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Transcript of --MPK-Introduction to Inorganic polymer--(1).pdf
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Introduction toIntroduction to
INORGANIC POLYMERSINORGANIC POLYMERS
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What is an inorganic polymer ?What is an inorganic polymer ?
► Inorganic by its name implies nonorganic or
nonh drocarbon. The most obvious definition
for an inorganic polymer is a polymer that hasinorganic repeating units in the backbone.
► A giant molecule linked by covalent bonds-
hydrocarbon units in the main molecular
► A polymer that don't have any carbon atoms
in the backbone chain.
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Why inorganic polymers ?
► The main reasons for scientist to be
interested in inorganic-base macromolecules
are connected with their unique propertyprofiles that make them different from their
.
these polymers.
► The relative high abundance of inorganicelements in the earth's crust.
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►Stronger bond formation, which are more resistantto cleavage reactions (Si-O 110, P-N 140, and C-C 85
kcal/mol).
► Different valencies for attachment of side groups.
.
► Tailoring new and interesting structures with manyvariations, which seem endless.
organic polymers are made of oil, according to the
decrease of oil storages, the existence of them will
.
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Classification schemes
field of chemical research and already have many
applications and any classification is necessarily
somewhat arbitrary.
►N. H. Ra in his book on inor anic ol mers 1978
uses connectivity as a method of classifying
inorganic polymers.
► The other classifying will be introduced
in the following:
- wholly inorganic polymers- inorganic-organic polymers
- or anometallic ol mers
- hybrid organic-inorganic polymers
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Classification by
connectivities
► Ray defines connectivity as the number of atomsattached to a defined atom that are a part of the
polymer chain or matrix. This polymer connectivity
can range from 1 for a side group atom or functional
-
and metal-cyclopentadienyl polymers, respectively.
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Connectivities of 1
► Anchored metal-containing polymers used for
catalysis can have connectivity values as low as 1
.
- ,
might be palladium or platinum with three other ligands. For catalytic activity, at
least one of the three must be easily removed by a substrate.
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Connectivities of 2
a b
bc
Examples of inorganic polymeric species with connectivity of 2:(a) linear polyphosphate; (b) poly(dichlorophosphazene)
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Connectivities of 3
Examples of connectivity of 3: (a) boric acid, (b) arsenic(III) sulfide,
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Mixed Connectivities of 2 and 3
Example of polymeric inorganic species with mixed connectivities of 2 and3:
an ultraphosphoric acid
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Connectivities of 4
silica with silicon atoms of connectivities of 4 and (b) boron phosphate withboth phosphorus and boron atoms with connectivities of 4.
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Connectivities of 6
Mixed Connectivities of 4 and 6
An orthophosphate of mixed connectivites of 4 and 6.
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Connectivities of 8
A Schiff-base polymer of zirconium with a connectivity of 8.
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wholly inorganic polymers► Inorganic polymers in this class constitute the major
components of soil, mountains and sand, and they are
also employed as abrasives and cutting materials
(diamond, silicon carbide (carborundum)), fibres (fibrous
glass, asbestos, boron fibres), coatings, flame
retardants, buildin and construction materials window
glass, stone, Portland cement, brick and tiles), and
lubricants and catalysts (zinc oxide, nickel oxide, carbon
black silica el aluminium silicate and cla s .
Structure of a typical silicon dioxide intensive glass
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Inorganic-organic Polymers► inorganic polymers containing organic portions
attached to inorganic elements in their backbone. The
- .
Some examples of this class are: Polysilanes,Polysiloxanes, Polyphosphazenes.
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Organometallic Polymers
►Organometallic polymers are made of over 40
elements including main group of metals (Si or Ge),
10 elements (C, H, N, O, B, P, halides) which is found inorganic polymers (Figure 10).The variations of
organometallic polymers seem endless.
Organometallic polymers are new materials which
combine the low densit and structural variations andfunctional group varieties of organic materials with
electrical conductivity and the high temperature stability
.
Different structures found in organometallic polymers
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Hybrid organic-inorganic polymers
► Hybrid organic-inorganic networks, prepared via sol-gel
process, are multi-functional materials offering a wide
.
different combinations of the organic and inorganicmoieties, a large number of applications are possible by
incorporation of inorganic building blocks such as silica
networks, porous materials and metals.
π-Conjugated polymers prepared via organometallic
condensation reactions
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INORGANIC
SYNTHESIS
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synthesis. We focus our discussion on some of them.
A classification of polymerization reactions
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► Polyphosphazenes are inorganic polymers with a
phosphazene repeating unit and general structure (-RR'P=N-). They
are genera y prepare rom t e nterme ate
poly(dichlorophosphazene) and either amines or sodium salts of
alcohols. Poly(dichlorophosphazene) is prepared from the ring
.
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► In 1949, Burkhard was invented a polysilane called
polydimethylsilane that it wasn't much good for anything. It formed crystals
that were so strong that nothing could dissolve them. In the seventies,
some scientists got the notion to make small rings of silicon atoms. But
unwittingly did something similar to what Burkhard had done. They
reacted sodium metal with dichlorodimethyl silane, but they also added
some dichloromethylphenylsilane to the brew. But they didn't get the ringsthey wanted. they got a copolymer that was soluble and can be processed
.
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► The major route to produce polysiloxane is Rochow process in
such as copper. These compounds react with water forming
dihydroxysilanes that in turn will be condensed, splitting out water,
eventually forming polysiloxanes.
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A dual thermal ring-opening polymerization reaction between a
silyl-bridged ferrocene and a cyclic silane.
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The cationic initiated polymerization of divinylferrocene.
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The synthesis and electropolymerization of copper(II) and nickel(II)
3,4-bis(salicylaldimino)thiophene Schiff-base chelates
The photo activated platinum-catalyzed hydrosilylation polymerization of
vinyldimethylsilane
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The synthesis of lanthanide polyelectrolytes with
Condensation Through Bridging Ligand Coordination.
(bis(tetradentate) Schiff-base bridging ligand).
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General synthesis pathway for hard type triazene polyurethanes were
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APPLICATIONS
OF
INORGANIC POLYMERS
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► Amorphous silicon dioxide-intensive materials
,window glasses, Vycor glasses, borosilicate glass, which
can be shaped by drawing, pressing, casting, and
ow ng. o our ess op ca g asses, um nescence an
laser glasses are produced by using rare earth elementsas components of these special glasses. A scintillating
glass with fluorescence properties uses PbO-Bi2O3
heavy-metal oxides based materials. A new superionic
organic monomer ions is reported, which exhibits high
ionic conductivity comparable to that of oxides based
super on c g asses, u o mes arger an otypical Li+ polymer electrolytes.
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►
Pol sul hur nitride is the first re ortednon-metallic covalent polymer, with electronic conductivity
properties comparable to that of metal, and is the first
examp e o a po ymer c supercon uctor.
It is used as conductive material in the manufacturing
conductive plastic light sources such as battery-
powered flash lights and lanterns. Battery housing or head assemblies for light sources are formed from
electrically conductive polymers such as poly(sulphur
.
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► Polysilanes are useful as precursors to silicon
car e ceram cs as p otores sts, n m croe ectron csas photoinitiators for radical reactions and as
hotoconductors.
s con car e ceram cs
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► Siloxane polymers have numerous medical applications such
as: prostheses, artificial organs, facial reconstruction and tubing
and catheters take advantage of the inertness, stability, and
pliability of these polymers; artificial skin, contact lenses, and drug
delivery systems utilize their high permeability as well. A wide
range of medical-purpose items were manufactured using of
unsaturated siloxane rubbers with silicon hydrides of variousstructures. These materials are biologically-compatible with a high
.
b
b
a
used to make vinyl sheet with detailed surface.
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► Polyphosphazenes or phosphonitrilic polymers are the most
Applications based on structure-property correlations in technology or
medicine are as follows:
- Advanced elastomers, design for a rechargeable lithium battery based
on the conductivity of lithium triflate in solid poly[bis-(methoxyethoxyethoxy) phosphazene.
- The extreme hydrophobicity of the surface minimizes the foreign body
interactions that normally occur when non-living materials are implanted, .
- Solid polymer electrolytes have been extensively
density batteries.
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► Polymeric copper phthalocyanine containing
peripheral carboxyl groups is converted into polyimides
through polycondensation with aromatic diamine to
the fabrication of electronic devices.