Article
  • Synthesis of Dendritic Polystyrene-block-Linear Poly(t-butyl acrylate) Copolymers by an Amide Coupling
  • Song J, Cho BK
  • 아미드 커플링을 통한 덴드리틱 Polystyrene-block-Linear Poly(t-butyl acrylate) 공중합체의 합성
  • 송걸, 조병기
Abstract
In this study, we synthesized a series of dendritic polystyrene-b-linear poly(t-butyl acrylate) copolymers with well-defined molecular architectures. The hydroxyl group located at the focal point of the second generation dendron bearing polystyrene(Mn=1000 g/mol) peripheries was converted into amine group via the following stepwise reactions: 1) tosylatoin, 2) azidation, and 3) reduction. On the other hand, the linear poly(t-butyl acrylate)s were prepared by an atom transfer radical polymerization(ATRP) of t-butyl acrylate where benzyl 2-bromopropanoate and Cu(I)Br/PMDETA were used as initiator and catalyst, respectively. To convert the end group of prepared poly(t-butyl acrylate)s into carboxylic acid, a debenzylation was performed using Pd/C catalyst under H2 atmosphere. In the final step, dendriticlinear block copolymers were obtained through a simple amide coupling reaction mediated by 4-(dimethylamino)pyridine(DMAP) and N,N′-diisopropylcarbodiimide(DIPC). The resulting diblock copolymers were shown to have well-defined molecular weights and narrow molecular weight distributions as supported by 1H-NMR spectroscopy and gel permeation chromatography(GPC).

본 연구에서는 잘 정의된 덴드리틱 폴리스티렌-블록-선형 폴리(3차 부틸 아크릴레이트) 공중합체를 성 공적으로 합성하였다. 음이온 중합법을 통해 합성된 폴리스티렌(Mn=1000 g/mol)을 외곽부분으로 함유하는 덴드론의 수산기 그룹을 토실화(tosylation), 아지드화(azidation), 환원(reduction) 반응을 통해 아민기로 전환하였다. 한편, 선형 poly(t-butyl acrylate)는 DMF 용매에서 benzyl 2- bromopropanoate/Cu(I)Br, PMDETA/t-butyl acrylate를 각각 개시제/촉매 시스템/단량체로 사용하여, 원자이동라디칼 중합법(atom transfer radical polymerization, ATRP)을 통해 합성할 수 있었고, 말단을 카르복시산 그룹으로 전환하기 위해 수소기체 환경하에서 Pd/C을 사용하여 탈벤질화(debenzylation) 반응을 수행하였다. 마지막으로, 합성된 덴드리틱 및 선형 블록들을 다이메틸아 미노피리딘(4-(dimethylamino)pyridine, DMAP)과 다이아이소프로필카보다이이미드(N,N′-diisopropylcarbodiimide, DIPC)를 이용한 아미드 커플링 방법을 통해 최종 덴드리틱-선형의 블록공중합체를 합성하였다. 합성된 블록공중합체를 수소원자핵공명법 및 겔침투크로마토그래피 방법을 통해 조사한 결과, 잘 정의된 분자량 및 낮은 분자량 분포를 확인할 수 있었다.

Keywords: dendritic-linear diblock copolymer; amide coupling; atom transfer radical polymerization (ATRP).

  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2022 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 2009; 33(2): 158-163

    Published online Mar 25, 2009

  • 10.7317/pk.
  • Received on Oct 17, 2008
  • Revised on Nov 30, -0001
  • Accepted on Nov 29, 2008

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