• Journal of the Korean Chemical Society
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• v.30 no.2
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• pp.237-242
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• 1986

(E,E)-p-Phenylene diacrylic acid derivatives were prepared in moderate to good yields by the palladium catalyzed vinylation of 4-bromoiodobenzene or 4-diiodobenzene with 2 equiv of acrylic acid derivatives in the presence of triethylamine. 4-Diiodobenzene was more reactive than 4-bromoiodobenzene in the above reactions and the reactions were proceeded stereospecifically. (E,E)-p-Phenylene diacrylic acid derivatives and several other 1,4-diolefinic aromatic compounds were also synthesized by utilizing the selective vinylation of 4-bromoiodobenzene.

• Korean Chemical Engineering Research
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• v.54 no.3
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• pp.425-430
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• 2016

p-Phenylenediamine (PPD) was synthesized by aromatic amination of p-diiodobenzene (PDIB) using liquid ammonia and Cu-catalysts. The effects of the catalyst, reductant, ammonia quantity and reaction temperature on PPD production were investigated. Cu(I) compounds and Cu powder were selected as catalyst due to a higher selectivity than Cu(II) compounds. As the catalyst quantity increased, rate of PPD production as well as side reaction of aniline decreased with increasing the quantity of ammonia. Reductants such as ascorbic acid, hydrazine and dihydroxyfumaric acid were tested to lower the catalyst loading. The use of reductants resulted in increasing the reaction rate but also increased the amount of aniline The rate of reaction using ascorbic acid or dihydroxyfumaric acid was faster than that using hydrazine. The lowest side reaction of aniline was found in dihydroxyfumaric acid of reductants investigated.

• Korean Chemical Engineering Research
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• v.53 no.1
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• pp.53-56
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• 2015

In this study, investigated the synthesis method of p-Phenylenediamine (PPD) by amination of p-Diiodobenzene (PDIB) under supercritical ammonia and CuI catalyst conditions. We examined the effects of various process variables (e.g., reaction temperature, pressure, amount of ammonia inserted, amount of catalyst inserted, and reaction time) on the production yield of PPD by analyzing the Gas Chromatography (GC). The experimental results demonstrated that PPD was not produced under non-catalyst conditions, and PPD production yield increased with increasing temperature, pressure, amount of catalyst inserted, and reaction time. However, for the reaction temperature case, it was found that $200^{\circ}C$ was the optimal temperature, because thermal degradation of PPD occurred above $250^{\circ}C$. In addition, we confirmed the structure of PPD and the bonding characteristics of the amine group via FT-IR and H-NMR analysis.

• Applied Chemistry for Engineering
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• v.26 no.3
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• pp.377-380
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• 2015

In this paper, we have investigated the optimization of $I_2$ recovery process from $NH_4I$ solution, which is generated as by-product during the amination reaction of p-diiodobenzene (PDIB) for p-phenylenediamine (PPD) synthesis. The recovered $I_2$ is then recycled as a raw material for PDIB synthesis. We have employed a cation exchange resin to recover $I_2$ from $NH_4I$ sample solution, and determined the breakthrough point and exchange capacity from the breakthrough curve. Furthermore, we have suggested optimum conditions of our $I_2$ recovery process by measuring the purity and yield of recovered $I_2$ with respect to the concentrations of $NH_4I$ and oxidant ($H_2O_2$) solutions, the oxidation time, and the temperature of drying process. Finally, the yield and purity as high as 94.96% and 96.65%, respectively were obtained by reusing the residual solution still containing unrecovered iodide ions.

• Applied Chemistry for Engineering
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• v.9 no.3
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• pp.440-444
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• 1998

Poly(phenylene sulfide-co-phenylene sulfide sulfone), PPS/PPSS copolymers were synthesized from p-dichlobenzene(DCB), p-dibromobenzene(DBB), p-diiodobenzene(DIB), 4-chlorophenyl sulfone(CPS) and sodium sulfide as comonomers under high temperature and pressure utilizing N-methyl-2-pyrrolidinone(NMP) as solvent. The yield of PPS/PPSS copolymer shoed maximum at $190^{\circ}C$ with [DBB]/[CPS] and [DIB]/[CPS] comonomer pair, while [DCB]/[CPS] pair exhibited maximum yield at $230^{\circ}C$. The change of yield is in the order of I>Br>Cl as leaving groups were in accordance with nucleophilic aromatic substitution reaction mechanism suggested for the synthesis of PPS type polymers. The molecular weight of PPS/PPSS copolymer was the highest($M_w=8,330g/mol$) with [DBB]/[CPS] comonomers in which [CPS] was 10 mole%. The PPS/PPSS copolymer made with 10 mole% of [CPS] showed about $15^{\circ}C$ higher $T_g$ and $15^{\circ}C$ lower $T_m$ than those of PPS homopolymer, which may be useful from the processing and thermal property point of view. The PPS/PPSS copolymer with 30 mole% of CPS or above did not exhibit Tm. The PPS/PPSS copolymer obtained with comonomer feed ratio of [DBB]/[CPS] = 95/5 mole% under $240^{\circ}C$ showed even higher molecular weight($M_w=10,300g/mole$) than PPS homopolymer made under similar reaction condition, retaining high crystallinity and thermal stability.