05 j schwab pdf
TRANSCRIPT
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POSS NANOSTRUCTURED CHEMICALS:
PROVIDING UTILITY THROUGH DIVERSITY
Joseph J. Schwab
18237 Mount Baldy Circle
Fountain Valley, CA 92708
www.hybridplastics.com
Presented at the Nanostructured Chemicals WorkshopSeptember 7th - 8th, 2000
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What is a Nanostructured Chemical
(1) A single molecule-not compositionally fluxional assemblies
(2) Size regime of approximately 0.7nm to 50nm-larger than small molecules/smaller than macromolecules
(3) Typically polyhedral 3-dimensional geometry-clusters provide excellent examples-not particulates, dendrimers, planar hydrocarbons
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(1) Unique nomenclatures-e.g. carboranes, carbon balls/tubes, polyoxometallates,
polyhedral oligomeric silsesquioxanes
(2) Systematic chemistries-specific to each nanochemical system
(3) Unique physical properties-compositionally dependant-structurally dependant
Characteristics of Nanostructured Chemicals
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Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R X
Anatomy of a Polyhedral OligomericSilsesquioxane (POSS) Molecule
May possess one or more
functional groups suitable for
polymerization or grafting.
Ther mally and chemically
robust hybrid
(organic-inorganic) framework.
Nanoscopic in size with an
Si-Si distance of 0.5 nm
and a R-R distance of 1.5 nm.
Nonr eactive organic (R)
groups for solubilization
and compatibilization.
Pr ecise thr ee-dimensional str uctur e for molecular level
reinforcement of polymer segments and coils.
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R = cyclopentyl
Si Si = 5.4 Cp Cp = 15
Space Filling Model of a POSS Macromer
Si
Si
O O
Si
Si
Si
Si
O O
OO
Si
O
Si
OO
O
O
O
R
R
R
R
R
R
R
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Nomenclature for POSS Nanostructures
Heteroleptics
{[RSiO1.5]7[RSiO1.5]1} 8
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R R'
Homoleptics
{[RSiO1.5]8} 8
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R R
Functionalized Heteroleptics
{[RSiO1.5]4[R(OH)SiO1.0]3} 7
Si
Si
O
O
Si
Si Si
O
O
OH
OH
SiO
Si
O
OO
O OH
R R
R
R
R
R
R
{[RSiO1.5]n} n for homoleptic compositons.
{[RSiO1.5]m[RSiO1.5]n} m&n for heteroleptic compositions, where R R.
{[RSiO1.5]m[R(OH)SiO1.0]n} m&n for functionalized heteroleptic compositions, where R
groups may be equivalent or inequivalent.
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Brown, J.F.; Vogt, L.H.J. Am. Chem. Soc. 1965, 87, 4313.
Feher, F.J.; Newman, D.A.; Walzer, J. F.J. Am. Chem. Soc. 1989, 111, 1741.
Historical Synthesis of POSS Structures
The desired product precipitates over a period of 2-36 months as a white
microcrystalline solid, along with two minor components.
Si
Si
O
O
Si
Si Si
O
O
OH
OH
SiO
Si
O
OO
O OH
Cy Cy
Cy
Cy
Cy
Cy
Cy
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
Cy Cy
Cy
Cy
Cy
Cy
CyOH
O
HOCy
Si
O
O
Si Si
O
O
O
Si
O
O
Cy Cy
CyCy
Si
SiO
Cy
O
Cy
SiCl3
Hydrolysis
T4D3 or "T7" T6D2 T6
The crude product was stirred with 5 times its weight of pyridine ....
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Pre-Commercialization Manufacturing Process
Optimal synthesis proceeds on the order of several days, scalable to
multiple kilogram quantities.
Carried out at maximum concentrations of 0.2 Molar.
Moderate reaction yields of T7, with up to 10% T8.
Feher, F.J.; Budzichowski, T. A..; Blanski, R. L.; Weller, K. J.; Ziller, J. W. Organometallics1991, 10, 2526-2528.
Si
Si
O
O
Si
Si Si
O
O
OH
OH
Si O
Si
O
OO
O OH
c-C5H9 c-C5H9
c-C5H9
c-C5H9
c-C5H9c-C5H9
c-C5H9
c-C5H9SiX3
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
Si O
Si
O
OO
O O
c-C5H9 c-C5H9
c-C5H9
c-C5H9c-C5H9
c-C5H9
c-C5H9 c-C5H9
+
T4D3 or "T7" T8
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Traditional POSS Nanostructures
Silanes
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
HH
H
H
H
H
H H
SiSi
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
O
O
Si
Si
Si
O
O
Si
Si Si
O
O
OH
OH
SiO
Si
O
OO
O OH
RR
R
R
R
R
R
H8T8
Vinyl8T
8
R = Cyclopentyl
Cyclohexyl
As recently as 1998 commercially available POSS and silicate type
nanostructures were synthesized solely from four silane feedstocks.
Q8M
8
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
O O
R4N+ -O O- +NR4
O- +NR4
R4N+ -OO- +NR4
R4N+ -O
R4N+ -O O- +NR4
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POSS Commercialization andCost Reduction Campaigns
Also in October 1998 Hybrid Plastics and the Air Force Research Laboratory entered into a
Cooperative Research and Development Agreement (CRADA) for the commercialization of
POSS Nanotechnology.
Technical Objective:
Commercialization of POSS Technology.
Technical Objective:
In October 1998 Hybrid Plastics was awarded a 3-year, $2 million grant by NISTs Advanced
Technology Program (ATP) to reduce the cost of POSS Nanostructured Chemical Technology
by a factor of 100.
Reduce costs of POSS Technology from $1000-$5000/lb to $10-50/lb.
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Develop processes for the synthesis of nanostructures from low cost feedstocks.
Increase efficiency of processes:
Increase concentration at least 5 fold.
Increase yield to >95%.Increase selectivity for desired products.
Decrease reaction times from days to hours.
Develop processes suitable for large scale (kilo-ton) production.
Develop technology portfolio which will allow:
Selective manipulation SiO framework.
Control of stereochemistry.
Control of functionality.
Type of reactive functionality.
Degree of reactive functionality
Technical Challenges:
POSS Commercialization andCost Reduction Campaign
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POSS Manufacturing Process
New PolymerChemistry Begins
Silanes Polysilsesquioxanes Sand Primary
Feedstocks
Molecular Silicas
POSS Silanols
POSS Monomers
Nanoreinforced
Plastics
New MaterialsScience
and Applications
a b c
e
f
g
NanostructuredFeedstocks
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R R
Si
Si
O
O
Si
Si Si
O
O
OH
OH
SiO
Si
O
OO
O OH
R R
R
R
R
R
R
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
Si
O
Si
O
OO
O
O
R R
R
RR
R
RReactive Group
d
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POSS Manufacturing Process
Silanes
Polysilsesquioxanes
Molecular Silicas
POSS Silanols
POSS Monomers
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R R
Si
Si
O
O
Si
Si Si
O
O
OH
OH
SiO
Si
O
OO
O OH
R R
R
R
R
R
R
HO
OSi
Si
O
R
OH
O
O
R
Si O
Si
Si
O
O
O Si
Si
O
R
R
R
R
O
OHO Si
HO
O
R
R
Si
Si
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R
R
R
R
R R
R RSi
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
Reactive GroupReactive Group
Reactive Group
Reactive GroupReactive Group
Reactive Group
Reactive Group Reactive Group
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POSS Manufacturing Process
Molecular Silicas POSS Silanols
Polysilsesquioxanes
HO
OSi
Si
O
R
OH
O
O
R
Si O
Si
Si
OO
O Si
Si
O
R
R
R
R
O
OHO Si
HO
O
R
R
Si
Si
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R
R
R
R
R R
R R
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R R
Si
Si
O
O
Si
Si Si
O
O
OH
OH
SiO
Si
O
OO
O OH
R R
R
R
R
R
R
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
RR
R
R Reactive Group
POSS Monomers
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POSS Manufacturing Process
New PolymerChemistry Begins
Silanes Polysilsesquioxanes Sand Primary
Feedstocks
Molecular Silicas
POSS Silanols
POSS Monomers
POSS Nanoreinforced
Plastics
New MaterialsScience
and Applications
a b c
d
e
f
g
NanostructuredFeedstocks
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R R
Si
Si
O
O
Si
Si Si
O
O
OH
OH
SiO
Si
O
OO
O OH
R R
R
R
R
R
R
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
Si
O
Si
O
OO
O
O
R R
R
R
R
R
RReactive Group
h
i
j
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POSS Manufacturing Process
Sand
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R4N
+ -
O O- +NR4
O- +NR4
R4N+ -O
O- +NR4
R4N+ -O
R4N+ -O O- +NR4
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
RO OR
OR
ROOR
RO
RO OR
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
RR
SandThe Final Frontier in the Manufacture of POSS Feedstocks
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Commercial Nanostructure Synthesis
Reaction Time: hours.
Concentration: 1 Molar or greater.
Product Yield: Excellent, 0-1% byproduct.Si
Si
O
O
Si
Si Si
O
O
OH
OH
SiO
Si
O
OO
O OH
i-C4H9 i-C4H9
i-C4H9
i-C4H9
i-C4H9i-C4H9
i-C4H9
i-C4H9SiX3
Si
Si
O
O
Si
Si Si
O
O
OH
OH
SiO
Si
O
OO
O OH
c-C5H9 c-C5H9
c-C5H9
c-C5H9
c-C5H9c-C5H9
c-C5H9
c-C5H9SiX3
Reaction Time: > 1 week.
Concentration:
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Cost Reduction for POSS Silanols
A switch from cyclopentyl based silane feedstocks to isobutyl based
feedstocks for the synthesis of POSS nanostructures results in a
94% decrease in cost.
vs.
Breakdown of the reduction is as follows:
Silane feedstock: 78%.
Increase in Yield: 1%.
Solvent: 6%.
Waste: 16%.
Si
Si
O
O
Si
Si Si
O
O
OH
OH
SiO
Si
O
OO
O OH
c-C5H9 c-C5H9
c-C5H9
c-C5H9
c-C5H9c-C5H9
c-C5H9
Si
Si
O
O
Si
Si Si
O
O
OH
OH
SiO
Si
O
OO
O OH
i-C4H9 i-C4H9
i-C4H9
i-C4H9
i-C4H9i-C4H9
i-C4H9
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POSS Nanostructure Diversity
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R R
Si
Si
O
O
Si
Si Si
O
O
OH
OH
SiO
Si
O
OO
O OH
R R
R
R
R
R
R
Si
Si
O
O
Si
Si
Si
Si
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R R
OH
OH
Si
O
SiO
Si
O
Si
O Si
O
Si
O
SiO
Si
O
SiOSi
O
SiO
O
Si
R
R
R
O
OR
R
R
OO
O
R
R
R
R
R
R
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R4N+ -O O- +NR4
O- +NR4
R4N+ -O
O- +NR4
R4N+ -O
R4N+ -O O- +NR4
Methyl
Isobutyl
CyclopentylCyclohexyl
Isooctyl
Phenyl
PhenethylOctadecene
R = Isobutyl
Cyclopentyl
CyclohexylIsooctyl
Ethyl
R = Isobutyl
Cyclopentyl
CyclohexylIsooctyl
R =
Phenyl
Trifluoromethylpropyl
R =MethylR =
Polydisperse Cages
(T8, T10, T12)
Vinyl
Phenethyl
R =
-
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Stereochemical and Topological Control
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
Si O
Si
O
OO
O
O
R R
R
RR
R
R R
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
Si O
Si
O
OO
R R
R
R
R
R
R
RO
OH
HO
Si
O
OH
Si
Si
Si
Si
O
O
O
O
Si OH
HOO
O HO
R
R
RR
R
R R
Si
Si
O
O
Si
Si
Si
Si
O
O
O
Si O
Si
O
OO
OO
R R
R
RR
R
R R
OH
OH
Si
Si
O
O
Si
Si Si
O
O
OH
OH
Si O
Si
O
OO
OOH
R R
R
R
RR
R
Si
Si
O
O
Si
Si
Si
Si
O
O
O
SiO
Si
O
OO
OO
R R
OH
R
R
R
R OH
R
R
Si
Si
O
O
Si
Si Si
O
O
R
R
SiO
Si
O
OO
O R
R R
OH
HO
R
OH
R
Si
Si
O
O
Si
Si Si
O
O
OH
O
SiO
Si
O
OO
O
R R
R
R
R
R
R
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Systematic Functionalization of Nanostructures
Y = nearly any polymerizable or graftable group
Si
Si
O
O
Si
Si Si
O
O
OH
OH
Si
O
Si
O
OO
O OH
R R
R
R
R
R
R
Si
Si
O
O
Si
Si
Si
Si
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R Y1
Y2
OH
Si
Si
O
O
Si
Si Si
O
O
SiY1Y2Y3
SiY1Y2Y3
SiO
Si
O
OO
O SiY1Y2Y3
R R
R
R
R
R
R
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R Y1
Si
Si
O
O
Si
Si Si
O
O
SiY1Y2Y3
OH
SiO
Si
O
OO
O OH
R R
R
R
R
R
R
Si
Si
O
O
Si
Si
Si
Si
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R Y1
Y2
SiY1Y2Y3
X2SiY1Y2 XSiY1Y2Y3
X3SiY1
XSiY1Y
2Y
3
X2SiY1Y2
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Systematic Functionalization of Nanostructures
Y = nearly any polymerizable or graftable group
Si
Si
O
O
Si
Si
Si
Si
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R R
OH
OH
Si
Si
O
O
Si
Si
Si
Si
O
O
O
SiO
Si
O
OO
O O
R R
R
R
R
R
R R
O
O
Si
Si
O
O
Si
Si
Si
Si
O
O
O
Si O
Si
O
OO
O O
R R
R
RR
R
R R
O
O
SiY2
Y1
X2SiY1Y2
XSiY1Y2Y3
SiY1Y2Y3
SiY1Y2Y3
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
R R
R
R
R
R
R
RO
OH
HO XSiY1Y
2Y
3
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
R R
R
RR
R
R
RO
SiY1Y2Y3
2Y31YYSi
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Functionalized POSS-Monomers
Hybrid Plastics currently offers over 120 Nanostructured Chemicals
Si
Si
O
O
Si
Si Si
O
O
OH
OH
Si
O
Si
O
OO
O OH
R R
R
R
R
R
R
Acrylics
-olefins
ChlorosilanesSilanesSilanols
NitrilesIsocyanates
PhosphinesAmines
AlcoholsPhenols
NorbornenesStyrenes
Carboxylic AcidsCarboxylic Esters
Epoxides
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R Reactive Group
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Physical Form of Nanostructured Chemicals
Waxes
Crystalline SolidsWide melting range 24C to 400C+
Liquids/OilsWide viscosity range 40cSt. to 400cSt
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4Develop processes for the synthesis of nanostructures from low cost feedstocks.
4Increase efficiency of processes:
4Increase concentration at least 5 fold.
4Increase yield to >95%.4Increase selectivity for desired products.
4Decrease reaction times from days to hours.
4Develop processes suitable for large scale (kilo-ton) production.
4Develop technology portfolio which will allow:
4Selective manipulation SiO framework.
4Control of stereochemistry.
4Control of functionality.
4Type of reactive functionality.
4Degree of reactive functionality
Technical Challenges:
POSS Commercialization andCost Reduction Campaign
-
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Key Aspects of POSS Technology
Hybrid (inorganic/organic) Composition Nanostructured Chemical Reinforcement
POSS technology does not
require manufacturers toretool or alter existingprocesses.
Lichtenhan et. al. Macromolecules 1993, 26, 2141.Lichtenhan, Polym. Mater. Encyclopedia1996, 10, 7768.
Si
SiO
O
Si
Si
Si
Si
O
O
O
OSi O
Si
O
O
O
O
O
R
R
R
R
RR
O
O
CH3
O
CH3
R
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
OO
R
THF
Catalyst
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
O
O
O
O
R
R
R
R
RR
O
R
O
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
O
O
O
O
R
R
R
R
RR
O
R
CH3
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POSS Organic-Inorganic Hybrids
POSS Nanostructures may be thought of as the smallest
silica particles possible.
As such their copolymerization with organic monomers could
provide materials which behave as silica-reinforced composites.
If POSS organic-inorganic hybrid polymers do in fact behave as
silica-reinforced composites, this approach represents a
breakthrough in this area since single-phase composite processing
becomes possible.
Sellenger, A,; Laine, R. M.,Macromolecules 1996, 29, 2327.
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Property Enhancements via POSSObserved in POSS-Copolymers and Blends
increased Tg increased Tdecenhanced blend
miscibility
reducedheat evolution
reducedflammability
extendedtemperature range
oxidationresistance
modifiedgas permeability
modifiedmechanicals
thermoplasticor curable
disposaalas silica
lower densitylower thermalconductivity
reduced
viscosity
Beatcompetitors
patents !
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Tg -vs- Composition Relationship for POSS-
POSS-Methacrylate/MMA Copolymers
Copolymers
100
150
200
250
300
0 10 20 30 40 50
Tg transitions measured via TMA
TMA
Tg(C)
Mol % CpPOSS
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
Si
O
Si
O
OO
O
O
R R
R
RR
R
OO
CH3
O
CH3
O
CH3
y
R = cyclopentyl
x
R
n
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Thermoplastic Urethane Material
0
20
40
60
80
100
0%(TMP)
17%(TMP)
34%(TMP)
0%(B
PA)
21%(B
PA)
36%(B
PA)
Hardness
(ShoreA)
32.4
59.0
80.4
39.5
75.5
84.4
Hardness Data for POSS Polyurethanes
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Markets for Nanostructured Chemicals
POSS Monomers New Polymer Synthesis
Grafting Reactions
POSS Reagents Catalysis
Models for Silica Supports
Ligands
Coupling Agents
Surface Modification
Drug Delivery
Combinatorial Scaffolds
POSS Resins
Coatings FR Materials
Dielectric Materials
POSS Polymers Coatings
Nanocomposite Plastics
Ablative Materials
POSS Molecular Silica Nanofillers
Lubricants Ligands
Resin Compounding
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POSS MetallasilsesquioxanesModels For Silica-Supported Catalysts
Trisilanol 1 is structurally similar to known SiO2 polymorphs.
Coordination geometry is dictated by the ligand.
Si-O-M frameworks are thermally very stable.
Ligand framework does not contain - or -H or C atoms.
Si/O Frameworks are -electron-withdrawing.
M = Ti, Zr , V, Cr, Mo, W, Pt
B, Al, Ga
Si, Ge, Sn,
P, As, Sb, BiSi
Si
O
O
Si
Si Si
O
O
OH
OH
SiO
Si
O
OO
O OH
R R
R
R
R
R
R
Si
Si
O
O
Si
Si
M
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R
1 POMSS
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POSS Metallasilsesquioxanes
Si
Si
O
O
Si
Si
V
Si
O
O
O
O
Si
O
Si
O
OO
OO
R R
R
R
R
R
R O
Me3Al (1-5 eq)
C2H4 (1 atm)
25 C
Polyethylene
0.5 mmol
2.04 g
~1500 turnovers/V
Same catalyst also produces polypropylene and 1,4-trans-Polybutadiene.
mmol of Catalyst Pressure t.o./Cr
0.031
0.088
1 atm
37 atm
~1100
~3250
Feher, F.J.; Walzer, J.F.; Blanski, R.L.J. Am. Chem. Soc. 1991, 113, 3618-3619.
Feher, F.J.; Blanski, R.L.J. Chem. Soc., Chem. Commun. 1990, 1614-1616.
Si
Si
O
O
Si
Si
Cr
Si
O
O
O
OTMS
SiO
Si
O
OO
OO
R R
R
R
R
R
RO
O
Me3Al (2 eq)
25 C
C2H4Polyethylene
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POSS Metallasilsesquioxanes
Si
Si
O
O
Si
Si Si
O
O
OTMS
SiO
Si
O
OO
O
R R
R
R
R
R
R O
O
Mo
H
C
N
Catalyst Rapidly Equilibrates Olefins
complete equilibration of
9300 equiv in 10 minutes
cis-2-octene
1octene
2-butenes + 6dodecenes
100 turnovers in 60 seconds
150 turnovers in 20 seconds
C2H4 + 7tetradecenes
methyl oleate 9octadecenes + diesters
complete equilibration of
400 equivs in ~3 hoursCH3(CH2)7-CH=CH-(CH2)7CO2Me
Feher, F. J.; Tajima, T. L.J. Am. Chem. Soc. 1994, 116, 2145-2146.
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POSS Metallasilsesquioxanes
Si
Si
O
O
Si
Si
Ti
Si
O
O
O
O
SiO
Si
O
OO
O O
R R
R
R
R
R
R L
+ Hydroperoxide + Oefin
O
R R
R R
L = phenoxy, isopropoxy, benzyl, trimethylsiloxy, dimethylimido.
R = alkyl, cycloalkyl, alkylaryl, alkoxy, aryloxy, siloxy, amido, and OH.
Hydroperoxide = benzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide.
Olefin = propylene, butylene, isobutylene, butadiene, 3-hexene, 1-octene, and 1-decene.
Crocker, M.; Herold, R.H.M. US Patent 5 750 741
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POSS Metallasilsesquioxanes
Duchateu, R.; Abbenhuis, H.C.L.; van Santen, R. A.; Thiele, S.K.-H.; van Tol, M.F.H.
Organometallics1998, 17, 5222-5224.
van Tol, M.F.H.; Thiele, S.K.-H.; Duchateu, R.; Abbenhuis, H.C.L.; van Santen, R. A.
European Patent Application EP 0 967 229 A1.
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
SiO
Si
O
OO
OO
R R
R
R
R
R
R O
R = cyclopentyl
Ti
CH2Ph
CH2Ph
SiMe3Me3Si
+ [Ph3C][B(C6F5)3] + Ethylene
or
1-Hexene
Polyethylene
or
Poly-1-Hexene
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Acknowledgements
NIST Advanced Technology Program
Air Force Research Laboratory
Dr. Shawn Phillips
Dr. Timothy Haddad
Dr. Rusty Blanski
University of California Irvine
Dr. Frank Feher
Hybrid Plastics
Dr. Yi-Zhong An
Mike Carr
Dawn Hilton
Dr. Joseph LichtenhanDr. Qibo Liu
Dr. William Reinerth