CHEME - Chemistry for Engineers

Engineering Materials – Polymer

A polymer is a molecular compound distinguished by a high molar mass, ranging into thousands and millions
of grams, and is constructed by the sequential stringing together of smaller molecules called monomers.

CLASSIFICATION OF POLYMERS ACCORDING TO ORIGIN

1. NATURAL: occur in nature. Examples: cellulose, natural rubber, cotton, natural silk, wool, starch, protein
2. SEMISYNTHETIC: modified natural polymers. Examples: hydrogenated natural rubber, cellulose
nitrate, methylcellulose
3. SYNTHETIC: those that are synthesized in the laboratory. Examples: plastics, Nylon, Dacron, polyvinyl
chloride

**C-C bonds are exceptionally strong and stable; it is advantageous for them to serve as the backbone of
most synthetic polymers available.

STRUCTURE OF ORGANIC COMPOUNDS

Carbon has four valence electrons ([He]2s2,2p2); hence, it forms four bonds in virtually all its compounds.
Because the valence shell of C—H can hold only two electrons, hydrogen forms only one covalent bond. As
a result, hydrogen atoms are always located on the surface of organic molecules whereas the bonds form the
backbone, or skeleton, of the molecule.
CHEME - Chemistry for Engineers
Engineering Materials – Polymer
CHEME - Chemistry for Engineers
Engineering Materials – Polymer
CHEME - Chemistry for Engineers
Engineering Materials – Polymer
 CHEME - Chemistry for Engineers
Engineering Materials – Polymer

CLASSIFICATION OF POLYMERS ACCORDING TO MODE OF FORMATION:

1. ADDITION POLYMERS: They are formed from the simple addition of monomer molecules to each
other in quick succession by a chain mechanism without the liberation of small molecules. Examples:
polyethylene, polypropylene, polystyrene
2. CONDENSATION POLYMERS: Occurs between monomers containing polar groups which form
polymers along with the elimination of small molecules. The reactions usually take place through the
functional groups. Examples: polyurethane, polycarbonate, polyesters
3. CO-POLYMERIZATION: Two or more molecules undergo joint polymerization. Example: SBR

CLASSIFICATION OF POLYMERS ACCORDING TO CHAIN STRUCTURE:

1. Homopolymer–when all the repeating units along a chain are of the same type.
2. Copolymer –when all the repeating units along a chain are different.

CLASSIFICATION OF POLYMERS ACCORDING TO MOLECULAR CONFIGURATION:

TYPES OF POLYMERIC STEREOISOMERS
Stereoisomerism denotes the situation in which atoms are linked together in the same order (head-to-tail) but
differ in their spatial arrangements.
1. Isotactic configuration –the R groups are situated on the same side of the chain
2. Syndiotactic configuration–the R groups are situated at the alternate sides of the chain.
3. Atactic configuration–the R groups are situated randomly at the alternate sides of the chain.

CLASSIFICATION OF POLYMERS ACCORDING TO MOLECULAR CONFIGURATION:

TYPES OF GEOMETRIC ISOMERS
1. Cis-structure –CH3 group and H are positioned on the same side of the double bond. Example: Natural
rubber (cis polyisoprene)
2. Trans-structure–CH3 group and H are positioned on opposite sides of the double bond. Example:
Guttapercha (trans-polyisoprene)
*Trans is less elastic because of the more ordered structure and more close packing of the molecule.

CLASSIFICATION OF POLYMERS ACCORDING TO MOLECULAR STRUCTURE:

The physical characteristics of a polymer depend not only on its molecular weight and shape but also on
differences in the structure of the molecular chains.
1. Linear –those in which the repeat units are joined together end to end in a single chain. The long chains
are flexible and may exhibit extensive van de Waals and hydrogen bonding between the chains. Examples:
polyethylene, poly (vinyl chloride), polystyrene, poly(methyl methacrylate) and nylon.
2. Branched polymers –those that have side-branch chains that are connected to the main ones. The chain
packing efficiency is reduced with the formation of the side branches which results in a lowering of the
polymer density.
3. Cross-linked –adjacent linear chains are joined one to another at various positions by covalent bonds.
Often, this cross-linking is accomplished by additive atoms or molecules that are covalently bonded to the
chains.
4. Network –a three-dimensional network polymer that is formed from three or more active covalent bonds
of multifunctional monomers. Examples: epoxies, polyurethanes, and phenol-formaldehyde.

CLASSIFICATION ACCORDING TO THERMAL RESPONSE

1. Thermoplastics (thermoplastic polymers) –soften when heated and harden when processes that are totally
reversible and may be repeated.
2. Thermosets (thermosetting polymers) –become permanently hard during formation and do not soften
upon heating.
 CHEME - Chemistry for Engineers
Engineering Materials – Polymer

INFLUENCE OF STRUCTURE ON POLYMER PROPERTIES

1. Strength of polymer
a. Cross-linked polymers are strong and tough due to the restricted movement of the intermolecular
chains that are linked through covalent bonds.
b. Polymers of low molecular weights are soft and gummy but brittle. Those with higher chain groups
are tougher and have higher resistance to heat.
c. Presence of polar groups along the polymer chain length has a higher strength due to the increased
intermolecular interactions.
2. Plastic deformation
a. Polymers consisting of linear-chain molecules are thermoplastics even with high molecular weight
and are soluble.
b. Three-dimensional polymer molecules are insoluble and are thermosets.
c. Cross-linking converts thermoplastic materials into thermosetting.
3. Solubility and chemical resistance
a. Polymers containing polar groups are more soluble in polar solvents but are chemically resistant
to non-polar solvents.
b. Nonpolar groups containing polymers are soluble in nonpolar solvents but are chemically resistant
to polar solvents.
4. Mechanical properties
a. The strength of a polymer is controlled by the length of the chain and its cross-linking.

COMPOUNDING: The process of mixing additives to plastics

COMMON ADDITIVES
1. Resins: bind all additives together
2. Fillers: modify the properties of plastic to make the final product better in hardness, tensile strength,
and workability.
3. Plasticizers: small molecules that penetrate the polymer matrix and neutralize a part of the
intermolecular forces of attraction between macromolecules and increase the mobility of the polymer
segments so that chains can slide over each other.
4. Coloring materials: added to improve the aesthetic effect of the material.
5. Catalysts: added to accelerate the cross-linking of the thermosetting.
6. Stabilizers: added to improve the thermal stability of polymers during processing.
7. Antistatic: added to dissipate the electrical charge developed by conducting it away.

POLYMER MOLECULAR WEIGHT

1. Number average molecular weight, Mn–obtained by dividing the chains into a series of size ranges and
determining the number fraction of chains within each size range
𝑀𝑛 = ∑ 𝑥𝑖 𝑀𝑖
where xi = the fraction of the total number of chains within the corresponding size range
Mi = the mean molecular weight of size range i
2. Weight-average molecular weight, Mw –based on the weight fraction of molecules within the various
size ranges
𝑀𝑤 = ∑ 𝑤𝑖 𝑀𝑖

where wi= the weight fraction of molecules within the same size interval
Mi = the mean molecular weight of the size range
 CHEME - Chemistry for Engineers
Engineering Materials – Polymer

3. Degree of Polymerization, DP represents the average number of repeat units in a chain.

𝑀𝑛
𝐷𝑃 =
𝑚
where m = repeat unit molecular weight
Mn= the number average molecular weight

Sample Problem:
Calculate the number-average molecular weight of a random poly(isobutylene-isoprene) copolymer in which
the fraction of isobutylene repeat units is 0.25. Assume that this concentration corresponds to a degree of
polymerization of 1500.