烯酸2,2,2-三氟乙酯(TFEMA)进行原子转移自由基聚合(ATRP),研究了TFEMA的反应动力学,并考察了引发/催化体系、引发剂EPN-B用量、配位剂bpy用量及单体配比对聚合反应的影响.结果表明,采用EPN-B/CuCl/bpy引发/催化体系对TFEMA进行ATRP,可得到窄分子量分布的聚甲基丙烯酸2,2,2-三氟乙酯(PTFEMA),在实验范围内,聚合速率对单体浓度呈一级动力学关系,该反应过程具有活性聚合特征;随着引发剂EPN-B和配位剂bpy用量的增加,聚合速率加快,当EPN-B相对摩尔用量为0.5,1.0,2.0时,其相应的表观链增长速率常数分别为3.143×10~(-4),3.478×10~(-4),4.435×10~(-4)s~(-1);增大[TFEMA]/[EPN-B](摩尔比),聚合速率明显降低,但无论[TFEMA]/[EPN-B]高与低,聚合物的分布指数均为1.15～1.23.     

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     

Grafting of titanium dioxide microspheres with a temperature‐responsive polymer via surface‐initiated atom transfer radical polymerization without the use of silane coupling agents

Titania microspheres with narrow size distribution and diameters of about 1 µm were prepared and subsequently functionalized using surface‐initiated atom transfer radical polymerization (ATRP) of N‐isopropylacrylamide. The ATRP initiator was immobilized on the particle surface via acylation of surface hydroxyl groups with α‐bromoisobutyryl bromide. Subsequently, an established ATRP reaction system was used for the preparation of titania surface‐grafted poly(N‐isopropylacrylamide) (PNiPAAm). Characterization was performed with electron microscopies, X‐ray diffraction, infrared spectroscopy and dynamic light scattering. It was found that the particle size in aqueous dispersions changed reversibly with temperature as expected for a shell of PNiPAAm, a polymer with a lower critical solution temperature at 32 °C. This confirmed the successful preparation of functional, stimuli‐responsive TiO₂ microparticles via a straightforward controlled surface‐initiated polymerization method.