Molecular Weight Polybutadiene Research Articles

The component miscibility evolution during polymerization of the polybutadiene containing styrene solutions

In situ graft copolymerization of polystyrene (PS) on polybutadiene (PB) during polymerization of PB solution in styrene monomer was investigated to determine the performance of grafting process, chain structure of generated copolymers, and their effectiveness as compatibilizing agents for incompatible PS-rich and PB-rich phases. The amount of copolymers and their chain structures at different stages of polymerization were determined by gel permeation chromatography (GPC) curves of the reactive blends (taken directly from the reaction) and physical blends (physically prepared based on total composition of reactive blends). It was demonstrated that copolymer formation started from the early stage of polymerization and continued up to the phase inversion stage. In addition, PS grafting on PB occurred initially via single-chain attachment and then converted to a double-chain scenario later on. Compatibilizing efficiency of the copolymers was evaluated by Huggins coefficient (k H) obtained by performing dilute solution viscometry (DSV) on samples taken at different stages of conversions. The effect of molecular weight of PB on the grafting process and the effectiveness of copolymers generated were also studied. It was found that while compatibilizing role of the copolymers produced from high molecular weight PB (HPB) increases as conversion goes further, the compatibilizing efficiency of the copolymers produced from low molecular weight PB (LPB) shows a very sharp variation in a small range of conversion. Plotting k H of physical blends against weight fraction of PB molecules in solid content of the solutions (w PB) showed negative deviation from mixture law with a W-like pattern containing two minima with a maximum in between. While a negative deviation was assumed as indication of immiscibility of the components, upward deviation at middle values of w PB was attributed to molecular segregations that reduce the interface between the incompatible PS-rich and PB-rich phases.

Compliant phase reduces polymerization shrinkage in dental composite resin

AbstractCommercially available dental composite resins undergo polymerization shrinkage during curing, setting up internal stress that can result in debonding at the tooth‐composite interface, tooth fracture and composite failure. Debonding can also lead to marginal leakage and recurrent decay. The presence of a compliant phase, in this case polybutadiene in aggregate form with fumed silica, is shown to reduce polymerization shrinkage in the bis‐GMA/TEGDMA resin system. The addition of a small amount of the plasticizer triphenylethylene promoted additional reduction in cure shrinkage by reducing the glass transition temperature, Tg. A trend toward reduced cure shrinkage was noted as the polybutadiene : silica ratio decreased within each molecular weight of polybutadiene tested. The optimal formulation tested was determined to be 0.25 wt. % triphenylethylene in bis‐GMA with aggregates formed from polybutadiene of molecular weight 2–3 million, in a polybutadiene : silica ratio of 0.005. Shrinkage reduction in this system was ∼ 42% without loss of Knoop hardness. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2306–2310, 2005

Numerical Studies of the Effect of Constitutive Model Parameters as Reflecting Polymer Molecular Structure on Extrudate Swell

Abstract PolyFlow, a software package based on the finite element method was employed to simulate the extrudate swell for polybutadiene of various molecular weight (Mw) and molecular weight distribution (MWD). We calculated the relaxation spectra for the different samples and then inserted the spectra into a standard K-BKZ constitutive model used in the numerical simulations. Accurate predictions of MWD confirm the completeness of frequency range in the oscillatory shear experimental data. In turn, the wholeness of relaxation spectra as substantiated by MWD predictions, sustain the level of confidence when using constitutive models based on these spectra. We demonstrate the importance of using the full range of relaxation spectrum rather than a short range around typical shear rates for the accuracy of the numerical predictions. We found extrudate swell ratio (ESR) to be strongly dependent on MWD and stress conditions at the die exit.

Viscoelastic behavior of polybutadienes with high 1,4-microstructure and narrow molecular weight distribution

Polybutadienes (PBs) of narrow molecular weight distributions with high 1,4-microstructure were synthesized by sec-butyllithium-initiated, living polymerization. The shoulder-like anomalous behavior of the storage modulus G′(ω) in the terminal zone for PBs was studied using size exclusion chromatography (SEC) and rheometric mechanical spectrometry (RMS). It was found that a high-molecular-weight fraction in the PBs was the main reason for the occurrence of the shoulders. The linear viscoelastic spectra were successfully obtained by the Pade–Laplace method from experimental dynamic data, using either the dynamic storage, G′(ω), or loss, G"(ω), modulus. Both the dynamic moduli and stress relaxation in the linear regime were then calculated with reasonable precision. The feasibility of time–temperature–molecular weight superposition for PBs using this method was demonstrated. The dependencies of relaxation spectra on temperature and molecular weight were obtained by a fitting procedure. Thus, with a known reference state, the relaxation spectrum for a given molecular weight PB at a given temperature can be predicted. The predicted dynamic moduli are in good agreement with experimental data. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1315–1324, 1999

Ternary ABC block copolymers based on one glassy and two crystallizable blocks: polystyrene-block-polyethylene-block- poly(ɛ-caprolactone)

The hydrogenation of polystyrene-block-polybutadiene-block-poly(£-caprolactone) SBC triblock copolymers was performed in the presence of the Wilkinson catalyst RhCl(P(C 6 H 5 ) 3 ) 3 . Reaction conditions (hydrogen pressure, temperature and reaction time) were varied to ensure quantitative hydrogenation without detectable side reactions. Gel permeation chromatography showed no broadening of the molecular weight distribution during hydrogenation. The efficiency of the catalyst is markedly influenced by the molecular weight of the copolymer. Due to the presence of the polyethylene (PE) block, the resulting polymers exhibit a reduced solubility in comparison to the starting materials. Using differential scanning calorimetry (DSC), preliminary results about the crystallization and melting behavior of the PE-block were obtained. In the triblock copolymers, the PE-block showed a marked depression of the melting point and crystallinity when compared to pure hydrogenated polybutadiene of equivalent molecular weight and microstructure or to a comparable PE-block within a polyethylene-block-poly(e-caprolactone) diblock copolymer. A fractionated crystallization process of the PCL-block was observed when the PCL component in the hydrogenated triblock copolymers was present as a minor phase.

Measurements of craze velocities in polystyrene‐polybutadiene blends

AbstractNormally brittle polystyrene (PS) can be toughened effectively by the inclusion of a few weight percent of low molecular weight polybutadiene (PB). The PB, which can be made to phase separate into submicron sized, randomly dispersed pools, locally plasticizes the glassy phase in the vicinity of a growing craze; the resulting reduction in craze flow stress and increased craze velocity lead to significant enhancement of toughness when strain rates are below approximately 10−1 s−1. Craze velocities were measured in PS containing 1 to 5 wt % of a low molecular weight PB (2300 g/mol). The results were compared to a version of the interface convolution mechanism for craze growth that has been modified to account for the localized plasticization effect of the low molecular weight diluent. Addition of 5 wt % PB led to craze velocities that are three orders of magnitude larger than observed for pure PS. The model deviated significantly from the experimental data at the higher and of the PB concentration range studied here, but it did exhibit the general form of the observed dependence of craze velocity on PB content. © 1993 John Wiley & Sons, Inc.

Block Polymers Derived from Poly(ethylene Oxide) and Hydroxy-Terminated Polybutadiene

Abstract Block polymers of AB, BAB, and ABA type, derived from preformed poly(ethylene oxide) (PEO) of different molecular weight and hydroxy-terminated polybutadiene (HTPB) were prepared. Poly(ethylene oxide-b-butadiene) and poly(butadiene-b-ethylene oxide-b-butadiene) were prepared by reaction of PEO, which was previously endcapped with TDI, with HTPB at a 1:1 or 1:2 reactants molar ratio. Poly(ethylene-oxide-b-butadiene-b-ethylene oxide) were prepared by reaction of isocyanate-endcapped HTPB with PEO at a molar ratio of reactants of 2:1. High reaction yields were obtained. Correlation between tensile properties and water absorption with block polymer composition was found.

Extensional stresses during polymer flow in ducts

During the flow of high molecular weight, narrow-, and broad-distribution polybutadienes and polyisoprenes rheo-optical measurements were conducted of extensional stresses acting along the flow axis in the preentrance and entrance regions of the duct and of their subsequent relaxation in the duct. The extensional stresses increase in the preentrance region, reach their maximum values at a distance of two or three tenths of the duct width from its edges, and then relax. The position of the maximum extensional stress is independent of polymer characteristics, shear stresses in the duct, and shape of the entrance and dimensions of the rectangular duct. The dependence of the maximum extensional stress on the shear stress of the duct wall can be assumed to be linear for small values. The length of the stress relaxation zone depends on the shear stress at the duct wall and the molecular mass distribution. It is independent of the molecular masses in narrow-distribution polymers. For the polymers investigated, a generalized dependence was obtained for the reduced duct length over which the extensional stresses relax to zero from the reduced deformation rate. This dependence takes into account the characteristic polymer relaxation times and the value of the molecular mass of the chain between the fluctuation entanglement. A considerable decrease in the duct's length-to-width ratio leads to an increase in the maximum values of the extensional stresses. A decreases in the duct entrance angle causes a reduction in the rate of increase of extensional stresses, the maximum values, and the acceleration of the relaxation processes in the duct. A decrease in the ratio of the width of the preentrance region to the duct width leads to a reduction in the maximum in extensional stresses. It is shown that one of the causes for the instability of the polymer flow in the ducts can be the rupture of polymers due to their extension in the preentrance and entrance regions. Calculations were done that describe satisfactorily the relationship between the values of the maximum extensional stresses and the shear rate and stresses on the duct wall.

The possibility of determination of branching in polybutadiene of low molecular weight by ozonolysis

The possibility of determination of branching in polybutadiene of low molecular weight by ozonolysis