결정성 폴리스터렌의 제조 및 성질; Ⅰ. 촉매의 영향

이동호; 윤근병; 이억형; 노석균

Polymer(Korea), Vol.19, No.5, 700-706, September, 1995

Export Citation

결정성 폴리스터렌의 제조 및 성질; Ⅰ. 촉매의 영향

Preparation and Properties of Crystalline Polystyrene; Ⅰ. Effects of Catalyst

이동호, 윤근병, 이억형, 노석균

초록

Half-sandwich형 titanocene 촉매인 cyclopentadienyltitanium trichloride (CpTiCl₃), indenyltitanium trichloride (IndTiC1₃), fluorenyltitanium trichloride (FluTiCl₃), trimethylsily-lindenyltitanium trichloride ((Me₃Si)IndTiC1₃) 및 Pentamethylcyclopentadienyltitanium trichloride (Cp^*TiC1₃) 등과 공촉매로 modified methylaluminoxane (MMAO)을 사용하여 스티렌중합을 행하고 그들의 중합거동을 조사하였다. IndTiC1₃가 CpTiCl₃ 보다 높은 촉매활성을 보였고, 폴리스티렌의 분자량 및 신디오탁틱 지수는 Cp^*TiCl₃ 촉매를 사용한 경우에 가장 높게 나타났다. 또한 IndTiC1₃ 및 Cp^*TiCl₃를 실리카 또는 시클로덱스트린에 담지시켜 제조한 촉매는 적은 양의 MMAO를 사용하고도 높은 촉매활성을 나타내었다. 중합체의 미세구조를 ¹³C-NMR로 조사한 결과, CpTiCl₃로 얻은 sPS에 비해 IndTiC1₃ 및 Cp^*TiC1₃로 얻은 것의 입체규칙성이 더 높았다. X-ray Diffractometer로 분석한 sPS의 결정구조는 대부분 δ형이었다.

Half-sandwich titanocene catalysts such as cyclopentadienyltitanium trichloride (CpTiC1₃), indenyltitanium trichloride (IndTiC1₃), fluorenyltitanium trichloride (FluTiC1₃), trimethylsilylindenyltitanium trichloride ((Me₃Si)IndTiCl₃) and pentamethylcyclopentadienyltitanium trichloride (Cp^*TiCl₃) have been examined with modified methylaluminoxane(MMAO) for styrene polymerization. IndTiC1₃ showed higher activity than CpTiC1₃. Polystyrene (PS) of the highest syndiotactic index and molecular weight was obtained by using Cp^*TiCl₃. By supporting IndTiC1₃ or Cp^*TiCl₃ on silica or cyclodextrin, the catalyst had a reasonable activity even with a smaller amount of MMAO compared to the unsupported catalysts. For microtacticity observed with ³C-NMR, PS of higher syndio triads [rr] was obtained by using IndTiCl₃ or Cp^*TiCl₃ instead of CpTiCl₃. Crystalline structure of sPS was found to be mainly δ form with X-ray Diffractometer.

Keywords:syndiotactic polystyrene;half-sandwich titanocene;activity;syndiotactic index

[References]

Lee DH, Lee DH, Polym. Sci. Technol., 3(6), 475 (1992)
Lee DH, Yoon KB, Polym. Sci. Technol., 5(3), 207 (1994)
Ishihara N, Kuramoto M, Uoi M, Macromolecules, 21, 3356 (1988)
Chien JCW, Salajka Z, J. Polym. Sci. A: Polym. Chem., 29, 1253 (1991)
Pellecchia C, Longo P, Grassi A, Ammendola P, Zambelli A, Makromol. Chem. Rapid Commun., 8, 2271 (1987)
Ready TE, Day RO, Chien JCW, Rausch MD, Macromolecules, 26, 5822 (1993)
Soga K, Nakatani H, Macromolecules, 23, 957 (1990)
Lee DH, Yoon KB, Macromol. Rapid Commun., 15, 841 (1994)
Guerra G, Musto P, Karasz FE, MacKnight WJ, Makromol. Chem., 191, 2111 (1989)
Rosa CD, Guerra G, Petraccone V, Corradini P, Polym. J., 23, 1435 (1991)
Rosa CD, Rapacciuolo M, Guerra G, Petraccone V, Corradini P, Polymer, 33, 1423 (1992)
Lee DH, Yoon KB, Kang KS, Macromol. Rapid Commun., 16, 223 (1995)
Kashiwa N, "Metallocenes as Promising Catalysts for New Generation of Polyolefins," ed. by K. Soga, p. 25, CMC, Tokyo (1993)
Chien JCW, Salajka Z, Dong S, Macromolecules, 25, 3199 (1992)
Grassi A, Longo P, Proto A, Zambelli A, Macromolecules, 22, 104 (1989)
Kobayashi M, Nakaoki T, Ishihara N, Macromolecules, 22, 4377 (1989)
Kaminaka M, Soga K, Makromol. Chem. Rapid Commun., 12, 367 (1991)
Kaminsky W, Renner F, Makromol. Chem. Rapid Commun., 14, 439 (1993)
Wang YK, Savage JD, Yang D, Hsu SL, Macromolecules, 25, 3659 (1992)

[Referenced By]

[1] Lee DH, Lee DH, Polym. Sci. Technol., 3(6), 475 (1992)

[2] Lee DH, Yoon KB, Polym. Sci. Technol., 5(3), 207 (1994)

[3] Ishihara N, Kuramoto M, Uoi M, Macromolecules, 21, 3356 (1988)

[4] Chien JCW, Salajka Z, J. Polym. Sci. A: Polym. Chem., 29, 1253 (1991)

[5] Pellecchia C, Longo P, Grassi A, Ammendola P, Zambelli A, Makromol. Chem. Rapid Commun., 8, 2271 (1987)

[6] Ready TE, Day RO, Chien JCW, Rausch MD, Macromolecules, 26, 5822 (1993)

[7] Soga K, Nakatani H, Macromolecules, 23, 957 (1990)

[8] Lee DH, Yoon KB, Macromol. Rapid Commun., 15, 841 (1994)

[9] Guerra G, Musto P, Karasz FE, MacKnight WJ, Makromol. Chem., 191, 2111 (1989)

[10] Rosa CD, Guerra G, Petraccone V, Corradini P, Polym. J., 23, 1435 (1991)

[11] Rosa CD, Rapacciuolo M, Guerra G, Petraccone V, Corradini P, Polymer, 33, 1423 (1992)

[12] Lee DH, Yoon KB, Kang KS, Macromol. Rapid Commun., 16, 223 (1995)

[13] Kashiwa N, "Metallocenes as Promising Catalysts for New Generation of Polyolefins," ed. by K. Soga, p. 25, CMC, Tokyo (1993)

[14] Chien JCW, Salajka Z, Dong S, Macromolecules, 25, 3199 (1992)

[15] Grassi A, Longo P, Proto A, Zambelli A, Macromolecules, 22, 104 (1989)

[16] Kobayashi M, Nakaoki T, Ishihara N, Macromolecules, 22, 4377 (1989)

[17] Kaminaka M, Soga K, Makromol. Chem. Rapid Commun., 12, 367 (1991)

[18] Kaminsky W, Renner F, Makromol. Chem. Rapid Commun., 14, 439 (1993)

[19] Wang YK, Savage JD, Yang D, Hsu SL, Macromolecules, 25, 3659 (1992)