POLYMERS

LEARNING OBJECTIVES
1. Describe a typical polymer molecule in term of its chain structure

2. Describe how the molecule may be generated from repeat units .

3. Draw repeat units for several polymers.

4. Name and briefly discuss the general types of polymer molecular

structures, the three types of stereoisomers and the two types of
geometrical isomers.

5. Cite the difference between thermoplastics and thermosets.

6. Calculate number-average and weight-average molecular weights, and

degree of polymerization of specified polymers.

7. Describe the interrelationship of material, structure, processing method

and properties of polymeric compunds.
Chemistry for Engineers, 2nd Ed, Holmes
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.

IMAGE SOURCE: hAp://www.pslc.ws IMAGE SOURCE: Callister, 2011

OCCURRENCES:
Natural: cellulose, rubber, cotton, silk, wool, starch, keratin
Synthetic: Plastics, Nylon, Dacron
An/a Introduction/review to/on
Organic Chemistry
Addition Polymerization Mechanism

Chemistry for Engineers, 2nd Ed, Holmes

Addition Polymerization Mechanism

Chemistry for Engineers, 2nd Ed, Holmes

IMAGE SOURCE: Roussack, 2013
Condensation Polymerization Mechanism

Chemistry for Engineers, 2nd Ed, Holmes

Condensation Polymerization Mechanism

Chemistry for Engineers, 2nd Ed, Holmes

Condensation Polymerization Mechanism

Chemistry for Engineers, 2nd Ed, Holmes

Condensation Polymerization Mechanism

Chemistry for Engineers, 2nd Ed, Holmes

Condensation Polymerization Mechanism

Chemistry for Engineers, 2nd Ed, Holmes

GENERAL CLASSIFICATIONS OF POLYMERS

1. Homopolymer – when all the repeating units along a

chain are of the same type

Chang, 2010
hAp://www.pslc.ws
GENERAL CLASSIFICATIONS OF POLYMERS

2. Copolymer – when all the repeating units along a chain

are different

Chemistry for Engineers, 2nd Ed, Holmes

COPOLYMERS: Lycra-Spandex

www.docbrown.info
GRAFT COPOLYMERS: Acrylonotrile Butadiene Styrene
(ABS)

Polystyrene provides ease of processing, glossiness and rigidity.

Acrylonitrile adds chemical resistance and hardness.
Butadiene provides impact assistance.

www.polycraN.utdallas.edu
GENERAL CLASSIFICATIONS OF POLYMERS

hAp://www.pslc.ws
GENERAL TYPES OF POLYMER MOLECULAR
STRUCTURES

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.

Callister, 2011
GENERAL TYPES OF POLYMER MOLECULAR
STRUCTURES

1. Linear – those in which the repeat units are joined

together end to end in single chain.

The long chains are flexible and may exhibit an 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 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.
 HDPE LDPE
Chemistry for Engineers, 2nd Ed, Holmes
GENERAL TYPES OF POLYMER MOLECULAR
STRUCTURES

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

Brown, 2012
IMAGE SOURCE: Roussack, 2013
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 group are situated at the

same side of the chain

2. Syndiotactic configuration – the R group are situated at

the alternate sides of the chain

3. Atactic configuration – the R group are situated radomly at

the alternate sides of the chain
TYPES OF POLYMERIC STEREOISOMERS

T->B: IsotacTc, syndiotacTc, atacTc

Chang, 2010
TYPES OF GEOMETRIC ISOMERS

1. Cis- structure – CH3 group and H are positioned on same

side of the double bond

Example: Natural rubber (cis-polyisporene)

2. Trans- stucture – CH3 group and H are positioned on

opposite sides of the double bond

Example: Gutta percha (trans-polyisoprene)

*Trans is less elastic because of the more ordered structure

and more close packing of the molecule
TYPES OF GEOMETRIC ISOMERS

*Trans is less elastic because of the more ordered structure

and more close packing of the molecule

IMAGE SOURCE: Roussack, 2013

CLASSIFICATION ACCORDING TO BEHAVIOR WITH
RISING TEMPERATURE

1. Thermoplastics (thermoplastic polymers) – soften when

heated and harden when cooled- processes that are totally
reversible and may be repeated

2. Thermosets (thermosetting polymers) – become

permanently hard during formation and do not soften upon
heating

Chemistry for Engineers, 2nd Ed, Holmes

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

where xi = the fraction of the total number of chains within the

corresponding size range

Mi = the mean molecular weight of size range i

POLYMER MOLECULAR WEIGHT

2. weight-average molecular weight, Mw – based on the

weight fraction of molecules within the various size ranges

where wi = the weight fraction of molecules within the same

size interval

Mi = the mean molecular weight of size range

.
POLYMER MOLECULAR WEIGHT

Distribution of molecular weight of a typical polymer

Callister, 2011
POLYMER MOLECULAR WEIGHT

3. Degree of Polymerization, DP represents the average

number of repeat units in a chain

where m = repeat unit molecular weight

Mn = the number average molecular weight

.
POLYMER MOLECULAR WEIGHT

IMAGE SOURCE: Roussack, 2013

POLYMER MOLECULAR WEIGHT

Given the following data, determine the polymer’s number

molecular weight, degree of polymerization and weight
average molecular weight.

.
Brown, 2012
SAMPLE EXERCISES

1. Compute repeat unit molecular weights for the following:

(a) polytetrafluoroethylene, (b) poly(methyl methacrylate), (c)
nylon 6,6, and (d) poly(ethylene terephthalate).

2. Below, molecular weight data for a polytetrafluoroethylene

material are tabulated. Compute (a) the number-average
molecular weight, (b) the weight-average molecular weight,
and (c) the degree of polymerization.
REFERENCES:

Brown, T.L., Lemay Jr., H.E., Bursten, B.E., Murphy,

C.J., and Woodward, P.M. (2012) Chemistry: The
Central Science, 12th Ed., USA: Pearson Education,
Inc.

Brown, L.S. and Holme, T.A. (2011) Chemistry for

Engineering Students, 2nd Edition, USA, Brooks/Cole,
Cengage Learning

Callister Jr., W., (2007) Material Science and

Engineering: An Introduction, USA, John Wiley & Sons

Chang, R. (2010) Chemistry, 10th Ed., New York,

McGraw Hill
REFERENCES:

Roussack, O.V., Gesser. H.D., (2013). Applied

Chemistry: A Textbook of Engineers and Technologists,
2nd Ed., London, Springer