프로필렌/1-헥센 공중합체의 제조와 성질

이동호; 김진태; 정영태

Polymer(Korea), Vol.16, No.4, 451-459, July, 1992

Export Citation

프로필렌/1-헥센 공중합체의 제조와 성질

Preparation and Properties of Propylene/1-Hexene Copolymer

이동호, 김진태, 정영태

초록

염화마그네슘을 2-ethyl-1-hexanol(EHA)에 녹인 용액으로부터 제조한 사염화티탄 담지촉매로 프로필렌과 1-헥센의 공중합을 행하였다. 이때 촉매의 제조 조건 및 중합 조건 등에 따른 촉매의 활성과 공중합체의 조성을 조사하였으며, 아울러 첨가제인 Lewis염기의 영향도 조사하였다. 프로필렌/1-헥센 공중합에서 [TEA]/[Ti]의 농도비가 60일 경우에 최대의 활성을 나타내었으며, 공중합체의 1-헥센 함량은 [TEA]/[Ti]의 농도비에 관계없이 일정하였다. Kelen-Tudos 방법으로 구한 단량체의 반응성비는 촉매의 제조조건 및 Lewis염기의 유무에 따라 변하였다. Lewis염기를 첨가함에 따라 촉매의 활성과 1-헥센의 함량은 감소하였다. 또한 공중합체의 열적 성질과 기계적 성질도 조사하였다.

The copolymerization of propylene and 1-hexene with MgCl₂/EHA/TiCl₄-TEA system has been studied in which MgCl₂ was dissolved in 2-ethyl-1-hexanol(EHA). The effects of catalyst preparation conditions and polymerization conditions on the activity and composition of copolymers have been investigated. The maximum activity was obtained at [TEA]/[Ti]=60 and the content of 1-hexene was constant irrespective to [TEA]/[Ti]. The monomer reactivity ratio was dependent on the catalyst preparation conditions and the presence of Lewis bases. With addition of Lewis bases, the activity and 1-hexene contents in copolymer decreased. Thermal properties and mechanical properties of copolymer were also investigated.

[References]

Boor J, "Ziegler-Natta Catalysts and Polymerization," p. 264, Academic Press, New York (1979)
Lee DH, Hsu CC, Hsu CC, J. Appl. Polym. Sci., 26, 653 (1981)
Lee DH, Jang JK, Ahn TO, J. Polym. Sci. A: Polym. Chem., 25, 1457 (1987)
Lee DH, Min KE, Kim CW, J. Korean Chem. Soc., 31, 110 (1987)
Lee DH, Min KE, Ahn TO, Polym. J., 8, 973 (1987)
Lee DH, Min KE, Ha KR, Jo WH, Polym.(Korea), 11(3), 278 (1987)
Lee DH, Lee DH, Ahn TO, Polymer, 29, 713 (1988)
Lee DH, Min KE, Jo WH, Jeong YT, Polym.(Korea), 13(1), 68 (1989)
Lee DH, You KH, Jeong HM, Jeong YT, Polym.(Korea), 13(9), 738 (1989)
Do JG, Jeong YT, Lee DH, Polym.(Korea), 14(3), 240 (1990)
Lee DH, Song KC, Jeong YT, Ha KR, Polym.(Korea), 16(1), 61 (1992)
Kissin YV, "Isospecific Polymerization of Olefin with Heterogeneous Zieger-Natta Catalysts," p. 105, Springer-Verlag, New York (1985)
Jeong YT, Lee DH, Makromol. Chem., 191, 1487 (1990)
Jeong YT, Lee DH, Soga K, Makromol. Chem. Rapid Commun., 12, 5 (1991)
Jeong YT, Lee DH, Shiono T, Soga K, Makromol. Chem., 192, 1727 (1991)
Nowlin TE, Kissin YV, Wagner KP, J. Polym. Sci. A: Polym. Chem., 26, 755 (1988)
Lindeman LP, Adams JQ, Anal. Chem., 43, 1245 (1971)
Hu Y, Chien JCW, J. Polym. Sci. A: Polym. Chem., 26, 2003 (1988)
Soga K, Yanagihara H, Lee DH, Makromol. Chem., 190, 995 (1989)
Soga K, Chen SI, Ohnishi R, Polym. Bull., 8, 473 (1982)
Kissin YV, Beach DL, J. Polym. Sci. A: Polym. Chem., 21, 1056 (1983)
Kasiwa N, Kawasaki M, Yoshitake J, "Catalytic Polymerization of Olefins," ed. by T. Keii, K. Soga, p. 43, Kodansha, Tokyo (1986)
Keii T, Suzuki E, Tamura M, Doi Y, "Transition Metal Catalyzed Polymerization," ed. by R.P. Quirk, p. 97, Harward Academic Publishers, New York (1983)
Kashiwa N, "Transition Metal Catalyzed Polymerization," ed. by R.P. Quirk, p. 379, Harward Academic Publishers, New York (1983)
Soga K, Shiono T, Doi Y, Markromol. Chem., 189, 1531 (1988)
Soga K, Shiono T, "Transition Metal Catalyzed Polymerization," ed. by R.P. Quirk, p. 266, Cambridge University Press, New York (1983)
Roedel MJ, J. Am. Chem. Soc., 75, 6110 (1953)
Florjanczyk Z, Deopura B, Stein RS, Vogel O, J. Polym. Sci. A: Polym. Chem., 20, 1051 (1982)
안태완, 이동호, 박이순, 이상원, 정한모, "고분자물성," p. 425, 대광문화사 (1989)

[Referenced By]

[1] Boor J, "Ziegler-Natta Catalysts and Polymerization," p. 264, Academic Press, New York (1979)

[2] Lee DH, Hsu CC, Hsu CC, J. Appl. Polym. Sci., 26, 653 (1981)

[3] Lee DH, Jang JK, Ahn TO, J. Polym. Sci. A: Polym. Chem., 25, 1457 (1987)

[4] Lee DH, Min KE, Kim CW, J. Korean Chem. Soc., 31, 110 (1987)

[5] Lee DH, Min KE, Ahn TO, Polym. J., 8, 973 (1987)

[6] Lee DH, Min KE, Ha KR, Jo WH, Polym.(Korea), 11(3), 278 (1987)

[7] Lee DH, Lee DH, Ahn TO, Polymer, 29, 713 (1988)

[8] Lee DH, Min KE, Jo WH, Jeong YT, Polym.(Korea), 13(1), 68 (1989)

[9] Lee DH, You KH, Jeong HM, Jeong YT, Polym.(Korea), 13(9), 738 (1989)

[10] Do JG, Jeong YT, Lee DH, Polym.(Korea), 14(3), 240 (1990)

[11] Lee DH, Song KC, Jeong YT, Ha KR, Polym.(Korea), 16(1), 61 (1992)

[12] Kissin YV, "Isospecific Polymerization of Olefin with Heterogeneous Zieger-Natta Catalysts," p. 105, Springer-Verlag, New York (1985)

[13] Jeong YT, Lee DH, Makromol. Chem., 191, 1487 (1990)

[14] Jeong YT, Lee DH, Soga K, Makromol. Chem. Rapid Commun., 12, 5 (1991)

[15] Jeong YT, Lee DH, Shiono T, Soga K, Makromol. Chem., 192, 1727 (1991)

[16] Nowlin TE, Kissin YV, Wagner KP, J. Polym. Sci. A: Polym. Chem., 26, 755 (1988)

[17] Lindeman LP, Adams JQ, Anal. Chem., 43, 1245 (1971)

[18] Hu Y, Chien JCW, J. Polym. Sci. A: Polym. Chem., 26, 2003 (1988)

[19] Soga K, Yanagihara H, Lee DH, Makromol. Chem., 190, 995 (1989)

[20] Soga K, Chen SI, Ohnishi R, Polym. Bull., 8, 473 (1982)

[21] Kissin YV, Beach DL, J. Polym. Sci. A: Polym. Chem., 21, 1056 (1983)

[22] Kasiwa N, Kawasaki M, Yoshitake J, "Catalytic Polymerization of Olefins," ed. by T. Keii, K. Soga, p. 43, Kodansha, Tokyo (1986)

[23] Keii T, Suzuki E, Tamura M, Doi Y, "Transition Metal Catalyzed Polymerization," ed. by R.P. Quirk, p. 97, Harward Academic Publishers, New York (1983)

[24] Kashiwa N, "Transition Metal Catalyzed Polymerization," ed. by R.P. Quirk, p. 379, Harward Academic Publishers, New York (1983)

[25] Soga K, Shiono T, Doi Y, Markromol. Chem., 189, 1531 (1988)

[26] Soga K, Shiono T, "Transition Metal Catalyzed Polymerization," ed. by R.P. Quirk, p. 266, Cambridge University Press, New York (1983)

[27] Roedel MJ, J. Am. Chem. Soc., 75, 6110 (1953)

[28] Florjanczyk Z, Deopura B, Stein RS, Vogel O, J. Polym. Sci. A: Polym. Chem., 20, 1051 (1982)

[29] 안태완, 이동호, 박이순, 이상원, 정한모, "고분자물성," p. 425, 대광문화사 (1989)