• Elastomers and Composites
• /
• v.55 no.3
• /
• pp.167-175
• /
• 2020

Various studies have been conducted to improve silica dispersion of silica filled tire tread compounds; among them, silica wet masterbatch (WMB) technology is known to be suitable for manufacturing silica filled compounds that have high silica content and high dispersibility. Till now, the WMB study is focused on the natural rubber (NR) or emulsion styrene-butadiene rubber (ESBR) that does not have a silica-affinity functional group, and a study of NR or ESBR having a silica-affinity functional group is still not well known. Unlike the dry masterbatch technology, the WMB technology can solve the problems associated with the high Mooney viscosity when applied to silica-friendly rubber. However, a coagulant suitable for each functional group has not yet been determined. Therefore, in this study, different coagulant applied silica WMB was prepared by applying calcium chloride, sulfuric acid, acetic acid, and propionic acid by using a carboxyl group functionalized reversible addition fragmentation chain transfer ESBR. The evaluation of the WMB compounds revealed that the calcium chloride added WMB compound showed excellent silica dispersion, abrasion resistance, and rolling resistance.

• Macromolecular Research
• /
• v.16 no.5
• /
• pp.446-456
• /
• 2008

A recent theoretical approach based on the coupling of both the Flory-Huggins (FH) and the Association Equilibria thermodynamic (AET) theories was modified and adapted to study the miscibility properties of a multi-component system formed by two polymers (a proton-donor and a proton-acceptor) and a proton-acceptor solvent, named copolymer(A)/solvent(B)/polymer(C). Compatibility between polymers was mainly attained by hydrogen-bonding between the hydroxyl group on the phenol unit of the poly(styrene-co-vinyl phenol) (PSVPh) and the carbonyl group of the biodegradable and environmentally friendly poly(3-hydroxybutyrate) (PHB). However, the self-association of PSVPh and specific interactions between the PSVPh and the H-acceptor group (an ether oxygen atom) of the epichlorohydrin (ECH) solvent were also established in a lower extension, which competed with the polymer-polymer association. All the binary specific interactions and their dependence with the system composition as well as with the copolymer content were evaluated and quantified by means of two excess functions of the Gibbs tree energy, ${\Delta}g_{AB}$ and ${\Delta}g_{AC}$. Experimental results from fluorescence spectroscopy were consistent with the theoretical simulations derived with the model, which could also be applied and extended to predict the miscibility in solution of any polymer blend with specific interactions.

• Elastomers and Composites
• /
• v.55 no.3
• /
• pp.215-221
• /
• 2020

Silica/SBR (styrene-butadiene rubber) compounds are the primary constituents of tire treads. Furthermore, the excellent dynamic viscoelastic properties of silica lead to good fuel efficiencies. However, the silanol group on the surface of silica does not mix well with non-polar rubber because of its polarity. This incompatibility causes aggregation due to the occurrence of hydrogen bonding between the hydroxyl groups, thereby reducing the dispersibility of silica. Recently, the wet master batch (WMB) process has been applied to overcome these disadvantages, and research on silica dispersants that can be used in the WMB process has been increasing. In this study, we prepared silica/SBR compounds by using three types of eco-friendly cellulose-based dispersants in the WMB process, namely: cellulose-, sodium carboxymethyl cellulose, and nanocellulose-based dispersants. Subsequently, we compared the vulcanization characteristics, viscoelastic properties, and mechanical properties of the compounds. The silica dispersibility in the rubber compounds was improved with the addition of the nano-cellulose dispersant, resulting in the enhancement of the workability, hardness, tensile strength, and wear resistance of the SBR compound.

• Macromolecular Research
• /
• v.17 no.5
• /
• pp.325-331
• /
• 2009

The synthesis and the characterization of crosslinked ABC triblock copolymer, i.e. polystyrene-b-poly (hydroxyethyl methacrylate)-b-poly(styrene sulfonic acid), (PS-b-PHEMA-b-PSSA) is reported. PS-b-PHEMA-b-PSSA triblock copolymer at 20:10:70 wt% was sequentially synthesized via atom transfer radical polymerization (ATRP). The middle block was crosslinked by sulfosuccinic acid (SA) via the esterification reaction between -OH of PHEMA and -COOH of SA, as demonstrated by FTIR spectroscopy. As increasing amounts of SA, ion exchange capacity (IEC) continuously increased from 2.13 to 2.82 meq/g but water uptake decreased from 181.8 to 82.7%, resulting from the competitive effect between crosslinked structure and the increasing concentration of sulfonic acid group. A maximum proton conductivity of crosslinked triblock copolymer membrane at room temperature reached up to 0.198 S/cm at 3.8 w% of SA, which was more than two-fold higher than that of Nafion 117(0.08 S/cm). Transmission electron microscopy (TEM) analysis clearly showed that the PS-b-PHEMA-b-PSSA triblock copolymer is microphase-separated with a nanometer range and well developed to provide the connectivity of ionic PSSA domains. The membranes exhibited the good thermal properties up to $250^{\circ}C$ presumably resulting from the microphase-separated and crosslinked structure of the membranes, as revealed by thermal gravimetric analysis (TGA).

• Korean Chemical Engineering Research
• /
• v.43 no.6
• /
• pp.722-727
• /
• 2005

Dow99Ca350 (Dowex monosphere 99Ca/350 separation resin), MFG-220, and Finex CS-10GC are ion-exchange resins, and primarily used to separate sugars, and all of these resins have poly styrene DVB backbone, and sulfonyl group. These resins are already used to separate sugars continuously at sugar industry at constant temperature. These resins are used in experiments for understanding temperature effect on retention or adsorption behavior. Using Dow99Ca350, swelling test, porosity test, pulse test, and frontal analysis at various temperatures were performed. In the cases of MFG-220, and Finex CS-10GC, the effect of temperature variation was verified by pulse test. The experimental results are shown that Dow99Ca350, MFG-220, and Finex CS-10GC, which are commercial resins for sugar separation, are stable to temperature variation because the maximum change of retention time of fructose, and glucose are 1.76, and 3.37％ respectively.

• Journal of Environmental Science International
• /
• v.11 no.4
• /
• pp.375-382
• /
• 2002

The total hydrocarbon distribution of oil products obtained from the pyrolysis of four kinds of mixtures of polyethylene-polystyrene waste has been studied by multidimensional chromatography(high performance liquid chromatography followed by capillary gas chromatography)/mass spectrometry. Saturated, unsaturated and aromatic hydrocarbons in oil products were selectively pre-separated according to structural groups by HPLC and the weight fraction of each group was estimated by analysis of each component using GC-FID response factors. The hydrocarbon distribution of aliphatic fraction consists of $C_{5}$ to $C_{25}$ saturated and unsaturated hydrocarbons. And that of aromatics fraction consists of benzene, toluene, xylene, styrene, propenyl benzene, naphthalene, and some of derivatives. Pyrolysis temperature did not affect the ratio of total weight fraction of aliphatic over aromatic hydrocarbon distribution in case of PS only and PE-PS mixtures (1:1 and 1:4 wt. ratio) as a feed while affected the ratio of total wt. fraction in case of PE only. The optimal temperature for the maximum oil production was $600^{\circ}C$ for pyrolysis of PS and 1:1 and 1:4 mixtures of PE and PS. The optimal condition for aromatic recovery was $600^{\circ}C$ with 1:1 mixture of PE and PS. In this condition, aromatic was produced up to 90% of total oil product. The maximum yield of toluene, xylene, styrene, and propenyl benzene were 8.6, 8.9, 51.0 and 7.4% of feed for pyrolysis PS at $700^{\circ}C$, respectively. However, only 1.3% naphthalene was recovered at $700^{\circ}C$ with 1:1 PE:PS(by wt.).

• Macromolecular Research
• /
• v.12 no.1
• /
• pp.100-106
• /
• 2004

We have prepared the polymethylene-bridged, dinuciear, half-sandwich constrained geometry catalysts (CGC)［Zr(η$\^$5/:η$^1$-C$\_$9/H$\_$5/SiMe$_2$NCMe$_3$)］$_2$［(CH$_2$)$\_$n/］［n=6(9), n=12(10)］by treating 2 equivalents of ZrCl$_4$with the corresponding tetralithium salts of the ligands in toluene. $^1$H and $\^$13/C NMR spectra of the synthesized complexes provide firm evidence for the anticipated dinuciear structure. In $^1$H NMR spectra, two singlets representing the methyl group protons bonded at the Si atom of the CGC are present at 0.88 and 0.64 ppm, which are considerably downfield positions relative to the shifts of 0.02 and 0.05 ppm of the corresponding ligands. To investigate the catalytic behavior of the prepared dinuciear catalysts, we conducted copolymerizations of ethylene and styrene in the presence of MMAO. The prime observation is that the two dinuclear CGCs 9 and 10 are not efficient for copo-lymerization, which definitely distinguishes them from the corresponding titanium-based dinuclear CGC. These species are active catalysts, however, for ethylene homopolymerization; the activity of catalyst 10, which contains a 12-methylene bridge, is larger than that of 9 (6-methylene bridge), which indicates that the presence of the longer bridge between the two active sites contributes more effectively to facilitate the polymerization activity of the dinuciear CGC. The activities increase as the polymerization temperature increases from 40 to 70$^{\circ}C$. On the other hand, the molecular weights of the polyethylenes are reduced when the polymerization temperature is increased. We observe that dinuciear metallocenes having different-length bridges give different polymerization results, which reconfirms the significant role that the nature of the bridging ligand has in controlling the polymerization properties of dinuclear catalysts.

• Polymer(Korea)
• /
• v.29 no.5
• /
• pp.486-492
• /
• 2005

Into a no-conjugated polymer chain we have introduced side chains with a styrene-linked triphenylamine segment as a $\pi-electron$ donor, styrene-]inked aminobenzaldehyde segment as a tunable reactive -CHO group, and PM (4-(dicyanomethylene)-2-(tert-butyl)-4H-pyran) moiety as a $\pi-electron$ acceptor for red emitting materials. The thermal stability and the optical properties of the statistical copolymers have been studied. All the polymers were electrochemically active and showed electroluminescent emission at around 700nm. The EL device of P5-PM based on the sturcture of $ITO/PPV/polymer/BCP/Alq_3/Al$ showed a maximum brightness of $120cd/m^2\;at\;50mA/cm^2$ with an external quantum efficiency of $0.67\%$. It was possible to enhance the external quantum efficiency by balancing the charge recombination. A red-emitting polymer with high external quantum efficiency was developed by incorporating bifunctionality.

• Macromolecular Research
• /
• v.15 no.5
• /
• pp.412-417
• /
• 2007

In the present study, crosslinked poly(vinyl alcohol) (PVA) membranes were prepared at different temperatures using poly(styrene sulfonic acid-co-maleic acid) (PSSA_MA) (PVA:PSSA_MA = 1:9). The hybrid mem-branes were prepared by varying the TEOS content between 5 and 30 wt%. The PSSA_MA was used both as a crosslinking agent and the hydrophilic group donor ($-SO_3H$ and/or-COOH). The proton conductivity increased with up to 20 wt% TEOS, but decreased above this level, although the water content decreased with increasing TEOS content. This result suggests that the silica doped into the membrane improved the formation of proton-conduction pathways due to the absorption of molecular water. The PVA/PSSA_MA/Silica containing TEOS 20% showed both high proton conductivity (0.026 S/cm at $90^{\circ}C$) and low methanol permeability ($5.55{\times}10^{-7}cm^2/s$).

• Applied Chemistry for Engineering
• /
• v.10 no.5
• /
• pp.796-803
• /
• 1999

Solution copolymerization of styrene(St.) with methyl methacrylate(MMA), ethyl methacrylate(EMA) and n-butyl methacrylate(BMA) was carried out with benzoylperoxide(BPO) as an initiator in toluene at $80^{\circ}C$ in a continuous stirred tank reactor. Reaction volume and residence time were 0.6 liters and 3hours, respectively. The monomer reactivity ratios, $r_1(St.)$ and $r_2(RMA)$ determined by both the Kelen-Tudos method and the Fineman-Ross method were $r_1(St.)=0.60(0.61),\;r_2(MMA)=0.59(0.60);\;r_1(St.)=0.65(0.62),\;r_2(EMA)=0.55(0.52);\;r_1(St.)=0.75(0.67),\;r_2(BMA)=0.63(0.56)$. The cross-termination factor $\Phi$ of the copolymer over the entire St. compositions ranged from 0.26 to 0.96. The $\Phi$ factors of St.-RMA copolymer were increased with increasing St. content. The simulated conversions and copolymerization rates were compared with the experimental results. The average time to reach dynamic steady-state was three times and half of the residence time.