Information and Communication Materials Lab. Inorganic Polymer 공업화학과 /...
Transcript of Information and Communication Materials Lab. Inorganic Polymer 공업화학과 /...
Information and Communication Materials Lab.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 )
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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, germaniu
m. 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
Si
R
R
O
n
Si
R
R n
P
R
R
N
n
New Polymers Based on Main Group Elements
Poly(carbosilane)s
Polygermanes & Polystannanes
Si
R
R
C
n
Ge
R
R n
Sn
R
R n
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poly(phthalocyaninato)siloxanes
Transition metal based Polymers poly(metallocenylene)s & derivatives
poly(ferrocenyl-silane)s
poly(metallocenylene arylene)s
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Polysilanes
In the 1920s, first silane polymer by Kipping. In the late 1970s, souble and processble polys
ilane 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
RR'SiCl2 Na, toluene
110oCSi
R
R' n
Adv. : High molecular weight
Disadv. : Low yield Side product
Polymer Mn x 10-3 Mw x 10-3 Mw / Mn Yield(%)
High mw 107 193 1.81(PhMeSi)n
Low mw 3.3 5.6 1.6955
High mw 66 213 3.23(p-TolMeSi)n
Low mw 4.7 5.9 1.2625
High mw 134 286 2.13(-phenethylMeSi)n
Low mw 3.3 4.4 1.3635
High mw 297 644 2.17(nPrMeSi)n
Low mw 7.4 13.3 1.7932
High mw 50 110 2.19(nBuMeSi)n
Low mw 4.4 5.9 1.3634
High mw 281 524 1.86(nHexylMeSi)n
Low mw 14.6 20.5 1.4011
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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
Si Si
SiSi
Ph
Me
Ph
Me
Ph
Me
Ph
Me
Si
Me
Me n
R-
Masked disilenes H. Sakurai, J. Am. Chem. Soc. 1989. 111. 7641
SiSi
Ph
Me
PhPh
Me
Si
Me
Ph n
RLi
-Ph-Ph
nRSiH3 Si
R
HH
H n
+ (n-1)H2catalyst
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Electrochemical polymerization A. Kuriyama, Organometallics 1995. 14. 2506
K. Subramanian, Rev. Macromol. Chem. Phys.
1998. C38(4). 637
Si
R
R
Cl Cl + 2n e-at or below RT
R
R
Sin
+ 2n Cl-
• 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
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Application Conductive polysilane T. Imai, Synthetic metals 1996. 82. 201
M. Fukushima, Synthetic metals 1998. 94. 299
1 2
3
4
(a) Specimen of polymer film on glass plates equipped with gold electrodes
(b) Apparatus for doping
Si
R'
R n
Si
R'
Si
R
R'
R n
Si
R'
Si
R
R'
R n
Si
R'
Si
R
R'
R n
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Side chain Conductivity(S/cm)Polymer
R R’Mw x 10-3 IP(eV)
I2 dopantFeCl3
dopant
Bu Bu 650 5.83 4 x 10-8 2 x 10-10
1Ph Me 46 5.42 1 x 10-6 6 x 10-6
Bu Bu 9.5 5.66 2 x 10-6 2 x 10-6
2Ph Me 27 5.53 1 x 10-6 1 x 10-4
Bu Bu 19 5.86 2 x 10-8 1 x 10-10
3Ph Me 130 5.31 2 x 10-8 8 x 10-6
Bu Bu 11 5.66 6 x 10-5 1 x 10-6
4Ph Me 4.8 5.92 6 x 10-5 8 x 10-4
Conductivity of organosilicon polymers doped with I2 or FeCl3
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Polysiloxane or Silicones
polysiloxanes were first developed in the 1930s and 1940s.
Silicon (Si)
Silica Silanes
Siloxanes Silsesquioxanes
Synthesis method
Si
Me
OOH
Me
H
n
Me2SiCl2H20
SiO
SiO
Si
O
MeMe
Me
Me
Me
Me
SiO
Si
OSi O
Si
O
Me Me
Me
Me
MeMe
Me
Me
Si
Me
O
Me n
heat and/or anionicor cationic initiators
Si
O
OO
O
X
Si
X
XX
R
Si
R
OO
R
Si
O
OO
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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
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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
N
PN
P
NP
ClCl
Cl
Cl
Cl
Cl
P
Cl
N
Cl
InsolubleCrosslinkedPolymer
P
OR
N
OR
P
NHR
N
NHR
P
R
N
Cl
RONa RNH2RM(Organometallic agent)
250oC
n
250oC
n n n
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P
RO
NOR
RO
SiMe3 P
OR
N
OR n
[Bu4N]F,110oC
-Me3SiOR
PCl3 N P(O)Cl2 P
Cl
N
Cl n-P(O)Cl3
200oC
P
Cl
NCl
Cl
SiMe3 P
Cl
N
Cl n
trace of PCl5, 25oC-Me3SiCl
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
P
R
NR
OR
SiMe3 P
R
N
R n
-Me3SiOR
190oC
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.
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Application • 전기적 , 광학적 materials
• 액정고분자 및 액정 고리 화합물 • 약물전달체
• 생체재료
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Poly(carbosilane)s
Cl2Si CH2
SiCl2H2C
Si
Cl
CH2
Cln
Si
H
CH2
Hn
Li[AIH4]H2PtCl6
Si
Me
Si
Me
CH2
Me
Me n
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
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Inorganic/Organic Polymer Hybrids
J.J.Scwab, J.D.Lichtenhan, Appl.Organometal.Chem. 1998, 12, 707S.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
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Chemical reaction of Sol-Gel process
Hydrolysis
Condensation
Si(OR) + H2O (RO)3Si-OH + ROH
Si-OH HO-Si Si-O-Si+ + H2O
Si-OH RO-Si Si-O-Si+ + ROH
And / or
Net Reaction
Si(OR)4 (liq)
H2O/H+ or OH-
Cosolvent
Solvent SwollenSiO2 Mareix
관련 특성 응용분야기계적 특성 및
광학 특성
Hard coating, Fiber reinforced plastics렌즈 : 고굴절 렌즈 , 안경 렌즈 , 통신 : Optical fibers, Micro lensesHologram : 3D display, Memory
열특성 내열 소재 , 적외선 반사용 박막 및 코팅
전자기 특성
LCD spacers, ResistSolar berreries(protective film)
화학 및 생체 . 의학 특성
촉매 ( 자동차용 , 중합용 ), 구조 제어 합성 , Filter, 분리막 , 인공 뼈 및 치아Bioreactor
표면특성 Anti-fog 코팅 , 내오염 코팅 , 내부식 코팅 , 도료 , 건축 및 건설용 코팅
Application field of Inorganic- Organic Hybrid
Highly Oriented Layered Silicate/Polymer Hybrids
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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