Cationic Polymerization Of Indene Research Articles

Indene polymerization under the action of titanium tetrachloride

The cationic polymerization of indene under the action of TiCl4 is considered, in the presence of toluene. The reaction is greatly affected by the competition between the solvent and the monomer in TiCl4 solvation. Active centers are formed on account of the direct addition of TiCl4 by the vinyl bond of the monomer. In the given system, polymerization is most likely due to chain growth at the contact pairs or solvationally separated ion pairs. Effective values of the rate constants of catalyst solvation and chain growth are calculated.

Cationic polymerization of styrene and indene in iodine/liquid sulfur dioxide system

The cationic polymerizations of indene (Ind) and styrene (Sty) initiated by iodine (I2) in liquid sulfur dioxide (SO2) were investigated. Reactions involving Ind were characterized by termination by neutralization between the growing carbocationic species and the nucleophilic counteranion, at low temperature. Sty polymerization is also termination-dominated and gives low conversion at -20°C. High resolution gas chromatography coupled with mass spectrometry (HGC-MS) analysis of non polymeric material in the Sty polymerization suggested that initiation of Sty polymerization involves the formation of 1,2 diiodide adduct prior to initiation with HI.

"Living" Cationic Polymerization of Indene. 3. Kinetic Investigation of the Polymerization of Indene Initiated with Cumyl Methyl Ether and Cumyl Chloride in the Presence of Titanium Derivatives

The kinetics of the polymerization of indene in dichloromethane solution, initiated with cumyl methyl ether and cumyl chloride, in the presence of titanium derivatives (TiCl 4 and TiCl 3 OBu), at variable temperatures (0 to -62 °C), have been investigated by adiabatic calorimetry under vacuum. At -40 °C, with cumyl methyl ether as an initiator, an internal first-order plot with respect to the monomer is observed after 60% yield, and initiation is completed before the end of the polymerization. The polymerization is apparently living or living, which means only that the molecular weight increases linearly with polymer yield. With the CumCl/TiCl 4 initiating system, complete initiation is obtained only in the presence of dimethyl sulfoxide (DMSO). Addition of DMSO increases the initiation rate, decreases the apparent propagation rate constant, and allows the observation of a first-order plot and an apparently living process. The use of a common ion salt (tetra-n-butylammonium pentachlorotitanate) has a similar effect. With the CumCl/TiCl 3 OBu initiating system, an apparently living polymer is obtained without additive. These data, and the negative apparent activation energies observed, imply that several types of chain ends are present in variable concentrations in the solution (covalent inactive species, ions pairs, and free ions), involving a reversible termination. These results, as well as the occurrence of transfer reactions, may be explained, as in conventional carbocationic polymerization, by a propagation involving ionic active centers.

Living carbocationic polymerization. 55. Living polymerization of indene

The cationic polymerization of indene (In) has been investigated using the 2-chloro-2,4,4- trimethylpentane (TMPCl)/TiCl 4 initiating system and a methyl chloride-methylcyclohexane solvent mixture at -80°C. According to kinetic studies, initiation is slow relative to propagation. The quantitative treatment of slow initiation in living cationic polymerization applied to this system led to the conclusion that this polymerization is living and the rate-determining step is cationation. The end-groups of polyindene are secondary chlorines.

"Living" cationic polymerization of indene. 1. Polymerization initiated with cumyl methyl ether/titanium tetrachloride and cumyl methyl ether/n-butoxytrichlorotitanium initiating systems

Polymerization of indene using cumyl methyl ether as initiator and TiCl 4 as coinitiator in CH 2 Cl 2 solution was apparently living polymerization. At -40 and -75°C, there is a linear relationship between the M n and the amount of monomer polymerized, with a number of macromolecules near to that of the initiator. However, it was shown that at -40°C significant transdfer reactions occur, the same tranfer constant being found for polymerizations which were and were not apparently living. At -75°C, transfer could no longer be detected. With Ti(OBu)Cl 3 as coinitiator, the transfer constant was near zero at -40°C

Electroinitiated Cationic Polymerization of Indene

Abstract The polymerization of indene by constant potential electrolysis in dichloromethane was achieved at low temperatures. Molecular weights were found to be inversely proportional to polymerization temperature. The oxidation peak potential of indene in the (C4H9)4-NBF4-CH3CN electrolyte-solvent system was measured by cyclic voltammetry. Polymers which were produced electrochemically by constant potential electrolysis have the same spectral properties with those obtained by chemical methods.

The Spontaneous Copolymerization of Indene with Polar Vinyl Monomers in the Presence of Zinc Chloride

Abstract Indene (ID) was found to copolymerize spontaneously with polar vinyl monomers containing a nitrile or ester group in the presence of ZnCb and to give rise simultaneously to its cationic homopolymer in the latter comonomer. The formation of a 1:1-charge transfer complex between ID with acrylonitrile coordi-nated to ZnCl2 ((AN)c) was confirmed by UV-spectroscopic studies and the equilibrium constant for it was estimated to be 0.121 L/mol in AN at 25°C. The overall activation energy for the copolymerization with (AN)c was obtained to be ∼9.8 kcal/mol. An increasing amount of ZnCl2 in AN resulted in increases in the copolymerization rate, viscosity, and alternating tendency of the copolymer. The addition of 1, 1-diphenyl-2-picrylhydrazyl to the System ID-(AN)c retarded the copolymerization and induced a cationic polymerization of ID. Further, terpolymers containing ∼50 mol % AN were formed spontaneously in the System ID-styrene-(AN)c. Comparing these results with the corresponding ones obtained for 1...

The electro‐initiated cationic polymerization of indene, 3. Kinetics of polymerization

The electro‐initiated cationic polymerization of indene, 3. Kinetics of polymerization

The electro‐initiated cationic polymerization of indene, 2. Kinetics of polymerization

AbstractThe electrolytically initiated anodic polymerization of indene in the solutions of tetraethylammonium hexachloroantimonate and tetrabutylammonium perchlorate in nitrobenzene under constant electric current and constant potential electrolysis conditions was studied. The polymerization was followed either under continuous electrolysis or by addition of the monomer to the pre‐electrolysed solution of the salt. The monomer consumption follows the first‐order rate‐law, log[M]0/[M]t=kt, and the rate constant of the polymerization increases with increasing current level. The polymer formation was greatly affected by the change of the dielectric constant of the medium, the anode material, and the nature of the supporting electrolyte. The mode of initiation process depends upon the type of the salt. Mechanisms for the initiation reaction were elucidated.

The electro‐initiated cationic polymerization of indene, 1

AbstractThe electro‐initiated anodic polymerization of indene in ethylene dichloride solutions of tetraethylammonium hexachloroantimonate and tetrabutylammonium perchlorate as background electrolytes was studied. The polymerization was conducted either under continuous electrolysis or by addition of the monomer to the pre‐electrolysed solution of the salt. The polymer formation was affected by the amount of electricity, the monomer concentration, and the nature of the electrolytes. The rate and degree of polymerization with the hexachloroantimonate salt are relatively high in comparison with the perchlorate salt. The characteristically colored species, formed during polymerization, were investigated spectrophotometrically. Mechanisms for the initiation processes of both procedures were elucidated.

Cationic polymerization of indene and acenaphthylene

The polymerizations of indene and acenaphthylene by TiCl 4 CCl 3CO 2H in dichloromethane take place in two stages, viz. a fast initial reaction followed by a slow stationary-state process. A mechanism involving the relaxation of active centres created by fast initiation to an equilibrium mixture of active and dormant centres satisfactorily accounts for the observed behaviour. Spectroscopy failed to reveal the presence of the acenaphthenium ion during polymerization, but paradoxically an ion of this type is slowly formed in large amounts after polymerization has ceased.

Studies on the cationic polymerization of indene initiated by methyl ethyl ketone peroxide in liquid sulfur dioxide

Studies on the cationic polymerization of indene initiated by methyl ethyl ketone peroxide in liquid sulfur dioxide

Cationic polymerization of indene initiated by methyl ethyl peroxide in liquid sulfur dioxide

Cationic polymerization of indene initiated by methyl ethyl peroxide in liquid sulfur dioxide

Cationic polymerization of indene

Cationic polymerization of indene in methylene dichloride was effected by two stable carbonium ion salt initiators, tropylium hexachloroantimonate and xanthylium perchlorate, the former being more efficient. Very high conversions of monomer to polyindene were obtained with catalyst concentrations ∼10 −2 M. Molecular weights were approximately 10 000 and it is concluded that whilst initiation is fairly rapid and complete, active centres are lost by creation of more stable cationic species from polyindene chains. Mechanisms are proposed to account for the formation, during polymerization, of characteristically coloured species.