Determination of kinetic rate constants in electrochemically initiated anionic polymerization of 1,3-butadiene

The rate constants for electrochemically initiated polymerization were determined by employing a pulsing technique. An electrochemical titration was conducted in which polymer chains were initiated electrochemically, propagated in the absence of current, and terminated electrochemically. The concentrations of supporting electrolyte and monomer were chosen to correspond to those employed in electropolymerization syntheses. The temperature range ?10°C to ?72°C gave k_p = 1.45 × 10² exp {2600/RT}. The Arrhenius parameters are compared to those from previous studies and are interpreted in terms of ion-pair propagation. Precise control of molecular weight distributions is implicit from an accurate knowledge of the kinetic parameters and is reported separately.     

Triallylstannyllithium-allyllithium as an initiator for the anionic reversible chain transfer polymerization of 1,3-butadiene

The anionic polymerization of 1,3-butadiene using a novel metalloidal anion initiator, triallylstannyllithium (TALi)-allyllithium (ALi), was studied. The TALi-ALi initiated anionic polymerization of 1,3-butadiene gave the star polymer along with the linear polybutadiene (PBD). The star polymer consisted of three PBD branches and a central tin atom. What is striking is a fact that the number-average molecular weights (M_n) and molecular weight distribution of three PBD branches and linear PBD were almost identical. A reversible chain transfer polymerization mechanism, which includes the equilibrium between tri(macroallyl)-stannyllithium and macroallylic anion, is proposed. © 1996 John Wiley & Sons, Inc.     

Cationic polymerization of 1-ethoxy-1,3-butadiene

cis- and trans-1-Ethoxy-1,3-butadienes were polymerized by a variety of cationic agents in various solvents at ?78°C. The trans ether, which is the more stable isomer, was found to have greater polymerizability than the cis ether. The trans monomer gave polymers predominantly of the trans-1,4 type, whereas the cis monomer showed a tendency toward the formation of polymers having the microstructure of the 1,2 type. It was concluded that, in the cis ether, the carbon atom which is the most vulnerable to the attack of carbonium ions is the one at the 2-position, whereas, in the case of the trans isomer, the terminal 4-carbon is the most reactive center. The conclusion was confirmed from the results of acetal addition reaction catalyzed by boron trifluoride etherate. The marked contrast in the mode of reaction of the two isomeric ethers toward carbonium ions was interpreted in terms of the difference in the degree of bonding in the transition state.     

Anionic polymerization of hexafluoro-1,3-butadiene and characterization of the polymer

The present review describes the anionic polymerization of hexafluoro-1,3 -butadiene (HFBD) and the characterization of the polymer. HFBD which is hardly polymerized under radical polymerization conditions yielded the polymer with cesium and rubidium compounds as initiators in moderate conditions. X-ray photoelectron spectra and Raman spectra showed the structure of the polymer was similar to that of poly(hexafluoro-2-butyne). The polymerization mechanism, an addition reaction of the propagating anion to the 2-carbon of HFBD followed by isomerization of the propagating end group to yield the polyene structure, is proposed from the results of the investigation of initiation reaction and the structure of the polymers. Poly(HFBD) shows higher thermostability than poly(tetrafluoroethylene) in spite of bearing functional -CC-groups in the polymer main chain.     

Radiation-induced polymerization of 2,3-dimethyl-1,3-butadiene clathrate in deoxycholic acid

Poly(dimethylbutadiene) (PDMB) was synthesized through the inclusion polymerization technique, by γ-irradiation of a clathrate of 2,3-dimethyl-1,3-butadiene in deoxycholic acid (DOCA) at 75, 150, 320 and 430 kGy. The resulting inclusion complexes PDMB@DOCA were studied by FTIR spectroscopy and by thermal analysis (DTA, TGA and DTG). Pure PDMB was isolated by extracting the complex PDMB@DOCA with ethanol. The best sample in terms of purity was that prepared at 75 kGy, while the other samples prepared at higher doses suffered of DOCA grafting on PDMB chains. Pure PDMB isolated from PDMB@DOCA complex was studied by FT-IR spectroscopy and by thermal analysis in comparison to a reference highly crystalline and ≈=100% trans-1,4-PDMB prepared by inclusion polymerization in thiourea and in comparison to PDMB prepared by emulsion polymerization. A lower degree of regularity and crystallinity has been found on the PDMB sample prepared as inclusion compound in DOCA in comparison to the reference PDMB obtained by inclusion polymerization in thiourea.     

Effect of enthalpy of polar modifiers interaction with n-butyllithium on the reaction enthalpy,kinetics and chain microstructure during anionic polymerization of 1,3-butadiene

The influence of interaction enthalpy (ΔH_MOD/BuLi) of μ, σ, σ+μ and σ-μ complexing polar modifiers with n-butyllithium on the 1,3-butadiene anionic polymerization enthalpy (ΔH_BD), polymerization reaction rate (k_p) and polybutadiene microstructure was studied. It has been found that enthalpy of interaction depends on complex type, molar ratio of polar modifier to n-butyllithium (MOD/BuLi) and temperature. For the first time it has been proven that with increasing ΔH_MOD/BuLi the content of 1,2 butadiene (vinyl) units in the chain increases individually for each complex type but the value of ΔH_BD decreases similarly for all complexes containing σ-donor groups, exhibiting linear nature. Since ΔH_MOD/BuLi controls the content of butadiene isomeric structures in the chain its value was compared with polymerization reaction rate, ranging from ∼46 to ∼5500 moL/L·min, and discussed on mechanistic level.     

Polymerization and copolymerization of 2-phthalimidomethyll 1,3-butadiene. II. Kinetic study of the polymerization of 1,3-butadiene and of the copolymerization of 1,3-butadiene with 2-phthalimidomethyl 1,3-butadiene initiated by bis-(η3-allyl nickel trifluoroacetate)

The kinetics of the polymerization of 1,3-butadiene initiated by bis(η³-allyl nickel trifluoroacetate) prepared in benzene was studied in methylene chloride at 40°C. The reaction is first order with respect to the monomer, second order with respect to the catalyst in contrast to the case in which solvent is benzene. We have shown that the presence of a polar molecule (fe, N-methyl phthalimide) decreases the overall rate of polymerization. The apparent reactivity ratios for the system 2-phthalimidomethyl 1,3-butadiene (1)-1,3-butadiene (2) are r₁ = 0.65 ± 0.006 and r₂ = 0.48 ± 0.015.     

Kinetics and molecular weights distribution study of neodymium-catalyzed polymerization of 1,3-butadiene

The homopolymerization of 1,3-butadiene in a stirred batch reactor with the catalytic system Nd octoate/diethyl-aluminium chloride/triisobutyl-aluminium in n-heptane was studied. The effect of various reaction conditions on especially high conversion and molecular weight is reported. Polymerization is shown to be first order with respect to both monomer and neodymium. Molecular weights are high and broadly distributed. Chain transfer to triisobutylaluminium is the main factor governing molecular weight development. A mechanism of polymerization is presented with the chain transfer process incorporated. © 1995 John Wiley & Sons, Inc.     

The dual-site alternating cyclocopolymerization of 1,3-butadiene with ethylene

The copolymerization of ethylene with 1,3-butadiene was studied with the series of ansa-metallocenes Me2Si(Cp)(9-Flu)ZrCl2 (1), Me2Si(1-Ind)(9-Flu)ZrCl2 (2), and Me2Si(9-Flu)2ZrCl2 (3) with methylaluminoxane (MAO) as cocatalyst. The catalyst 2/MAO yields a cyclocopolymer composed of two ethylene monomer units for every one butadiene in a novel periodic architecture of 1,2-enchained cyclopentane units separated by three methylenes. The high butadiene content in the copolymer and the high selectivity for alternating cyclocopolymerization to form methylene-1,2-cyclopentane units implicate a dual-site mechanism where butadiene and ethylene are enchained at different coordination sites.     

Comparison of the electrophilic and free-radical addition of halogens with hexafluoro-1,3-butadiene and 1,3-butadiene

Ionic and photochemical reaction of chlorine (Cl₂), bromine (Br₂) and iodine monochloride (ICl) to hexafluoro-1,3-butadiene (1) and 1,3-butadiene (2) were carried out under conditions that would provide product distributions under controlled ionic or free-radical conditions. Product distributions for ionic reaction of Cl₂ and Br₂ with 1 are similar and suggest a weakly-bridged halonium ion species. Theoretical calculations support weakly-bridged chloronium and bromonium ions for both dienes 1 and 2. There are more of the 1,4-dihalo-2-butene products from ionic halogenation of 1 than 2 which correlates with the greater charge density on carbon-4 of halonium ions from 1. Ionic and free-radical reactions of ICl with 1 give 8 and 2% of 3-chloro-4-iodohexafluoro-1-butene and 4-chloro-3-iodohexafluoro-1-butene, respectively. The minor cis-1,4-dihalo-2-butene products from 1 and 2 are reported when formed.     

Neodymium Ziegler-Natta catalysts: Evaluation of catalyst ageing effect on 1,3-butadiene polymerization

Catalysts constituted by neodymium versatate, diisobutylaluminium hydride and t-butyl chloride were used in this work. After their synthesis, they were aged at 40 °C for 48 h. Afterwards, they were maintained at 10 °C for more 5, 15, 40, 80, 160 and 250 days and finally the aged catalysts were evaluated in butadiene polymerization. The polybutadienes were characterized by size exclusion chromatography (SEC) to determine the molecular weight characteristics and by infrared spectroscopy (FTIR) to determine the microstructure. The aim of this work is to evaluate the effect of ageing time on 1,4 polymerization of butadiene. The results showed that the stereoselectivity of the active sites was not affected by the ageing conditions. However, the catalyst activity increased for long times of ageing.     

Living polymerization of 1,3-butadiene catalyzed by half-titanocene complex bearing dibenzhydryl-substituted aryloxide ligand

Half-titanocene complexes bearing dibenzhydryl-substituted aryloxide ligands(2a-2d) were prepared. Among them, 2c adopted a three-legged distorted tetrahedral geometry evidenced by X-ray crystallography. The poly-1,3-butadiene with high molecular weight and narrow molecular weight distribution was obtained by using these complexes as the catalysts activated with methylaluminoxane(MAO). The catalytic activities of the complexes depended on their structures. The Ti―O―C bond in the complexes with large angle afforded them with higher activity, while Cp*-based complexes exhibited lower activities than the Cp-based analogues. The activity of complex increased with increasing the polymerization temperature while the selectivity remained no change, indicating the high thermal stability. Furthermore, the polymerization of 1,3-butadiene catalyzed by 2a/MAO at 0 °C has been found in a living fashion.     

A Nd-carboxylate catalyst for the polymerization of 1,3-butadiene: The effect of alkylaluminums and alkylaluminum chlorides

The ternary neodymium-based catalyst for the polymerization of 1,3-butadiene, Nd(versatate)₃/Ali-Bu₂H/tert-butyl chloride, has been examined with respect to the effects of a range of alkylaluminums and alkylaluminum chlorides. Using either pre-formed or in situ catalysts, observations pertaining to catalyst activity and physical state and the characteristics of the final polymer are discussed. The catalyst activity series with the type of alkylaluminum was found to be: Aln-Pr₃ ? Aln-Dodec₃ = Aln-Oct₃ = Aln-Hex₃ > Ali-Bu₂H > Ali-Bu₃ > AlEt₃ ? AIMe₃. Polybutadiene cis content was found to vary with the type of alkylaluminum used. Pre-formed catalysts using methylaluminum chlorides as chloride source were found to be the most active; AlMe₂Cl chloride gave the highest activity. The activity of in situ catalysts prepared using alkylaluminum chlorides was found to be independent of alkylaluminum chloride structure. Polybutadiene prepared using catalysts based on different alkylaluminums and alkylaluminum chlorides was found to decrease in cis content with conversion. © 1995 John Wiley & Sons, Inc.     

Palladium-catalyzed dimerization disilylation of 1,3-butadiene with chlorosilanes

[reaction: see text] 1,3-Butadiene reacted with chlorosilanes and Grignard reagents at 20 degrees C in the presence of a catalytic amount of Pd(acac)(2) to give disilylated dimers 2 regioselectively, which have two silyl groups (R(3)Si) at the 3- and 8-positions of a 1,6-octadiene skeleton. When phenyl- or allyl-substituted chlorosilanes were used, coupling product was obtained stereo- as well as regioselectively, giving rise to only (E)-olefins. It is proposed that Pd-ate complexes play important roles in both C-Si bond-forming processes.     

Aminobutadienes. V. Polymers of 1-phthalimido-1,3-butadiene and 1-succinimido-1,3-butadiene

The radical polymerizations of 1-phthalimido-1,3-butadiene (1-PB) and 1-succinimido-1,3-butadiene (1-SB) were carried out in bulk and in solution. The polymers obtained had reduced viscosities in the ranges of 1.0–4.0 (1-PB) and 0.2–0.6 (1-SB). Both polymers had a similar softening point of 190–200°C. The radical polymerization of 1-phthalimido-1,3-butadiene clearly showed a tendency to give crosslinked polymer. Steric arguments about these polymer structures as a result of the infrared and ozonolysis data led to the conclusion that these polymers contained approximately 20% of the 3,4 form but no 1,2 configuration, and, therefore, that the 1,4 addition was preferred.