Olefin polymerization styrene

A more complicated behaviour was obtained with divinyl ether due to the formation of both cyclic structures and pendent vinyl groups in the chain. The failure of such olefins as styrene and isopropenylbenzene to give copolymers with 2-fural-dehyde, and in fact to homopolymerize in its presence, was blamed on the strength of the complex formed between the initiator and the aldehyde, believed too stable to initiate polymerization. 

Inhibition of olefin polymerization occurred when its basicity was not sufficient to produce an appreciable displacement of initiator from the aldehyde-acid complex isoprene, cyclopentadiene and styrene were in this category. 

The mechanisms of stereoselectivity which have been proposed for chain-end stereocontrolled polymerizations involving secondary monomer insertion also present a general pattern of similarity. In fact, molecular modeling studies suggest that for olefin polymerizations (both syndiospecific and isospecific, Section 4.1.2) as well as for styrene polymerization (syndiospecific, Section 4.2), the chirality of the growing chain would determine the chirality of a fluxional site, which in turn would discriminates between the two monomer enantiofaces. 

In one of the earliest investigations of spin trapping, olefin polymerization was employed to demonstrate the utility of the method as a qualitative probe for free-radical reactions (Chalfont et al., 1968). The polymerization of styrene, initiated by t-butoxyl radicals, proved to be an excellent system with which to obtain spectra attributable to spin adducts with MNP (a) of the initiator radical... 

In polymers that exhibit tacticity, the extent of the stereoregularity determines the crystallinity and the physical properties of the polymers. The placement of the monomer units in the polymer is controlled first by the steric and electronic characteristics of the monomer. However, the presence or absence of tacticity, as well as the type of tacticity, is controlled by the catalyst employed in the polymerization reaction. Some common polymers, which can be prepared in specific configuration, include poly(olefins), poly(styrene), poly(methyl methacrylate), and poly(butadiene). 

Examples are the sulfonating of polyethylene film with chloro-sulfonic acid (60) the sulfonating of sheets of phenolformaldehyde resin (77) the treatment of a film consisting of polystyrene and polyvinylchloride with concentrated sulfuric acid (4) the sulfonating of films consisting of aliphatic vinylpolymers with chlorosulfonic acid (125) the sulfonating of copolymers of a monovinyl- and a polyvinyl compound (30). Also are used copolymers of aromatic monovinyl-compounds and linear aliphatic polyene hydrocarbons (3) copolymers of an unsaturated aromatic compound and an unsaturated aliphatic compound (76), and of reaction products of poly olefines and partially polymerized styrene (173). 

MC MDI MEKP MF MMA MPEG MPF NBR NDI NR OPET OPP OSA PA PAEK PAI PAN PB PBAN PBI PBN PBS PBT PC PCD PCT PCTFE PE PEC PEG PEI PEK PEN PES PET PF PFA PI PIBI PMDI PMMA PMP PO PP PPA PPC PPO PPS PPSU Methyl cellulose Methylene diphenylene diisocyanate Methyl ethyl ketone peroxide Melamine formaldehyde Methyl methacrylate Polyethylene glycol monomethyl ether Melamine-phenol-formaldehyde Nitrile butyl rubber Naphthalene diisocyanate Natural rubber Oriented polyethylene terephthalate Oriented polypropylene Olefin-modified styrene-acrylonitrile Polyamide Poly(aryl ether-ketone) Poly(amide-imide) Polyacrylonitrile Polybutylene Poly(butadiene-acrylonitrile) Polybenzimidazole Polybutylene naphthalate Poly(butadiene-styrene) Poly(butylene terephthalate) Polycarbonate Polycarbodiimide Poly(cyclohexylene-dimethylene terephthalate) Polychlorotrifluoroethylene Polyethylene Chlorinated polyethylene Poly(ethylene glycol) Poly(ether-imide) Poly(ether-ketone) Polyethylene naphthalate Polyether sulfone Polyethylene terephthalate Phenol-formaldehyde copolymer Perfluoroalkoxy resin Polyimide Poly(isobutylene), Butyl rubber Polymeric methylene diphenylene diisocyanate Poly(methyl methacrylate) Poly(methylpentene) Polyolefins Polypropylene Polyphthalamide Chlorinated polypropylene Poly(phenylene oxide) Poly(phenylene sulfide) Poly(phenylene sulfone)... 

This review will feature the kinetics and mechanism of RLi-initiated, homo- and copolymerization of hydrocarbon diene and olefin monomers, with and without polar ligands. Hydrocarbon olefin homopolymerization in nonpolar media will not be discussed per se because simple olefins such as ethylene do not polymerize under such conditions, and such reactive, hydrocarbon a-olefins as styrene behave similarly to dienes in... 

Titanium—Vanadium Mixed Metal Alkoxides. Titanium—vanadium mixed metal alkoxides, VO(OTi(OR)3)2, are prepared by reaction of titanates, eg, TYZOR TBT, with vanadium acetate in a high boiling hydrocarbon solvent. The by-product butyl acetate is distilled off to yield a product useful as a catalyst for polymerizing olefins, dienes, styrenics, vinyl chloride, acrylate esters, and epoxides (159,160). 

Some half sandwich titanium compounds with cyclopentadienyl ligands have proven to be most active, but soluble tetraethyoxytitanium also shows a certain amount of activity. In contrast to olefin polymerization, titanocenes are more active than zirconocenes and fluoro ligands are better than chloro ligands. Table 24 [207] compares some catalysts for the polymerization of styrene. 

Polymers with even narrower mass distributions, e.g. with PDI values close to 1, arise in living polymerization systems, in which no chain termination processes can occur at all, such that all chains remain bound to the metal centre from which they have started to grow at the same time. Living polymerizations, which offer useful opportunities, e.g. with regard to the production of block copolymers by exchange of one monomer for another, occur in anionic polymerizations of styrenes or butadienes such as are induced by simple lithium alkyls. For a-olefin polymerization catalysts of the type discussed above, living polymerizations are rare. These more elaborate catalysts can thus release a newly formed polymer chain within a time interval of typically less than one... 

Conjugated olefins, like styrene, butadiene, and isoprene, can be caused to polymerize by cationic and anionic as well as by free-radical processes because the active site is delocalized in all cases. The most practical ionic polymerizations for these species are anionic, because such reactions involve fewer side reactions and better control of the diene polymer microstructure than in cationic systems. Free-radical polymerization of styrene is preferred over ionie proeesses, however, for cost reasons. 

Organolanthanides of several classes were examined by Bochkarev et al. as potential styrene and propene polymerization catalysts.891 Developments of rare earth metal catalysts for olefin polymerization have been highlighted by Yasuda et al. 19S... 

Mono-Cp titanium derivatives show reactivity as catalyst precursors for olefin polymerizations, particularly for the polymerization of styrene and functionalized monomers. A review highlighting the developments in the design and applications of non-metallocene complexes, including mono-Cp derivatives, as catalyst systems for a-olefin polymerization has appeared.440 Titanium complexes bearing Cp in addition to chloro ligands and activated by aluminum... 

Metallocene derivatives are the most extensively studied class of homogeneous catalysts for the polymerization of olefins. Less saturated and less hindered mono-Gp group 4 metal species of the type [Cp MR2]+ (Cp denotes Cp or a substituted cyclopentadienyl ring) may also behave as useful catalysts or initiators for olefin polymerization. Catalysts for syndiospecific polymerization of styrene based on mono-Cp titanium derivatives with different substituents on the Gp ligand and with various types of tetraphenylborates have been examined. A good relationship between the... 

While rare-earth metals are proven powerful olefin polymerization catalysts [21-24], there are only limited reports on controlled olefin oligomerizations or selective olefin dimerizations utilizing these elements [204,207,208], An ansa-scandocene [207] and the bis(indenyl)yttrium complex 41 (Fig. 25) [204] were reported to produce head-to-tail dimers from monosubstimted aliphatic alkenes (57). Complex 41 produces predominantly the tail-to tail adduct with styrene. The codimerization of an aliphatic alkene (including substrates containing various functionalities) with styrene affords tran -tail-to-tail dimers, apparently as a result of 1,2-insertion of the a-olefin followed by 2,1-insertion of styrene directed by the phenyl group (58). 

Very recently, an aqueous olefin polymerization using an early transition metal catalyst has also been reported [84]. A toluene solution of styrene is prepolymerized briefly by a catalyst prepared by combination of [(CsMesjTifOMe),] with a borate and an aluminum-alkyl as activators. The reaction mixture is then emulsified in water, where further polymerization occurs to form syndiotactic polystyrene stereoselectively. It is assumed that the catalyst is contained in emulsified droplets and is thus protected from water, with the formation of crystalline polymer enhancing this effect. Cationic or neutral surfactants were found to be suitable, whereas anionic surfactants deactivated the catalyst. The crystalline polystyrene formed was reported to precipitate from the reaction mixture as relatively large particles (500 pm). 

Mn 2 to 4). In olefin polymerization as well as CO copolymerization, a Umited conversion of liquid 1-olefin (co)monomers is yet to be overcome in many cases. As an example of properties that could find potential appUcation, polyolefins contain a negligible proportion of double bonds by comparison to styrene-butadiene copolymers, a hydrocarbon polymer currently prepared by free-radical emulsion polymerization on a large scale. This can result in a considerably higher stability towards UV-Ught and air of polymer films formed from polyolefin latexes. 

Ti complexes containing Tp or Tp have been investigated as polymerization precatalysts for ethylene, propylene, and styrene. A patent on olefin polymerization catalysts and polymerization of olefins has been presented by Michiue2 which describes the use of [TiCl3 (TpMs )] as cocatalyst and its reaction with K in toluene. 

Most addition polymerizations involve vinyl or diene monomers. The opening of a double bond can be catalyzed in several ways. Free-radical polymerization is the most common method for styrenic monomers, whereas coordination metal catalysis (Zigler-Natta and metallocene catalysis) is important for olefin polymerizations. The specitic reaction mechanism may generate some catalyst residues, but there are no true coproducts. There are no stoichiometry requirements, and equilibrium limitations are usually unimportant so that quite long chains are formed 7iv > 500 is typical of addition polymers. 

A closed-loop comprehensive model uniting impurity-induced and purposely-added initiator-induced isobutylene (IB) and styrene (St) polymerizations was developed. Both impurity-induced and purposely-induced olefin polymerizations can be both conventional or living, and the reaction conditions will determine whether the prevailing mechanism will be conventional or living. The model was used to elucidate the detailed mechanism of olefin polymerizations and to provide guidance toward preparative advances. The heart of the model is the Winstein tonicity spectrum which in its simplest form consists of three fundamental entities connected by two equilibria a) a dormant species (in fact the initiator) which can be either a protic impurity or a purposefully added... 

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