• Bulletin of the Korean Chemical Society
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• 제25권4호
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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.

• 한국산업보건학회지
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• 제19권4호
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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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• 제55권4호
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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.

• 대한화학회지
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• 제38권9호
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• pp.676-681
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• 1994

4-Acetoxyazetidine-2-one과 (3R,4R)-4-acetoxy-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]azetidin-2-one에 2-(tert-butyldimethylsilyloxy)-1,3-butadiene 또는 3-(tert-butyldimethylsilyloxy)-1,3-pentadiene을 염화아연의 존재하에 반응시켰을 때 Diels-Alder 첨가생성물인 cephem 유도체가 얻어졌다. 이 반응에서 diene으로 tert-butyldiemethylsilyl acrylate를 사용하였을 때에는 azetidin-2-one의 4-위치의 acetoxy기가 acryloyloxy로 치환된 화합물이 얻어졌다. 4-phenylsulfonylazetidin-2-one을 dienophile로 사용하여 2-(tert-butyldimethylsilyloxy)-1,3-butadiene과 반응시켰을 때에는 carbacephem은 생성되지 않았고 4-phenylsulfoyl-2-butanone이 얻어졌다. Thiochalcone dimer를 염화아연의 존재하에 4-acetoxyazetidin-2-one과 반응시켰을 때 azetidin-2-one의 고리가 깨어진 화합물이 생성되었고, N-methylacrylamide를 trimethylsilyl trifluoromethanesulfonate와 triethylamine의 존재하에 반응시켜 얻은 2-trimethylsilyloxy-1-aza-1,3-butadiene은 4-acetoxyazetidin-2-one과 Diels-Alder 유형의 반응을 하지 않았다.

• Korean Chemical Engineering Research
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• 제40권6호
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• pp.669-675
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• 2002

액상 NaK alloy, Na metal 그리고 지지체에 담지된 Na metal을 촉매로 이용하여 o-xylene과 1,3-butadiene의 alkenylation을 통한 OTP(ortho-tolyl pentene)의 합성 반응을 연구하였다. 액상의 NaK alloy 촉매인 경우 metal의 분산도를 증가시키기 위해서 ultrasound로 처리하였고 촉매상은 매우 작은 입자로 쪼개져 emulsion을 형성하면서 분산도를 증가시킬수록 전화율과 선택도를 향상시킬 수 있었다. Na metal의 경우 분산도를 증가시키기 위해 전처리가 필요하였으며 미립자로 분산이 진행되는 동안 지체(induction) 시간이 필요하였다. 지지체에 담지된 Na metal의 경우 지지체에 관계없이 80 % 이상의 전화율을 지체 시간 없이 얻을 수 있었다. 하지만 slurry 액상 반응계에서는 담지된 금속의 85 % 이상이 촉매에서 떨어져 나와 반응에 참여하는 것으로 보인다. 반응물인 1,3-butadiene과 생성물인 OTP간의 반응에 의한 부반응이 진행되어 1,3-butadiene의 양이 증가하면 부반응으로 생성된 oligomer 양이 증가하였으며 전화율이 증가하면 선택도가 반비례 관계로 감소하였다.

• 자연과학논문집
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• 제5권2호
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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 $(C_4H_6)_x$.

• 폴리머
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• 제29권5호
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• pp.445-450
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• 2005

인체 보형물의 생체 재료로 사용할 목적으로 히아루론산 비드를 제조하였다. 히아루론산 수용액과 콩기름을 섞어서 얻어진 현탁상태에서 히아루론산을 1,3-butadiene diepoxide로 가교시켰다. 제조된 비드의 물성을 살펴보기 위해 직경, 표면적과 팽윤도를 측정하였고 전자현미경으로 표면상태를 관찰하였다. 가교제의 농도가 $5-12\;vol\%$ 범위에서 비드가 형성되었으며 제조된 비드는 단순분산성을 보였다. 히아루론산 농도 혹은 가교제 농도가 증가할수록, 가교 온도가 감소할수록, BET표면적과 팽윤도가 감소하였다. 혼합속도의 변화에 의해 비드의 물성은 거의 변하지 않았으나 비드의 크기는 효과적으로 조절되었다.

• 청정기술
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• 제18권1호
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• pp.51-56
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• 2012

상업적으로 이용 가능한 과산화초산을 산화제로 사용하고, 적은 양으로 매우 빠르게 산화시킬 수 있는 효율적인 철복합체 $[((phen){_2}(H_2O)Fe^{III}){_2}({\mu}-O)](ClO_4){_4}$ 촉매를 사용하여 $-10^{\circ}C$에서 1,3-부타다이엔을 에폭시화하였다. 에폭시화반응에 대한 온도(-10 ~ $-40^{\circ}C$)와 시간의 효과에 관하여 연구하였다. 에폭시화반응은 $-20^{\circ}C$에서 약 5분 내에 거의 완결될 정도로 빨랐으나, 그 이하의 온도에서는 느려졌다. 부타다이엔의 수율은 반응시간에 따라 증가하였으며, 부타다이엔 양이 증가하면 수율도 증가하는 경향을 보였다. 실험에서 얻은 부타다이엔모노에폭사이드의 최고 수율은 90%였다.

• Elastomers and Composites
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• 제54권1호
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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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• 제57권4호
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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.