• 제목/요약/키워드: sequential monomer addition

검색결과 6건 처리시간 0.021초

Synthesis of Norbornene Block Copolymers Containing Polyhedral Oligomeric Silsesquioxane by Sequential Ring-Opening Metathesis Polymerization

  • Kwon Young-Hwan;Kim Kyung-Hoe
    • Macromolecular Research
    • /
    • 제14권4호
    • /
    • pp.424-429
    • /
    • 2006
  • The synthesis of a series of poly(POSS-NBE-b-MTD) copolymers was successfully accomplished, taking advantage of sequential, ring-opening, metathesis block copolymerization using $RuCl_2(=CHPh)(PCy_3)_2$ catalyst. By using cyclopentyl-POSS-norbornene (POSS-NBE) monomer as the first block in the block copolymer, living poly(POSS-NBE) with controlled molecular weight and narrow molecular weight distribution was produced. Then, poly(POSS-NBE-b-MTD) copolymers were successfully prepared, in which sequential monomer addition of methyltetracyclododecene (MTD) to the living poly(POSS-NBE) chain ends was utilized to achieve quantitative crossover efficiency. Characterization by $^1H$ NMR spectroscopy and GPC confirmed the high definition and structural integrity of the poly(PO$S-NBE-b-MTD) copolymers. Thermal properties-and morphologies of the POSS-containing block copolymer nanocomposites were also investigated by using thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and wide-angle X-ray scattering (WAXS).

Amphiphilic Norbornene-Based Diblock Copolymers Containing Polyhedral Oligomeric Silsesquioxane Prepared by Living Ring Opening Metathesis Polymerization

  • Park, Su-Dong;Xu, Wentao;Chung, Chan-Hong;Kwon, Young-Hwan
    • Macromolecular Research
    • /
    • 제16권2호
    • /
    • pp.155-162
    • /
    • 2008
  • We report the successful synthesis of poly(NBECOOH-b-NBEPOSS) copolymers, taking advantage of the sequential, living ring opening metathesis polymerization of NBETMS and NBEPOSS using the $RuCl_2(=CHPh)(PCY_3)_2$/$CH_2Cl_2$/$20^{\circ}C$ system, followed by the hydrolysis of trimethylsilyl groups in poly(NBETMS-b-NBEPOSS) copolymers. The living behavior of ROMP of NBETMS was first investigated using two diagnostic plots, a first order kinetic plot and a $\bar{M}_n$ vs. conversion plot. The plots confirmed that no termination and chain transfer reaction had occurred during polymerization. Poly(NBECOOH-b-NBEPOSS) copolymers were prepared using the sequential monomer addition of NBEPOSS to living poly(NBETMS) chain ends, followed by the hydrolysis of trimethylsilyl groups in the poly(NBETMS-b-NBEPOSS) copolymers. The high structural integrity of poly(NBE-COOH-b-NBEPOSS) copolymers was confirmed by $^1H$-NMR, $^{13}C$-NMR spcctroscopy and GPC.

Synthesis of New pH-Sensitive Poly(ethylene oxide-b-maleic acid) from Modification of Poly(ethylene oxide-b-N-phenylmaleimide)

  • Go, Da-Hyeon;Jeon, Hee-Jeong;Kim, Tae-Hwan;Kim, Geun-Seok;Choi, Jin-Hee;Lee, Jae-Yeol;Kim, Jung-Ahn;Yoo, Hyun-Oh;Bae, You-Han
    • Macromolecular Research
    • /
    • 제16권7호
    • /
    • pp.659-662
    • /
    • 2008
  • A new and useful poly(ethylene oxide)-based pH-sensitive block copolymer is introduced. Poly(ethylene oxide-b-N-phenylmaleimide) was first synthesized by anionic polymerization of N-phenylmaleimide (N-PMI) using mixed alkali metal polymeric alkoxide by sequential monomer addition method in the mixture of benzene/THF/DMSO (10/5/3, v/v/v) at room temperature. Reductive deimidation of the resulting block copolymer was performed using hydrazine monohydrate leading to the formation of the corresponding pH-sensitive poly(ethylene oxide-b-maleic acid).

연속가교를 통한 피부 진피세포 담지 콜라겐 겔의 강도 제어 (Tuning the Stiffness of Dermal Fibroblast-encapsulating Collagen Gel by Sequential Cross-linking)

  • 정문희;신성규;임준우;한사라;김희진;정재현
    • 대한화장품학회지
    • /
    • 제44권1호
    • /
    • pp.23-29
    • /
    • 2018
  • 본 연구에서는 생체재료인 콜라겐과 합성 단량체인 아크릴아마이드를 연속가교 하여, 하이드로젤 기반의 콜라겐 겔을 제조하였다. 아크릴아마이드의 함량 및 가교 정도에 따라, 1.5 kPa에서 3.0 kPa까지 다양한 강도(E)를 갖는 콜라겐 겔을 제조할 수 있었다. 또한, 콜라겐 겔에 다공성 기공을 도입하고 진피세포를 내부에 담지하여, 겔 강도에 따른 세포 성장 및 거동을 확인하였다. 상대적으로 강도가 높은 겔에서 세포의 성장은 느렸지만 GAG 합성 및 분비는 활성화되는 것을 확인하였다. 콜라겐 겔의 기계적 물성에 따라 세포의 성장 및 활성이 영향을 받는 것을 알 수 있었으며, 이는 향후 인공피부 제조 및 응용, 나아가 다양한 조직공학 분야의 기반 기술로 활용 가능하리라 기대된다.

New Characterization Methods for Block Copolymers and their Phase Behaviors

  • Park, Hae-Woong;Jung, Ju-Eun;Chang, Tai-Hyun
    • Macromolecular Research
    • /
    • 제17권6호
    • /
    • pp.365-377
    • /
    • 2009
  • In this feature article, we briefly review the new methods we have utilized recently in the investigation of morphology and phase behavior of block copolymers. We first describe the chromatographic fractionation method to purify block copolymers from their side products of mainly homopolymers or block copolymer precursors inadvertently terminated upon addition of the next monomer in the sequential anionic polymerization. The chromatographic method is extended to the fractionation of the individual block of diblock copolymers which can yield the diblock copolymer fractions of different composition and molecular weight, which also have narrower distributions in both molecular weight and composition. A more detailed phase diagram could be constructed from the set of block copolymer fractions without the need of acquiring many block copolymers each prepared by anionic polymerization. The fractions with narrow distribution in both molecular weight and composition exhibit better long-range ordering and sharper phase transition. Next, epitaxial relationships between two ordered structures in block copolymer thin film is discussed. We employed the direct visualization method, transmission electron microtomography(TEMT) to scrutinize the grain boundary structure.

Drug Release from the Enzyme-Degradable and pH-Sensitive Hydrogel Composed of Glycidyl Methacrylate Dextran and Poly{acrylic acid)

  • Kim In-Sook;Oh In-Joon
    • Archives of Pharmacal Research
    • /
    • 제28권8호
    • /
    • pp.983-987
    • /
    • 2005
  • Hydrogels composed of glycidyl methacrylate dextran (GMD) and poly(acrylic acid, PM) were prepared by UV irradiation method for colon-specific drug delivery. GMD was synthesized by coupling of glycidyl methacrylate to dextran in the presence of 4-(N,N-dimethylamino)pyridine. GMD was photo-polymerized by ammonium peroxydisulfate as initiating system in phosphate­buffered solution (0.1 M, pH 7.4). And then, acrylic acid monomer was added and subsequently heat-polymerized by 2,2'-azobisisobutyronitrile as an initiator. The hydrogels exhibited high swelling ratio (about 20) at $37^{\circ}C$, and showed a pH-dependent swelling behavior. In addition, the swelling ratio of the hydrogel was remarkably enhanced to about 45 times in the presence of dextranase at pH 7.4. The swelling-deswelling behavior proceeded reversibly for the GMD/PM hydrogels between pH 2 and pH 7.4. Release of 5-aminosalicylic acid from the GMD/PAA hydrogels was evaluated in simulated gastrointestinal pH fluids in the absence or presence of dextranase. We concluded that the hydrogels prepared could be used as a dual-sensitive drug carrier for sequential release in gastrointestinal tract.