• 제목/요약/키워드: condensation polymerization

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폴리(페닐렌 설파이드)로 기능화된 다중벽 탄소나노튜브의 제조와 특성분석 (Preparation and Characterization of Poly(phenylene sulfide)-Functionalized MWNTs)

  • 홍성연;김영호
    • 폴리머
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    • 제38권6호
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    • pp.791-800
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    • 2014
  • Friedel-Crafts 직접 아실화 반응을 이용하여 $P_2O_5$/폴리인산 매질에서 다중벽 탄소나노튜브(MWNT)와 4-클로로벤조산(CBA)을 반응시켜 클로로벤조일(CB)기가 도입된 MWNT(c-MWNT)를 제조하였다. 이때 반응시키는 CBA양을 조절하여 염소원자 함량이 최대 5.3 wt%(CB기 함량 20.86 wt%)인 c-MWNT를 얻었다. 한편, 열가소성 엔지니어링 플라스틱 소재인 폴리(페닐렌 설파이드) (PPS)와 MWNT의 계면접착력을 증가시키기 위하여, 4-클로로벤젠티올(CBT)의 자기축합에 의한 PPS 중합시 c-MWNT를 함께 넣고 중합시킨 후 호모 PPS를 제거하여 MWNT-g-PPS를 얻었다. 이 MWNT-g-PPS의 열 및 표면 특성들을 분석하였으며, c-MWNT와 CBT가 반응하여 c-MWNT 표면에 PPS가 생성되었음을 확인하였다.

Radical Ring-Crossover Polymerization of Macrocycles with Radically Exchangeable Dynamic Covalent Bonds

  • Otsuka, Hideyuki;Yamaguchi, Go;Takahara, Atsushi
    • 한국고분자학회:학술대회논문집
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    • 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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    • pp.320-320
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    • 2006
  • The authors report the synthesis and radical ring-crossover polymerization of macrocycles with radically exchangeable dynamic covalent bonds. The macrocyclic compounds with alkoxyamine units were designed and synthesized by condensation from alkoxyamine-based diol and the corresponding acid chlorides in the presence of pyridine under high-dilution condition. The macrocycles can thermally polymerize by intermolecular radical crossover reaction. Furthermore, the poly(alkoxyamine)s depolymerized to the monomers principally by the intramolecular radical exchange process under high-dilution conditions.

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Allyloxy-and Benzyloxy-Substituted Pyridine-bis-imine Iron(II) and Cobalt(II) Complexes for Ethylene Polymerization

  • Kim Il;Han Byeong Heui;Kim Jae Sung;Ha Chang-Sik
    • Macromolecular Research
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    • 제13권1호
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    • pp.2-7
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    • 2005
  • A series of ethylene polymerization catalysts based on tridentate bis-imine ligands coordinated to iron and cobalt was reported. The ligands were prepared through the condensation of sterically bulky anilines with allyloxy-and benzyloxy-substituted 2,6-acetylpyridines. The pre-catalyst complexes were penta-coordinate species of the general formula $\{[(ArN=C(Me))_2(4-RO-C_5H_3N)]MCl_2\}$ (Ar=ortho dialkyl-substituted aryl ring; R=allyl, benzyl; M=Fe, Co). In the presence of ethylene and methyl alumoxane cocatalysts, these complexes were active for the polymerization of ethylene, with activities lower than those of metal complexes of the general formula $\{[(2-ArN=C(Me)_2C_5H_3N]MCl_2\}$ (Ar=ortho dialkyl-substituted aryl ring; M=Co, Fe), containing no substituents in 2,6-acetylpyridine ring. The effects of the catalyst structure and temperature on the polymerization activity, thermal properties, and molecular weight were discussed.

A Novel Synthetic Route to Highly Cross-Linked Poly(alkylvinylether)s. Synthesis and Free Radical Polymerization of a Vinyl Ether Monomer Containing Electron Acceptors in Side Chain

  • 이주연;이현주;김무용
    • Bulletin of the Korean Chemical Society
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    • 제17권3호
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    • pp.257-262
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    • 1996
  • p-(2-Vinyloxyethoxy)benzylidenemalononitrile 2 and methyl p-(2-vinyloxyethoxy)benzylidenecyanoacetate 3 was prepared by the condensation of p-(2-vinyloxyethoxy)benzaldehyde 1 with malononitrile or methyl cyanoacetate, respectively. Vinyl ether monomers 2 and 3 polymerized quantitatively with radical initiators in γ-butyrolactone solution at 65 ℃. The trisubstituted terminal double bond participated in the vinyl polymerization and radical polymerization of 2 and 3 led to swelling polymers 4 and 5 that were not soluble in common solvents due to cross-linking. Under the same polymerization conditions ethylvinyl ether polymerized well with model compounds of p-methoxybenzylidenemalononitrile 6 and methyl p-methoxybenzylidenecyanoacetate 7, respectively, to give 1:1 alternating copolymers 8 and 9 in high yields. Polymers 4 and 5 showed a thermal stability up to 300 ℃ without any characteristic Tg peaks in DSC thermograms. Alternating copolymers 8 and 9 were soluble in common solvents such as acetone and DMSO, and the inherent viscosities of the polymers were in the range of 0.36-0.74 dL/g. Films cast from acetone solution were cloudy and tough and Tg values obtained from DSC thermograms were in the range of 59-60 ℃.

Characterization of Residual Lignins from Chemical Pulps of Spruce (Picea abies) and Beech (Fagus sylvatica) by KMnO4 Oxidation

  • Choi, J.-W.;Faix, O.
    • Journal of the Korean Wood Science and Technology
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    • 제31권6호
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    • pp.31-39
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    • 2003
  • The enzymatic isolation of residual lignins obtained from spruce and beech pulps (obtained by sulfite, kraft, ASAM and soda/AQ/MeOH pulping processes) and their characterization was described in previous publications. Here, the residual lignins have been submitted to potassium permanganate oxidation (KMnO4 degradation), and 9 aromatic carboxylic acids (3 of them are dimeric) were identified after methylation with diazomethane by GC/MS. The analytical challenge during qantification by the internal standard methods was the partly high protein content of the samples, which resulted in elevated anisic acid yields in the degradation mixture of sulfite residual lignins. The results are compared with the KMnO4 degradation of the corresponding MWLs and discussed in terms of S/G ratios and degrees of condensation. The latter was calculated as a quotient between the aromatic carboxylic acids derived from condensed and non-condensed lignin structures. Typical degradation patterns for the various processes have been observed. Among other parameter, the relative compositions between iso-hemipinic acid (which is for condensation in pos. 5 of the aromatic ring) and meta-hemipinic acid and 3,4,5-trimethoxyphthalic acid (both are for condensation in pos. 6 of the aromatic ring) was found to be process specific. Kraft and soda/AQ/MeOH residual lignins yielded higher amounts of iso-hemipinic acid. In contrast, the relative yields of meta-hemipinic acid and 3,4,5-trimethoxyphthalic acid (the latter in beech lignins) are higher in sulfite and particularly in ASAM residual lignin. In case of beech residual lignins the amount of acids originated from non-condensed syringyl type lignin units was surprisingly high. The condensation degree of residual lignins was shown to be generally higher than that of MWLs. This was especially true for the G units. ASAM residual lignin exhibited very high S/G ratios and degrees of polymerization. Causality between condensation degree and total yield of degradation products was demonstrated.

DEVELOPMENT OF MEMBRANE AND COLD-CONDENSATION PROCESS FOR REMOVAL AND RECOVERY OF VOLATILE ORGANIC COMPOUNDS

  • Kim, Sung-Soo;Lee, Jong-Hwa;Kim, Hyunki;Kim, Sang-Yong
    • 한국막학회:학술대회논문집
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    • 한국막학회 2003년도 The 4th Korea-Italy Workshop
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    • pp.69-72
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    • 2003
  • Volatile organic compounds (VOC) cause air pollution problem and deterioration of atmosphere of petrochemical and fine chemical plants. Hybrid process of membrane and cold-condensation were developed and it effectively removed and recycled the VOC. Operation parameters of the process were optimized to attain hish removal and recycle of VOC. Composite membranes for organic vapor separation were developed in this work by PDMS coating and plasma polymerization on polypropylene and polysulfone support membranes. PDMS and various silicone monomers were tested for several organic vapors such as benzene, toluene, TCE, and HCFC, which are produced in petrochemical and fine chemical industry and causes air pollution problems if are released to atmosphere. Composite membranes prepared in this work showed appreciable performance in terms of organic vapor removal and reuse. Performance variation of the membranes was correlated with their surface characteristics.

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Synthesis, Characterization and Application of Poly(4-Methyl Vinylpyridinium Hydroxide)/SBA-15 Composite as a Highly Active Heterogeneous Basic Catalyst for the Knoevenagel Reaction

  • Kalbasi, Roozbeh Javad;Kolahdoozan, Majid;Massah, Ahmadreza;Shahabian, Keinaz
    • Bulletin of the Korean Chemical Society
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    • 제31권9호
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    • pp.2618-2626
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    • 2010
  • In this paper poly (4-methyl vinylpyridinium hydroxide)/SBA-15 composite was prepared as a highly efficient heterogeneous basic catalyst by in situ polymerization method for the first time. It was characterized by XRD, FT-IR, BET, TGA, SEM and back titration using NaOH. This catalyst exhibited the excellent catalytic activities for the Knoevenagel condensation of various aldehydes with ethyl cyanoacetate. Over this catalyst, ${\alpha},{\beta}$-unsaturated carbonyl compounds were obtained in the reasonable yield at $95^{\circ}C$ in 10 - 30 min in $H_2O$ as a solvent with a 100% selectivity to the condensation products. Catalyst could be easily recycled after the reaction and it could be reused without the significant loss of activity/selectivity performance. No by-product formation, high yields, short reaction times, mild reaction conditions and operational simplicity with reusability of the catalyst were the salient features of the present synthetic protocol. Presence of $H_2O$ as a solvent was also recognized as a "green method".