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Inorganic-Organic

Hybrid Materials

Bressanone Sept. 2006

Hybrid Materials

Bressanone Sept. 2006

Hybrid Materials

Composites Hybrid Materials

cm

nm

CLASSICAL COMPOSITES

Property Improvement:
mechanical stability
thermal stability
photochemical stability

Hybrid Materials

From Molecules to Nanobuilding Blocks

Various properties possible depending on precursors and processing

Bressanone Sept. 2006

Hybrid Materials

Hybrid Materials

Composite Material

Compound 1

Macroscopic
phases

Compound 2

Hybrid Material

Molecular or
nanoscale
building blocks

The goal is to create materials with specific combinations of properties by


combining different molecular building blocks in various ratios and by controlling
their mutual arrangement
Control at the nanolevel

Bressanone Sept. 2006

Hybrid Materials

Homogeneity

vs.

Problems: scatters light,


mechanical properties, etc
Control over homogeneity:
precursor selection (functional group)
reaction conditions: kinetics, solvent, etc.
interactions between the components

Bressanone Sept. 2006

Hybrid Materials

Typical Properties of Organic and Inorganic Materials

Properties

Organic materials
(polymers)

Inorganic materials
(glass, ceramics)

Nature of bonds

covalent [CC], van der


Waals, H-bonding
low
low (except polyimides)
low
low
elastic
flexible
rubbery (depending on Tg)
hydrophilic or hydrophobic

ionic or covalent
high
high
high
high
hard
strong
brittle
hydrophilic

insulating to conductive
non-magnetic
at low temperatures and
pressures (molding, casting,
etc.)

insulating to semiconductors
magnetic
at high temperatures and/or
pressures (sintering, glass
forming)

Tg
Thermal stability
Density
Refractive index
Mechanical properties

Hydrophobicity
Electronic and
magnetic properties
Processability

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Hybrid Materials

Nanolego

Form
Function
Geometry of the linkage
Connectivity
Kind of linkage

Bressanone Sept. 2006

Hybrid Materials

Nanolego: Building Blocks


Inorganic Building Blocks
O

O
O

Si

O
Ti

Mechanical, optical, electrical,


magnetical properties

O
O

Connecting Blocks

H2C

Si

O
O

X
Ti

Y
O

Reduction of the crosslinking density,


coupling sites between inorganic /
organic components

Organic Building Blocks


Functional groups, crosslinking,
polymerizability

Flexibility, elasticity, processability


H2
C

H2
C
C
H2

C
H2

Bressanone Sept. 2006

Hybrid Materials

Nanolego: Linking the Building Blocks


Polymerization / Polycondensation
CH3

COOR

CH3

COOR

CH3

COOR

HO

OR

+
O

H2N

HN

HN

NH2

OH

NH

Sol-Gel-Process
RO

Si

OR
OR

HO
+ H2O

Si

OH
OH

OH

OR

HO
- H2O

+ H+

HO

Si

OH
OH

OH
Na4SiO4

Si

HO

Si

OH
OH

OH
OH

Self-Organization
Zn(NO3)2 +
HO
O

Zn4O(terephthalate)6

OH

Bressanone Sept. 2006

Hybrid Materials

Nanolego: Critical Issues

Homogeneous distribution of the building blocks in the material


Stable distribution: no microphase separation
Interaction between the two components
Structure-property relationships
Inclusion of functionalities
Tailoring of
molecular structure nanostructure microstructure
(= hierarchical structure design)

Bressanone Sept. 2006

Hybrid Materials

10

Precursors
Molecular precursors
Clusters (nano-building blocks, NBB)
Alkoxysilyl-substituted organic polymers
Pre-formed nanostructures

Classes of sol-gel hybrid materials


Physically entrapped components
Functionalized inorganic networks
Interpenetrating networks
Dual networks

Bressanone Sept. 2006

Hybrid Materials

11

Molecular Precursors
Network Modifiers (non-reactive organic groups)
(RO)3Si CH3

(RO)3Si

(RO)3Si

Precursors with Functional Organic Groups


(RO)3Si
(RO)3Si

O
O

+ HS-Si(OR)3

(RO)3Si

(RO)3Si

O
RO

(EtO)3Si

O
Ti

H
N

O
O

N
R

OR

OR

(RO)3TiSO3(Co-phthalocyanine)

polymerizable organic groups


inorganic-organic hybrid polymers

Bressanone Sept. 2006

NO2

NH2

N
H

groups with other organic functions

Hybrid Materials

12

Nano Building Blocks: Polyhedral Oligomeric Silsesquioxanes (POSS)

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Hybrid Materials

13

Nano Building Blocks: Functionalized Metal Oxide Clusters

Ti16O16(OEt)24(OPr)8
(same with
OCH2CH2OC(O)C(Me)=CH2)

Zr6O4(OH)4(methacrylate)12
covalent interaction

[(BuSn)12O14(OH)6]2+2 methacrylate[SiW11O39(OSi2(C6H4CH=CH2)2)]4-

Bressanone Sept. 2006

Hybrid Materials

electrostatic interaction

14

Bridged Alkoxysilanes

(RO)3Si

(RO)3Si-(CH2)n-Si(OR)3

Si(OR)3

H
N

(RO)3Si-(CH2)m

H
(CH2)n N

H
N (CH2)n

H
N

H
N (CH2)m-Si(OR)3

O
(EtO)3Si

O
O
N

N
H

(EtO)3Si

H
N

SO2(CH2)2O

O
O

Si(OEt)3

2+
NH

(RO)3Si

H2N

Bressanone Sept. 2006

NH2
Ni

NH

Si(OR)3

Hybrid Materials

15

Alkoxysilyl-Substituted Organic Polymers

CH3
(EtO)3SiO

Si

Si(OEt)3
n

CH3

(EtO)3Si-(CH2)3 O

Bressanone Sept. 2006

CH3

H2
C

n
C

(CH2)4-O

Si(OMe)3

(CH2)3-Si(OEt)3

Hybrid Materials

16

Pre-formed Nanostructures
(Nano)Particles

Preformed Oligomers
and Polymers

Clays / Layered Materials

Porous Materials

Bressanone Sept. 2006

(Nano)Fibres, Nanotubes

Hybrid Materials

17

Consequences of Introducing Organic Substituents

Reduced degree of crosslinking of the inorganic network


Polarity changes (changes in hydrogen bonding)
Reactivity change of the remaining alkoxide groups
(electronic and steric effect of the organic substituents)

These effects are an inevitable consequence


of the organic modification

Bressanone Sept. 2006

Hybrid Materials

18

Degree of Crosslinking
Si(OR)4-nRn
n = 1-3

Si(OR)2R2

Si(OR)3R
R

Si

Si

Si

O
O

R
Si

Si

O
O

Si

Si

Si

Si

Silsesquioxanes
R
R

O Si O
Si
O

R
R

O
n

Si(OR)R3
R

Si O

Si R

R'

Oligo- and Polysiloxanes

Dimers

R
Si
O
O
R
O
Si

Si

OR
Si
O
O
Si
Si O
O
R
R

Polyhedral Oligomeric
Silsesquioxanes

Bressanone Sept. 2006

Hybrid Materials

19

Influence on Reaction Rates


Example:

(RO)3Si

Si(OR)3

0.6 M in methanol, 25C


The dashed line is pH vs. gel time for
Si(OMe)4 (2.0 M in methanol, 60C).

Bressanone Sept. 2006

Hybrid Materials

20

10

Influence on Reaction Rates

(acac = acetylacetonate, ftac =trifluoroacetylacetonate, dbzm = dibenzoylmethanide)

Bressanone Sept. 2006

Hybrid Materials

21

Precursors
Molecular precursors
Clusters (nano-building blocks, NBB)
Alkoxysilyl-substituted organic polymers
Pre-formed nanostructures

Classes of sol-gel hybrid materials


Physically entrapped components
Functionalized inorganic networks
Interpenetrating structures
Dual networks

Bressanone Sept. 2006

Hybrid Materials

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11

Types of Inorganic-Organic Hybrid Materials by Sol-Gel Processing


Physically entrapped
molecules, particles, etc.

Interpenetrating inorganic
and organic networks

Class I materials:
weak interactions

R R
RR
R

Class II materials:
strong interactions

RR

R R
R R
RR

RR

R R

RR
R
R
R R
R

R RR
RR
R
R

R
R

RRR
R
R

Modification of the gel


network by organic groups

Bressanone Sept. 2006

Dual inorganic and organic networks


connected by covalent bonds

Hybrid Materials

23

Entrapped Biomolecules

Bressanone Sept. 2006

Hybrid Materials

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12

Entrapped Biomolecules: Glucose Sensor


NO-releasing glucose biosensor
(cleaved NO suppresses degradation by bacteria)

Glucose oxidase in MeSi(OEt)3 Gel

SiO2

Si

CH3
OH

N NO
H
O Si (CH2)3 N (CH2)6 N
H

in polyurethan

M.H.Schoenfisch et al., 2004

Bressanone Sept. 2006

Hybrid Materials

25

Entrapped Inorganic Particles: Dental Filling


abrasion 9 m

shrinkage 1,97 vol%


adhesion 25,8 / 27,6 MPa

pyrogenic
silica
( 40 nm)

+
standard
dental glass
particles
( 0,7 m)

Bressanone Sept. 2006

Hybrid Materials

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13

Entrapped Inorganic Particles: Controlled Release

in SiO2

Bressanone Sept. 2006

Hybrid Materials

27

Precursors
Molecular precursors
Clusters (nano-building blocks, NBB)
Alkoxysilyl-substituted organic polymers
Pre-formed nanostructures

Classes of sol-gel hybrid materials


Physically entrapped components
Functionalized inorganic networks
Interpenetrating structures
Dual networks

Bressanone Sept. 2006

Hybrid Materials

28

14

Heterogenization of Homogeneous Catalysts


Classical approach
RO

RO

RO

Si

RO

Sol-gel approach

+ MLn

RO

Si

RO

MLn

+ MLn

O
Si

Si

MLn

MLn

+ MLn

+ MLn

Si

RO

Bressanone Sept. 2006

Si

Si

E(OR) n

RO

RO

RO

RO
Si

MLn

+ E(OR) n

RO

RO

Si

RO

RO

RO

RO

RO

Si

Hybrid Materials

29

Heterogenization of Catalysts by Sol-Gel Processing


RO
Si

RO

MLn

Examples:

+ Si(OR)4

RO

Si

Ph

C
O

Ph
P

Si(OR)3

Ph

MLn

(EtO)3Si

Poren
pores

(EtO)3Si

sol-gel
Sol-GelProze
processing

Ph Cl
P
Ru
P
Ph Cl

Ph
P
P
Ph

Si(OEt)3

Si(OEt)3

Synthesis of N,N-diethylformamide from CO2, H2


and diethylamine
A. Baiker et al., 1999

K
K

Cl
Rh

More active in the hydrosilation of 1-hexene than


Rh(CO)Cl(PR3)2
U. Schubert et al., 1989

SiO2 /

Ph
(RO)3Si

K
K

(RO)3Si

K
K

aktive
Spezies
= katalytisch
catalytically
active
species

N
H

NH2 N

Cu2+

NH
2

Catalyst for the oxidation of 3,5-di-tert.butylcatechol


to the quinone
M. Louloudi et al., 1998

Bressanone Sept. 2006

Hybrid Materials

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15

Coatings with Optical Properties


Photochromism: fast for optical switches, for eye protection, privacy shields
slow for optical data storage, energy conserving coatings, etc...
Example: Spirooxazine derivative

h1

N
N

or h2

N
N

Embedding in sol-gel coatings:


For sufficient photochromism: dye concentration > 25 wt% mechanical stability of
sol-gel film is deteriorated.
Grafting of the dye to the
sol-gel matrix higher chromophore
concentrations can be achieved
without affecting the mechanical integrity
of the sol-gel matrix

Si(OEt)3
HN

O
N
N

Photochromic coating on paper

Bressanone Sept. 2006

Hybrid Materials

31

Precursors
Molecular precursors
Clusters (nano-building blocks, NBB)
Alkoxysilyl-substituted organic polymers
Pre-formed nanostructures

Classes of sol-gel hybrid materials


Physically entrapped components
Functionalized inorganic networks
Interpenetrating structures
Dual networks

Bressanone Sept. 2006

Hybrid Materials

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16

Interpenetrating Networks
Sequential
Sequentialtwo-step
two-stepprocess:
process:
Second
Secondnetwork
networkis
is
formed
formedin
inthe
thefirst
first

IPN
Examples:
Generation of the organic polymer in the pores of an inorganic porous material
(in channels of zeolites or mesoporous materials, between sheets of a layered
lattice, such as a clay mineral) rigid inorganic moiety with a regular pore or
channel structure in the nanoscale
Inorganic structures form and interpenetrate an organic polymer (difficulties:
incompatibility between the moieties phase separation)

Bressanone Sept. 2006

Hybrid Materials

33

Interpenetrating Networks
Interaction via hydrogen bonds to silanol groups of the forming silica
Organic polymers with hydrogen bonding ability:

n
NMe2

OH

OMe

n
O

OH
poly(VP)

poly(DMAA)

poly(VA)

poly(VAc)

poly(MMA)

poly(HEMA)

Si(OR)4 and/or RSi(OR)3


H2O, [Kat]

No macro phase separation


Resulting materials: high degree of homogeneity
and optical transparency

Important reaction parameter: pH


Change of crosslinking density and interaction with polymer using RSi(OR)3/Si(OR)4 mixtures

Bressanone Sept. 2006

Hybrid Materials

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17

Interpenetrating Networks

+
Sol from GLYMO and Al(OsBu)3 (H2O/HCl)

Poly(isopren-block-ethylenoxide)
swollen in THF/CH3Cl

(RO)3Si

O
O

Nanostructured hybrid polymer


U.Wiesner et al., 2004

Bressanone Sept. 2006

Hybrid Materials

35

Interpenetrating Networks
Organic
Monomer

Inorganic Monomer

Catalyst

Solvent

AIBN

TEOS

HF

Water

OH

C. L. Jackson et al. Chem. Mater. 1996, 8, 727

Initiator

Addition of tetrakis(2-(acryloxy)ethoxy)silane
improves homogenity

TEM images of the nanocomposites:

Increasing Sol-Gel Catalyst Concentration => Faster Reaction

Bressanone Sept. 2006

Hybrid Materials

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18

Nanocomposites: Polymer-Clay

Layered solid

Layered solid

+ Monomer
(Polymerization)

Exfoliated layers

+ Polymer

+ Monomer
(Polymerization)
or
+ Polymer

Bressanone Sept. 2006

Hybrid Materials

37

Nanocomposites: Polymer-Clay

Bressanone Sept. 2006

Hybrid Materials

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19

Nanocomposites: Polymer-Clay
15 m glass fibre in polyolefin

1 nm thick montmorillonite
sheet in epoxy resin

Bressanone Sept. 2006

Hybrid Materials

39

Nanocomposites: Intercalation of Polymers in Pores

Direct Intercalation

Polymer

Porous Host

Problems:
Pore diameter size of Polymer
Diffusion of polymer
Usually only end of polymer sits in pore but not the whole chain

Bressanone Sept. 2006

Hybrid Materials

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20

Nanocomposites: Polymerization in Pores

Monomer
Intercalation

Monomer

Polymerization

Porous Host

Monomer is interacalated into the pores


(vapor, liquid), then polymerization

T. Aida et al. 2000

Bressanone Sept. 2006

Hybrid Materials

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Nanocomposites: Polymerization in Pores

T. Aida et al. 2000

T. Bein et al. 1992

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Hybrid Materials

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21

Precursors
Molecular precursors
Clusters (nano-building blocks, NBB)
Alkoxysilyl-substituted organic polymers
Pre-formed nanostructures

Classes of sol-gel hybrid materials


Physically entrapped components
Functionalized inorganic networks
Interpenetrating structures
Dual networks

Bressanone Sept. 2006

Hybrid Materials

43

Dual Network Structures


Preparation strategies
Concomitant formation of the inorganic and organic structures
Stepwise formation of the organic and inorganic networks
from pre-formed organic structures
from pre-formed inorganic structures
Options

Chemical composition of the inorganic component(s)


Chemical composition of the organic component(s)
Proportion of the inorganic/organic components
Curing method (thermal / photochemical)
Dimension of the inorganic / organic components (molecular, nanometer,
extended)

Bressanone Sept. 2006

Hybrid Materials

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22

Concomitant Formation of Inorganic and Organic Network


Typical procedure

Metal Alkoxides
Metal Salts
+ water (ev. catalyst or additives)
- alcohol

Precursors

Hydrolysis
Condensation

Sol
Gelation

formation of inorganic network

Gel
formation of organic network

Hardening
(thermal or uv)

Many Examples:
Coatings Section

Hybrid Polymer

Bressanone Sept. 2006

Hybrid Materials

45

Concomitant Formation of Inorganic and Organic Network


Often used precursors
O
(RO)3Si

(RO)3Si

(RO)3Si

O
O

or
O

OH

+ Zr(OR)4

+ Si(OR)4, Zr(OR)4, Al(OR)3,


etc.

+ acrylate, epoxide
monomers, etc.

increase of inorganic /
organic ratio

decrease of inorganic /
organic ratio

Bressanone Sept. 2006

Hybrid Materials

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23

Concomitant Formation of Inorganic and Organic Network


O
O

O
O

Sequential
formation of
the organic
network

UV-polymerization
of methacryl groups

photo-initiator, h
O
O

O
O

O
O

O
O

O
O

thermal polymerization
of epoxy groups

T
O
O

O
O

O
O
O

O
O

O
O

O
O

Bressanone Sept. 2006

Hybrid Materials

47

*) SBU: Sequentially Built-up

Concomitant Formation of Inorganic and Organic Network


O
H2O / NaF
Si
CH2O

SiO2

CH2OH n

H2O / NaF
O(CH2)2O Si
4

Bressanone Sept. 2006

aq. ROMP

O
+

Free Radical
Polymerization

SiO2 +

Hybrid Materials

O(CH2)2OH 4

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24

Photochemical Crosslinking (3D Laser Lithography)


Coating or forming of
ORMOCER
(with chromophor as UV initiator)

Direct 3D-laser writing


(2-photon polymerisation with
femtosecond laser pulses)
Requirements for hardening:
Development of the structure
(removal of uncured
ORMOCER)

precise focussing

2-photon process

polymerisation in Ormocer layer


(O2 protection)

chromophor as initiator

Ormocer = Organically modified Ceramics

Bressanone Sept. 2006

Hybrid Materials

49

Photochemical Crosslinking (3D Laser Lithography)


CAD File

Layer model

Venus of Milo in
ORMOCER (REM)

I am made
from
ORMOCER!

Bressanone Sept. 2006

Hybrid Materials

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25

Photochemical Crosslinking (3D Laser Lithography)

Bressanone Sept. 2006

Hybrid Materials

51

Hybrid Polymers from Pre-Formed Organic Polymers


CH3

Low shrinkage by the use of


prepolymerized materials

CH3

acrylic component
silane component

(MeO)3Si(H2C)3O

y
MeO

1. inorganic condensation
2. organic polymerization

acrylic monomer + polymer


(incomplete polymerization)

inorganic condensation
between fully
polymerized polyacrylate

Bressanone Sept. 2006

Hybrid Materials

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26

Hybrid Polymers from Pre-Formed Organic Polymers


A.-M. Caminade, J.-P. Majoral, J. Mater. Chem., 2005, 15, 3643-3649

Hybrid Materials applying Dendrimers

Porous Materials using Dendrimers as Templates

Bressanone Sept. 2006

Hybrid Materials

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Hybrid Polymers from Pre-Formed Inorganic Structures

Bressanone Sept. 2006

Hybrid Materials

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27

Hybrid Polymers from Pre-Formed Inorganic Structures


Improved Properties through Controlled
Reinforcement of Polymer Chains at the Molecular Level

R
O
Si

Si

Si

O
Si

O R
Si
O
Si

R'

O
O

O
RO
O

Si

Si O
R

www.hybridplastics.com

Bressanone Sept. 2006

Property enhancements via POSS


observed in POSS-copolymers and blends
Increased Tdec
Increased Tg
Reduced Flammability
Reduced Heat Evolution
Lower Density
Disposal as Silica
Extended Temperature Range
Increased Oxygen Permeability
Lower Thermal Conductivity
Thermoplastic or Curable
Enhanced Blend Miscibility
Oxidation Resistance
Altered Mechanicals
Reduced Viscosity

Hybrid Materials

55

Hybrid Polymers from Pre-Formed Inorganic Structures


POSS for fire retardant materials

Bressanone Sept. 2006

Hybrid Materials

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28

Hybrid Polymers from Pre-Formed Inorganic Structures


Polymerizable Metal Oxo Clusters
X

X
X

X
X

X
X
Polymerizable groups X

Zr6O4(OH)4(methacrylate)12
for free radical polymerization

Zr6O4(OH)4(5-norbornene-2-carboxylate)12 for ROMP

Bressanone Sept. 2006

Hybrid Materials

57

Hybrid Polymers from Pre-Formed Inorganic Structures


Metal Oxo Clusters as Initiators for ATRP
multifunctional initiator + monomer
X

catalyst

X
X
X

X
X
X

+ solvent

= PMMA, PS, PtBuA

catalyst = pmdeta / CuBr or CuCl

e.g. Ti6O4(OOCCBrMe2)(OiPr)8

0.9

100

0.7

ln (M0/M)

G.Kickelbick et al.

Bressanone Sept. 2006

80

Y=0,0058*X
R=0,997

70
60

0.5

50

0.4

40

0.3

Polydispersities <1.5. 0.2


90% of the chain ends 0.1
still active after isolation 0.0 0

Hybrid Materials

30

Conversion [%]

0.6

90

ln (M 0/M)
linear Fit for ln (M 0/M)

0.8

20
10
0
20

40

60

80

100 120 140 160

Time [min]

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29

Hybrid Polymers from Pre-Formed Inorganic Structures


Combination of polyoxometallates (electrochromism, photochromism,
conductivity, redox activitities) + conjugated molecules and polymers
electrically active organic materials (light emitting diodes, field-effect
transistors, solid-state lasers)
Monofunctionalization of Mo6O192-

Examples:

Z. Peng et al. 2004

Bressanone Sept. 2006

Hybrid Materials

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Hybrid Polymers from Pre-Formed Inorganic Structures

Z. Peng et al. 2004

Bressanone Sept. 2006

Hybrid Materials

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Hybrid Polymers from Pre-Formed Inorganic Structures


Magnetic Polymers

Mn12O12(OOC-CH=CH2)16

Radical polymerization

+ CH2=CMe-COOMe

PMMA crosslinked by Mn12


Mn12
total cluster spin S = 10
(4 MnIV, S = 3/2 + 8 MnIII, S = 2)

Bressanone Sept. 2006

Superparamagnetic

Hybrid Materials

61

Hybrid Polymers from Pre-Formed Inorganic Structures

Preparation of nanoparticles
Stber-Process

Si(OEt)4 + NH4OH
FG

Surface modification
O
N
NC

CH3

CH3
CH3
CN

SiO

FG

Si
Si
FG
O O O OO O
O
Si
O
O
O
O
O
O
Si O
2
O
O
O Si
O
O
FG
O
O O OO
Si
FG

FG

Si

Initiators at the surface, e.g.


(EtO)3Si(H2C)3O

HO HO OH OH
HO
OH
HO
HO
OH
HO
OH
2
HO
OH
HO
OH
HO
OH
HO
HO HO OHOH

FG

O
CH3
(EtO)3Si(H2C)3O

Br
CH3

SiO

(RO) 3 Si

FG

FG

Polymerization from the functionalised surface

AFM

G.Kickelbick et al.

Bressanone Sept. 2006

Hybrid Materials

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