“Living”/controlled polymerization of methyl acrylate mediated by dithiocarbamates under γ‐ray irradiation

γ‐Ray initiated reversible addition–fragmentation chain transfer (RAFT) polymerizations of methyl acrylate (MA) were investigated in bulk using five different dithiocarbamate structures, 2‐phenyl‐benzoimidazole‐1‐carbodithioic acid benzyl ester ( 1b ), 2‐methyl‐benzoimidazole‐1‐carbodithioic acid benzyl ester ( 1c ), 2‐pheny‐indole‐1‐cardithioic acid benzyl ester ( 1d ), 2‐(carbazole‐9‐carbothioylsulfanyl)‐2‐methyl‐propionic acid ester ( 1e ), and carbazole‐9‐carbodithioic acid naphthalene‐1‐ylmethyl ester ( 1f ), as RAFT agents. The experiment results showed that MA polymerized in a controlled way under a low irradiation dose rate, i.e., first‐order kinetic plots, the experimental molecular weights increased linearly with monomer conversions. The polydispersity indices of polymers generally remained at a relatively low value (lower than 1.4). The effect of irradiation dose on the polymerization results was investigated. The obtained polymers were characterized with ¹H NMR and GPC. Chain‐extension reaction was also successfully carried out using the obtained polymer as the macro‐RAFT agent and styrene as the second monomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1769–1775, 2007     

Atom‐transfer radical polymerization of methyl methacrylate with α,α′‐dichloroxylene/CuCl/N,N,N′,N″,N″‐pentamethyldiethylenetriamine initiation system under microwave irradiation

The atom‐transfer radical polymerization (ATRP) of methyl methacrylate (MMA), using α,α′‐dichloroxylene as initiator and CuCl/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as catalyst was successfully carried out under microwave irradiation (MI). The polymerization of MMA under MI showed linear first‐order rate plots, a linear increase of the number‐average molecular weight with conversion, and low polydispersities, which indicated that the ATRP of MMA was controlled. Using the same experimental conditions, the apparent rate constant (k) under MI (k = 7.6 × 10^?4 s^?1) was higher than that under conventional heating (k = 5.3 × 10^?5 s^?1). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2189–2195, 2004     

Surface modification of PTFE by 60Co γ-ray irradiation

Surface carboxyl groups were formed during the ⁶⁰Co γ-ray irradiation of poly(tetrafluoroethylene) (PTFE) in air. Fourier transform infrared spectroscopy enables the detection of surface carboxyl groups. The contact angles were used to calculate the dispersive and polar components of the surface free energy according to a two-liquid method. The γ-ray irradiation of PTFE mainly caused degradation of the polymer. The concentration of carboxyl groups, the wettability, the friction, and the dispersive and polar components of the surface energy and the crystallinity on PTFE surface were increased, while the particle size of PTFE decreased with increasing irradiation dose. A highly modified PTFE was used to reduce the aqueous liquid repellent properties of PTFE. A 20 kGy dose for modified PTFE surface was suitable in air additivity in antifriction, anticorrosion, antifouling, lubrication, and noise reduction coatings. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 435–441, 1998     

Influence of γ‐irradiation on poly(methyl methacrylate)

Poly(methyl methacrylate) (PMMA) was γ‐irradiated (5–20 kGy) by a ¹³⁷Cs source at room temperature in air. The changes in the molecular structure attributed to γ‐irradiation were studied by mechanical testing (flexure and hardness), size‐exclusion chromatography, differential scanning calorimetry, thermal gravimetric analysis, and both Fourier transform infrared and solution ¹³C‐NMR spectroscopy. Scanning electron microscopy was used to investigate the influence of the dose of γ rays on the fracture behavior of PMMA. The experimental results confirm that the PMMA degradation process involves chain scission. It was also observed that PMMA presents a brittle fracture mechanism and modifications in the color, becoming yellowish. The mechanical property curves show a similar pattern when the γ‐radiation dose increases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 886–895, 2002     

Synthesis and thermal properties of polystyrene/montmorillonite nanocomposites by γ‐ray radiation polymerization

Polystyrene/montmorillonite nanocomposites were prepared by γ‐ray radiation polymerization. X‐ray diffraction and high‐resolution transmission electron microscopy confirmed that polystyrene (PS) could be easily inserted between the sheets of montmorillonite (MMT) to form intercalated nanocomposites. In these PS/MMT nanocomposites, the distance between the sheets of MMT was barely influenced by varying the content of the MMT. Thermal stabilities of the samples were studied by thermal gravimetric analysis and differential scanning calorimetry. The glass‐transition temperature of PS/MMT nanocomposites was obviously higher than that of the pure PS. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1692–1696, 2003     

Characterization of mechanical properties of γAl2O3 dispersed epoxy resin cured by γ‐ray radiation

Epoxy resins are widely utilized as high performance thermosetting resins for many industrial applications, but they are characterized by relatively low toughness. Incorporation of rigid inorganics is suggested to improve the mechanical properties of epoxy resins. An attempt is made to disperse nanosized γ‐Al₂O₃ particles into diglycidyl ether of bisphenol A epoxy resins for the improvement of the mechanical properties. These hybrid epoxy–alumina composites are prepared using by the γ‐ray curing technique conducted at 100 kGy under nitrogen at room temperature. The composites are characterized by determining the gel content, flexural strength, Youngis modulus, and toughness at room temperature using scanning electron microscopy and FTIR studies. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1898–1903, 2004     

Homogeneous graft copolymerization of chitosan with butyl acrylate by γ‐irradiation via a 6‐O‐maleoyl‐N‐phthaloyl‐chitosan intermediate

The graft copolymerization of butyl acrylate (BA) onto chitosan was tried via a new protection‐graft‐deprotection procedure. About 6‐O‐maleoyl‐N‐phthaloyl‐chitosan was synthesized and characterized by Fourier transform infrared spectra analysis (FT‐IR) and ¹H‐NMR. Because the intermediate 6‐O‐maleoyl‐N‐phthaloyl‐chitosan was soluble in organic solvents, the graft copolymerization was carried out in a homogeneous system. Grafting was initiated by γ‐irradiation. The graft extent was dependent on the irradiation dose and the concentration of BA monomer, and copolymers with grafting above 100% were readily prepared. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 489–493, 2006     

Direct Decarboxylative Alkynylation of α,α‐Difluoroarylacetic Acids under Transition Metal‐Free Conditions

An efficient and generally applicable protocol for decarboxylative coupling of α,α‐difluoroarylacetic acids with ethynylbenziodoxolone (EBX) reagents has been developed, affording α,α‐difluoromethylated alkynes bearing various functional groups in moderate to excellent yields. Remarkably, this potassium persulfate (K₂S₂O₈)‐promoted reaction employs water as solvent under transition metal‐free conditions, thus providing a green synthetic approach to α,α‐difluoromethylated alkynes.

     

Synthesis of ω‐amino‐α‐phenylcarbonate alkanes and their polymerization to [n]‐polyurethanes

Aliphatic [n]‐polyurethanes have recently been synthesized from ω‐isocyanato‐α‐alkanols or, more traditionally, by cationic ring‐opening polymerization of cyclourethanes or by the Bu₂Sn(OMe)₂‐promoted polycondensation of ω‐hydroxy‐α‐O‐phenylurethane alkanes. For the latter procedures, the conditions employed do not seem to be suitable for highly functionalized monomers. In contrast, the polymerization of ω‐amino‐α‐phenylcarbonate alkanes is expected to occur under milder conditions. ω‐Amino‐α‐phenylcarbonate alkanes have been synthesized from 6‐aminohexanol (1) and 3‐aminopropanol (6). The procedure involves the N‐Boc protection of the amino group, followed by activation of the alcohol. Removal of the N‐Boc affords the corresponding ω‐amino‐1‐O‐phenyloxycarbonyloxyalkane hydrochlorides. Other oligomeric comonomers between 1 and 6 have been prepared. The polymerization of these precursors takes place in the absence of metal catalysts to afford the corresponding linear and regioregular [n]‐polyurethanes. The procedure described is useful for the preparation of stable ω‐amino‐α‐phenylcarbonate alkane derivatives, which possess varied chain lengths between the terminal functions. These monomers yield [n]‐polyurethanes having various structures starting from just two aminoalkanols. The polyurethanes were obtained in high yields, with reasonable molecular weight and polydispersity values, and they were characterized spectroscopically and thermally. These studies reveal constitutionally uniform structures that are free of carbonate or urea linkages. Copyright © 2010 Society of Chemical Industry     

Evaluation of the termination mode in the radical polymerization of 2,2,2‐trifluoroethyl α‐fluoroacrylate

The mode of termination of 2,2,2‐trifluoroethyl α‐fluoroacrylate (FATRIFE) in radical polymerization was studied, and only termination by recombination occurred, which led to telechelic macromolecular structures. The radical polymerization in acetonitrile was carried out to synthesize oligomers with a low number average degree of polymerization ( )_cum (about 20), using tert‐butylcyclohexyl peroxydicarbonate (TBCPC) as initiator at 75 °C. The initial [TBCPC]₀/[FATRIFE]₀ molar ratio was monitored to evaluate its influence on the ( )_cum of α‐fluoroacrylic oligomers. The ¹H NMR analysis of the polymers showed that the ( )_cum values obtained were higher than 40, in spite of a high C₀ value. To explain these results, the mode of termination was evaluated using the following kinetic law: . The development of kinetic relationships allowed us to calculate the ratio k_prt/k_i·k_p as about 17–30 mol s l^?1, and to confirm that primary radical termination (PRT) was in competition with bimolecular macromolecular termination (BMT). © 2002 Society of Chemical Industry     

Surface modification of aramid fibers with γ‐ray radiation for improving interfacial bonding strength with epoxy resin

Co⁶⁰ γ‐ray radiation as a simple and convenient method for surface modification of Armos aramid fibers was introduced in this article. Two kinds of gas mediums, N₂ and air, were chosen to modify aramid fiber surface by γ‐ray irradiation. After fiber surface treatment, the interlaminar shear strength values of aramid/epoxy composites were enhanced by about 17.7 and 15.8%, respectively. Surface elements of aramid fibers were determined by XPS, the analysis of which showed that the ratio of oxygen/carbon was increased. The crystalline state of aramid fibers was determined by X‐ray diffraction instrument. The surface topography of fibers was analyzed by atomic force microscopy and scanning electron microscope. The degree of surface roughness and the wettability of fiber surface were both enhanced by γ‐ray radiation. The results indicated that γ‐ray irradiation technique, which is a suitable way of batch process for industrialization, can significantly improve the surface properties of aramid fibers reinforced epoxy resin matrix composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and properties of polydimethylsiloxane/polyacrylate composite latex initiated by 60Co γ‐ray irradiation

In this study, polydimethylsiloxane (PDMS)/polyacrylate composite polymer latex was synthesized via polymerization of the acrylate monomer in the presence of vinyl‐containing PDMS seeded latex. The polymerization was initiated by ⁶⁰Co γ‐ray irradiation. The morphology of the PDMS/polyacrylate composite polymer latex was a core–shell structure with PDMS as the core and polyacrylate as the shell. There was an interpenetration layer between the PDMS core and the polyacrylate shell. The composition of the vinyl‐containing PDMS and the PDMS/polyacrylate composite latex were investigated with NMR and Fourier transform infrared spectroscopy, respectively. The effect of irradiation dose on the seeded emulsion polymerization conversion is discussed. Finally, the mechanical properties of latex film, such as water‐absorption ratio, tensile strength, pendulum hardness, and heat‐decomposed temperature, were tested. The results showed that the mechanical properties of the PDMS/polyacrylate film were remarkably improved when compared to the polyacrylate film. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2732–2736, 2003     

Homogeneous graft copolymerization of chitosan with methyl methacrylate by γ‐irradiation via a phthaloylchitosan intermediate

The graft copolymerization of methyl methacrylate (MMA) onto chitosan was tried via a new protection‐graft‐deprotection procedure. Because the intermediate phthaloylchitosan was soluble in organic solvents, the graft copolymerization was carried out in a homogeneous system. Grafting was initiated by γ‐irradiation. The graft percentage extent was dependent on the irradiation dose and the concentration of MMA monomer, and copolymers with grafting above 100 % were readily prepared. The graft copolymers exhibited a high affinity not only for aqueous acid but also for some organic solvents. Differential scanning calorimetry measurements revealed the presence of a glass transition phenomenon, which could be ascribed to the poly(methyl methacrylate) side‐chains. Copyright © 2004 Society of Chemical Industry     

Cationic copolymers of α,β‐poly‐(N‐2‐hydroxyethyl)‐DL‐aspartamide (PHEA) and α,β‐polyasparthylhydrazide (PAHy): synthesis and characterization

In the present study the derivatization of two water‐soluble synthetic polymers, α,β‐poly(N‐2‐hydroxyethyl)‐DL ‐aspartamide (PHEA) and α,β‐polyasparthylhydrazide (PAHy), with glycidyltrimethylammonium chloride (GTA) is described. This reaction permits the introduction of positive charges in the macromolecular chains of PHEA and PAHy in order to make easier the electrostatic interaction with DNA. Different parameters affect the reaction of derivatization, such as GTA concentration and reaction time. PHEA reacts partially and slowly with GTA; on the contrary the reaction of PAHy with GTA is more rapid and extensive. The derivatization of PHEA and PAHy with GTA is a convenient method to introduce positive groups in their chains and it permits the preparation of interpolyelectrolyte complexes with DNA. © 2000 Society of Chemical Industry     

Effects of reaction conditions on laccase‐catalyzed α‐naphthol polymerization

Enzymatic oxidative polymerization of α‐naphthol was carried out batch‐wise with the laccase enzyme, produced by Trametes versicolor (ATCC 200801). The polymerization reaction was conducted in a closed, temperature controlled system containing acetone (solvent) and sodium acetate buffer for pH control. The effects of the organic solvent (acetone) composition, monomer (α‐naphthol) and enzyme concentrations, buffer pH and temperature on the polymerization rate were investigated with respect to initial reaction conditions and depletion rate of dissolved oxygen. The optimum acetone composition, pH, monomer, dissolved oxygen and enzyme concentrations were determined as 50% (v/v), 5, 3409 gm⁻³, 20.3 gm⁻³ and 0.173 U cm⁻³, respectively; these values provided the most desirable conditions for initial reaction rate. Temperature rise supported the rate increase up to 37 °C, after which the rate tended to be stable due to a drop in dissolved oxygen concentration. The product polymer, poly(α‐naphthol), with an average molecular weight of 4920 Da was soluble in common organic solvents. © 2000 Society of Chemical Industry     

Dissolution of latex films after γ‐ray treatment

Latex films were prepared by annealing pyrene (Py)‐labeled poly(methyl methacrylate) particles at glass‐transition temperature (100°C). These films were then irradiated by γ‐rays from ⁶⁰Co in a gamma cell at room temperature at the same dose rate (rad/h) for 30 min. Before dissolution films were annealed at elevated temperatures for a 30‐min time interval to complete the film formation process. Steady‐state fluorescence (SSF) technique were used to monitor the dissolution of these irradiated latex films. The dissolution of films in chloroform–heptane (80–20%) mixture was monitored in real time by the Py fluorescence intensity change. Relaxation constants k₀ and desorption coefficients D_d of polymer chains were measured. It was observed that both D_d and k₀ values first increased and then decreased by increasing the annealing temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 129–137, 2002     

Highly Enantioselective Phase‐Transfer Catalytic α‐Alkylation of α‐tert‐Butoxycarbonyllactams: Construction of β‐Quaternary Chiral Pyrrolidine and Piperidine Systems

A new enantioselective α‐alkylation of α‐tert‐butoxycarbonyllactams for the construction of β‐quaternary chiral pyrrolidine and piperidine core systems is reported. α‐Alkylations of N‐methyl‐α‐tert‐butoxycarbonylbutyrolactam and N‐diphenylmethyl‐α‐tert‐butoxycarbonylvalerolactam under phase‐transfer catalytic conditions (solid potassium hydroxide, toluene, −40 °C) in the presence of (S,S)‐3,4,5‐trifluorophenyl‐3,3′,5,5′‐tetrahydro‐2,6‐bis(3,4,5‐trifluorophenyl)‐4,4′‐spirobi[4H‐dinaphth[2,1‐c:1′,2′‐e]azepinium] bromide [(S,S)‐NAS Br] (5 mol%) afforded the corresponding α‐alkyl‐α‐tert‐butoxycarbonyllactams in very high chemical (up to 99%) and optical yields (up to 98% ee). Our new catalytic systems provide attractive synthetic methods for pyrrolidine‐ and piperidine‐based alkaloids and chiral intermediates with β‐quaternary carbon centers.     

Rapid ambient temperature atom transfer radical polymerization of tert‐butyl acrylate

BACKGROUND: Atom transfer radical polymerization (ATRP) is considered to be one of the better and easier synthetic tools for the preparation of polymers with controlled molecular weights and polydispersities. Ambient temperature ATRP of tert‐butyl acrylate (tBA) was studied in a detailed manner with ethyl 2‐bromoisobutyrate (EBrB) and tert‐butyl 2‐bromoisobutyrate (tBuBrB) as the initiators for three different degrees of polymerization. RESULTS: Details pertaining to the kinetics of polymerization using different initiators are reported. It is observed that dimethylsulfoxide accelerates the polymerization at room temperature. The use of Cu(II) as the deactivator produces very narrow dispersity polymers. A diblock copolymer, poly(tert‐butyl acrylate)‐block‐poly(methyl methacrylate), was synthesized from the poly(tBA) macroinitiator demonstrating the controlled living nature of the polymerizations. CONCLUSIONS: The rate of polymerization is more rapid with a secondary initiator (ethyl 2‐bromopropionate) compared to the tertiary initiators EBrB and tBuBrB. From the detailed kinetic results it is observed that tris(2‐dimethylaminoethyl)amine was a better ligand compared to tris(2‐aminoethyl)amine in terms of achieving controlled polymerization. Copyright © 2007 Society of Chemical Industry     

Copolymerization of styrene with an α‐olefin via atom transfer radical polymerization

This investigation reports the preparation of styrene–α‐olefinic random copolymers, using 1‐octene as an α‐olefin, via atom transfer radical polymerization. Atom transfer radical copolymerization of styrene with 1‐octene was successfully carried out using phenylethyl bromide as initiator and CuBr as catalyst in combination with N, N, N′, N″, N″‐pentamethyldiethylenetriamine as ligand. The copolymers had controlled molecular weight, narrow dispersity and well‐defined end groups with significant 1‐octene incorporation in the polymer. Incorporation of 1‐octene in the copolymers was confirmed using ¹H NMR and matrix‐assisted laser desorption ionization time‐of‐flight mass spectroscopy. An increase in 1‐octene content in the monomer feed led to an increase in the level of incorporation of the α‐olefin in the copolymer. An increase in the concentration of 1‐octene led to a decrease in the rate of polymerization and an increase in dispersity. The glass transition temperature of the copolymer gradually decreased as the incorporation of 1‐octene increased. Copyright © 2011 Society of Chemical Industry     

Degradation and initiation polymerization mechanism of α‐methylstyrene‐containing macroinitiators

Copolymers obtained from radical copolymerization of α‐methylstyrene (AMS) and glycidyl methacrylate (GMA) behave as macroinitiators, when heated in the presence of a second monomer, giving rise to block copolymers. The relevant degradation and initiation polymerization mechanism of the macroinitiators were studied. Thermal depropagation of the macroinitiators generated monomers, identified by ¹H‐NMR, photoionization mass spectroscopy and FT‐IR. According to the results of structure analysis by GPC, ESR and NMR spectroscopy, the AMS‐GMA (head‐head) and AMS‐AMS (head‐head) bonds in the macroinitiators are easily scissored providing free radicals when the temperature is above 80°C. The radicals lead to subsequent polymerization of the second monomer, and thereby block copolymers are formed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011