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Polymerization Mechanism (polymerization + mechanism)
Selected AbstractsA New View of the Anionic Diene Polymerization MechanismMACROMOLECULAR SYMPOSIA, Issue 1 2004A.Z. Niu Abstract We investigated the anionic polymerization of butadiene in d-heptane solvent using tert -butyl lithium as initiator. Two complementary techniques were used to follow the polymerization processes: 1H NMR and small angle neutron scattering (SANS). The time resolved 1H NMR measurements allowed us to evaluate quantitatively the kinetics of the processes involved. The initiation event commences slowly and then progressively accelerates. This indicates an autocatalytic mechanism. The microstructure of the first monomer units attached is to a high extent 1,2. The disappearance of initiator --- at about 10% monomer conversion --- signals the onset of the normal ,6% vinyl content of the chain. Small angle neutron scattering was used to study the aggregation behavior of the carbon lithium head groups. It is well known that the polar head groups aggregate and form micellar structures. For dienes in non-polar solvents the textbook mechanism assumes the formation of only tetramers during the propagation reaction. By combining 1H NMR and SANS results we were able to determine quantitatively the aggregation number during all stages of the polymerization. Our measurements show the existence of large-scale structures during the initiation period. The initial degree of aggregation of more than 100 living polymer chains diminished as the polymerization progressed. In addition, even larger, giant structures with Nagg >>1000 and Rg , 1000Å were found. [source] Matrix Representation of Polymer Chain Size Distributions, 3 , Case Studies for Linear Polymerization Mechanisms at Transient ConditionsMACROMOLECULAR THEORY AND SIMULATIONS, Issue 4-5 2008Heloísa L. Sanches Abstract The mass balance equations used to describe different polymerization systems are represented and analyzed with the help of a general matrix framework previously developed. Some of its properties were presented in previous works and are illustrated here in three examples. The first example regards the dynamics of a copolymerization reactor. It is shown that terminal and penultimate models may predict qualitatively different responses in batch reactions. The second example also regards the dynamics of copolymerization reactions. It is shown how manipulation of initial conditions and monomer feed rates can be used to keep copolymer composition constant throughout the batch. The third example concerns the existence of oscillating chain size distributions when there are multiple monomer insertion steps. [source] Synthesis and crystallization behavior of acetal copolymer/silica nanocomposite by in situ cationic ring-opening copolymerization of trioxane and 1,3-dioxolaneJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2008Lanhui Sun Abstract The acetal copolymer/silica nanocomposite was prepared by in situ bulk cationic copolymerization of trioxane and 1,3-dioxolane in the presence of nanosilica. The crystallization behavior of acetal copolymer/silica nanocomposite was studied by AFM, DSC, XRD, and CPOM, and the macromolecular structure of acetal copolymer/silica nanocomposite was characterized by FTIR and 1H-NMR. The 1H-NMR results showed that the macromolecular chain of acetal copolymer had more than two consecutive 1,3-dioxolane units in an oxymethylene main chain, while that of acetal copolymer/silica nanocomposite had only one 1,3-dioxolane unit in an oxymethylene main chain. There existed interaction between the macromolecular chains and nanoparticles (such as hydrogen bonds and coordination). On one hand, nanoparticles acted as nucleation center, which accelerated the crystallization rate but reduced the crystallinity. The spherulite sizes also decreased with addition of nanoparticles attributed to the nucleation effect. On the other hand, the presence of nanoparticles interrupted the spherical symmetry of the crystallite. In conclusion, the high surface energy and small scale of nanoparticles have a prominent impact on the polymerization mechanism and crystallization behavior of nanocomposite. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Preparation of high cis -1,4 polyisoprene with narrow molecular weight distribution via coordinative chain transfer polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2010Changliang Fan Abstract High cis -1,4 polyisoprene with narrow molecular weight distribution has been prepared via coordinative chain transfer polymerization (CCTP) using a homogeneous rare earth catalyst composed of neodymium versatate (Nd(vers)3), dimethyldichlorosilane (Me2SiCl2), and diisobutylaluminum hydride (Al(i -Bu)2H) which has strong chain transfer affinity is used as both cocatalyst and chain transfer agent (CTA). Differentiating from the typical chain shuttling polymerization where dual-catalysts/CSA system has been used, one catalyst/CTA system is used in this work, and the growing chain swapping between the identical active sites leads to the formation of high cis -1,4 polyisoprene with narrowly distributed molecular weight. Sequential polymerization proves that irreversible chain termination reactions are negligible. Much smaller molecular weight of polymer obtained than that of stoichiometrically calculated illuminates that, differentiating from the typical living polymerization, several polymer chains can be produced by one neodymium atom. The effectiveness of Al(i -Bu)2H as a CTA is further testified by much broad molecular weight distribution of polymer when triisobutylaluminum (Al(i -Bu)3), a much weaker chain transfer agent, is used as cocatalyst instead of Al(i -Bu)2H. Finally, CCTP polymerization mechanism is validated by continuously decreased Mw/Mn value of polymer when increasing concentration of Al(i -Bu)2H extra added in the Nd(ver)3/Me2SiCl2/Al(i -Bu)3 catalyst system. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 [source] One-pot synthesis of surface-functionalized molecularly imprinted polymer microspheres by iniferter-induced "living" radical precipitation polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2010Junyi Li Abstract This article describes for the first time the development of a new polymerization technique by introducing iniferter-induced "living" radical polymerization mechanism into precipitation polymerization and its application in the molecular imprinting field. The resulting iniferter-induced "living" radical precipitation polymerization (ILRPP) has proven to be an effective approach for generating not only narrow disperse poly(ethylene glycol dimethacrylate) microspheres but also molecularly imprinted polymer (MIP) microspheres with obvious molecular imprinting effects towards the template (a herbicide 2,4-dichlorophenoxyacetic acid (2,4-D)), rather fast template rebinding kinetics, and appreciable selectivity over structurally related compounds. The binding association constant Ka and apparent maximum number Nmax for the high-affinity sites of the 2,4-D imprinted polymer were determined by Scatchard analysis and found to be 1.18 × 104 M,1 and 4.37 ,mol/g, respectively. In addition, the general applicability of ILRPP in molecular imprinting was also confirmed by the successful preparation of MIP microspheres with another template (2-chloromandelic acid). In particular, the living nature of ILRPP makes it highly useful for the facile one-pot synthesis of functional polymer/MIP microspheres with surface-bound iniferter groups, which allows their direct controlled surface modification via surface-initiated iniferter polymerization and is thus of great potential in preparing advanced polymer/MIP materials. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3217,3228, 2010 [source] Cyclic alkoxyamine-initiator tethered by azide/alkyne-"click"-chemistry enabling ring-expansion vinyl polymerization providing macrocyclic polymersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2010Atsushi Narumi Abstract A cyclic initiator for the nitroxide-mediated controlled radical polymerization (NMP) is a powerful tool for the preparation of macrocyclic polymers via a ring-expansion vinyl polymerization mechanism. For this purpose, we prepared a Hawker-type NMP-initiator that includes an azide and a terminal alkyne as an acyclic precursor, which is subsequently tethered via an intramolecular azide/alkyne-"click"-reaction, producing the final cyclic NMP-initiator. The polymerization reactions of styrene with cyclic initiator were demonstrated and the resultant polymers were characterized by the gel permeation chromatography (GPC) and the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). These results prove that the ring-expansion polymerization of styrene occurred together with the radical ring-crossover reactions originating from the exchange of the inherent nitroxides generating macrocyclic polystyrenes with higher expanded rings. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3402,3416, 2010 [source] Vinylic and ring-opening metathesis polymerization of norbornene with bis(,-ketoamine) cobalt complexes,JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2005Feng Bao Abstract Cobalt complexes 1,4 bearing N,O -chelate ligands based on condensation products of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone with aniline, o -methylaniline, ,-naphthylamine, and p -nitroaniline, respectively, were synthesized, and the structures of 1 and 4 were characterized by single-crystal X-ray diffraction analyses. The bis(,-ketoamine) cobalt complexes could act as moderately active catalyst precursors for norbornene polymerization with the activation of methylaluminoxane. This catalytic reaction proceeded mainly through a vinyl-type polymerization mechanism. 1H NMR and IR showed that in all cases, a small amount of double bonds raised from ring-opening metathesis polymerization (ROMP) was present in the polymerization products. The variation of the polymerization conditions affected the ROMP unit ratio in the polynorbornenes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5535,5544, 2005 [source] Kinetics and Molecular Weight Development of Dithiolactone-Mediated Radical Polymerization of StyreneMACROMOLECULAR REACTION ENGINEERING, Issue 4 2009Jesús Guillermo Soriano-Moro Abstract Calculations of polymerization kinetics and molecular weight development in the dithiolactone-mediated polymerization of styrene at 60,°C, using 2,2,-azobisisobutyronitrile (AIBN) as initiator and , -phenyl- , -butirodithiolactone (DTL1) as controller, are presented. The calculations were based on a polymerization mechanism based on the persistent radical effect, considering reverse addition only, implemented in the PREDICI® commercial software. Kinetic rate constants for the reverse addition step were estimated. The equilibrium constant (K,=,kadd/k -add) fell into the range of 105,106 L,·,mol,1. Fairly good agreement between model calculations and experimental data was obtained. [source] Biodegradable polyester layered silicate nanocomposites based on poly(,-caprolactone)POLYMER ENGINEERING & SCIENCE, Issue 9 2002Nadège Pantoustier Nanocomposites based on biodegradable poly(,-caprolactone) (PCL) and layered silicates (montmorillonite, MMT) were prepared either by melt interaction with PCL or by in situ ring-opening polymerization of ,-caprolactone as promoted by the so-called coordination-insertion mechanism. Both non-modified clays (Na+ -MMT) and silicates modified by various alkylammonium cations were studied. Mechanical and thermal properties were examined by tensile testing and thermogravimetric analysis. Even at a filler content as low as 3 wt% of inorganic layered silicate, the PCL-layered silicate nanocomposites exhibited improved mechanical properties (higher Young's modulus) and increased thermal stability as well as enhanced flame retardant characteristics as a result of a charring effect. It was shown that the formation of PCL-based nanocomposites depended not only on the nature of the ammonium cation and related functionality but also on the selected synthetic route, melt intercalation vs. in situ intercalative polymerization. Interestingly enough, when the intercalative polymerization of ,-caprolactone was carried out in the presence of MMT organo-modified with ammonium cations bearing hydroxyl functions, nanocomposites with much improved mechanical properties were recovered. Those hybrid polyester layered silicate nanocomposites were characterized by a covalent bonding between the polyester chains and the clay organo-surface as a result of the polymerization mechanism, which was actually initiated from the surface hydroxyl functions adequately activated by selected tin (II) or tin (IV) catalysts. [source] Synthesis, Microwave-Assisted Polymerization, and Polymer Properties of Fluorinated 2-Phenyl-2-oxazolines: A Systematic StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 33 2008Matthias Lobert Dr. Abstract We present a detailed systematic study of the synthesis and ability of fluorinated 2-phenyl-2-oxazolines to undergo polymerization. The synthesis of these compounds is based on a two-step procedure that gives the desired 2-oxazolines in moderate-to-good yields. All the compounds were fully characterized by IR and NMR (1H, 13C, and 19F) spectroscopy, mass spectrometry, and elemental analysis. The 2-oxazolines were subsequently used as monomers for living cationic ring-opening polymerization (CROP) with microwave irradiation as the heat source (T=140,°C), nitromethane as the solvent, and methyl tosylate as the initiator. The linear first-order kinetic plots of the polymerizations accompanied by a linear increase of the molecular weight with conversion and low polydispersity index (PDI) values (generally below 1.30) indicate a living polymerization mechanism. The resulting polymerization rates reflect a strong sensitivity to the quantity of fluorine substituents in general and the presence or absence of ortho -fluoro substituents of the phenyl ring in particular. All the polymers were isolated and characterized by size-exclusion chromatography and MALDI-TOF mass spectrometry. Finally, a detailed investigation of selected polymer properties was performed by using differential scanning calorimetry, thermogravimetric analysis, and contact-angle measurements, thus resulting in structure,property relationships. Whereas the thermal properties of the polymers are mostly influenced by the presence of ortho -fluoro substituents, the surface properties are mainly determined by the presence of para - and/or meta -fluoro substituents. [source] Ring-opening polymerization of ,-caprolactone by lanthanide tris (2, 6-dimethylphenolate) sCHINESE JOURNAL OF CHEMISTRY, Issue 9 2003Li-Fang Zhang Abstract Lanthanide tris (2,6-dimethylphenolate)s [Ln(ODMP)3] were used as initiators for ring-opening polymerization of s -caprolactone (CL) for the first time. The influence of different rare earth elements and solvents was investigated. 1H NMR spectral data of polycaprolactone (PCL) obtained showed that the polymerization mechanism is in agreement with the coordination-insertion mechanism and the selective cleavage of the acyl-oxygen bond of CL. [source] Monitoring ultrathin film photopolymerization of tetra-alkylepoxyporphyrin by UV-Vis spectroscopyJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2009Kalle Lintinen Abstract Cationic photopolymerization is a convenient in situ polymerization method for organic thin film preparation. In this work, the polymerization mechanisms is applied for highly viscous cross-linking monomers, using tetra-alkylepoxyporphyrin (TAEP) as a case study. By comparing the UV-Vis spectra of the polymerized sample before and after the unreacted monomers have been dissolved, it is possible to estimate the polymerization yield. An IR spectrum of a reference thick film confirms full polymerization. Scanning fluorescence lifetime microscopy and AFM show the uniformity of the polymer. It was shown that photopolymerization is highly dependent on the substrate nature and requires at best case a 10 min illumination at 90 °C. Thermal polymerization of the same sample requires 10 min heating at 150 °C in dark. It was also shown that TAEP works as a self-sensitizer for cationic photopolymerization. The proposed method is a mild and versatile technique for in situ preparation of thin polymeric films directly from chromophore monomers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6095,6103, 2009 [source] Dendrimer-like miktoarm star terpolymers: A3 -(B-C)3 via click reaction strategyJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 17 2008Ozcan Altintas Abstract Two samples of dendrimer-like miktoarm star terpolymers: (poly(tert -butyl acrylate))3 -(polystyrene-poly(,-caprolactone))3 (PtBA)3 -(PS-PCL)3, and (PS)3 -(PtBA-poly(ethylene glycol)3 were prepared using efficient Cu catalyzed Huisgen cycloaddition (click reaction). As a first step, azido-terminated 3-arm star polymers PtBA and PS as core (A) were synthesized by atom transfer radical polymerization (ATRP) of tBA and St, respectively, followed by the conversion of bromide end group to azide. Secondly, PS-PCL and PtBA-PEG block copolymers with alkyne group at the junction as peripheral arms (B-C) were obtained via multiple living polymerization mechanisms such as nitroxide mediated radical polymerization (NMP) of St, ring opening polymerization (ROP) of ,-CL, ATRP of tBA. Thus obtained core and peripheral arms were linked via click reaction to give target (A)3 -(B-C)3 dendrimer-like miktoarm star terpolymers. (PtBA)3 -(PS-PCL)3 and (PS)3 -(PEG-PtBA)3 have been characterized by GPC, DSC, AFM, and SAXS measurements. (PtBA)3 -(PS-PCL)3 did not show any self-organization with annealing due to the miscibility of the peripheral arm segments. In contrast, the micro-phase separation of the peripheral arm segments in (PS)3 -(PtBA-PEG)3 resulted in self-organized phase-separated morphology with a long period of , 13 nm. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5916,5928, 2008 [source] Transition from microemulsion to emulsion polymerization: Mechanism and final propertiesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 20 2004Kevin D. Hermanson Abstract Microemulsion and emulsion polymerization can have some similarities in starting conditions and polymerization mechanisms, but the resulting latices are unalike in particle size and molecular weight. Here we show that polymerizations can be formulated that display the characteristics often separately associated with microemulsion or emulsion polymerization. Kinetic modeling and particle size measurements show that emulsion polymerizations with initial concentrations close to the microemulsion,emulsion phase boundary demonstrate relatively fast consumption of monomer droplets and produce smaller particles. Because of their high surfactant concentrations, none of the emulsion polymerizations examined demonstrate the classical Smith,Ewart kinetics usually associated with emulsion polymerization. Instead these emulsion polymerizations have a long period of particle nucleation that subsides only after the disappearance of monomer droplets. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5253,5261, 2004 [source] Synthesis and Functionalization of Isotactic Poly(propylene) Containing Pendant Styrene GroupsMACROMOLECULAR RAPID COMMUNICATIONS, Issue 20 2004Junfeng Zou Abstract Summary: Copolymerization of propylene and 1,4-divinylbenzene was successfully performed by a MgCl2 -supported TiCl4 catalyst, yielding isotactic poly(propylene) (i -PP) polymers containing a few pendant styrene groups. With a metalation reaction with butyllithium and a hydrochlorination reaction with dry hydrogen chloride, the pendant styrene groups were quantitatively transformed into benzyllithium and 1-chloroethylbenzene groups, respectively, which allowed the synthesis of i -PP-based graft copolymers by living anionic and atom transfer radical (ATRP) polymerization mechanisms. The incorporation of styrene pendant groups into isotactic poly(propylene) using a Zeigler,Natta catalyst gave functionalized polymers able to undergo living anionic and atom transfer radical (ATRP) polymerizations. [source] Trends in industrial polymer researchMACROMOLECULAR SYMPOSIA, Issue 1 2003Volker Warzelhan Abstract In the past decades a shift in paradigm took place in industrial polymer research for structural materials. Only a few new polymers based on new monomeric building blocks were developed. The main focus is now on tailoring improved "old polymers" with well-defined structure and properties based on a set of low cost "old" monomers using controlled polymerization mechanisms. [source] | |||||||||||||