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STRUCTURE OF POLYMERS

Introduction

Poly & mers Greek ; meros=part; polymer=many parts Natural polymer derived from animals & plants wood, rubber, cotton, wool, leather, and silk Other natural polymers such as proteins, enzymes, starches, and cellulose this group of materials and the development of numerous polymers synthesized from small organic molecules. Many of our useful plastics, rubbers, and ber materials are synthetic polymers. It can be produced inexpensively, and their properties can be managed to the degree that many are superior to their natural counterparts. In some applications metal and wood parts have been replaced by plastics that have satisfactory properties and may be produced at a lower cost. Most of polymers are organic in origin & based on hydrocarbon (H & C)

Hydrocarbon - HC

HC Intramolecular bonds are covalent Each C atom has 4 e to participate in covalent bonding, every H has 1 bonding e Single covalent bondeach of 2 bonding atoms contributes 1 e; CH4 Double & triple bond 2 C atoms share 2 & 3 pairs of e; C2H4 Saturated HC all single bond No new atom may be joined without removal of atoms that are already bonded Double & triple covalent bonds unsaturated; each C is not bonded to max atoms other atoms are possible to be bonded to the molecule

Some of the simple hydrocarbons belong to the parafn family; the chainlike parafn molecules include methane (CH4), ethane (C2H6), propane (C3H8), and butane (C4H10) The covalent bonds in each molecule are strong, but only weak hydrogen and van der Waals bonds exist between molecules, and thus these hydrocarbons have relatively low melting and boiling points. HC comp with same composition but different arrangement isomerism; affect the properties E.g. N-buthane & isobuthane

Polymer molecules

Large molecule built up by repetition of small, simple chemical units Because of their size macromolecules Atomsre bound by covalent bonds For C polymer C the backbone Many times each carbon atom singly bonds to two adjacent carbons atoms on either side 2 remaining valence of C may involve in side-bonding with atoms/radical that are positioned adjacent to the chain

C2H4-ethylene (P&Tr) gas If the ethylene gas is reacted under appropriate conditions, it will transform to polyethylene (PE), which is a solid polymeric material. This process begins when an active center is formed by the reaction between an initiator or catalyst species (R*) the ethylene monomer, as follows: R*+C2H4 R-C*2H4 The polymer chain then forms by the sequential addition of monomer units to this active growing chain molecule. The active site, or unpaired electron (denoted by *), is transferred to each successive end monomer as it is linked to the chain. This may be represented schematically as follows:

The nal result, after the addition of many ethylene monomer units, is the polyethylene molecule;

This polyethylene chain structure can also be represented as

Here the repeat units are enclosed in parentheses, and the subscript n indicates the number of times it repeats.

The vinyl chloride monomer is a slight variant of that for ethylene, in which one of the four H atoms is replaced with a Cl atom. Its polymerization is represented as

Some polymers may be represented using the following generalized form:

where the R depicts either an atom [i.e., H or Cl, for polyethylene or poly(vinylchloride), respectively], or an organic group such as CH3,C2H5, and C (methyl, ethyl, and phenyl). For example, when R represents a CH group, the polymer isvpolypropylene (PP).

The molecules are composed of structure called repeat units (Mers) Monomer: small molecule from which a polymer is synthesized

When all of the repeating units are the same homopolymer Chain may be composed of 2 or more different repeat units copolymer Ex: General N-alkane HC Higher MW increase viscosity

MOLECULAR WEIGHT

Extremely large molecular weights are observed in polymers with very long chains. During polymerization process, not all polymer chains grow the same length Result in distribution of chain length/MW length Ordinarily,an average molecular weight is specied the melting or softening temperature increases with increasing molecular weight At Tr polymers with very short chains (M ~100 g/mol) liquid; ~ 1000 g/mol are waxy solids (such as parafn wax) and soft resins; Solid polymers (sometimes termed high polymers), commonly have M ranging 10,000 - several million g/mol) Thus, the same polymer material can have quite different properties if it is produced with a different molecular weight. There are several ways of dening average molecular weight: 1) the number-ave MW, 2) weight-ave MW, and 3) degree of polymerisation

1)The number-average MW

Dividing the chains into series of size range then determining the number fraction of chain within each size range. Expressed as:

Mi=mean/middle MW of size

range i xi = fraction of total number of chain within the corresponding size range

2) The weight-average MW

weight fraction of molecules within various size ranges. Calculated as:

Mi=mean MW within size range i wi =weight fraction of molecules


within the same size interval

=degree of distribution of MW

A typical molecular weight distribution along with these molecular weight averages

3)Degree of polymerization

DP Average chain size of polymer DP average number of repeat units (mers) in a chain Can be expressed as :

Mn & m = number average MW & repeat


unit (mer) MW

Example

Figures of MW distribution are for PVC. Calculate a) number-average MW b) weight-average MW & c) degree of polymerisation

a) Table for number-average MW 21,150 g/mol

b) Table for weight-average MW 23,200 g/mol

c) PVC 2 C, 3 H & 1 Cl

Molecular Structure
Linear, branced, crosslinked, network LINIER POLYMERS repeat units are joined end to end in single chains each circle represents a repeat unit Melt on heating Mechanical strength increases with entangle chain

Example of Linier Polymer

Polyethylene HDPE PVC Polystyrene Nylon fluorocarbon

BRANCHED POLYMERS

The branch considered to be part of the main chain molecules side-branch chains are connected to the main one May result from side reactions that occur during the synthesis The chain packing efficiency reduces with formation of side branches lowering polymer density By changing T, the branched polymer can be hardened or softened Those polymers that form linear structures may also be branched. E.g. HDPE (primarily a linear Polymer), while LDPE contains short chain branches.

CROSSLINKED POLYMERS

Adjacent linear chains are joined one to another at various positions by covalent bonds increase strength, reduce plasticity Achieved during synthesis or by nonreversible chemical reaction Often, accomplish by additive atom/molecules that are covalently bonded to the chains The movement of adjacent chains is greatly restricted, affected the mechanical properties to a great extent E.g. rubber elastic material

Networking polymer

Multifunctional monomers forming three or more a polymer that is highly crosslinked may also be classied as a network polymer. These materials have distinctive mechanical and thermal properties; the epoxies, polyurethanes, and phenol-formaldehyde belong to this group. Polymers are not usually of only one distinctive structural type. For example, a predominantly linear polymer might have limited branching and crosslinking.

Thermoplastic Polymers

Soften when heated (eventually liquefy), harden when cooled reversible & may be repeated Plastic & flexible properties Formed at high T, cooled, remelted & reformed into different shape without changing properties Overheat material decomposes, irreversible degradation Most linear, some branches polymer Fabricated by simultaneous heat & pressure Example: polyethylene, polystyrene, PVC, poly(ethylene terephthalate)

Thermosetting

Network polymers Strong bonds, often formed by condensation Permanently hard during formation when heat applied Do not softened/reshaped upon subsequent heating loss of part of the molecule Further heat burn/decompose Generally harder, stronger & better stability than thermoplastic Most crosslinked, in that 10 to 50% of the chain repeat units are crosslinked. Only heating to excessive temperatures causes severance of these crosslink bonds and polymer degradation. Ex: phenolic, vulcanized rubber, epoxies

Copolymers

Polymers with more than 1 repeat unit Different type depends on method synthesis & repeat unit type Sequencing arrangement: random, alternating, block & graft copolymer 1) Random copolymer random distribution of various mers E.g nitrile rubber

2)

Alternating copolymer 2 mer units alternate chain position

4) Grafted copolymer homopolymer side branches of one type may be grafted to homopolymer main chain that are composed of different mer

3) Block copolymer identical repeat units are clustered in blocks along the chain