Inorganic polymer - Ferdowsi University of Mashhad - …r.takjoo.profcms.um.ac.ir/imagesm/1006/stories/POlymer... · 2014-09-29 · the number of side groups attached to a skeletal

Inorganic polymer

SECTION TWO

Ferdowsi University of Mashhad 2

INO

RGA

NIC

POLYM

ER

BO

ND

ING

(ATTRA

CT

ION

S)Function of distance between atoms

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Cl

Covalent

Non-metal : Non-metal

Cl

Shared electrons4Ferdowsi University of Mashhad

INO

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Si

Covalent

Non-metal : Non-metal

Si

Shared electrons

5Ferdowsi University of Mashhad

INO

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ER

Metals Non-MetalsCeramics(Ionic Bonds)

Metals(Metallic Bonds)

Polymers(Covalent Bonds)

INO

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6

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How Polymers Are Depicted

n or x


INO

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n or x


INO

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n or x


INO

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POLYMER CLASSIFICATIONS:


INO

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INO

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Reasons for Interest in Inorganic Polymers

Most of synthetic polymers are organic materials.

Synthetic polymers

•Nylon

•Dacron

•Lucite

Naturally occurring polymers

•Proteins

•Nucleic acids

•Cellulose

•Rubber

Styrene-butadiene rubber

INO

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NIC

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ER


Organic Polymer

Inorganic Polymer

Presence of “C“ in backbone

Mainly petroleum less frequently plants, animals, or microorganisms

INO

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Organic Polymer vs. Inorganic Polymer

Many organic polymers are not suitable for high temperatures applications.

Organic polymers become very brittle at very low temperatures.

At high temperatures they are oxidatively degraded.

Organic backbone polymers react with oxygen or ozone over a long period of time and lose their advantageous properties. Organic polymers degrade when exposed to ultraviolet or gamma radiation

Organic polymers have excellent flammability properties. So, most organic polymers are a fire hazard with toxic smoke. (required to blend fire-retardant additives )

Limitation petroleum sources.

INO

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Organic Polymer vs. Inorganic Polymer cont.

Organic polymers swell or dissolve in organic solvents, oils, or hydraulic fluids.

Environmental pollution (undegradable)

INO

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Organic Polymer vs. Inorganic Polymer cont.

Inorganic elements generate different combinations of properties in polymers than do carbon atoms.

Inorganic elements bonds in polymers are longer, stronger, and more resistant to free radical cleavage reactions.

Inorganic polymers have bond angles and bond torsional mobility (inorganic elements). So, they have unique properties.

Inorganic elements can have different valencies than carbon, and this means that the number of side groups attached to a skeletal atom may be different from the situation in an organic polymer.

Abundance of some inorganic element ( Si (27.2 % by weight, second), while carbon ranks fourteenth).

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Conclusion:Organic Polymer vs. Inorganic Polymer

Flexibility of the macromolecule

Ability to react with chemical reagents

Stability at high temperatures

Interactions with solvents and with other polymer molecules

Moreover, the use of non-carbon elements in the backbone provides opportunities for tailoring the chemistry in ways that are not possible in totally organic macromolecules.

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pure inorganic polymers is rare.

Presence of organic or inorganic side-group make them vary in shape, characteristics and …

Note:

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A: Polymerization of unsaturated organic monomers.

B: Condensation of (usually) two difunctional monomers with each other.

C: Ring-opening polymerization of cyclic organic rings to linear chain polymers.

Modification of Preformed Polymers

Organic Polymers Synthesis

INO

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1. Addition Chain GrowthPolymerization of Vinyl Monomers

Ring Opening Polymerization HeterocylicsMetathesis of Cyclic Olefins

2. Condensation Step GrowthPolymerization of A-B or AA/BB Monomers

3. Modification of Preformed PolymersPolysaccharides

Peptides and ProteinsSynthetic Precursors

INO

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carbon-carbon double bonds

INO

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polypropylene

Polystyrene

poly(vinyl chloride)

INO

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1. Addition Chain Growth

Ring Opening Polymerization ROPHeterocylicsMetathesis of Cyclic Olefins

INO

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Ring Opening Polymerization ROPHeterocylics cyclic monomer

INO

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Ring Opening Polymerization ROPHeterocylics

Radical ring-opening polymerization of vinyl cyclopropane

INO

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Ring Opening Polymerization ROPHeterocylics

The anionic ring-opening polymerization of ε -caprolactone, initiated by alkoxide function

INO

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INO

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Ring Opening Polymerization

Metathesis polymerization

(ROMP)

Ring-opening metathesis (ROM)Ring-closing metathesis (RCM)

INO

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Ring Opening Polymerization

Metathesis polymerization

Ring-opening metathesis polymerisation (ROMP)

Cross metathesis (CM)

Ring-opening metathesis (ROM)Ring-closing metathesis (RCM)

INO

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INO

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Aromatic polysulfides

INO

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INO

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INO

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REVIEW SOME COMPLIMENT AND CONCEPTS

Ferdowsi University of Mashhad 35

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Monomer (One Unit)-any molecule capable of reacting to form repeating units

Oligomer (Few Units)-few monomers (usually 2-10) reacted with each other

Polymer (Many Units)A giant molecule made up of many monomers (Molecular Wt typically

greater than 5,000)

INO

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INO

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OLIGOMERS

Oligomer – Greek: oligos fewmer parts

• Find commercial application in a variety of fields:Elastomers

- poly(ethylene oxide) oligomers in Spandex®

Coatings & Adhesives

Lubricants- fluorinated oligomers used as lubricants on satellites, disk drives, etc…

DEGREE OF POLYMERIZATIONNo of monomeric unit present in polymer is DP

FUNCTIONALITY: The number of bonding sites in a monomer.

Functionality two :It can form straight chain polymers: CH2=CHX

Functionality three: It can form three dimensional network: Phenol, Melamine

When tri functional monomer is mixed with small amounts of bi functional monomer than brached chain polymer is formed.

INO

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INO

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1- Linear – a chain with two ends

Skeletal Structure

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2- Branched – have side chains

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3- Crosslinked (Networked) – chains are connected to other chains


Branched Cross-Linked NetworkLinear

secondarybonding

Branched Cross-Linked NetworkLinear

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INO

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Homopolymer – only one monomer (repeating unit)-A-A-A-A-A-A-A-A-A-A-A-A-

Copolymer – more than one monomer

1- Alternating - A – B – A – B – A – B – A – B -- A – A – B – B – A – A – B – B –

2- Block -A-A-A-A-A-B-B-B-B-B-A-A-A-A--A-A-A-A-A-A-A-B-B-B-B-B-B-B-

3- Graft

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BASED ON INTERACTION WITH WATER (Environmental friendly)

oNon-biodegradable hydrophobic Polymers

Soluble biodegradable Polymers

Polymerization


random

block

graft

alternating

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INO

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BASED ON POLYMERISATION METHOD:

tAddition Polymers

Condensation polymers

Rearrangement polymers

Polymerization

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BASED ON POLYMERIZATION MECHANISM:

Chain Polymerization

Step growth PolymerizationPolymerization

INO

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Based on Conductance

Insulators

Conducting

INO

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Based on Isomerism/Polymer Tacticity

Isotactic

Sindiotactic

Random/Atactic

Classification scheme for the characteristics of polymer molecules

isomerism – different molecular configurations for molecules (polymers) of the same compositionStereoisomerismGeometrical Isomerism

INO

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Bulkmonomer and initiator in a tank

Solutionmonomer and initiator with a solvent in which the product is soluble

Suspensionsame as above but product precipitates out

Emulsiontwo phases with surfactant micelles

Based on PREPARTION TECHNIQUESIN

ORG

AN

ICPO

LYMER

INO

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Thermoplastic Elastomer Thermoset

Based on Response to heat

INO

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Linear or branched polymers which can be melted when heat is applied. A polymer that turns to a liquid when heated and freezes to a very glassy state when cooled sufficiently.

Primary bonds along the chains. Secondary bonding between chains.

Can be molded into any shape with processing techniques such as injection molding or extrusion.

Most are recyclable

Natural thermoplastics – silk, cellulose (proteins), polylactic acid

Thermoplastics

INO

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Elastomer

An elastomer is defined as a cross-linked amorphous polymer above its glass transition temperature.

Crosslinked (networked) rubbery polymers that can be stretched easily (3-10 original size)

Rapidly recover original dimensions when applied stress is released.

Low degree of crosslinkingOpposite of Fibers

INO

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Uses –gloves, rubber bands, bouncing balls

Not recyclable

Degrades (burns/scorches) when heat is added

Natural elastomers – natural rubber, latex

Elastomer

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Thermoset

Normally are rigid materials.

Network polymers in which chain motion is greatly

restricted by a high degree of crosslinking.

Much primary bonding, little secondary.

Cannot be reshaped. once formed.

Epoxy

INO

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ER


Uses – high temperature electrical applications, super

glue, counter top laminates, epoxy resins, tires

(vulcanized rubber)

Cannot be recycled (burn/scorch with heat)

Natural* thermosets – vulcanized rubber

Thermoset

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Inorganic polymer - Ferdowsi University of Mashhad - …r.takjoo.profcms.um.ac.ir/imagesm/1006/stories/POlymer... · 2014-09-29 · the number of side groups attached to a skeletal