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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