화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of the Korean Industrial and Engineering Chemistry, Vol.13, No.2, 109-118, April, 2002
Export Citation
실리콘(Silicone) 원료의 합성법 개발
Synthetic Methods for New Starting Materials for Silicone
유복렬, 정일남†
  • 한국과학기술연구원 유기규소화학연구실, 서울 130-650
Bok Ryul Yoo, and Il Nam Jung†
  • Organosilicon Chemistry Laboratory, Korea Institute of Science & Technolog, Cheongryang, Seoul 130-650, Korea
E-mail:
초록
실리콘 산업에서 실리콘의 주원료로 사용되는 단순 구조의 유기클로로실란들은 알킬클로라이드와 금속규소의 직접반응에 의해 합성되고 있다. 반면에 긴 사슬의 유기클로로실란들은 올레핀과 Si-H 결합을 갖고 있는 실란의 규소수소화 반응 또는 유기 염 촉매를 사용한 알킬클로라이드와 Si-H 결합을 갖고있는 실란의 Si-C 커플링 반응으로 합성할 수 있다. 일반적으로 유기금속 시약은 실험실에서 소규모의 실리콘 원료 합성에 이용되고 있다. 본 총설에서는 실리콘 산업에서 대량 생산에 이용되는 직접반응과 규소수소화 반응을 중심으로 실리콘 원료의 합성법 개발의 최근 동향을 기술하였다.
Simple organochlorosilanes, an important starting material for the production of silicones in the industry, are commercially produced by the direct reaction of organic halides and elemental silicon. However, the long-chained organochlorosilanes are obtained by the hydrosilylation of olefins with silanes containing Si-H bond or by Si-C coupling reaction of alkyl chlorides and silane containing Si-H bond using an organic salt catalyst. Generally organometal reagents are useful for the synthesis of organosilanes in small scale. This review describe the recent developments and trends of synthetic methods for new starting materials for silicones, in particular, via the direct and hydrosilylation reactions.
Keywords:direct reaction;alkyl chloride;silicon;hydrosilylation;olefin;silicon hydride;phosphonium chloride;Si-C coupling
  1. Liebhafsky HA, Silicones Under the Monogram, John Wiley & Sons. Inc., New York (1978)
  2. 정일남, 제3세대 실리콘 화학, 아카데미 (1997)
  3. 동양실리콘 주식회사, 실리콘과 그 응용, 충무문화사 (1992)
  4. 김홍재, 규소수지, 대광서림 (1975)
  5. Lickiss PD, Silicon:Inorganic Chemistry in Encyclopedia of Inorganic Chemistry, Ed., King RR, John Wiley & Sons, New York, 7, 3770 (1999)
  6. 유복렬, 정일남, 직접법에 의한 실리콘 원료의 합성, 공업화학 전망, 2(4), 11 (1999)
  7. Yoo BR, Jung IN, Adv. Organoment. Chem., Direct Process for Synthesis of Organochlorosilanes, Manuscript in preparation by invitation (2003)
  8. Lewis KM, Reghwisch DG, Catalyzed Direct Reactions of Silicon, Elsevier, New York (1993)
  9. Marciniec B, Comprehensive Handbook on Hydrosilylation, Pergamon Press, New York (1992)
  10. Rochow EG, J. Am. Chem. Soc., U.S. patent 2,380,995: 2,380,996 (1945), 67, 963 (1995)
  11. U.S. Patent 6,242,629 B1 (2001)
  12. Sun DH, Bent BE, Wright AP, Naasz BM, Catal. Lett., 46(1-2), 127 (1997)
  13. Wessel TJ, Rethwisch DG, J. Catal., 161(2), 861 (1996) 
  14. Yilmaz S, Floquet N, Falconer JL, J. Catal., 159(1), 31 (1996) 
  15. Potochnik SJ, Falconer JL, J. Catal., 147(1), 101 (1994) 
  16. Floquet N, Yilmaz S, Falconer JL, J. Catal., 148(1), 348 (1994) 
  17. Kim JP, Rethwisch DG, David G, J. Catal., 134(1), 168 (1992) 
  18. Petrov AD, Mironov BF, Ponomarenko VA, Chernyshev EA, Synthesis of Organosilicon Monomers, Consultants Bureau, NY (1964)
  19. Chem. Abstr., PCT Int. Appl. WO 2001081354 A2, 135, 344592 (2001)
  20. Chem. Abstr., Ger DE. 19,951,773 C1, 134, 207965 (2001)
  21. Chem. Abstr., Eur. Pat. Appl. EP 832895 A1, 128, 217499 (1998)
  22. Chem. Abstr., Eur. Pat. Appl. EP 893448 A2, 130, 125217 (1999)
  23. Chem. Abstr., Eur. Pat. Appl. EP 900802 A2, 130, 224605 (1999)
  24. Okamoto M, Onodera S, Yamamoto Y, Suzuki E, Ono Y, Direct synthesis of organometallic compounds by the reaction of metallic silicon, hydrogen chloride and alkene/alkyne
  25. Oeye HA, Trondheim, Silcon Chem. Ind. IV, 339 (1998)
  26. Jung IN, Lee GH, Yeon SH, Suk MY, Bull. Korean Chem. Soc., 12, 445 (1991)
  27. Jung IN, Han JS, Yeon SH, Organometallics, 12, 2360 (1993) 
  28. Hurd DT, J. Am. Chem. Soc., 67, 1813 (1945) 
  29. Rochow EG, Gilliam WF, J. Am. Chem. Soc., 67, 1772 (1945) 
  30. Wright A, J. Organomet. Chem., 145, 307 (1978) 
  31. Yeon SH, Lee BW, Kim SI, Jung IN, Organometallics, 12, 4887 (1993) 
  32. Lee BW, Yoo BR, Kim SI, Jung IN, Organometallics, 13, 1312 (1994) 
  33. Yeon SH, Lee BW, Yoo BR, Suk MY, Jung IN, Organometallics, 14, 2361 (1995) 
  34. Jung IN, Yoo BR, Adv. Organomet. Chem., 46, 145 (2001)
  35. Jung IN, Yoo BR, Synlett., 519 (1999)
  36. Jung IN, Yoo BR, Organometallics, in press, 21 (2002)
  37. Masse CE, Panek JS, Chem. Rev., 95(5), 1293 (1995) 
  38. Jung IN, Yeon SH, Han JS, Bull. Korean Chem. Soc., 14, 315 (1993)
  39. Fritz G, Matern E, Carbosilanes: Synthesis and Reactions, Springer, New York, 46 (1986)
  40. Yeon SH, Han JS, Yoo BR, Jung IN, J. Org. Chem., 516, 91 (1996)
  41. Han JS, Yeon SH, Yoo BR, Jung IN, Organometallics, 16, 93 (1997) 
  42. Yeon SH, Han JS, Jung IN, Bull. Korean Chem. Soc., 16, 692 (1995)
  43. Lee CY, Han JS, Oh HS, Yoo BR, jung IN, Bull. Korean Chem. Soc., 21, 1020 (2000)
  44. Drake JE, Riddle CR, Glavincevski B, Gorzelska K, Henderson HE, Inorg. Chem., 17, 2333 (1978) 
  45. Lewis KM, Mcload D, Kanner B, Ward JW, Catalysis, 38, 415 (1988)
  46. Franke Tc, Kester KB, Falconer JL, J. Catal., 95, 396 (1985) 
  47. Franke TC, Kester KB, Falconer JL, J. Catal., 91, 44 (1985) 
  48. Voorhoeve RJH, Organohalosilanes: Precursors to Silicones, Elsevier, Amsterdam (1967)
  49. Bell TN, perkins Ka, Perkins PG, J. Chem. Soc.-Faraday Trans., 77, 1779 (1981)
  50. Walsh R, Organometallics, 8, 1973 (1989) 
  51. Sharma AK, Gupta SK, J. Catal., 93, 68 (1985) 
  52. Sharma AK, Gupta SK, J. Catal., 103, 236 (1987) 
  53. Okamoto M, Onodera S, Okano T, suzuki E, Ono Y, J. Organomet. Chem., 513(1-2), 67 (1997)
  54. Hurd Dt, Rochow EG, J. Am. Chem. Soc., 67, 1057 (1945) 
  55. Voorhoeve RJH, Vlugter JC, J. Catal., 4, 220 (1965) 
  56. Gorbunow AI, Belyi AP, Filippov GG, Russ. Chem. Rev., 43, 291 (1974) 
  57. De Cooker, Dejong J, Van Den Berg P, J. Organomet. Chem., 86, 175 (1975) 
  58. Kim Jp, Rethwisch DG, J. Catal., 134(1), 168 (1992) 
  59. Sun DH, Bent BE, Wright AP, Naasz BM, Catal. Lett., 46(1-2), 127 (1997)
  60. Hanbucken M, Netois J, mathiez P, Salvan F, Surf. Sci., 162, 622 (1985) 
  61. Turetskaya RA, Andrianov KA, Trofimova IV, Chernyshev EA, Russ. Chem. Rev., 44, 212 (1975) 
  62. Sun DH, Bent BE, Wright AP, Brian M, J. Mol. Catal. A-Chem., 131(1-3), 169 (1998) 
  63. Gaspar P, In Reactive Intermediates, Jones M and Moss R Eds., Tohn Wiley & Sons, New York, 1, 229 (1978)
  64. Gaspar P, In Reactive Intermediates, Jones M and Moss R Eds., Tohn Wiley & Sons, New York, 2, 336 (1980)
  65. Barton TJ, Burns GT, J. Am. Chem. Soc., 100, 5246 (1978) 
  66. Sosa C, Schlegel HB, J. Am. Chem. Soc., 106, 5847 (1984) 
  67. Bazant V, Chevalovsky V, Chemistry of Organosilicon Compounds, Academic Press, New York and London, 1, 180 (1965)
  68. Tacke R, Linoh H, Bioorganosilicon Chemistry, In the Chemistry of Organic Silicon Compounds, Part II, eds., Patai S and Rappoport Z, John Wiley & Sons, Chichester UK, 1143 (1989)
  69. Yoo BR, Suk MY, Han JS, Yu YM, Hong SG, Jung IN, Pestic. Sci., 52, 138 (1998) 
  70. Sommer LH, Pietrusza EW, Whitmore FC, J. Am. Chem. Soc., 69, 188 (1947)
  71. Speier JL, Webster JA, Barnes GH, J. Am. Chem. Soc., 79, 974 (1957) 
  72. Speier JL, Adv. Organomet. Chem., 17, 407 (1978)
  73. Ojima I, The Hydrosilylation Reaction in The Chemistry of Organic Silicon Compounds, Part 2, Eds.: Patai S and Rapporport Z, John Wiley & Sons, New York, 1479
  74. Armitage DA, 9.1 Organosilane In Comprehensive Organometallic Chemistry, Eds., Gordon F and Stone A, Pergamon Press, Oxford, UK, 2, 115 (1982)
  75. Benkeser RA, Dunny S, Li GS, Nerlekar PG, Work SD, J. Am. Chem. Soc., 90, 1871 (1968) 
  76. El-Durini NMK, Jackson RA, J. Organomet. Chem., 232, 117 (1982) 
  77. Benkeser RA, Foley KM, Grutzner JB, Smith WE, J. Am. Chem. Soc., 92, 697 (1970) 
  78. Benkeser RA, Snyder DC, J. Organomet. Chem., 225, 107 (1982) 
  79. Song YS, Yoo BR, Lee GH, Jung IN, Organometallics, 18, 3109 (1999) 
  80. Oertle K, Wetter HF, Tetrahedron Lett., 26, 5511 (1985) 
  81. Yamamoto K, Takemae M, Synlett, Stereochemistry of Aluminum Chloride Catalyzed Hydrosilylation of Methylcyclohexenes, 259 (1990) 
  82. Lee BW, Yoo BR, Yeon SH, Lee KB, Jung IN, Main Group Chem., 1, 53 (1995)
  83. Chandra G, Lo PY, Hitchock PB, Lappert MF, Organometallics, 6, 191 (1987) 
  84. Horrod JF, Chalk AJ, J. Am. Chem. Soc., 88, 3491 (1866) 
  85. Eaborn C, Bott RW, Organometallic Compounds of the Group IV elements, Ed., MacDiarmid MG, Marcel Dekker, New York (1968)
  86. Burkhand CA, Kriebie RH, J. Am. Chem. Soc., 69, 2687 (1947) 
  87. Benkeser RA, Muench WC, J. Organomet. Chem., 184, 3 (1980) 
  88. Benkeser RA, Gaul Jm, Smith WE, J. Am. Chem. Soc., 91, 3666 (1969) 
  89. Cho YS, Kang SH, Han JS, Yoo BR, Jung IN, J. Am. Chem. Soc., 123(23), 5584 (2001)