Diffusion Characteristics and Removal of Cyclohexane in Polyolefin Elastomer Melt

The diffusion coefficient of volatiles in polymer solutions is a crucial parameter to describe the mass transfer efficiency and ability of volatiles.In this research,polyolefin elastomer(POE)was used as a polymer,and cyclohexane was used as a volatile.A gravimetric analysis was applied to measure the diffusion coefficient of cyclohexane in POE.The devolatilization rate of the POE-cyclohexane system under different conditions was measured.The effects of temperature,film sample thickness,and initial concentration of volatiles on the devolatilization rate were discussed.Based on the devolatilization rate data,the average diffusion coefficient of cyclohexane in POE was obtained by fitting with a mathematical model.The experimental results indicate that the devolatilization rate increased with increasing temperature and initial concentration of volatiles,but it decreased with increasing sample thickness.As the thickness increased,the overall diffusion resistance increased.As the temperature increased,the molecular movement increased,resulting in the increase of average diffusion coefficient.The relationship between the diffusion coefficient of the POE-cyclohexane system and temperature follows the Arrhenius law.The diffusion activation energy E=6201.73 J/mol,and the pre-exponential factor of the diffusion coefficient D0=2.64×10^(-10) m^(2)/s.This work can provide basic data for exploring the devolatilization of POE polymers and serves as a useful reference for enhancing the effect of devolatilization.

A METHOD TO QUANTIFY CRAZING DEFORMATION BY TENSILE TESTS FOR POLYSTYRENE/POLYOLEFIN ELASTOMER IMMISCIBLE BLENDS

A method to quantify crazing deformations by tensile tests for polystyrene （PS） and polyolefin elastomer （POE） blends was investigated. The toughness of PS/POE blends, reflected by the Charpy impact strength, increased with the content of POE. SEM micrographs showed the poor compatibility between PS and POE. In simple tensile tests, it is very easy to achieve the ratio of crazing deformation, i.e. K by measuring the size changes of samples. The K values decreased with increasing the content of POE, and the deformations of PS/POE blends were dominated by crazing. The plots of the change of volume （△V） against longitudinal variation （△I） showed a linear relationship, and the slope of lines decreased with the content of POE. Measuring samples at the tensile velocities of 5 mm/min, 50 mm/min, and 500 mm/min respectively, the K values kept unchanged for each PS/POE blends.

Determination of the Henry’s Law Constant of Hexane in High-Viscosity Polymer Systems

The Henry’s law constant of volatiles in polymer systems is a crucial parameter reflecting the gas-liquid equilibrium,which is very important for devolatilization.In this research,polyolefin elastomer(POE)-cyclohexane and polydimethylsiloxane(PDMS)-hexane systems were studied,and the Henry’s law constant was obtained by measuring the gas phase equilibrium partial pressure when polymer solutions containing different mass fractions of volatiles reached a saturated state.The effects of temperature,type of volatiles,and polymer viscosity on the gas phase equilibrium partial pressure and Henry’s law constant of the volatiles were investigated.The results indicate that,with the increase of temperature and polymer viscosity,the gas phase equilibrium partial pressure and Henry’s law constant of volatiles increase.As temperature increases,the solubility of gas in liquid decreases.The relationship between the Henry’s law constant and temperature is consistent with the Arrhenius law.In the PDMS-hexane system,the gas phase equilibrium partial pressure and Henry’s law constant of n-hexane are higher than those of cyclohexane.The obtained Henry’s law constants can be used as a reference for perfecting the devolatilization process and improving the devolatilization effect.

Fractionation of Polyolefin Elastomer by a Modified SSA Technique

As an important part of semicrystalline polymer materials,polyolefin elastomers are widely used,and the in-depth analysis of their molecular chain structure information is of great significance to promote their rapid development.We show in this work an effort in characterizing a commercial polyolefin elastomer of ethylene/1-octene copolymer by a modified successive self-nucleation and annealing(SSA)technique.A small amount of linear polyethylene was blended with the ethylene/1-octene copolymer serving as nucleation agent during SSA.It turned out that a tiny fraction of linear polyethylene can significantly promote the crystallization of the copolymer during cooling from different annealing temperatures and increase the melting temperature of the fractions so that providing apparent methylene sequence length much closer to the real value than obtained by traditional SSA technique.

Ring-opening metathesis polymerization of cyclopropene derivatives towards polyolefin elastomer analogues

Polyolefin elastomers(POEs) are important reprocessable industrial materials with high strain-recovery performance. Traditional POEs are prepared from transition-metal-catalyzed polymerization of ethylene and α-olefins, while because of the complicated coordination polymerization mechanism, defining the actual distribution and length of alkyl branches in POEs is extremely challenging. We herein propose an alternative approach of synthesizing POE analogues from ring-opening metathesis polymerization(ROMP) of highly strained 3,3-alkyl-substituted cyclopropenes(CPEs). The structures of monomers and the substituents of Ru-catalysts are investigated in detail to evaluate the homobenzyl-substituted CPE derivative as a new living ROMP monomer. After copolymerization with cyclooctene and backbone hydrogenation, POE analogues with well-defined alkyl branches are prepared. Since the ROMP reactions have little isomerization and can also give good control of molecular weight and copolymer composition, it is hypothesized that this synthetic approach provides a novel platform to assist understanding the influence of branches on the properties of POEs.

Synthesis of Ultralow-Density Polyethylene Elastomers Using Triarylnaphthyl Iminopyridyl Ni(II)Catalysts

Recently,the chain-walking ethylene polymerization strategy has garnered widespread attention as an efficient and straightforward method for preparing polyolefin elastomers.In this study,a series of 2,4,8-triarylnaphthyl iminopyridyl nickel catalysts were synthesized and used in ethylene polymerization.These catalysts demonstrated moderate catalytic activity(105 g mol^(−1) h^(−1)),producing high-molecular-weight(up to 145.5 kg/mol)polyethylene materials with high branching degrees(75−95/1000C)and correspondingly low melting points.Detailed analysis using 13C NMR spectroscopy revealed that the polyethylenes primarily featured methyl and long-chain branches.Mechanical testing of the polyethylene samples obtained from catalysts Ni1−Ni3 exhibited moderate stress at break(4.64−6.97 MPa)coupled with a very high strain at break(1650−3752%),indicating their very good ductility.Furthermore,these polyethylenes showcased great elastic recovery abilities,with strain recovery values ranging from 72%to 85%.In contrast,the polyethylene produced by Ni4 displayed notably inferior tensile strength(0.16 MPa)and tensile recovery(43%).To the best of our knowledge,this study represents the inaugural utilization of a nickel iminopyridyl catalyst in the preparation of a polyethylene thermoplastic elastomer.