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
  • 이동주
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.

References
  • 1. Allcock HR, Chem. Eng. News, 63, 22 (1985)
  •  
  • 2. Neilson RH, Neilson PW, J. Macromol. Sci.-Chem., A16, 425 (1981)
  •  
  • 3. Singler RE, Schneider NS, Hagnauer GL, Polym. Eng. Sci., 15, 321 (1975)
  •  
  • 4. Neilson RH, Hani R, Neilson PW, Meister JJ, Roy AK, Hagnauer GL, Macromolecules, 20, 910 (1987)
  •  
  • 5. Allcock HR, Chang JW, Macromolecules, 24, 993 (1991)
  •  
  • 6. Tanaka K, Yamashita S, Yamabe T, Macromolecules, 19, 2062 (1986)
  •  
  • 7. Kim CH, Allcock HR, Macromolecules, 20, 1726 (1987)
  •  
  • 8. Yamakawa HModern Theory of Polymer Solutions, Harper and Row, New York (1971)
  •  
  • 9. Allcock HR, Kugel RL, Valan KJ, J. Inorg. Chem., 5, 1709 (1966)
  •  
  • 10. Schultz AR, Flory PJ, J. Am. Chem. Soc., 74, 4760 (1952)
  •  
  • 11. Allcock HR, Connolly MS, Sisko JT, Al-Shali S, Macromolecules, 21, 323 (1988)
  •  
  • 12. Hario TY, Teramoto A, Sato TH, Norisuye T, Masuda T, Higahimura TN, Polym. J., 23, 925 (1991)
  •  
  • 13. Yamakawa H, Pure Appl. Chem., 31, 179 (1972)
  •  
  • 14. Tsuji T, Norisuye T, Fujita H, Polym. J., 7, 558 (1975)
  •  
  • 15. Stockmayer WH, Fixman M, J. Polym. Sci. C: Polym. Lett., 1, 13 (1963)
  •  
  • 16. Kitakawa T, Sadanobu J, Norisuye T, Macromolecules, 23, 602 (1990)
  •  
  • 17. Yamakawa H, Fujii M, Macromolecules, 6, 407 (1973)
  •  
  • 18. Yamakawa H, Fujii M, Macromolecules, 7, 128 (1974)
  •  
  • 19. Yamakawa H, Yoshizaki T, Macromolecules, 13, 633 (1980)
  •  
  • 20. Bohdanecky M, Macromolecules, 16, 1483 (1983)
  •  
  • 21. Allcock HR, Arcus RA, Stroh EG, Macromolecules, 13, 919 (1980)
  •  
  • 22. Benoit H, Doty P, J. Phys. Chem., 57, 958 (1953)
  •  
  • 23. Miyaki YDoctoral Thesis, Osaka Univ. (1981)
  •  
  • 24. Flory PJ, Fox TG, J. Am. Chem. Soc., 73, 1904 (1951)
  •  
  • 25. Kashiwaki Y, Norisuye T, Fujita H, Macromolecules, 14, 1220 (1981)
  •  
  • 26. Murakami H, Norisuye T, Fujita H, Macromolecules, 13, 345 (1980)
  •  
  • 27. Motowoka M, Fujita H, Norisuye T, Polym. J., 10, 331 (1978)
  •  
  • 28. Oyama T, Shiokawa K, Baba K, Polym. J., 13, 167 (1981)
  •  
  • 29. Sadanobu J, Norisuye T, Fujita H, Polym. J., 13, 75 (1981)
  •  
  • 30. Kratky O, Porod G, Real. Trav. Chim. Paysbas, 68, 1106 (1949)
  •  
  • 31. Yamakawa H, Stockmayer WH, J. Chem. Phys., 57, 2843 (1972)
  •  
  • 32. Domb C, Barett AJ, Polymer, 17, 179 (1976)
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2023 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 1992; 16(3): 351-362

    Published online May 25, 1992