• 제목/요약/키워드: Alternating copolymer

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이산화탄소로부터 Poly(alkylene carbonate)의 합성 (Synthesis of Poly(alkylene carbonate) from Carbon Dioxide)

  • 이윤배;최정현
    • 공업화학
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    • 제7권5호
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    • pp.813-822
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    • 1996
  • 온실효과에 주요한 기여를 하는 이산화탄소를 줄이기 위하여 새로운 형태의 고분자인 폴리(알킬렌 카보네이트)가 합성되어졌다. 이산화탄소와 여러 가지 에폭시드로부터 칼복시산의 아연염을 촉매로 하여 교대 공중합체가 만들어졌다. 중합체의 수 평균 분자량은 50,000 정도이면 중합 분산도는 5~10 정도로 비교적 넓은 분포를 갖는다. 이 중합체는 비 결정성이고, 투명한 물질로써 열분해가 쉽게 일어난다. 높은 온도와 불활성 분위기 하에서도 완벽한 분해가 일어나 탄소 잔류물을 남기지 않는 것으로 알려졌다. 간단한 에폭시드와의 공중합체의 물리적인 성질을 개선하기 위하여 입체 장애가 큰 에폭시드와의 삼원 공중합체도 만들 수 있다. 이러한 분해성을 이용하여 세라믹, 금속, 전자 산업용 바인더나 lost-foam casting에 활용이 검토되었다. 또한 포장용 필름이나 가소제로의 활용도 연구될 수 있을 것으로 기대된다.

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PCL/PCL-g-PEG 생분해성 블렌드에서 그래프트 공중합체의 조성에 따른 상용성의 영향 (Effect of Graft Copolymer Composition on the Compatibility of Biodegradable PCL/PCL-g-PEG Blend)

  • 조국영;이기석;박정기
    • 폴리머
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    • 제33권3호
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    • pp.248-253
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    • 2009
  • 의료용으로 적용될 수 있는 새로운 재료를 제조하기 위하여 폴리카프로락톤(PCL)과 양친성 구조를 갖는 폴리(에틸렌 글리콜)(PEG)이 그래프트된 PCL을 이용하여 생분해성 블렌드를 제조하였다. 제조된 블렌드는 PCL을 기본으로 하고 여기에 그래프트 공중합체의 함량을 변화시키며 열적 그리고 결정화 특성을 관찰하였다. 그래프트 공중합체의 함량 변화에 따라 결정화 온도의 변화 및 결정화 속도가 변화하였고 이를 통해 그래프트 공중합체가 PCL의 결정화 거동에 영향을 미침을 확인하였다. 이는 광학현미경을 통한 결정의 교대 소광 밴드의 관찰을 통하여서도 확인할 수 있었다. 약물방출시스템과 같은 의료용 응용을 고려하여 블렌드 필름의 흡수거동과 단백질 흡착에 대한 특성도 평가하였다.

비닐포스폰산 비스-${\beta}$-클로로에틸과 초산비닐의 혼성중합 (Copolymerization of Bis(${\beta}$-chloroethyl)vinylphosphonate and vinyl Acetate)

  • 진정일;변회섭;박유미
    • 대한화학회지
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    • 제21권3호
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    • pp.219-224
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    • 1977
  • 비닐포스폰산 비스-${\beta}$-클로로에틸(BCVP)과 초산비닐(VAc)의 혼성중합을 $50^{\circ{C$에서 행하여 단위체 반응성비를 구하였다. 이때 과산화벤조일을 개시제로 사용하였으며, 얻은 반응성비는 아래와 같다. $r_1 (VAc) = 0.33,\;r_2 (BCVP) = 0.47$ 이 값과 Alfrey-Price식을 이용하여 비닐포스폰산 비스-${\beta}$-클로로에틸의 Q와 e값을 계산하니 Q = 0.06 및 e = 1.1을 얻었다. 이 두 단위체로부터 얻어지는 혼성중합체중의 단위체 서열분포와 평균서열 길이를 통계적으로 분석한 결과 혼성중합체가 비교적 높은 교대경향을 갖고 있음을 알았다. 또한 혼성중합체중에 비닐포스폰산 비스-${\beta}$-클로로에틸의 함량이 많을 수록 열안정성이 나뻐짐을 열시차분석에서 관찰하였다.

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Copolymerization of N-Vinyl Pyrrolidone with Functionalized Vinyl Monomers: Synthesis, Characterization and Reactivity Relationships

  • Vijaykumar, S.;Prasannkumar, S.;Sherigara, B.S.;Shelke, N.B.;Aminabhavi, Tejraj M.;Reddy, B.S.R.
    • Macromolecular Research
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    • 제17권12호
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    • pp.1003-1009
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    • 2009
  • Copolymers of N-vinylpyrrolidone (NVP) comonomer with styrene (St), hydroxypropyl methacrylate (HPMA) and carboxyphenyl maleimide (CPMI) were synthesized by free radical polymerization using 2,2'-azobisisobutyronitrile (AIBN) initiator in 1,4-dioxane solvent. The copolymers formed were characterized by FTIR, $^1H$ NMR and $^{13}C$ NMR techniques and their thermal properties were studied by DSC and TGA. Copolymer composition was determined by $^1H$ NMR and/or by elemental analysis and monomer reactivity ratios (MRR) were estimated by the linear methods of Kelen-Tudos (K-T) and extended Kelen-Tudos (EK-T) and the non-linear approach. Copolymers of St and HPMA with NVP formed blocks of one of the monomer units, whereas alternating copolymers were obtained in CPMI-NVP, depending upon the side chain substitution. The MRR values are discussed in terms of monomer structural properties such as electronegativity and electron delocalization. The sequence distribution of monomers in the copolymers was studied by statistical method based on the average reactivity ratios obtained by EK-T method.

방사무늬김(Porphyra yezoensis)에서 추출한 Porphyran 효소 분해물의 화학적 결합 특성 (Structural Features of Enzymatic Hydrolysate of Porphyran Isolated from Porphyra yezoensis)

  • 박진희;구재근
    • 한국수산과학회지
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    • 제44권6호
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    • pp.630-634
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    • 2011
  • Enzymatic hydrolysate of porphyran from Porphyra yezoensis was prepared by treatment with ${\beta}$-agarase. The hydrolysate was fractioned into molecular sizes of <3, 3-30, and 30-300 kDa using an ultrafiltration membrane. The membrane fractions were further separated into neutral and anionic fractions using Dowex $1{\times}8$ ion exchange chromatography. After hydrolysis of porphyran with ${\beta}$-agarase, 23.2% of the starting porphyran was recovered as a neutral fraction of low-molecular weight (<3 kDa), and 28.9% remained as an enzyme-resistant anionic fraction of high molecular weight (>300 kDa). Desulfation of porphyran and $^{13}C$-NMR analysis of the anionic fraction of low molecular weight (<3 kDa) showed that the anionic fraction has a backbone consisting of 3-linked ${\beta}$-D-galactose units alternating with either 4-linked a-L-galactose 6-sulfate or 3, 6-anhydro-a-L-galactose units. These results indicate that porphryan is a copolymer of two moieties, about 25% of which are composed of neoagarose moieties and 75% as anionic moieties.

Preparation of Red Perylene Fluoroionophore Containing Calix[4]azacrown Ether and Their Ionophoric Properties

  • Jeon, Young-Min;Lim, Tae-Ho;Kim, Jong-Gyu;Kim, Jong-Seung;Gong, Myoung-Seon
    • Bulletin of the Korean Chemical Society
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    • 제28권5호
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    • pp.816-820
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    • 2007
  • Novel new red-light emitting perylene fluoroionophore N,N'-dipropyl-1,7-bis(calix[4]azacrown-5-crown-5)- 3,4,9,10-perylene tetracarboxy diimide (3) was prepared by reacting N,N'-dipropyl-1,7-dibromo-3,4,9,10- perylene tetracarboxy diimide (1) with calix[4]azacrown-5-crown-5. Also the alternating copolymer (4) with similar repeating unit was prepared reacting by calix[4]bisazacrown-5 with 1. Metal ion binding by 3 and 4 leads to a blue-shift of absorption band and emission spectra. When ionophoric characteristics were investigated by binding alkali, alkali earth metal and various metal ions, polymeric ionophores displayed large fluorescence decreasing effects with K+, Ag+ and Ba2+, which was rationalized by photo-induced charge transfer (PCT).

Copolymerization of Ethylene and Norbornene via Polymethylene Bridged Dinuclear Constrained Geometry Catalysts

  • Zhu, Yin-Bang;Jeong, Eung-Yeong;Lee, Bae-Wook;Kim, Bong-Shik;Noh, Seok-Kyun;Lyoo, Won-Seok;Lee, Dong-Ho;Kim, Yong-Man
    • Macromolecular Research
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    • 제15권5호
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    • pp.430-436
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    • 2007
  • The dinuclear half-sandwich CGCs (constrained geometry catalyst) with a polymethylene bridge, $[Ti({\eta}^5 : {\eta}^1-indenyl)SiMe_2NCMe_3]_2(CH_2)_n]$[n = 6 (1) and 12 (2)], have been employed in the copolymerization of ethylene and norbornene (NBE). To compare the mononuclear metallocene catalysts; $Ti({\eta}^5 : {\eta}^1-2-hexylindenyl)SiMe_2NCMe_3$ (3), $(Cp^* SiMe_2NCMe_3)$Ti (Dow CGC) (4) and ansa-$Et(Ind)_2ZrCI_2$ (5), were also studied for the copolymerization of ethylene and NBE. It was found that the activity increased in the order: 1 < 2 < 3 < 5 < 4, indicating that the presence of the bridge between two the CGC units contributed to depressing the polymerization activity of the CGCs. This result strongly suggests that the implication of steric disturbance due to the presence of the bridge may playa significant role in slowing the activity. Dinuclear CGCs have been found to be very efficient for the incorporation of NBE onto the polyethylene backbone. The NBE contents in the copolymers formed ranged from 10 to 42%, depending on the polymerization conditions. Strong chemical shifts were observed at ${\delta}$42.0 and 47.8 of the isotactic alternating NBE sequences, NENEN, in the copolymers with high NBE contents. In addition, a resonance at 47.1 ppm for the sequences of the isolated NBE, EENEE, was observed in the $^{13}C-NMR$ spectra of the copolymers with low NBE contents. The absence of signals for isotactic dyad at 48.1 and 49.1 ppm illustrated there were no isotactic or microblock (NBE-NBE) sequences in the copolymers. This result indicated that the dinuclear CGCs were effective for making randomly distributed ethylene-NBE copolymers.

레이저 광산란법에 의한 폴리에스터/실세스키옥세인 나노복합재료 응집체의 구조분석 (Structural Analysis of Microphase-separated Aggregates of Polyester/Polyhedral Oligomeric Silsesquioxane Nanocomposite by Laser Light Scattering)

  • 유영철;김장경;윤관한;박일현
    • 폴리머
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    • 제31권6호
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    • pp.461-468
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    • 2007
  • 폴리에스터와 trisilanolisobutyl polyhedral oligomeric silsesquioxane(TBPOSS)으로 제조된 나노복합재료에 존재하는 응집체의 구조를 이해하기 위하여 SEM-EDS 분석과 1,1,1,3,3,3-hexafluoro-2-propanol(HFIP) 용매에 녹인 뒤 레이저 광산란법이 실시되었다. SEM에서 평균 직경 120 nm로 나타난 구형 응집체는 가교화된 마이크로겔이 아니라, 320개의 TBPOSS 분자들과 폴리에스터 분절들이 교대로 연결된 선형 중합체 사슬(무게평균 분자량=$2.3{\times}10^6\;g/mol$)이며, 이들은 매트릭스의 폴리에스터와의 화학조성 차이 때문에 상분리된 것으로 여겨진다. 반면에 무게평균 분자량이 $4.0{\times}10^4\;g/mol$인 매트릭스의 폴리에스터는 분자당 2.5개의 TBPOSS 분자를 포함하고 있는 것으로 나타났다. 또한 넣어준 TBPOSS의 약 93%가 매트릭스에 존재하며 나머지 7%는 구형 응집체에 분포하고 있다는 것도 밝혀졌다.

Modeling Studies of an Exotype Alginate Lyase Atu3025 from Agrobacterium Tumefaciens Strain C58, a Member of Polysaccharide Lyase Family 15

  • ;조승주
    • 통합자연과학논문집
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    • 제3권2호
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    • pp.72-77
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    • 2010
  • Alginate lyases, also known as alginases or alginate depolymerases, catalyze the degradation of alginate by a ${\beta}$-elimination mechanism that has yet to be fully elucidated. Alginate is a copolymer of ${\alpha}$-L-guluronate (G) and its C5 epimer ${\beta}$-D-mannuronate (M), arranged as homopolymeric G blocks, M blocks, alternating GM or random heteropolymeric G/M stretches. Almost all alginate lyases depolymerize alginate in an endolytical fashion via a ${\beta}$-elimination reaction. The alginate lyase Atu3025 from Agrobacterium tumefaciens strain C58, consisting of 776 amino-acid residues, is a novel exotype alginate lyase classified into polysaccharide lyase family 15. Till now there is no crystal structure available for this class of proteins. Since there is no template with high sequence identity, three-dimensional coordinates for exotype alginate lyase (PL 15 family) were determined using modeling methods (Comparitive modeling and Fold recognition). The structures were modeled using the X-ray coordinates from Heparinase protein family (PDB code: 3E7J). This enzyme (Atu3025) displays enzymatic activity for both poly-M and poly-G alginate. Since poly-M is widespread; docking of a tri-mannuronate against the modeled structure was performed. We identified some of those residues which are crucial for lyase activity. The results from this study should guide future mutagenesis studies and also provides a starting point for further proceedings.

Novel 4,7-Dithien-2-yl-2,1,3-benzothiadiazole-based Conjugated Copolymers with Cyano Group in Vinylene Unit for Photovoltaic Applications

  • Kim, Jin-Woo;Heo, Mi-Hee;Jin, Young-Eup;Kim, Jae-Hong;Shim, Joo-Young;Song, Su-Hee;Kim, Il;Kim, Jin-Young;Suh, Hong-Suk
    • Bulletin of the Korean Chemical Society
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    • 제33권2호
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    • pp.629-635
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    • 2012
  • Two novel conjugated copolymers utilizing 4,7-dithien-2-yl-2,1,3-benzothiadiazole (DTBT) coupled with cyano (-CN) substituted vinylene, as the electron deficient moeity, have been synthesized and evaluated in bulk heterojunction solar cell. The electron deficient moeity was coupled with carbazole and fluorene unit by Knoevenagel condition to provide poly(bis-2,7-((Z)-1-cyano-2-(5-(7-(2-thienyl)-2,1,3-benzothiadiazol-4-yl)-2-thienyl)ethenyl)-alt-9-(1-octylnonyl)-9H-carbazol-2-yl-2-butenenitrile) (PCVCNDTBT) and poly(bis-2,7-((Z)-1-cyano-2-(5-(7-(2-thienyl)-2,1,3-benzothiadiazol-4-yl)-2-thienyl)ethenyl)-alt-9,9-dihexyl-9H-fluoren-2-yl) (PFVCNDTBT). The optical band gaps of PCVCNDTBT (1.74 eV) and PFVCNDTBT (1.80 eV) are lower than those of PCDTBT (1.88 eV) and PFVDTBT (2.13 eV), which is advantageous to provide better coverage of the solar spectrum in the longer wavelength region. The high $V_{oc}$ value of the PSC of PCVCNDTBT (~0.91 V) is attributed to its lower HOMO energy level ( 5.6 eV) as compared to PCDTBT ( 5.5 eV). Bulk heterojunction solar cells based on the blends of the polymers with [6,6]phenyl-$C_{61}$-butyric acid methyl ester ($PC_{61}BM$) gave power conversion efficiencies of 0.76% for PCVCNDTBT under AM 1.5, 100 mW/$cm^2$.