Copolymerization of styrene and isoprene with Ni(acac)2‐methylalumoxane catalyst
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Abstract Copolymerization of styrene (St) and isoprene (IP) with nickel(II) acetylacetonate [Ni(acac) 2 ] and methylalumoxane (MAO) catalyst was investigated. It was found that the Ni(acac) 2 ‐MAO catalyst is effective for the copolymerization of St and IP. From the copolymerization of St (M 1 ) and IP (M 2 ) and IP (M 2 ) with the Ni(acac) 2 ‐methylalumoxane catalyst, the monomer‐reactivity ratios were determined to be r 1 = 1,18 and r 2 = 0,88, i.e., ideal copolymerization was found to proceed to give perfectly random copolymers without formation of any homopolymer. The microstructure of IP units in the copolymers exhibits high cis‐1,4 contents.Keywords:
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Abstract An extensive and detailed analysis of copolymers was made by developing a rapid spectrophotometric method. Successful analysis of composition in styrene‐ p ‐methoxystyrene, styrene‐ p ‐chlorostyrene, and styrene‐ p ‐fluorostyrene copolymers were performed by UV spectrometry. Their absorption bands were investigated either with respect to pure polystyrene or with respect to the homopolymer of the other constituent at the same wavelength. Attempts to analyze copolymers of styrene‐4‐vinylpyridine and styrene‐ N ‐vinylcarbazole by similar methods were unsuccessful.
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Abstract There is little published work dealing with the emulsion copolymerization of isoprene and styrene. In ascertaining the effect of varying conditions on the emulsion copolymerization of a 40:60 mixture of isoprene and styrene, an approximately equimolecular mixture, it was observed that the initially formed copolymer contained about 80 per cent of styrene. As the reaction was continued to maximum conversion, the styrene content decreased to approximately 60 per cent. These results show that at this monomer ratio styrene enters the copolymer faster than does isoprene. This behavior is similar to that of styrene when copolymerized with acrylonitrile and with vinylidene chloride. The evidence indicates also that the copolymer is not homogeneous with respect to composition.
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The copolymerization of styrene with eight polymerizable fluorescent dyes, naphthalimide derivatives, was investigated. Their effect on the polymerization rate was established. It was found that the chemical structure of the dye influences the copolymerization process. © 1996 John Wiley & Sons, Inc.
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Se estudio la copolimerizacion de estireno con para-metilestireno usando sistemas combinados difenilcinc-aditivo como iniciadores de la copolimerizacion. Se emplearon los sistemas difenilcinc, Ph2Zn, un metaloceno: ciclopentadienil titanio tricloruro, CpTiCl3, junto con metilaluminoxano, MAO, y tambien el sistema binario: CpTiCl3-MAO. Ambos sistemas resultaron ser activos iniciadores tanto de la copolimerizacion S/p-MeS, como de las respectivas homopolimerizaciones. Los resultados alcanzados indican que la conversion a copolimero aumenta con el aumento de la proporcion de p-MeS en la carga inicial, mientras que la homopolimerizacion de p-MeS produjo mayores conversiones que la homopolimerizacion de S. De los copolimeros obtenidos mediante estos sistemas iniciadores solo los producidos a partir de la carga inicial S/p-MeS = 95/5 resultaron ser cristalinos con valores de Tm menores que para el s-PS, lo que los hace mas facil de procesar
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Abstract Styrene was copolymerized in bulk with cinnamonitrile, benzylidenemalononitrile, ethyl benzylidenecyanoacetate, and atroponitrile at 80°C. up to low conversions. The usual reaction scheme of copolymerization fitted only the pair styrene‐atroponitrile. The kinetic scheme of the other three pairs fitted the scheme proposed by Barb, taking into account the effect of the penultimate unit.
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Abstract The sequence distribution of the monomelic units in the styrene-acrylic acid copolymer has been obtained by calculation. The probability of long sequences of styrene increases with an increase in the content of the monomer in the copolymer. The highest distribution of short sequences of styrene takes place for the copolymer containing equimolecular amounts of styrene and acrylic acid. The copolymer which has this latter structure is inadequate for the synthesis of highly active supported complexes. When the distributions of long and short sequences of styrene are approximately equal, the activity of the Nd and Fe prepared polymer complexes is higher.
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Abstract Free radical-initiated copolymerization of 2-vinylnaphthalene (2-VNA) with benzylidenemalononitrile (BzMN) was performed in toluene to low conversion and to high conversion in a Calvet microcalorimeter. Under different monomer-to-monomer ratios in the feed at low and high conversion copolymerization, it was found that the usual terminal scheme of copolymerization fitted and that there was no significant kinetic effect of the penultimate unit. The reactivity ratios in low conversion copolymerizations were r1 = 0.85 and r2 = 0. In all cases, regardless to the monomer-to-monomer ratios in the feed, an excess of 2-VNA was present in copolymers. T g values of copolymers are between 186 and 220 °C, and they decrease with the increase of 2-VNA sequences in copolymer chains. Poly(2-VNA-co-BzMN) are film-forming materials which decompose by a one-step mechanism. Depending on the comonomers content in the copolymer, the weight loss is 50% between 325 and 360 °C, and 90% at 400 °C.
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Styrene/maleic anhydride (MA) copolymerization was carried out using benzoyl peroxide (BPO) and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO). Styrene/MA copolymerization proceeded faster and yielded higher molecular weight products compared to styrene homopolymerization. When styrene/MA copolymerization was approximated to follow the first-order kinetics, the apparent activation energy appeared to be lower than that corresponding to styrene homopolymerization. Molecular weight of products from isothermal copolymerization of styrene/MA increased linearly with the conversion. However products from the copolymerization at different temperatures had molecular weight deviating from the linear relationship indicating that the copolymerization did not follow the perfect living polymerization characteristics. During the copolymerization, MA was preferentially consumed by styrene/MA random copolymerization and then polymerization of practically pure styrene continued to produce copolymers with styrene-co-MA block and styrene-rich block. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2239–2244, 2000
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