Article
  • Molecula Dimension of Poly(organophosphazene) : 2. Unperturbed Molecular Dimension of Poly[bis(phenylphenoxy)phosphazene]
  • Lee DC
  • Poly(grganophosphazene) 고립연쇄의 분자형태 : 2. Poly[bis(phenylphenoxy)phosphazene] 고립연쇄의 분자형태
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Abstract
Molecular characterization by dilute solution technique was made on those well fractionated samples of poly[bis(phenylphenoxy)phosphazene](PBPPP) ranging in number-average molar mass Mn from 8.3×104 to 176×104g/㏖. In cyclohexanone at 50℃, the excluded volume effect vanished and the intrinsic viscosity under theta condition was not proportional to Ml/2. In cyclohexanone at 60℃, it is found that the molecules are found to be unperturbd below Mn=8.7×105g/㏖ even they have positive value of second virial coefficient, and perturbed above it. When modeled by the wormlike cylinder, the unperturbed PBPPP chain was characterized by a persistence length q=4.2nm and a molar mass per unit contour length ML=1300nm-1, Values of the radius-expansion factor αs for the PBPPP fractions were calculated on the basis of the relation αη 3=αs 1.79. The mean square radius of gyration 2> data, being computed with the combination of αs values and Flory-Fox expression, was treated in terms of Blenoit-Doty theory to yield 80 for the critical segment number nk c. The binary cluster integral βfound at above nk c=80 in perturbed state was 77.6×10-24㎤, which suggests the chain is flexible but expanded. All the experimental result so far obtained indicated that the overall chain conformation of PBPPP is essentially semiflexible and changes continuously from a short rod to a long expanded coil with an increase in molar mass.

Poly[bis(phenylphenoxy)phosphazene](PBPPP)를 합성하고 분별하였으며, 분별시 료들에 대한 분자특성을 용액론적 방법으로 결정하였다. 분별시료들의 분자량범위는 8.3×104에서 176×104g/㏖이었다. Cyclohexanone 50℃에서 배제체 적효과가 사라졌으며, 이 θ-상태에서 본성점도는 M1/2에 비례하지 않았다. 이것으로 미루어 PBPPP분자는 반굴곡성 분자특성을 갖는 것으로 판단되었다. Cyclohexanone 60℃에서 분자량 8.7×105g/㏖ 이하의 분자들은 A2가 양의 값이었으나 근본적으로 비섭동상태이었으며 분자량 8.7×105g/㏖ 이상에서는 섭동상태이었다. Yamakawa와 Fujii의 wormlike cylinder 이론에 의한 비섭동 PBPPP 분자의 persistence length, q는 4.2nm 및 shift factor, ML은 1300nm-1이었다. αη 3=αs 1.79 의 관계와 Flory-Fox식을 이용하여 관성반경, 2> 값을 계산하였고, Benoit-Doty의 식을 이용, nk c값 80을 산출하였다. Cyclohexanone 60℃에서 nk c > 80에서는 배제체적효과가 나타났으며 이때 binary cluster integral, β 값은 77.6×10-24 ㎤로서 확장된 coil형 연쇄의 거동을 보였다. 이상의 모든 실험적 결과로 PBPPP분자는 근본적으로 반굴곡성 분자특성을 취하나, 저분자량측에서는 막대형의 경직성을 나타내고 분자량이 증가할수록 배제체적효과에 의하여 유연해지는 분자특성을 지닌 것으로 밝혀졌다.

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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

  • 1992; 16(3): 351-362

    Published online May 25, 1992