hybrid_lecture_4.ppt........................................................................................

........................................................................................................................................................................................

1. Hybrid Organic-Inorganic, POSS
Materials
Lecture 4 & Quiz
September 28th

2. Today
First hour:
•Some definitions
•Strategies for making Hybrids
Second hour:
•Quiz
•Discussion of quiz answers

3. Course website
•For lecture slides and other info.
•Not at HIT website, at Loy research
website:http://www.loyresearchgroup.com/
• Go to loy research group home page and select
“courses” on menu at top.
• Class website “Harbin Institute of Technology,
Hybrid Materials Course” is the first entry.
Direct url:http://www.loyresearchgroup.com/harbin-
institute-technology---hybrid-materials-course.html

4. What are Hybrid Materials?
Composite materials mixtures of organic and
inorganic components
Improvement on either organic or inorganic components
Metal
oxide
network

5. Introduction to
polysilsesquioxanes
RSiO
1.5
n
Si
R
Si
Si
R
Si
O
O
O
Si
Si
O
Si
O
R
Si
O
O
O
Si
O
R
OH
O
Si
O
O
SiOR
O
O
R
Si
O
R
Si
O
OH
O
R
O
R
OH
R Si
R
O
O
R
Si
Si
R
HO
Si
OH
R
HO O
OH
R
R
R
n = 17
Si
O
Si Si
O
RR
R
Si
O
O
Si
O
Si Si
O
O
O
O
Si
O
O
O
R
R R
R
R
n = 8
RSiO
1.5
8
R
8Si
8O
12
Network of Si-O-Si
Organic group (alkyl, aryl, alkenyl) attached through Si-C bond
Fully condensed: 1.5 oxygens per Si
Three siloxane bonds per silicon

6. Where are the organic and inorganic
phases?
Si
R
Si
Si
R
Si
O
O
O
Si
Si
O
Si
O
R
Si
O
O
O
Si
O
R
OH
O
Si
O
O
SiOR
O
O
R
Si
O
R
Si
O
OH
O
R
O
R
OH
R Si
R
O
O
R
Si
Si
R
HO
Si
OH
R
HO O
OH
R
R
R
RSi(OMe)
3
H
2O
catalyst
Si
O
Si Si
O
RR
R
Si
O
O
Si
O
Si Si
O
O
O
O
Si
O
O
O
R
R R
R
Ror
Blue is inorganic
Black is organic
•Segregation only at sub-molecular length scales.
•Hybrid, synergistic properties come from very high surface
area contact between phases

7. Silsesquioxane
Silicon 1.5
Oxygens
Polysilsesquioxane
Many
RSiO
1.5
n
Many generally means more than 10,000 Dalton Mw

8. Oligosilsesquioxane
Silicon 1.5
Oxygens
A few
RSiO
1.5
n
Oligo means > 1 and < 50-100 (depends on Mw or R group)
Si
O
Si Si
O
RR
R
Si
O
O
Si
O
Si Si
O
O
O
O
Si
O
O
O
R
R R
R
R
n = 8
RSiO
1.5
8
R
8Si
8O
12

9. Nomenclature of silsesquioxanes
•Polymers: poly(name of organic-silsesquioxane)
eg. R = Ph or phenyl
poly(phenylsilsesquioxane)
PhSiO
1.5
n

10. Nomenclature of silsesquioxanes
•oligomers: oligo(name of organic-silsesquioxane)
eg. R = Ph or phenyl
poly(oligosilsesquioxane)
PhSiO
1.5
n

11. Nomenclature of silsesquioxanes
•Polyhedral oligomers: need to describe size of
rings
eg. R = Ph or phenyl
T
8: n = 8
Si
O
Si Si
O
PhPh
Ph
Si
O
O
Si
O
Si Si
O
O
O
O
Si
O
O
O
Ph
Ph Ph
Ph
Ph
n = 8
PhSiO
1.5
8
Ph
8Si
8O
12
Ph = phenyl
Polyhedral refers to multi-sided geometric shapes like cubes.
1,3,5,7,9,11,13,15-octaphenyl
pentacyclo[9.5.1.13,9.15,15.17,13]octasiloxane
IUPAC Name:

12. Si
O
Si
Si
O
Si
O
CH
2
CH
2
Si
Si
O
Si
O
O
Si
O
O
O
Si
CH
2
O
CH
2
O
Si
O
O
Si
CH
2
O
O
O
CH
2
Si
CH
2
Si
O
O
CH
2
O
O
O
O
Si
O
O
CH
2
Si
O
Si
Si
O
O
OO
C
H
2
(MeO)
3
SiCH
2
Si(OMe)
3
(MeO)
3
Si Si(OMe)
3
(MeO)
3Si Si(OMe)
3
HH
+ 3n H
2
O
-6 n MeOHn
O
1.5Si SiO
1.5
n
or
or
or
Si Si
n
O
O
O
or
Drawing bridged polysilsesquioxane structures:
Fully condensed: 1.5 oxygens per Si.
Methylene-bridged polysilsesquioxane

13. bridged polysilsesquioxane nomenclature:
Methylene-bridged polysilsesquioxane
Si
O
Si
Si
O
Si
O
CH
2
CH
2
Si
Si
O
Si
O
O
Si
O
O
O
Si
CH
2
O
CH
2
O
Si
O
O
Si
CH
2
O
O
O
CH
2
Si
CH
2
Si
O
O
CH
2
O
O
O
O
Si
O
O
CH
2
Si
O
Si
Si
O
O
OO
C
H
2
O
1.5Si SiO
1.5
n
or
Si Si
n
O
O
O
or
Not “methane-bridged”
Not “methano-bridged”
Not “methano-silica”
Not “methylene modified silicate”
These are not silicas
These are not silicates

14. Different ways to put hybrids together
Class 1: No covalent bonds between inorganic and organic phases
Class 2: Covalent bonds between inorganic and organic phases
Example: particle filled polymer
Monomers in solvent Gel or dry gel (xerogel)
Close-up of hybrid
particle

15. In practice, how do you make these
hybrids?
Inorganic Organic
Physical mixing
Colloidal dispersion
Aggregation or coalescence
Class 1:Try to use high viscosity of polymer to hinder aggregation
Class 2: Use covalent bonds to prevent aggregation of phases
Like oil and water

16. Making Hybrid Materials: Class 1A
(pre-formed particles and fibers)
Pre-formed Particles
Polymers
Si
O
Si Si
O
RR
R
Si
O
OSi
O
Si Si
O
O
O
O
Si
O
O
O
R
R R
R
R
=
or SiO
2
or MO
x
or O
1.5Si-R-SiO
1.5
or R-SiO
1.5
or
Physical mixing of particles in melt
or solution
Easiest hybrid to make

17. Inorganic Phases
Metal Oxide Networks
Organically modified Metal Oxide Networks

18. Inorganic Phases
Silica Particles
Preformed inorganic clusters
Ti
12O
16(OPr
i
)
16 Ti
17
O
24
(OPr
i
)
20
Ti
18
O
22
(OBu
n
)
26
(Acac)
2
Ti(OR)
4-x
(acac)
x
POSS

19. Making silsesquioxanes as
inorganic phase
Si
R
Si
Si
R
Si
O
O
O
Si
Si
O
Si
O
R
Si
O
O
O
Si
O
R
OH
O
Si
O
O
SiOR
O
O
R
Si
O
R
Si
O
OH
O
R
O
R
OH
R Si
R
O
O
R
Si
Si
R
HO
Si
OH
R
HO O
OH
R
R
R
RSi(OMe)
3
H
2O
catalyst
Si
O
Si Si
O
RR
R
Si
O
O
Si
O
Si Si
O
O
O
O
Si
O
O
O
R
R R
R
Ror
Blue is inorganic Black is organic
Surface modified inorganic

20. Class 1A: POSS physically dispersed in
polypropylene
Si
OR'
R
OR'
OR'
Si
O
Si Si
O
RR
R
Si
O
O
Si
O
Si Si
O
O
O
O
Si
O
O
O
R
R R
R
R
R"
n
=
POSS

21. Inorganic Phases
Isolated metal atoms in polymeric
architectures (organometallic polymers)
While formally “inorganic” these behave more like organic

22. Organic phases: Polymers
Commercially available from Dow, BASF \
or from research chemical vendors: Aldrich or Polyscience

23. Inorganic Phases
Carbon Buckeyballs, nanotubes
and graphene
Nature Materials 9, 868–871 (2010)
Organic need more
than just carbon:
CHNO

24. Class 1: No covalent bonds between inorganic
and organic phase (easiest hybrid to prepare)
Example: particle filled polymer
1) First need to prepare or buy inorganic particles
2) then, depending on polymer melting point, mix into
melt or solution of polymer
3) Cool (if melt) or evaporate solvent (if solution)
If you were making this hybrid, what would you be worrying
about? And how would you check experimentally?

25. Making Hybrid Materials: Class 1B
(in situ particle growth)
Si
OR'
R
OR'
OR'
Si
OR'
R
OR'
OR'
Si
OR'
R'O
R'O
M(OR')
x Si
OR'
R'O
OR'
OR'
No Solvent except for monomer(s)
Generally uses low t
g
organic polymers
or in polymer melts (< 100 °C).
Viscous environment. Confined growth.

26. Making Hybrid Materials: Class 1B
(in situ particle growth)
CH
3Si(OMe)
3
Melt
LInear polymer
"Inorganic
monomer"
H
2O
tin catalyst
Particles form in situ 10-10000 nm
Polymerize
inorganic
monomer
Grow
inorganic
particles
What must happen for this method to work?

27. Making Hybrid Materials: Class 1C
(Polymerizing in pores)
•Porous metal oxide
•Liquid monomer (no solvent)
•UV, heat, radiation
R
R
R R
R
R
R
R
R
R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
RR
R
R
R
R
R
R
R
R
R
R
R
catalyst
Non-porous composite material
Same issues as in 1B, but organic polymerization must not be
chemically hindered by metal oxide
What polymerization chemistry is incompatible with silica or
silsesquioxanes? Why?

28. Making Hybrid Materials: Class 1D
(encapsulation of small organics)
• Polymerize metal oxide around organic
• pores must be small or leakage will
occur
•Solid state dye lasers, filters, colored
glass
catalyst
OOHO
OOHO
O
O
OH
O
O
HO
O
O
HO
H
2O
© Asahi-
Kirin
Describe how the starting materials
must behave for this to work

29. Ancient Humans also made Hybrid
organic-inorganic materials: Maya
Blue
L. A. Polette, N. Ugarte, M. José Yacamán and R. Chianelli, Sci. Am. Discovering
Archaeology, 2000, July–August, 46
Indigo
+
white clay palygorskite
(Mg,Al)
2Si4O10(OH)·4(H
2O)
(also called Fullers Earth)
Class 1B or Class 1C or Class 1D??

30. Making Hybrid Materials: Class 1E
(Interpenetrating network)
• Both organic and inorganic phases
grow simultaneously
•Timing is more difficult
• Reproducibility is a challenge
• May need to use crosslinking organic
monomers to ensure solid product
R
R
R
R
R
R
R
R
R
R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
catalystR
R
What does this assume
about the reaction
kinetics?

31. Making Hybrid Materials: Class 2A
(Covalent links at molecular level)
• Organic group is attached to network
at molecular level
•Hypercrosslinking is possible
•Pendant or bridging monomers
•Bridging groups can be small or
macromolecule
•This class also includes the
organometallic polymers
catalystR
R
R
R
R
R
R
R
R
R
R
R
R R
R
R
RR
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
H
2O
Chromatographic
Materials
Low Dielectrics
Photoresists for
Lithography

32. Making Hybrid Materials: Class 2B
(Covalent links at polymer level)
• ligands attached to polymer
• Reaction rates slow unless in sol. or
melt
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
RR
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
In Melt
or in solution

33. excess water
H+, OH- or F-
Making Hybrid Materials: Class 2C
Templating with block copolymers and
surfactants
Self-assembly surfactant into 3-D biphase system then
polymerize in one of the phases (usually in the water
phase)

34. Making Hybrid Materials: Class 2C
(Templating) Shown here with block
copolymer
O
n m
A B
hydrophobic
polyisoprene
hydrophilic
polethylene oxide
Heat polymer then cool
or cast from solvent

35. Making Hybrid Materials: Class 2C
(Templating) Shown here with block copolymer
PEO, Al
2O
3 and
RSiO
1.5
polyisoprene
Block copolymer
Block copolymer
Sol-gel system
Multiple phases
created by varying
size of blocks

36. 1. Davis, H. T., Bodet, J. F., Scriven, L. E., Miller, W. G. Physics of
Amphiphilic Layers, 1987, Springer-Verlag, New York
Templating with surfactants:(Class 2C)
• First prepare two
phase surfactant
system
•
 
Add monomer. Sol-
gel monomers move
into aqueous phase
with hydrolysis
•
 
Filter precipitate
• remove surfactant
by calcining or
extraction
Many different
phases can be
accessed

37. Surfactant templating to make
hierarchical materials (Class 2C)

38. Surfactant templating (Class 2C)
Benzene-silica hybrid material
with 3.8 nm pore diameter
(Inagaki, Nature, 2002).

39. Classes 2D Covalent coupling agents
Attaching organic group onto inorganic material
O
Si
O
O
Si
O
Si
O
OH
O
O
HO
Si
O
Si
O
Si
O
SiO
SiO
Si
O
Si
O
Si
O
Si
O
Si
O
Si
O
Si
O
O
HO
HO
O
HO
O
HO
OH
HO
O
HO
O
HO
O
OH
O
OH
O
OO
OH
O
HO
OH
Si
Si
Si
Si
Si OHO
O
O
OSi
O
OH
Si
OOH
O
OSi
Si
HO
O
O
Si
O
O
Si
O
SiO
HO
O
O
O
Si
O
Si
O
Si
O
Si
OSi
O
Si
O
Si
O
Si
O
Si
O
Si
O
SiO
SiO
O
HO
HO
O
HO
O
HO
OHOH
O
OH
O
OH
O
OH
O
OH
O
O
O
OH
OHO
OH
Si
Si
Si
Si
Si
Si
OH
O
O
O
O
Si
O
OH
Si
O
OH
O
Si
Si
HO
O
HO
HO
O
O
O
OO O Si(OEt)
3
O
O
O
OH
OH

40. Classes 2E Covalent coupling agents-
Attaching inorganic group onto organic
polymer
γ hν
Si(OEt)
3
polyethylene
Si(OEt)
3
For tough electrical wire coating
& shrink fit wrap

41. Summary
•Silsesquioxane nomenclature is hard to
pronounce
•Organosilica is improper nomenclature
•Mixing polymer with anything is hard & may
not work
•Good mixing is necessary for hybrids
•Surfactants can template hierarchical
structures