고활성, 고입체규칙성 촉매에 의한 슬러리상 및 기상 프로필렌 중합의 비교연구

김일; 우성일

Polymer(Korea), Vol.15, No.5, 514-521, October, 1991

Export Citation

고활성, 고입체규칙성 촉매에 의한 슬러리상 및 기상 프로필렌 중합의 비교연구

A Comparative Study of Slurry and Gas Phase Polymerization of Propylene Using a Highly Active and Isospecific Catalyst

김일, 우성일

초록

이에톡시 마그네슘을 사부톡시 티탄, 무수프탈산 및 사염화 티탄과 반응시켜 합성한 새로운 염화마그네슘 담지 염화티탄촉매를 이용하여 슬러리상 및 기상 프로필렌중합의 비교연구를 행하였다. 25~60℃의 온도범위에서 삼에틸알루미늄/삼에톡시페닐 실란(PTES)를 첨가하여 수행한 프로필렌중합의 중합속도는 슬러리상에서보다 기상에서 더 낮았으나 중합속도-시간곡선은 60℃에서 행한 기상중합을 제외하고는 공히 일차로 비활성화 되었다. 이와같은 중합매체의 변화에 따른 중합속도의 변화는 특수하게 설계한 중합실험으로 확인할 수 있었다. 슬러리상 중합의 겉보기활성화에너지(25~60℃의 온도범위에서 10.3 kcal/mol)는 기상중합의 겉보기활성화에너지(25~50℃의 온도범위에서 4.3 kcal/mol)보다 훨씬 컸는데 이와같은 차이는 중합활성점의 형성과정의 차이로 설명할 수 있었다. 고분자의 입체규칙도(II)의 변화는 활성의 변화와 비교하여 볼 때 중합공정이나 온도에 상관없이 무시할 수 있을 정도였다.

A comparative study has been made for propylene polymerization in gas phase and slurry phase reactors using a new MgCl₂-supported TiCl₄ catalyst prepared by the reaction of Mg(OEt)₂ with Ti(OBu)₄, phthalic anhydride, and TiCl₄. The experimental results obtained from polymerizations combined with AlEt₃/phenyltriethoxy silane (PTES) showed that the rate of polymerization was lower for gas phase than for slurry phase within an experimental temperature range (25-60℃), even if rate-time profiles obeyed first-order deactivation for both cases except the gas phase polymerization at 60℃. The change of polymerization rate according to the variation of polymerization medium could be confirmed by a specially designed polymerization. The apparent activation energy of slurry phase polymerization (10.3 kcal/mol over a temperature of 25-60℃) was much larger than that of gas phase (4.3 kcal/mol over a temperature range of 25-50℃), and the differences could be explained by referring the formation process of polymerization centers. The change of isotacticity(II) of polymer was negligible without regard to the process and temperature of polymerization compared with the large differences of activity.

[References]

Brockmeier NF, "Transition Metal Catalyzed Polymerization," R.P. Quirk, ed., Harwood Academic Pub., 671 (1983)
Choi KY, Ray WH, J. Macromol. Sci.-Rev. Macromol. Chem. Phys., C25(1), 57 (1985)
Short JN, "Transition Metal Catalyzed Polymerization," R.P. Quirk, ed., Harwood Academic, Pub., 651 (1983)
Kim I, Woo SI, Polym.(Korea), 15(3), 348 (1991)
Kanetaka S, Takagi T, Kogyo Kagaku Zashi, 69, 695 (1966)
Floyd S, Choi KY, Taylor TW, Ray WH, J. Appl. Polym. Sci., 31, 2231 (1986)
Natta G, Pasquon I, Adv. Catal., 11, 1 (1959)
Vesely K, Ambroz J, Mejzlik J, Spousta E, J. Polym. Sci. C: Polym. Lett., 16, 417 (1967)
Burfield DR, Makromol. Chem., 183, 2709 (1982)
Natta G, Makromol. Chem., 76, 54 (1964)
Chien JCW, Wu JC, Kuo CI, J. Polym. Sci. A: Polym. Chem., 20, 2019 (1982)
Chien JCW, Wu JC, Kuo CI, J. Polym. Sci. A: Polym. Chem., 20, 2445 (1982)
Chien JCW, Wu JC, Kuo CI, J. Polym. Sci. A: Polym. Chem., 20, 2461 (1982)
Tang S, "Catalytic Polymerization of Olefins," T. Keil and K. Soga, Ed., Kodansha, Tokyo, 165 (1985)
Keii T, Suzuki E, Tamura M, Murata M, Doi Y, Makromol. Chem., 183, 2285 (1982)
Doi Y, Murata M, Yano K, Ind. Eng. Chem. Prod. Res. Dev., 21, 580 (1982)
Kim I, Woo SI, J. Polym. Sci. A: Polym. Chem., to submitted

[Referenced By]

[1] Brockmeier NF, "Transition Metal Catalyzed Polymerization," R.P. Quirk, ed., Harwood Academic Pub., 671 (1983)

[2] Choi KY, Ray WH, J. Macromol. Sci.-Rev. Macromol. Chem. Phys., C25(1), 57 (1985)

[3] Short JN, "Transition Metal Catalyzed Polymerization," R.P. Quirk, ed., Harwood Academic, Pub., 651 (1983)

[4] Kim I, Woo SI, Polym.(Korea), 15(3), 348 (1991)

[5] Kanetaka S, Takagi T, Kogyo Kagaku Zashi, 69, 695 (1966)

[6] Floyd S, Choi KY, Taylor TW, Ray WH, J. Appl. Polym. Sci., 31, 2231 (1986)

[7] Natta G, Pasquon I, Adv. Catal., 11, 1 (1959)

[8] Vesely K, Ambroz J, Mejzlik J, Spousta E, J. Polym. Sci. C: Polym. Lett., 16, 417 (1967)

[9] Burfield DR, Makromol. Chem., 183, 2709 (1982)

[10] Natta G, Makromol. Chem., 76, 54 (1964)

[11] Chien JCW, Wu JC, Kuo CI, J. Polym. Sci. A: Polym. Chem., 20, 2019 (1982)

[12] Chien JCW, Wu JC, Kuo CI, J. Polym. Sci. A: Polym. Chem., 20, 2445 (1982)

[13] Chien JCW, Wu JC, Kuo CI, J. Polym. Sci. A: Polym. Chem., 20, 2461 (1982)

[14] Tang S, "Catalytic Polymerization of Olefins," T. Keil and K. Soga, Ed., Kodansha, Tokyo, 165 (1985)

[15] Keii T, Suzuki E, Tamura M, Murata M, Doi Y, Makromol. Chem., 183, 2285 (1982)

[16] Doi Y, Murata M, Yano K, Ind. Eng. Chem. Prod. Res. Dev., 21, 580 (1982)

[17] Kim I, Woo SI, J. Polym. Sci. A: Polym. Chem., to submitted