A rheological method for selecting nano-kaolin powder as filler in SBR rubber

This paper shows that the stiffness of styrene-butadiene solid rubber with added kaolin powder is related to the yield stress of kaolin dispersion in liquid polybutadiene rubber up to the percolation threshold.For five kinds of kaolin powder,the value of τ spans the range of 100-430Pa,while the corresponding compressive elastic constant of SBR varies from 12 to 21MPa.A relationship between τ° and ΔE*i/E*R is proposed.Critical examination of these data infers that kaolin powder dispersed in solid rubber matrix acts as an additive which decreases the random movement of the polybutadiene chains.Consequently,dispersions of nano-particles in liquid and in solid SBR are considered to be related,thus leading to a rheological method for selecting nano-particles as fillers in solid SBR.     

Diversified Applications of Chemically Modified 1,2‐Polybutadiene

Commercially available 1,2‐PB was transformed into a well‐defined reactive intermediate by quantitative bromination. The brominated polymer was used as a polyfunctional macroinitiator for the cationic ring‐opening polymerization of 2‐ethyl‐2‐oxazoline to yield a water‐soluble brush polymer. Nucleophilic substitution of bromide by 1‐methyl imidazole resulted in the formation of polyelectrolyte copolymers consisting of mixed units of imidazolium, bromo, and double bond. These copolymers, which were soluble in water without forming aggregates, were used as stabilizers in the heterophase polymerization of styrene and were also studied for their ionic conducting properties.

     

用Co(naph)2-Al2(C2H5)3Cl3-P(OPh)3催化体系合成中乙烯基液体聚丁二烯

为获得适中乙烯基含量的液体聚丁二烯为目的, 对Co(naph)2-Al2(C2H5)3Cl3-P(OPh)3催化体系进行了较为系统的研究, 考察了该体系的催化剂配比、浓度及供电子试剂对分子量、微观结构和转化率的影响. 实验结果表明, 该体系在一定的条件下可以制备出分子量在700~3500、1,2结构含量在35%~40%且转化率高于55%的液体聚丁二烯.     

Synthesis of hydroxyl-terminated polybutadiene possessing high content of 1,4-units via anionic polymerization

<正>The hydroxyl-terminated polybutadiene(HTPB) possessing high content of 1,4-units was synthesized by anionic polymerization of butadiene,using alkyllithium containing silicon-protected hydroxyl group as initiator and cyclohexane as solvent.The polymers were characterized by GPC,IR and ~1H-NMR.The mechanical properties of cured films were also evaluated.The results show that the content of 1,4-units for HTPBs made by anionic polymerization reaches up to 90%.The molecular weight distribution is very narrow(≤1.05).The functionality of hydroxyl groups approaches 2.Compared with free radical HTPB,the elongation at break of anionic HTPB films increased by 70%,while the tensile strength remained nearly unchanged.This new HTPB can be very useful in solid propellant.     

Initiator‐fragment incorporation radical copolymerization of vinyl acetate and 1,2‐polybutadiene as a multivinyl monomer

The copolymerization of vinyl acetate (VAc) with 1,2‐polybutadiene (1,2‐PB; 85.5% 1,2‐units and 14.5% 1,4‐units) as a multivinyl monomer was carried out at 80 °C in dioxane with dimethyl 2,2′‐azobisisobutyrate (MAIB) at high concentrations (0.10–0.50 mol/L) as an initiator. The copolymerization of 1,2‐PB [0.80 mol/L (monomer unit)] and VAc (1.20 mol/L) with MAIB (0.30 mol/L) for 4 h proceeded homogeneously without gelation to yield a soluble copolymer. The resulting copolymer was divided into methanol‐ and n‐hexane‐insoluble parts, of which the yields based on the total weight of the comonomers and initiator were 46 and 20%, respectively. The methanol‐insoluble part consisted of the fractions of the 1,2‐PB units with (9 mol %) and without (39 mol %) an intact double bond, the 1,4‐PB unit (8 mol %), the VAc unit (32 mol %), and the methoxycarbonylpropyl group (12 mol %) as the MAIB fragment, whereas the hexane‐insoluble one was composed of the fraction of the 1,2‐PB units with (4 mol %) and without (17 mol %) a double bond, the 1,4‐PB unit (4 mol %), the VAc unit (60 mol %), and the methoxycarbonylpropyl group (15 mol %). The use of higher concentrations of 1,2‐PB and VAc and lower concentrations of MAIB resulted in gelation. The cast film from a chloroform solution of the methanol‐insoluble part contained spherical pores organized in a hexagonal way with a monodisperse pore size of 3 μm. The copolymer molecules seemed to be arranged in an ordered way on the surface layer of the pores, as shown by an optical microscopy image under crossed polarizers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2328–2337, 2006     

Synthesis of polybutadiene‐based particles via dispersion ring‐opening metathesis polymerization

Latex particles based on 1,4‐polybutadiene were synthesized via dispersion ring‐opening metathesis copolymerization of 1,5‐cyclooctadiene with a α‐norbornenyl poly(ethylene oxide) macromonomer. Stable but polydisperse colloidal dispersions in the 50 nm to 10 μm size range were obtained. In this work, particular attention was paid to the effects of the kinetics of copolymerization on the structure of the graft copolymers formed and on the onset of turbidity. Strategies to prepare monodisperse polybutadiene particles were also designed through the growth of a polybutadiene shell from a well‐defined polynorbornene seed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1154–1163, 2004     

Interaction of Polystyryl Radical with Tris Azido-Iron(III) Complex

The polymerization of styrene initiated by 2,2′-azobisisobutyro-nitrile (AIBN) had been studied in N, N-dimethylformamide (DMF) at 60°C in presence of tris azido-iron(III) complex. The complex was prepared in situ by mixing solid sodium azide with hexakis(N, N-dimethylformamide)iron(m) perchlorate, [Fe(DMF)₆] (ClO₄)₃, in the ratio 3:1. The nature of the complex formed was established by Job's method. The equilibrium constant for Fe³⁺ + 3N₃ ^? ? Fe(N₃)₃ determined by the limiting logarithmic method is 6.14 ± 10⁶ liter³/mole³. The velocity constant for the polystyryl radical towards the complex is 3.13 ± 10⁴ liter/mole-sec.     

Circularly polarized emission from a narrow bandwidth dye doped into a chiral nematic liquid crystal

We report on circularly polarized light emitted from a chiral nematic liquid crystal doped with a luminescent organolanthanide dye. The organolanthanide emission displays an extremely narrow spectral bandwidth of Δ λ_E≈ 8 nm. This is considerably narrower than the CNLC selective reflection bandwidth Δ λ_R≈60 nm. When conventional dyes with broader emission bandwidths are dissolved into CNLCs, the average degree of circular polarization g of emitted light is reduced from the maximum degree g _MAX ; this is due to the overlap of the emission band with the reflection band edges, and spectral regions outside the reflection band. Here, however, we can place the entire emission band inside the reflection band and achieve g ≈ g _MAX=1.27. Furthermore, a high degree of circular polarization is maintained under off-axis viewing up to a viewing angle of ≈ 30° to the normal.     

Crystallization kinetics and melting behavior of syndiotactic 1,2‐polybutadiene

Differential scanning calorimetry was used to investigate the isothermal crystallization, subsequent melting behavior, and nonisothermal crystallization of syndiotactic 1,2‐polybutadiene (st‐1,2‐PB) produced with an iron‐based catalyst system. The isothermal crystallization of two fractions was analyzed according to the Avrami equation. The morphology of the crystallite was observed with polarized optical microscopy. Double melting peaks were observed for the samples isothermally crystallized at 125–155 °C. The low‐temperature melting peak, which appeared approximately 5 °C above the crystallization temperature, was attributed to the melting of imperfect crystals formed by the less stereoregular fraction. The high‐temperature melting peak was associated with the melting of perfect crystals formed by the stereoregular fraction. With the Hoffman–Weeks approach, the value of the equilibrium melting temperature was derived. During the nonisothermal crystallization, the Ozawa method was limited in obtaining the kinetic parameters of st‐1,2‐PB. A new method that combined the Ozawa method and the Avrami method was employed to analyze the nonisothermal crystallization of st‐1,2‐PB. The activation energies of crystallization under nonisothermal conditions were calculated. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 553–561, 2005     

Synthesis and characterization of model polybutadiene‐1,4‐b‐polydimethylsiloxane‐b‐polybutadiene‐1,4 copolymers

Model copolymers of poly(butadiene) (PB) and poly(dimethylsiloxane) (PDMS), PB‐b‐PDMS‐b‐PB, were synthesized by sequential anionic polymerization (high vacuum techniques) of 1,3‐butadiene and hexamethylciclotrisiloxane (D₃) on sec‐BuLi followed by chlorosilane‐coupling chemistry. The synthesized copolymers were characterized by nuclear magnetic resonance (¹H NMR), size‐exclusion chromatography (SEC), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). SEC and ¹H NMR results showed low polydispersity indexes (M_w/M_n) and variable siloxane compositions, whereas DSC and TGA experiments indicated that the thermal stability of the triblock copolymers depends on the PDMS composition. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2726–2733, 2007