• Polymer(Korea)
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• v.38 no.4
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• pp.425-433
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• 2014

In this study, microstructure and gel content (C-C) of polybutadiene rubber (PBR) were investigated using various techniques including ASTM D 3616, attenuated total reflectance Fourier transform infrared spectrometry (ATR FTIR), differential scanning calorimetry (DSC) and nuclear magnetic resonance spectroscopy (NMR). The ATR FTIR spectra of the samples were investigated to determine the cis, trans, 1, 2-vinyl and the C-C gel content in PBR. The absorbance ratios of specific peaks in different grades of PBR were correlated with the C-C gel content measured by the ATR FTIR techniques. Physico-mechanical and rheological properties of rubber compounds based on BR with various amounts of gel were determined. The results showed that there is an acceptable correlation between these properties and the C-C gel content of PBR.

• Elastomers and Composites
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• v.50 no.1
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• pp.1-6
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• 2015

Polybutadiene rubber (BR) has been well known that its physical and chemical properties are changed when it is exposed to ultraviolet light undergoing photooxidation. In this study, photooxdiation process of BR vulcanizate was investigated using a high pressure mercury lamp used as an outdoor lighting, which has high UV radiation efficiency and reasonable cost. Discoloration and crack formation of photooxdized BR vulcanite surface were examined using an image analyzer. Change of chemical functional groups of BR vulcanite surface by photooxidation was investigated using ATR-FTIR, and variation of the crosslink density with the UV irradiation time was investigated. By increasing the UV irradiation time, the crosslink density steeply increased after a period of time and did not increase any more. Formation of hydroxyl (~OH) and carbonyl (~C=O) groups on the BR vulcanizate surface increased and the1,4-cis unit was converted to the 1,4-trans unit as the photooxidation was proceeded.

• Elastomers and Composites
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• v.48 no.1
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• pp.61-66
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• 2013

A family of Cr(III) complexes supported on tridentate dibenzimidazolyl ligands having a general formula: $[N(CH_3)(CH_2)_2(Bm-R)_2]CrCl_3$ [where Bm = benzimidazolyl, R = H (3a); -Me(3b); -Bn (3c)] have been synthesized and utilized them for the trans-1,4-specific polymerizations of 1,3-butadiene (BD), activated with methylalumoxane (MAO). The activity of BD polymerizations was sensitive to the type of ligand on the Cr metal, so that the activity decreases in the order of 3a > 3c > 3b. All the catalysts combined with MAO yielded polybutadienes with perfect trans-1,4 structure with moderate molecular weight.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4028-4034
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• 2012

Tris(2-phenylphenoxo)aluminum ($(2-PhC_6H_4O)_3Al$) exists as a dimeric form in toluene. When toluene-insoluble anhydrous cobalt acetate is treated with tris(2-phenylphenoxo)aluminum in toluene, the toluene-soluble adduct $(2-PhC_6H_4O)_3Al{\cdot}Co(OAc)_2$ is formed. The 2-phenylphenoxo ligand in the adduct can be replaced with another aryloxo ligand to give (aryloxo)$(2-PhC_6H_4O)_2Al{\cdot}Co(OAc)_2$ (aryloxo = 2-methylphenoxo, 2-isopropylphenoxo, 4-methylphenoxo, 4-isopropylphenoxo, or 4-tert-butylphenoxo). These complexes are active for butadiene polymerization without gel formation when activated with an equivalent amount of $(2-PhC_6H_4O)AlEt_2$ for 2 h. The highest activity, 175 kg/mol-Co (turnover number, 3200) was achieved with $(2-PhC_6H_4O)_3Al{\cdot}Co(OAc)_2$ at $65^{\circ}C$ for 2 h. The microstructure of the polymer chains is mostly trans-1,4-configuration (70-75%) with the remaining being 1,2-vinyl. The cis-1,4-configuration observed by IR is minimal (1-5%). By replacing the 2-phenylpheoxo with a 4-alkylphenoxo ligand, the amount of 1,4-configuration slightly increases, resulting in increase in the endothermic melting signal at $-30{\sim}50^{\circ}C$ in the DSC curve. The molecular weights of the polymers are high ($M_n$: 300000~800000) with a fairly narrow molecular weight distribution ($M_w/M_n$, 2.0-2.7).