• Title/Summary/Keyword: polymerization reaction

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Preparation of Polyenaryloxynitriles from Dicyanovinyl Chloride and Diphenol Derivatives in the Presence of DABCO

  • Geum, Ne Ri;Gong, Myeong Seon
    • Bulletin of the Korean Chemical Society
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    • v.21 no.11
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    • pp.1111-1114
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    • 2000
  • The kinetic study of the enaryloxynitriles via the nucleophilic vinylic substitution reaction of various phenol derivatives with 1-chloro-1-phenyl-2,2-dicyanoethene (1) was conducted in the presence of 1,4-diazabicyclo[2,2,2]octane (DABCO). Nucleo philic vinylic substitution of phenol derivatives with electrophilic olefins carrying sluggish leaving group involves a third-order reaction. The reaction was applied to solution polymerization of diphenol derivatives with p-bis(1-chrolo-2,2-dicyanovinyl)benzene (2), which yielded various polyenaryloxynitriles with moderate molecular weight.

Preparation of Core/Shell Nanoparticles Using Poly(3,4-ethylenedioxythiophene) and Multi-Walled Carbon Nanotube Nanocomposites via an Atom Transfer Radical Polymerization (Poly(3,4-ethylenedioxythiophene)을 이용한 Core/shell 나노입자와 원자이동 라디칼중합 공정에 의한 다중벽 탄소나노튜브 나노복합체 제조)

  • Joo, Young-Tae;Jin, Seon-Mi;Kim, Yang-Soo
    • Polymer(Korea)
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    • v.33 no.5
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    • pp.452-457
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    • 2009
  • Hybrid nanomaterials consisting of multi-walled carbon nanotube(MWNT) and/or PEDOT of conductive polymer were prepared in this study. In the presence of catalyst and ligand, the MWNT-Br compound prepared by the successive surface treatment reaction was mixed with MMA to initiate the atom transfer radical polymerization process. PMMA was covalently linked to the surface of MWNT for the formation of MWNT/PMMA nanocomposites. The EDOT and oxidant were added in the aqueous emulsion of PS produced via a miniemulsion polymerization process and then it proceeded to carry out the oxidative chemical polymerization of EDOT for the preparation of PEDOT/PS nanoparticles with the core-shell structure. The aqueous dispersion of PEDOT:poly(styrene sulfonate) (PSS) was mixed with the silica particles treated with a silane compound and thus PEDOT:PSS-clad silica nanoparticles were prepared by the surface chemistry reaction. The hybrid nanomaterials were analyzed by using TEM, FE-SEM, TGA, EDX, UV, and FT-IR.

Synthesis of High Molecular Weight Poly(vinyl alcohol) by Low Temperature Polymerization of Vinyl Acetate in Tertiary Butyl Alcohol and the Following Saponification (아세트산비닐의 삼차부틸알코올계 저온 중합 및 비누화에 의한 고분자량 폴리비닐알코올의 합성)

  • 류원석;한성수;최진현;유상우;홍성일
    • Polymer(Korea)
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    • v.24 no.5
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    • pp.610-620
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    • 2000
  • Vinyl acetate (VAc) was polymerized at 30, 40, and 5$0^{\circ}C$ using 2,2'-azobis (2,4-dimethylvaleronitrile) (ADMVN) and tertiary butyl alcohol (TBA) as the initiator and the solvent, respectively. High molecular weight (HMW) atactic poly(vinyl alcohol) (PVA) was prepared by saponifying the poly(vinyl acetate) (PVAc) synthesized. The effect of polymerization conditions were investigated in terms of conversion, degree of branching for acetyl group of PVAc, and molecular weight of both PVAc and PVA. The polymerization rate of VAc in TBA was proportional to the 0.49th power of ADMVN concentration in good accordance with the theoretical value of 0.5. HMW-PVA with high yield could be obtained successfully, probably due to lower polymerization temperature and decreased chain transfer reaction rate which was achieved by adopting ADMVN and TBA. PYAc having average degree of polymerization (P$_{n}$) of 10000~13000 was obtained at the conversion of 35~70%. Saponification of so prepared PVAc yielded PVA having P$_{n}$ of 2400~6100. The syndiotactic diad content increased with decreasing polymerization temperature and increasing VAc concentration due to a steric hindrance effect of TBA during polymerization.

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Suspension Polymerization with Hydrophobic Silica as a Stabilizer III. Poly(butyl methacrylate) Composite Particles Containing Carbon Black (소수성 실리카를 안정제로 하는 현탁중합 III. 카본블랙을 함유하는 폴리부틸메타크릴레이트 복합체 입자의 합성)

  • Moon, Ji-Yeon;Park, Moon-Soo
    • Polymer(Korea)
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    • v.33 no.5
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    • pp.477-484
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    • 2009
  • Suspension polymerization with hydrophobic silica as a stabilizer and AIBN as an initiator was conducted to synthesize PBMA particles and PBMA composite particles containing carbon black. Surface modification of silica particles by controlling pH revealed that 90% of them functioned as stabilizer and 10% were incorporated into PBMA particles. While stabilizer concentration had no impact on reaction kinetics and particle diameter, an increase in stabilizer concentration displayed an increase in molecular weights when it exceeded 1.67 wt%. An increase in initiator concentration and reaction temperature decreased molecular weights in close agreement with the theoretical equation. An increase in carbon black concentration from 1 to 7 wt%, relative to the monomer, showed a progressive decrease in reaction conversion. As carbon black was increased from 3 to 5 wt%, glass transition showed a $4^{\circ}C$ increase. The presence of carbon black was confirmed by TEM while its concentration was measured by TGA.

Effects of pressure during the synthesis of petroleum pitch precursors in open and closed systems

  • Choi, Jong-Eun;Ko, Seunghyun;Kim, Jong Gu;Jeon, Young-Pyo
    • Carbon letters
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    • v.25
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    • pp.95-102
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    • 2018
  • We examined the pressure effects on petroleum pitch synthesis by using open and closed reaction systems. The pressure effects that occur during the pitch synthesis were investigated in three pressure systems: a closed system of high pressure and two open systems under either an atmosphere or vacuum. A thermal reaction in the closed system led to the high product yield of a pitch by suppressing the release of light components in pyrolysis fuel oil. Atmospheric treatment mainly enhanced the polymerization degree of the pitch via condensation and a polymerization reaction. Vacuum treatment results in a softening point increase due to the removal of components with low molecular weights. To utilize such characteristic effects of system pressure during pitch preparations, we proposed a method for synthesizing cost-competitive pitch precursors for carbon materials. The first step is to increase product yield by using a closed system; the second step is to increase the degree of polymerization toward the desired molecular distribution, followed by the use of vacuum treatment to adjust softening points. Thus, we obtained an experimental quinoline insolubles-free pitch of product yield over 45% with softening points of approximately $130^{\circ}C$. The proposed method shows the possibility to prepare cost-competitive pitch precursors for carbon materials by enhancing product yield and other properties.

Characteristics of Pitch Production of Pyrolyzed Fuel Oil/Coal-tar Blending Feedstock by Thermal Polymerization Reaction (Pyrolyzed Fuel Oil/Coal-tar 혼합원료의 열중합 반응에 따른 Pitch 제조 특성)

  • Lee, Eunbyul;Kim, Hyeong Gi
    • Applied Chemistry for Engineering
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    • v.31 no.3
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    • pp.328-333
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    • 2020
  • In this study, blended feedstock derived pyrolyzed fuel oil (PFO) and coal-tar was prepared to produce a pitch by thermal polymerization reaction for manufacturing artificial graphite materials. The aromaticity value of 0.355 and 0.818 was obtained for PFO and coal-tar, respectively. In addition, PFO and coal-tar exhibited the difference tendency of weight loss curve for thermogravimetric analysis, which is related to the structural stability depending on the aromaticity and functional groups. The production characteristics confirmed that the pitch derived PFO showed lower production yield and higher softening point than that using blended feedstock. In particular, when comparing P360 (138.5 ℃) and B420 (141.4 ℃) having similar softening points, the production yields of both pitches exhibited 29.89 and 49.03 wt%, respectively. This is mainly due to the blending of PFO and coal-tar having high pitch polymerization reactivity including a large amount of alkyl groups and coal-tar having high thermal stability. This phenomenon indicated that the increased production yield is because of a synergic effect of both the high reactivity of PFO and thermal stability of coal-tar.

Synthesis of Multi Hydroxyl Chain-End Functionalized Polyolefin Elastomer with Poly(t-butylstyrene) Graft (Poly(t-butylstyrene) 그라프트를 가지는 수산기 말단 관능화 폴리올레핀 탄성체의 합성)

  • Lee, Hyoung Woo;Cho, Hee Won;Lee, Sang Min;Park, Sat Byeol;Kim, Dong Hyun;Lee, Bum Jae
    • Elastomers and Composites
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    • v.48 no.1
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    • pp.10-17
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    • 2013
  • Polyolefin-g-poly(t-butylstyrene) as one of the high-temperature polyolefin-based thermoplastic elastomers was synthesized by the graft-from anionic living polymerization from the styrene moieties of the linear poly(ethylene-ter-1-hexene-ter-divinylbenzene) as a soft block to form the hard end blocks, poly(t-butylstyrene). The chemistry of the anionic graft-from polymerization involved complete lithiation of the pendant styrene unit of the soft polyolefin elastomer with sec-BuLi/TMEDA followed by the subsequent graft anionic polymerization of 4-tert-butylstyrene with Mn=10,000~30,000 g/mol. The graft-from living anionic polymerization were very effective and the grafting size increased proportionally with increasing monomer concentration and the reaction times. The synthetic methodology for the multi-hydroxyl chain-end modified polyolefin-g-poly(t-butylstyrene) was proposed by using the thiol-ene click reaction between 2-mercaptoethanol and the polyolefin-g-[poly(t-butylstyrene)-b-high vinyl polyisoprene], which was obtained from the subsequent living block copolymerization using polyolefin-g-Poly(t-butylstyrene) with isoprene. The result indicated that this process produced a new well-defined functionalized graft-type polyolefin-based TPE with high $T_g$ hard block(> $145^{\circ}C$).