음이온 중합법 기반 P3HT-b-P4VP 블록공중합체 정밀 합성 및 이의 용매에 따른 물리적 특성 변화 연구

황성연; 박제영; 오동엽; Sung Yeon Hwang; Jeyoung Park; Dongyeop X. Oh

Applied Chemistry for Engineering, Vol.29, No.3, 336-341, June, 2018

DOI10.14478/ace.2018.1031 Export Citation

음이온 중합법 기반 P3HT-b-P4VP 블록공중합체 정밀 합성 및 이의 용매에 따른 물리적 특성 변화 연구

Synthesis of P3HT-b-P4VP via Anionic Polymerization and its Physical Properties in Various Solvents

황성연, 박제영^†, 오동엽^†

과학기술연합대학원대학교

Sung Yeon Hwang, Jeyoung Park^†, and Dongyeop X. Oh^†

Advanced Materials and Chemical Engineering, University of Science and Technology (UST), Daejeon 34113, Republic of Korea

E-mail:,

초록

기존의 문헌에서는 poly(3-hexylthiophene)(P3HT) 기반의 블록공중합체를 합성하기 위해서 최소 4-5단계 이상의 복잡한 공정을 거쳐야 했고, 일반적으로 분자량, 분자량 분포 및 블록의 비를 조절하기 위해서 단량체 전환율 및 반응 시간을 계속해서 모니터링 해야 한다. 또한, 여러 가지 이유에서 합성 스케일이 수 mg에서 수 g으로 제한되었다. 본 연구에서는 음이온 중합법을 이용해서 P3HT-b-poly(4-vinylprydine) (P4VP)를 오직 2단계로 중합할 수 있었으며, 중합 스케일은 수십 g 정도가 가능하였다. 반응 도중 단량체 전환율 및 농도를 계속 모니터링 해야 하는 번거로움 없이 초기 단량체 당량비만으로 블록 비율과 분자량 분포를 정밀 조절할 수 있었다. 만들어진 P3HT-b-P4VP를 친수성 및 소수성 용매에 녹여 분자 거동을 살펴보았다. 용액의 특성이 용액 속 미셸 구조와 필름 코팅 후 모포로지에 영향을 미친다는 것을 확인했다. P3HT-b-P4VP의 물리적 특성은 적외선-자외선 분광분석법, 원자힘현미경 및 자외선 광전자 분광분석법을 이용하여 평가하였다.

In general, the synthesis of poly(3-hexylthiophene)(P3HT)-based block copolymers requires at least a 4-5 step process. To control the molecular weight, molecular weight distribution, and block ratio, the reaction conversion and time should be monitored. In addition, the reaction scale usually limited to several mg to g was difficult to increase due to the limitations of living radical polymerizations. In this study, we synthesized P3HT-b-poly(4-vinylprydine) (P3HT-b-P4VP) with a final product quantity of > 19 g via a 2-step synthetic method with an anionic polymerization. In this method, the molecular weight and molecular weight distribution of P3HT-b-P4VP can be well controlled without monitoring the reaction conversion. We also studied physical properties of P3HT-b-P4VP depending on different solvent systems, which were investigated by UV-vis spectroscopy, atomic force microscopy, and ultraviolet photoelectron spectroscopy.

Keywords:block copolymers;anionic polymerzation;polythiophenes;conductive polymers

[References]

Kim JK, Yang SY, Lee Y, Kim Y, Prog. Polym. Sci, 35, 1325 (2010)
Moon HC, Anthonysamy A, Kim JK, Hirao A, Macromolecules, 44(7), 1894 (2011)
Liang YY, Xu Z, Xia JB, Tsai ST, Wu Y, Li G, Ray C, Yu LP, Adv. Mater., 22(20), E135 (2010)
Qian DP, Ye L, Zhang MJ, Liang YR, Li LJ, Huang Y, Guo X, Zhang SQ, Tan ZA, Hou JH, Macromolecules, 45(24), 9611 (2012)
Jang M, Yu YC, Jeon H, Youk JH, Yang H, ACS Appl. Mater. Interfaces, 7, 5274 (2015)
McCullough RD, Adv. Mater., 10(2), 93 (1998)
Lee D, Sin DH, Kim SW, Lee H, Byun HR, Mun J, Sung W, Kang B, Kim DG, Ko H, Song SW, Jeong MS, Rho J, Cho K, Macromolecules, 50(21), 8487 (2017)
Lee D, Lee J, Song KH, Rhee H, Jang DJ, Phys. Chem. Chem. Phys., 18, 2087 (2016)
Kim HJ, Lee YJ, Hwang SS, Choi DH, Yang H, Baek KY, J. Polym. Sci. A: Polym. Chem., 49(19), 4221 (2011)
Craley CR, Zhang R, Kowalewski T, McCullough RD, Stefan MC, Macromol. Rapid Commun., 30(1), 11 (2009)
Iovu MC, Zhang R, Cooper JR, Smilgies DM, Javier AE, Sheina EE, Kowalewski T, McCullough RD, Macromol. Rapid Commun., 28(17), 1816 (2007)
Iovu MC, Craley CR, Jeffries-EL M, Krankowski AB, Zhang R, Kowalewski T, McCullough RD, Macromolecules, 40(14), 4733 (2007)
Palaniappan K, Hundt N, Sista P, Nguyen H, Hao J, Bhatt MP, Han YY, Schmiedel EA, Sheina EE, Biewer MC, Stefan MC, J. Polym. Sci. A: Polym. Chem., 49(8), 1802 (2011)
Kern MR, Boyes SG, J. Polym. Sci. A: Polym. Chem., 52(24), 3575 (2014)
Lohwasser RH, Thelakkat M, Macromolecules, 45(7), 3070 (2012)
Sary N, Richard F, Brochon C, Leclerc N, Leveque P, Audinot JN, Berson S, Heiser T, Hadziioannou G, Mezzenga R, Adv. Mater., 22(6), 763 (2010)
Gernigon V, Leveque P, Richard F, Leclerc N, Brochon C, Braun CH, Ludwigs S, Anokhin DV, Ivanov DA, Hadziioannou G, Heiser T, Macromolecules, 46(22), 8824 (2013)
Kamigaito M, Ando T, Sawamoto M, Chem. Rev., 101(12), 3689 (2001)
Matyjaszewski K, Macromolecules, 45(10), 4015 (2012)
Dai CA, Yen WC, Lee YH, Ho CC, Su WF, J. Am. Chem. Soc., 129(36), 11036 (2007)
Lee M, Jeon H, Jang M, Yang H, ACS Appl. Mater. Interfaces, 8, 4819 (2016)
Lee S, Jeon H, Jang M, Baek KY, Yang H, ACS Appl. Mater. Interfaces, 7, 1290 (2015)
Lee YJ, Kim SH, Yang H, Jang M, Hwang SS, Lee HS, Baek KY, J. Phys. Chem. C, 115, 4228 (2011)
Kim J, Choi SY, Kim KM, Go DH, Jeon HJ, Lee JY, Park HS, Lee CH, Park HM, Macromol. Res., 15(4), 337 (2007)
Kang NG, Changez M, Lee JS, Macromolecules, 40(24), 8553 (2007)

[1] Kim JK, Yang SY, Lee Y, Kim Y, Prog. Polym. Sci, 35, 1325 (2010)

[2] Moon HC, Anthonysamy A, Kim JK, Hirao A, Macromolecules, 44(7), 1894 (2011)

[3] Liang YY, Xu Z, Xia JB, Tsai ST, Wu Y, Li G, Ray C, Yu LP, Adv. Mater., 22(20), E135 (2010)

[4] Qian DP, Ye L, Zhang MJ, Liang YR, Li LJ, Huang Y, Guo X, Zhang SQ, Tan ZA, Hou JH, Macromolecules, 45(24), 9611 (2012)

[5] Jang M, Yu YC, Jeon H, Youk JH, Yang H, ACS Appl. Mater. Interfaces, 7, 5274 (2015)

[6] McCullough RD, Adv. Mater., 10(2), 93 (1998)

[7] Lee D, Sin DH, Kim SW, Lee H, Byun HR, Mun J, Sung W, Kang B, Kim DG, Ko H, Song SW, Jeong MS, Rho J, Cho K, Macromolecules, 50(21), 8487 (2017)

[8] Lee D, Lee J, Song KH, Rhee H, Jang DJ, Phys. Chem. Chem. Phys., 18, 2087 (2016)

[9] Kim HJ, Lee YJ, Hwang SS, Choi DH, Yang H, Baek KY, J. Polym. Sci. A: Polym. Chem., 49(19), 4221 (2011)

[10] Craley CR, Zhang R, Kowalewski T, McCullough RD, Stefan MC, Macromol. Rapid Commun., 30(1), 11 (2009)

[11] Iovu MC, Zhang R, Cooper JR, Smilgies DM, Javier AE, Sheina EE, Kowalewski T, McCullough RD, Macromol. Rapid Commun., 28(17), 1816 (2007)

[12] Iovu MC, Craley CR, Jeffries-EL M, Krankowski AB, Zhang R, Kowalewski T, McCullough RD, Macromolecules, 40(14), 4733 (2007)

[13] Palaniappan K, Hundt N, Sista P, Nguyen H, Hao J, Bhatt MP, Han YY, Schmiedel EA, Sheina EE, Biewer MC, Stefan MC, J. Polym. Sci. A: Polym. Chem., 49(8), 1802 (2011)

[14] Kern MR, Boyes SG, J. Polym. Sci. A: Polym. Chem., 52(24), 3575 (2014)

[15] Lohwasser RH, Thelakkat M, Macromolecules, 45(7), 3070 (2012)

[16] Sary N, Richard F, Brochon C, Leclerc N, Leveque P, Audinot JN, Berson S, Heiser T, Hadziioannou G, Mezzenga R, Adv. Mater., 22(6), 763 (2010)

[17] Gernigon V, Leveque P, Richard F, Leclerc N, Brochon C, Braun CH, Ludwigs S, Anokhin DV, Ivanov DA, Hadziioannou G, Heiser T, Macromolecules, 46(22), 8824 (2013)

[18] Kamigaito M, Ando T, Sawamoto M, Chem. Rev., 101(12), 3689 (2001)

[19] Matyjaszewski K, Macromolecules, 45(10), 4015 (2012)

[20] Dai CA, Yen WC, Lee YH, Ho CC, Su WF, J. Am. Chem. Soc., 129(36), 11036 (2007)

[21] Lee M, Jeon H, Jang M, Yang H, ACS Appl. Mater. Interfaces, 8, 4819 (2016)

[22] Lee S, Jeon H, Jang M, Baek KY, Yang H, ACS Appl. Mater. Interfaces, 7, 1290 (2015)

[23] Lee YJ, Kim SH, Yang H, Jang M, Hwang SS, Lee HS, Baek KY, J. Phys. Chem. C, 115, 4228 (2011)

[24] Kim J, Choi SY, Kim KM, Go DH, Jeon HJ, Lee JY, Park HS, Lee CH, Park HM, Macromol. Res., 15(4), 337 (2007)

[25] Kang NG, Changez M, Lee JS, Macromolecules, 40(24), 8553 (2007)