메탈로센 촉매를 이용한 에틸렌과 시클로올레핀의 공중합: Ⅰ. 촉매의 영향

이동호; 정희경; 김우식; 민경은; 박이순; 서관호; 강인규; 노석균; Dong-ho Lee; Hee-kyung Jung; Woo-sik Kim; Kyung-eun Min; Lee-soon Park; Kwan-ho Seo; Inn-kyu Kang; Seok-kyun Noh

Polymer(Korea), Vol.24, No.4, 445-452, July, 2000

Export Citation

메탈로센 촉매를 이용한 에틸렌과 시클로올레핀의 공중합: Ⅰ. 촉매의 영향

Copolymerization of Ethylene and Cycloolefin with Metallocene Catalyst: Ⅰ. Effect of Catalyst

이동호^†, 정희경, 김우식, 민경은, 박이순, 서관호, 강인규 , 노석균¹

경북대학교 공과대학 고분자공학과
¹영남대학교 공과대학 화학공학 및 공업화학부

Dong-ho Lee^†, Hee-kyung Jung, Woo-sik Kim, Kyung-eun Min, Lee-soon Park, Kwan-ho Seo, Inn-kyu Kang , and Seok-kyun Noh¹

Department of Polymer Science, Kyungpook National University, Taegu, Korea
¹School of Chemical Engineering and Technology, Yeongnam University, Kyungsan, Korea

E-mail:

초록

다양한 종류의 메탈로센 촉매와 공촉매인 개질-MAO(MMAO)을 이용한 에틸렌(E)과 노르보르넨(N)의 공중합에서 중합조건이 촉매 활성 및 공중합체의 구조와 성질 등에 미치는 영향을 조사하였다. 즉 C₂-대칭구조를 가지는 rac-Et(Ind)₂ZrCI₂, M₂Si(Ind)₂ZrCl₂, Me₂Si-(Cp)₂ZrCl₂ 및 C_S-대칭구조를 가지는 iPr(FluCp)ZrCl₂, 그리고 constrained geometry catalyst(CGC)와 이중다리(di-bridged) 지그코노센 등의 다양한 메탈로센 촉매를 사용하여 [N]/[E]공급비에 따른 촉매 활성, 공중합체(COC)의열적 성질 및 N 함량을 조사하였다. rac-Et(Ind)₂ZrCI₂를 촉매로 사용한 경우에 공촉매의 몰비, 중합 온도 및 공촉매 종류 등의 중합조건을 조사한 결과 [Al]/[Zr]=3000, 40℃, MMAO 공촉매 등이 적합하였다. [N]/[E]공급비가 증가됨에 따라 COC내의 N 함량이 증가하는 일반적인 경향을 보였으나, 촉매 활성은 감소하였으나 C_s-대칭구조의 경우에는 증가하였다 촉매활성과 N함량 등을 고려해 보면 rac-Et(Ind)₂ZrCI₂/MMAO계에서 비교적 높은 촉매 활성과 COC의 T_g제어가 용이한 결과를 얻을 수 있었다. 촉매종류에 따른 단랑체의 반응성비를 Kelen-Tudos방법으로 구하였다.

The copolymerization to ethylene (E) and norbornene (N) was examined by using various metallocene catalysts and modified-MAO(MMAO) cocatalyst. For C₂-symmetry catalysts such as rac-Et(Ind)₂ZrCl₂, Me₂Si(Ind)₂ZrCl₂, Me₂Si(Cp)₂ZrCl₂ and Cs-symmetrical iPr(FluCp)ZrCl₂ as well as CGC and di-briged zirconocene, the effects of catalyst structure and [N]/[E] feed ratio on catalyst activity, thermal property and [N] content of copolymer (COC) was investigated. For rac-Et(Ind)₂ZrCl₂ catalyst of a constant [N]/[E] feed ratio, the appropriate conditions of [Al]/[Zr] mole ratio, polymerization temperature and cocatalyst structure were found to be 3000, 40℃, MMAO cocatalyst, respectively. As [N]/[E] feed ratio increased, the incorporation of norbornene to copolymer increased while the activity of catalyst decreased except fro iPr(FluCp)ZrCl₂. With consideration of catalyst activity as well as N content, it was found that rac-Et(Ind)₂ZrCl₂/MMAO system exhibited relatively high activity and controllable T_g. Monomer reactivity ratio was determined by Kelen-00 method.

Keywords:metallocene;ethylene;morbornene;copolymer;cycloolefin

[References]

Sinn H, Kaminsky W, Adv. Organomet. Chem., 18, 99 (1980)
Kaminsky W, Spiedhl R, Makromol. Chem., 190, 515 (1989)
Kaminsky W, Moller-Lindenhof N, Bull. Soc. Chem. Belg., 99, 103 (1990)
Kaminsky W, Bark A, Arndt M, Makromol. Chem. Makromol. Symp., 47, 83 (1991)
Kaminsky W, Noll A, Polym. Bull., 31, 175 (1993)
Sekka M, Eur. Patent, 283,164 (1987)
Hoechst AG, Eur. Patent, 304,671 (1987)
Hoechst AG, Eur. Patent, 503,422 (1987)
Hoechst AG, U.S. Patent, 5,204,429 (1987)
Hoechst AG, German Patent, 3,835,044 (1988)
Kaminsky W, Noll A, "Ziegler Catalysts," eds. by G. Fink, R. Mulhaupt, and H.H. Brintzinger, p. 149, Springer Verlag, Berlin, 1995 (1995)
Bergstrom CH, Starck PG, Seppala JV, J. Appl. Polym. Sci., 67(3), 385 (1998)
Marathe S, Sivaram S, Macromolecules, 27(5), 1083 (1994)
Lasarvov H, Pakkanen T, Macromol. Rapid Commun., 20, 356 (1999)
Arndt M, Engehausen R, Kaminsky W, Zoumis K, J. Mol. Catal., 101, 171 (1995)
Henshcke O, Koller F, Arnold M, Macromol. Rapid Commun., 18, 617 (1997)
Hoechst/Mitsui extend COC deal, Asian Chemical News, January 30, 23 (1995)
Arndt M, Beulich I, Kaminsky W, Proceedings of MetCon'96, Catalyst Consultant Inc., Houston, Tx, 1996 (1996)
Weiss K, Neugebauer U, Blau S, Lang HJ, J. Org. Chem., 520, 171 (1996)
Noh SK, Jung JH, Lee DH, Park SK, Kim HJ, J. Org. Chem., 592, 147 (2000)
Dow, Eur. Patent, 0416815A2 (1990)
Dow, Eur. Patent, 0514828A1 (1992)
Devor DD, Timmers FJ, Hasha DL, Rosen RK, Marks TJ, Deck PA, Stern CL, Organometallics, 14, 3132 (1995)
McKnight AL, Waymouth RM, Macromolecules, 32(9), 2816 (1999)
Kaminsky W, Arndt M, Adv. Polym. Sci., 127, 177 (1997)
Fineman M, Ross SD, J. Polym. Sci., 5, 259 (1950)
Kelen T, Tudos F, React. Kinet. Catal. Lett., 1, 487 (1974)
Bergstrom CH, Vaananen TL, Seppala JV, J. Appl. Polym. Sci., 63(8), 1071 (1997)
Pietikainen P, Seppala JV, Macromolecules, 27(6), 1325 (1994)
Herfert N, Montag P, Finck G, Macromol. Chem., 194, 3167 (1993)
Sishta C, Hathoron R, Marks T, J. Am. Chem. Soc., 114, 122 (1992)
Hedden D, Marks TJ, J. Am. Chem. Soc., 110, 1649 (1988)
Jordan RF, La Pointe WE, Baenziger NC, Hinch GD, Organometallics, 8, 1539 (1990)
Chien JCW, Song W, Rausch MD, Macromolecules, 26, 3239 (1993)
Kaminsky W, Engehausen R, Zoumis K, Spaleck W, Rohrmann J, Makromol. Chem., 193, 1643 (1992)
Dorer B, Prosenc MH, Rief U, Brintzinger HH, Organometallics, 13, 3868 (1994)
Roth H, Meyer U, Koinzer JP, Wiegand G, Plast. Kautsch, 32, 291 (1985)
Kaminsky W, Arndt M, Bark A, Polym. Prepr., 32, 467 (1990)
Montag P, Ruchatz D, Fink G, Kautsch. Gummi Kunstst, 49, 582 (1996)
Rische T, Waddon AJ, Dickinson LC, MacKnight WJ, Macromolecules, 31(6), 1871 (1998)

[Referenced By]

[Related Articles]

[1] Sinn H, Kaminsky W, Adv. Organomet. Chem., 18, 99 (1980)

[2] Kaminsky W, Spiedhl R, Makromol. Chem., 190, 515 (1989)

[3] Kaminsky W, Moller-Lindenhof N, Bull. Soc. Chem. Belg., 99, 103 (1990)

[4] Kaminsky W, Bark A, Arndt M, Makromol. Chem. Makromol. Symp., 47, 83 (1991)

[5] Kaminsky W, Noll A, Polym. Bull., 31, 175 (1993)

[6] Sekka M, Eur. Patent, 283,164 (1987)

[7] Hoechst AG, Eur. Patent, 304,671 (1987)

[8] Hoechst AG, Eur. Patent, 503,422 (1987)

[9] Hoechst AG, U.S. Patent, 5,204,429 (1987)

[10] Hoechst AG, German Patent, 3,835,044 (1988)

[11] Kaminsky W, Noll A, "Ziegler Catalysts," eds. by G. Fink, R. Mulhaupt, and H.H. Brintzinger, p. 149, Springer Verlag, Berlin, 1995 (1995)

[12] Bergstrom CH, Starck PG, Seppala JV, J. Appl. Polym. Sci., 67(3), 385 (1998)

[13] Marathe S, Sivaram S, Macromolecules, 27(5), 1083 (1994)

[14] Lasarvov H, Pakkanen T, Macromol. Rapid Commun., 20, 356 (1999)

[15] Arndt M, Engehausen R, Kaminsky W, Zoumis K, J. Mol. Catal., 101, 171 (1995)

[16] Henshcke O, Koller F, Arnold M, Macromol. Rapid Commun., 18, 617 (1997)

[17] Hoechst/Mitsui extend COC deal, Asian Chemical News, January 30, 23 (1995)

[18] Arndt M, Beulich I, Kaminsky W, Proceedings of MetCon'96, Catalyst Consultant Inc., Houston, Tx, 1996 (1996)

[19] Weiss K, Neugebauer U, Blau S, Lang HJ, J. Org. Chem., 520, 171 (1996)

[20] Noh SK, Jung JH, Lee DH, Park SK, Kim HJ, J. Org. Chem., 592, 147 (2000)

[21] Dow, Eur. Patent, 0416815A2 (1990)

[22] Dow, Eur. Patent, 0514828A1 (1992)

[23] Devor DD, Timmers FJ, Hasha DL, Rosen RK, Marks TJ, Deck PA, Stern CL, Organometallics, 14, 3132 (1995)

[24] McKnight AL, Waymouth RM, Macromolecules, 32(9), 2816 (1999)

[25] Kaminsky W, Arndt M, Adv. Polym. Sci., 127, 177 (1997)

[26] Fineman M, Ross SD, J. Polym. Sci., 5, 259 (1950)

[27] Kelen T, Tudos F, React. Kinet. Catal. Lett., 1, 487 (1974)

[28] Bergstrom CH, Vaananen TL, Seppala JV, J. Appl. Polym. Sci., 63(8), 1071 (1997)

[29] Pietikainen P, Seppala JV, Macromolecules, 27(6), 1325 (1994)

[30] Herfert N, Montag P, Finck G, Macromol. Chem., 194, 3167 (1993)

[31] Sishta C, Hathoron R, Marks T, J. Am. Chem. Soc., 114, 122 (1992)

[32] Hedden D, Marks TJ, J. Am. Chem. Soc., 110, 1649 (1988)

[33] Jordan RF, La Pointe WE, Baenziger NC, Hinch GD, Organometallics, 8, 1539 (1990)

[34] Chien JCW, Song W, Rausch MD, Macromolecules, 26, 3239 (1993)

[35] Kaminsky W, Engehausen R, Zoumis K, Spaleck W, Rohrmann J, Makromol. Chem., 193, 1643 (1992)

[36] Dorer B, Prosenc MH, Rief U, Brintzinger HH, Organometallics, 13, 3868 (1994)

[37] Roth H, Meyer U, Koinzer JP, Wiegand G, Plast. Kautsch, 32, 291 (1985)

[38] Kaminsky W, Arndt M, Bark A, Polym. Prepr., 32, 467 (1990)

[39] Montag P, Ruchatz D, Fink G, Kautsch. Gummi Kunstst, 49, 582 (1996)

[40] Rische T, Waddon AJ, Dickinson LC, MacKnight WJ, Macromolecules, 31(6), 1871 (1998)