Dr. S.

Ray_Chem Engg_NIT Agratala

1/7/2013

What are Polymers?

Polymers are MACROMOLECULES: traces as Early as Life Began

A-DNA

Loop RNA

Cellulose

Proteins and Polypeptides

Natural rubbers

Hemoglobin

Silk

What are Polymers?

As Broad as in Daily Life: synthetic polymers

polystyrene

cis-polyisoprene

poly(vinyl pyrrolidone)

polycarbonate

poly(vinyl chloride)

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Polymer applications

Construction and Home Applications Transportation Applications Industrial Applications Information Technology Applications Textile Applications Entertainment Applications Recreational Applications Medical Applications Packaging Applications
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Polymer applications
Packaging Applications
Bottles Blister packs, Grocery sacks Shrink wrap, Foam packing

Recreational Applications
Boat hulls, kayaks, surfboards, sails Rackets, vaulting poles, athletic shoes Skis, ski poles, ski boots Golf ball covers and golf club shafts Bicycle parts, helmets, and pads

Medical Applications
Catheters, gloves, disposables Surgical prosthesis, Dental fillings, coatings Eyeglass frames and lenses

Textile Applications
Clothing, Carpets, non woven fabrics Diapers and other disposables Upholstered fabrics for furniture Draperies and wall paper material

Industrial Applications
Pipes, valves, and tanks Gears and housings Adhesives and coatings Vibration damping pads Electrical circuit boards Wire insulation and connectors Gaskets and sealants

Transportation Applications
Automotive bodies, and parts Aerospace components Train, monorail, and light rail cars Truck bed liners and gas tanks 4

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Polymers - Definition

Definition of Polymers: Poly + Meros = many + parts or units Long-chain-like molecules or macromolecules consisting of many repeating units (monomers) that are covalently linked, instead of physically-associated aggregates Molecular weight higher than ~10,000 g/mol (different from oligomers, which is composed of a few repeating units)

Polymer, Macromolecule and Polymerization In strict term, a polymer is a substance composed of molecules which have long sequences of one or more species of atoms or groups of atoms linked to each other by primary, usually covalent, bonds. Macromolecules are formed by linking together monomer molecules through chemical reactions, the process by which this is achieved being known as polymerization. Although the words polymer and macromolecule are usually interchangeable, the latter strictly defines the molecules of which the former is composed.
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Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Definitions
Monomer - molecule with minimum functionality of two that reacts to form the structural units of the polymer Oligomer - short chain synthesized from reaction of several monomers (dimer, trimer, tetramer) Polymer - macromolecule generated through sequential reaction of a small number of elementary units reaction of a small number of elementary units Repeating unit - structure composed of the minimum number of structural units necessary to generate the polymer Degree of polymerization number of repeating units
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History of Macromolecules and Polymers

1846
Christian Schnbein invented nitrocellulose (gun cotton). Cellulose nitrate is a hard elastic material which is soluble and easy to be shaped. 1862 Alexander Parkes made articles from plasticized cellulose nitrate 1870 John and Isaiah Hyatt patented celluloid

1892 Charles Cross, Edward Bevan, and Clayton Beadle patented regenerated cellulose, i.e., viscose rayon fibers and cellophane films

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

History of Macromolecules and Polymers

History of Macromolecules and Polymers

1977 Alan Heeger, Alan MacDiarmid, and Hideki Shirakawa discovered and developed conducting polymers

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Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Classification of polymers
1. 2. 3. 4. 5. 6.
7.

Classification by Application Classification by Origin Classification by Thermal Behavior Classification by Chain Structure Classification by Monomer Composition Classification by type of polymerization
Classification by Chain Configuration

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Classification of polymers
1. Classification by Application 1. Plastics 2. Fibers 3. Elastomers 4. Coatings 5. Adhesives

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Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Differences between Natural Polymers and Synthetic Polymers

Natural Polymers

Synthetic Polymers

Repeating units Structure MW distribution

many kinds well-defined 1.0 for proteins

one or a few kinds poorly defined from 1.0 to ~30

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Classification of polymers
2. Classification by Origin 1. Synthetic organic polymers

2. Natural polymers or Biopolymers (proteins, polypeptides, polynucleotides, polysaccharides, natural rubber)

3. Semi-synthetic polymers (chemically modified biopolymers)

4. Inorganic polymers (siloxanes, silanes)

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Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Classification of polymers
3. Classification by Thermal behavior Thermoplastics - materials become fluid and processible upon heating, allowing them to be transformed into desired shapes that are stabilized by cooling Thermosets - initial mixture of reactive, low molar mass compounds that reacts upon heating in the mold to form an insoluble, infusible network

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Classification of polymers
4. Classification by Chain/molecular structure 1. Linear chains 2. Branched chains 3. Cross-linked 4. Star 5. Interpenetrating networks 6. Semi- Interpenetrating networks

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Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

4. Classification by Chain structure (molecular architecture)

Linear chains :a polymer consisting of a single continuous chain of repeat units Branched chains :a polymer that includes side chains of repeat units connecting onto the main chain of repeat units Hyper branched polymer consist of a constitutional repeating unit including a branching groups Cross linked polymer :a polymer that includes interconnections between chains Net work polymer :a cross linked polymer that includes numerous interconnections between chains

Linear

Branched

Cross-linked

Network
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Direction of increasing strength

Classification of polymers
4. Classification by Chain structure Interpenetrating polymer network - Intimate combination of two polymers both in network form, at least one of which is synthesized and/or cross-linked in the immediate presence of the other. Semi-interpenetrating polymer network - Combination of two polymers, one cross-linked and one a linear, at least one of which was synthesized and/or cross-linked in the immediate presence of the other. Star polymer Three or more chains linked at one end through a central moiety.
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Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Chain Structures of Polymers

linear

branched (short, long, and hyperbranched)

star

graft or comb

laddered

cross-linked or network

dendritic
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Classification of polymers
5. Classification by Monomer Composition

Homopolymer

Copolymer

Block

Graft

Alternating

Homopolymer Consist of only one type of constitutional repeating unit (A) AAAAAAAAAAAAAAA

Random or Statistical

Copolymer - Consists of two or more constitutional repeating units (A.B ) with various arrangements, which define the type of copolymer
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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Classification of polymers
5. Classification by Monomer composition

1. Homopolymer - a polymer derived from one species of monomer. Structure-based definition: a polymer whose structure can be represented by multiple repetition of single type of repeat unit which may contain one or more species of monomer units (structural units). Homopolymer AAAAAAAAAAAAAAA

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Classification of polymers
5. Classification by Monomer composition 2. Copolymer - a polymer with two different monomers is known as a copolymer. a) Random/Statistical copolymer ABAABABBBAABAABB b) Alternating copolymer c) Block copolymer d) Graft copolymer ABABABABABABABAB AAAAAAAAABBBBBBBBB AAAAAAAAAAAAAAAAAA B B B B B B
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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Several classes of copolymers are (a) Statistical copolymer (Random) ABAABABBBAABAABB two or more different repeating unit are distributed randomly (b) Alternating copolymer ABABABABABABABAB are made of alternating sequences of the different monomers (c) Block copolymer AAAAAAAAABBBBBBBBB long sequences of a monomer are followed by long sequences of another monomer (d) Graft copolymer AAAAAAAAAAAAAAAAAA B B B B B B Consist of a chain made from one type of monomers with branches of another type

(d)

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Classification of polymers
5. Classification by Monomer composition 2a) Random copolymer is a statistical copolymer in which the probability of finding a given monomeric unit at any given site in the chain is independent of the nature of the neighboring units at that position.

2b) Alternating copolymer is caused either one monomer being unable to add itself, or the rate of addition of the other monomer being much faster than the addition of itself. An important example of an alternating copolymer is poly [styrene alt - maleic anhydride]
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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Classification of polymers
5. Classification by Monomer composition 2c) Block copolymer - Combination of two or more chains of constitutionally or configurationally different features linked in a linear fashion. Block copolymer AAAAAAAAABBBBBBBBB

2d) Graft copolymer Combination of two or more chains of constitutionally or configurationally different features, one of which serves as a backbone main chain, and at least one of which is bonded at some point(s) along the backbone and constitutes a side chain. Graft copolymer AAAAAAAAAAAAAAAAAA B B B B B B

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Classification of polymers
6. Classification by type of polymerization (A) Mechanism: 1.Chain growth (free radical) 2.Step growth (B) Method: 1. Addition 2. Condensation 3. Rearragement

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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Classification of polymers
7. Classification by Chain configuration 1. Monomer orientation: a) Head-to tail:

a) Head to-head

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Classification of polymers
7. Classification by Chain configuration 2. Geometric or cis-trans trans isomerism

The cistrans isomerism arises because rotation about the double bond is impossible without disrupting the structure. 3. Substitutional Isomerism: In the synthesis of diene type polymers, yet another type of isomerism may occur, that of 1,2 versus 1,4 addition.
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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Classification of polymers
7. Classification by Chain configuration 4. Stereoisomerism or tacticity Isotactic Syndiotactic Atactic

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Microstructure - Tacticity

atactic
Side groups on random Sides of the backbone

syndiotactic
Side groups on alternating sides of the backbone

isotactic
Side groups on the same side of the backbone

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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Nomenclature I
Homopolymers: A polymer derived from one species of monomer. 1. Conventional: based on source (poly + monomer) or structures 2. Commercial trade names
Trade names Alkathene, Lupolen Propathene, Novolen

Teflon, Fluon

Styron, Hostyren HIPS ABS

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Nomenclature I

Trade names Perspex, Diakon, Lucite, Oroglass, Plexiglas

Darvic, Welvic, Vinoflex, Hostalit

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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Nomenclature I

Trade names
O

HO

Carbowax Terylene, Dacron, Melinex, Mylar

Ethylene oxide

Poly(ethylene oxide)

Ultramid 6.10

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Nomenclature II
3. IUPAC Nomenclature: based on Constitutional Repeating Unit (CRU) It should be named as: poly(CRU); CRU is from left to right with the subunit of highest seniority; Seniority is heterocyclic rings > heteroatoms or acyclic subunits containing heteroatoms > carbocyclic rings > acyclic subunits containing only carbon; For heterocyclic rings, the seniority is: the largest number of rings > the largest individual ring > a ring with greatest number of heteroatoms > a ring with greatest variety of heteroatoms; The seniority for heteroatoms: O>S>Se(Selenium)>Te(Tellurium)>N>P>As (Arsenic)>Sb(Antimony), Bi(Bismuth)>Si>Ge(Germanium)>Sn(Tin)> Pb(Lead). For carbocyclic rings, the seniority is: largest number of rings > the largest individual ring > a ring system with the most unsaturation; The CRU should be a divalent group wherever possible; Where there is a choice subunits should be oriented so that the lowest location number results for substituents or groupings.
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Polymer Processing Engineering

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Dr. S.Ray_Chem Engg_NIT Agratala

1/7/2013

Nomenclature: II
Example 1

II

III

IV

VI

poly[oxy(fluoromethylene -methylene)]

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Nomenclature III
Copolymers

Random Copolymers

Alternating Copolymers

Block Copolymers

Graft Copolymers

-B-B-A-B-A-A-B- -A-B-A-B-A-B-A-B- -A-A-A-A-B-B-B-B- -A-A-A-A-A-A-A-A-A-A-A-B-B-B-A-A-AB B B B B B B B B

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Polymer Processing Engineering

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