Poly(grganophosphazene) 고립연쇄의 분자형태 : 2. Poly[bis(phenylphenoxy)phosphazene] 고립연쇄의 분자형태

이동주

Polymer(Korea), Vol.16, No.3, 351-362, May, 1992

Molecula Dimension of Poly(organophosphazene) : 2. Unperturbed Molecular Dimension of Poly[bis(phenylphenoxy)phosphazene]

이동주

초록

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 M^1/2에 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, M_L은 1300nm^-1이었다. α_η ³=α_s ^1.79 의 관계와 Flory-Fox식을 이용하여 관성반경, 2> 값을 계산하였고, Benoit-Doty의 식을 이용, n_k ^c값 80을 산출하였다. Cyclohexanone 60℃에서 n_k ^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.

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 M_n 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 M^l/2. In cyclohexanone at 60℃, it is found that the molecules are found to be unperturbd below M_n=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 M_L=1300nm^-1, Values of the radius-expansion factor α_s for the PBPPP fractions were calculated on the basis of the relation α_η ³=α_s ^1.79. The mean square radius of gyration 2> data, being computed with the combination of α_s values and Flory-Fox expression, was treated in terms of Blenoit-Doty theory to yield 80 for the critical segment number n_k ^c. The binary cluster integral βfound at above n_k ^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.

[References]

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[Referenced By]

[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 H, "Modern 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 Y, "Doctoral 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)