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Polymerization Techniques (polymerization + techniques)
Kinds of Polymerization Techniques Selected AbstractsEnhancing therapeutic loading and delaying transport via molecular imprinting and living/controlled polymerizationAICHE JOURNAL, Issue 1 2010Asa D. Vaughan Abstract This work demonstrates for the first time molecular imprinting using a "living/controlled" polymerization (LCP) strategy to enhance template loading/affinity and delay release in weakly crosslinked gels. Two gel systems were studied: poly(DEAEM- co -HEMA- co -PEG200DMA) gels imprinted for diclofenac sodium and poly(MAA- co -EGDMA) gels imprinted for ethyl adenine-9-acetate. Experimental evidence confirms that template diffusion coefficients within imprinted gels can be heavily influenced by template binding affinity. Recognition studies revealed significant increases in template loading/affinity with large increases in loading for LCP, and dynamic template release studies showed that imprinting via LCP extends the template release profile by twofold over that of imprinting via conventional free-radical polymerization techniques and fourfold over the control network (less Fickian and toward zero-order release with a profile coefficient of 0.70). Analysis of reaction kinetics indicated that LCP with reversible termination events increases the chemically controlled chain propagation mechanism, and that binding sites are formed during this phase of the polymerization. © 2009 American Institute of Chemical Engineers AIChE J, 2010 [source] Controlled synthesis of poly(dimethylsiloxane) homopolymers using high-vacuum anionic polymerization techniquesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2009Mario D. Ninago Abstract The controlled synthesis of poly(dimethylsiloxane) homopolymers (PDMS) using hexamethyl(cyclotrisiloxane) monomer (D3), a mixture of ciclohexane/tetrahydrofuran 50/50 v/v and sec- Bu,Li+ as initiator was studied using different experimental conditions, and whole-sealed glass reactors according to standards procedures in high-vacuum anionic polymerization. It was observed that polydispersity indexes (PD) and conversions strongly depend on temperature and reaction times. For PDMS homopolymers with molar masses below 100,000 g/mol, high conversion (>90%) and PD < 1.1 can be achieved at long reaction times (24 h) and mild temperature conditions (below or up to 30 °C). On the other hand, to synthesize PDMS homopolymers with molar masses higher than 100,000 g/mol and PD < 1.1 it is necessary to increase the temperature up to 50 °C and decrease the reaction time (8 h). However, under these reaction conditions, it was observed that the conversion decreases (about 65,70% conversion is achieved). Apparently, the competition between propagation and secondary reactions (redistribution, backbiting, and reshuffling) depends on the molar masses desired. According to the results obtained in this study,which were compared with others found in the scientific literature,propagation is favored when Mn < 100,000 g/mol, whereas secondary reactions seem to become important for higher molar masses. Nevertheless, model PDMS homopolymers with high molar masses can still be obtained increasing the reaction temperature and shortening the total reaction time. It seems that the combined effect of these two facts favors propagation against secondary reactions, and provides model PDMS homopolymers with molar masses quite close to the expected ones. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4774,4783, 2009 [source] Synthesis of well-defined polymeric activated estersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 20 2008Patrick Theato Abstract Monomers bearing an activated ester group can be polymerized under various controlled polymerization techniques, such as ATRP, NMP, RAFT polymerization, or ROMP. Combining the functionalization of polymers via polymeric activated esters with these controlled polymerization techniques generate possibilities to realize highly functionalized polymer architectures. Within this highlight two different research areas of activated esters in polymer science will be discussed: (i) the preparation of defined reactive polymer architectures by controlled polymerization techniques and (ii) the preparation of defined reactive thin films. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6677,6687, 2008 [source] Hydroxyl-terminated hyperbranched aromatic poly(ether-ester)s: Synthesis, characterization, end-group modification, and optical propertiesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2008Thiyagarajan Shanmugam Abstract Novel AB2 -type monomers such as 3,5-bis(4-methylolphenoxy)benzoic acid (monomer 1), methyl 3,5-bis(4-methylolphenoxy) benzoate (monomer 2), and 3,5-bis(4-methylolphenoxy)benzoyl chloride (monomer 3) were synthesized. Solution polymerization and melt self-polycondensation of these monomers yielded hydroxyl-terminated hyperbranched aromatic poly(ether-ester)s. The structure of these polymers was established using FTIR and 1H NMR spectroscopy. The molecular weights (Mw) of the polymers were found to vary from 2.0 × 103 to 1.49 × 104 depending on the polymerization techniques and the experimental conditions used. Suitable model compounds that mimic exactly the dendritic, linear, and terminal units present in the hyperbranched polymer were synthesized for the calculation of degree of branching (DB) and the values ranged from 52 to 93%. The thermal stability of the polymers was evaluated by thermogravimetric analysis, which showed no virtual weight loss up to 200 °C. The inherent viscosities of the polymers in DMF ranged from 0.010 to 0.120 dL/g. End-group modification of the hyperbranched polymer was carried out with phenyl isocyanate, 4-(decyloxy)benzoic acid and methyl red dye. The end-capping groups were found to change the thermal properties of the polymers such as Tg. The optical properties of hyperbranched polymer and the dye-capped hyperbranched polymer were investigated using ultraviolet-absorption and fluorescence spectroscopy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5414,5430, 2008 [source] Heteroarm H-shaped terpolymers through the combination of the Diels,Alder reaction and controlled/living radical polymerization techniquesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2006Hakan Durmaz Abstract Heteroarm H-shaped terpolymers (PS)(PtBA),PEO,(PtBA)(PS) and (PS)(PtBA),PPO,(PtBA)(PS) [where PS is polystyrene, PtBA is poly(tert -butyl acrylate), PEO is poly(ethylene oxide), and PPO is poly(propylene oxide)], containing PEO or PPO as a backbone and PS and PtBA as side arms, were prepared via the combination of the Diels,Alder reaction and atom transfer radical and nitroxide-mediated radical polymerization routes. Commercially available PEO or PPO containing bismaleimide end groups was reacted with a compound having an anthracene functionality, succinic acid anthracen-9-yl methyl ester 3-(2-bromo-2-methylpropionyloxy)-2-methyl-2-[2-phenyl-2-(2,2,6,6-tetramethylpiperidin-1-yloxy)ethoxycarbonyl]propyl ester, with a Diels,Alder reaction strategy. The obtained macroinitiator with tertiary bromide and 2,2,6,6-tetramethylpiperidin-1-oxy functional end groups was used subsequently in the atom transfer radical polymerization of tert -butyl acrylate and in the nitroxide-mediated free-radical polymerization of styrene to produce heteroarm H-shaped terpolymers with moderately low molecular weight distributions (<1.31). The polymers were characterized with 1H NMR, ultraviolet, gel permeation chromatography, and differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3947,3957, 2006 [source] Direct measurements of the addition and recombination of acrylate radicals: Access to propagation and termination rate constants?JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2006J. Lalevée Abstract Acrylate radicals produced by the addition of an aminoalkyl radical to five acrylate monomers were directly observed by transient absorption spectroscopy, which allowed us to easily follow their chemical reactivity. It was possible (1) to characterize their absorption in the visible part of the spectrum, (2) to calculate their absorption properties, (3) to determine the energy barriers of the addition through quantum mechanical calculations, (4) to monitor the kinetics of the subsequent addition to another monomer unit, and (5) to follow the recombination of two acrylate radicals. These two latter points could mimic the propagation and termination reactions of polymerization-propagating acrylate radicals. Methacrylate and acrylonitrile radicals were also studied. The obtained results were in good agreement with the propagation rate constants determined by the well-established pulsed laser polymerization techniques. Our method could likely provide rapid access to both the propagation and termination rate constants in suitable systems and appears to be powerful and promising for studying and comparing the reactivities of different acrylate monomer structures. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3577,3587, 2006 [source] Living polymerization of substituted acetylenesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2005Martin G. Mayershofer Abstract For many years, considerable research efforts have been dedicated to ,-conjugated polymers because of their extraordinary electronic, optical, and structural properties. The employed transition-metal-based initiating systems comprise not only simple transition-metal salts but also rather sophisticated mixtures of two, three, or four compounds and even highly defined single-component systems such as transition-metal alkylidene complexes. Extensive fine-tuning of the electronic and steric properties of initiator,monomer systems eventually allowed the tailor-made synthesis of conjugated materials via living polymerization techniques. This article focuses on recent developments in the field of the living polymerization of substituted acetylene derivatives. Ill-defined group 5 and 6 transition metal halide-based initiators, well-defined transition-metal alkylidene complexes, and rhodium(I)-based systems that induce the living polymerization of numerous substituted acetylenes are reviewed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5723,5747, 2005 [source] Macromolecular design via reversible addition,fragmentation chain transfer (RAFT)/xanthates (MADIX) polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2005Sébastien Perrier Abstract Among the living radical polymerization techniques, reversible addition,fragmentation chain transfer (RAFT) and macromolecular design via the interchange of xanthates (MADIX) polymerizations appear to be the most versatile processes in terms of the reaction conditions, the variety of monomers for which polymerization can be controlled, tolerance to functionalities, and the range of polymeric architectures that can be produced. This review highlights the progress made in RAFT/MADIX polymerization since the first report in 1998. It addresses, in turn, the mechanism and kinetics of the process, examines the various components of the system, including the synthesis paths of the thiocarbonyl-thio compounds used as chain-transfer agents, and the conditions of polymerization, and gives an account of the wide range of monomers that have been successfully polymerized to date, as well as the various polymeric architectures that have been produced. In the last section, this review describes the future challenges that the process will face and shows its opening to a wider scientific community as a synthetic tool for the production of functional macromolecules and materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43:5347,5393, 2005 [source] Living/controlled copolymerization of acrylates with nonactivated alkenesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 24 2004Shengsheng Liu Abstract The living/controlled copolymerization of methyl acrylate with 1-alkenes and norbornene derivatives through several radical polymerization techniques has been achieved. These techniques include atom transfer radical polymerization, reversible addition,fragmentation transfer polymerization, nitroxide-mediated polymerization, and degenerative transfer polymerization. These systems display many of the characteristics of a living polymerization process: the molecular weight increases linearly with the overall conversion, but the polydispersity remains low. Novel block copolymers have been synthesized through the sequential addition of monomers or chain extension. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6175,6192, 2004 [source] The fast and the curious: High-throughput experimentation in synthetic polymer chemistryJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2003Richard Hoogenboom Abstract The application of automated synthetic parallel methods in polymer chemistry is described. A brief overview of all different polymerization techniques that have been used is provided. Furthermore, the equipment and methodologies that were used in our approach for automated parallel polymerization reactions are discussed followed by detailed insight into recent developments on automated cationic ring-opening polymerization, atom transfer radical polymerization, and emulsion polymerizations. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2425,2434, 2003 [source] Densely grafted polyisocyanides synthesized by two types of polymerization techniquesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2003Yanqing Tian Abstract A series of novel polyisocyanide- graft -polystyrenes and polyisocyanide- graft -[polystyrene- block -poly(butyl acrylate)]s were synthesized through the grafting-through and grafting-from routes with two types of living polymerization techniques: polymerization with the Pd,Pt ,-ethynediyl dinuclear complex as the initiator and catalyst for the polyisocyanide backbone and atom transfer radical polymerization for the grafted side chain. Through the introduction of a chiral center at the side chain of the polyisocyanide backbone, helical grafted and graft block polyisocyanides were prepared through the grafting-from method. All of the obtained polymers exhibited polydispersities in the range of 1.07,1.41. This might have been the first time grafted polyisocyanides were prepared, especially helical grafted polyisocyanides, through the operation of two living polymerization techniques. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1871,1880, 2003 [source] Synthesis of proton-conducting membranes by the utilization of preirradiation grafting and atom transfer radical polymerization techniquesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 4 2002Svante Holmberg Abstract The atom transfer radical polymerization (ATRP) of styrene onto poly(vinylidene fluoride)- graft -poly(vinylbenzyl chloride) (PVDF- g -PVBC) membranes was investigated. Novel membranes were designed for fuel-cell applications. The benzyl chloride groups in the PVDF- g -PVBC membranes functioned as initiators, and a Cu-based catalytic system with the general formula Cu(n)Xn/ligand [where X is Cl or Br and the ligand is 2,2,-bipyridyl (bpy)] was employed for the ATRP. In addition, 10 vol % dimethylformamide was added for increased solubility of the catalyst complex in styrene. The system was homogeneous, except for the membrane, when the initiator/copper halide/ligand/monomer molar ratio was 1/1/3/500. As anticipated, the fastest polymerization rate of styrene was observed with the copper bromide/bpy-based catalyst system. The reaction rate was strongly temperature-dependent within the studied temperature interval of 100,130 °C. The degree of grafting increased linearly with time, thereby indicating first-order kinetics, regardless of the polymerization temperature. Furthermore, 120 °C was the maximum polymerization temperature that could be used in practice because the membrane structure was destroyed at higher temperatures. The degree of styrene grafting reached 400% after 3 h at 120 °C. Such a high degree of grafting could not be reached with conventional uncontrolled radiation-induced grafting methods because of termination reactions. On the basis of an Arrhenius plot, the activation energy for the homogeneous ATRP of styrene was 217 kJ/mol. The prepared membranes became proton-conducting after sulfonation of the polystyrene grafts. The highest conductivity measured for the prepared membranes was 70 mS/cm, which is comparable to the values normally measured for commercial Nafion membranes. The scanning electron microscopy/energy-dispersive X-ray results showed that the membranes had to be grafted through the matrix with both PVBC and polystyrene to become proton-conducting after sulfonation. In addition, PVDF- g -[PVBC- g -(styrene- block - tert -butyl acrylate)] membranes were also synthesized by ATRP. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 591,600, 2002; DOI 10.1002/pola.10146 [source] Thick Nb-Doped Bismuth Titanate Film with Controllable Grain OrientationJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 8 2006Weiwu Chen In the current work, we reported a potential approach to obtain thick ceramic films with controllable grain orientation based on magnetic alignment and polymerization techniques. The slurry containing 40 vol% Bi4Ti2.96Nb0.04O12 (BINT) ceramic powder, monomer, initiator, and catalyst was drop coated on a Pt substrate and then moved into a vertical 10 T magnetic field. In 1,2 min, the ceramic particles were aligned by a strong magnetic force in slurry and then in situ locked by polymerization on the substrate. After sintering at 1000°C, a BINT ceramic film (50,80 ,m in thickness) with a highly a/b plane orientation was obtained. Theoretically, the grain orientation in the films can be easily controlled by adjusting the magnetic field direction. This approach is readily applicable to other materials with a non-cubic structure and is expected to facilitate the fast preparation of grain-oriented thick films. [source] Acrylonitrile-Butadiene Rubber (NBR) Prepared via Living/Controlled Radical Polymerization (RAFT)MACROMOLECULAR RAPID COMMUNICATIONS, Issue 18 2010Andreas Kaiser Abstract In the current work we present results on the controlled/living radical copolymerization of acrylonitrile (AN) and 1,3-butadiene (BD) via reversible addition fragmentation chain transfer (RAFT) polymerization techniques. For the first time, a solution polymerization process for the synthesis of nitrile butadiene rubber (NBR) via the use of dithioacetate and trithiocarbonate RAFT agents is described. It is demonstrated that the number average molar mass, , of the NBR can be varied between a few thousand and 60,000,g,·,mol,1 with polydispersities between 1.2 and 2.0 (depending on the monomer to polymer conversion). Excellent agreement between the experimentally observed and the theoretically expected molar masses is found. Detailed information on the structure of the synthesized polymers is obtained by variable analytical techniques such as infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry, and electrospray ionization-mass spectrometry (ESI-MS). [source] Solution self-assembly of tailor-made macromolecular building blocks prepared by controlled radical polymerization techniquesPOLYMER INTERNATIONAL, Issue 9 2006Jean-François Lutz Abstract This review describes the preparation of colloidal aggregates (spherical micelles, cylindrical micelles, polymer vesicles, multicompartment micelles, polyion complexes, schizophrenic micelles) using bottom-up self-assembly approaches. In particular, it focuses primarily on the self-organization of well-defined macromolecular building blocks (macrosurfactants, polysoaps, polyelectrolytes) synthesized by controlled radical polymerization techniques such as atom transfer radical polymerization, reversible addition fragmentation transfer polymerization and nitroxide-mediated polymerization. The goal of this review is to highlight that these versatile techniques of polymer synthesis allow the preparation of unprecedented nanostructures in dilute solutions. Copyright © 2006 Society of Chemical Industry [source] Synthesis and utilization of E. coli -encapsulated PEG-based microdroplet using a microfluidic chip for biological applicationBIOTECHNOLOGY & BIOENGINEERING, Issue 4 2010Kyoung G. Lee Abstract We report herein an effective strategy for encapsulating Escherichia coli in polyethylene glycol diacrylate (PEGDA) microdroplets using a microfluidic device and chemical polymerization. PEGDA was employed as a reactant due to the biocompatibility, high porosity, and hydrophilic property. The uniform size and shape of microdroplets are obtained in a single-step process using microfluidic device. The size of microdroplets can be controlled through the changing continuous flow rate. The combination of microdroplet generation and chemical polymerization techniques provide unique environment to produce non-toxic ways of fabricating microorganism-encapsulated hydrogel microbeads. Due to these unique properties of micro-sized hydrogel microbeads, the encapsulated E. coli can maintain viability inside of microbeads and green fluorescent protein (GFP) and red fluorescent protein (RFP) genes are efficiently expressed inside of microbeads after isopropyl- , - D -thiogalactopyranoside induction, suggesting that there is no low-molecular weight substrate transfer limitation inside of microbeads. Furthermore, non-toxic, gentle, and outstanding biocompatibility of microbeads, the encapsulated E. coli can be used in various applications including biotransformation, biosensing, bioremediation, and engineering of artificial cells. Biotechnol. Bioeng. 2010;107:747,751. © 2010 Wiley Periodicals, Inc. [source] | ||||||||||