1. Information and Communication Materials Lab. Inorganic Polymer 공업화학과 / 정보통신소재연구실 / 석사 2 기 김경아 Inorganic Polymer 공업화학과 / 정보통신소재연구실 / 석사 2 기 김경아 — Contents — Introduction Structures and Classification Polysilanes Polysiloxane and Silicones Polyphosphazenes Poly(carbosilane)s Inorganic / Organic polymer Hybrids 2.OCTOBER.2000 고분자신합성법 (Prof. 서동학 )

2. Information and Communication Materials Lab. Introduction Angew. Chem. Int. Ed. Engl. 1996.35.1602 S.S. Zumdahl Chemical Principles 2nd ed. 1995.p835 “Inorganic polymer” Main chain element is organized Ⅲ ~ Ⅵ group element. Especially, boron, silcon, phosphate, germanium. and sulfur Properties low temperature flexibility high thermal and oxidative stability flame retardancy novel forms of chemical reactivity Structures and Classification Classical main group inorganic polymers Polysiloxanes Polysilanes Polyphosphazene New Polymers Based on Main Group Elements Poly(carbosilane)s Polygermanes & Polystannanes

3. Information and Communication Materials Lab. poly(phthalocyaninato)siloxanes Transition metal based Polymers poly(metallocenylene)s & derivatives poly(ferrocenyl-silane)s poly(metallocenylene arylene)s

4. Information and Communication Materials Lab. Polysilanes  In the 1920s, first silane polymer by Kipping.  In the late 1970s, souble and processble polysilane Synthesis method Wurtz coupling polymerization S. Yajima, Chem. Lett. 1975. 931 R. D. Miller, Macromolecules 1994. 27. 5921 R. G. Jones, Macromolecules 1993. 26. 4878 Adv. : High molecular weight Disadv. : Low yield Side product

5. Information and Communication Materials Lab. Hanyang University Dehydrogenative coupling polymerization Acc. Chem. Res 1993. 26. 22 J. F. Harrod, J. Am. Chem. Soc. 1986. 108. 4059 Lower MW (Mn.<.8000) than Wurtz - coupling Slow rate of reaction Transition metal catalyst Advanced method for high MW Reduced amount of solvent Low temp. Slow addition rate of silane New catalyst Ultrasonic polymerization K. Matyjaszewski, J.Am.Chem.Soc. 1991.113 1046 K. Matyjaszewski, Macromolecules 1995. 28. 59-72 Masked disilenes H. Sakurai, J. Am. Chem. Soc. 1989. 111. 7641

6. Information and Communication Materials Lab. Hanyang University Electrochemical polymerization A. Kuriyama, Organometallics 1995. 14. 2506 K. Subramanian, Rev. Macromol. Chem. Phys. 1998. C38(4). 637 Unlike the wurtz methods, Very low temperature Potential required for reductive f formation(-1.3 to -2.1V) Polysilane forms initially coating on the cathode

7. Information and Communication Materials Lab. Hanyang University Application Conductive polysilane T. Imai, Synthetic metals 1996. 82. 201 M. Fukushima, Synthetic metals 1998. 94. 299 12 3 4 (a)Specimen of polymer film on glass plates equipped with gold electrodes (b) Apparatus for doping

8. Information and Communication Materials Lab. Hanyang University Conductivity of organosilicon polymers doped with I 2 or FeCl 3

9. Information and Communication Materials Lab. Hanyang University Polysiloxane or Silicones polysiloxanes were first developed in the 1930s and 1940s. Silicon (Si) Silica Silanes Siloxanes Silsesquioxanes Synthesis method

10. Information and Communication Materials Lab. Hanyang University Properties 내열성 / 내후성 낮은 표면장력 전기절연성 무색특성 Application 실리콘 오일 : 대상물질 표면에 엷은 막을 형성하 여 이형성, 미끄럼성, 광택성을 부여  자동차 / 가구 광택제 건축 / 섬유 발수제 대상물질에 첨가하여 사용하는 방법  극소량의 첨가로도 상당한 효과 도료의 부유방지, 흐름성 증진 광택성 증진 오일 자체  각종 계기 및 유압기의 충전액, 열 매체유, 변압기액, 소포제 실리콘 수지 : 고온용도료, 주방기구의 코팅 내후성 건축성 도료, 발수 코팅 실리콘 고무 실리콘 분산제품

11. Information and Communication Materials Lab. Hanyang University Polyphosphazenes The phosphazene backbone possesses a unique range of unusual properties. Poly phosphazenes are also of interest as biomedical materials, bioinert, bioactive, membrane forming, and bioerodable materials. synthesis method

12. Information and Communication Materials Lab. Hanyang University By Neilson and Wisian-Neilson R.H.Neilson.P. Wisian-Neilson. Chem.Rev 1988. 88. 541 N-silyl-P-(trifluoroethoxy)phosphoranimine R=alkyl or aryl By Matyjaszewski Macromolecular.1993. 26. 6471 Polymer.1994. 35. 5005 Polymer.1995. 36. 3493 N-silylphosphoranimine R=alkyl or aryl By De Janger Macromolecular.1992.25.1254 By Allcock and Manners J.Am.Chem.Soc.1995.117.7035 Synthesis operates at room temperature and allows molecular weight control.

13. Information and Communication Materials Lab. Hanyang University Application 전기적, 광학적 materials 액정고분자 및 액정 고리 화합물 약물전달체 생체재료

14. Information and Communication Materials Lab. Hanyang University Poly(carbosilane)s Synthesis of poly(silaethylene) by Interrante. Macromolecular 1992.25.1840 Macromolecular 1995.28.5160 Properties of poly(silaethylene) Air – stable Soluble in organic solvents. Aviscous liquid at room temperature On cooling to below room temperature forms a Translucent white solid. Low Tg Excellent yield(87%) on pyrolysis to 1000 ℃ poly(silaethylenepoly(dichlorosilaethylene). By Isaka Macromolecular. 1995.28.4733

15. Information and Communication Materials Lab. Hanyang University Inorganic/Organic Polymer Hybrids J.J.Scwab, J.D.Lichtenhan, Appl.Organometal.Chem. 1998, 12, 707 S.Sakka, Chem. Tech.News, 1997. 4(2), 54 Advantage of Hybrid System Thermal stability New electronic properties Optical transparency Mechanical strength Much functionalties Solubility Sol-Gel Process 금속 알콕사이드 M(OR)n 의 가수분해 - 축합반응을 이용해서 저온에서 유리나 세라믹을 합성하는 기술 M = Na,Ba,Cu,Al,Si,Ti,Ge etc R = methyl, ethyl…etc Conceptual model or organic-inorganic hybrid. Composite material Nano-composite Molecular hybrid

16. Information and Communication Materials Lab. Hanyang University Chemical reaction of Sol-Gel process Hydrolysis Condensation And / or Net Reaction Solvent Swollen SiO 2 Mareix 관련 특성응용분야 기계적 특성 및 광학 특성 Hard coating, Fiber reinforced plastics 렌즈 : 고굴절 렌즈, 안경 렌즈, 통신 : Optical fibers, Micro lenses Hologram : 3D display, Memory 열특성내열 소재, 적외선 반사용 박막 및 코팅 전자기 특성 LCD spacers, Resist Solar berreries(protective film) 화학 및 생체. 의학 특성 촉매 ( 자동차용, 중합용 ), 구조 제어 합성, Filter, 분리막, 인공 뼈 및 치아 Bioreactor 표면특성 Anti-fog 코팅, 내오염 코팅, 내부식 코 팅, 도료, 건축 및 건설용 코팅 Application field of Inorganic- Organic Hybrid

17. Highly Oriented Layered Silicate/Polymer Hybrids Information and Communication Materials Lab. Y.Kojima, A.Usaki, A.Okada, T.Kurauchi, O.Kamigaito, J.Polym.Sci.A. 1993. 31. 983 E.P.Giannelis, Appl.Organomet.Chem. 1998. 12. 675 Schematic Representations Synthetic methods Direct melt intercalation of organic polymers into layered inorganic solids Intercalation of organic polymers from solvents In-situ polym. of organic monomers between inorganic layers Advantages Lightness in weight Stronger mechanical properties Alkyl ammonium modification Render silicate organophilic Lower surface energy of solids