• Bulletin of the Korean Chemical Society
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• v.25 no.4
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• pp.452-459
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• 2004

The geometrical structures of various isomers of hexafluoro-1,3-butadiene (HFBD), tetrafluoro-1,3-butadiene (TFBD), and difluoro-1,3-butadiene (DFBD) have been studied theoretically. Natural steric and natural resonance theory (NRT) analyses indicate that the lower energy of skew s-cis conformer of hexafluoro-1,3-butadiene than that of the s-trans conformer is originated from the strong steric repulsions between fluorine atoms particularly in the s-trans conformer. The resonance structures generated by NRT also show that the lone electron pairs of fluorine atoms effectively extend the conjugation, and the large differences in energy among the structural isomers of tetrafluoro-1,3-butadiene and difluoro-1,3-butadiene are in part attributed to the differences in the delocalization energies, in addition to the steric repulsion between fluorine atoms. Other interatomic interactions, such as hydrogen bonding, also play important roles in determination of the structures of isomers of tetrafluoro-1,3-butadiene and difluoro-1,3-butadiene.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.19 no.4
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• pp.321-327
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• 2009

1,3-butadiene is classified as suspected human carcinogen, group A2(American Conference of Governmental Industrial Hygienists, ACGIH). In Korea, 1,3-butadiene has been used as a raw material; monomer, homopolymer, polybutadiene latex, acrylonitrile-butadiene-styrene(ABS) and styrene-butadiene rubber(SBR), in the petrochemistry and precision chemistry industry. As petrochemistry industry in Korea has been developed, the potential exposure possibility of 1,3-butadiene to workers can be increased. Therefore the purpose of this study is to evaluate airborne 1,3-butadiene concentration and workers' exposure levels in the workplace using 1,3-butadiene. Air samples were collected with 4-tert-butyl catechol(TBC) charcoal tube(100 mg/50 mg) and were analyzed by gas chromatograph/flame ionization detector(GC/FID) according to the Choi's method(2002). Geometric mean (GM) and arithmetic mean (AM) of total 59 workers' exposure concentrations to airborne 1.3-butadiene were 0.042 ppm and 1.51 ppm, respectively. Although most samples were lower than 1ppm, 2 samples(21.5ppm and 33.1ppm as 8hr-TWA) were exceeded the Korean standard(2ppm) over 10 times at the repair process in synthetic rubber and resin manufacture industry. 14 samples(41%) of total 34 short-term air samples were exceeded the Korean standard(10ppm as STEL) of Ministry Labor. 1,3-butadiene concentration(GM) in the synthetic rubber and resin manufacture industry(7.87ppm) was significantly higher than that in the monomer manufacure industry (0.35ppm)(p<0.05). Also in the sampling and repair process, each GM(range) was 1.39ppm(N.D.-469.6ppm) and 7.85ppm(N.D.-410.2ppm). In conclusion, it depends on the industry and process, 1,3-butadiene can be exposed to workers as high concentration for short-term.

• Elastomers and Composites
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• v.55 no.4
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• pp.281-288
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• 2020

A calibration curve is needed to determine the SBR and BR blend ratio of SBR/BR blend rubber compounds using pyrolysis-gas chromatography/mass chromatography (Py-GC/MS) or Py-GC. In general, a calibration curve is obtained using reference SBR/BR vulcanizates with various blend ratios. In this study, the calibration curves were obtained using reference samples made of rubber solutions and were compared to those plotted using the reference SBR/BR vulcanizates. Calibration curves using variations of 1,3-butadiene/styrene, 4-vinylcyclohexene (VCH)/styrene, 2-phenylpropene (PhP)/butadiene, PhP/VCH, 4-phenylcyclohexene (PhCH)/butadiene, and PhCH/VCH ratios with the BR content were examined for the suitability. We found that the calibration curves obtained using the mixed rubber solution references (1,3-butadiene/styrene and PhP/butadiene) could replace those constructed using the reference SBR/BR vulcanizates. The calibration curves of 1,3-butadiene/styrene and PhP/butadiene obtained using the raw references can be used for the determination of the SBR/BR blend ratios by applying some correction factors.

• Journal of the Korean Chemical Society
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• v.38 no.9
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• pp.676-681
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• 1994

Diels-Alder adducts, carbacephems were obtained when 4-acetoxyazetidine-2-one or (3R,4R)-4-acetoxy-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]azetidin-2-one was reacted with 2-(tert-butyldimethylsilyloxy)-1,3-butadiene or with 3-(tert-butyldimethylsilyloxy)-1,3-pentadiene. When tert-butyldiemethylsilyl acrylate was used as the diene, products in which was acetoxy group of 4-acetoxyazetidin-2-one derivatives was substituted by an acryloyloxy group were isolated. When the same reaction was carried out with 4-phenylsulfonylazetidin-2-one as a dienophile with 2-(tert-butyldimethylsilyloxy)-1,3-butadiene, 4-phenylsulfoyl-2-butanone was obtained instead of the expected carbacephem. When dimeric form of thiochalcone was reacted with 4-acetoxyazetidin-2-one in the presence of zinc chloride, the $\beta-lactam$ ring of the azetidin-2-one was destructed and no product was isolated. Also, the reaction of 2-trimethylsilyloxy-1-aza-1,3-butadiene, which was obtained from N-methylacrylamide by treatment of trimethylsilyl trifluoromethanesulfonate in the presence of triethylamine, with 4-acetoxyazetidin-2-one did not give any products.

• Korean Chemical Engineering Research
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• v.40 no.6
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• pp.669-675
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• 2002

The alkenylation of o-xylene with 1,3-butadiene to make OTP(ortho-tolyl Pentene) was carried out over liquid phase NaK alloy, Na metal and the metallic sodium dispersed on the specific support such as NaX and $Al_2O_3$. Liquid phase NaK alloy showed the improved conversion and selectivity when they were pretreated by ultrasound to increase the dispersion. For the case of metallic sodium, the induction period for the formation of homogeneous metal sodium solution with high dispersion was needed before the reaction. In the case of metallic sodium dispersed on support, more than 80 % conversion could be obtained without induction period regardless of supports used. But 85 % of the metallic sodium was resolved into the reaction mixture after reaction for 7 hours. The amount of byproducts, oligomers, produced from OTP and 1,3-butadiene increased with the amount of 1,3-butadiene introduced and the selectivity to OTP was in inversely proportional to the conversion.

• The Journal of Natural Sciences
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• v.5 no.2
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• pp.63-73
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• 1992

There are many methods of obtaining butadiene described in the literature. In the america it is produced largely from petroleum gases, i.e., by catalytic dehydrogenation of butene of butene-butane mixtures. Butadiene can be recovered from the $C_4$ residue of an olefin plant by distilling off a fraction containing most of the butadiene, catalytically hydrogenating the higher acetylenes to olefins and separating the product from other olefins and isobutane by extraction. Also it can be obtained by cracking naphtha and light oil. Among the individual dienes of commercial importance, 1, 3-butadiene is of first importance. It is used primarily for the production of polymers.In the present paper, it was investigated for a effect of the formation and the growth inhibition of popped corn polymer in butadiene extraction unit. As a result of study, inhibitors, $NaNO_2$ and TBC were good effective for inhibition of the formation and growth in popcorn polymer. The rational formula of popcorn polymer obtained was $(C_4H_6)_x$.

• Polymer(Korea)
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• v.29 no.5
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• pp.445-450
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• 2005

Hyaluronic acid-based beads were prepared in order to develop a biomedical material for augumentation. Hyaluronic acid was crosslinked by 1,3-butadiene diepoxide in a suspension state maintained by rapid mixing of soybeen oil and hyaluronic acid solution. The particle size, surface area and swelling ratio were measured to investigate the physical properties of the synthesized beads and the bead surface was examined by scanning electron microscopy. The beads were formed in the range of $5-12vol\%$ concentration of crosslinking agent, which showed monodisperse size distribution. Both BET surface area and swelling ratio decreased as the concentration of either hyaluronic acid or crosslinking agent increased, and crosslinking temperature decreased. Bead size could be effectively controlled by mixing speed without affecting other physical property.

• Clean Technology
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• v.18 no.1
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• pp.51-56
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• 2012

Here, we report an efficient iron complex $[((phen){_2}(H_2O)Fe^{III}){_2}({\mu}-O)](ClO_4){_4}$, that can rapidly epoxidize 1,3-butadiene at $-10^{\circ}C$ with low catalyst loadings by using commercially available peracetic acid as an oxidant. The main aspect of our study is to investigate the effect of temperature (from -10 to $-40^{\circ}C$) and time on the epoxidation reaction. The epoxidation reaction was fast and almost completed within 5 min at temperatures above $-20^{\circ}C$, whereas it became slow at temperatures below $-20^{\circ}C$. The yield of butadiene monoepoxide (BMO)increased with increasing the reaction time. Generally, when the more butadiene was used, the higher yield was obtained. The highest yield of BMO was 90%.

• Elastomers and Composites
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• v.54 no.1
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• pp.54-60
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• 2019

The rapid development of the automobile industry is an important factor that led to the dramatic development of synthetic rubber. The tread part of tire that comes in direct contact with the road surface is related to the service life of the tire. Rubber compounds used in tire treads are often blended with SBR (styrene-butadiene rubber) and BR (butadiene rubber) to satisfy physical property requirements. However, when two or more kinds of rubber are blended, phase separation and silica dispersion problems may occur due to non-uniform mixing of the rubber. Therefore, in this study, we synthesized an SBR copolymer with the same composition as that of a typical SBR/BR blend compound by controlling butadiene content during ESBR (emulsion styrene-butadiene rubber) synthesis. Subsequently, silica filled compounds were manufactured using the synthesized ESBR, and their mechanical properties, dynamic viscoelasticity, and crosslinking density were compared with those of the SBR/BR blended compound. When the content of butadiene was increased in the silica filled compound, the cure rate accelerated due to an increased number of allylic positions, which typically exhibit higher reactivity. However, the T-2 compound with increased butadiene content by synthesis less likely to show an increase in crosslink density due to poor silica dispersion. In addition, the T-3 compound containing high cis BR content showed high crosslink density due to its monosulfide crosslinking structure. Because of the phase separation, SBR/BR blend compounds were easily broken and showed similar $M_{100%}$ and $M_{300%}$ values as those of other compounds despite their high crosslink density. However, the developed blend showed excellent abrasion resistance due to the high cis-1,4 butadiene content and low rolling resistance due to the high crosslink density.

• Elastomers and Composites
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• v.57 no.4
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• pp.188-196
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• 2022

Styrene-butadiene rubber(SBR) is a copolymer of styrene and butadiene. It is composed of 1,2-unit, 1,4-unit, and styrene, and its properties are dependent on its microstructure. In general, rubber composites contain a single rubber or a blended rubber. Similarly, SBR is used by mixing with natural rubber(NR) and butadiene rubber(BR). The composition of a rubber article affects its physical and chemical properties. Herein, an analytical method for determining the microstructure of SBR using via pyrolysis is introduced. Pyrolysis-gas chromatography/mass spectrometry is widely used to analyze the microstructure of polymeric materials. The microstructure of SBR can be determined by analyzing the principal pyrolysis products formed from SBR, such as 4-vinylcyclohexene, styrene, 2-phenylpropene, 3-phenylcyclopentene, and 4-phenylcyclohexene. An analytical method for determining the composition of SBR/NR, SBR/BR, and SBR/NR/BR blends via pyrolysis is introduced. The composition of blended rubber can be determined by analyzing the principal pyrolysis products formed from each rubber component.