• Elastomers and Composites
• /
• v.41 no.2
• /
• pp.116-124
• /
• 2006

Cloud-point data to $160^{\circ}C$ and 1,000 bar are presented with poly(ethylene-co-15.3 mole% octene) copolymers ($PEO_{15}$) in pure 1-octene and mixtures of ethylene - 1-octene. The cloud-point curves for $PEO_{15}$ - ethylene - 1-octene mixture dramatically increase in pressure to as high as 1,000 bar with an increasing ethylene concentration. At ethylene concentrations less than 18 wt%, the ternary mixture has bubble- and cloud-point curves. As the ethylene concentration of the ternary mixture increases, the bubble-point curve and the single-phase region reduce. The reduction in the single phase region with increasing ethylene concentrations is the result of reduced dispersion interactions between $PEO_{15}$ and the mixed solvent. The single-phase region decreases with increasing temperatures when ethylene concentrations are lower than 36 wt%, whereas the single-phase region increases with temperatures at ethylene concentrations greater than 50 wt%. At ethylene concentrations greater than 50 wt% the effect of the polar interactions of the mixed solvent, which is unfavorable to dissolve PEO, is greater than the effect of the density of the mixed solvent. Therefore, the cloud-point pressures increase with a decreasing temperature. However, at ethylene concentrations less than 50 wt%, the cloud-point pressures decrease with temperature, because the effect of the polar interactions is less than the density effect.

• Elastomers and Composites
• /
• v.38 no.1
• /
• pp.51-56
• /
• 2003

Cloud-point and bubble-point data to $170^{\circ}C$ and 50 bar are presented for four different solvents, normal pentane. n-hexane, n-heptane, and n-octane with poly(ethylene-co-42 wt% octene) ($PEO_{42}$) copolymer. The pressure-concentration isotherms measured for $PEO_{42}$ - normal pentane have maximums at around 5 wt% of the copolymer concentrations in the solution. $PEO_{42}$- normal pentane system exhibits LCST-type phase behavior at temperatures greater than $130^{\circ}C$. Below $120^{\circ}C$, bubble-point type transitions are observed. However, the binary mixtures for $PEO_{42}$ in n-hexane, n-heptane, and n-octane have only bubble-point type transitions at the pressure-temperature region investigated in this study. The single-phase region of PEO - alkane mixtures increases with the molecular size of alkane solvent due to the increasing dispersion interactions between PEO and the alkane.

• Elastomers and Composites
• /
• v.40 no.4
• /
• pp.277-283
• /
• 2005

LV transition curves for poly(ethylene-co-15.3 mol% octene) ($PEO_{15}$) and poly(ethylene- co-17.0 mol% octene) ($PEO_{17}$) were measured in cyclo-pentane and cyclo-hexane. Between $40{\sim}150^{\circ}C$, the LV curve for ($PEO_{15}$ + cyclo pentane) located $1.1{\sim}2.7$ bar higher than that for ($PEO_{17}$+ cyclo-pentane). In cyclo-hexane, similar behavior was observed for $PEO_{15}$ and $PEO_{17}$ solution except the pressure difference reduced to $0.9{\sim}l.6$ bar. If the backbone structure of $PEO_{15}$ were identical to that of $PEO_{17}$, the LV line for $PEO_{17}$ would locate at high pressures than that for $PEO_{15}$, since the number average molecular weight of $PEO_{17}$ (Ave. Mn=153,040) is 1.9 times higher 4han that of $PEO_{15}$ (Ave. Mn=82,200). The difference in the octene comonomer content between $PEO_{15}$ and $PEO_{17}$ is only 1.7 mole%, nevertheless this small difference in the backbone structure of the PEO greatly affected the location of the L-V curves in the mixtures comprised of PEO and cyclo-alkane.

• Applied Chemistry for Engineering
• /
• v.18 no.5
• /
• pp.516-521
• /
• 2007

The copolymerization characteristics of a newly-synthesized catalyst, $rac-Me_2Si(2-p-tolylindenyl)_2ZrCl_2$, and its analogue, $rac-Me_2Si(Ind)_2ZrCl_2$, were examined in the ethylene/1-octene copolymerization while varying the concentration of 1-octene in the reaction mixture. The activity of $rac-Me_2Si(2-p-tolylindenyl)_2ZrCl_2$ catalyst was decreased with increase of comonomer concentration, which is different from the usual comonomer effect of the metallocene catalysts with a bridge structure. The contents of 1-octene in the copolymer from the catalyst with 2-p-tolyl substituent were higher than those from the catalyst without that substituent. The melting point, crystallinity, and molecular weight decreased with comonomer content which was more apparent for $rac-Me_2Si(2-p-tolylindenyl)_2ZrCl_2$ catalyst.

• Advances in materials Research
• /
• v.6 no.3
• /
• pp.303-316
• /
• 2017

In this article, novel olefin polymerization catalyst with lower cost and simple synthetic process were developed, $ArOTiCl_3$ complexes [$(2-OMeC_6H_4O)TiCl_3(C1)$, $(2,4-Me_2C_6H_3O)TiCl_3(C2)$, $TiCl_3(1,4-OC_6H_4O)TiCl_3(C3)$, $TiCl_3(1,4-OC_6H_2O-Me_2-2,5)$ $TiCl_3(C4)$] and corresponding $(ArO)_2TiCl_2$ complexes [$TiCl_2(OC_6H_4-OMe-2)_2(C5)$ and $TiCl_2(OC_6H_3-Me_2-2,6)_2(C6)$] have been synthesized by the reaction of $TiCl_4$ with phenol, all these complexes were well characterized with $^1H$ NMR, $^{13}C$ NMR, MASS and EA. When combined with methylaluminoxane (MAO), the $ArOTiCl_3/MAO$ system shows high activity for ethylene copolymerization with 1-octene and copolymer was obtained with broaden molecular weight distribution (MWD). The $^{13}C$ NMR result of polymer indicates that the 1-octene incorporation in polymer reached up to 8.29 mol%. The effects of polymerization temperature, concentration of polymerization monomer and polymerization time on the catalytic activity have been investigated.

• Macromolecular Research
• /
• v.13 no.4
• /
• pp.297-305
• /
• 2005

The compatibilizing effect of maleic anhydride (MA) in the immiscible blends of EVA22 (vinyl acetate content 22%)/ethylene-${\alpha}$-olefin copolymers with 1-butene (EtBC) and 1-octene (EtOC)) comonomers was studied. By adding 1, 2, and 3 phr of MA in the presence of dicumylperoxide, the morphology, tensile strength at break, and 100 and 300 % modulus of EVA22/EtBC and EVA22/EtOC blends were significantly enhanced. The melting point and crystallization point depression were observed upon the addition of MA. The changes in the ${\beta}$ transition and glass transition temperature of ethylene-${\alpha}$-olefin copolymers and ethylene-vinyl acetate copolymers, respectively, indicate that MA plays a role of compatibilizer for these immiscible blends. The TGA thermograms, measured from the blends with MA, show that thermal stability is slightly enhanced with MA, indicating that MA acts as a reinforcing agent either by grafting or crosslinking with other copolymers.

• Macromolecular Research
• /
• v.8 no.1
• /
• pp.34-43
• /
• 2000

The melt rheology of four binary blends of ethylene 1-octene copolymers (EOCs) which consist of one component by Ziegler-Natta and another by metallocene catalysts, was studied to elucidate miscibility in the melt by using torsion rheometer at 200$\^{C}$ and different shear rates. The four blend systems, designated into the FA+FM, SF+FM, RF+EN, and RF+PL blend, are divided and interpreted based on the melt index (MI), the density and the comonomer contents. The melt viscosity such asη', η", and η$\^$*/ is weight average value if the comonomer contents are similar, otherwise they show different manner. The experimental resole are analyzed based on the Cole-Cole plot of logη' uersus log η", the logarithmic plots of the dynamic storage modulus (G') versus the dynamic loss modulus (G") for various blend compositions, and the melt viscosity of 11', n", and f" as a function of blend compositions. As a cerise-quence, the FA+FM blend is miscible, but the SF+FM, RF+EN, and RF+PL blends are not in the melt. Thus miscibility of the blends studied in this communication is suggested to strongly influence by the comonomer contents rather than the density or the MI.

• Transactions of the Korean Society of Automotive Engineers
• /
• v.18 no.1
• /
• pp.74-85
• /
• 2010

In order to formulate the compounded polypropylene(C-PP) which is suitable to an automotive door trim panel, 9 sorts of properties were measured after manufacturing the C-PP using an extruder and an injection machine with polypropylene(PP), ethylene-octene rubber(EOR) and talc. Mixture design, especially extreme vertices design, in DOE with MINITAB - commercial software was used to analyze the data. The relations between each property and each component, for example, $y=0.00907222x_1+0.00870556x_2+0.0155722x_3$ for specific gravity, were found out by the regression analysis and the variance analysis. The optimized formulation of the C-PP for an automotive door trim panel was acquired at PP(77.6962), EOR(11.0238) and talc(10.2800) by use of the response optimizer(mixture) in MINITAB.

• Elastomers and Composites
• /
• v.47 no.4
• /
• pp.329-335
• /
• 2012

In this study, we synthesized poly(ethylene-ter-high ${\alpha}$-olefin-ter-p-methylstyrene) using Zr metallocene catalyst/borate type cocatalyst system. Various effects of the high ${\alpha}$-olefin (1-hexene, 1-octene, 1-decene, and 1-dodecene) were observed. The structure and composition of the terpolymers were characterized using $^{13}C$ NMR and $^1H$ NMR. Catalytic activity, polymer yield, molecular weight and molecular weight distribution were analyzed according to the chain length of high ${\alpha}$-olefin. We determined morphology, crystallinity and thermal properties of the terpolymers.

• Elastomers and Composites
• /
• v.55 no.4
• /
• pp.263-269
• /
• 2020

Novel flexible terpolymers with a reactive moiety were synthesized by coordination polymerization with a metallocene catalyst and a cocatalyst system. C2-symmetric rac-Et(Ind)2ZrCl2 and tri-iso-butylaluminum/dimethylanilinium tetrakis (pentafluorophenyl) borate were employed as the catalyst and cocatalyst, respectively. We synthesized reactive terpolymers consisting of ethylene, a high α-olefin content (1-hexene, 1-octene, 1-decene, and 1-dodecene), and divinylbenzene. The structure and composition of the terpolymers were characterized by 1H-nuclear magnetic resonance analysis. The catalytic activity, polymer yield, molecular weight, and molecular weight distribution were measured as functions of the chain length and high content of α-olefins. Furthermore, the thermal properties and crystallinity of the terpolymers were determined by differential scanning calorimetry and wide-angle X-ray scattering.