α-Methylstyrene-수소화 Isoprene 디블럭 공중합체의 합성 및 분석

김민종; 노시태; 임승순

Polymer(Korea), Vol.17, No.5, 477-483, September, 1993

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α-Methylstyrene-수소화 Isoprene 디블럭 공중합체의 합성 및 분석

Synthesis and Characterization of α- Methylstyrene-Hydrogenated Isoprene Diblock Copolymer

김민종, 노시태, 임승순

초록

스티렌계/올레핀계 비상용성 중합체 블렌드의 상용화제로 사용하기 위하여 α- methylstyrenc-isoprene 블록공중합체를 음이온 중합법으로 합성하고 디엔블럭을 수소화시켰다. 음이온 중합의 개시제로는 n-butyllithium을 중합용매로는 THF를 사용하였으며 α- methylstyrene 블럭 중합시는 -78℃에서, isoprene블럭은 상온에서 중합하였다. Isoprene블럭의 수소화에는 가압반응기내에서 Pd/C촉매를 사용하였다. 블럭 공중합체의 분자량은 GPC를 이용하여 산출하였으며, 블록 중합체내의 상대 블록 길이와 isoprene내의 미세 구조는 IR 및 ¹H NMR을 이용하여 분석하였다. 합성된 4종의 블록 공중합체의 분자량은 각각 65K, 80K, 99K 및 144K이었으며 분자량분포(M_w/M _n)와 분자량 순서에 따라 1.2, 1.03, 1.06 및 1.07의 값을 나타냈다. ¹H NMR 분석 결과에 따라 α-methylsryrene/isoprene 상대 블록 길이는 분자량 크기 별로 45/55, 65/35, 46/54 및 25/75의 비율을 이루고 있음을 알 수 있었다. 또한 Isoprene 블록의 미세 구조는 70%이상이 3,4 부가반응으로 이루어져 있으며, isoprene의 수소화는 70∼75%임을 알 수 있었다.

Poly(α-methylstyrene)(PαMS)-hydrogenated polyisoprene(PI) block copolymers with different compositions were synthesized by sequential monomer addition technology in anionic living polymerization and hydrogenation reaftion, in order to be used as a compatibilizer for immiscible styrenic/olefinic polymer blends. First block of PαMS was po1ymerized at -78℃ under high vacuum with n-butyllithium initiator in THF, but PI block was propagated at room temperature. Hydrogenation of isoprene block was carried out with Pc/C catalyst under H₂ pressure. Weight average molecular weight(M_w) and polydispersity of the 7 diblock copolymers were determined by gel permeation chromatography(GPC). Characterization of relative block length and microstructure of PI was carried out witg IR and ¹H NMR. Four diblock copolymers with M_w of 65K, 80K, 99K and 144k and polydispersiy of 1.2, 1.07, 1.06 and 1.07 respcctively, weresynthesized. The relative block compositions (PαMS/PI ratio) of the copolymers was showed as 45/55, 65/35, 46/54 and 25/75 by weight, but over 70% of microstructure of PI block was 3,4-addition linkage. The extent of gydrogenation of isoprene units was about 70∼75%.

[References]

Morton M, Fetters LJ, Rubber Chem. Technol., 48, 359 (1975)
Morton M, "Anionic Polymerization, Principles and Practice," Academic Press, Inc., NY (1983)
Szware M, "Ions and Ion Pairs in Organic Reactions," Wiley-Interscience, New York, Vol. 1 (1972)
Szware M, "Ions and Ion Pairs in Organic Reactions," Wiley-Interscience, New York, Vol. 2 (1974)
Morton M, McGrath JE, Juliano PC, J. Polym. Sci. C: Polym. Lett., 26, 99 (1969)
Allen RD, Long TE, McGrath JE, Polym. Bull., 15, 127 (1986)
Roovers JEL, Bywater S, Macromolecules, 7, 443 (1974)
Lutz P, Masson P, Beinert G, Rempp P, Polym. Bull., 12, 79 (1984)
Kinning DJ, Thomas EL, Alward DB, Fetters LJ, Handlin DL, Macromolecules, 19, 1288 (1986)
Tant MR, Sung JH, Wilkes GL, Horrion J, Jerome R, Polymer, 27, 1815 (1986)
Smith SD, Polym. Prepr., 29, 48 (1988)
Quirk RP, Guo SH, Alsamarraie M, Hoover FI, Polym. Prepr., 29, 298 (1988)
Jerome R, Forte R, Varshney SK, Fayt R, Teyssie P, In Recent Advances in Mechanistic and Synthetic Aspects of Polymerization: Fontanille, M., Guyot, A., Eds.: NATO ASI, Ser. C, 215, 101 (1987)
Ouhadi T, Jerome R, Forte R, Fayt R, Teyssie P, J. Polym. Sci. A: Polym. Chem., 28, 2233 (1990)
Varshney SK, Hauteker JP, Fayt R, Jerome R, Teyssie P, Macromolecules, 23, 2618 (1990)
Whitby GS, Stephens HL, Report CR-3133 (1952)
Whitby GS, Stephens HL, NTIS. U.S. Dep. Commer, Off. Tech. Serv., PB Rep. PB 118310 (1955)
Krigas TM, Carella JM, Struglinski MJ, Crist B, Graessley W, J. Polym. Sci. B: Polym. Phys., 23, 509 (1985)
Harwood HJ, Russell DB, Verthe JJA, Zymonas J, Makromol. Chem., 163, 1 (1973)
Rosen SL, "Fundamental Principles of Polymeric Materials," John Wiley & Sons, New York (1981)
Uraneck CA, J. Polym. Sci. A: Polym. Chem., 9, 2273 (1971)
Antkowiak TA, Oberster AE, Halasa AF, Tate DP, J. Polym. Sci. A: Polym. Chem., 10, 1319 (1972)
Forman LE, "Polymer Chemistry of Synthetic Elastomers," (J.P. Kennedy and E. Tornqvist, eds.), Part II, pp. 552, 567-569, Wiley(Interscience), New York (1969)
Kraft M, Struktur und Absorptions-spektroskopie der kunststotte,verlag Chemie (1973)

[1] Morton M, Fetters LJ, Rubber Chem. Technol., 48, 359 (1975)

[2] Morton M, "Anionic Polymerization, Principles and Practice," Academic Press, Inc., NY (1983)

[3] Szware M, "Ions and Ion Pairs in Organic Reactions," Wiley-Interscience, New York, Vol. 1 (1972)

[4] Szware M, "Ions and Ion Pairs in Organic Reactions," Wiley-Interscience, New York, Vol. 2 (1974)

[5] Morton M, McGrath JE, Juliano PC, J. Polym. Sci. C: Polym. Lett., 26, 99 (1969)

[6] Allen RD, Long TE, McGrath JE, Polym. Bull., 15, 127 (1986)

[7] Roovers JEL, Bywater S, Macromolecules, 7, 443 (1974)

[8] Lutz P, Masson P, Beinert G, Rempp P, Polym. Bull., 12, 79 (1984)

[9] Kinning DJ, Thomas EL, Alward DB, Fetters LJ, Handlin DL, Macromolecules, 19, 1288 (1986)

[10] Tant MR, Sung JH, Wilkes GL, Horrion J, Jerome R, Polymer, 27, 1815 (1986)

[11] Smith SD, Polym. Prepr., 29, 48 (1988)

[12] Quirk RP, Guo SH, Alsamarraie M, Hoover FI, Polym. Prepr., 29, 298 (1988)

[13] Jerome R, Forte R, Varshney SK, Fayt R, Teyssie P, In Recent Advances in Mechanistic and Synthetic Aspects of Polymerization: Fontanille, M., Guyot, A., Eds.: NATO ASI, Ser. C, 215, 101 (1987)

[14] Ouhadi T, Jerome R, Forte R, Fayt R, Teyssie P, J. Polym. Sci. A: Polym. Chem., 28, 2233 (1990)

[15] Varshney SK, Hauteker JP, Fayt R, Jerome R, Teyssie P, Macromolecules, 23, 2618 (1990)

[16] Whitby GS, Stephens HL, Report CR-3133 (1952)

[17] Whitby GS, Stephens HL, NTIS. U.S. Dep. Commer, Off. Tech. Serv., PB Rep. PB 118310 (1955)

[18] Krigas TM, Carella JM, Struglinski MJ, Crist B, Graessley W, J. Polym. Sci. B: Polym. Phys., 23, 509 (1985)

[19] Harwood HJ, Russell DB, Verthe JJA, Zymonas J, Makromol. Chem., 163, 1 (1973)

[20] Rosen SL, "Fundamental Principles of Polymeric Materials," John Wiley & Sons, New York (1981)

[21] Uraneck CA, J. Polym. Sci. A: Polym. Chem., 9, 2273 (1971)

[22] Antkowiak TA, Oberster AE, Halasa AF, Tate DP, J. Polym. Sci. A: Polym. Chem., 10, 1319 (1972)

[23] Forman LE, "Polymer Chemistry of Synthetic Elastomers," (J.P. Kennedy and E. Tornqvist, eds.), Part II, pp. 552, 567-569, Wiley(Interscience), New York (1969)

[24] Kraft M, Struktur und Absorptions-spektroskopie der kunststotte,verlag Chemie (1973)