Article
  • Reactivity and Solvent Effect on the Cationic Copolymerization of 1- or 2-Vinylnaphthalenes with a-Methylstyrene
  • Oh ST, Jeong JG, Ha CS, Park DK, Kang DP, Cho WJ
  • 1- 및 2-Vinylnaphthalene과 α-Methylstyrene의 양이온 공중합에 관한 반응성과 용매 효과
  • 오상택, 정진곤, 하창식, 박동규, 강동필, 조원제
Abstract
The cationic copolymerizations of 1- or 2-vinylnaphthalenes with α-methylstyrene were carried out with titanium tetrachloride as an initiator at -60℃ in dichloromethane, chloroform, and toluene, respectively. Reactivity and solvent effects for the cationic copolymerizations were investigated. The monomer reactivity ratios, rl and r2(r2 is for α-methylstyrene) were determined by the Kelen-Tudos method; for the 1-vinylnaphthalene and α-methylstyrene system, rl=0.62 and r2=2.67 in dichloromethane, rl=0.26 and r2=3.55 in chloroform, and rl=0.10 and r2=5.23 in toluene, and for the 2-vinylnaphthalene and α-methylstyrene system, rl=0.76 and r2=3.01 in dichloromethane, rl=0.43 and r2=5.14 in chloroform, and rl=0.20 and r2=6.55 in toluene. The values of 1/rl for the copolymerization of 1- or 2-vinylnaphthalenes with α-methylstyrene decreased with increasing dielectric constants of solvent, but the 1/r2 values increased with incresing dielectric constants of solvents. The reactivity of 1-vinylnaphthalene to α-methylstyrene cation was greater than that of 2-vinylnaphthalene. The values of 1/r2 for the copolymerization of 1- or 2-vinylnaphthalene with α-methylstyrene cation increased with increasing superdelocalizability values of 1- or 2-vinylnaphthalene. The 1/r2 values increased with decreasing values of chemical shift of β-carbon in 13-NMR spectra of 1- and 2-vinylnaphthalene.

1-vinylnaphthalene(1-VN) 혹은 2-vinylnaphthalene(2-VN)과 α-methylstyrene의 양이온공중합에 대한 반응성과 용매의 영향을 연구하였다. 용매로서는 dichloromethane, chloroform 및 toluene 을 사용하여 -60℃에서 TiC14를 개시제로 1-VN혹은 2-VN을 α-methylstyrene과 각각 양이온공중합하였다. 단량체 상대 반응성비 rl과 r2값(r2는α-methylstyrene에 대한 값)은 Kelen-Tudos방법에 의해 구하였다. 1-VN과 α-MeSt의 공중합계는 dichloromethane에서 rl=0.62, r2=2.67, choroform에서 rl=0.26, r2=3.55, toluene에서 rl=0.10, r2=5.23이었으며, 2-VN과 α-MeSt의 공중합계는 dichloromethane에서 rl=0.76, r2=3.01, chloroform에서 rl=0.43, r2=5.14, toluene에서 rl=0.20, r2=6.55이었다. 1-VN 및 2-VN과 α-MeSt의 공중합에 있어서 1/rl의 값들은 용매의 유전 상수가 증가할수록 감소하였으나 1/r2의 값들은 용매의 유전 상수가 증가함에 따라 증가하였다. α-MeSt 양이온에 대한 1-VN의 반응성은 2-VN의 반응성보다 컸다. α-MeSt 양이온과 1-VN 덴 2-VN의 공중합에 있어서 1/r2 값은 1-VN혹은 2-VN의 초국재화값(superdelocalizability)이 증가할수록 그리고 1-VN과 2-VN의 13C-NMR 스펙트럼에서 β탄소의 chemical shift의 값이 감소할수록 증가했다.

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  • 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

  • 1993; 17(2): 152-160

    Published online Mar 25, 1993