• Korea-Australia Rheology Journal
• /
• v.13 no.2
• /
• pp.83-87
• /
• 2001

The morphology and mechanical properties of the blends of a syndiotactic polystyrene (SPS) and poly-styrene-block-poly(ethylene-co-butylene)-block-polystyrene copolymers (SEBS) with various polystyrene block contents are studied. Mechanical properties, especially elongation at break and impact strength (IS), of the blend depend upon the morphology and interfacial adhesion, which in rum are affected by the viscosity ratio of constituent components and the styrene block content in SEBS. The IS of a blend was affected by the combined effect of rubber content and the interfacial adhesion. A maximum IS was found for a blend with the weight fraction of the PS block in an SEBS of 0.18. The IS of blends with smaller weight fractions of the PS block exhibited lower due to poor interfacial adhesion between SPS/SEBS in spite of a larger amount of rubber block. On the other hand, the IS of blends with larger weight fraction of the PS block becomes smaller due to lower amounts of rubber block in spite of better interfacial adhesion.

• Polymer(Korea)
• /
• v.35 no.4
• /
• pp.314-319
• /
• 2011

The syndiotactic and atactic poly (2-N-carbazoylrnethyl) styrenes were obtained by a half-titanocene catalyst and a radical initiator for the investigation of photophysical properties, especially excimer formation. The atactic polymer exhibited only monomer emission, but the syndiotactic polymer showed both excimer emission and monomer emission resulting from the partial overlapping arrangement of carbazole pendants, The emission band of syndiotactic polymer was considerably dependent on solution concentration and temperature, however atactic polymer was independent because the excimer formation of syndiotactic helical conformation was more favorable than that of the random coil conformation of atactic polymer.

• Polymer(Korea)
• /
• v.27 no.6
• /
• pp.603-608
• /
• 2003

Syndiotactic polystyrene (s-PS) presents a very complex polymorphic behavior depending on the sample preparation history and exhibits a solid-solid phase transition. Each different polymorphic structures of the s-PS sample were prepared by annealing the samples from room temperature to 220 $^{\circ}C$. The structural changes induced by annealing were investigated using FTIR and FT-Raman spectroscopy. Although the crystallization kinetics of s-PS are difficult to investigate with DSC due to its fast crystallization rate, it was possible to determine crystallinity changes in the s-PS sample using infrared characteristic peaks with Beer-Lambert's law.

• Proceedings of the Korean Fiber Society Conference
• /
• 1996.10a
• /
• pp.185-189
• /
• 1996

• Polymer(Korea)
• /
• v.30 no.1
• /
• pp.64-69
• /
• 2006

A series of dinuclear half-sandwich titanium complexes with aryloxy substituent at titanium$[(\eta^5-cyclopentadienyl)(aryloxy)TiCl_2]_2[(CH_2)_n]$ (n=3, n=6, n=9) have been successfully synthesized and their styrene polymerization properties have been investigated. All complexes are characterized by $^1H\;NMR,\;^{13}C\;NMR$, elemental analysis, and mass spectrometry. In order to examine the catalytic properties of the dinuclear complexes styrene polymerization has beer conducted in the presence of MMAO. It was found that (i) all the prepared complexes were very effective catalyst for the production of SPS (syndiotactic polystyrene), (ii) the complex with the longest bridge between the two active sites exhibited greatest catalytic activity among the three catalysts, but produced SPS with the smallest molecular weight, (iii) the activities of dinuclear half-titanocens with aryloxy substitution at titanium metal were greater than those of the chloride substituted compounds. These results indicate that not only the nature of the bridge between the two active sites but also the property of substituents at the metal exert a significant influence on the polymerization behaviors of the dinuclear half-titanocene.

• Bulletin of the Korean Chemical Society
• /
• v.25 no.11
• /
• pp.1648-1652
• /
• 2004

A set of unprecedented syndiospecific dimethyl- and diethylamino-functionalized polystyrenes was prepared by catalytically polymerizing the corresponding monomers using (pentamethylcyclopentadienyl)titanatrane/MMAO catalytic system. Dialkylamino-functionalized styrene monomers were synthesized by Wittig reaction from the corresponding aldehyde in high yield. The resulting polymers are soluble in polar organic solvents such as THF and show good thermal stability. The chemical transformation of the syndiospecific poly(4-diethylaminostyrene) also gave new polar polymers, namely syndiotactic poly(4-diethylaminostyrene hydrochloride), which is unattainable by traditional synthetic methods.

• Fibers and Polymers
• /
• v.6 no.1
• /
• pp.19-27
• /
• 2005

High-speed melt spinning of syndiotactic polystyrene was carried out using high and low molecular weight poly­mers, HM s-PS and LM s-PS, at the throughput rates of 3 and 6 g/min. The effect of take-up velocity on the structure and properties of as-spun fibers was investigated. Wide angle X-ray diffraction (WAXD) patterns of the as-spun fibers revealed that the orientation-induced crystallization started to occur at the take-up velocities of 2-3 km/min. The crystal modification was a-form. Birefringence of as-spun fibers showed negative value, and the absolute value of birefringence increased with an increase in the take-up velocity. The cold crystallization temperature analyzed through the differential scanning calorimetry (OSC) decreased with an increase in the take-up velocity in the low speed region, whereas as the melting temperature increased after the on-set of orientation-induced crystallization. It was found that the fiber structure development proceeded from lower take-up velocities when the spinning conditions of higher molecular weight and lower throughput rate were adopted. The highest tensile modulus of 6.5 GPa was obtained for the fibers prepared at the spinning conditions of LM s-PS, 6 g/min and 5 km/min, whereas the highest tensile strength of 160 MPa was obtained for the HM s-PS fibers at the take-up velocity of 2 km/min. Elongation at break of as-spun fibers showed an abrupt increase, which was regarded as the brittle-duc­tile transition, in the low speed region, and subsequently decreased with an increase in the take-up velocity. There was a uni­versal relation between the thermal and mechanical properties of as-spun fibers and the birefringence of as-spun fibers when the fibers were still amorphous. The orientation-induced crystallization was found to start when the birefringence reached -0.02. After the starting of the orientation-induced crystallization, thermal and mechanical properties of as-spun fibers with similar level of birefringence varied significantly depending on the processing conditions.

• Journal of the Korea Academia-Industrial cooperation Society
• /
• v.11 no.4
• /
• pp.1348-1353
• /
• 2010

At the early stage of a bulk syndiotactic polymerization of styrene, the homogeneous reactant mixture transforms to a slurry state consisting of a precipitated solid syndiotactic PS and a liquid reactant mixture. As the reaction proceeds, the slurry transforms into a wet and then a dried powder if proper methods are used to prevent agglomeration. When a large amount of catalyst and co-catalyst is added to the styrene to achieve a high conversion rate, the reactant mixture becomes a lumpy agglomeration and further control of the reaction is impossible. In this study, we introduce a novel approach to avoid such agglomeration while maintaining a high conversion rate. Instead of adding the catalyst and co-catalyst at once, the total amount of the catalyst and co-catalyst is divided into several parts and added successively. This method is found to be very effective to avoid the formation of agglomerate and to maintain a fairly high conversion rate of slurry into powdery product (up to 70 %). It is also observed that this method produces syndiotactic PS of a higher molecular weigh.

• Polymer(Korea)
• /
• v.24 no.2
• /
• pp.159-167
• /
• 2000

The polymethylene-bridged dinuclear half-titanocenes [(CH$_2$)$_{n}$(C$_{5}$ H$_4$)$_2$][TiCl$_3$]$_2$ (n=5(10), 7(11), 9(12)) have been synthesized by treating the distannylated derivatives of the ligands with two equivalents of TiCl$_4$ in toluene. All complexes are characterized by IR, $^1$H NMR, $^{13}$ C NMR and mass spectrometry. In order to examine the catalytic properties of the dinuclear complexes styrene polymerization has been conducted in the presence of MMAO. From the polymerization experiments it was found that ( i ) all the prepared complexes 10-12 produced syndiotactic polystyrenes, ( ii ) the complex 12 holding the longest bridging ligand exhibited the highest activity but produced a polymer having the smallest molecular weight among the polymethylene-bridged dinuclear half-titanocenes. This behavior was attributed to the influence of electron-donating caused by the polymethylene bridge between two active centers as well as the effect of steric congestion around metal center caused by the proximal distance between two active sites.s.

• Macromolecular Research
• /
• v.8 no.1
• /
• pp.44-52
• /
• 2000

Styrenic macromonomers with/without a silyloxy-functional group were synthesizedvia chain-end functionalization using 4-vinylbenzyl chloride as a terminating agent insec-butyllithium-initiated polymerization of styrene. The yields were 92 mol% for the silyloxy group and 88 mol% for the styrenic unit. Crystalline polystyrene-g-amorphous polystyrenes were synthesized by (η$^{5}$ -indenyl)-trichlorotitanium ((Ind)TiCl$_3$)-catalyzed copolymerizations of the macromonomers with styrene in the presence of methyl-aluminoxane (MAO) in toluene at 4$0^{\circ}C$. The macromonomer having $\alpha$, $\alpha$'-bis (4-[tert-butyldimethylsilyl-oxy]phenyl) group was also utilized for the preparation of a precursor of hydroxyl-functionalized syndio-tactic polystyrene. The obtained polymers were characterized by a combination of$^1$H, $^{13}$ C NMR spectroscopic, size exclusion chromatographic, and differential scanning calorimetric analysis. The (Ind)TiCl$_3$-catalyzed copolymerization of styrene with the macromonomer carrying the silyloxy functional group was found to be an efficient method to modify syndiotactic polystyrene without a great loss of physica] property by controlling the feud ratio of the macromonomer.