--mpk-introduction to inorganic polymer--(1).pdf

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Introduction toIntroduction to

INORGANIC POLYMERSINORGANIC POLYMERS



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.



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.



►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

.



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 polymersinorganic-organic polymers

- or anometallic ol mers

- hybrid organic-inorganic polymers



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.



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.



Connectivities of 2

a b

bc

Examples of inorganic polymeric species with connectivity of 2:(a) linear polyphosphate; (b) poly(dichlorophosphazene)



Connectivities of 3

Examples of connectivity of 3: (a) boric acid, (b) arsenic(III) sulfide,



Mixed Connectivities of 2 and 3

Example of polymeric inorganic species with mixed connectivities of 2 and3:

an ultraphosphoric acid



Connectivities of 4

silica with silicon atoms of connectivities of 4 and (b) boron phosphate withboth phosphorus and boron atoms with connectivities of 4.



Connectivities of 6

Mixed Connectivities of 4 and 6

An orthophosphate of mixed connectivites of 4 and 6.



Connectivities of 8

A Schiff-base polymer of zirconium with a connectivity of 8.



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



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.



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



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



INORGANIC

SYNTHESIS



synthesis. We focus our discussion on some of them.

A classification of polymerization reactions



► 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

.



► 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

.



► 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.



A dual thermal ring-opening polymerization reaction between a

silyl-bridged ferrocene and a cyclic silane.



The cationic initiated polymerization of divinylferrocene.



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



The synthesis of lanthanide polyelectrolytes with

Condensation Through Bridging Ligand Coordination.

(bis(tetradentate) Schiff-base bridging ligand).



General synthesis pathway for hard type triazene polyurethanes were



APPLICATIONS

OF

INORGANIC POLYMERS



► 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.



►

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

.



► 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



► 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.



► 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.



► Polymeric copper phthalocyanine containing

peripheral carboxyl groups is converted into polyimides

through polycondensation with aromatic diamine to

the fabrication of electronic devices.

--mpk-introduction to inorganic polymer--(1).pdf

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