저분자형 폴리에테르 변성 실리콘의 합성에 관한 연구

정대원; Dae-won Chung

Journal of the Korean Industrial and Engineering Chemistry, Vol.19, No.3, 332-337, June, 2008

Export Citation

저분자형 폴리에테르 변성 실리콘의 합성에 관한 연구

Study on the Synthesis of Low Molecular Weight Silicones Modified with Polyethers

정대원 ^†

수원대학교 공과대학 신소재공학과

Dae-won Chung^†

Department of Polymer Engineering, College of Engineering, Suwon University, Suwon 400-600, Korea

E-mail:

초록

트리실록산(1,1,1,3,5,5,5-heptamethyl trisiloxane, HMTS)과 말단에 불포화기를 포함하는 폴리옥시에틸렌(unsaturated poly (oxyethylene), UPOE)의 수소규소화 반응을 Speier 촉매 하에서 수행하여, 두 반응물의 몰비 변화에 따른 반응성 및 생성물 (HMTS-POE)의 구조 차이를 FT-IR 및 1H-NMR을 이용하여 분석하였다. UPOE를 과량의 HMTS와 수소규소화 반응시킨 후 진공 건조 과정을 통하여 미반응 HMTS를 제거함으로써 미반응 UPOE 및 HMTS이 잔존하지 않는 HMTS-POE를 합성할 수 있었다. 또한 다양한 분자량의 UPOE를 사용하여 다양한 HMTS-POE를 합성하여 표면장력을 비교 분석한 결과, EO 함량 49∼57%의 HMTS-POE가 계면활성 특성의 저분자형 폴리에테르 변성 실리콘으로의 응용 가능성을 나타내었다.

Hydrosilylation reaction of 1,1,1,3,5,5,5-heptamethyl trisiloxane (HMTS) and unsaturated poly(oxyethylene) (UPOE) was carried out in the presence of Speier’s catalyst. The effect of molar ratio of two reagents on the reactivity and the structure of the product (HMTS-POE) were investigated by FT-IR and 1H-NMR. The pure HMTS-POE without containing unreacted HMTS or UPOE could be obtained by the reaction with excess amount of HMTS and followed by removing unreacted HMTS under vacuum. Under the same reaction conditions, various HMTS-POEs composed of UPOEs with a different molecular weight were synthesized, and the surface tensions of HMTS-POEs were analyzed. HMTS-POE, whose EO contents are in the range of 49∼57%, exhibited lower surface tension and a potential application for low molecular weight silicone modified with polyethers.

Keywords:heptamethyl trisiloxane;poly(oxyethylene);hydrosilylation;silicone polyethers

[References]

Marciniec B, Gulinski J, Urbaniak W, Kornetka ZW, Comprehensive Handbook on Hydrosilylation, ed. B. Marciniec, Pergamon, Oxford (1992)
Chung DW, Kim JP, Kim D, Lim J, J. Ind. Eng. Chem., 12(5), 783 (2006)
Hill RM, Specialist Surfactants, ed. I. D. Robb, Blackie, London (1997)
Stirmer A, Thunig C, Hoffmann H, Gruening B, Tenside Surf. Det., 31, 90 (1994)
Hill RM, He MT, Davis HT, Scriven LE, Langmuir, 10(6), 1724 (1994)
Hill RM, Curr. Opin. Colloid Interface Sci., 7, 255 (2002)
O’Lenick AJ, Allured’s Cosmetics & Toiletries magazine, 116, 49 (2001)
De Charenteney F, Osborn JA, Wilkinson GJ, J. Chem. Soc. A, 786 (1968)
Fryzuk MD, Rosenberg L, Retting SJ, Organometallics, 15, 2871 (1996)
Marciniec B, Krzyzanowski P, Walczuk-Gusciora E, Duczmal W, J. Mol. Catal. A-Chem., 144, 263 (1999)
Oi S, Taira A, Honma Y, Inoue Y, Org. Lett., 5, 97 (2003)
Speier JL, Adv. Organomet. Chem., 17, 407 (1979)
Sacarescu L, Ardeleanu R, Sacarescu G, Simionescu M, Eur. Polym. J., 40, 57 (2004)
Lim CH, Kim DW, Noh ST, J. Ind. Eng. Chem., 9(5), 526 (2003)
US Patent 3,220,972 (1965)
Lewis LN, Sumpter CA, J. Mol. Catal. A-Chem., 104, 293 (1996)
Cai GP, Weber WP, Polymer, 45(9), 2941 (2004)
Louis E, Jussofie I, Kuhn FE, Herrmann WA, J. Org. Chem., 691, 2031 (2003)
US Patent 2,632,013 (1953)
Benkeser RA, Cunico RF, Dunny S, Jones PR, Nerlekar PG, J. Org. Chem., 32, 2634 (1974)
Lewis LN, Chem. Rev., 93, 2693 (1993)
Chung DW, Kim TG, J. Ind. Eng. Chem., 13(4), 571 (2007)
Wagner R, Richter L, Wu Y, Weimuller J, Reiners J, Hengge E, Kliiwein A, Hassler K, Appl. Organomet. Chem., 11, 645 (1997)
Vick SC, Soap/cosmetics/chemical specialties, May, 36 (1984)
Hill RM, Silicone Surfactants, Marcel Dekker, Inc., New York (2000)
Chung DW, Kim TG, J. Ind. Eng. Chem., 13(6), 979 (2007)
Vadala ML, Rutnakornpituk M, Zalich MA, St Pierre TG, Riffle JS, Polymer, 45(22), 7449 (2004)
Pasquali RC, Taurozzi MP, Bregni C, Int. J. Pharm. (2007)
Sabia AJ, American dyestuff reporter, May, 45 (1982)

[Related Articles]

[1] Marciniec B, Gulinski J, Urbaniak W, Kornetka ZW, Comprehensive Handbook on Hydrosilylation, ed. B. Marciniec, Pergamon, Oxford (1992)

[2] Chung DW, Kim JP, Kim D, Lim J, J. Ind. Eng. Chem., 12(5), 783 (2006)

[3] Hill RM, Specialist Surfactants, ed. I. D. Robb, Blackie, London (1997)

[4] Stirmer A, Thunig C, Hoffmann H, Gruening B, Tenside Surf. Det., 31, 90 (1994)

[5] Hill RM, He MT, Davis HT, Scriven LE, Langmuir, 10(6), 1724 (1994)

[6] Hill RM, Curr. Opin. Colloid Interface Sci., 7, 255 (2002)

[7] O’Lenick AJ, Allured’s Cosmetics & Toiletries magazine, 116, 49 (2001)

[8] De Charenteney F, Osborn JA, Wilkinson GJ, J. Chem. Soc. A, 786 (1968)

[9] Fryzuk MD, Rosenberg L, Retting SJ, Organometallics, 15, 2871 (1996)

[10] Marciniec B, Krzyzanowski P, Walczuk-Gusciora E, Duczmal W, J. Mol. Catal. A-Chem., 144, 263 (1999)

[11] Oi S, Taira A, Honma Y, Inoue Y, Org. Lett., 5, 97 (2003)

[12] Speier JL, Adv. Organomet. Chem., 17, 407 (1979)

[13] Sacarescu L, Ardeleanu R, Sacarescu G, Simionescu M, Eur. Polym. J., 40, 57 (2004)

[14] Lim CH, Kim DW, Noh ST, J. Ind. Eng. Chem., 9(5), 526 (2003)

[15] US Patent 3,220,972 (1965)

[16] Lewis LN, Sumpter CA, J. Mol. Catal. A-Chem., 104, 293 (1996)

[17] Cai GP, Weber WP, Polymer, 45(9), 2941 (2004)

[18] Louis E, Jussofie I, Kuhn FE, Herrmann WA, J. Org. Chem., 691, 2031 (2003)

[19] US Patent 2,632,013 (1953)

[20] Benkeser RA, Cunico RF, Dunny S, Jones PR, Nerlekar PG, J. Org. Chem., 32, 2634 (1974)

[21] Lewis LN, Chem. Rev., 93, 2693 (1993)

[22] Chung DW, Kim TG, J. Ind. Eng. Chem., 13(4), 571 (2007)

[23] Wagner R, Richter L, Wu Y, Weimuller J, Reiners J, Hengge E, Kliiwein A, Hassler K, Appl. Organomet. Chem., 11, 645 (1997)

[24] Vick SC, Soap/cosmetics/chemical specialties, May, 36 (1984)

[25] Hill RM, Silicone Surfactants, Marcel Dekker, Inc., New York (2000)

[26] Chung DW, Kim TG, J. Ind. Eng. Chem., 13(6), 979 (2007)

[27] Vadala ML, Rutnakornpituk M, Zalich MA, St Pierre TG, Riffle JS, Polymer, 45(22), 7449 (2004)

[28] Pasquali RC, Taurozzi MP, Bregni C, Int. J. Pharm. (2007)

[29] Sabia AJ, American dyestuff reporter, May, 45 (1982)