Poly(2-trialkylstannylthioethyl acrylate) 필름의 표면 활성화를 통한 발색단 도입

윤종철; 도정윤; Jong Chul Yun; Jung Yun Do

Polymer(Korea), Vol.36, No.6, 795-802, November, 2012

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Poly(2-trialkylstannylthioethyl acrylate) 필름의 표면 활성화를 통한 발색단 도입

Introduction of Chromophores on the Activated Surface of Poly(2-trialkylstannylthioethyl acrylate) Films

윤종철, 도정윤^†

부산대학교 화학교육과

Jong Chul Yun, and Jung Yun Do^†

Department of Chemistry Education, Pusan National University, Busan 609-735, Korea

E-mail:

초록

소수성 고분자 표면을 화학적 처리를 통해 활성화시키고 화학반응을 통해 발색단을 도입하는 연구를 진행하였다. 2-Triphenylstannylthioethyl acrylate를 자외선 조사시켜 고분자 필름을 만들었다. 필름 표면에 노출된 주석치환체를 불소이온으로 처리하여 SH를 형성함으로써 필름표면에 많은 SH를 생성시켰고 적외석 흡수스펙트럼으로 이를 확인하였다. 아크릴 유도체로 만든 발색단 물질을 노출된 SH와 반응시켜 필름 표면에 여러 발색단을 도입할 수 있었고 이를 자외선-가시광선 흡수스펙트럼으로 관찰할 수 있었다. 2-Triphenylstannylthioethyl acrylate와 tris(hydroxymethyl) ethane에서 유도된 triacrylate를 혼합하여 얻은 광경화 필름에서 단분자 함량 변화에 따른 SH의 표면 노출량을 변화시킬 수 있음을 흡수스펙트럼을 통해 관찰하였다. 유사하게, 2-tributylstannylthioethyl acrylate를 이용한 광경화 필름을 만들어 표면반응 연구를 진행하였다. 이 경우, 불소이온 처리를 통한 표면 활성화는 약 5분 이내로 빠르게 진행되었다. 이소시안 작용기를 갖는 발색단을 합성하여 필름과 반응시켜 표면에 발색단 도입하는 비교연구를 진행하였다. 아크릴 유도체가 표면 SH와 반응이 24시간 이상을 요구하는 반면 이소시안 유도체는 10분 이내에 결합반응이 완료되었다.

Surface modification of a hydrophobic acrylic polymer film has been performed through simple chemical treatment to give a reactive surface. 2-Triphenylstannylthioethyl acrylate was polymerized under UV-illumination with various contents of a comonomer. When the polymer film was treated with fluoride ion, thiol functional group (SH) was generated on the film surface, which was observed through infrared absorption spectroscopy. The surface was functionalized by thiol addition reaction to acrylic chromophores. The SH content on the surface was controlled with a comonomer, tris(hydroxymethyl)ethane triacrylate, and examined with UV-Vis absorbance of the chromophore attached film. Similarly, a polymer film from 2-tributylstannylthioethyl acrylate was prepared. Destannylation from the triphenylstannyl and tributylstannyl surface completed after 30 and 5 min, respectively. The SH-exposed surface was modified with an isocyanate attached chromophore within 10 min, while acrylic chromophore required 24 h.

Keywords:surface modification;Ph3SnS-acrylate;UV-polymerizaion;chromophore;SH-rich surface.

[References]

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Poirier GE, Tarlov MJ, J. Phys. Chem., 99(27), 10966 (1995)
Camillone N, Chidsey CED, Liu GY, Scoles G, J.Chem. Phys., 98, 3503 (1993)
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Flaim T, Wang Y, Mercado R, Proceedings of SPIE: Optical Systems Design., 5250, 423 (2003)
Nebioglu A, Leon JA, Khudyakov IV, Ind. Eng. Chem. Res., 47(7), 2155 (2008)
Maheswara M, Oh SH, Ju JJ, Park SK, Park S, Do JY, Polym. J., 42, 249 (2010)
Maheswara M, Kim M, Yun SJ, Ju JJ, Do JY, Tetrahedron Lett., 50, 480 (2009)

[Referenced By]

[1] Kang ET, Neoh KG, Li ZF, Tan KL, Liaw DJ, Polymer, 39(12), 2429 (1998)

[2] Hegemann D, Brunner H, Oehr C, Nucl. Instrum. Meth. B., 208, 281 (2003)

[3] Yang S, Gupta MC, Surf. Coat. Technol., 187, 172 (2004)

[4] Dabhade RV, Bodas DS, Gangal SA, Sensor Actuat. B Chem., 98, 37 (2004)

[5] Liston EM, Martinu L, Wertheimer MR, J. Adhesion Sci.Technol., 7, 1091 (1993)

[6] Folkes JA, Surface Coat. Techn., 63, 65 (1994)

[7] Ryan ME, Badyal JP, Macromolecules, 28(5), 1377 (1995)

[8] Jang JH, Eom SI, Kim YH, J. Korean Fiber Society., 39, 100 (2002)

[9] Huang CY, Chen CL, Surf. Coat. Techn., 153, 194 (2002)

[10] Vakula VL, Pritykin LM, Polymer Adhesion: Phsicochemical Principles, Ellis Horwood Ltd, New York (1991)

[11] Cho DL, Polym. Sci. Technol., 6(5), 499 (1995)

[12] Tatoulian M, Arefi-Khonsari F, Shahid-zadeh-Ahmadi N, Amouroux J, Int. J. Adhes., 15, 177 (1995)

[13] Rodriguez JA, Hrbek J, Acc. Chem. Res., 32, 719 (1999)

[14] Bartholomew CH, Agrawal PK, Katzer JR, Adv. Catal., 31, 135 (1982)

[15] Martin H, Vericat C, Andreasen G, Creus AH, Vela ME, Salvarezza RC, Langmuir, 17(8), 2334 (2001)

[16] Tong YY, Rice C, Wieckowski A, Oldfield E, J. Am. Chem. Soc., 122(48), 11921 (2000)

[17] Kolb DM, Advances in Electrochemistry and Electrochemical Engineering, Gerischer H, Tobias CW, Editors, Wiley Interscience, New York (2002)

[18] Yang Z, Wu R, Rodriguez JA, Phys. Rev. B., 65, 155409 (2002)

[19] Demuth JE, Jepsen DW, Marcus PM, Phys. Rev. Lett., 31, 540 (1973)

[20] Ulman A, Chem. Rev., 96(4), 1533 (1996)

[21] Zharnikov M, Frey S, Rong H, Yang YJ, Heister K, Buck M, Grunze M, Phys. Chem. Chem. Phys., 2, 3359 (2000)

[22] Poirier GE, Tarlov MJ, J. Phys. Chem., 99(27), 10966 (1995)

[23] Camillone N, Chidsey CED, Liu GY, Scoles G, J.Chem. Phys., 98, 3503 (1993)

[24] Chhabra P, Gupta R, Suri G, Tyagi M, Seshadri G, Sabharwal S, Niyogi UK, Khandal RK, Int. J. Polym. Sci., 10, 1155 (2009)

[25] Flaim T, Wang Y, Mercado R, Proceedings of SPIE: Optical Systems Design., 5250, 423 (2003)

[26] Nebioglu A, Leon JA, Khudyakov IV, Ind. Eng. Chem. Res., 47(7), 2155 (2008)

[27] Maheswara M, Oh SH, Ju JJ, Park SK, Park S, Do JY, Polym. J., 42, 249 (2010)

[28] Maheswara M, Kim M, Yun SJ, Ju JJ, Do JY, Tetrahedron Lett., 50, 480 (2009)